Bis(η⁵-cyclo­penta­dienyl)­bis­(thio­cyanato-κN)­vanadium(IV)

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.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](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

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Computing details

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)

Crystal data

[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) Å^3	0.2 × 0.2 × 0.15 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.064	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0188P)^2 + 0.9617P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)