μ-Oxo-bis­[tri­chloro­bis­(di­methyl­sulfane)­titanium(IV)]

The structure of [Ti₂Cl₆O(Me₂S)₄] shows a distorted octahed­ral arrangement around the Ti atom. The mol­ecule does not possess an inversion centre at the O atom.

Key indicators

• Single-crystal X-ray study
• T = 140 K
• Mean [sigma](S-C) = 0.004 Å
• R factor = 0.029
• wR factor = 0.077
• Data-to-parameter ratio = 20.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of Tmax/Tmin expected RT(exp) is > 1.10
          Absorption corrections should be applied.
          Tmin and Tmax expected:      0.514     0.598
          RT(exp) =      1.164

STRVAL_01
         From the CIF: _refine_ls_abs_structure_Flack    0.450
         From the CIF: _refine_ls_abs_structure_Flack_su    0.030
           Alert C Flack test results are ambiguous.

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.43
         From the CIF: _reflns_number_total               4153
         Count of symmetry unique reflns         2319
         Completeness (_total/calc)            179.09%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1834
         Fraction of Friedel pairs measured     0.791
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

Computing details

Data collection: R-AXIS Control Software (Molecular Structure Corporation, 1994); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: XS in SHELXTL (Sheldrick, 1997); program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XL in SHELXTL.

µ₂-Oxo-bis[trichlorobis(dimethylsulfane)titanium(IV)]

Crystal data

[Ti2Cl6O(C2H6S)4]	F(000) = 1160
Mr = 573.01	Dx = 1.620 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 221 reflections
a = 25.311 (5) Å	θ = 1.6–22.7°
b = 9.801 (2) Å	µ = 1.71 mm^−1
c = 9.4720 (19) Å	T = 140 K
V = 2349.7 (8) Å^3	Block, orange
Z = 4	0.40 × 0.35 × 0.30 mm

Data collection

Rigaku R-AXIS-IIc diffractometer	4021 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.053
Graphite monochromator	θmax = 25.4°, θmin = 3.0°
image–plate oscillation photos scans	h = −30→30
11796 measured reflections	k = −11→11
4350 independent reflections	l = −11→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.077	w = 1/[σ^2(Fo^2) + (0.0544P)^2 + 0.4789P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
4153 reflections	Δρmax = 0.29 e Å^−3
201 parameters	Δρmin = −0.46 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1846 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.45 (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	Occ. (<1)
Ti1	0.593491 (19)	0.66459 (5)	0.72521 (6)	0.02846 (13)
Cl1	0.59434 (3)	0.49193 (8)	0.88274 (9)	0.03829 (18)
Cl2	0.66945 (3)	0.60197 (8)	0.60999 (11)	0.04270 (19)
Cl3	0.50865 (3)	0.73528 (8)	0.76186 (9)	0.03869 (18)
S1	0.54541 (3)	0.49035 (9)	0.55118 (9)	0.03780 (18)
C11	0.59109 (16)	0.3521 (4)	0.5210 (5)	0.0519 (10)
H11A	0.6204	0.3844	0.4661	0.078*
H11B	0.5735	0.2801	0.4710	0.078*
H11C	0.6037	0.3183	0.6100	0.078*
C12	0.49657 (16)	0.4004 (4)	0.6533 (5)	0.0542 (10)
H12A	0.4686	0.4619	0.6786	0.081*
H12B	0.5126	0.3648	0.7374	0.081*
H12C	0.4825	0.3266	0.5984	0.081*
S2	0.58655 (3)	0.80773 (8)	0.48956 (9)	0.03339 (17)
C21	0.64171 (13)	0.9240 (4)	0.4858 (4)	0.0408 (8)
H21A	0.6741	0.8731	0.4849	0.061*
H21B	0.6407	0.9812	0.5681	0.061*
H21C	0.6397	0.9796	0.4026	0.061*
C22	0.53303 (13)	0.9276 (4)	0.4906 (4)	0.0447 (8)
H22A	0.5001	0.8793	0.4927	0.067*
H22B	0.5347	0.9830	0.4071	0.067*
H22C	0.5357	0.9849	0.5725	0.067*
O1	0.62347 (9)	0.7974 (2)	0.8315 (3)	0.0374 (5)
Ti2	0.64473 (2)	0.94158 (5)	0.93019 (6)	0.02713 (12)
Cl4	0.58629 (3)	0.92278 (8)	1.11430 (9)	0.03542 (17)
Cl5	0.59995 (3)	1.10740 (7)	0.81455 (9)	0.03686 (17)
Cl6	0.72394 (3)	0.96757 (7)	0.81372 (9)	0.03655 (17)
S3	0.68496 (3)	1.14255 (8)	1.09402 (9)	0.03569 (17)
C31	0.71321 (15)	1.2685 (3)	0.9783 (5)	0.0441 (8)
H31A	0.7441	1.2316	0.9336	0.066*
H31B	0.7228	1.3478	1.0320	0.066*
H31C	0.6878	1.2935	0.9076	0.066*
C32	0.63002 (15)	1.2401 (4)	1.1591 (4)	0.0478 (9)
H32A	0.6101	1.1858	1.2245	0.072*
H32B	0.6078	1.2662	1.0816	0.072*
H32C	0.6428	1.3204	1.2060	0.072*
S4	0.70410 (3)	0.79506 (9)	1.10212 (10)	0.04073 (19)
C41	0.66427 (14)	0.6608 (3)	1.1719 (4)	0.0414 (7)
H41A	0.6381	0.6984	1.2341	0.062*
H41B	0.6862	0.5982	1.2234	0.062*
H41C	0.6471	0.6135	1.0959	0.062*
C42A	0.7424 (10)	0.680 (2)	0.9811 (16)	0.052 (4)	0.59 (7)
H42A	0.7676	0.7324	0.9289	0.079*	0.59 (7)
H42B	0.7185	0.6357	0.9167	0.079*	0.59 (7)
H42C	0.7605	0.6118	1.0359	0.079*	0.59 (7)
C42B	0.7576 (13)	0.722 (4)	1.023 (6)	0.079 (10)	0.41 (7)
H42D	0.7797	0.7921	0.9834	0.118*	0.41 (7)
H42E	0.7459	0.6624	0.9485	0.118*	0.41 (7)
H42F	0.7773	0.6707	1.0910	0.118*	0.41 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0260 (2)	0.0280 (2)	0.0314 (3)	0.00019 (19)	−0.0008 (2)	0.0002 (2)
Cl1	0.0482 (4)	0.0308 (4)	0.0360 (4)	−0.0010 (3)	−0.0080 (3)	0.0050 (3)
Cl2	0.0296 (4)	0.0421 (4)	0.0563 (5)	0.0054 (3)	0.0064 (4)	−0.0009 (4)
Cl3	0.0297 (4)	0.0458 (4)	0.0405 (4)	0.0048 (3)	0.0050 (3)	0.0062 (3)
S1	0.0429 (4)	0.0376 (4)	0.0329 (4)	−0.0071 (3)	−0.0068 (3)	0.0000 (3)
C11	0.067 (3)	0.0419 (19)	0.047 (2)	0.0001 (17)	−0.0063 (18)	−0.0094 (17)
C12	0.051 (2)	0.058 (2)	0.054 (2)	−0.0256 (19)	−0.0043 (18)	−0.0012 (18)
S2	0.0319 (4)	0.0379 (4)	0.0303 (4)	−0.0005 (3)	0.0007 (3)	0.0027 (3)
C21	0.0378 (18)	0.0435 (19)	0.0409 (18)	−0.0047 (14)	0.0020 (14)	0.0075 (15)
C22	0.0333 (17)	0.057 (2)	0.044 (2)	0.0085 (15)	0.0002 (15)	0.0133 (17)
O1	0.0397 (12)	0.0319 (10)	0.0406 (13)	0.0012 (9)	−0.0018 (10)	0.0020 (10)
Ti2	0.0268 (2)	0.0268 (3)	0.0278 (3)	−0.00061 (19)	−0.00061 (19)	0.0018 (2)
Cl4	0.0301 (3)	0.0406 (4)	0.0356 (4)	0.0016 (3)	0.0038 (3)	0.0071 (3)
Cl5	0.0422 (4)	0.0327 (4)	0.0357 (4)	0.0048 (3)	−0.0053 (3)	0.0046 (3)
Cl6	0.0347 (4)	0.0386 (4)	0.0364 (4)	−0.0038 (3)	0.0069 (3)	0.0008 (3)
S3	0.0371 (4)	0.0341 (4)	0.0358 (4)	−0.0002 (3)	−0.0052 (3)	−0.0033 (3)
C31	0.0377 (17)	0.0355 (16)	0.059 (2)	−0.0066 (14)	0.0009 (16)	−0.0070 (16)
C32	0.057 (2)	0.0389 (18)	0.048 (2)	0.0041 (16)	0.0133 (18)	−0.0074 (15)
S4	0.0314 (4)	0.0430 (4)	0.0478 (5)	0.0007 (3)	−0.0070 (4)	0.0125 (4)
C41	0.0397 (17)	0.0404 (18)	0.0443 (19)	0.0027 (15)	−0.0039 (15)	0.0082 (15)
C42A	0.042 (7)	0.051 (7)	0.065 (6)	0.023 (5)	0.015 (4)	0.026 (5)
C42B	0.036 (10)	0.080 (14)	0.12 (2)	0.013 (10)	0.028 (11)	0.034 (17)

Geometric parameters (Å, º)

Ti1—O1	1.812 (2)	Ti2—Cl4	2.2940 (10)
Ti1—Cl1	2.2562 (10)	Ti2—Cl6	2.3025 (10)
Ti1—Cl3	2.2829 (9)	Ti2—S4	2.6405 (10)
Ti1—Cl2	2.2943 (10)	Ti2—S3	2.7064 (10)
Ti1—S2	2.6422 (10)	S3—C32	1.797 (4)
Ti1—S1	2.6672 (10)	S3—C31	1.799 (4)
S1—C12	1.800 (4)	C31—H31A	0.9600
S1—C11	1.804 (4)	C31—H31B	0.9600
C11—H11A	0.9600	C31—H31C	0.9600
C11—H11B	0.9600	C32—H32A	0.9600
C11—H11C	0.9600	C32—H32B	0.9600
C12—H12A	0.9600	C32—H32C	0.9600
C12—H12B	0.9600	S4—C42B	1.71 (3)
C12—H12C	0.9600	S4—C41	1.785 (4)
S2—C22	1.793 (3)	S4—C42A	1.880 (13)
S2—C21	1.803 (3)	C41—H41A	0.9600
C21—H21A	0.9600	C41—H41B	0.9600
C21—H21B	0.9600	C41—H41C	0.9600
C21—H21C	0.9600	C42A—H42A	0.9600
C22—H22A	0.9600	C42A—H42B	0.9600
C22—H22B	0.9600	C42A—H42C	0.9600
C22—H22C	0.9600	C42B—H42D	0.9600
O1—Ti2	1.778 (2)	C42B—H42E	0.9600
Ti2—Cl5	2.2639 (9)	C42B—H42F	0.9600
O1—Ti1—Cl1	99.64 (8)	Cl5—Ti2—Cl6	97.16 (4)
O1—Ti1—Cl3	95.24 (8)	Cl4—Ti2—Cl6	159.15 (4)
Cl1—Ti1—Cl3	97.82 (4)	O1—Ti2—S4	93.69 (8)
O1—Ti1—Cl2	96.06 (8)	Cl5—Ti2—S4	166.83 (4)
Cl1—Ti1—Cl2	96.08 (4)	Cl4—Ti2—S4	81.62 (3)
Cl3—Ti1—Cl2	160.34 (4)	Cl6—Ti2—S4	81.96 (3)
O1—Ti1—S2	96.64 (8)	O1—Ti2—S3	173.68 (8)
Cl1—Ti1—S2	163.25 (4)	Cl5—Ti2—S3	86.75 (3)
Cl3—Ti1—S2	84.53 (3)	Cl4—Ti2—S3	82.25 (3)
Cl2—Ti1—S2	78.22 (3)	Cl6—Ti2—S3	82.34 (3)
O1—Ti1—S1	173.87 (8)	S4—Ti2—S3	80.10 (3)
Cl1—Ti1—S1	86.15 (3)	C32—S3—C31	98.70 (18)
Cl3—Ti1—S1	81.90 (3)	C32—S3—Ti2	107.02 (14)
Cl2—Ti1—S1	85.25 (4)	C31—S3—Ti2	107.44 (13)
S2—Ti1—S1	77.73 (3)	S3—C31—H31A	109.5
C12—S1—C11	99.1 (2)	S3—C31—H31B	109.5
C12—S1—Ti1	107.14 (14)	H31A—C31—H31B	109.5
C11—S1—Ti1	106.63 (13)	S3—C31—H31C	109.5
S1—C11—H11A	109.5	H31A—C31—H31C	109.5
S1—C11—H11B	109.5	H31B—C31—H31C	109.5
H11A—C11—H11B	109.5	S3—C32—H32A	109.5
S1—C11—H11C	109.5	S3—C32—H32B	109.5
H11A—C11—H11C	109.5	H32A—C32—H32B	109.5
H11B—C11—H11C	109.5	S3—C32—H32C	109.5
S1—C12—H12A	109.5	H32A—C32—H32C	109.5
S1—C12—H12B	109.5	H32B—C32—H32C	109.5
H12A—C12—H12B	109.5	C42B—S4—C41	107.6 (12)
S1—C12—H12C	109.5	C41—S4—C42A	94.2 (8)
H12A—C12—H12C	109.5	C42B—S4—Ti2	114.0 (15)
H12B—C12—H12C	109.5	C41—S4—Ti2	107.95 (12)
C22—S2—C21	99.83 (18)	C42A—S4—Ti2	104.1 (5)
C22—S2—Ti1	113.18 (13)	S4—C41—H41A	109.5
C21—S2—Ti1	107.50 (12)	S4—C41—H41B	109.5
S2—C21—H21A	109.5	H41A—C41—H41B	109.5
S2—C21—H21B	109.5	S4—C41—H41C	109.5
H21A—C21—H21B	109.5	H41A—C41—H41C	109.5
S2—C21—H21C	109.5	H41B—C41—H41C	109.5
H21A—C21—H21C	109.5	S4—C42A—H42A	109.5
H21B—C21—H21C	109.5	S4—C42A—H42B	109.5
S2—C22—H22A	109.5	H42A—C42A—H42B	109.5
S2—C22—H22B	109.5	S4—C42A—H42C	109.5
H22A—C22—H22B	109.5	H42A—C42A—H42C	109.5
S2—C22—H22C	109.5	H42B—C42A—H42C	109.5
H22A—C22—H22C	109.5	S4—C42B—H42D	109.5
H22B—C22—H22C	109.5	S4—C42B—H42E	109.5
Ti2—O1—Ti1	171.86 (14)	H42D—C42B—H42E	109.5
O1—Ti2—Cl5	99.47 (8)	S4—C42B—H42F	109.5
O1—Ti2—Cl4	98.09 (8)	H42D—C42B—H42F	109.5
Cl5—Ti2—Cl4	95.90 (4)	H42E—C42B—H42F	109.5
O1—Ti2—Cl6	95.71 (8)