Compounds With Planar Shape

Featured in this post are compounds having planar shape other than trigonal planar.

The following compounds are all planar, with the last two having more than one central atom.

xenon tetrafluoride, XeF4

benzene molecule, C6H6

CH2=NH

Geometry of Xenon Tetrafluoride, XeF₄

The Lewis structure of xenon tetrafluoride, XeF4, below shows that the compound's central atom has four bonding electron pairs and two lone electron pairs.

According to the VSEPR theory, the arrangement that affords the maximum distance between each of the mentioned electron pairs is a square bipyramidal.





The axial positions of the two lone electron pairs offer the least net repulsion than it would have been if one or both of these non-bonding electron pairs were in the equatorial positions.



In the illustration shown above, a square bipyramidal outline is superimposed on the xenon tetrafluoride molecule.

• shape of xenon tetrafluoride: square planar
• F-Xe-F bond angle: 90°

Geometry of Benzene, C₆H₆

The resonance structures of benzene are shown below; the third structure is a suggested representation of the delocalization state of the pi electrons.





Each of the six carbon atoms can be taken as a central atom about which the geometry is trigonal planar.





The result is a hexagonal planar molecule with one carbon atom and one hydrogen atom jutting out at each of the six vertices.

Geometry of CH₂=NH

The CH2=NH molecule has two central atoms, carbon and nitrogen (see the Lewis structure below).





About each center, the geometry is trigonal planar.





However, the shape about the nitrogen atom is angular due to the presence of a lone electron pair.



All of the atoms lie in one plane.

Compounds With Bent Shape

The following chemical species have bent geometry:

water molecule, H2O

nitrogen dioxide molecule, NO2

nitrite ion, NO2-

sulfur dioxide molecule, SO2

The illustrations and discussion below show how the presence of non-bonding electron pair(s) on a molecule's central atom affects the geometry of the molecule and the bond angle of its atoms.

Geometry of Water, H₂O

As shown in its Lewis structure below, the central atom of water has four pairs of electrons: two bonding pairs and two non-bonding or lone pairs.

These pairs of electrons are presumed to take a tetrahedral arrangement in space.





Here, the water molecule is depicted as being superimposed in a tetrahedral outline.





The lone pairs of electrons are relatively closer to the nucleus of the central atom and they tend to crowd the two bonding pairs together so that the H-O-H bond angle is less than the ideal tetrahedral angle of 109.5°.

• shape of water: bent or angular
• H-O-H bond angle: 104.5°

Geometry of Nitrogen Dioxide, NO₂

The central atom of nitrogen dioxide, nitrogen, has two sigma bond electron pairs and an unpaired non-bonding electron as shown in its Lewis electron dot structure below.





In order for this group of electrons to be farthest from each other, it is predicted that they take a trigonal planar arrangement.





Shown in the next illustration is the nitrogen dioxide molecule superimposed on a trigonal planar outline.





The observed O-N-O bond angle of 134.1° in nitrogen dioxide molecule, being closer to trigonal angle of 120°, confirms this prediction.

The opening out of the O-N-O bond angle is due to the less crowding affected by the half filled non-bonding orbital of the central atom.

This half-filled orbital accounts for the nitrogen dioxide (NO₂) being paramagnetic.

• shape of nitrogen dioxide: bent or angular
• O-N-O bond angle: 134.1°

Geometry of Nitrite Ion, NO₂^-

An addition of an electron to the central atom of nitrogen dioxide (NO₂) creates the nitrite anion, NO₂^-.





In the above diagram, the resonance structures of nitrite ion is shown. The oxygen atoms in red partial shades are atoms with negative formal charge.

As is the case with the nitrogen dioxide, the arrangement of the two sigma bond electron pairs and the lone electron pair of nitrite ion's central atom lies on a trigonal plane.

The only difference is the observed O-N-O bond angle of 115° for the nitrite ion. This bond angle now being much closer but less than the trigonal angle of 120° is attributed to the filling up of the non-bonding orbital of the nitrite ion's central atom.

The lone electron pair is relatively closer to the central atom and occupies more space than the adjacent bonding electron pairs do.

• shape of nitrite ion: bent or angular
• O-N-O bond angle: 115°

Geometry of Sulfur Dioxide, SO₂

Referring to the contributing Lewis structures of sulfur dioxide below, there is a -1 formal charge on one of the oxygen atoms and +1 formal charge on the sulfur atom which cancel each other out, leaving the molecule with zero net charge.

Given the two sigma bond electron pairs and one lone electron pair on the central atom of sulfur dioxide, as shown in the figure above, SO₂ is predicted to have a trigonal planar geometry.

A trigonal planar outline is shown below superimposed on the sulfur dioxide molecule.

Given this geometry, it is expected that SO₂ molecule has an angular shape. This is supported by the fact that sulfur dioxide has a dipole moment.

The O-S-O bond angle is expected to be somewhat less than the trigonal angle of 120° due to the presence of a lone electron pair on the central atom.

• shape of sulfur dioxide: bent or angular
• O-S-O bond angle: less than 120°