Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100017418/bm1436sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100017418/bm1436Isup2.hkl |
CCDC reference: 159974
For related literature, see: Duncan et al. (1997); Kojima et al. (1983); Li et al. (1988); Lindquist et al. (1973); Meichang et al. (1988); Mokry & Carrano (1993); Pal & Pal (2001); Rath et al. (1997); Rehder (1991); Sangeetha & Pal (2000).
A solution of Hpach (198 mg, 0.75 mmol) in acetonitrile (20 ml) was added to a solution of [VO(acac)2] (200 mg, 0.75 mmol) in acetonitrile (20 ml) and the mixture was heated on a water bath for 15 min. The resulting dark-brown solution was concentrated by slow evaporation at room temperature. The crystalline solid which separated out was collected by filtration, washed with acetonitrile and finally dried under vacuum over anhydrous CaCl2. Yield: 116 mg (45%). Analysis calculated for C13H9ClN3O3V: C 45.71, H 2.65, N 12.30%; found: C 45.67, H 2.55, N 12.14%. Selected IR bands (cm-1): 1595 (s), 1493 (s), 1449 (s), 1391 (s), 1343 (m), 1296 (w), 1263 (w), 1219 (w), 1173 (m), 1146 (m), 1071 (s), 1013 (w), 949 (s), 916 (m), 845 (m), 775 (w), 745 (s), 677 (w), 648 (w). Electronic spectral data in CH2Cl2 [nm (dm3 mol-1 cm-1)]: 402 (19500), 292 (13600), 237 (14500). A single-crystal suitable for structure determination was chosen from this material.
H atoms were placed geometrically and refined using a riding model, with C—H constrained to 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: Xtal3.4 (Hall et al., 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX6a (McArdle, 1995); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I) showing the atom-numbering scheme. All non-H atoms are represented by 40% probability displacement ellipsoids. |
[VO2(C13H9ClN3O)] | F(000) = 2064 |
Mr = 341.62 | Dx = 1.658 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 7.1139 (9) Å | θ = 9.5–12.4° |
b = 39.501 (5) Å | µ = 0.93 mm−1 |
c = 14.7094 (13) Å | T = 298 K |
β = 96.636 (9)° | Block, brown |
V = 4105.7 (8) Å3 | 0.40 × 0.36 × 0.32 mm |
Z = 12 |
Enraf-Nonius MACH3 four-circle diffractometer | 3565 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.018 |
Graphite monochromator | θmax = 25.0°, θmin = 1.7° |
Profile data from ω scans | h = 0→8 |
Absorption correction: empirical (using intensity measurements) based on ψ scan (DATCOR; Reibenspies, 1989) | k = 0→46 |
Tmin = 0.884, Tmax = 0.990 | l = −17→17 |
7956 measured reflections | 3 standard reflections every 90 min |
7219 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | See text |
S = 1.01 | Calculated w = 1/[σ2(Fo2) + (0.0418P)2 + 1.770P] where P = (Fo2 + 2Fc2)/3 |
7219 reflections | (Δ/σ)max < 0.001 |
568 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
[VO2(C13H9ClN3O)] | V = 4105.7 (8) Å3 |
Mr = 341.62 | Z = 12 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.1139 (9) Å | µ = 0.93 mm−1 |
b = 39.501 (5) Å | T = 298 K |
c = 14.7094 (13) Å | 0.40 × 0.36 × 0.32 mm |
β = 96.636 (9)° |
Enraf-Nonius MACH3 four-circle diffractometer | 3565 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) based on ψ scan (DATCOR; Reibenspies, 1989) | Rint = 0.018 |
Tmin = 0.884, Tmax = 0.990 | 3 standard reflections every 90 min |
7956 measured reflections | intensity decay: none |
7219 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.126 | See text |
S = 1.01 | Δρmax = 0.30 e Å−3 |
7219 reflections | Δρmin = −0.39 e Å−3 |
568 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 | ||
V | 1.23430 (14) | 0.07160 (2) | −0.13772 (6) | 0.0469 (3) | |
Cl | 1.3010 (2) | −0.03093 (4) | 0.38527 (9) | 0.0607 (4) | |
O1 | 1.2521 (6) | 0.05515 (8) | −0.0105 (2) | 0.0568 (11) | |
O2 | 1.0500 (6) | 0.09539 (9) | −0.1452 (2) | 0.0604 (11) | |
O3 | 1.4179 (6) | 0.09509 (9) | −0.1395 (2) | 0.0622 (11) | |
N1 | 1.2082 (6) | 0.05769 (10) | −0.2792 (3) | 0.0456 (11) | |
N2 | 1.2406 (6) | 0.01812 (10) | −0.1431 (3) | 0.0410 (11) | |
N3 | 1.2565 (6) | 0.00056 (10) | −0.0619 (3) | 0.0442 (11) | |
C1 | 1.1826 (9) | 0.07954 (14) | −0.3483 (4) | 0.0602 (17) | |
H1 | 1.1758 | 0.1025 | −0.3355 | 0.072* | |
C2 | 1.1658 (8) | 0.06931 (14) | −0.4377 (3) | 0.0572 (16) | |
H2 | 1.1460 | 0.0852 | −0.4844 | 0.069* | |
C3 | 1.1782 (8) | 0.03597 (14) | −0.4582 (4) | 0.0529 (15) | |
H3 | 1.1673 | 0.0288 | −0.5188 | 0.063* | |
C4 | 1.2071 (8) | 0.01293 (14) | −0.3874 (3) | 0.0499 (15) | |
H4 | 1.2183 | −0.0100 | −0.3997 | 0.060* | |
C5 | 1.2191 (7) | 0.02415 (12) | −0.2992 (3) | 0.0401 (13) | |
C6 | 1.2418 (7) | 0.00300 (13) | −0.2193 (3) | 0.0434 (13) | |
H6 | 1.2565 | −0.0203 | −0.2231 | 0.052* | |
C7 | 1.2599 (7) | 0.02261 (13) | 0.0035 (3) | 0.0431 (13) | |
C8 | 1.2719 (7) | 0.01030 (13) | 0.0991 (3) | 0.0415 (13) | |
C9 | 1.2801 (8) | 0.03186 (14) | 0.1725 (3) | 0.0525 (15) | |
H9 | 1.2804 | 0.0551 | 0.1625 | 0.063* | |
C10 | 1.2881 (8) | 0.01976 (14) | 0.2610 (4) | 0.0530 (15) | |
H10 | 1.2932 | 0.0346 | 0.3103 | 0.064* | |
C11 | 1.2882 (7) | −0.01466 (14) | 0.2746 (3) | 0.0419 (13) | |
C12 | 1.2846 (8) | −0.03675 (13) | 0.2034 (3) | 0.0515 (15) | |
H12 | 1.2881 | −0.0600 | 0.2140 | 0.062* | |
C13 | 1.2757 (8) | −0.02428 (13) | 0.1156 (3) | 0.0535 (16) | |
H13 | 1.2722 | −0.0393 | 0.0667 | 0.064* | |
VA | 0.81376 (14) | 0.09490 (2) | 0.34054 (6) | 0.0445 (3) | |
ClA | 0.6745 (2) | 0.19456 (4) | 0.85228 (9) | 0.0631 (4) | |
O1A | 0.7987 (5) | 0.11082 (8) | 0.4660 (2) | 0.0513 (10) | |
O2A | 1.0029 (5) | 0.07223 (9) | 0.3508 (2) | 0.0585 (10) | |
O3A | 0.6355 (5) | 0.07040 (9) | 0.3214 (2) | 0.0621 (11) | |
N1A | 0.8262 (7) | 0.10921 (11) | 0.2022 (3) | 0.0484 (12) | |
N2A | 0.7866 (6) | 0.14794 (10) | 0.3341 (3) | 0.0377 (10) | |
N3A | 0.7694 (6) | 0.16551 (10) | 0.4144 (3) | 0.0412 (11) | |
C1A | 0.8591 (10) | 0.08806 (16) | 0.1356 (4) | 0.0729 (19) | |
H1A | 0.8862 | 0.0656 | 0.1506 | 0.087* | |
C2A | 0.8548 (11) | 0.09779 (16) | 0.0457 (4) | 0.080 (2) | |
H2A | 0.8802 | 0.0822 | 0.0013 | 0.096* | |
C3A | 0.8128 (10) | 0.13058 (17) | 0.0228 (4) | 0.075 (2) | |
H3A | 0.8051 | 0.1377 | −0.0378 | 0.090* | |
C4A | 0.7822 (9) | 0.15287 (16) | 0.0909 (4) | 0.0647 (18) | |
H4A | 0.7539 | 0.1754 | 0.0769 | 0.078* | |
C5A | 0.7935 (8) | 0.14182 (13) | 0.1798 (3) | 0.0430 (13) | |
C6A | 0.7739 (7) | 0.16330 (13) | 0.2578 (4) | 0.0458 (14) | |
H6A | 0.7536 | 0.1865 | 0.2525 | 0.055* | |
C7A | 0.7806 (7) | 0.14286 (13) | 0.4798 (3) | 0.0416 (13) | |
C8A | 0.7595 (7) | 0.15483 (13) | 0.5736 (3) | 0.0393 (13) | |
C9A | 0.7664 (7) | 0.18934 (13) | 0.5922 (3) | 0.0420 (13) | |
H9A | 0.7895 | 0.2045 | 0.5463 | 0.050* | |
C10A | 0.7397 (7) | 0.20145 (14) | 0.6772 (4) | 0.0458 (14) | |
H10A | 0.7421 | 0.2246 | 0.6887 | 0.055* | |
C11A | 0.7094 (7) | 0.17883 (15) | 0.7451 (3) | 0.0462 (14) | |
C12A | 0.7063 (8) | 0.14427 (14) | 0.7291 (4) | 0.0539 (16) | |
H12A | 0.6862 | 0.1292 | 0.7756 | 0.065* | |
C13A | 0.7332 (8) | 0.13260 (14) | 0.6436 (4) | 0.0542 (16) | |
H13A | 0.7338 | 0.1094 | 0.6326 | 0.065* | |
VB | 0.20484 (14) | 0.23928 (2) | 0.67727 (6) | 0.0471 (3) | |
ClB | 0.3006 (2) | 0.13832 (4) | 0.16422 (10) | 0.0686 (5) | |
O1B | 0.2122 (5) | 0.22242 (8) | 0.5522 (2) | 0.0519 (10) | |
O2B | 0.0305 (6) | 0.26545 (9) | 0.6650 (2) | 0.0606 (11) | |
O3B | 0.3982 (5) | 0.26027 (9) | 0.6983 (3) | 0.0619 (11) | |
N1B | 0.1669 (6) | 0.22577 (11) | 0.8148 (3) | 0.0466 (11) | |
N2B | 0.2236 (6) | 0.18599 (10) | 0.6857 (3) | 0.0401 (10) | |
N3B | 0.2466 (6) | 0.16821 (10) | 0.6073 (3) | 0.0436 (11) | |
C1B | 0.1246 (9) | 0.24721 (14) | 0.8792 (4) | 0.0619 (17) | |
H1B | 0.1064 | 0.2699 | 0.8637 | 0.074* | |
C2B | 0.1066 (9) | 0.23750 (17) | 0.9667 (4) | 0.0692 (19) | |
H2B | 0.0722 | 0.2532 | 1.0090 | 0.083* | |
C3B | 0.1396 (10) | 0.20469 (17) | 0.9915 (4) | 0.0703 (19) | |
H3B | 0.1321 | 0.1978 | 1.0515 | 0.084* | |
C4B | 0.1847 (8) | 0.18139 (16) | 0.9259 (4) | 0.0610 (17) | |
H4B | 0.2087 | 0.1588 | 0.9410 | 0.073* | |
C5B | 0.1925 (8) | 0.19284 (13) | 0.8386 (4) | 0.0446 (13) | |
C6B | 0.2272 (8) | 0.17103 (13) | 0.7629 (4) | 0.0485 (15) | |
H6B | 0.2503 | 0.1480 | 0.7700 | 0.058* | |
C7B | 0.2374 (7) | 0.19017 (14) | 0.5408 (3) | 0.0416 (13) | |
C8B | 0.2549 (7) | 0.17786 (13) | 0.4477 (3) | 0.0405 (13) | |
C9B | 0.3071 (7) | 0.14455 (13) | 0.4343 (3) | 0.0472 (14) | |
H9B | 0.3348 | 0.1303 | 0.4844 | 0.057* | |
C10B | 0.3184 (7) | 0.13240 (14) | 0.3473 (4) | 0.0467 (14) | |
H10B | 0.3498 | 0.1099 | 0.3383 | 0.056* | |
C11B | 0.2824 (8) | 0.15406 (15) | 0.2737 (4) | 0.0512 (15) | |
C12B | 0.2338 (8) | 0.18751 (15) | 0.2845 (4) | 0.0537 (15) | |
H12B | 0.2112 | 0.2018 | 0.2342 | 0.064* | |
C13B | 0.2195 (8) | 0.19927 (14) | 0.3721 (4) | 0.0542 (15) | |
H13B | 0.1858 | 0.2217 | 0.3807 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V | 0.0656 (7) | 0.0286 (5) | 0.0453 (5) | 0.0023 (5) | 0.0023 (5) | 0.0010 (4) |
Cl | 0.0734 (11) | 0.0643 (10) | 0.0459 (8) | 0.0065 (9) | 0.0131 (7) | 0.0087 (7) |
O1 | 0.098 (3) | 0.033 (2) | 0.038 (2) | 0.004 (2) | 0.000 (2) | 0.0005 (16) |
O2 | 0.077 (3) | 0.047 (2) | 0.057 (2) | 0.013 (2) | 0.008 (2) | 0.0032 (18) |
O3 | 0.076 (3) | 0.049 (3) | 0.060 (2) | −0.018 (2) | 0.000 (2) | −0.0050 (19) |
N1 | 0.063 (3) | 0.031 (2) | 0.041 (3) | −0.002 (2) | −0.001 (2) | 0.001 (2) |
N2 | 0.053 (3) | 0.030 (3) | 0.040 (2) | 0.003 (2) | 0.004 (2) | 0.003 (2) |
N3 | 0.064 (3) | 0.033 (3) | 0.035 (2) | −0.001 (2) | 0.005 (2) | 0.003 (2) |
C1 | 0.090 (5) | 0.034 (3) | 0.054 (4) | 0.003 (3) | −0.003 (3) | 0.003 (3) |
C2 | 0.082 (5) | 0.049 (4) | 0.038 (3) | −0.003 (3) | −0.004 (3) | 0.012 (3) |
C3 | 0.064 (4) | 0.057 (4) | 0.037 (3) | −0.002 (3) | 0.004 (3) | −0.001 (3) |
C4 | 0.062 (4) | 0.043 (3) | 0.044 (3) | 0.008 (3) | 0.003 (3) | −0.003 (3) |
C5 | 0.041 (3) | 0.035 (3) | 0.044 (3) | 0.000 (3) | 0.004 (3) | −0.001 (2) |
C6 | 0.055 (4) | 0.029 (3) | 0.046 (3) | 0.001 (3) | 0.005 (3) | −0.002 (2) |
C7 | 0.049 (4) | 0.032 (3) | 0.047 (3) | 0.004 (3) | 0.000 (3) | 0.006 (2) |
C8 | 0.047 (3) | 0.037 (3) | 0.040 (3) | 0.000 (3) | 0.001 (3) | 0.001 (2) |
C9 | 0.078 (4) | 0.034 (3) | 0.044 (3) | 0.000 (3) | 0.006 (3) | 0.000 (3) |
C10 | 0.065 (4) | 0.047 (4) | 0.047 (3) | 0.002 (3) | 0.008 (3) | −0.007 (3) |
C11 | 0.039 (3) | 0.047 (3) | 0.041 (3) | −0.002 (3) | 0.011 (3) | 0.004 (3) |
C12 | 0.071 (4) | 0.033 (3) | 0.050 (3) | 0.002 (3) | 0.006 (3) | 0.005 (3) |
C13 | 0.083 (5) | 0.034 (3) | 0.042 (3) | −0.002 (3) | 0.002 (3) | −0.007 (2) |
VA | 0.0572 (7) | 0.0305 (5) | 0.0464 (5) | 0.0026 (5) | 0.0090 (5) | −0.0009 (4) |
ClA | 0.0676 (11) | 0.0754 (11) | 0.0459 (8) | 0.0055 (9) | 0.0051 (8) | −0.0096 (7) |
O1A | 0.079 (3) | 0.031 (2) | 0.046 (2) | 0.010 (2) | 0.013 (2) | 0.0010 (16) |
O2A | 0.066 (3) | 0.057 (2) | 0.052 (2) | 0.021 (2) | 0.005 (2) | −0.0008 (19) |
O3A | 0.069 (3) | 0.045 (2) | 0.073 (3) | −0.010 (2) | 0.015 (2) | −0.003 (2) |
N1A | 0.066 (3) | 0.037 (3) | 0.044 (3) | 0.002 (2) | 0.015 (2) | −0.003 (2) |
N2A | 0.041 (3) | 0.033 (3) | 0.040 (2) | 0.001 (2) | 0.009 (2) | 0.003 (2) |
N3A | 0.050 (3) | 0.029 (3) | 0.045 (3) | 0.001 (2) | 0.011 (2) | 0.001 (2) |
C1A | 0.110 (6) | 0.050 (4) | 0.062 (4) | −0.010 (4) | 0.024 (4) | −0.008 (3) |
C2A | 0.133 (7) | 0.059 (5) | 0.052 (4) | −0.024 (4) | 0.024 (4) | −0.017 (3) |
C3A | 0.115 (6) | 0.068 (5) | 0.041 (4) | −0.008 (4) | 0.002 (4) | 0.007 (3) |
C4A | 0.084 (5) | 0.064 (4) | 0.047 (4) | 0.005 (4) | 0.010 (3) | 0.014 (3) |
C5A | 0.048 (4) | 0.034 (3) | 0.047 (3) | 0.004 (3) | 0.004 (3) | 0.002 (3) |
C6A | 0.052 (4) | 0.033 (3) | 0.054 (3) | 0.006 (3) | 0.011 (3) | 0.008 (3) |
C7A | 0.040 (3) | 0.037 (3) | 0.048 (3) | 0.001 (3) | 0.007 (3) | −0.005 (3) |
C8A | 0.039 (3) | 0.033 (3) | 0.046 (3) | 0.002 (3) | 0.008 (3) | −0.006 (2) |
C9A | 0.043 (3) | 0.041 (3) | 0.042 (3) | 0.004 (3) | 0.004 (3) | 0.004 (3) |
C10A | 0.045 (4) | 0.038 (3) | 0.054 (3) | 0.000 (3) | 0.006 (3) | −0.003 (3) |
C11A | 0.039 (4) | 0.056 (4) | 0.044 (3) | 0.003 (3) | 0.005 (3) | −0.004 (3) |
C12A | 0.067 (4) | 0.047 (4) | 0.048 (4) | 0.005 (3) | 0.008 (3) | 0.008 (3) |
C13A | 0.073 (5) | 0.032 (3) | 0.059 (4) | 0.009 (3) | 0.013 (3) | 0.006 (3) |
VB | 0.0552 (7) | 0.0291 (6) | 0.0582 (6) | −0.0028 (5) | 0.0122 (5) | −0.0022 (4) |
ClB | 0.0686 (11) | 0.0832 (12) | 0.0538 (9) | 0.0040 (9) | 0.0065 (8) | −0.0119 (8) |
O1B | 0.075 (3) | 0.030 (2) | 0.053 (2) | −0.001 (2) | 0.021 (2) | 0.0050 (17) |
O2B | 0.072 (3) | 0.038 (2) | 0.073 (3) | 0.012 (2) | 0.015 (2) | 0.0055 (19) |
O3B | 0.062 (3) | 0.044 (2) | 0.081 (3) | −0.016 (2) | 0.017 (2) | −0.012 (2) |
N1B | 0.052 (3) | 0.038 (3) | 0.050 (3) | −0.005 (2) | 0.007 (2) | −0.004 (2) |
N2B | 0.042 (3) | 0.029 (3) | 0.050 (3) | −0.002 (2) | 0.009 (2) | −0.002 (2) |
N3B | 0.050 (3) | 0.034 (3) | 0.048 (3) | 0.002 (2) | 0.011 (2) | −0.004 (2) |
C1B | 0.084 (5) | 0.037 (3) | 0.067 (4) | −0.010 (3) | 0.019 (4) | −0.013 (3) |
C2B | 0.085 (5) | 0.067 (5) | 0.060 (4) | −0.019 (4) | 0.022 (4) | −0.023 (3) |
C3B | 0.097 (5) | 0.073 (5) | 0.041 (3) | −0.014 (4) | 0.004 (3) | 0.005 (3) |
C4B | 0.075 (5) | 0.055 (4) | 0.053 (4) | −0.003 (3) | 0.007 (3) | 0.004 (3) |
C5B | 0.048 (4) | 0.036 (3) | 0.049 (3) | −0.003 (3) | 0.003 (3) | −0.001 (3) |
C6B | 0.058 (4) | 0.034 (3) | 0.054 (4) | 0.004 (3) | 0.008 (3) | −0.002 (3) |
C7B | 0.037 (3) | 0.039 (3) | 0.049 (3) | −0.001 (3) | 0.005 (3) | −0.001 (3) |
C8B | 0.034 (3) | 0.038 (3) | 0.049 (3) | −0.001 (3) | 0.003 (3) | 0.004 (3) |
C9B | 0.049 (4) | 0.047 (4) | 0.048 (3) | 0.000 (3) | 0.012 (3) | 0.003 (3) |
C10B | 0.044 (3) | 0.041 (3) | 0.056 (4) | 0.004 (3) | 0.008 (3) | 0.002 (3) |
C11B | 0.042 (4) | 0.062 (4) | 0.050 (4) | 0.001 (3) | 0.009 (3) | −0.003 (3) |
C12B | 0.053 (4) | 0.060 (4) | 0.048 (3) | 0.005 (3) | 0.004 (3) | 0.006 (3) |
C13B | 0.061 (4) | 0.039 (4) | 0.062 (4) | 0.003 (3) | 0.006 (3) | 0.001 (3) |
V—N1 | 2.140 (4) | C1A—C2A | 1.374 (8) |
V—N2 | 2.114 (4) | C2A—C3A | 1.363 (8) |
V—O1 | 1.972 (3) | C3A—C4A | 1.370 (8) |
V—O2 | 1.607 (4) | C4A—C5A | 1.372 (7) |
V—O3 | 1.605 (4) | C5A—C6A | 1.447 (7) |
Cl—C11 | 1.742 (5) | C7A—C8A | 1.482 (7) |
O1—C7 | 1.302 (5) | C8A—C13A | 1.382 (7) |
N1—C1 | 1.330 (6) | C8A—C9A | 1.390 (6) |
N1—C5 | 1.361 (6) | C9A—C10A | 1.373 (6) |
N2—C6 | 1.271 (6) | C10A—C11A | 1.376 (7) |
N2—N3 | 1.374 (5) | C11A—C12A | 1.385 (7) |
N3—C7 | 1.295 (6) | C12A—C13A | 1.374 (7) |
C1—C2 | 1.366 (7) | VB—N1B | 2.139 (4) |
C2—C3 | 1.356 (7) | VB—N2B | 2.112 (4) |
C3—C4 | 1.380 (7) | VB—O1B | 1.963 (3) |
C4—C5 | 1.364 (6) | VB—O2B | 1.608 (4) |
C5—C6 | 1.436 (6) | VB—O3B | 1.605 (4) |
C7—C8 | 1.481 (6) | ClB—C11B | 1.745 (5) |
C8—C9 | 1.370 (7) | O1B—C7B | 1.300 (6) |
C8—C13 | 1.387 (6) | N1B—C1B | 1.331 (6) |
C9—C10 | 1.382 (7) | N1B—C5B | 1.354 (6) |
C10—C11 | 1.375 (7) | N2B—C6B | 1.278 (6) |
C11—C12 | 1.361 (7) | N2B—N3B | 1.376 (5) |
C12—C13 | 1.377 (6) | N3B—C7B | 1.303 (6) |
VA—N1A | 2.124 (4) | C1B—C2B | 1.364 (7) |
VA—N2A | 2.105 (4) | C2B—C3B | 1.359 (8) |
VA—O1A | 1.965 (3) | C3B—C4B | 1.398 (8) |
VA—O2A | 1.609 (3) | C4B—C5B | 1.368 (7) |
VA—O3A | 1.594 (4) | C5B—C6B | 1.452 (7) |
ClA—C11A | 1.739 (5) | C7B—C8B | 1.472 (7) |
O1A—C7A | 1.291 (5) | C8B—C9B | 1.388 (7) |
N1A—C1A | 1.328 (7) | C8B—C13B | 1.397 (7) |
N1A—C5A | 1.344 (6) | C9B—C10B | 1.377 (7) |
N2A—C6A | 1.271 (6) | C10B—C11B | 1.380 (7) |
N2A—N3A | 1.386 (5) | C11B—C12B | 1.380 (7) |
N3A—C7A | 1.310 (6) | C12B—C13B | 1.385 (7) |
N1—V—N2 | 72.98 (15) | C2A—C3A—C4A | 118.6 (6) |
N1—V—O1 | 145.87 (16) | C3A—C4A—C5A | 119.7 (6) |
N1—V—O2 | 96.01 (18) | N1A—C5A—C4A | 121.9 (5) |
N1—V—O3 | 96.42 (18) | N1A—C5A—C6A | 113.4 (5) |
N2—V—O1 | 72.95 (15) | C4A—C5A—C6A | 124.7 (5) |
N2—V—O2 | 127.05 (19) | N2A—C6A—C5A | 114.7 (5) |
N2—V—O3 | 123.80 (19) | O1A—C7A—N3A | 123.6 (5) |
O1—V—O2 | 102.73 (17) | O1A—C7A—C8A | 118.8 (5) |
O1—V—O3 | 104.08 (17) | N3A—C7A—C8A | 117.5 (5) |
O2—V—O3 | 108.6 (2) | C13A—C8A—C9A | 118.8 (5) |
C7—O1—V | 118.2 (3) | C13A—C8A—C7A | 121.8 (5) |
C1—N1—C5 | 118.2 (4) | C9A—C8A—C7A | 119.4 (5) |
C1—N1—V | 124.5 (4) | C10A—C9A—C8A | 121.0 (5) |
C5—N1—V | 117.3 (3) | C9A—C10A—C11A | 119.0 (5) |
C6—N2—N3 | 121.4 (4) | C10A—C11A—C12A | 121.2 (5) |
C6—N2—V | 120.3 (4) | C10A—C11A—ClA | 118.5 (4) |
N3—N2—V | 118.2 (3) | C12A—C11A—ClA | 120.3 (4) |
C7—N3—N2 | 107.4 (4) | C13A—C12A—C11A | 119.0 (5) |
N1—C1—C2 | 122.1 (5) | C12A—C13A—C8A | 120.9 (5) |
C3—C2—C1 | 120.0 (5) | N1B—VB—N2B | 73.14 (16) |
C2—C3—C4 | 118.7 (5) | N1B—VB—O1B | 145.25 (16) |
C5—C4—C3 | 119.4 (5) | N1B—VB—O2B | 94.94 (18) |
N1—C5—C4 | 121.5 (5) | N1B—VB—O3B | 98.36 (18) |
N1—C5—C6 | 113.2 (4) | N2B—VB—O1B | 73.04 (15) |
C4—C5—C6 | 125.3 (5) | N2B—VB—O2B | 133.62 (18) |
N2—C6—C5 | 115.9 (5) | N2B—VB—O3B | 117.16 (19) |
N3—C7—O1 | 123.4 (4) | O1B—VB—O2B | 102.54 (18) |
N3—C7—C8 | 118.6 (5) | O1B—VB—O3B | 103.94 (18) |
O1—C7—C8 | 118.1 (5) | O2B—VB—O3B | 108.8 (2) |
C9—C8—C13 | 118.4 (5) | C7B—O1B—VB | 118.2 (3) |
C9—C8—C7 | 122.4 (5) | C1B—N1B—C5B | 117.5 (5) |
C13—C8—C7 | 119.2 (5) | C1B—N1B—VB | 125.3 (4) |
C8—C9—C10 | 121.3 (5) | C5B—N1B—VB | 117.2 (3) |
C11—C10—C9 | 118.6 (5) | C6B—N2B—N3B | 121.1 (5) |
C12—C11—C10 | 121.5 (5) | C6B—N2B—VB | 120.5 (4) |
C12—C11—Cl | 118.5 (4) | N3B—N2B—VB | 118.2 (3) |
C10—C11—Cl | 120.0 (4) | C7B—N3B—N2B | 106.7 (4) |
C11—C12—C13 | 119.2 (5) | N1B—C1B—C2B | 123.1 (6) |
C12—C13—C8 | 121.0 (5) | C3B—C2B—C1B | 119.3 (6) |
N1A—VA—N2A | 72.91 (16) | C2B—C3B—C4B | 119.3 (6) |
N1A—VA—O1A | 145.89 (16) | C5B—C4B—C3B | 117.9 (6) |
N1A—VA—O2A | 96.34 (18) | N1B—C5B—C4B | 122.8 (5) |
N1A—VA—O3A | 96.46 (18) | N1B—C5B—C6B | 113.6 (5) |
N2A—VA—O1A | 73.06 (15) | C4B—C5B—C6B | 123.6 (5) |
N2A—VA—O2A | 129.02 (19) | N2B—C6B—C5B | 114.8 (5) |
N2A—VA—O3A | 121.95 (19) | O1B—C7B—N3B | 123.5 (5) |
O1A—VA—O2A | 103.08 (16) | O1B—C7B—C8B | 118.1 (5) |
O1A—VA—O3A | 103.41 (18) | N3B—C7B—C8B | 118.4 (5) |
O2A—VA—O3A | 108.6 (2) | C9B—C8B—C13B | 119.2 (5) |
C7A—O1A—VA | 118.6 (3) | C9B—C8B—C7B | 119.9 (5) |
C1A—N1A—C5A | 117.6 (5) | C13B—C8B—C7B | 120.9 (5) |
C1A—N1A—VA | 124.7 (4) | C10B—C9B—C8B | 120.5 (5) |
C5A—N1A—VA | 117.7 (3) | C9B—C10B—C11B | 119.2 (5) |
C6A—N2A—N3A | 120.6 (4) | C12B—C11B—C10B | 122.0 (5) |
C6A—N2A—VA | 120.8 (4) | C12B—C11B—ClB | 119.6 (4) |
N3A—N2A—VA | 118.5 (3) | C10B—C11B—ClB | 118.5 (5) |
C7A—N3A—N2A | 106.2 (4) | C11B—C12B—C13B | 118.3 (5) |
N1A—C1A—C2A | 123.2 (6) | C12B—C13B—C8B | 120.8 (5) |
C3A—C2A—C1A | 118.9 (6) |
Experimental details
Crystal data | |
Chemical formula | [VO2(C13H9ClN3O)] |
Mr | 341.62 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 7.1139 (9), 39.501 (5), 14.7094 (13) |
β (°) | 96.636 (9) |
V (Å3) | 4105.7 (8) |
Z | 12 |
Radiation type | Mo Kα |
µ (mm−1) | 0.93 |
Crystal size (mm) | 0.40 × 0.36 × 0.32 |
Data collection | |
Diffractometer | Enraf-Nonius MACH3 four-circle diffractometer |
Absorption correction | Empirical (using intensity measurements) based on ψ scan (DATCOR; Reibenspies, 1989) |
Tmin, Tmax | 0.884, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7956, 7219, 3565 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.126, 1.01 |
No. of reflections | 7219 |
No. of parameters | 568 |
H-atom treatment | See text |
Δρmax, Δρmin (e Å−3) | 0.30, −0.39 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, Xtal3.4 (Hall et al., 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX6a (McArdle, 1995), SHELXL97.
V—N1 | 2.140 (4) | VA—O2A | 1.609 (3) |
V—N2 | 2.114 (4) | VA—O3A | 1.594 (4) |
V—O1 | 1.972 (3) | VB—N1B | 2.139 (4) |
V—O2 | 1.607 (4) | VB—N2B | 2.112 (4) |
V—O3 | 1.605 (4) | VB—O1B | 1.963 (3) |
VA—N1A | 2.124 (4) | VB—O2B | 1.608 (4) |
VA—N2A | 2.105 (4) | VB—O3B | 1.605 (4) |
VA—O1A | 1.965 (3) | ||
N1—V—N2 | 72.98 (15) | N2A—VA—O2A | 129.02 (19) |
N1—V—O1 | 145.87 (16) | N2A—VA—O3A | 121.95 (19) |
N1—V—O2 | 96.01 (18) | O1A—VA—O2A | 103.08 (16) |
N1—V—O3 | 96.42 (18) | O1A—VA—O3A | 103.41 (18) |
N2—V—O1 | 72.95 (15) | O2A—VA—O3A | 108.6 (2) |
N2—V—O2 | 127.05 (19) | N1B—VB—N2B | 73.14 (16) |
N2—V—O3 | 123.80 (19) | N1B—VB—O1B | 145.25 (16) |
O1—V—O2 | 102.73 (17) | N1B—VB—O2B | 94.94 (18) |
O1—V—O3 | 104.08 (17) | N1B—VB—O3B | 98.36 (18) |
O2—V—O3 | 108.6 (2) | N2B—VB—O1B | 73.04 (15) |
N1A—VA—N2A | 72.91 (16) | N2B—VB—O2B | 133.62 (18) |
N1A—VA—O1A | 145.89 (16) | N2B—VB—O3B | 117.16 (19) |
N1A—VA—O2A | 96.34 (18) | O1B—VB—O2B | 102.54 (18) |
N1A—VA—O3A | 96.46 (18) | O1B—VB—O3B | 103.94 (18) |
N2A—VA—O1A | 73.06 (15) | O2B—VB—O3B | 108.8 (2) |
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It is well known that vanadate acts as a potent inhibitor of phosphate-metabolizing enzymes (Rehder, 1991). During phosphate hydrolysis, it has been proposed that enzyme-bound pentavalent vanadium mimics the trigonal bipyramidal phosphorus(V) intermediate (Lindquist et al., 1973; Mokry & Carrano, 1993). A pentacoordinated metal centre in cis-dioxovanadium(V) complexes with tridentate Schiff base ligands may have either square pyramidal or trigonal bipyramidal coordination geometry. Square pyramidal species typically dimerize by sharing oxo groups and the metal centre becomes pseudo-octahedral (Li et al., 1988; Meichang et al., 1988; Mokry & Carrano, 1993; Duncan et al., 1997). It has been shown that by using bulky substituents on the ligand, dimerization can be prevented and trigonal bipyramidal geometry can be stabilized (Mokry & Carrano, 1993). In our earlier work, we have found that the reaction of bis(acetylacetonato)oxovanadium(IV) with the N,N,O-donor ligand N-(anisoyl)-N'-(picolinylidene)hydrazine produces a dimeric pervanadyl complex in which the metal centres are hexacoordinated (Pal & Pal, 2001). However, the title mononuclear distorted trigonal bipyramidal complex, [VO2(pach)], (I), was isolated from the same vanadium starting material and N-(4-chlorobenzoyl)-N'-(picolinylidene)hydrazine (Hpach) under identical reaction conditions. \scheme
The title complex crystallizes with three independent molecules in the asymmetric unit. The structure of one of these molecules is shown in Fig. 1. The bond distances and angles for each of the three molecules are essentially identical. The N2O3 coordination sphere around the metal centre in (I) is formed by the monoanionic planar pyridine-N, imine-N and amide-O donor pach- ligand and the two oxo groups. The N—N [1.374 (5)–1.386 (5) Å], N—C [1.295 (6)–1.310 (6) Å] and C—O [1.291 (5)–1.302 (5) Å] distances in the ═N—N═C(—O-)— fragments of the ligands in all three molecules are consistent with the enolate form of the amide functionality (Rath et al., 1997; Sangeetha & Pal, 2000). The ligand forms two five-membered chelate rings. The chelate bite angles are very similar, all falling within the range 72.91 (16)–73.14 (16)°. In all three molecules, the V—O(oxo) distances [1.594 (4)–1.609 (3) Å] are typical for terminal oxo group to vanadium(V) bonds (Sangeetha & Pal, 2000). The V—N(pyridine) [2.124 (4)–2.140 (4) Å], V—N(imine) [2.105 (4)–2.114 (4) Å] and V—O(amide) [1.963 (3)–1.972 (3) Å] bond lengths are unexceptional with respect to known vanadium(V) to pyridine-N, imine-N, and deprotonated amide-O linkages (Kojima et al., 1983; Rath et al., 1997).
The coordination geometry around the metal centre in each of the three molecules can be best described as distorted trigonal bipyramidal. The deviations of both oxo groups from the plane formed by the coordinated pyridine-N, imine-N and amide-O donor atoms are too large to allow any plausible NNOO square plane; the maximum and the minimum deviations are 1.68 and 0.86 Å, respectively. On the other hand, the maximum and the minimum deviations from the mean plane formed by the metal centre, the imine-N and the two oxo groups are only 0.054 and 0.015 Å, respectively. Thus, the molecular structure of [VO2(pach)] approximates much more closely to trigonal bipyramidal than to square pyramidal. The tridentate ligand occupies one equatorial and two axial sites, the remaining two equatorial sites being occupied by the two oxo groups.