Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010001564X/gg1031sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010001564X/gg1031Isup2.hkl |
CCDC reference: 159977
Detailed experimental procedures for the precursors to this complex and related species, namely [(Me3Si)NC(Ph)N(SiMe3)]2V(allyl) (Brussee et al., 1996) and [(Me3Si)NC(Ph)N(SiMe3)]2VCl (Hao et al., 1996) have been described. Complex (I) was recrystallized from hexane/dichloromethane solution.
Two of the methyl groups on Si3 display large displacement parameters but no suitable refinement model for disorder was found. Aromatic H atoms were constrained and allowed to ride on their C atoms with Uiso(H) = 1.2Ueq(C). Methyl H atoms (except those on C32? or C33?) were constrained to an ideal geometry with Uiso(H) = 1.5Ueq(C), and allowed to rotate freely about the C—C bonds. The H atoms on C33 were equally disordered over two positions and were refined with 50% site occupancy factors.
Data collection: Locally modified CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: DIRDIF97 (Beurskens et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: PLATON (Spek, 2000).
Fig. 1. The molecular view of (I) showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. |
[VCl(C7H7N)(C13H23N2Si2)2] | F(000) = 1528 |
Mr = 718.55 | Dx = 1.197 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1600 (5) Å | Cell parameters from 25 reflections |
b = 18.4257 (10) Å | θ = 11.5–14.0° |
c = 22.6430 (13) Å | µ = 0.46 mm−1 |
β = 109.808 (5)° | T = 150 K |
V = 3988.1 (4) Å3 | Block, dark red |
Z = 4 | 0.25 × 0.25 × 0.25 mm |
Enraf-Nonius CAD-4 diffractometer | 5838 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.027 |
Graphite monochromator | θmax = 27.5°, θmin = 1.5° |
ω/2θ scans | h = −13→13 |
Absorption correction: part of the refinement model (ΔF) (PLATON; Spek, 2000) | k = 0→23 |
Tmin = 0.819, Tmax = 0.890 | l = −19→29 |
11788 measured reflections | 2 standard reflections every 60 min |
9132 independent reflections | intensity decay: 1% |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0436P)2] where P = (Fo2 + 2Fc2)/3 |
9132 reflections | (Δ/σ)max = 0.002 |
410 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
[VCl(C7H7N)(C13H23N2Si2)2] | V = 3988.1 (4) Å3 |
Mr = 718.55 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.1600 (5) Å | µ = 0.46 mm−1 |
b = 18.4257 (10) Å | T = 150 K |
c = 22.6430 (13) Å | 0.25 × 0.25 × 0.25 mm |
β = 109.808 (5)° |
Enraf-Nonius CAD-4 diffractometer | 5838 reflections with I > 2σ(I) |
Absorption correction: part of the refinement model (ΔF) (PLATON; Spek, 2000) | Rint = 0.027 |
Tmin = 0.819, Tmax = 0.890 | 2 standard reflections every 60 min |
11788 measured reflections | intensity decay: 1% |
9132 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.39 e Å−3 |
9132 reflections | Δρmin = −0.34 e Å−3 |
410 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
V1 | 0.90549 (5) | 0.25735 (2) | 0.17747 (2) | 0.02086 (11) | |
Cl1 | 1.03238 (7) | 0.15425 (4) | 0.17477 (4) | 0.03517 (19) | |
Si1 | 0.69220 (8) | 0.39276 (4) | 0.21639 (4) | 0.02535 (18) | |
Si2 | 1.23094 (8) | 0.28072 (4) | 0.29659 (4) | 0.02325 (18) | |
Si3 | 0.77672 (8) | 0.13030 (4) | 0.28117 (4) | 0.02579 (18) | |
Si4 | 0.64611 (8) | 0.23749 (5) | 0.03693 (4) | 0.02856 (19) | |
N1 | 0.8394 (2) | 0.33811 (11) | 0.22618 (10) | 0.0193 (5) | |
N2 | 1.0487 (2) | 0.28550 (11) | 0.26525 (10) | 0.0207 (5) | |
N3 | 0.7743 (2) | 0.18243 (11) | 0.21625 (10) | 0.0219 (5) | |
N4 | 0.7251 (2) | 0.22738 (11) | 0.11872 (10) | 0.0220 (5) | |
N5 | 0.9667 (2) | 0.30844 (12) | 0.13229 (10) | 0.0247 (5) | |
C1 | 0.5386 (3) | 0.35383 (16) | 0.15436 (13) | 0.0318 (7) | |
H1A | 0.4556 | 0.3832 | 0.1504 | 0.048* | |
H1B | 0.5232 | 0.3040 | 0.1656 | 0.048* | |
H1C | 0.5558 | 0.3537 | 0.1143 | 0.048* | |
C2 | 0.7213 (3) | 0.48464 (17) | 0.18869 (19) | 0.0572 (11) | |
H2A | 0.7898 | 0.5110 | 0.2231 | 0.086* | |
H2B | 0.6327 | 0.5115 | 0.1748 | 0.086* | |
H2C | 0.7565 | 0.4798 | 0.1536 | 0.086* | |
C3 | 0.6501 (3) | 0.39911 (18) | 0.28967 (14) | 0.0418 (8) | |
H3A | 0.5612 | 0.4249 | 0.2812 | 0.063* | |
H3B | 0.7246 | 0.4257 | 0.3214 | 0.063* | |
H3C | 0.6422 | 0.3502 | 0.3051 | 0.063* | |
C4 | 0.9587 (3) | 0.33261 (14) | 0.27413 (12) | 0.0204 (6) | |
C5 | 0.9913 (3) | 0.37256 (14) | 0.33519 (12) | 0.0211 (6) | |
C6 | 1.0181 (3) | 0.33273 (16) | 0.38999 (13) | 0.0307 (7) | |
H6 | 1.0106 | 0.2813 | 0.3879 | 0.037* | |
C7 | 1.0556 (3) | 0.36699 (17) | 0.44740 (14) | 0.0379 (8) | |
H7 | 1.0741 | 0.3393 | 0.4847 | 0.046* | |
C8 | 1.0662 (3) | 0.44142 (17) | 0.45044 (14) | 0.0369 (8) | |
H8 | 1.0924 | 0.4650 | 0.4900 | 0.044* | |
C9 | 1.0392 (3) | 0.48174 (16) | 0.39685 (14) | 0.0341 (7) | |
H9 | 1.0460 | 0.5331 | 0.3993 | 0.041* | |
C10 | 1.0018 (3) | 0.44741 (15) | 0.33872 (13) | 0.0279 (6) | |
H10 | 0.9836 | 0.4753 | 0.3015 | 0.033* | |
C11 | 1.3009 (3) | 0.28694 (18) | 0.23118 (14) | 0.0376 (8) | |
H11A | 1.4027 | 0.2811 | 0.2475 | 0.056* | |
H11B | 1.2774 | 0.3344 | 0.2108 | 0.056* | |
H11C | 1.2595 | 0.2486 | 0.2005 | 0.056* | |
C12 | 1.2890 (3) | 0.19375 (15) | 0.33893 (14) | 0.0352 (7) | |
H12A | 1.3914 | 0.1913 | 0.3540 | 0.053* | |
H12B | 1.2507 | 0.1531 | 0.3104 | 0.053* | |
H12C | 1.2556 | 0.1910 | 0.3747 | 0.053* | |
C13 | 1.3111 (3) | 0.35744 (15) | 0.35031 (13) | 0.0305 (7) | |
H13A | 1.4133 | 0.3538 | 0.3638 | 0.046* | |
H13B | 1.2812 | 0.3554 | 0.3871 | 0.046* | |
H13C | 1.2810 | 0.4035 | 0.3283 | 0.046* | |
C14 | 0.6890 (4) | 0.1826 (2) | 0.32693 (17) | 0.0663 (12) | |
H14A | 0.6958 | 0.1560 | 0.3653 | 0.099* | |
H14B | 0.5903 | 0.1896 | 0.3017 | 0.099* | |
H14C | 0.7345 | 0.2300 | 0.3380 | 0.099* | |
C15 | 0.9628 (3) | 0.11782 (17) | 0.32945 (14) | 0.0381 (8) | |
H15A | 1.0070 | 0.0845 | 0.3080 | 0.057* | |
H15B | 0.9692 | 0.0975 | 0.3703 | 0.057* | |
H15C | 1.0107 | 0.1648 | 0.3356 | 0.057* | |
C16 | 0.6967 (4) | 0.03875 (19) | 0.26253 (17) | 0.0705 (13) | |
H16A | 0.5959 | 0.0437 | 0.2405 | 0.106* | |
H16B | 0.7128 | 0.0115 | 0.3015 | 0.106* | |
H16C | 0.7392 | 0.0128 | 0.2358 | 0.106* | |
C17 | 0.6921 (3) | 0.17969 (14) | 0.15851 (12) | 0.0223 (6) | |
C18 | 0.5746 (3) | 0.12682 (14) | 0.13388 (12) | 0.0209 (6) | |
C19 | 0.4485 (3) | 0.13710 (16) | 0.14407 (13) | 0.0288 (7) | |
H19 | 0.4350 | 0.1789 | 0.1659 | 0.035* | |
C20 | 0.3428 (3) | 0.08640 (17) | 0.12248 (14) | 0.0348 (7) | |
H20 | 0.2565 | 0.0936 | 0.1294 | 0.042* | |
C21 | 0.3615 (3) | 0.02577 (16) | 0.09120 (13) | 0.0331 (7) | |
H21 | 0.2883 | −0.0088 | 0.0765 | 0.040* | |
C22 | 0.4863 (3) | 0.01488 (16) | 0.08104 (13) | 0.0317 (7) | |
H22 | 0.4996 | −0.0274 | 0.0597 | 0.038* | |
C23 | 0.5927 (3) | 0.06581 (15) | 0.10203 (13) | 0.0273 (6) | |
H23 | 0.6782 | 0.0587 | 0.0945 | 0.033* | |
C24 | 0.6773 (3) | 0.33160 (17) | 0.01507 (14) | 0.0415 (8) | |
H24A | 0.6099 | 0.3433 | −0.0264 | 0.062* | |
H24B | 0.7725 | 0.3354 | 0.0138 | 0.062* | |
H24C | 0.6659 | 0.3657 | 0.0462 | 0.062* | |
C25 | 0.7283 (3) | 0.17255 (18) | −0.00296 (14) | 0.0445 (9) | |
H25A | 0.6935 | 0.1819 | −0.0482 | 0.067* | |
H25B | 0.7046 | 0.1228 | 0.0050 | 0.067* | |
H25C | 0.8301 | 0.1787 | 0.0133 | 0.067* | |
C26 | 0.4545 (3) | 0.22298 (18) | 0.01118 (13) | 0.0383 (8) | |
H26A | 0.4349 | 0.1709 | 0.0110 | 0.057* | |
H26B | 0.4109 | 0.2426 | −0.0312 | 0.057* | |
H26C | 0.4164 | 0.2478 | 0.0401 | 0.057* | |
C27 | 1.0324 (3) | 0.34425 (15) | 0.09657 (12) | 0.0244 (6) | |
C28 | 1.0816 (3) | 0.30588 (17) | 0.05523 (14) | 0.0350 (7) | |
H28 | 1.0681 | 0.2549 | 0.0510 | 0.042* | |
C29 | 1.1493 (3) | 0.34123 (18) | 0.02061 (14) | 0.0373 (8) | |
H29 | 1.1804 | 0.3142 | −0.0079 | 0.045* | |
C30 | 1.1736 (3) | 0.41499 (17) | 0.02595 (13) | 0.0327 (7) | |
C31 | 1.1240 (3) | 0.45264 (17) | 0.06698 (14) | 0.0389 (8) | |
H31 | 1.1387 | 0.5036 | 0.0713 | 0.047* | |
C32 | 1.0538 (3) | 0.41850 (16) | 0.10181 (14) | 0.0335 (7) | |
H32 | 1.0203 | 0.4459 | 0.1293 | 0.040* | |
C33 | 1.2532 (4) | 0.4523 (2) | −0.01052 (16) | 0.0514 (10) | |
H331 | 1.2449 | 0.5050 | −0.0072 | 0.077* | 0.50 |
H332 | 1.2146 | 0.4378 | −0.0547 | 0.077* | 0.50 |
H333 | 1.3520 | 0.4383 | 0.0066 | 0.077* | 0.50 |
H334 | 1.2962 | 0.4158 | −0.0297 | 0.077* | 0.50 |
H335 | 1.3264 | 0.4829 | 0.0178 | 0.077* | 0.50 |
H336 | 1.1890 | 0.4824 | −0.0434 | 0.077* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.0212 (2) | 0.0222 (3) | 0.0202 (2) | −0.00269 (19) | 0.00824 (18) | −0.0039 (2) |
Cl1 | 0.0318 (4) | 0.0310 (4) | 0.0437 (5) | 0.0030 (3) | 0.0141 (3) | −0.0134 (3) |
Si1 | 0.0231 (4) | 0.0196 (4) | 0.0335 (4) | 0.0027 (3) | 0.0099 (3) | −0.0004 (3) |
Si2 | 0.0191 (4) | 0.0239 (4) | 0.0259 (4) | −0.0009 (3) | 0.0064 (3) | −0.0032 (3) |
Si3 | 0.0266 (4) | 0.0252 (4) | 0.0239 (4) | −0.0034 (3) | 0.0064 (3) | 0.0037 (3) |
Si4 | 0.0293 (4) | 0.0359 (5) | 0.0194 (4) | −0.0047 (4) | 0.0068 (3) | −0.0009 (4) |
N1 | 0.0213 (11) | 0.0181 (11) | 0.0193 (11) | −0.0009 (9) | 0.0080 (9) | −0.0017 (9) |
N2 | 0.0199 (11) | 0.0207 (12) | 0.0218 (12) | −0.0002 (9) | 0.0077 (9) | −0.0048 (9) |
N3 | 0.0221 (11) | 0.0213 (12) | 0.0201 (12) | −0.0028 (9) | 0.0043 (9) | −0.0005 (9) |
N4 | 0.0222 (11) | 0.0246 (13) | 0.0197 (11) | −0.0042 (9) | 0.0079 (9) | −0.0022 (10) |
N5 | 0.0260 (12) | 0.0282 (13) | 0.0220 (12) | −0.0058 (10) | 0.0107 (10) | −0.0054 (10) |
C1 | 0.0228 (14) | 0.0392 (18) | 0.0319 (16) | 0.0052 (13) | 0.0071 (13) | 0.0003 (14) |
C2 | 0.0393 (19) | 0.031 (2) | 0.089 (3) | 0.0044 (15) | 0.0062 (19) | 0.0210 (19) |
C3 | 0.0298 (16) | 0.056 (2) | 0.0423 (19) | 0.0057 (15) | 0.0153 (15) | −0.0205 (17) |
C4 | 0.0256 (14) | 0.0159 (14) | 0.0219 (14) | −0.0063 (11) | 0.0108 (11) | 0.0003 (11) |
C5 | 0.0207 (13) | 0.0229 (15) | 0.0208 (14) | −0.0005 (11) | 0.0086 (11) | −0.0016 (11) |
C6 | 0.0404 (17) | 0.0253 (16) | 0.0290 (16) | −0.0007 (13) | 0.0151 (14) | −0.0014 (13) |
C7 | 0.052 (2) | 0.041 (2) | 0.0222 (16) | 0.0014 (16) | 0.0147 (15) | 0.0034 (14) |
C8 | 0.0366 (17) | 0.045 (2) | 0.0271 (16) | 0.0030 (15) | 0.0082 (14) | −0.0144 (15) |
C9 | 0.0344 (16) | 0.0272 (17) | 0.0353 (17) | 0.0040 (13) | 0.0047 (14) | −0.0103 (14) |
C10 | 0.0305 (15) | 0.0221 (15) | 0.0275 (15) | 0.0033 (12) | 0.0051 (12) | 0.0004 (12) |
C11 | 0.0229 (14) | 0.057 (2) | 0.0355 (17) | −0.0050 (14) | 0.0124 (13) | −0.0069 (16) |
C12 | 0.0239 (15) | 0.0285 (17) | 0.0473 (19) | 0.0008 (13) | 0.0044 (14) | 0.0017 (14) |
C13 | 0.0257 (14) | 0.0273 (16) | 0.0356 (17) | −0.0045 (12) | 0.0064 (13) | −0.0035 (13) |
C14 | 0.073 (3) | 0.092 (3) | 0.048 (2) | 0.038 (2) | 0.039 (2) | 0.026 (2) |
C15 | 0.0348 (17) | 0.0382 (19) | 0.0381 (18) | 0.0040 (14) | 0.0083 (14) | 0.0140 (15) |
C16 | 0.087 (3) | 0.051 (2) | 0.047 (2) | −0.036 (2) | −0.013 (2) | 0.0220 (19) |
C17 | 0.0211 (13) | 0.0215 (15) | 0.0253 (14) | 0.0028 (11) | 0.0092 (11) | −0.0023 (12) |
C18 | 0.0197 (13) | 0.0208 (14) | 0.0195 (13) | −0.0013 (11) | 0.0031 (11) | 0.0018 (11) |
C19 | 0.0275 (15) | 0.0288 (17) | 0.0330 (16) | −0.0022 (12) | 0.0139 (13) | −0.0026 (13) |
C20 | 0.0241 (15) | 0.0422 (19) | 0.0381 (18) | −0.0040 (14) | 0.0107 (13) | 0.0070 (15) |
C21 | 0.0301 (16) | 0.0316 (18) | 0.0288 (16) | −0.0118 (13) | −0.0016 (13) | 0.0061 (13) |
C22 | 0.0410 (17) | 0.0229 (16) | 0.0250 (15) | −0.0033 (13) | 0.0034 (13) | −0.0015 (12) |
C23 | 0.0238 (14) | 0.0265 (16) | 0.0295 (15) | 0.0004 (12) | 0.0064 (12) | −0.0013 (12) |
C24 | 0.0418 (18) | 0.053 (2) | 0.0280 (17) | −0.0025 (16) | 0.0093 (15) | 0.0106 (15) |
C25 | 0.054 (2) | 0.053 (2) | 0.0321 (18) | −0.0040 (17) | 0.0222 (16) | −0.0131 (16) |
C26 | 0.0341 (17) | 0.051 (2) | 0.0229 (15) | −0.0037 (15) | 0.0010 (13) | 0.0026 (14) |
C27 | 0.0241 (13) | 0.0273 (15) | 0.0222 (14) | −0.0033 (12) | 0.0086 (11) | −0.0030 (12) |
C28 | 0.0487 (19) | 0.0272 (17) | 0.0386 (18) | −0.0031 (14) | 0.0270 (16) | −0.0057 (14) |
C29 | 0.0439 (18) | 0.0406 (19) | 0.0377 (18) | 0.0013 (15) | 0.0273 (16) | −0.0022 (15) |
C30 | 0.0280 (15) | 0.043 (2) | 0.0271 (16) | −0.0046 (14) | 0.0097 (13) | 0.0068 (14) |
C31 | 0.052 (2) | 0.0279 (18) | 0.0408 (19) | −0.0082 (15) | 0.0203 (16) | 0.0003 (14) |
C32 | 0.0443 (18) | 0.0296 (17) | 0.0323 (17) | −0.0041 (14) | 0.0204 (15) | −0.0071 (13) |
C33 | 0.051 (2) | 0.062 (2) | 0.051 (2) | −0.0115 (18) | 0.0292 (19) | 0.0134 (19) |
V1—Cl1 | 2.3082 (8) | N3—C17 | 1.292 (3) |
V1—N1 | 2.094 (2) | N4—C17 | 1.379 (3) |
V1—N2 | 2.092 (2) | N5—C27 | 1.379 (3) |
V1—N3 | 2.291 (2) | C4—C5 | 1.501 (3) |
V1—N4 | 1.944 (2) | C5—C10 | 1.384 (4) |
V1—N5 | 1.659 (2) | C5—C6 | 1.387 (4) |
Si1—N1 | 1.754 (2) | C6—C7 | 1.378 (4) |
Si1—C3 | 1.852 (3) | C7—C8 | 1.375 (4) |
Si1—C1 | 1.854 (3) | C8—C9 | 1.369 (4) |
Si1—C2 | 1.863 (3) | C9—C10 | 1.392 (4) |
Si2—N2 | 1.746 (2) | C17—C18 | 1.495 (3) |
Si2—C11 | 1.851 (3) | C18—C23 | 1.381 (4) |
Si2—C12 | 1.858 (3) | C18—C19 | 1.389 (4) |
Si2—C13 | 1.863 (3) | C19—C20 | 1.382 (4) |
Si3—N3 | 1.749 (2) | C20—C21 | 1.370 (4) |
Si3—C15 | 1.849 (3) | C21—C22 | 1.379 (4) |
Si3—C14 | 1.851 (3) | C22—C23 | 1.388 (4) |
Si3—C16 | 1.858 (3) | C27—C32 | 1.384 (4) |
Si4—N4 | 1.761 (2) | C27—C28 | 1.394 (4) |
Si4—C26 | 1.853 (3) | C28—C29 | 1.370 (4) |
Si4—C25 | 1.859 (3) | C29—C30 | 1.379 (4) |
Si4—C24 | 1.860 (3) | C30—C31 | 1.384 (4) |
N1—C4 | 1.329 (3) | C30—C33 | 1.504 (4) |
N2—C4 | 1.325 (3) | C31—C32 | 1.381 (4) |
N1—V1—N2 | 64.36 (8) | C4—N2—Si2 | 131.52 (18) |
N1—V1—N3 | 83.93 (8) | C4—N2—V1 | 90.74 (15) |
N1—V1—N4 | 99.57 (9) | Si2—N2—V1 | 132.37 (12) |
N1—V1—N5 | 100.12 (10) | C17—N3—Si3 | 130.47 (19) |
N2—V1—N3 | 95.33 (8) | C17—N3—V1 | 84.05 (16) |
N2—V1—N4 | 155.68 (9) | Si3—N3—V1 | 143.98 (12) |
N2—V1—N5 | 99.19 (9) | C17—N4—Si4 | 128.99 (18) |
N3—V1—N4 | 63.59 (8) | C17—N4—V1 | 96.64 (16) |
N3—V1—N5 | 165.27 (9) | Si4—N4—V1 | 132.66 (12) |
N4—V1—N5 | 101.70 (10) | C27—N5—V1 | 172.2 (2) |
N1—V1—Cl1 | 151.71 (6) | N2—C4—N1 | 114.3 (2) |
N2—V1—Cl1 | 90.82 (6) | N2—C4—C5 | 120.9 (2) |
N3—V1—Cl1 | 85.24 (6) | N1—C4—C5 | 124.8 (2) |
N4—V1—Cl1 | 98.82 (7) | C10—C5—C6 | 119.2 (3) |
N5—V1—Cl1 | 96.96 (8) | C10—C5—C4 | 122.1 (2) |
N1—Si1—C3 | 111.65 (12) | C6—C5—C4 | 118.7 (2) |
N1—Si1—C1 | 109.66 (12) | C7—C6—C5 | 120.6 (3) |
C3—Si1—C1 | 108.21 (13) | C8—C7—C6 | 119.7 (3) |
N1—Si1—C2 | 109.80 (13) | C9—C8—C7 | 120.5 (3) |
C3—Si1—C2 | 110.80 (17) | C8—C9—C10 | 120.0 (3) |
C1—Si1—C2 | 106.57 (15) | C5—C10—C9 | 119.9 (3) |
N2—Si2—C11 | 108.26 (12) | N3—C17—N4 | 114.8 (2) |
N2—Si2—C12 | 111.15 (12) | N3—C17—C18 | 124.3 (2) |
C11—Si2—C12 | 108.99 (15) | N4—C17—C18 | 120.8 (2) |
N2—Si2—C13 | 113.33 (12) | C23—C18—C19 | 119.4 (2) |
C11—Si2—C13 | 105.91 (14) | C23—C18—C17 | 119.6 (2) |
C12—Si2—C13 | 108.99 (13) | C19—C18—C17 | 120.9 (2) |
N3—Si3—C15 | 106.59 (12) | C20—C19—C18 | 120.0 (3) |
N3—Si3—C14 | 108.18 (14) | C21—C20—C19 | 120.4 (3) |
C15—Si3—C14 | 108.88 (16) | C20—C21—C22 | 120.1 (3) |
N3—Si3—C16 | 115.29 (14) | C21—C22—C23 | 119.9 (3) |
C15—Si3—C16 | 107.59 (16) | C18—C23—C22 | 120.2 (3) |
C14—Si3—C16 | 110.1 (2) | N5—C27—C32 | 121.1 (3) |
N4—Si4—C26 | 111.82 (12) | N5—C27—C28 | 120.4 (3) |
N4—Si4—C25 | 108.84 (13) | C32—C27—C28 | 118.5 (3) |
C26—Si4—C25 | 110.56 (15) | C29—C28—C27 | 120.5 (3) |
N4—Si4—C24 | 108.69 (12) | C28—C29—C30 | 121.9 (3) |
C26—Si4—C24 | 107.85 (15) | C29—C30—C31 | 117.2 (3) |
C25—Si4—C24 | 109.01 (15) | C29—C30—C33 | 121.0 (3) |
C4—N1—Si1 | 130.51 (18) | C31—C30—C33 | 121.7 (3) |
C4—N1—V1 | 90.56 (16) | C32—C31—C30 | 122.1 (3) |
Si1—N1—V1 | 138.90 (12) | C31—C32—C27 | 119.9 (3) |
C3—Si1—N1—C4 | −39.7 (3) | N3—V1—N4—C17 | −5.70 (14) |
C1—Si1—N1—C4 | −159.7 (2) | Cl1—V1—N4—C17 | 74.46 (15) |
C2—Si1—N1—C4 | 83.6 (3) | N5—V1—N4—Si4 | 7.87 (19) |
C3—Si1—N1—V1 | 137.64 (18) | N2—V1—N4—Si4 | 156.56 (16) |
C1—Si1—N1—V1 | 17.7 (2) | N1—V1—N4—Si4 | 110.40 (17) |
C2—Si1—N1—V1 | −99.1 (2) | N3—V1—N4—Si4 | −171.3 (2) |
N5—V1—N1—C4 | −96.81 (16) | Cl1—V1—N4—Si4 | −91.19 (16) |
N4—V1—N1—C4 | 159.37 (15) | Si2—N2—C4—N1 | 153.55 (19) |
N2—V1—N1—C4 | −1.40 (14) | V1—N2—C4—N1 | −2.2 (2) |
N3—V1—N1—C4 | 97.50 (15) | Si2—N2—C4—C5 | −29.0 (4) |
Cl1—V1—N1—C4 | 29.5 (2) | V1—N2—C4—C5 | 175.3 (2) |
N5—V1—N1—Si1 | 85.19 (19) | Si1—N1—C4—N2 | −179.54 (18) |
N4—V1—N1—Si1 | −18.64 (19) | V1—N1—C4—N2 | 2.2 (2) |
N2—V1—N1—Si1 | −179.4 (2) | Si1—N1—C4—C5 | 3.1 (4) |
N3—V1—N1—Si1 | −80.50 (18) | V1—N1—C4—C5 | −175.2 (2) |
Cl1—V1—N1—Si1 | −148.54 (12) | N2—C4—C5—C10 | 118.4 (3) |
C11—Si2—N2—C4 | −119.0 (3) | N1—C4—C5—C10 | −64.4 (4) |
C12—Si2—N2—C4 | 121.3 (3) | N2—C4—C5—C6 | −58.5 (3) |
C13—Si2—N2—C4 | −1.9 (3) | N1—C4—C5—C6 | 118.7 (3) |
C11—Si2—N2—V1 | 27.2 (2) | C10—C5—C6—C7 | −0.3 (4) |
C12—Si2—N2—V1 | −92.52 (18) | C4—C5—C6—C7 | 176.6 (3) |
C13—Si2—N2—V1 | 144.33 (16) | C5—C6—C7—C8 | 0.2 (5) |
N5—V1—N2—C4 | 98.28 (16) | C6—C7—C8—C9 | 0.2 (5) |
N4—V1—N2—C4 | −50.7 (3) | C7—C8—C9—C10 | −0.5 (5) |
N1—V1—N2—C4 | 1.40 (14) | C6—C5—C10—C9 | 0.1 (4) |
N3—V1—N2—C4 | −79.24 (15) | C4—C5—C10—C9 | −176.7 (2) |
Cl1—V1—N2—C4 | −164.53 (14) | C8—C9—C10—C5 | 0.3 (4) |
N5—V1—N2—Si2 | −57.10 (18) | Si3—N3—C17—N4 | −176.98 (18) |
N4—V1—N2—Si2 | 153.93 (18) | V1—N3—C17—N4 | −8.5 (2) |
N1—V1—N2—Si2 | −153.98 (19) | Si3—N3—C17—C18 | −0.6 (4) |
N3—V1—N2—Si2 | 125.38 (16) | V1—N3—C17—C18 | 167.9 (2) |
Cl1—V1—N2—Si2 | 40.09 (16) | Si4—N4—C17—N3 | 176.43 (19) |
C15—Si3—N3—C17 | 143.8 (3) | V1—N4—C17—N3 | 10.0 (2) |
C14—Si3—N3—C17 | −99.2 (3) | Si4—N4—C17—C18 | −0.1 (4) |
C16—Si3—N3—C17 | 24.5 (3) | V1—N4—C17—C18 | −166.5 (2) |
C15—Si3—N3—V1 | −16.5 (2) | N3—C17—C18—C23 | −100.2 (3) |
C14—Si3—N3—V1 | 100.5 (2) | N4—C17—C18—C23 | 76.0 (3) |
C16—Si3—N3—V1 | −135.8 (2) | N3—C17—C18—C19 | 78.0 (4) |
N5—V1—N3—C17 | 3.0 (4) | N4—C17—C18—C19 | −105.8 (3) |
N4—V1—N3—C17 | 6.07 (15) | C23—C18—C19—C20 | 0.1 (4) |
N2—V1—N3—C17 | 173.38 (16) | C17—C18—C19—C20 | −178.1 (3) |
N1—V1—N3—C17 | 109.93 (16) | C18—C19—C20—C21 | 0.2 (4) |
Cl1—V1—N3—C17 | −96.24 (15) | C19—C20—C21—C22 | 0.0 (4) |
N5—V1—N3—Si3 | 168.1 (3) | C20—C21—C22—C23 | −0.6 (4) |
N4—V1—N3—Si3 | 171.2 (2) | C19—C18—C23—C22 | −0.7 (4) |
N2—V1—N3—Si3 | −21.5 (2) | C17—C18—C23—C22 | 177.5 (2) |
N1—V1—N3—Si3 | −85.0 (2) | C21—C22—C23—C18 | 1.0 (4) |
Cl1—V1—N3—Si3 | 68.8 (2) | N5—C27—C28—C29 | −178.7 (3) |
C26—Si4—N4—C17 | 36.1 (3) | C32—C27—C28—C29 | −0.1 (4) |
C25—Si4—N4—C17 | −86.3 (2) | C27—C28—C29—C30 | 1.2 (5) |
C24—Si4—N4—C17 | 155.1 (2) | C28—C29—C30—C31 | −1.3 (5) |
C26—Si4—N4—V1 | −162.36 (17) | C28—C29—C30—C33 | 177.5 (3) |
C25—Si4—N4—V1 | 75.2 (2) | C29—C30—C31—C32 | 0.5 (5) |
C24—Si4—N4—V1 | −43.4 (2) | C33—C30—C31—C32 | −178.3 (3) |
N5—V1—N4—C17 | 173.52 (16) | C30—C31—C32—C27 | 0.6 (5) |
N2—V1—N4—C17 | −37.8 (3) | N5—C27—C32—C31 | 177.9 (3) |
N1—V1—N4—C17 | −83.95 (16) | C28—C27—C32—C31 | −0.7 (4) |
Experimental details
Crystal data | |
Chemical formula | [VCl(C7H7N)(C13H23N2Si2)2] |
Mr | 718.55 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 10.1600 (5), 18.4257 (10), 22.6430 (13) |
β (°) | 109.808 (5) |
V (Å3) | 3988.1 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.46 |
Crystal size (mm) | 0.25 × 0.25 × 0.25 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Part of the refinement model (ΔF) (PLATON; Spek, 2000) |
Tmin, Tmax | 0.819, 0.890 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11788, 9132, 5838 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.108, 0.99 |
No. of reflections | 9132 |
No. of parameters | 410 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.34 |
Computer programs: Locally modified CAD-4 Software (Enraf-Nonius, 1989), SET4 (de Boer & Duisenberg, 1984), HELENA (Spek, 1997), DIRDIF97 (Beurskens et al., 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2000).
V1—Cl1 | 2.3082 (8) | N1—C4 | 1.329 (3) |
V1—N1 | 2.094 (2) | N2—C4 | 1.325 (3) |
V1—N2 | 2.092 (2) | N3—C17 | 1.292 (3) |
V1—N3 | 2.291 (2) | N4—C17 | 1.379 (3) |
V1—N4 | 1.944 (2) | N5—C27 | 1.379 (3) |
V1—N5 | 1.659 (2) | ||
N1—V1—N2 | 64.36 (8) | N3—V1—N5 | 165.27 (9) |
N1—V1—N3 | 83.93 (8) | N4—V1—N5 | 101.70 (10) |
N1—V1—N4 | 99.57 (9) | N1—V1—Cl1 | 151.71 (6) |
N1—V1—N5 | 100.12 (10) | N2—V1—Cl1 | 90.82 (6) |
N2—V1—N3 | 95.33 (8) | N3—V1—Cl1 | 85.24 (6) |
N2—V1—N4 | 155.68 (9) | N4—V1—Cl1 | 98.82 (7) |
N2—V1—N5 | 99.19 (9) | N5—V1—Cl1 | 96.96 (8) |
N3—V1—N4 | 63.59 (8) | C27—N5—V1 | 172.2 (2) |
Vanadium complexes play a pivotal role in several diverse biological systems, but until recently have not been as extensively studied as complexes containing zinc or iron (Rehder, 1999). Vanadium compounds coordinated to various biologically important functionalities, such as N2 and nitrogen-containing ligands (e.g. pyrrole), have been proposed as functional models for nitrogenases (Veith, 1976; Bultitude et al., 1986). Other studies have probed the varying oxidation states of vanadium (essential in these biological processes) by coordinating bidentate nitrogen ligands with numerous halogen and oxo ligands (Mohan et al., 1995).
The title complex, (I), has a vanadium centre surrounded by two nitrogen-bound PhC(NSiMe3)2 ligands, a p-tolylimine group and a chloride ligand. The distorted octahedral geometry of the metal is clearly shown by the dissimilar trans angles of 151.71 (6), 155.68 (9) and 165.27 (9)°, and the small N—V—N ligand bite angles of 63.59 (8) and 64.36 (8)°. The chelate bond angles are considerably smaller than the other cis N—V—N and N=V—N bond angles, ranging from 83.93 (8) to 101.7 (1)°, but are comparable with those in other bis(trimethylsilyl)benzamidinato complexes (Hao et al., 1996; Patt-Siebel et al., 1990). \sch
The V—N and C—N bonds within the two benzamidinato ligands (bound to V) are distinct. Each ligand forms a non-planar four-membered V—N—C—N ring and the two are inequivalent: the V1—N3—C17—N4 group is more puckered than the V1—N1—C4—N2 group [mean deviation from least-squares plane 0.045 (16) and 0.011 (3)°, respectively]. The C—N distances in the N1—C4—N2 group have partial bond orders of 1.5, suggesting electron delocalization within the NCN group, whilst those for N3—C17—N4 are more localized. The phenyl groups at C4 and C17 are almost orthogonal to the NCN plane [dihedral angles 61.2 (3) and 77.2 (3)°, respectively], and this therefore excludes the possibility of extending the π-conjugation. The two chelate groups are essentially perpendicular with respect to each other [83.17 (13)°], presumably to minimize the repulsion of the trimethylsilyl groups.
The V1—N3 bond is significantly longer than V1—N1, and V1—N4 is significantly shorter than V1—N2. These distances in (I) are generally in accord with those observed previously in [(Me3Si)NC(Ph)N(SiMe3)]2V(allyl) [Brussee et al., 1998; V—N 2.051 (1)–2.164 (1) Å] and in [V(C18H32Cl2N3OSi)] [Brandsma et al., 1998; V—N 2.124 (1) and 2.016 (1) Å]*. Thus, the V1—N3 and V1—N4 distances in (I) also reflect the general asymmetry of this ligand and presumably the greater trans influence, or steric bulk, of the p-tolylimine group compared with the Cl- ligand. The p-tolylimido ligand is almost linearly bound [V1—N5—C27 172.2 (2)°] and is located cis to the Cl-. Although the V1=N5 distance of 1.659 (2) Å falls within the range of V—Nimido values found in the Cambridge Structural Database (Allen & Kennard, 1993), the majority of these vanadium complexes contain V(V) centres or have different geometric environments to (I). The V—Cl bond length [2.3082 (8) Å] is of a similar magnitude to that found in the related vanadium complex [V(C18H32Cl2N3OSi)] (Brandsma et al., 1998). *Query rephrasing.