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Trigonal planar molecular geometry

Trigonal planar molecular geometry describes a molecular shape in which a central atom is bonded to three surrounding atoms or groups arranged in a flat, equilateral triangular configuration within a single plane, with ideal bond angles of 120° between each pair of bonds.^[1]^[2] This geometry occurs when the central atom has a steric number of three, consisting of three bonding electron pairs and no lone pairs, as determined by the Valence Shell Electron Pair Repulsion (VSEPR) theory, which minimizes electron pair repulsions to achieve maximum stability.^[1]^[2] In VSEPR notation, such molecules are classified as AX₃, where A is the central atom and X represents each peripheral atom or group.^[3] The electron geometry and molecular geometry for trigonal planar arrangements are identical, both forming a trigonal planar structure due to the absence of lone pairs that could distort the shape.^[1] Common examples include boron trifluoride (BF₃), where the boron central atom bonds to three fluorine atoms, and the carbonate ion (CO₃²⁻), in which the carbon atom is surrounded by three oxygen atoms (one via a double bond and two via single bonds in resonance structures).^[1]^[4] Other notable instances are sulfur trioxide (SO₃) and formaldehyde (H₂CO), the latter exhibiting slight bond angle deviations (approximately 116°–122°) due to differences in electronegativity and bond types among the ligands.^[4] These molecules often feature a central atom with sp² hybridization, involving one s orbital and two p orbitals to form three equivalent sp² hybrid orbitals in the plane, with the remaining p orbital available for π-bonding if applicable.^[5] This geometry is significant in chemistry for understanding molecular polarity, reactivity, and properties such as planarity, which facilitates conjugation in organic compounds like alkenes (e.g., ethene, C₂H₄).^[4] In ideal symmetric cases with identical ligands, trigonal planar molecules are nonpolar despite polar bonds, as the symmetry cancels dipole moments; however, asymmetry from differing substituents can lead to polarity.^[3] Deviations from 120° bond angles typically arise from ligand electronegativity differences or multiple bond influences, but the overall planar arrangement remains a hallmark of this geometry.^[4]

Fundamentals

Definition

Trigonal planar molecular geometry refers to a molecular shape in which a central atom is bonded to three outer atoms arranged in a flat, triangular configuration, with no lone pairs of electrons on the central atom. This arrangement positions the three surrounding atoms at the vertices of an equilateral triangle in a single plane, maximizing the separation between the bonding pairs of electrons.^[3] In the framework of Valence Shell Electron Pair Repulsion (VSEPR) theory, this geometry is denoted by the AX₃ notation, where A is the central atom and each X represents a bonding group, indicating three electron domains without any non-bonding pairs.^[6] The VSEPR model predicts this shape based on the mutual repulsion among the electron domains surrounding the central atom. The trigonal planar geometry was first systematically described as part of the VSEPR theory by Ronald J. Gillespie and Ronald S. Nyholm in their seminal 1957 paper on inorganic stereochemistry, which laid the groundwork for predicting molecular shapes from electron pair arrangements.^[2]

Structural Characteristics

In trigonal planar molecular geometry, the central atom forms three sigma bonds with peripheral atoms, resulting in ideal bond angles of 120° between each pair of adjacent bonds. This angular separation arises from the symmetric distribution of the three bonding electron pairs around the central atom, ensuring maximal separation in the absence of lone pairs.^[7] The structure is strictly planar, with the central atom and all three peripheral atoms coplanar, forming a two-dimensional arrangement. In ideal cases, this configuration possesses D_{3h} point group symmetry, featuring a principal C_3 rotation axis perpendicular to the molecular plane, three C_2 axes in the plane, a horizontal mirror plane (\sigma_h) coinciding with the molecular plane, and three vertical mirror planes (\sigma_v) passing through the central atom and each peripheral atom.^[8] The ideal geometry can be represented in Cartesian coordinates with the central atom at the origin (0, 0, 0) and the peripheral atoms at the vertices of an equilateral triangle in the xy-plane. For a uniform bond length r, the positions are (r, 0, 0), \left(r \cos 120^\circ, r \sin 120^\circ, 0\right), and \left(r \cos 240^\circ, r \sin 240^\circ, 0\right), yielding a side length of r \sqrt{3} between peripheral atoms. Deviations from these ideal parameters occur in real molecules due to differences in atomic radii between the central and peripheral atoms, which introduce steric interactions that distort the bond angles slightly—typically by a few degrees—to optimize bond lengths and minimize energy. For instance, larger peripheral atoms may compress angles toward values less than 120° to reduce repulsion, while smaller ones can allow slight expansions.^[9] This geometry is commonly linked to sp^2 hybridization of the central atom.^[10]

Theoretical Basis

VSEPR Theory

The Valence Shell Electron Pair Repulsion (VSEPR) theory originated from the work of Nevil V. Sidgwick and Herbert M. Powell in 1940, who proposed that the spatial arrangement of electron pairs around a central atom is determined by the repulsion between bonding and lone pair electrons in the valence shell. This foundational idea was refined in 1957 by Ronald J. Gillespie and Ronald S. Nyholm, who formalized the model to predict molecular geometries by emphasizing the minimization of electron pair repulsions. At its core, VSEPR theory posits that the valence electron pairs surrounding a central atom repel each other due to electrostatic forces, adopting positions that minimize these repulsions and thus achieve the lowest energy configuration.^[11] For a central atom with three bonding pairs and no lone pairs, denoted as AX₃ in VSEPR notation, the electron geometry is trigonal planar, where the three electron domains arrange themselves in a single plane to maximize separation.^[11] The prediction process involves first counting the total number of electron domains (bonding pairs plus lone pairs) around the central atom using the Lewis structure, then arranging these domains to minimize repulsions; in the case of three domains, they position at 120-degree intervals in a plane to equalize the pairwise repulsions.^[11] While effective for predicting the trigonal planar geometry in AX₃ systems, VSEPR theory has limitations, particularly in that it treats electron pairs as localized and ignores the role of atomic orbital hybridization in forming bonds./Molecular_Geometry/Limitations_of_VSEPR) This qualitative repulsion-based approach provides geometric predictions without delving into quantum mechanical details, serving as a complementary tool to models like hybridization that incorporate orbital mixing.^[12]

Hybridization Model

In valence bond theory, the trigonal planar molecular geometry arises from sp² hybridization of the central atom's valence orbitals. This process involves the linear combination of one s orbital and two p orbitals (typically p_x and p_y), resulting in three equivalent sp² hybrid orbitals that are symmetrically arranged in a plane at 120° angles to each other. The hybridization equalizes the energy and spatial distribution of these orbitals, promoting optimal overlap for bonding and explaining the observed planarity and bond angles in such molecules. This concept was foundational to directed valence in Pauling's early quantum mechanical treatment of chemical bonds.^[13] Each of the three sp² hybrid orbitals contains a single electron in the valence shell and overlaps end-to-end (head-on) with an orbital from a surrounding atom—such as an s or p orbital—to form a sigma (σ) bond. The remaining unhybridized p orbital (usually p_z) is oriented perpendicular to the plane of the sp² orbitals, allowing for sideways overlap with a parallel p orbital on an adjacent atom to form a pi (π) bond if the central atom participates in multiple bonding. This arrangement accounts for the directional nature of bonds in trigonal planar systems, where sigma bonds lie in the molecular plane and any pi bonds extend above and below it.^[14] Qualitatively, the energy levels of the sp² hybrid orbitals lie between those of the pure s and p atomic orbitals, as hybridization produces a set of degenerate orbitals whose average energy is (1/3)E_s + (2/3)E_p, where E_s is lower than E_p. This intermediate energy enhances bonding efficiency by balancing the greater penetration of s orbitals with the directional lobes of p orbitals, leading to stronger and more stable sigma bonds compared to unhybridized p-p overlaps. The unhybridized p orbital retains its pure p energy, facilitating selective pi interactions.^[14] Spectroscopic evidence supporting sp² hybridization in trigonal planar molecules includes UV-Vis absorption spectra, which reveal characteristic π → π* transitions arising from the perpendicular unhybridized p orbitals. For instance, in systems with sp²-hybridized carbons forming conjugated structures, absorption bands in the 170-300 nm range confirm the presence and alignment of these p orbitals, consistent with the valence bond description. Infrared spectroscopy further corroborates this by showing C=C stretching frequencies around 1600-1680 cm⁻¹, indicative of the partial double-bond character from sigma and pi overlap in planar configurations.^[15]^[16]

Examples

Neutral Molecules

Boron trifluoride (BF₃) is a classic example of a neutral molecule with trigonal planar geometry, featuring a central boron atom bonded to three fluorine atoms arranged symmetrically around it. The boron atom utilizes sp² hybridization, resulting in bond angles of exactly 120° and an empty p orbital perpendicular to the molecular plane. The B–F bond length is approximately 1.30 Å, reflecting the partial double bond character due to π-backbonding from fluorine to the empty p orbital on boron. BF₃ is typically prepared by the reaction of boron trioxide with hydrofluoric acid: B₂O₃ + 6 HF → 2 BF₃ + 3 H₂O. Boron trichloride (BCl₃) similarly exhibits trigonal planar geometry, with a central boron atom bonded to three chlorine atoms and bond angles of 120°. Like BF₃, the boron center has an empty p orbital, and the B–Cl bond length is about 1.75 Å. BCl₃ can be synthesized by passing chlorine gas over a mixture of boron trioxide and carbon at elevated temperatures around 700–1000°C. Aluminum trichloride (AlCl₃) in the gas phase adopts a monomeric trigonal planar structure, with the central aluminum atom bonded to three chlorine atoms at 120° angles. The Al–Cl bond length in this monomeric form is approximately 2.06 Å, and the aluminum atom also features an empty p orbital consistent with sp² hybridization. Anhydrous AlCl₃ is prepared industrially by direct combination of aluminum metal and chlorine gas: 2 Al + 3 Cl₂ → 2 AlCl₃. Sulfur trioxide (SO₃) represents another key neutral example, where the central sulfur atom is bonded to three oxygen atoms in a trigonal planar arrangement with bond angles of 120°. The S–O bonds are equivalent at about 1.42 Å due to resonance delocalization, involving partial double bond character across the three bonds without a distinct empty orbital on sulfur. SO₃ is produced on an industrial scale via the Contact process, involving the catalytic oxidation of sulfur dioxide over vanadium(V) oxide: 2 SO₂ + O₂ → 2 SO₃.

Ionic Species

The carbonate ion (CO₃²⁻) exemplifies a polyatomic anion adopting trigonal planar geometry, with a central carbon atom bonded to three oxygen atoms arranged symmetrically at 120° bond angles. This structure arises from the sp² hybridization of the carbon atom and is stabilized by resonance, where the negative charge is delocalized over the three oxygen atoms through three equivalent resonance structures, resulting in identical C-O bond lengths of approximately 1.29 Å.^[17]^[18] The delocalization enhances the ion's stability, allowing it to form numerous salts such as sodium carbonate (Na₂CO₃), which occurs naturally as trona and is widely used in industrial applications.^[19] Similarly, the nitrate ion (NO₃⁻) exhibits trigonal planar geometry, featuring a central nitrogen atom surrounded by three oxygen atoms with bond angles of 120°. Resonance delocalizes the π electrons across the three N-O bonds, making them equivalent with lengths around 1.24 Å, intermediate between single and double bonds.^[20] This delocalized bonding contributes to the ion's high stability in compounds like sodium nitrate (NaNO₃), a common fertilizer and preservative.^[21] The negative charge in these ions generally lengthens bonds compared to neutral analogs, affecting reactivity and lattice energies in ionic salts.

Properties and Applications

Polarity and Symmetry

Trigonal planar molecules typically belong to the D_{3h} point group, which encompasses a set of symmetry elements that confer high symmetry to the structure. This includes a principal C_3 rotation axis passing through the central atom and perpendicular to the molecular plane, three C_2 rotation axes perpendicular to the C_3 axis and intersecting it at the central atom, a horizontal mirror plane (σ_h) coinciding with the molecular plane, three vertical mirror planes (σ_v) each containing the C_3 axis and one of the C_2 axes, and an S_3 improper rotation axis aligned with the C_3 axis.^[22] The high symmetry of the D_{3h} point group results in trigonal planar molecules being non-polar when all three substituents are identical, as the symmetric arrangement causes the individual bond dipole moments to cancel out completely. For instance, in boron trifluoride (BF_3), the three B-F bonds are equivalent and oriented at 120° angles, leading to a vector sum of the dipole moments equal to zero.^[23]^[24] This cancellation can be understood through the vector addition of bond dipoles. The total dipole moment μ_total is the vector sum of the individual bond dipoles μ_bond, where each μ_bond points from the central atom toward the substituent. In a symmetric trigonal planar arrangement with equal bond dipoles at 120° intervals, the components resolve such that:

\vec{\mu}_{\text{total}} = \sum_{i=1}^{3} \vec{\mu}_{\text{bond},i}

For identical μ_bond, the x- and y-components sum to zero due to the cos(120°) = -1/2 and sin terms canceling (e.g., μ_bond [1 + 2 cos(120°)] = μ_bond [1 - 1] = 0 for the aligned direction).^[25]^[26] However, if the substituents differ in electronegativity or other properties, the symmetry is reduced (often to C_{2v} or lower), resulting in a non-zero net dipole moment and making the molecule polar. For example, phosgene (COCl_2) maintains trigonal planar geometry but has one oxygen and two chlorine substituents, leading to unbalanced bond dipoles and overall polarity. In ideal symmetric cases, though, the D_{3h} symmetry ensures non-polarity.^[27]^[23]

Role in Chemistry

Trigonal planar molecular geometry plays a pivotal role in organic chemistry, particularly through the sp2 hybridization of carbon atoms in alkenes and aromatic systems. In alkenes, the trigonal planar arrangement around the double-bonded carbon atoms enforces 120° bond angles and enables the formation of pi bonds via sideways overlap of p orbitals, which restricts rotation and imparts specific reactivity such as electrophilic addition.^[28] This geometry extends to aromatic compounds like benzene, where the planar sp2-hybridized carbons facilitate delocalized pi electron systems and conjugation, stabilizing the molecule through resonance and influencing properties like electrophilic aromatic substitution.^[29] The geometry also underpins Lewis acidity in certain inorganic molecules, exemplified by boron trifluoride (BF3). The central boron atom, with its empty p orbital perpendicular to the molecular plane, accepts electron pairs from Lewis bases to form adducts, such as BF3·NH3, where ammonia donates its lone pair to boron, resulting in a tetrahedral coordination.^[30] This reactivity arises directly from the electron-deficient nature enforced by the planar structure and is widely exploited in synthetic chemistry for catalysis and complexation. Industrially, trigonal planar geometry is essential in the production of sulfuric acid via the contact process, where sulfur dioxide is catalytically oxidized to sulfur trioxide (SO3) over vanadium pentoxide. The trigonal planar structure of SO3 contributes to its Lewis acidity, allowing efficient absorption in concentrated sulfuric acid to form oleum, which is then diluted to yield the final product; this process accounts for the majority of global sulfuric acid output.^[31] Spectroscopic techniques further highlight the role of this geometry in molecular identification. Trigonal planar molecules exhibit characteristic infrared absorption bands due to their symmetric vibrations; for instance, the asymmetric B-F stretch in BF3 appears around 1450 cm⁻¹, providing a diagnostic feature for confirming the geometry in experimental spectra.^[32]

References

[1]
9.2: The VSEPR Model - Chemistry LibreTexts
Jul 7, 2023 · The VSEPR model can predict the structure of nearly any molecule or polyatomic ion in which the central atom is a nonmetal.The VSEPR Model · Two Electron Groups · Six Electron GroupsMissing: characteristics | Show results with:characteristics
[2]
Inorganic stereochemistry - Quarterly Reviews, Chemical Society ...
Inorganic stereochemistry. R. J. Gillespie and R. S. Nyholm, Q. Rev. Chem. Soc., 1957, 11, 339 DOI: 10.1039/QR9571100339. To request permission to reproduce ...Missing: PDF | Show results with:PDF
[3]
Molecular Geometry – Introductory Chemistry
Trigonal planar: triangular and in one plane, with bond angles of 120°. Tetrahedral: four bonds on one central atom with bond angles of 109.5°. Trigonal ...Missing: characteristics | Show results with:characteristics
[4]
Trigonal Planar in Molecular Geometry | Shape, Angle & Structure
In chemistry, trigonal planar means three electron groups sticking out from an atom in the shape of a triangle. Those electron groups may be lone pairs and/or ...Missing: characteristics | Show results with:characteristics
[5]
9.3: sp² Hybrid Orbitals and the Structure of Ethylene
Aug 20, 2021 · Atoms surrounded by three electron groups can be said to have a trigonal planar geometry and sp2 hybridization. The unhybridized 2pz orbital is ...
[6]
vsepr - FSU Chemistry & Biochemistry
VSEPR theory is a model used in chemistry to predict the geometry of individual molecules from the number of electron pairs surrounding their central atoms.Missing: definition | Show results with:definition
[7]
[PDF] Chemical Bonding and Molecular Geometry
This molecule has regions of high electron density that consist of two single bonds and one double bond. The basic geometry is trigonal planar with 120° bond ...
[8]
[PDF] Review Notes on Point Groups and Symmetry from undergraduate ...
An example of a molecule that belongs to the D3h point group is eclipsed ethane. As shown on the left, eclipsed ethane has a C3 axis that contains the C-C ...
[9]
[PDF] Molecular Shape
The basic geometry is trigonal planar with 120° bond angles, but we see that the double bond causes slightly larger angles (121°), and the angle between the ...
[10]
Variations From Ideal Geometry - St. Olaf College
Many factors lead to variations from the ideal bond angles of a molecular shape. Size of the atoms involved, presence of lone pairs, multiple bonds, large ...
[11]
Molecular Structure and Polarity – Chemistry - UH Pressbooks
The basic geometry is trigonal planar with 120° bond angles, but we see that the double bond causes slightly larger angles (121°), and the angle between the ...
[12]
https://www.sciencedirect.com/science/article/abs/pii/S0010854507001476
[13]
Review Fifty years of the VSEPR model - ScienceDirect.com
It is 50 years since the ideas of the VSEPR model were first introduced in an article by Ron Nyholm and myself entitled Inorganic Stereochemistry.
[14]
Journal of the American Chemical Society
Article April 1, 1931. THE NATURE OF THE CHEMICAL BOND. APPLICATION OF RESULTS OBTAINED FROM THE QUANTUM MECHANICS AND FROM A THEORY OF PARAMAGNETIC ...
[15]
https://pmc.ncbi.nlm.nih.gov/articles/PMC8746022/
[16]
Formation and Evolution of sp2 Hybrid Conjugate Structure of ... - NIH
Dec 21, 2021 · UV-Vis Absorption Spectra Analysis. The sp2 hybrid conjugated structures of stabilized PAN fibers were traced by UV-vis method. In the UV-vis ...
[17]
UV-Vis Spectroscopy of Conjugated Alkenes Explained - Pearson
Aug 7, 2024 · Energy from ultraviolet (UV) or visible light can promote an electron from a lower energy state to a higher energy molecular orbital (MO).
[18]
https://www.sciencedirect.com/topics/engineering/carbonate-ion
[19]
Carbonate Ion - an overview | ScienceDirect Topics
Carbonic acid, a weak acid with a pK of ∼6.38, serves as an important buffer in blood. All the C–O bonds in the carbonate ion are equal in length, but the ...
[20]
Sodium Carbonate | Na2CO3 | CID 10340 - PubChem
Sodium Carbonate is the disodium salt of carbonic acid with alkalinizing property. When dissolved in water, sodium carbonate forms carbonic acid and sodium ...
[21]
Nitrosonium nitrate (NO+NO3 −) structure solution using in situ ...
At the same pressure of 37 GPa, the nitrate anion has two N–O bond lengths of 1.231 (5) Å and one of 1.249 (5) Å, and two O–N–O angles of 118.92 (19)° and one ...
[22]
Sodium Nitrate | NaNO3 | CID 24268 - PubChem
Sodium nitrate is the inorganic nitrate salt of sodium. It has a role as a fertilizer. It is an inorganic sodium salt and an inorganic nitrate salt.
[23]
Boron Trifluoride (BF3) - D3h - ChemTube3D
BF 3 belongs to the D 3h point group and contains; one C 3 rotation axis, Three C 2 axes perpendicular to the C 3 Axis, 3σ v planes of symmetry.Missing: trigonal | Show results with:trigonal
[24]
4.14: Shapes and Properties- Polar and Nonpolar Molecules
Jun 13, 2023 · BF3 is a trigonal planar molecule and all three peripheral atoms are the same. ... If the net dipole moment is zero, it is non-polar. Otherwise, ...
[25]
Dipole Moments and Dipoles - Master Organic Chemistry
Oct 17, 2025 · Dipole Moment In Molecules With One Polar Covalent Bond ... geometry of bf3 boron trifluoride is trigonal planar and there is no dipole moment.
[26]
2.1: Polar Covalent Bonds - Dipole Moments - Chemistry LibreTexts
Apr 4, 2024 · The dipole moment of a molecule is therefore the vector sum of the dipole moments of the individual bonds in the molecule. If the individual ...
[27]
3.3 Molecular Polarity and Dipole Moment - UCalgary Chemistry ...
Their geometries are oriented to yield nonpolar molecules, resulting in a dipole moment of zero. Molecules of less geometric symmetry, however, may be polar ...
[28]
Trigonal Planar Molecular Geometry - BYJU'S
The sp2 hybridisation is often used to describe planar, three-connected carbon centres that are trigonal planar. When all of the bonds are in place, the shape ...
[29]
[PDF] Chapter 2: Structure and Bonding II - Organic Chemistry
fig 68 The three sp2 hybrids are arranged with trigonal planar geometry, pointing to the three corners of an equilateral triangle, with angles of 120° between ...
[30]
[PDF] ELECTRON DELOCALIZATION AND RESONANCE
Substances containing neutral sp2 carbons are regular alkenes. ... The central carbon in a carbocation has trigonal planar geometry, and the unhybridized p ...
[31]
Infrared spectrum of the boron trifluoride dimer - ScienceDirect.com
In the uncomplexed BF3 the ν3 (asymmetric stretching) mode was at ca. 1445 cm−1. The value of the ν2 (symmetric deformation) mode is reported from 654 to ...Missing: frequency | Show results with:frequency