Combined Electron-Diffraction, Spectroscopic, and Theoretical Determination of the Structure of N-Deuterio- trans-Methyldiazene, CH3N═ND. Conformational Effects of the N═N Double Bond.

Gas phase electron-diffraction (GED) data obtained at a nozzle-tip temperature of 273 K have been combined with spectroscopic vibrational-rotational constants to determine the structure of trans-methyldiazene, an important prototype for the N═N double bond. The N-deuterio form CH3N═ND was used in the study since it is appreciably more stable than CH3N═NH. Both the theoretical and experimental results are consistent with a planar C s trans-CNND framework. The experimental results ( rα0/ rg273) are 1.465(2)/1.467(2) Å for the CN bond, 1.248(1)/1.251(1) Å for the N═N double bond, and 1.037(17)/1.048(17) Å for the ND bond. The NND angle is 105.9(20)/105.6(20)° and the CNN angle is 112.4(5)/112.2(5)°, where the uncertainties in parentheses are twice the standard deviation from a simultaneous least-squares fit of the GED and microwave data. For the methyl group, both theory and experiment indicate that two CH bonds are symmetrically arranged out of the molecular plane while the third CH' lies in the plane in an eclipsed (not staggered) cis-H'CNN arrangement. Theoretical calculations (B3LYP/cc-PVnZ and CCSD(T)/cc-PVnZ) suggest a slight distortion of the methyl group, with a tilt of the methyl top axis about 5° away from the N═N bond. The experimental data are consistent with this picture but are equally consistent with an undistorted methyl group. Inclusion of distortions predicted by theory in a complete basis set limit (CBS) lead to a preferred analysis with average values of 1.086(5)/1.106(5) Å for the CH bond length and an average HCH angle of 108.3(8)/107.8(8)°. Features of the structure of methyldiazene and related compounds are discussed. It is found that the short N═N bond length in the diazenes produces much greater steric repulsion than in analogous ethylene compounds and this effect leads to some interesting conformational and distortion differences for attached CH3 groups.

Molecular Structure, Equilibrium Conformation, and Ring-Puckering Motion in 1,1,3,3-Tetramethylcyclobutane. An Electron-Diffraction Investigation Augmented by Molecular Orbital and Normal Coordinate Calculations.

The molecule cyclobutane (CB) has a nonplanar carbon skeleton folded around a line connecting diagonally opposite atoms. The puckering angle (the change from planarity) of ∼30° is generally attributed to steric repulsion between the four sets of adjacent methylene groups that would be opposed in a planar ring and is relieved by the puckering. According to this criterion, a similar molecule, 1,1,3,3-tetramethylcyclobutene (TMCB), in which adjacent methylene groups do not exist, would be expected to have a planar ring in the equilibrium form. We have investigated the structure of TMCB to test this expectation. Two models were designed for the tests: one having D2h symmetry (planar ring) and one of C2v symmetry (nonplanar ring). Each model incorporated the dynamics of large-amplitude bending around a line joining the methylene groups. Our results suggest the D2h model is to be preferred. Dynamic averages (rg/Å; ∠g/deg) of the more important distances and angles in the D2h model with estimated 2σ uncertainties, are as follows. = 1.105 (5), C1-C5 = 1.524 (10), C1-C2 = 1.559 (11), C2-C1-C4 = 87.4 (8), C1-C2-C3 = 92.0 (7), C5-C1-C6 = 109.0 (13), and C2-C1-C5 = 115.8 (8). The large-amplitude bending of the ring leads to a thermal average value of the folding angle equal to 177.1°. The results, including the differences between TMCB and CB, are discussed.

Combined Electron-Diffraction and Spectroscopic Determination of the Structure of Spiropentane, C5H8.

Gas-phase electron-diffraction (GED) data have been combined with recent spectroscopic rotational constants to determine the rα0 structural parameters for spiropentane, C5H8. The structure has D2d symmetry, and the results yield values of 1.105(2) Å for the CH bond length, 1.557(3) Å for the distal CC bond length, and a smaller value of 1.482(1) Å for the four lateral CC bonds that connect to the central carbon atom. The HCH angle is 113.7(13)°, and the HCH flap angle, defined as the angle of the HCH bisector and the distal CC bond, is 150.2(16)°. Corresponding rg values are 1.122(2) Å, 1.560(3) Å, 1.485(1) Å, 115.1(13)°, and 148.9 (16)°. The results are in good accord with values from density functional calculations (B3LYP/cc-pVTZ) and resolve some questions about the structure reported in an earlier GED study, in particular about the HCH angle and anomalous rotational constants calculated for the structure.

Molecular structure and conformations of 1,2-dimethoxycyclobutene-3,4-dione. An electron-diffraction investigation augmented by quantum mechanical and normal coordinate calculations.

The structure and conformations of 1,2-dimethoxycyclobutene-3,4-dione in the vapor at a temperature of 185 °C have been measured by gas-phase electron diffraction. The molecule exists in two forms, one of symmetry C2v with the methyl groups trans to the double bond, and one of Cs symmetry with a methyl group cis and the other trans to this bond (these forms hereafter designated as trans and cis). The molar ratio trans/cis is 68/32 with a 2σ uncertainty of about 24. Many of the parameter values for the two forms are very nearly alike and could not be measured experimentally. With the adoption of parameter differences calculated at the B3LYP/cc-pVTZ level, the following bond distances (r(g)/Å) and bond angles (∠/deg) with estimated 2σ uncertainties were obtained for trans/cis: C1═C2 = 1.381(9)/1.381, C1-C4 = 1.493(11)/1.495, C3-C4 = 1.543(20)/1.545, C═O = 1.203(4)/⟨1.200⟩, C1-O = 1.316(6)/⟨1.320⟩, O-CH3 = 1.444(9)/⟨1.443⟩, C═C-C3 = 93.1(5)/⟨93.1⟩, C3-C4═O = 136.7(29)/⟨136.9⟩, C═C-O = 131.0(23)/137.5, and 131.8, C-O-C = 117.2(12)/118.2 and 116.9; the individual angle values for the cis form listed as averages differ very little. The bond distances and bond angles are in excellent qualitative agreement with prediction based on conventional ideas about the effects of conjugation and hybridization, and their relative values agree very well with predictions from quantum mechanical calculations.

1,4-Cyclohexanedione. Composition, molecular structures, and internal dynamics of the vapor: an electron diffraction investigation augmented by molecular orbital calculations.

Electron diffraction experiments on the vapor of 1,4-cyclohexanedione have been carried out at a nominal temperature of 435 K. The results are consistent with the presence of a mixture of a chair form of C2h symmetry and a twisted boat form of D2 symmetry. The former has the familiar dynamic properties of a semirigid molecule, but the D2 form undergoes a large-amplitude twisting motion (pseudorotation) that degrades the symmetry to C2. The analysis was designed to elucidate parameter values and internal dynamics of each conformer and the composition of the system. The large-amplitude motion of the twisted boat form was modeled by placement of 10 pseudoconformers at approximately 5° intervals along a pseudorotational coordinate that began at the D2 position and that reflected the angle between the C═O bond vectors. A Gaussian weighting of the pseudeoconformers centered on the (lowest-energy) D2 position was assumed. Differences in the interatomic distances and bond angles of these pseudoconformers were calculated via B3LYP/cc-pVTZ theory and introduced as constraints. The bond length averages over the twisted boat forms followed by values for the chair in square brackets are (rg/Å; [angle]α/deg) r(C-H) = 1.115(11) [1.124(11)], r(C═O) = 1.211(3) [1.233(6)], r(C1-C2) = 1.524(5) [1.526(5)], and r(C2-C3) = 1.533(11) [1.539(11)]. The corresponding ring angle values are [angle](C1C2C3) = 111.1(5) [111.0(4)] and [angle](C6C1C2) = 116.3(8) [115.7(8)]. In the twisted boat form, pseudorotation leads to a weighted average displacement of the angle between the C═O bond vectors, [angle]Δ(CO,CO), equal to 21.3° from the 180° value in the D2 form corresponding to an average angle between the CO bond vectors of 158.7(1)°. The amount of the chair form in the gas at 435 K is 24(10)%. The listed uncertainties are estimated at 2σ.

High-resolution infrared and electron-diffraction studies of trimethylenecyclopropane ([3]-radialene).

Combined high-resolution spectroscopic, electron-diffraction, and quantum theoretical methods are particularly advantageous for small molecules of high symmetry and can yield accurate structures that reveal subtle effects of electron delocalization on molecular bonds. The smallest of the radialene compounds, trimethylenecyclopropane, [3]-radialene, has been synthesized and examined by these methods. The first high-resolution infrared spectra have been obtained for this molecule of D3h symmetry, leading to an accurate B0 rotational constant value of 0.1378629(8) cm(-1), within 0.5% of the value obtained from electronic structure calculations (density functional theory (DFT) B3LYP/cc-pVTZ). This result is employed in an analysis of electron-diffraction data to obtain the rz bond lengths (in Å): C-H = 1.072(17), C-C = 1.437(4), and C═C = 1.330(4). The results indicate that the effects of rehybridization and π-electron delocalization affects each result in a shortening of about 0.05 Å for the C-C bond in radialene compared to ethane. The analysis does not lead to an accurate value of the HCH angle; however, from comparisons of theoretical and experimental angles for similar compounds, the theoretical prediction of 117.5° is believed to be reliable to within 2°.

Structure and torsional properties of oxalyl chloride fluoride in the gas phase: an electron-diffraction investigation.

The structure and torsional properties of oxalyl chloride fluoride in the gas phase have been measured by electron diffraction at temperatures of 22, 81, 158, and 310 °C. The molecule may be regarded as a hybrid of oxalyl chloride and oxalyl fluoride. Since the former exists as a more stable periplanar anti form (ϕ = 180°) in equilibrium with a less stable gauche form (ϕ ≃ 60°) and the latter as an equilibrium between two periplanar forms, anti and syn, the second form of oxalyl chloride fluoride is an interesting question. It was found to be gauche. The system was modeled as two rotational conformers related by a potential of the form 2V = V(1)(1 + cos ϕ) - V(2)(1 - cos 2ϕ) + V(3)(1 + cos 3ϕ). The anti/gauche bond distances and bond angles (r(g)/Angstroms, ∠(α)/degrees) with estimated 2σ uncertainties at 22 °C are = 1.183(2)/1.182(2), Δr(C═O) = 0.003(6)/0.002(6) (assumed from theory), r(C-F) = 1.329(3)/1.335(3), r(C-Cl) = 1.738(2)/1.753(2), ∠(C-C-Cl) = 112.0(3)/111.9(3), ∠(C-C═O3) = 123.0(4)/123.2(4), ∠(O═C-Cl) = 125.0(2)/1.249(2), ∠(O═C-F) = 123.0(3)/125.1(3), and ∠(Cl-C-C-F) = 180.0/59.8. The variation of composition with temperature afforded a determination of the standard enthalpy and entropy of the reaction anti → gauche. The results are ΔH° = 2.5(12) kcal/mol and ΔS° = -6.5(33) cal/(mol·K). The structures and equilibria are discussed.

The puzzle of bond length variation in substituted cyclobutenes. A new example: molecular structure and conformations of 1,2-dimethoxy-3,3,4,4-tetrafluorocyclobut-1-ene.

The structure and composition of 1,2-dimethoxy-3,3,4,4-tetrafluorocyclobut-1-ene (DMCB) have been measured by electron diffraction from the gas at a temperature of 370 K with the help of auxiliary data from molecular orbital and normal coordinate calculations, the former at several levels of theory and basis-set size, most importantly B3LYP/cc-pVTZ. The compound was found to exist primarily as a rotamer of C(s) symmetry (ca. 98%; 2sigma = 11%) with the remainder one of C(2v) symmetry; theory predicts about 88% C(s). Values for some of the more important parameters (r(g)/A; angle(alpha)/deg) of the C(s) form are r(C=C) = 1.337(21), r(C1-C4) = 1.496(8), r(C2-C3) = 1.501(8), r(C3-C4) = 1.567(12), r(C1-O) = 1.318(12), r(C2-O) = 1.340(12), r(C3-F) = 1.375(4), r(C4-F) = 1.368(4), angle(ave)(C=C-C) = 94.4(4), angle(ave)(C=C-O) = 133.5(12), angle(ave)(C-O-C) = 119.6(13), and angle(ave)(F-C-F) = 104.4(7). Surprisingly, although electron-diffraction values for the fluorinated C3-C4 bond in other cyclobutenes are greater than that for cyclobutene itself, that is not the case for DMCB where it is found to be about the same. Details of the DMCB structure, together with possible reasons for the observed variations in the length of the C3-C4 bond in fluorinated cyclobutene-like molecules, are discussed.

Conformational analysis. 24. Structure and composition of gaseous oxalyl fluoride, C(2)F(2)O(2): electron-diffraction investigation augmented by data from microwave spectroscopy and molecular orbital calculations.

The molecular structure and composition of gaseous oxalyl fluoride (OXF) has been investigated by electron diffraction (GED) at nozzle-tip temperatures of -10, 149, and 219 degrees C. The GED data were augmented by molecular orbital calculations, and the analysis was aided by use of rotational constants from microwave (MW) spectroscopy. As in the other oxalyl halides, there are two stable species, of which the more stable is periplanar anti (i.e., trans). However, unlike these other halides in which the second form is gauche, the second form of oxalyl fluoride was known from MW work to be periplanar syn (i.e., cis). Our results are consistent with a mixture of trans and cis forms, and yield values for the structural parameters, the composition of the system at the three temperatures cited, and the thermodynamic quantities deltaG(o), deltaH(o), and deltaS(o) for the reaction trans --> cis. Some trans/cis distances (r(g)/Angstrom) and angles (<(alpha)/deg) at -10 degrees C are r(C=O) = 1.178(2)/1.176(2), r(C-F) = 1.323(2)/1.328(2); r(C-C) = 1.533(3)/1.535(3), <(C-C=O) = 126.4(2)/124.2(2), <(C-C-F) = 109.8(2)/112.2(2), and <(O-C-F) = 123.8(2)/123.6(2). The mixture compositions (percent trans) at -10 degrees C/149 degrees C/219 degrees C are 75(3)/58(7)/52(8), from which deltaH(o) and deltaSO) are found to be 1.14 kcal/mol and 2.12 cal/(mol x deg). The system properties are discussed.

Molecular structures and compositions of trans-1,2-dichlorocyclohexane and trans-1,2-difluorocyclohexane in the gas phase: an electron-diffraction investigation.

The structures and compositions of gaseous trans-1,2-dichloro- (DCCH) and trans-1,2-difluorocyclohexane (DFCH), each of which may exist with the halogen atoms in a diaxial (aa) or diequatorial (ee) conformation, have been investigated by electron diffraction. The analysis was aided by rotational constants from microwave spectroscopy for the ee form of DFCH and by ab initio and density functional theory molecular orbital calculations for all species. The skeletons of the molecules have similar parameter values, but for the Cl-C-C-Cl and F-C-C-F fragments there are significant differences between the corresponding C-C-X bond angles and the X-C-C-X torsion angles in the two systems. There are also significant differences between the values of these parameters in the aa and ee forms of the same system. The composition of DCCH at 100 degrees C was measured to be 60(4)% aa, and that of DFCH at 70 degrees C was 42(7)% aa; the uncertainties are estimated 2sigma. From the preferred B3LYP/aug-cc-pVTZ calculations, the predicted theoretical composition is 51.2% aa for DCCH and 40.8% aa for DFCH. (Calculations at the levels B3LYP/6-31G(d) and MP2/6-31G(d) give similar results for DCCH, but both predict more aa than ee for DFCH.) Values (r(g)/A and angle(alpha)/degree) for some of the more important parameters of the aa/ee forms of DCCH are = 1.525(4)/1.525(6), C-Cl = 1.806(2)/1.787(2), angleC2-C1-Cl = 107.3(3)/111.5(3), angleC1-C2-C3 = 113.9(5)/111.6(5), angleC2-C3-C4 = 111.3(12)/109.9(12), and Cl-C2-C3-Cl = 165.3(9)/-59.4(9); and for DFCH C-C = 1.525(6)/1.520(9), C-F = 1.398(2)/1.390(2), angleC2-C1-F = 106.5(6)/109.2(6), angleC1-C2-C3 = 111.4(9)/110.9(9), angleC2-C3-C4 = 113.1(10)/113.1(10), and F-C2-C3-F = 171.1(37)/-67.2(37). The structures and compositions are discussed.

Chalcogenide-halides of niobium (V). 1. Gas-phase structures of NbOBr(3), NbSBr(3), and NbSCl(3). 2. Matrix infrared spectra and vibrational force fields of NbOBr(3), NbSBr(3), NbSCl(3), and NbOCl(3).

The molecular structures of NbOBr(3), NbSCl(3), and NbSBr(3) have been determined by gas-phase electron diffraction (GED) at nozzle-tip temperatures of 250 degrees C, taking into account the possible presence of NbOCl(3) as a contaminant in the NbSCl(3) sample and NbOBr(3) in the NbSBr(3) sample. The experimental data are consistent with trigonal-pyramidal molecules having C(3)(v)() symmetry. Infrared spectra of molecules trapped in argon or nitrogen matrices were recorded and exhibit the characteristic fundamental stretching modes for C(3)(v)() species. Well resolved isotopic fine structure ((35)Cl and (37)Cl) was observed for NbSCl(3), and for NbOCl(3) which occurred as an impurity in the NbSCl(3) spectra. Quantum mechanical calculations of the structures and vibrational frequencies of the four YNbX(3) molecules (Y = O, S; X = Cl, Br) were carried out at several levels of theory, most importantly B3LYP DFT with either the Stuttgart RSC ECP or Hay-Wadt (n + 1) ECP VDZ basis set for Nb and the 6-311G basis set for the nonmetal atoms. Theoretical values for the bond lengths are 0.01-0.04 A longer than the experimental ones of type r(a), in accord with general experience, but the bond angles with theoretical minus experimental differences of only 1.0-1.5 degrees are notably accurate. Symmetrized force fields were also calculated. The experimental bond lengths (r(g)/A) and angles ( 90 degree angle (alpha)()/deg) with estimated 2sigma uncertainties from GED are as follows. NbOBr(3): r(Nb=O) = 1.694(7), r(Nb-Br) = 2.429(2), 90 degree angle (O=Nb-Br) = 107.3(5), 90 degree angle (Br-Nb-Br) = 111.5(5). NbSBr(3): r(Nb=S) = 2.134(10), r(Nb-Br) = 2.408(4), 90 degree angle (S=Nb-Br) = 106.6(7), 90 degree angle (Br-Nb-Br) = 112.2(6). NbSCl(3): r(Nb=S) = 2.120(10),r(Nb-Cl) = 2.271(6), 90 degree angle (S=Nb-Cl) = 107.8(12), 90 degree angle (Cl-Nb-Cl) = 111.1(11).