In the crystal structure of the title vanadocene complex, [V(η5-C5H5)2(NCS)2], the V atom has distorted tetrahedral coordination with two η5-bonded cyclopentadienyl rings and two N-bonded thiocyanate ligands.
Supporting information
CCDC reference: 255420
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.003 Å
- R factor = 0.029
- wR factor = 0.064
- Data-to-parameter ratio = 18.4
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for S1 - C11 .. 9.21 su
| Author Response: :
The anisotropic displacement parameters of atoms of thiocyanate moieties
are affected by large deviations of their electron density from approximation
of independent atom model due delocalization into multiple
bonds system. However the bond distances S-C and C-N are in reasonable
agreement with average distances taken from 645 fragments in CSD database
(1.639 A and 1.165 A respectively)
|
PROBLEM: PLAT230_ALERT_2_C Hirshfeld Test Diff for S2-C12 6.46 su
RESPONSE:
see above
Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for S2 - C12 .. 6.46 su
| Author Response: :
The anisotropic displacement parameters of atoms of thiocyanate moieties
are affected by large deviations of their electron density from approximation
of independent atom model due delocalization into multiple
bonds system. However the bond distances S-C and C-N are in reasonable
agreement with average distances taken from 645 fragments in CSD database
(1.639 A and 1.165 A respectively)
|
PROBLEM: PLAT230_ALERT_2_C Hirshfeld Test Diff for S2-C12 6.46 su
RESPONSE:
see above
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) V1 - N2 .. 5.22 su
| Author Response:
see above
|
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors for V1
| Author Response:
The alert was switch on rather by large displacement parameters of cyclopenta
dienyls, which are freely librating in their planes, then by low U(eq) for V1
Thereofore the alert can be regarded as a false with regard of wrong
atom type.
|
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
Bis(
η5-cyclopentadienyl)bis(thiocyanato-
κN)vanadium(IV)
top
Crystal data top
[V(C5H5)2(NCS)2] | F(000) = 604 |
Mr = 297.28 | Dx = 1.605 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2982 reflections |
a = 9.6500 (3) Å | θ = 1–27.5° |
b = 9.6740 (2) Å | µ = 1.12 mm−1 |
c = 13.6410 (4) Å | T = 150 K |
β = 104.9680 (14)° | Block, green |
V = 1230.24 (6) Å3 | 0.2 × 0.2 × 0.15 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2480 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 27.5°, θmin = 2.3° |
Detector resolution: 9.091 pixels mm-1 | h = −12→12 |
φ and ω scans | k = −12→12 |
19398 measured reflections | l = −17→17 |
2827 independent reflections | |
Refinement top
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0188P)2 + 0.9617P] where P = (Fo2 + 2Fc2)/3 |
2827 reflections | (Δ/σ)max = 0.001 |
154 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
V1 | 0.51464 (3) | 0.09819 (3) | 0.73353 (2) | 0.01718 (8) | |
C1 | 0.2980 (2) | 0.1236 (2) | 0.61371 (14) | 0.0287 (4) | |
H1 | 0.2374 | 0.0497 | 0.5888 | 0.034* | |
C2 | 0.29372 (19) | 0.2047 (2) | 0.69700 (14) | 0.0273 (4) | |
H2 | 0.2324 | 0.1931 | 0.7390 | 0.033* | |
C3 | 0.4010 (2) | 0.3092 (2) | 0.70623 (16) | 0.0327 (4) | |
H3 | 0.4214 | 0.3790 | 0.7547 | 0.039* | |
C4 | 0.4695 (2) | 0.2869 (2) | 0.62906 (17) | 0.0353 (5) | |
H4 | 0.5434 | 0.3402 | 0.6167 | 0.042* | |
C5 | 0.4082 (2) | 0.1715 (2) | 0.57376 (14) | 0.0320 (4) | |
H5 | 0.4361 | 0.1329 | 0.5194 | 0.038* | |
C6 | 0.4880 (3) | 0.0033 (3) | 0.87930 (14) | 0.0479 (7) | |
H6 | 0.4120 | −0.0569 | 0.8768 | 0.058* | |
C7 | 0.4854 (2) | 0.1449 (3) | 0.89133 (15) | 0.0467 (6) | |
H7 | 0.4082 | 0.1964 | 0.9003 | 0.056* | |
C8 | 0.6187 (2) | 0.1973 (2) | 0.88776 (15) | 0.0390 (5) | |
H8 | 0.6449 | 0.2901 | 0.8914 | 0.047* | |
C9 | 0.7054 (2) | 0.0861 (2) | 0.87776 (15) | 0.0334 (5) | |
H9 | 0.8008 | 0.0909 | 0.8756 | 0.040* | |
C10 | 0.6240 (3) | −0.0336 (2) | 0.87159 (15) | 0.0390 (5) | |
H10 | 0.6551 | −0.1230 | 0.8637 | 0.047* | |
N1 | 0.47294 (17) | −0.09650 (16) | 0.67644 (12) | 0.0266 (3) | |
C11 | 0.44167 (18) | −0.20564 (19) | 0.64203 (13) | 0.0219 (4) | |
S1 | 0.39742 (5) | −0.35795 (5) | 0.59403 (4) | 0.02642 (11) | |
N2 | 0.68994 (16) | 0.09260 (17) | 0.67665 (12) | 0.0279 (3) | |
C12 | 0.78732 (18) | 0.09008 (18) | 0.64138 (13) | 0.0214 (4) | |
S2 | 0.92382 (5) | 0.08660 (5) | 0.59174 (4) | 0.02532 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
V1 | 0.01565 (14) | 0.01918 (15) | 0.01684 (15) | −0.00041 (11) | 0.00443 (11) | 0.00005 (11) |
C1 | 0.0210 (9) | 0.0368 (11) | 0.0237 (9) | 0.0027 (8) | −0.0025 (7) | −0.0007 (8) |
C2 | 0.0185 (8) | 0.0391 (11) | 0.0244 (9) | 0.0082 (8) | 0.0060 (7) | 0.0037 (8) |
C3 | 0.0338 (10) | 0.0229 (9) | 0.0367 (11) | 0.0090 (8) | 0.0008 (9) | −0.0012 (8) |
C4 | 0.0310 (10) | 0.0308 (10) | 0.0462 (13) | 0.0058 (9) | 0.0137 (9) | 0.0193 (9) |
C5 | 0.0331 (10) | 0.0437 (12) | 0.0198 (9) | 0.0118 (9) | 0.0080 (8) | 0.0076 (8) |
C6 | 0.0476 (14) | 0.0789 (18) | 0.0143 (9) | −0.0321 (13) | 0.0025 (9) | 0.0075 (11) |
C7 | 0.0336 (12) | 0.089 (2) | 0.0146 (9) | 0.0206 (12) | 0.0014 (8) | −0.0105 (11) |
C8 | 0.0513 (13) | 0.0270 (10) | 0.0259 (10) | −0.0004 (10) | −0.0130 (9) | −0.0053 (8) |
C9 | 0.0216 (9) | 0.0484 (12) | 0.0247 (10) | 0.0023 (9) | −0.0036 (8) | 0.0024 (9) |
C10 | 0.0586 (14) | 0.0252 (10) | 0.0234 (10) | 0.0051 (10) | −0.0073 (10) | 0.0040 (8) |
N1 | 0.0329 (9) | 0.0227 (8) | 0.0252 (8) | −0.0032 (7) | 0.0093 (7) | −0.0013 (6) |
C11 | 0.0208 (8) | 0.0275 (9) | 0.0193 (8) | −0.0004 (7) | 0.0089 (7) | 0.0022 (7) |
S1 | 0.0302 (2) | 0.0226 (2) | 0.0286 (2) | −0.00512 (19) | 0.01146 (19) | −0.00497 (18) |
N2 | 0.0224 (8) | 0.0316 (9) | 0.0315 (9) | 0.0008 (7) | 0.0104 (7) | 0.0005 (7) |
C12 | 0.0191 (8) | 0.0204 (8) | 0.0235 (9) | −0.0016 (7) | 0.0034 (7) | −0.0024 (7) |
S2 | 0.0209 (2) | 0.0293 (2) | 0.0284 (2) | −0.00044 (18) | 0.01111 (18) | −0.00198 (19) |
Geometric parameters (Å, º) top
V1—N2 | 2.0358 (15) | C3—H3 | 0.9300 |
V1—N1 | 2.0381 (15) | C4—C5 | 1.391 (3) |
V1—C6 | 2.264 (2) | C4—H4 | 0.9300 |
V1—C5 | 2.2696 (18) | C5—H5 | 0.9300 |
V1—C7 | 2.287 (2) | C6—C7 | 1.380 (4) |
V1—C4 | 2.2875 (19) | C6—C10 | 1.391 (3) |
V1—C10 | 2.2936 (19) | C6—H6 | 0.9300 |
V1—C8 | 2.2942 (19) | C7—C8 | 1.396 (3) |
V1—C3 | 2.3013 (19) | C7—H7 | 0.9300 |
V1—C2 | 2.3034 (17) | C8—C9 | 1.391 (3) |
V1—C1 | 2.3104 (18) | C8—H8 | 0.9300 |
V1—C9 | 2.3243 (19) | C9—C10 | 1.389 (3) |
C1—C2 | 1.390 (3) | C9—H9 | 0.9300 |
C1—C5 | 1.394 (3) | C10—H10 | 0.9300 |
C1—H1 | 0.9300 | N1—C11 | 1.163 (2) |
C2—C3 | 1.429 (3) | C11—S1 | 1.6241 (19) |
C2—H2 | 0.9300 | N2—C12 | 1.161 (2) |
C3—C4 | 1.397 (3) | C12—S2 | 1.6295 (18) |
| | | |
N2—V1—N1 | 86.06 (6) | C1—V1—C9 | 168.05 (7) |
N2—V1—C6 | 128.17 (8) | C2—C1—C5 | 108.57 (18) |
N1—V1—C6 | 84.55 (8) | C2—C1—V1 | 72.19 (10) |
N2—V1—C5 | 81.76 (7) | C5—C1—V1 | 70.69 (10) |
N1—V1—C5 | 85.76 (7) | C2—C1—H1 | 125.7 |
C6—V1—C5 | 147.58 (8) | C5—C1—H1 | 125.7 |
N2—V1—C7 | 132.90 (7) | V1—C1—H1 | 123.0 |
N1—V1—C7 | 118.81 (9) | C1—C2—C3 | 107.31 (17) |
C6—V1—C7 | 35.30 (10) | C1—C2—V1 | 72.74 (10) |
C5—V1—C7 | 134.98 (8) | C3—C2—V1 | 71.84 (10) |
N2—V1—C4 | 80.05 (7) | C1—C2—H2 | 126.3 |
N1—V1—C4 | 120.82 (8) | C3—C2—H2 | 126.3 |
C6—V1—C4 | 145.49 (10) | V1—C2—H2 | 120.9 |
C5—V1—C4 | 35.54 (8) | C4—C3—C2 | 107.31 (18) |
C7—V1—C4 | 112.26 (9) | C4—C3—V1 | 71.74 (11) |
N2—V1—C10 | 92.67 (8) | C2—C3—V1 | 72.00 (11) |
N1—V1—C10 | 78.67 (7) | C4—C3—H3 | 126.3 |
C6—V1—C10 | 35.52 (9) | C2—C3—H3 | 126.3 |
C5—V1—C10 | 163.81 (8) | V1—C3—H3 | 121.7 |
C7—V1—C10 | 58.64 (9) | C5—C4—C3 | 108.37 (18) |
C4—V1—C10 | 158.21 (8) | C5—C4—V1 | 71.53 (11) |
N2—V1—C8 | 98.66 (8) | C3—C4—V1 | 72.82 (11) |
N1—V1—C8 | 137.16 (7) | C5—C4—H4 | 125.8 |
C6—V1—C8 | 59.08 (8) | C3—C4—H4 | 125.8 |
C5—V1—C8 | 137.08 (8) | V1—C4—H4 | 121.5 |
C7—V1—C8 | 35.47 (9) | C4—C5—C1 | 108.37 (18) |
C4—V1—C8 | 101.86 (8) | C4—C5—V1 | 72.93 (11) |
C10—V1—C8 | 58.66 (7) | C1—C5—V1 | 73.88 (11) |
N2—V1—C3 | 111.72 (7) | C4—C5—H5 | 125.8 |
N1—V1—C3 | 135.97 (7) | C1—C5—H5 | 125.8 |
C6—V1—C3 | 110.13 (10) | V1—C5—H5 | 119.2 |
C5—V1—C3 | 59.27 (7) | C7—C6—C10 | 108.1 (2) |
C7—V1—C3 | 78.91 (9) | C7—C6—V1 | 73.26 (13) |
C4—V1—C3 | 35.44 (7) | C10—C6—V1 | 73.40 (12) |
C10—V1—C3 | 136.47 (8) | C7—C6—H6 | 125.9 |
C8—V1—C3 | 81.67 (7) | C10—C6—H6 | 125.9 |
N2—V1—C2 | 138.00 (7) | V1—C6—H6 | 119.3 |
N1—V1—C2 | 104.49 (7) | C6—C7—C8 | 108.1 (2) |
C6—V1—C2 | 93.59 (9) | C6—C7—V1 | 71.44 (12) |
C5—V1—C2 | 59.25 (7) | C8—C7—V1 | 72.54 (12) |
C7—V1—C2 | 77.46 (7) | C6—C7—H7 | 125.9 |
C4—V1—C2 | 59.44 (7) | C8—C7—H7 | 125.9 |
C10—V1—C2 | 129.07 (8) | V1—C7—H7 | 121.8 |
C8—V1—C2 | 99.96 (8) | C9—C8—C7 | 107.8 (2) |
C3—V1—C2 | 36.16 (7) | C9—C8—V1 | 73.65 (12) |
N2—V1—C1 | 114.98 (7) | C7—C8—V1 | 71.99 (11) |
N1—V1—C1 | 76.97 (7) | C9—C8—H8 | 126.1 |
C6—V1—C1 | 112.15 (8) | C7—C8—H8 | 126.1 |
C5—V1—C1 | 35.43 (7) | V1—C8—H8 | 120.1 |
C7—V1—C1 | 109.61 (7) | C10—C9—C8 | 107.83 (19) |
C4—V1—C1 | 58.83 (7) | C10—C9—V1 | 71.29 (11) |
C10—V1—C1 | 141.30 (8) | C8—C9—V1 | 71.29 (11) |
C8—V1—C1 | 134.92 (7) | C10—C9—H9 | 126.1 |
C3—V1—C1 | 59.00 (7) | C8—C9—H9 | 126.1 |
C2—V1—C1 | 35.07 (7) | V1—C9—H9 | 123.0 |
N2—V1—C9 | 76.52 (7) | C9—C10—C6 | 108.1 (2) |
N1—V1—C9 | 108.17 (7) | C9—C10—V1 | 73.70 (11) |
C6—V1—C9 | 58.73 (8) | C6—C10—V1 | 71.08 (12) |
C5—V1—C9 | 153.07 (8) | C9—C10—H10 | 125.9 |
C7—V1—C9 | 58.44 (7) | C6—C10—H10 | 125.9 |
C4—V1—C9 | 123.33 (8) | V1—C10—H10 | 121.0 |
C10—V1—C9 | 35.01 (8) | C11—N1—V1 | 176.43 (15) |
C8—V1—C9 | 35.06 (7) | N1—C11—S1 | 179.79 (18) |
C3—V1—C9 | 114.96 (8) | C12—N2—V1 | 177.99 (15) |
C2—V1—C9 | 133.80 (7) | N2—C12—S2 | 179.9 (2) |
Selected geometric parameters (Å, °). topCg1—V1 | 1.9614 (9) | N1—C11 | 1.163 (2) |
Cg2—V1 | 1.9647 (9) | N2—C12 | 1.161 (2) |
V1—N1 | 2.0381 (15) | C11—S1 | 1.6241 (19) |
V1—N2 | 2.0358 (15) | C12—S2 | 1.6295 (18) |
Cg1—V1—Cg2 | 133.86 (4) | N1—V1—N2 | 86.06 (6) |
V1—N1—C11 | 176.43 (15) | V1—N2—C12 | 177.99 (15) |
N1—C11—S1 | 179.79 (18) | N2—C12—S2 | 179.9 (2) |
Notes: Cg1 is the centroid of ring C1—C5 and Cg2 is the centroid of
ring C6-C10. |