Molecular structure and conformation of chloronitromethane as determined by gas-phase electron diffraction and theoretical calculations.
The molecular structure of chloronitromethane was studied in the gas phase at a nozzle-tip temperature of 373 K. The experimental data were interpreted using a dynamic model where the molecules are undergoing torsional motion governed by a potential function: V = V2/2x(1 - cos 2tau) + V4/2x(1 - cos 4tau) with V2 = 0.81(30) and V4 = 0.12(40) kcal/mol (tau is the dihedral angle between the C-Cl and N-O bond). The conformer with a zero degree dihedral angle is the most stable conformer. Comparison with results from HF/MP2/B3LYP 6-311G(d,p) calculations were made. The important geometrical parameter values (for the eclipsed form) obtained from least-squares refinements are the following: r(C-H) = 1.061(18)A, r(C-N) = 1.509 (5)A, r(N-O) = 1.223(1)A, r(C-Cl) = 1.742(2)A, angleClCN = 115.2(7) degrees, angleO4NC = 118.9(10) degrees, angleO5NC = 114.9(16) degrees, and angleClCH 115(4) degrees.
Shen
Quang
Q
Department of Chemistry, 13 Oak Drive, Colgate University, Hamilton, New York 13346, USA. mshen@mail.colgate.edu
Brown
Jeffrey W
JW
Malona
John A
JA
Cochran
John C
JC
Richardson
Alan D
AD
D003198:Computer Simulation; D004583:Electrons; D005740:Gases / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D009574:Nitro Compounds / Q000737:chemistry*; D012542:Scattering, Radiation; D013057:Spectrum Analysis / Q000379:methods
D005740:Gases; D009574:Nitro Compounds; C521982:chloronitromethane; D008697:Methane