Tetrakis­(di­methyl­amido)­vanadium(IV)

The title compound, [V(C₂H₆N)₄], (I), has non-crystallographic D_2d molecular symmetry and contains an approximately tetrahedrally coordinated V atom with di­methyl­amido ligands. Each N atom features a nearly trigonal planar geometry. There are two independent mol­ecules of (I) in the asymmetric unit. The results are compared with those previously reported for gas-phase electron-diffraction studies [Haaland, Rypdal, Volden & Andersen (1992). J. Chem. Soc. Dalton Trans. pp. 891-895].

S1. Comment

The study of transition metal amido complexes has been an important area of chemistry since the pioneering work in the 1960 s and early 1970 s (Lappert et al., 1980, and references therein), and continues to attract considerable interest (Gade, 2000, and references therein). Within the large family of complexes with secondary amido ligands of the type NR₂ (where R = a hydrocarbyl or other non-H group), the simplest are the mononuclear, homoleptic dimethylamido species [M(NMe₂)_n] (n = 4, 5 or 6). The following members of this family have been crystallographically characterized: [Nb(NMe₂)₅] (Heath & Hursthouse, 1971), [Ta(NMe₂)₅] (Batsanov et al., 1999), [Mo(NMe₂)₄] (Chisholm et al., 1978), [Mo(NMe₂)₆] (Chisholm et al., 1987) and [W(NMe₂)₆] (Bradley et al., 1969). Tetrakis(dimethylamido)zirconium, usually referred to as a four-coordinate species '[Zr(NMe₂)₄]' actually adopts the NMe₂-bridged dimeric structure [Zr₂(µ-NMe₂)₂(NMe₂)₆] in the solid state (Chisholm et al., 1988). While no first row transition metal dimethylamido complex has been crystallographically characterized, gas-phase diffraction studies of [M(NMe₂)₄] [M = Ti or V (I)] have been reported (Haaland et al., 1992). \sch

During the course of our studies of early transition metal amido chemistry (Skinner et al., 2000) we obtained crystals of (I). The unit cell contains two crystallographically independent molecules, the geometric features of which are essentially identical. Molecules of (I) feature molecular D_{2 d} symmetry as illustrated in Fig. 1 where (I) is viewed along the molecular C₂ (coincident with S₄) axis; the molecular mirror planes contain V1(A)/N1(A)/N4(A) and V1(A)/N2(A)/N3(A). The angles between the normals to the planes comprising these atoms is 91.6 (2) and 91.7 (2)° for the systems containing V1 and V1A, respectively. The V—N distances and V—N—C angles span the typical ranges reported for vanadium amides (Fletcher et al., 1996; Allen & Kennard, 1993). The angles subtended at V1 and V1A fall into two groups, with the division between the values being more pronounced for V1 on which further discussion will focus. The N1—V1—N4 and N2—V1—N3 angles of 115.28 (6) and 111.42 (6)° are significantly larger than the ideal tetrahedral angle of ca 109.5°, while the remaining four N—V1—N angles [range 106.26 (5)–100.00 (6)°] are less. The nitrogen atoms are approximately sp²-hybridized (i.e., having a near-trigonal planar coordination). However, the sums of the angles subtended at each N atom span the range 355.2 (3)–358.1 (3)° (for V1, average = ca 357.2°) and 355.4 (3)–356.7 (3)° (for V1A, average = ca 356.1°) showing that there is a slight but persistent degree of pyramidalization of these atoms. As Fig. 2 emphasizes for atoms N2 and N3 of the molecule containing V1, the sense of distortion is to move the methyl carbons (i.e. C3, C4, C5 and C6) into the more 'open' N2—V1—N3 aperture (N2—V1—N3 = 111.52°). This feature is repeated for all of the NMe₂ groups and may reflect intramolecular steric effects.

The molecular structure of [V(NMe₂)₄], (I), is analogous to that of the d² molybdenum tetrakis(dimethylamido) complex [Mo(NMe₂)₄] (Chisholm et al., 1978) which also has molecular D_{2 d} symmetry but shows no apparent trends in the N—Mo—N angles within reported errors. No congeneric Group 5 d¹ dimethylamido complexes [M(NMe₂)₄] (M = Nb or Mo) have been crystallographically characterized. However, homologous pseudo-tetrahedral heavier congeners of (I) with the bulkier amido ligands, NPh₂ and NEt₂, have been reported, namely [Nb(NPh₂)₄] (Bott et al., 1995) and [Ta(NEt₂)₂(NPh₂)₂] (Suh & Hoffman, 1996), respectively. These Nb and Ta complexes have approximate D_{2 d} symmetry within the core M(NC₂)₄ units.

As mentioned, Haaland et al. (1992) have reported the gas-phase electron diffraction (GED) structure of [V(NMe₂)₄], (I) (Haaland et al., 1992), which was found to be approximately D_{2 d} symmetrical. It is interesting to compare the X-ray and GED results. The GED model was fitted assuming S₄ molecular symmetry and planar amido groups (i.e. local C₂ symmetry for the NMe₂ fragments). The agreement between the X-ray and GED structures is excellent (for non-H atom distances) to very good (for non-H atom angles) as shown by the following data (given as GED values, followed by X-ray derived values in brackets for both molecules): V—N = 1.879 (4) Å [range 1.8652 (12)–1.8721 (12), average ca 1.87 Å], N—C = 1.457 (3) Å [range 1.4512 (19)–1.457 (2), average ca 1.45 Å], V—N—C = 123.2 (3)° [range 120.0 (1)–124.7 (1), average ca 122.7°], N—V—N (two independent values) = 100.6 (5) and 114.1 (1)° [between pairs of atoms lying on the same molecular mirror planes: range 110.73 (5)–115.28 (6), average ca 112.2°; between pairs of atoms related by molecular C₂^' axes: range 106.26 (5)–110.03 (6), average ca 108.1°]. >From the two structure determinations (GED and X-ray) it is evident that there is a clear and persistent deviation of the N—V—N angles from those expected for a regular tetrahedron, as expected on electronic grounds (Haaland et al., 1992).

Comparisons can also be made between the neutral, d¹ vanadium(+4) complex (I) and the d² anionic tetrakis(diphenylamido)vanadium(+3) species [V(NPh₂)₄]^- (Song et al., 1996), and with the cationic d⁰ tetrakis(diethylamido)vanadium(+5) species [V(NEt₂)₄]⁺ (Choukroun et al., 1998). For [V(NEt₂)₄]⁺ the V—N distances span the range 1.817 (3)–1.847 (3) Å (average = ca 1.83 Å) and for [V(NPh₂)₄]^- the V—N distances span the range 1.988 (7)–2.004 (7) Å (average = ca 1.99 Å). The average V—N distances for the vanadium(5+) and vanadium(3+) complexes lie either side of that (ca 1.87 Å) for (I), in line with the general expected changes in atomic radius with formal oxidation state (without taking into particular account the different N-substituents in the three complexes) and their electronic structures (Chisholm et al., 1978; Chisholm & Clark, 1987). Neither of the complexes [V(NEt₂)₄]⁺ or [V(NPh₂)₄]^- possess D_{2 d} symmetry in the solid state, also as predicted by theoretical treatments of the bonding in [M(NR₂)₄] complexes, nor are there any apparent trends in the N—V—N angles.

Related literature

For related literature, see: Allen & Kennard (1993); Batsanov et al. (1999); Bott et al. (1995); Bradley et al. (1969); Chisholm & Clark (1987); Chisholm et al. (1978, 1988); Chisholm, Hammond & Huffman (1987); Choukroun et al. (1998); Fletcher et al. (1996); Gade (2000); Haaland et al. (1992); Heath & Hursthouse (1971); Lappert et al. (1980); Skinner et al. (2000); Song & Gambarotta (1996); Suh & Hoffman (1996).

S2. Experimental

Tetrakis(dimethylamido)vanadium was prepared according to previously described procedures (Haaland et al., 1992). Sublimation (298 K, 2 x 10^-3 mbar) of the crude product afforded the title compound as very air-sensitive, dark green blocks.

S3. Refinement

Three low-angle reflections (100, 110, 020) with severely underestimated |F_o| were omited from refinement cycles. Otherwise refinement was carried out against all unique data. The range of refined C—H bond lengths is 0.89 (3) to 1.02 (3) Å.

Computing details

Data collection: Kappa-CCD software COLLECT (Nonius, 2000); cell refinement: DENZO; data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Watkin, Prout et al., 1996); molecular graphics: CAMERON (Watkin, Prout & Pearce et al., 1996); software used to prepare material for publication: CRYSTALS.

Figures

	Fig. 1. View of one of the two crystallographically independent molecules of (I) along the molecular C2 (S4) axis with the atom-numbering scheme. The numbering scheme for the second molecule is the same except that the suffix 'A' is added to the numerical labels. The displacement parameters are drawn at the 25% probability level and H atoms are omitted for clarity.
	Fig. 2. View of one of the two crystallographically independent molecules of (I) perpendicular to one of the molecular mirror planes and emphasizing the pyramidilization of N2 and N3 atoms. The displacement parameters are drawn at the 25% probability level and H atoms are omitted for clarity.

Tetrakis(dimethylamido)vanadium

Crystal data

C8H24N4V	Z = 4
Mr = 227.25	F(000) = 492
Triclinic, P1	Dx = 1.151 Mg m^−3
a = 8.2903 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.0158 (2) Å	Cell parameters from 5348 reflections
c = 13.8350 (3) Å	θ = 1.0–27.5°
α = 75.6616 (10)°	µ = 0.73 mm^−1
β = 79.4036 (11)°	T = 150 K
γ = 84.9664 (9)°	Block, dark green
V = 1311.18 (5) Å^3	0.30 × 0.20 × 0.20 mm

Data collection

Nonius Kappa-CCD diffractometer	4773 reflections with I > 2σ(I)
CCD scans	Rint = 0.02
Absorption correction: multi-scan (DENZO; Otwinowski & Minor, 1997)	θmax = 27.5°, θmin = 1.0°
Tmin = 0.864, Tmax = 0.864	h = −10→10
10654 measured reflections	k = −15→15
5886 independent reflections	l = −17→17

Refinement

Refinement on F	Primary atom site location: direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	All H-atom parameters refined
wR(F^2) = 0.043	Chebychev polynomial with 5 parameters, (Carruthers & Watkin, 1979), 0.895 0.532 0.456 -.541E-01 -.147
S = 1.05	(Δ/σ)max = 0.006
5883 reflections	Δρmax = 0.71 e Å^−3
427 parameters	Δρmin = −0.83 e Å^−3
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
V1	0.22069 (3)	0.248426 (19)	−0.473572 (17)	0.0206
N1	0.34951 (15)	0.36961 (11)	−0.5522 (1)	0.0261
N2	0.36549 (15)	0.13317 (11)	−0.4167 (1)	0.0267
N3	0.07447 (15)	0.30263 (11)	−0.37399 (9)	0.0266
N4	0.09240 (15)	0.18648 (11)	−0.5438 (1)	0.0254
C1	0.2858 (2)	0.48730 (15)	−0.58253 (14)	0.0364
C2	0.5100 (2)	0.35317 (17)	−0.61184 (13)	0.0344
C3	0.5067 (2)	0.15807 (15)	−0.37819 (14)	0.0329
C4	0.3247 (2)	0.01340 (15)	−0.37757 (16)	0.0386
C5	0.1192 (2)	0.38497 (16)	−0.32295 (13)	0.0348
C6	−0.0607 (2)	0.23496 (17)	−0.31178 (14)	0.0360
C7	−0.06547 (19)	0.23800 (16)	−0.56632 (13)	0.0316
C8	0.1552 (2)	0.10298 (15)	−0.60336 (13)	0.0308
H11	0.180 (3)	0.496 (2)	−0.5433 (18)	0.044 (6)*
H12	0.278 (3)	0.5101 (19)	−0.6558 (17)	0.037 (5)*
H13	0.360 (3)	0.539 (2)	−0.5697 (19)	0.053 (7)*
H21	0.508 (3)	0.3714 (19)	−0.6859 (17)	0.037 (5)*
H22	0.547 (3)	0.273 (2)	−0.594 (2)	0.052 (7)*
H23	0.596 (3)	0.396 (2)	−0.599 (2)	0.055 (7)*
H31	0.491 (3)	0.132 (2)	−0.301 (2)	0.055 (7)*
H32	0.610 (3)	0.115 (2)	−0.4042 (19)	0.049 (6)*
H33	0.529 (3)	0.238 (2)	−0.4011 (17)	0.044 (6)*
H41	0.232 (3)	−0.000 (2)	−0.3986 (18)	0.043 (6)*
H42	0.311 (3)	−0.008 (2)	−0.304 (2)	0.055 (7)*
H43	0.408 (3)	−0.038 (2)	−0.402 (2)	0.059 (7)*
H51	0.210 (3)	0.427 (2)	−0.3627 (19)	0.049 (6)*
H52	0.151 (3)	0.348 (2)	−0.256 (2)	0.051 (6)*
H53	0.026 (3)	0.444 (2)	−0.3121 (18)	0.048 (6)*
H61	−0.158 (3)	0.284 (2)	−0.296 (2)	0.055 (7)*
H62	−0.036 (3)	0.195 (2)	−0.246 (2)	0.052 (6)*
H63	−0.098 (3)	0.183 (2)	−0.346 (2)	0.054 (7)*
H71	−0.108 (3)	0.291 (2)	−0.5275 (17)	0.037 (5)*
H72	−0.148 (3)	0.182 (2)	−0.5511 (19)	0.050 (6)*
H73	−0.059 (3)	0.280 (2)	−0.636 (2)	0.052 (7)*
H81	0.165 (3)	0.138 (2)	−0.678 (2)	0.050 (6)*
H82	0.262 (3)	0.0739 (19)	−0.5909 (16)	0.036 (5)*
H83	0.089 (3)	0.039 (2)	−0.5861 (17)	0.045 (6)*
V1A	0.20452 (3)	0.247431 (19)	0.023480 (17)	0.0198
N1A	0.28403 (15)	0.27243 (11)	0.13365 (9)	0.0251
N2A	−0.02305 (14)	0.27234 (11)	0.04767 (9)	0.0238
N3A	0.26320 (16)	0.09759 (11)	0.00992 (11)	0.0289
N4A	0.29526 (15)	0.34829 (11)	−0.09637 (9)	0.0253
C1A	0.2228 (2)	0.36610 (15)	0.18210 (13)	0.0310
C2A	0.4500 (2)	0.23409 (17)	0.15061 (15)	0.0368
C3A	−0.1259 (2)	0.30240 (15)	−0.03036 (12)	0.0292
C4A	−0.11677 (19)	0.22405 (14)	0.14691 (12)	0.0285
C5A	0.2706 (3)	−0.00061 (16)	0.09426 (18)	0.0443
C6A	0.2459 (2)	0.06276 (17)	−0.08104 (16)	0.0394
C7A	0.2451 (2)	0.46969 (14)	−0.11801 (13)	0.0318
C8A	0.4560 (2)	0.32859 (17)	−0.15403 (14)	0.0350
H11A	0.217 (3)	0.341 (2)	0.2577 (18)	0.041 (6)*
H12A	0.116 (3)	0.393 (2)	0.1693 (17)	0.041 (6)*
H13A	0.287 (3)	0.430 (2)	0.1590 (18)	0.044 (6)*
H21A	0.526 (3)	0.301 (2)	0.126 (2)	0.059 (7)*
H22A	0.496 (3)	0.177 (2)	0.1162 (19)	0.048 (6)*
H23A	0.447 (3)	0.204 (2)	0.224 (2)	0.050 (6)*
H31A	−0.210 (3)	0.361 (2)	−0.0175 (17)	0.042 (6)*
H32A	−0.059 (3)	0.333 (2)	−0.0935 (18)	0.043 (6)*
H33A	−0.187 (3)	0.233 (2)	−0.0333 (18)	0.049 (6)*
H41A	−0.187 (3)	0.161 (2)	0.1499 (17)	0.040 (5)*
H42A	−0.050 (3)	0.200 (2)	0.1970 (19)	0.044 (6)*
H43A	−0.193 (3)	0.281 (2)	0.1718 (17)	0.041 (6)*
H51A	0.357 (4)	−0.055 (3)	0.083 (2)	0.063 (8)*
H52A	0.285 (3)	0.020 (2)	0.151 (2)	0.054 (7)*
H53A	0.184 (4)	−0.043 (3)	0.105 (2)	0.070 (8)*
H61A	0.143 (3)	0.022 (2)	−0.0730 (18)	0.048 (6)*
H62A	0.244 (3)	0.130 (2)	−0.137 (2)	0.050 (6)*
H63A	0.342 (3)	0.016 (2)	−0.104 (2)	0.057 (7)*
H71A	0.140 (3)	0.482 (2)	−0.0799 (19)	0.050 (6)*
H72A	0.325 (3)	0.510 (2)	−0.1031 (19)	0.049 (6)*
H73A	0.237 (3)	0.4982 (19)	−0.1882 (18)	0.038 (5)*
H81A	0.488 (3)	0.253 (2)	−0.1345 (19)	0.048 (6)*
H82A	0.455 (3)	0.351 (2)	−0.2251 (19)	0.047 (6)*
H83A	0.539 (4)	0.368 (2)	−0.139 (2)	0.060 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.02026 (12)	0.02027 (13)	0.02093 (13)	−0.00315 (9)	−0.00304 (9)	−0.00368 (9)
N1	0.0253 (6)	0.0245 (6)	0.0271 (6)	−0.0052 (5)	−0.0035 (5)	−0.0025 (5)
N2	0.0255 (6)	0.0230 (6)	0.0315 (6)	−0.0025 (5)	−0.0076 (5)	−0.0035 (5)
N3	0.0266 (6)	0.0293 (6)	0.0241 (6)	−0.0039 (5)	−0.0024 (5)	−0.0072 (5)
N4	0.0227 (6)	0.0267 (6)	0.0282 (6)	−0.0021 (5)	−0.0048 (5)	−0.0084 (5)
C1	0.045 (1)	0.0246 (8)	0.0353 (9)	−0.0031 (7)	−0.0046 (7)	−0.0006 (6)
C2	0.0271 (7)	0.0402 (9)	0.0334 (8)	−0.0103 (7)	0.0002 (6)	−0.0050 (7)
C3	0.0290 (8)	0.0324 (8)	0.0392 (9)	−0.0007 (6)	−0.0129 (6)	−0.0071 (7)
C4	0.0417 (9)	0.0263 (8)	0.046 (1)	−0.0065 (7)	−0.0152 (8)	0.0027 (7)
C5	0.0409 (9)	0.0376 (9)	0.0298 (8)	−0.0046 (7)	−0.0063 (7)	−0.0139 (7)
C6	0.0338 (8)	0.0396 (9)	0.0306 (8)	−0.0084 (7)	0.0054 (6)	−0.0064 (7)
C7	0.0250 (7)	0.0383 (9)	0.0344 (8)	−0.0003 (6)	−0.0077 (6)	−0.0125 (7)
C8	0.0326 (8)	0.0307 (8)	0.0316 (8)	−0.0019 (6)	−0.0049 (6)	−0.0122 (7)
V1A	0.01867 (12)	0.01888 (12)	0.02131 (13)	−0.00163 (8)	−0.00251 (9)	−0.00414 (9)
N1A	0.0202 (5)	0.0285 (6)	0.0268 (6)	−0.0014 (5)	−0.0058 (4)	−0.0057 (5)
N2A	0.0217 (5)	0.0258 (6)	0.0242 (6)	−0.0013 (4)	−0.0050 (4)	−0.0057 (5)
N3A	0.0292 (6)	0.0205 (6)	0.0364 (7)	−0.0005 (5)	−0.0044 (5)	−0.0066 (5)
N4A	0.0272 (6)	0.0240 (6)	0.0240 (6)	−0.0031 (5)	−0.0019 (5)	−0.0055 (5)
C1A	0.0324 (8)	0.0303 (8)	0.0327 (8)	−0.0020 (6)	−0.0086 (6)	−0.0096 (6)
C2A	0.0221 (7)	0.046 (1)	0.044 (1)	−0.0009 (7)	−0.0099 (7)	−0.0115 (8)
C3A	0.0257 (7)	0.0356 (8)	0.0296 (8)	0.0017 (6)	−0.0090 (6)	−0.0117 (6)
C4A	0.0228 (7)	0.0335 (8)	0.0277 (7)	−0.0039 (6)	−0.0027 (6)	−0.0047 (6)
C5A	0.0492 (11)	0.0239 (8)	0.0548 (12)	−0.0043 (8)	−0.0110 (9)	0.0025 (8)
C6A	0.0393 (9)	0.0312 (9)	0.0528 (11)	−0.0018 (7)	−0.0074 (8)	−0.0197 (8)
C7A	0.0402 (9)	0.0221 (7)	0.0320 (8)	−0.0049 (6)	−0.0035 (7)	−0.0048 (6)
C8A	0.0291 (8)	0.0361 (9)	0.0355 (9)	−0.0051 (7)	0.0034 (6)	−0.0053 (7)

Geometric parameters (Å, º)

V1—N1	1.8721 (12)	V1A—N1A	1.8652 (12)
V1—N2	1.8692 (13)	V1A—N2A	1.8653 (12)
V1—N3	1.8664 (13)	V1A—N3A	1.8691 (13)
V1—N4	1.8721 (12)	V1A—N4A	1.8681 (13)
N1—C1	1.453 (2)	N1A—C1A	1.457 (2)
N1—C2	1.456 (2)	N1A—C2A	1.4539 (19)
N2—C3	1.4536 (19)	N2A—C3A	1.4541 (19)
N2—C4	1.453 (2)	N2A—C4A	1.4552 (19)
N3—C5	1.457 (2)	N3A—C5A	1.446 (2)
N3—C6	1.455 (2)	N3A—C6A	1.455 (2)
N4—C7	1.4512 (19)	N4A—C7A	1.454 (2)
N4—C8	1.455 (2)	N4A—C8A	1.454 (2)
C1—H11	0.96 (3)	C1A—H11A	1.01 (2)
C1—H12	1.00 (2)	C1A—H12A	0.94 (2)
C1—H13	0.98 (3)	C1A—H13A	0.93 (2)
C2—H21	1.00 (2)	C2A—H21A	1.01 (3)
C2—H22	0.97 (3)	C2A—H22A	0.94 (3)
C2—H23	0.98 (3)	C2A—H23A	0.98 (3)
C3—H31	1.02 (3)	C3A—H31A	0.97 (2)
C3—H32	1.01 (3)	C3A—H32A	0.95 (2)
C3—H33	0.96 (2)	C3A—H33A	1.02 (2)
C4—H41	0.91 (3)	C4A—H41A	0.98 (2)
C4—H42	0.98 (3)	C4A—H42A	0.94 (3)
C4—H43	0.96 (3)	C4A—H43A	0.98 (2)
C5—H51	0.95 (3)	C5A—H51A	0.94 (3)
C5—H52	0.99 (3)	C5A—H52A	0.91 (3)
C5—H53	1.02 (3)	C5A—H53A	0.89 (3)
C6—H61	0.98 (3)	C6A—H61A	1.00 (2)
C6—H62	0.97 (3)	C6A—H62A	0.97 (3)
C6—H63	0.97 (3)	C6A—H63A	0.98 (3)
C7—H71	0.94 (2)	C7A—H71A	0.95 (3)
C7—H72	0.96 (3)	C7A—H72A	0.94 (3)
C7—H73	0.96 (3)	C7A—H73A	0.96 (2)
C8—H81	1.00 (3)	C8A—H81A	0.92 (3)
C8—H82	0.96 (2)	C8A—H82A	0.96 (3)
C8—H83	0.94 (2)	C8A—H83A	0.94 (3)
N1—V1—N2	106.53 (6)	N1A—V1A—N2A	107.16 (5)
N1—V1—N3	108.41 (6)	N1A—V1A—N3A	109.74 (6)
N2—V1—N3	111.42 (6)	N2A—V1A—N3A	111.48 (6)
N1—V1—N4	115.28 (6)	N1A—V1A—N4A	110.73 (5)
N2—V1—N4	109.00 (6)	N2A—V1A—N4A	110.03 (6)
N3—V1—N4	106.26 (5)	N3A—V1A—N4A	107.73 (6)
V1—N1—C1	123.67 (11)	V1A—N1A—C1A	123.3 (1)
V1—N1—C2	123.62 (11)	V1A—N1A—C2A	120.92 (11)
C1—N1—C2	110.81 (14)	C1A—N1A—C2A	111.22 (13)
V1—N2—C3	122.5 (1)	V1A—N2A—C3A	124.7 (1)
V1—N2—C4	123.70 (11)	V1A—N2A—C4A	120.0 (1)
C3—N2—C4	111.12 (13)	C3A—N2A—C4A	112.02 (12)
V1—N3—C5	122.77 (11)	V1A—N3A—C5A	124.03 (13)
V1—N3—C6	121.60 (11)	V1A—N3A—C6A	120.92 (11)
C5—N3—C6	110.85 (13)	C5A—N3A—C6A	111.45 (15)
V1—N4—C7	122.6 (1)	V1A—N4A—C7A	121.02 (11)
V1—N4—C8	123.8 (1)	V1A—N4A—C8A	123.65 (11)
C7—N4—C8	111.74 (12)	C7A—N4A—C8A	111.20 (13)
N1—C1—H11	109.4 (14)	N1A—C1A—H11A	111.5 (13)
N1—C1—H12	112.3 (13)	N1A—C1A—H12A	111.4 (14)
H11—C1—H12	109.3 (19)	H11A—C1A—H12A	107.5 (19)
N1—C1—H13	109.0 (15)	N1A—C1A—H13A	113.2 (15)
H11—C1—H13	109 (2)	H11A—C1A—H13A	107.4 (19)
H12—C1—H13	108.0 (19)	H12A—C1A—H13A	105 (2)
N1—C2—H21	112.8 (13)	N1A—C2A—H21A	110.6 (16)
N1—C2—H22	110.0 (15)	N1A—C2A—H22A	113.4 (15)
H21—C2—H22	105 (2)	H21A—C2A—H22A	106 (2)
N1—C2—H23	113.6 (15)	N1A—C2A—H23A	108.0 (15)
H21—C2—H23	109.4 (19)	H21A—C2A—H23A	109 (2)
H22—C2—H23	105 (2)	H22A—C2A—H23A	110 (2)
N2—C3—H31	111.3 (14)	N2A—C3A—H31A	111.5 (14)
N2—C3—H32	111.4 (14)	N2A—C3A—H32A	108.8 (14)
H31—C3—H32	106 (2)	H31A—C3A—H32A	107.3 (19)
N2—C3—H33	110.7 (14)	N2A—C3A—H33A	111.5 (14)
H31—C3—H33	111 (2)	H31A—C3A—H33A	106.3 (19)
H32—C3—H33	105.8 (19)	H32A—C3A—H33A	111 (2)
N2—C4—H41	110.5 (15)	N2A—C4A—H41A	115.3 (13)
N2—C4—H42	111.5 (16)	N2A—C4A—H42A	112.6 (14)
H41—C4—H42	110 (2)	H41A—C4A—H42A	109 (2)
N2—C4—H43	112.5 (16)	N2A—C4A—H43A	111.7 (13)
H41—C4—H43	105 (2)	H41A—C4A—H43A	104.1 (18)
H42—C4—H43	107 (2)	H42A—C4A—H43A	103.2 (19)
N3—C5—H51	110.5 (15)	N3A—C5A—H51A	114.5 (17)
N3—C5—H52	113.2 (15)	N3A—C5A—H52A	111.9 (17)
H51—C5—H52	107 (2)	H51A—C5A—H52A	105 (2)
N3—C5—H53	111.4 (14)	N3A—C5A—H53A	111 (2)
H51—C5—H53	107 (2)	H51A—C5A—H53A	101 (3)
H52—C5—H53	108 (2)	H52A—C5A—H53A	113 (3)
N3—C6—H61	111.3 (16)	N3A—C6A—H61A	112.8 (14)
N3—C6—H62	112.4 (15)	N3A—C6A—H62A	110.0 (15)
H61—C6—H62	104 (2)	H61A—C6A—H62A	108 (2)
N3—C6—H63	112.4 (15)	N3A—C6A—H63A	111.3 (16)
H61—C6—H63	105 (2)	H61A—C6A—H63A	111 (2)
H62—C6—H63	112 (2)	H62A—C6A—H63A	104 (2)
N4—C7—H71	112.6 (14)	N4A—C7A—H71A	110.5 (16)
N4—C7—H72	111.9 (15)	N4A—C7A—H72A	108.1 (16)
H71—C7—H72	105 (2)	H71A—C7A—H72A	112 (2)
N4—C7—H73	112.2 (15)	N4A—C7A—H73A	110.9 (13)
H71—C7—H73	106 (2)	H71A—C7A—H73A	107 (2)
H72—C7—H73	109 (2)	H72A—C7A—H73A	108 (2)
N4—C8—H81	112.0 (14)	N4A—C8A—H81A	109.0 (16)
N4—C8—H82	110.5 (13)	N4A—C8A—H82A	111.2 (15)
H81—C8—H82	106.8 (19)	H81A—C8A—H82A	111 (2)
N4—C8—H83	111.7 (14)	N4A—C8A—H83A	112.5 (17)
H81—C8—H83	109 (2)	H81A—C8A—H83A	104 (2)
H82—C8—H83	106.3 (19)	H82A—C8A—H83A	109 (2)