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Coordination number

In chemistry, the coordination number of a central atom or is defined as the number of other atoms directly linked to it through σ-bonds, excluding π-bonds. In the context of coordination compounds, it specifically denotes the number of donor atoms from ligands that are bonded to a central metal atom or , forming a . This concept, originally introduced by in 1893, is fundamental to understanding the structure and bonding in both molecular complexes and extended solid-state materials. Coordination numbers typically range from 2 to 12 or higher, depending on the size of the central atom, the nature of the ligands or surrounding ions, and steric factors; common values include 4 and 6 for molecular , and 4, 6, 8, and 12 in ionic crystals. The value of the coordination number dictates the of the or , such as linear (CN=2), tetrahedral or square planar (CN=4), octahedral (CN=6), or cubic (CN=8), which in turn influences the physical and chemical properties of the compound. For instance, in aqueous solutions, [Co(NH₃)₆]³⁺ exhibits an octahedral with a coordination number of 6, while [Cu(NH₃)₄]²⁺ is square planar with CN=4. In , the coordination number arises from the close packing of ions and is governed by the radius ratio between cations and anions, leading to structures like tetrahedral (CN=4) for smaller cations or octahedral (CN=6) for larger ones. This principle underlies the stability of minerals and ceramics, as outlined in . Overall, coordination numbers play a crucial role in diverse fields, including , (e.g., the iron center in oxyhemoglobin with CN=6), and , where they determine reactivity, electronic properties, and structural integrity.

Fundamentals

Definition and scope

The coordination number (CN) of a central atom in a is defined as the number of atoms directly linked to it through coordinate bonds, typically bonds in coordination compounds. In coordination entities, it specifically denotes the number of connections from ligands to the central metal atom or , excluding other interactions. This concept, introduced by in his foundational work on coordination chemistry, originates from the German term "Koordinationszahl," emphasizing the fixed number of surrounding groups around a metal center. In molecular and ionic systems, the primary coordination sphere comprises the directly bonded ligands, while the secondary coordination sphere includes surrounding ions or molecules that interact through weaker, non-covalent forces such as hydrogen bonding or electrostatic effects, influencing reactivity without altering the core bonding. For example, in the hexaamminecobalt(III) ion, [Co(NH₃)₆]³⁺, the cobalt atom has a coordination number of 6 due to the six ammonia ligands forming sigma bonds. Beyond discrete complexes, the coordination number extends to solid-state structures, where it represents the number of nearest-neighbor atoms surrounding a given atom in a crystal lattice. In face-centered cubic (FCC) metals like , each atom has a coordination number of 12, reflecting the close-packed arrangement. The concept also applies to surfaces, where reduced coordination numbers at edges or defects drive reconstructions, and to disordered systems like amorphous solids, where it denotes an average number of nearest neighbors.

Historical development

The concept of coordination number emerged in the late through the pioneering work of , who in 1893 proposed it as a key parameter to explain the isomerism observed in coordination compounds, such as metal ammines. Werner distinguished primary valences from secondary or auxiliary valences, with the coordination number defining the fixed number of attachments to the central metal , enabling predictions of spatial arrangements like octahedral (CN=6) or tetrahedral (CN=4) geometries. This framework resolved longstanding puzzles in and culminated in Werner receiving the in 1913 for his coordination theory. In the 1920s, the application of coordination number expanded into crystal chemistry, particularly through Victor Moritz Goldschmidt's studies on ionic radii and crystal packing. Goldschmidt established radius-ratio rules that correlated the ratio of cation to anion radii with preferred coordination numbers, such as CN=4 for ratios around 0.225–0.414 and CN=6 for 0.414–0.732, providing a predictive tool for the structures of ionic solids in geochemistry and mineralogy. Building on this foundation in the 1930s, Linus Pauling incorporated repulsion principles into his five rules for the structures of complex ionic crystals, emphasizing how coordination numbers influence polyhedral linkages and electrostatic balance in minerals like silicates. Pauling's valence theory, detailed in his 1939 monograph The Nature of the Chemical Bond, further linked electron pair repulsions to preferred coordination geometries, laying groundwork for later models of molecular shape. The mid-20th century saw coordination number applied to surface phenomena, spurred by advances in () techniques during the , which enabled atomic-scale analysis of surface atom arrangements and reduced coordination relative to bulk structures. Early LEED studies revealed surface reconstructions where coordination numbers drop—for instance, from 12 in face-centered cubic metals to 7–9 at (110) facets—highlighting deviations driven by dangling bonds and strain relief. Following the 1970s, the concept broadened significantly in , accommodating higher coordination numbers, such as 9 in [ReH₉]²⁻, with rare cases up to 16 in cluster compounds. This era also witnessed its extension to aperiodic solids via Dan Shechtman's 1982 discovery of quasicrystals in Al-Mn alloys, where local coordination environments, often icosahedral with CN=12, persist without , challenging classical crystallographic assumptions. In the , computational methods have enabled prediction of even higher coordination numbers, such as 16 in clusters (e.g., CoB₁₆²⁻, 2015), expanding the concept to and .

Molecular and Ionic Systems

Coordination complexes and polyatomic ions

In coordination complexes, the coordination number (CN) plays a pivotal in determining the geometric arrangement of ligands around the central metal , which in turn governs the and reactivity of . Higher coordination numbers often enhance by maximizing metal-ligand interactions and optimizing steric packing, as seen in the chelate effect where multidentate ligands effectively increase the CN while forming more thermodynamically favorable rings. For reactivity, the CN influences mechanistic pathways; for instance, octahedral complexes with CN=6 typically undergo substitutions where a ligand departs to create a five-coordinate , whereas lower CN geometries like tetrahedral may favor associative mechanisms due to less crowding. This geometric dependence affects bond strengths and electronic properties, enabling tailored applications in and bioinorganic systems. A classic example of CN=6 is found in transition metal aquo ions, such as [Fe(H₂O)₆]³⁺ and [Co(H₂O)₆]²⁺, which adopt octahedral geometries due to the six water ligands coordinating to the metal center, providing hydration stability in aqueous environments. In contrast, Zn²⁺ complexes predominantly exhibit tetrahedral CN=4, as in [Zn(NH₃)₄]²⁺ or [Zn(OH)₄]²⁻, where the d¹⁰ configuration and smaller ionic radius favor this geometry over octahedral, leading to high-spin states and enhanced solubility in polar solvents. These preferences highlight how metal identity and ligand type dictate CN, impacting properties like ligand exchange rates. In polyatomic ions, the CN of the central atom similarly defines structure and reactivity. For (SO₄²⁻), the central atom has a CN=4, coordinated tetrahedrally to four oxygen atoms, which confers high stability and resistance to under neutral conditions. (PO₄³⁻) mirrors this with the central also at CN=4 in a tetrahedral arrangement, but its higher makes it more prone to and nucleophilic attack compared to , influencing biochemical roles in energy transfer. The preference for specific CNs in transition metal complexes is further modulated by ligand field strength, which dictates spin states and thus geometric stability. Strong-field ligands like CN⁻ generate large crystal field splitting (Δ), favoring low-spin configurations that stabilize square planar CN=4 for d⁸ metals (e.g., Ni²⁺ in [Ni(CN)₄]²⁻), while weak-field ligands like H₂O promote high-spin octahedral CN=6 (e.g., [Ni(H₂O)₆]²⁺) by minimizing pairing energy penalties. This interplay allows fine-tuning of electronic properties and reactivity without altering the metal center.

Common coordination geometries

In coordination chemistry, the geometry of a is primarily determined by the coordination number (CN), which dictates the spatial arrangement of ligands around the central metal to minimize repulsion and maximize . For CN=2, the linear is prevalent, featuring a 180° bond angle, as seen in complexes like [Ag(NH₃)₂]⁺. At CN=3, trigonal planar arrangements dominate with ideal 120° angles between ligands, common in main-group or early species. For CN=4, two primary geometries occur: tetrahedral, with bond angles of approximately 109.5°, favored for smaller metals or when electronic factors like d¹⁰ configurations stabilize it, as in [NiCl₄]²⁻; and square planar, with 90° angles, typical for d⁸ metals such as Pt(II) in [PtCl₄]²⁻ due to crystal field stabilization energy preferences. CN=5 yields trigonal bipyramidal (TBP) as the most common, characterized by 120° equatorial angles, 90° axial-equatorial angles, and 180° axial-axial angles, exemplified by [Fe(CO)₅]; square pyramidal is less frequent but occurs with bulkier ligands. Octahedral geometry prevails at CN=6, with 90° cis angles and 180° trans angles, ubiquitous across d-block metals like [Co(NH₃)₆]³⁺, owing to its high symmetry and ligand packing efficiency. Higher CNs include CN=7 with pentagonal bipyramidal (ideal equatorial angles 72°, axial-equatorial 90°), as in [ZrF₇]³⁻, and CN=8 with cubic or dodecahedral forms for larger ions like [Mo(CN)₈]⁴⁻. The preferred geometry for a given CN is influenced by steric repulsion from ligand size and bulk, which favors more open arrangements to reduce crowding, and electronic effects such as the metal's d-electron count, where predicts stabilization for certain configurations (e.g., square planar for d⁸ due to larger splitting in the xy plane)./CHEM_431_Readings/10:Coordination_Chemistry_I-_Structure_and_Isomers/10.04:_Coordination_Numbers_and_Structures) Exceptions arise from distortions, notably the Jahn-Teller effect in octahedral complexes with degenerate ground states (e.g., high-spin d⁴, d⁹ like Cu²⁺ in [Cu(H₂O)₆]²⁺), where elongation or compression along an axis lowers energy by splitting the e_g orbitals. This distortion energy is described by the vibronic coupling expression: E = E_0 - A q + \frac{1}{2} k q^2 where E_0 is the undistorted energy, q is the distortion coordinate, A is the linear coupling constant, and k is the force constant; minimization yields a net stabilization of -\frac{A^2}{2k}. Polyhapto ligands, such as η⁵-Cp, can effectively increase CN by bridging multiple sites but do not alter the underlying geometric framework.

Polyhapto ligands

Polyhapto ligands are unsaturated ligands that coordinate to a metal center through multiple contiguous atoms, typically via involving conjugated systems. The hapticity, denoted by the Greek letter η followed by a superscript n (η^n), indicates the number of such atoms bound to the metal, where n ≥ 2 distinguishes polyhapto from monohapto (η^1) binding. This notation reflects the ligand's contribution to the coordination number (CN), as each η^n ligand occupies n coordination sites, influencing the overall electron count and steric environment around the metal. A classic example is the (C_5H_5^-, abbreviated ), which often binds as η^5, coordinating through all five carbon atoms in a delocalized π-fashion. In , (η^5-C_5H_5)_2, the iron center achieves an effective CN of 10, with each η^5- ligand contributing five sites, resulting in a geometry that stabilizes the 18-electron configuration. Similarly, allyl ligands (C_3H_5^-) commonly adopt η^3 coordination, binding through three carbons and contributing three to the CN, as seen in complexes like (η^3-C_3H_5)PdCl(PPh_3), where this mode supports square-planar arrangements around . The use of polyhapto ligands often deviates from geometries expected with simple σ-donors, favoring structures like bent metallocenes or half-sandwich motifs due to the extended π-overlap and directional preferences of the ligand's molecular orbitals. For instance, the η^5 binding in enforces parallel Cp rings separated by the metal, optimizing d-orbital overlap and rotational freedom. This contrasts with variable hapticity cases, where ligands like Cp can slip to η^3 or η^1 modes under steric pressure or electronic demands, dynamically adjusting the effective CN. Unlike chelating multidentate ligands, which bind through separate donor atoms via localized σ-bonds (e.g., EDTA forming six η^2-like interactions for CN=6), polyhapto ligands involve delocalized bonding across contiguous atoms in unsaturated frameworks, emphasizing π-backbonding over multiple discrete sites. This distinction arises because polyhapto coordination treats the ligand as a single unit occupying multiple sites, whereas multidentate ligands are counted by their individual donor groups.

Solid-State and Surface Applications

Bulk crystal structures

In bulk crystal structures, the coordination number (CN) refers to the number of nearest neighbors surrounding an or in extended lattices, which directly influences the packing efficiency and stability of the solid. In metallic systems, close-packed structures such as face-centered cubic (FCC) and hexagonal close-packed (HCP) lattices exhibit a CN of 12, where each is surrounded by 12 equivalent nearest neighbors, maximizing atomic density and contributing to high mechanical strength in metals like (FCC) and magnesium (HCP). In ionic crystals like (NaCl), which adopts the rock salt structure, both Na⁺ and Cl⁻ ions have a CN of 6, forming an octahedral arrangement that balances electrostatic attractions in compounds with similar ionic sizes.) The preferred CN in ionic crystals is often predicted by the radius ratio rule, which compares the of the cation (r⁺) to that of the anion (r⁻), guiding the geometry for optimal packing and minimizing repulsion. For tetrahedral coordination (CN=4), the ratio r⁺/r⁻ ranges from 0.225 to 0.414, as seen in (); octahedral coordination (CN=6) occurs for ratios between 0.414 and 0.732, typical of many alkali halides like NaCl; and cubic coordination (CN=8) is favored above 0.732, as in cesium chloride (CsCl)./09%3A_Ionic_and_Covalent_Solids_-_Energetics/9.01%3A_Ionic_Radii_and_Radius_Ratios) This Goldschmidt tolerance framework, refined through empirical observations, helps explain structural preferences without assuming perfect sphericity of ions. In covalent network solids, such as and , each atom forms four equivalent bonds in a tetrahedral arrangement, resulting in a CN of 4 that extends throughout the , yielding exceptional due to the continuous three-dimensional framework./Crystal_Lattices/Lattice_Basics/Covalent_Network_Solids) Polymorphism in ionic crystals demonstrates how CN can vary with external conditions like or temperature, reflecting adaptations to minimize . For instance, NaCl maintains its rock salt structure (CN=6) at ambient conditions but transitions to a CsCl-like body-centered cubic structure (CN=8) under (around 30 GPa), allowing closer packing of ions; conversely, CsCl is stable in the CN=8 form at due to its larger cation but can adopt the CN=6 structure upon heating above approximately 470°C. These phase changes highlight the dynamic role of CN in stabilizing bulk structures under varying thermodynamic conditions.

Surface coordination and reconstruction

At solid surfaces, atoms in the topmost layer experience a reduction in coordination number () compared to the bulk interior due to the absence of neighboring atoms beyond the surface plane. In face-centered cubic (FCC) metals, bulk atoms have a CN of 12, but on the close-packed (111) surface, surface atoms are coordinated to only 9 nearest neighbors: 6 in the surface plane, 3 in the subsurface layer. This undercoordination leads to higher surface and drives structural relaxations or to minimize dangling bonds and stabilize the surface. Surface reconstruction often involves rearrangements that result in a variety of local coordination environments to reduce the overall energy. A prominent example is the Si(111) surface, which undergoes a 7×7 reconstruction described by the dimer-adatom-stacking-fault (DAS) model. In this structure, adatoms bond to three underlying silicon atoms (CN=3), dimers form pairs with CN=2 each, and rest atoms in the second layer have reduced coordination with dangling bonds, while corner hole atoms exhibit even lower effective connectivity. These variable CNs across the reconstructed unit cell—ranging from 2 to 4 compared to the bulk tetrahedral CN of 4—effectively passivate 49 of the 49 potential dangling bonds in the unreconstructed surface, leaving only 19 exposed. Adsorption of molecules can modify local coordination by binding to undercoordinated surface sites, effectively increasing the CN of the adsorbing atom. For instance, on surfaces, () preferentially adsorbs atop or in bridge positions on low-CN sites such as steps or terraces, adding one or two ligands to the surface metal atom and raising its effective CN from 9 (on Pt(111)) to 10 or 11. This ligand-like interaction alters the electronic structure and bond strengths at the site, influencing adsorption energetics and reaction pathways. In catalysis, sites with lower CN, such as edges, corners, or defects on metal nanoparticles and single-crystal surfaces, serve as active centers due to their enhanced reactivity from undercoordination. These sites bind adsorbates more strongly than high-CN terrace atoms, facilitating bond breaking and formation in processes like CO oxidation or , as evidenced by correlations between CN and turnover frequencies across surfaces. This principle underpins the design of high-surface-area catalysts where low-CN motifs maximize activity while minimizing material use.

Determination Techniques

Experimental methods

Experimental methods for determining coordination numbers have evolved from qualitative chemical tests to advanced spectroscopic and imaging techniques, providing insights into both molecular and solid-state systems. In the late 19th century, pioneered precipitation tests to elucidate coordination numbers in complexes. By reacting coordination compounds like [Co(NH₃)₆]Cl₃ with , Werner observed the number of precipitated AgCl ions, which corresponded to ionic versus coordinated ligands, confirming a coordination number of 6 for octahedral (III) ammines. These tests, combined with measurements, laid the foundation for modern coordination chemistry by distinguishing primary and secondary valences. Diffraction techniques offer precise structural data for coordination numbers in crystalline materials. determines coordination numbers by analyzing patterns to resolve atomic positions and bond lengths in coordination complexes, such as identifying tetrahedral (CN=4) or octahedral (CN=6) geometries in metal-ligand frameworks. For disordered or solution-phase systems, (EXAFS) spectroscopy probes local environments around absorbing atoms, yielding coordination numbers from oscillations in absorption spectra; for instance, EXAFS has quantified a coordination number of approximately 9 with oxygen neighbors at 2.87 in hydrated ions. sources enhance both methods by delivering high-brilliance s, improving signal-to-noise ratios for accurate CN determination in complex samples like catalysts. Spectroscopic methods provide indirect but complementary evidence of coordination numbers through ligand-metal interactions. Nuclear magnetic resonance (NMR) spectroscopy correlates chemical shifts and coupling patterns with coordination environments, enabling CN estimation in solution; for example, ²⁷Al NMR distinguishes tetrahedral (CN=4, shifts ~60 ppm) from octahedral (CN=6, shifts ~0 ppm) aluminum species in aqueous complexes. Infrared (IR) and count ligands by monitoring vibrational frequency shifts upon coordination, such as C≡N stretches in cyano complexes shifting from ~2100 cm⁻¹ (free) to ~2050 cm⁻¹ (bound), allowing CN determination in octahedral [Cr(CN)₆]³⁻ derivatives. Microscopy techniques visualize coordination at surfaces with atomic resolution. images electronic density to reveal coordination motifs, such as CN=3 in surface-adsorbed metal atoms on reconstructed Si(111) facets. , particularly non-contact modes, maps interatomic forces to identify coordination geometries on insulators or in , complementing for hybrid surface studies.

Computational approaches

Computational approaches to determining coordination numbers (CN) rely on theoretical modeling to predict atomic environments in molecules, liquids, solids, and surfaces, often complementing experimental observations by providing insights into dynamic or hypothetical structures. These methods leverage quantum mechanical calculations, statistical simulations, and data-driven algorithms to quantify the number of nearest neighbors around a central atom, typically by analyzing , interatomic distances, or geometric partitions. In , (DFT) combined with the (QTAIM) is widely used to analyze bonding in coordination complexes and polyatomic ions. QTAIM identifies bond critical points (BCPs) in the topology, where the density gradient is zero and the indicates a , allowing the delineation of atomic basins and the confirmation of bonding interactions. For instance, in homoleptic nickel(II) complexes like [Ni(NHC)4]2+ (where NHC is N-heterocyclic ), QTAIM analysis at the B3LYP-D3/def2-TZVP level reveals shared-interaction regions consistent with a CN of 4, distinguishing covalent metal-ligand bonds from weaker interactions. This approach is particularly valuable for validating CN in systems with ambiguous bonding, such as those involving π-backbonding ligands, by quantifying at BCPs (ρ(r) > 0.02 a.u. for strong bonds). Molecular dynamics (MD) simulations compute time-averaged CN in dynamic environments like liquids and surfaces by integrating the (RDF), g(r), up to the first minimum, which defines the for nearest neighbors. The CN is given by N = 4\pi \rho \int_0^{r_m} g(r) r^2 \, dr where ρ is the and rm is the RDF minimum. In MD studies of liquid using embedded-fragment stochastic-DFT, the oxygen CN averages 4.7, reflecting tetrahedral coordination with occasional defects, while hydrogen bonding yields an of 3.8 per . For surfaces, classical MD with reactive force fields simulates adsorption sites, averaging CN over trajectories to capture fluctuations, as in Fe-C melts where surface atoms exhibit reduced CN compared to bulk (e.g., ~11-12 vs. 14). In solid-state crystal prediction, Voronoi tessellation partitions space into polyhedra around each atom, with the CN determined by the number of faces shared with neighboring polyhedra, providing a geometry-independent neighbor count. This method, implemented in tools like VORO++, analyzes the Inorganic Crystal Structure Database (ICSD) entries by weighting connections via solid angles or edge lengths to handle anisotropic bonding. For example, in machine-learning-enhanced structure searches, Voronoi-derived attributes predict formation energies and local geometries in over 100,000 hypothetical crystals, achieving CN accuracies within 0.5 for common motifs like octahedral (CN=6) in oxides. Recent (ML) models, trained on post-2010 ICSD data exceeding 200,000 structures, predict CN directly from compositional and structural descriptors, bypassing expensive simulations. Algorithms like crystal-near-neighbor (CrystalNN), which incorporate with solid-angle weighting, against 1,000+ ICSD entries with mean absolute errors below 0.3 for metals and ionic solids, outperforming distance-based cutoffs by 20-30% in disordered systems. Graph convolutional networks further integrate these predictions into , enabling CN forecasting for novel materials like perovskites with up to 95% accuracy on valence-matched test sets.

Measurement complications

Determining coordination numbers in molecular and ionic systems is complicated by thermal disorder, which arises from atomic vibrations and leads to blurred in data. This thermal motion, quantified through anisotropic displacement parameters, distorts bond lengths and angles, making it challenging to distinguish true coordinating ligands from those affected by vibrational smearing, particularly in complexes with low or high flexibility. As a result, coordination numbers may appear artificially reduced or ambiguous when atomic positions cannot be resolved with sufficient precision, especially at elevated temperatures where vibrational amplitudes increase. In fluxional complexes, rapid intramolecular rearrangements on the NMR timescale introduce further ambiguities, often resulting in apparent fractional coordination numbers due to time-averaged structures. For instance, in seven-coordinate iron(II) complexes, variable-temperature NMR reveals pairwise ligand exchanges that coalesce signals, yielding spectra consistent with an averaged geometry rather than discrete integer coordination sites. This dynamic averaging complicates assignment of a static coordination number, as the observed ligand environment reflects a population-weighted average rather than a fixed arrangement. Solvent effects exacerbate these challenges by inducing variations in coordination numbers between solution and solid states, as solvation shells can alter ligand binding strengths and geometries. Such discrepancies arise because solvents like or compete with primary s, leading to labile coordination environments that differ markedly from the rigid solid-state packing. Additional error sources stem from the distinction between dynamic and static coordination numbers, as well as inherent resolution limits in techniques like EXAFS. Dynamic coordination, influenced by thermal vibrations, contributes to Debye-Waller factors that dampen the EXAFS signal, while static disorder from structural heterogeneity (e.g., multiple lengths in a ) further broadens these factors, reducing accuracy in extracting coordination numbers to within ±20-25%. In EXAFS, statistical correlations between coordination number, distance, and Debye-Waller parameters limit reliable determination, particularly for low-Z scatterers or noisy data, where non-Gaussian distributions in ligand positions cannot be adequately modeled without advanced fitting strategies. These limitations highlight the need for complementary techniques to resolve true coordination environments.

Specialized and Disordered Systems

Quasicrystals

Quasicrystals represent a class of aperiodic solids characterized by long-range quasiperiodic order and sharp peaks, where coordination numbers play a crucial role in defining local atomic arrangements despite the absence of translational periodicity. In these structures, the average coordination number approximates 12, akin to close-packed crystalline solids, but local geometries often deviate toward icosahedral coordination, which inherently favors a coordination number of 12 with five-fold elements. This can be analogized to three-dimensional extensions of Penrose tilings, where tiles correspond to polyhedral clusters with icosahedral motifs, enabling efficient packing without periodic repetition while maintaining an average vertex coordination of approximately 12, as seen in models of atomic arrangements in quasicrystals. In icosahedral quasicrystals such as alloys, atomic coordination polyhedra exhibit coordination numbers ranging from 10 to 14, reflecting distorted icosahedra and related Frank-Kasper polyhedra that accommodate the quasiperiodic lattice. For instance, in the icosahedral phase, (EXAFS) studies reveal Mn atoms surrounded by an average of 12.1 Al nearest neighbors at distances of 2.55–2.78 Å, forming polyhedra with coordination numbers around 12, while some sites show 10–11 neighbors in distorted configurations compared to crystalline (coordination number 10). These variations arise from the competition between ideal icosahedral bonding (coordination number 12) and the need to tile space quasiperiodically, leading to polyhedra such as triacontahedra and rhombic triacontahedra with 12–14 vertices. The determination of coordination numbers in quasicrystals is complicated by their patterns, which display sharp Bragg peaks indicative of atomic order, yet lack the periodic that simplifies analysis in . These peaks arise from the quasiperiodic arrangement, allowing Fourier transforms to reveal coordination shells despite aperiodicity, but modeling requires higher-dimensional projections or cluster-based approaches to accurately resolve local polyhedra with coordination numbers 10–14. The discovery of in the 1980s, particularly the icosahedral Al-Mn phase reported in , revolutionized understanding of order in solids by demonstrating that non-periodic structures could exhibit perfect long-range orientational order with local icosahedral coordination numbers near 12, serving as an order parameter to distinguish quasicrystalline phases from amorphous or crystalline counterparts. This finding implied that coordination number distributions could quantify the degree of icosahedral short-range order in non-periodic solids, influencing subsequent models of quasicrystal stability and growth.

Liquids and amorphous solids

In liquids and amorphous solids, coordination numbers (CN) are typically determined from the (RDF), g(r), which describes the probability of finding an atom at a r from a reference atom. The average CN is calculated by integrating the area under the first peak of the RDF up to its first minimum, providing a measure of the local atomic packing in these disordered systems. This approach reveals that CN values in liquids often deviate from ideal crystalline values due to thermal disorder and dynamic fluctuations, resulting in non-integer averages that reflect a of local environments. A classic example is liquid , where the oxygen-oxygen RDF exhibits a first peak around 2.8 , corresponding to an average of approximately 4.5 at ambient conditions, lower than the tetrahedral 4 in due to broken bonds and motion. In metallic glasses, such as Fe-based alloys, the is typically around 12-14, closely resembling that in their crystalline counterparts but with structural defects and a broader distribution of polyhedral arrangements that contribute to the amorphous nature. These systems maintain high local despite lacking long-range , with variations arising from chemical short-range ordering. Coordination numbers in liquids exhibit dependence on temperature and pressure; for instance, increasing pressure densifies the structure, leading to higher CN values as atoms are forced into closer proximity, as observed in liquid tin where CN rises from about 6-7 at low pressure to higher values under compression. In silicate glasses, silicon atoms predominantly adopt a tetrahedral CN of 4 at ambient pressure, but under higher pressures or in compositions with network-modifying cations, the CN can vary to 5 or 6, enabling structural adaptation and influencing properties like density and viscosity. This variability highlights the flexibility of coordination polyhedra in amorphous silicates compared to crystalline forms.

Biological and other disordered contexts

In biological systems, coordination numbers (CN) in metalloproteins typically range from 4 to 6, enabling diverse functions through metal-ligand interactions with side chains. For instance, in heme-containing proteins such as and , the iron(II) or iron(III) center exhibits a CN of 6, forming an octahedral with four nitrogen atoms from the ring and two axial ligands, often a residue and either oxygen or another donor. This configuration facilitates oxygen transport by allowing reversible binding at the sixth coordination site. In enzymes like carbonic anhydrase, the zinc(II) ion maintains a tetrahedral CN of 4, coordinated by three imidazole nitrogens from histidine residues and a water molecule, which deprotonates to generate a hydroxide nucleophile essential for CO₂ hydration. Variable coordination, such as transient expansion to CN=5 upon substrate binding or pH changes, enhances catalytic efficiency by stabilizing intermediates. Metal binding to nucleic acids often involves specific CN geometries that stabilize structures or enable recognition. In zinc finger proteins, which regulate through DNA binding, the zinc(II) adopts a tetrahedral CN=4, coordinated by two sulfurs and two nitrogens, folding the into a compact domain that inserts into the DNA major groove. This motif's rigidity ensures sequence-specific interactions, with disruptions in CN leading to loss of binding affinity. In disordered biological contexts, such as and colloidal assemblies, coordination numbers influence assembly and dynamics. Multivalent metal ions act as crosslinkers in biopolymers like or proteins, often achieving CN=4 to 6 with oxygen donors, promoting gelation or aggregation in cellular environments. Recent studies (2020s) on folding dynamics highlight how fluctuating CN during conformational changes—driven by intrinsic protein flexibility and extrinsic factors—stabilize transient states, as seen in simulations of zinc-binding sites where coordination motifs evolve to minimize energy barriers. The flexibility of coordination numbers plays a pivotal role in biological catalysis and signaling. In metalloenzymes, dynamic shifts in CN (e.g., from 4 to 5) facilitate substrate access and , as in where copper-zinc coordination adjusts for cycling. For signaling, such adaptability in calcium-binding proteins allows rapid conformational responses, though in metalloproteins, it more directly enables by modulating exchange rates. These mechanisms underscore how CN variability, rather than fixed geometries, underpins functional versatility in disordered biomolecular environments.