Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008262/fl6030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008262/fl60302sup2.hkl |
CCDC reference: 214572
The title compound was prepared as a powder following the procedure of Kato et al. (1991). Dissolving of this powder in CDCl3 (initially performed for a NMR characterization) and following crystallization afforded crystals suitable for X-ray analysis.
H atoms were found by difference Fourier maps, except those belonging to the disordered terminal ethylene groups of the dddse ligand. These latter were placed geometrically at 0.99 Å and riding the adjacent C atom with an isotropic displacement parameter 20% higher than the one of the adjacent C atom, like H12A and H13A (placed at 0.95 Å from C12A and C13A). Others H atoms were refined isotropicaly (coordinates and Uiso values).
Data collection: IPDS Software (Stoe & Cie, 1996); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SIR97 (Altomare, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Ti(C5H5)2(C4H4S2Se2)] | F(000) = 1760 |
Mr = 452.18 | Dx = 2.008 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.7474 (8) Å | Cell parameters from 8000 reflections |
b = 10.9055 (10) Å | θ = 2.8–26° |
c = 21.5888 (13) Å | µ = 5.70 mm−1 |
β = 94.648 (7)° | T = 180 K |
V = 2991.3 (4) Å3 | Plate, dark green |
Z = 8 | 0.33 × 0.25 × 0.04 mm |
Stow Imaging Plate Diffraction System diffractometer | 5732 independent reflections |
Radiation source: fine-focus sealed tube | 4603 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ϕ scans | θmax = 26.1°, θmin = 2.1° |
Absorption correction: analytical (see. N.W. Alcock (1970). Cryst. Computing, p271) | h = −15→15 |
Tmin = 0.341, Tmax = 0.765 | k = −13→13 |
26415 measured reflections | l = −26→26 |
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)] = 0.035 | Hydrogen site location: mixed |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0532P)2 + 4.9237P] where P = (Fo2 + 2Fc2)/3 |
5732 reflections | (Δ/σ)max = 0.001 |
449 parameters | Δρmax = 0.76 e Å−3 |
0 restraints | Δρmin = −0.76 e Å−3 |
[Ti(C5H5)2(C4H4S2Se2)] | V = 2991.3 (4) Å3 |
Mr = 452.18 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.7474 (8) Å | µ = 5.70 mm−1 |
b = 10.9055 (10) Å | T = 180 K |
c = 21.5888 (13) Å | 0.33 × 0.25 × 0.04 mm |
β = 94.648 (7)° |
Stow Imaging Plate Diffraction System diffractometer | 5732 independent reflections |
Absorption correction: analytical (see. N.W. Alcock (1970). Cryst. Computing, p271) | 4603 reflections with I > 2σ(I) |
Tmin = 0.341, Tmax = 0.765 | Rint = 0.055 |
26415 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.76 e Å−3 |
5732 reflections | Δρmin = −0.76 e Å−3 |
449 parameters |
Experimental. The data were collected on a Stoe Imaging Plate Diffraction System (IPDS) equipped with an Oxford Cryosystems cooler device. The crystal-to-detector distance was 70 mm. 188 exposures (3 min per exposure) were obtained with 0 < ϕ < 225° and with the crystals rotated through 1.2° in ϕ. Crystal decay was monitored by measuring 200 reflections per image. |
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) | |
Ti1A | 0.37235 (6) | 0.32573 (7) | 0.87218 (4) | 0.02135 (18) | |
Se1A | 0.44696 (4) | 0.20155 (4) | 0.78622 (2) | 0.02446 (12) | |
Se2A | 0.20436 (4) | 0.31308 (4) | 0.80001 (2) | 0.02541 (12) | |
C1A | 0.3748 (4) | 0.2937 (4) | 0.7212 (2) | 0.0249 (10) | |
C2A | 0.2756 (4) | 0.3378 (4) | 0.7273 (2) | 0.0243 (10) | |
S3A | 0.19674 (10) | 0.42365 (11) | 0.67313 (6) | 0.0289 (3) | |
S4A | 0.44838 (11) | 0.30968 (12) | 0.65621 (6) | 0.0329 (3) | |
C3A | 0.2605 (5) | 0.4037 (5) | 0.6017 (2) | 0.0328 (11) | |
C4A | 0.3776 (5) | 0.4264 (5) | 0.6105 (3) | 0.0335 (12) | |
C5A | 0.3974 (4) | 0.5169 (5) | 0.8170 (3) | 0.0315 (11) | |
C6A | 0.3410 (4) | 0.5436 (5) | 0.8677 (3) | 0.0330 (12) | |
C9A | 0.4965 (4) | 0.4727 (4) | 0.8391 (3) | 0.0302 (11) | |
C8A | 0.5015 (4) | 0.4714 (5) | 0.9041 (2) | 0.0325 (12) | |
C7A | 0.4043 (5) | 0.5164 (5) | 0.9216 (3) | 0.0347 (12) | |
C12A | 0.3997 (7) | 0.2722 (6) | 0.9781 (3) | 0.058 (2) | |
H12A | 0.4351 | 0.3284 | 1.0062 | 0.070* | |
C10A | 0.3684 (5) | 0.1193 (5) | 0.9104 (3) | 0.0410 (14) | |
C11A | 0.4454 (5) | 0.1795 (5) | 0.9451 (3) | 0.0375 (13) | |
C13A | 0.2888 (7) | 0.2663 (7) | 0.9614 (4) | 0.063 (2) | |
H13A | 0.2361 | 0.3178 | 0.9761 | 0.076* | |
C14A | 0.2735 (5) | 0.1716 (7) | 0.9198 (4) | 0.054 (2) | |
Ti1B | 0.14408 (6) | 0.88080 (7) | 0.66810 (4) | 0.01933 (18) | |
Se1B | 0.28104 (4) | 0.75052 (4) | 0.61967 (2) | 0.02455 (12) | |
Se2B | 0.02242 (4) | 0.70804 (4) | 0.62819 (2) | 0.02281 (12) | |
C1B | 0.1894 (4) | 0.7172 (4) | 0.5481 (2) | 0.0230 (10) | |
C2B | 0.0842 (4) | 0.7009 (4) | 0.5511 (2) | 0.0213 (9) | |
S3B | −0.01012 (10) | 0.67595 (12) | 0.48877 (6) | 0.0309 (3) | |
S4B | 0.25818 (11) | 0.71289 (14) | 0.48091 (6) | 0.0358 (3) | |
C3B | 0.0754 (10) | 0.6130 (11) | 0.4308 (5) | 0.037 (2) | 0.65 |
H3B1 | 0.1063 | 0.5345 | 0.4465 | 0.045* | 0.65 |
H3B2 | 0.0320 | 0.5956 | 0.3917 | 0.045* | 0.65 |
C3B' | 0.0553 (18) | 0.667 (2) | 0.4204 (9) | 0.034 (4) | 0.35 |
H3B3 | 0.0124 | 0.6186 | 0.3890 | 0.041* | 0.35 |
H3B4 | 0.0632 | 0.7509 | 0.4034 | 0.041* | 0.35 |
C4B | 0.1632 (7) | 0.6999 (9) | 0.4173 (4) | 0.0366 (19) | 0.65 |
H4B1 | 0.1331 | 0.7818 | 0.4071 | 0.044* | 0.65 |
H4B2 | 0.1975 | 0.6700 | 0.3806 | 0.044* | 0.65 |
C4B' | 0.1631 (12) | 0.6088 (14) | 0.4320 (7) | 0.029 (3) | 0.35 |
H4B3 | 0.1921 | 0.5917 | 0.3918 | 0.035* | 0.35 |
H4B4 | 0.1561 | 0.5297 | 0.4539 | 0.035* | 0.35 |
C7B | 0.0836 (4) | 0.8114 (5) | 0.7631 (2) | 0.0281 (10) | |
C6B | 0.1109 (5) | 0.9355 (5) | 0.7704 (2) | 0.0331 (12) | |
C5B | 0.2210 (5) | 0.9462 (5) | 0.7657 (2) | 0.0331 (12) | |
C8B | 0.1752 (4) | 0.7454 (5) | 0.7543 (2) | 0.0271 (10) | |
C9B | 0.2604 (4) | 0.8276 (5) | 0.7565 (2) | 0.0299 (11) | |
C14B | 0.2011 (5) | 1.0651 (5) | 0.6214 (3) | 0.0378 (13) | |
C11B | 0.0460 (6) | 0.9819 (5) | 0.5830 (3) | 0.0442 (16) | |
C12B | 0.0291 (5) | 1.0431 (5) | 0.6384 (3) | 0.0408 (14) | |
C13B | 0.1242 (5) | 1.0967 (5) | 0.6602 (3) | 0.0358 (13) | |
C10B | 0.1517 (7) | 0.9950 (5) | 0.5728 (3) | 0.0469 (17) | |
H10A | 0.370 (8) | 0.045 (10) | 0.883 (5) | 0.11 (3)* | |
H14A | 0.210 (9) | 0.146 (10) | 0.903 (5) | 0.11 (3)* | |
H10B | 0.192 (5) | 0.968 (6) | 0.548 (3) | 0.042 (19)* | |
H9B | 0.330 (4) | 0.806 (4) | 0.754 (2) | 0.017 (12)* | |
H8A | 0.559 (5) | 0.445 (5) | 0.932 (3) | 0.038 (16)* | |
H6A | 0.270 (4) | 0.573 (5) | 0.864 (2) | 0.021 (13)* | |
H7B | 0.013 (5) | 0.779 (5) | 0.766 (3) | 0.036 (16)* | |
H5B | 0.264 (5) | 1.023 (5) | 0.771 (3) | 0.034 (15)* | |
H5A | 0.377 (5) | 0.531 (5) | 0.778 (3) | 0.032 (15)* | |
H7A | 0.389 (5) | 0.532 (6) | 0.961 (3) | 0.051 (19)* | |
H13B | 0.138 (5) | 1.141 (6) | 0.695 (3) | 0.040 (16)* | |
H9A | 0.546 (5) | 0.456 (5) | 0.814 (3) | 0.027 (14)* | |
H6B | 0.065 (6) | 1.001 (7) | 0.780 (4) | 0.07 (2)* | |
H14B | 0.272 (5) | 1.087 (6) | 0.626 (3) | 0.039 (17)* | |
H8B | 0.185 (5) | 0.659 (6) | 0.746 (3) | 0.044 (17)* | |
H11B | −0.014 (6) | 0.933 (8) | 0.559 (4) | 0.07 (2)* | |
H3A2 | 0.245 (4) | 0.319 (5) | 0.585 (2) | 0.017 (12)* | |
H3A1 | 0.225 (4) | 0.458 (5) | 0.573 (3) | 0.028 (14)* | |
H4A2 | 0.402 (6) | 0.427 (7) | 0.567 (4) | 0.06 (2)* | |
H11A | 0.510 (6) | 0.165 (6) | 0.947 (3) | 0.043 (18)* | |
H4A1 | 0.390 (5) | 0.501 (6) | 0.627 (3) | 0.044 (17)* | |
H12B | −0.032 (6) | 1.049 (7) | 0.657 (3) | 0.05 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti1A | 0.0201 (4) | 0.0249 (4) | 0.0190 (4) | 0.0003 (3) | 0.0016 (3) | −0.0004 (3) |
Se1A | 0.0248 (2) | 0.0241 (2) | 0.0246 (2) | 0.00352 (18) | 0.00263 (19) | −0.00186 (17) |
Se2A | 0.0193 (2) | 0.0323 (2) | 0.0246 (2) | −0.00171 (18) | 0.00162 (19) | −0.00119 (19) |
C1A | 0.028 (2) | 0.020 (2) | 0.026 (2) | −0.0063 (18) | 0.000 (2) | −0.0067 (18) |
C2A | 0.027 (2) | 0.023 (2) | 0.023 (2) | −0.0055 (18) | −0.002 (2) | −0.0045 (17) |
S3A | 0.0286 (6) | 0.0283 (6) | 0.0292 (6) | 0.0015 (5) | −0.0018 (5) | 0.0016 (5) |
S4A | 0.0341 (7) | 0.0389 (7) | 0.0269 (6) | 0.0061 (5) | 0.0095 (6) | 0.0030 (5) |
C3A | 0.042 (3) | 0.030 (3) | 0.026 (3) | 0.002 (2) | 0.000 (2) | 0.005 (2) |
C4A | 0.049 (3) | 0.024 (3) | 0.029 (3) | 0.001 (2) | 0.009 (3) | 0.001 (2) |
C5A | 0.039 (3) | 0.026 (2) | 0.029 (3) | −0.008 (2) | −0.006 (2) | −0.001 (2) |
C6A | 0.031 (3) | 0.027 (2) | 0.040 (3) | 0.005 (2) | −0.002 (2) | −0.005 (2) |
C9A | 0.028 (3) | 0.022 (2) | 0.041 (3) | −0.0077 (19) | 0.007 (2) | −0.006 (2) |
C8A | 0.033 (3) | 0.031 (3) | 0.031 (3) | −0.004 (2) | −0.011 (2) | −0.006 (2) |
C7A | 0.048 (3) | 0.028 (3) | 0.029 (3) | 0.001 (2) | 0.006 (3) | −0.011 (2) |
C12A | 0.112 (7) | 0.043 (3) | 0.017 (3) | −0.018 (4) | −0.007 (3) | 0.003 (2) |
C10A | 0.060 (4) | 0.032 (3) | 0.031 (3) | −0.007 (3) | 0.002 (3) | 0.012 (2) |
C11A | 0.026 (3) | 0.045 (3) | 0.041 (3) | 0.006 (2) | 0.002 (2) | 0.022 (3) |
C13A | 0.074 (5) | 0.072 (5) | 0.052 (4) | 0.039 (4) | 0.050 (4) | 0.036 (4) |
C14A | 0.034 (3) | 0.070 (5) | 0.057 (4) | −0.015 (3) | −0.006 (3) | 0.040 (4) |
Ti1B | 0.0211 (4) | 0.0185 (4) | 0.0181 (4) | −0.0005 (3) | 0.0006 (3) | −0.0006 (3) |
Se1B | 0.0190 (2) | 0.0294 (2) | 0.0250 (2) | −0.00009 (18) | 0.00048 (18) | −0.00481 (18) |
Se2B | 0.0210 (2) | 0.0256 (2) | 0.0221 (2) | −0.00459 (17) | 0.00359 (19) | −0.00248 (17) |
C1B | 0.025 (2) | 0.021 (2) | 0.023 (2) | −0.0029 (17) | 0.002 (2) | −0.0032 (17) |
C2B | 0.023 (2) | 0.023 (2) | 0.018 (2) | 0.0003 (17) | 0.0058 (19) | −0.0021 (17) |
S3B | 0.0263 (6) | 0.0410 (7) | 0.0244 (6) | −0.0041 (5) | −0.0031 (5) | −0.0046 (5) |
S4B | 0.0303 (7) | 0.0538 (8) | 0.0248 (6) | −0.0028 (6) | 0.0106 (6) | −0.0033 (6) |
C3B | 0.050 (8) | 0.038 (6) | 0.024 (5) | −0.007 (5) | 0.001 (5) | −0.008 (5) |
C3B' | 0.048 (11) | 0.036 (11) | 0.017 (8) | 0.011 (9) | 0.001 (7) | 0.005 (8) |
C4B | 0.034 (4) | 0.055 (6) | 0.022 (4) | −0.006 (4) | 0.007 (4) | −0.004 (4) |
C4B' | 0.030 (9) | 0.028 (8) | 0.028 (8) | 0.001 (6) | −0.007 (6) | −0.011 (6) |
C7B | 0.025 (2) | 0.042 (3) | 0.018 (2) | −0.005 (2) | 0.007 (2) | 0.003 (2) |
C6B | 0.046 (3) | 0.036 (3) | 0.018 (2) | 0.010 (2) | 0.006 (2) | −0.006 (2) |
C5B | 0.042 (3) | 0.035 (3) | 0.020 (2) | −0.012 (2) | −0.007 (2) | −0.004 (2) |
C8B | 0.035 (3) | 0.029 (2) | 0.017 (2) | 0.001 (2) | −0.005 (2) | 0.0028 (19) |
C9B | 0.024 (3) | 0.043 (3) | 0.022 (2) | 0.006 (2) | −0.002 (2) | 0.000 (2) |
C14B | 0.042 (3) | 0.026 (3) | 0.047 (3) | −0.005 (2) | 0.013 (3) | 0.008 (2) |
C11B | 0.072 (4) | 0.018 (2) | 0.038 (3) | 0.002 (3) | −0.024 (3) | 0.008 (2) |
C12B | 0.041 (3) | 0.026 (3) | 0.055 (4) | 0.011 (2) | 0.001 (3) | 0.011 (2) |
C13B | 0.053 (3) | 0.020 (2) | 0.033 (3) | 0.002 (2) | −0.006 (3) | −0.003 (2) |
C10B | 0.092 (6) | 0.021 (3) | 0.031 (3) | 0.016 (3) | 0.021 (4) | 0.012 (2) |
Ti1A—C8A | 2.351 (5) | Ti1B—C7B | 2.373 (5) |
Ti1A—C7A | 2.357 (5) | Ti1B—C8B | 2.383 (5) |
Ti1A—C12A | 2.359 (6) | Ti1B—C14B | 2.388 (5) |
Ti1A—C13A | 2.365 (6) | Ti1B—C9B | 2.391 (5) |
Ti1A—C11A | 2.377 (5) | Ti1B—C11B | 2.404 (5) |
Ti1A—C14A | 2.383 (6) | Ti1B—C10B | 2.414 (6) |
Ti1A—C10A | 2.399 (5) | Ti1B—Se1B | 2.5408 (9) |
Ti1A—C9A | 2.402 (5) | Ti1B—Se2B | 2.5456 (9) |
Ti1A—C6A | 2.410 (5) | Se1B—C1B | 1.895 (5) |
Ti1A—C5A | 2.435 (5) | Se2B—C2B | 1.900 (5) |
Ti1A—Se1A | 2.5433 (10) | C1B—C2B | 1.359 (7) |
Ti1A—Se2A | 2.5478 (9) | C1B—S4B | 1.755 (5) |
Se1A—C1A | 1.902 (5) | C2B—S3B | 1.752 (5) |
Se2A—C2A | 1.895 (5) | S3B—C3B' | 1.76 (2) |
C1A—C2A | 1.370 (7) | S3B—C3B | 1.857 (12) |
C1A—S4A | 1.758 (5) | S4B—C4B | 1.762 (8) |
C2A—S3A | 1.750 (5) | S4B—C4B' | 1.914 (14) |
S3A—C3A | 1.814 (6) | C3B—C4B | 1.513 (14) |
S4A—C4A | 1.806 (5) | C3B—H3B1 | 0.9900 |
C3A—C4A | 1.510 (8) | C3B—H3B2 | 0.9900 |
C3A—H3A2 | 1.01 (5) | C3B'—C4B' | 1.52 (2) |
C3A—H3A1 | 0.94 (6) | C3B'—H3B3 | 0.9900 |
C4A—H4A2 | 1.01 (8) | C3B'—H3B4 | 0.9900 |
C4A—H4A1 | 0.89 (7) | C4B—H4B1 | 0.9900 |
C5A—C6A | 1.388 (8) | C4B—H4B2 | 0.9900 |
C5A—C9A | 1.399 (8) | C4B'—H4B3 | 0.9900 |
C5A—H5A | 0.88 (6) | C4B'—H4B4 | 0.9900 |
C6A—C7A | 1.393 (8) | C7B—C8B | 1.398 (7) |
C6A—H6A | 0.96 (5) | C7B—C6B | 1.404 (8) |
C9A—C8A | 1.400 (8) | C7B—H7B | 0.97 (6) |
C9A—H9A | 0.89 (6) | C6B—C5B | 1.420 (8) |
C8A—C7A | 1.412 (8) | C6B—H6B | 0.96 (8) |
C8A—H8A | 0.96 (6) | C5B—C9B | 1.406 (8) |
C7A—H7A | 0.92 (7) | C5B—H5B | 1.00 (6) |
C12A—C11A | 1.392 (10) | C8B—C9B | 1.406 (8) |
C12A—C13A | 1.432 (12) | C8B—H8B | 0.97 (7) |
C12A—H12A | 0.9500 | C9B—H9B | 0.92 (5) |
C10A—C11A | 1.355 (9) | C14B—C13B | 1.383 (9) |
C10A—C14A | 1.367 (10) | C14B—C10B | 1.406 (9) |
C10A—H10A | 1.01 (11) | C14B—H14B | 0.94 (7) |
C11A—H11A | 0.84 (7) | C11B—C10B | 1.390 (11) |
C13A—C14A | 1.372 (12) | C11B—C12B | 1.402 (9) |
C13A—H13A | 0.9500 | C11B—H11B | 1.03 (8) |
C14A—H14A | 0.91 (11) | C12B—C13B | 1.393 (9) |
Ti1B—C12B | 2.353 (5) | C12B—H12B | 0.91 (8) |
Ti1B—C6B | 2.358 (5) | C13B—H13B | 0.91 (6) |
Ti1B—C5B | 2.361 (5) | C10B—H10B | 0.83 (7) |
Ti1B—C13B | 2.373 (5) | ||
H4B2···C7Bi | 2.827 (5) | C1B···H3A1 | 2.89 (6) |
H4B2···C6Bi | 2.790 (5) | H3B3···S3Aiii | 2.921 (1) |
H4B2···C5Bi | 2.823 (5) | H3B4···C12Biv | 2.659 (6) |
H4B2···C8Bi | 2.873 (5) | H4B3···C6Bi | 2.754 (5) |
H4B2···C9Bi | 2.8595 (5) | H4B3···C5Bi | 2.806 (5) |
H3B2···C6Bi | 2.900 (5) | H4B4···C14Aii | 2.789 (8) |
H4A2···C12Aii | 2.90 (8) | H4B4···H14Aii | 2.3 (1) |
Se1B···H4A1 | 3.05 (7) | C4B'···C14Aii | 3.38 (2) |
C8A—Ti1A—C7A | 34.9 (2) | C6B—Ti1B—C7B | 34.52 (19) |
C8A—Ti1A—C12A | 80.7 (2) | C5B—Ti1B—C7B | 57.70 (18) |
C7A—Ti1A—C12A | 76.9 (2) | C13B—Ti1B—C7B | 109.8 (2) |
C8A—Ti1A—C13A | 107.3 (3) | C12B—Ti1B—C8B | 137.6 (2) |
C7A—Ti1A—C13A | 86.9 (3) | C6B—Ti1B—C8B | 57.10 (18) |
C12A—Ti1A—C13A | 35.3 (3) | C5B—Ti1B—C8B | 57.28 (18) |
C8A—Ti1A—C11A | 91.8 (2) | C13B—Ti1B—C8B | 132.89 (19) |
C7A—Ti1A—C11A | 104.4 (2) | C7B—Ti1B—C8B | 34.18 (18) |
C12A—Ti1A—C11A | 34.2 (2) | C12B—Ti1B—C14B | 57.0 (2) |
C13A—Ti1A—C11A | 57.0 (2) | C6B—Ti1B—C14B | 105.4 (2) |
C8A—Ti1A—C14A | 137.1 (2) | C5B—Ti1B—C14B | 90.2 (2) |
C7A—Ti1A—C14A | 120.4 (3) | C13B—Ti1B—C14B | 33.8 (2) |
C12A—Ti1A—C14A | 56.6 (3) | C7B—Ti1B—C14B | 139.9 (2) |
C13A—Ti1A—C14A | 33.6 (3) | C8B—Ti1B—C14B | 144.5 (2) |
C11A—Ti1A—C14A | 55.5 (2) | C12B—Ti1B—C9B | 137.0 (2) |
C8A—Ti1A—C10A | 124.5 (2) | C6B—Ti1B—C9B | 57.36 (19) |
C7A—Ti1A—C10A | 132.8 (2) | C5B—Ti1B—C9B | 34.42 (19) |
C12A—Ti1A—C10A | 56.0 (2) | C13B—Ti1B—C9B | 110.69 (19) |
C13A—Ti1A—C10A | 55.9 (2) | C7B—Ti1B—C9B | 57.09 (18) |
C11A—Ti1A—C10A | 33.0 (2) | C8B—Ti1B—C9B | 34.26 (18) |
C14A—Ti1A—C10A | 33.2 (2) | C14B—Ti1B—C9B | 110.5 (2) |
C8A—Ti1A—C9A | 34.25 (19) | C12B—Ti1B—C11B | 34.3 (2) |
C7A—Ti1A—C9A | 56.8 (2) | C6B—Ti1B—C11B | 118.5 (2) |
C12A—Ti1A—C9A | 113.9 (2) | C5B—Ti1B—C11B | 134.11 (19) |
C13A—Ti1A—C9A | 140.9 (3) | C13B—Ti1B—C11B | 56.25 (19) |
C11A—Ti1A—C9A | 114.4 (2) | C7B—Ti1B—C11B | 128.4 (2) |
C14A—Ti1A—C9A | 169.5 (2) | C8B—Ti1B—C11B | 157.5 (2) |
C10A—Ti1A—C9A | 139.6 (2) | C14B—Ti1B—C11B | 56.5 (2) |
C8A—Ti1A—C6A | 57.02 (18) | C9B—Ti1B—C11B | 166.2 (2) |
C7A—Ti1A—C6A | 33.96 (18) | C12B—Ti1B—C10B | 56.4 (2) |
C12A—Ti1A—C6A | 107.1 (2) | C6B—Ti1B—C10B | 133.6 (2) |
C13A—Ti1A—C6A | 102.6 (2) | C5B—Ti1B—C10B | 124.2 (2) |
C11A—Ti1A—C6A | 138.0 (2) | C13B—Ti1B—C10B | 55.8 (2) |
C14A—Ti1A—C6A | 128.4 (3) | C7B—Ti1B—C10B | 160.0 (2) |
C10A—Ti1A—C6A | 158.6 (2) | C8B—Ti1B—C10B | 165.8 (2) |
C9A—Ti1A—C6A | 56.02 (19) | C14B—Ti1B—C10B | 34.0 (2) |
C8A—Ti1A—C5A | 56.51 (18) | C9B—Ti1B—C10B | 137.8 (2) |
C7A—Ti1A—C5A | 56.03 (19) | C11B—Ti1B—C10B | 33.5 (3) |
C12A—Ti1A—C5A | 132.2 (2) | C12B—Ti1B—Se1B | 137.90 (18) |
C13A—Ti1A—C5A | 135.9 (2) | C6B—Ti1B—Se1B | 135.08 (14) |
C11A—Ti1A—C5A | 146.98 (19) | C5B—Ti1B—Se1B | 106.65 (15) |
C14A—Ti1A—C5A | 155.5 (2) | C13B—Ti1B—Se1B | 126.75 (16) |
C10A—Ti1A—C5A | 168.1 (2) | C7B—Ti1B—Se1B | 117.36 (13) |
C9A—Ti1A—C5A | 33.61 (18) | C8B—Ti1B—Se1B | 84.17 (13) |
C6A—Ti1A—C5A | 33.3 (2) | C14B—Ti1B—Se1B | 93.11 (15) |
C8A—Ti1A—Se1A | 106.20 (15) | C9B—Ti1B—Se1B | 77.91 (13) |
C7A—Ti1A—Se1A | 137.61 (16) | C11B—Ti1B—Se1B | 105.91 (18) |
C12A—Ti1A—Se1A | 122.8 (2) | C10B—Ti1B—Se1B | 82.03 (17) |
C13A—Ti1A—Se1A | 131.9 (2) | C12B—Ti1B—Se2B | 96.65 (16) |
C11A—Ti1A—Se1A | 88.65 (16) | C6B—Ti1B—Se2B | 110.71 (15) |
C14A—Ti1A—Se1A | 100.4 (2) | C5B—Ti1B—Se2B | 136.30 (14) |
C10A—Ti1A—Se1A | 76.75 (16) | C13B—Ti1B—Se2B | 130.67 (15) |
C9A—Ti1A—Se1A | 81.01 (13) | C7B—Ti1B—Se2B | 79.89 (13) |
C6A—Ti1A—Se1A | 124.48 (15) | C8B—Ti1B—Se2B | 82.18 (12) |
C5A—Ti1A—Se1A | 91.56 (14) | C14B—Ti1B—Se2B | 132.70 (16) |
C8A—Ti1A—Se2A | 138.58 (14) | C9B—Ti1B—Se2B | 114.33 (14) |
C7A—Ti1A—Se2A | 115.49 (14) | C11B—Ti1B—Se2B | 79.40 (14) |
C12A—Ti1A—Se2A | 129.1 (2) | C10B—Ti1B—Se2B | 99.14 (18) |
C13A—Ti1A—Se2A | 94.1 (2) | Se1B—Ti1B—Se2B | 82.36 (3) |
C11A—Ti1A—Se2A | 129.30 (15) | C1B—Se1B—Ti1B | 92.52 (15) |
C14A—Ti1A—Se2A | 77.17 (16) | C2B—Se2B—Ti1B | 92.43 (14) |
C10A—Ti1A—Se2A | 96.86 (16) | C2B—C1B—S4B | 126.6 (4) |
C9A—Ti1A—Se2A | 113.29 (13) | C2B—C1B—Se1B | 122.1 (4) |
C6A—Ti1A—Se2A | 84.27 (13) | S4B—C1B—Se1B | 111.3 (3) |
C5A—Ti1A—Se2A | 83.35 (12) | C1B—C2B—S3B | 127.1 (4) |
Se1A—Ti1A—Se2A | 82.56 (3) | C1B—C2B—Se2B | 121.1 (3) |
C1A—Se1A—Ti1A | 94.04 (15) | S3B—C2B—Se2B | 111.8 (2) |
C2A—Se2A—Ti1A | 93.65 (14) | C2B—S3B—C3B' | 108.1 (7) |
C2A—C1A—S4A | 126.8 (4) | C2B—S3B—C3B | 99.8 (4) |
C2A—C1A—Se1A | 120.6 (4) | C1B—S4B—C4B | 106.8 (3) |
S4A—C1A—Se1A | 112.6 (3) | C1B—S4B—C4B' | 97.7 (5) |
C1A—C2A—S3A | 127.5 (4) | C4B—C3B—S3B | 112.4 (7) |
C1A—C2A—Se2A | 122.5 (4) | C4B—C3B—H3B1 | 109.1 |
S3A—C2A—Se2A | 110.0 (3) | S3B—C3B—H3B1 | 109.1 |
C2A—S3A—C3A | 103.4 (2) | C4B—C3B—H3B2 | 109.1 |
C1A—S4A—C4A | 103.3 (3) | S3B—C3B—H3B2 | 109.1 |
C4A—C3A—S3A | 112.3 (4) | H3B1—C3B—H3B2 | 107.8 |
C4A—C3A—H3A2 | 111 (3) | C4B'—C3B'—S3B | 111.6 (13) |
S3A—C3A—H3A2 | 109 (3) | C4B'—C3B'—H3B3 | 109.3 |
C4A—C3A—H3A1 | 113 (3) | S3B—C3B'—H3B3 | 109.3 |
S3A—C3A—H3A1 | 105 (4) | C4B'—C3B'—H3B4 | 109.3 |
H3A2—C3A—H3A1 | 106 (4) | S3B—C3B'—H3B4 | 109.3 |
C3A—C4A—S4A | 113.5 (4) | H3B3—C3B'—H3B4 | 108.0 |
C3A—C4A—H4A2 | 105 (4) | C3B—C4B—S4B | 111.9 (7) |
S4A—C4A—H4A2 | 109 (4) | C3B—C4B—H4B1 | 109.2 |
C3A—C4A—H4A1 | 109 (4) | S4B—C4B—H4B1 | 109.2 |
S4A—C4A—H4A1 | 112 (4) | C3B—C4B—H4B2 | 109.2 |
H4A2—C4A—H4A1 | 107 (6) | S4B—C4B—H4B2 | 109.2 |
C6A—C5A—C9A | 108.4 (5) | H4B1—C4B—H4B2 | 107.9 |
C6A—C5A—Ti1A | 72.4 (3) | C3B'—C4B'—S4B | 111.5 (11) |
C9A—C5A—Ti1A | 71.9 (3) | C3B'—C4B'—H4B3 | 109.3 |
C6A—C5A—H5A | 126 (4) | S4B—C4B'—H4B3 | 109.3 |
C9A—C5A—H5A | 125 (4) | C3B'—C4B'—H4B4 | 109.3 |
Ti1A—C5A—H5A | 125 (4) | S4B—C4B'—H4B4 | 109.3 |
C5A—C6A—C7A | 108.1 (5) | H4B3—C4B'—H4B4 | 108.0 |
C5A—C6A—Ti1A | 74.3 (3) | C8B—C7B—C6B | 108.0 (5) |
C7A—C6A—Ti1A | 70.9 (3) | C8B—C7B—Ti1B | 73.3 (3) |
C5A—C6A—H6A | 123 (3) | C6B—C7B—Ti1B | 72.2 (3) |
C7A—C6A—H6A | 128 (3) | C8B—C7B—H7B | 127 (4) |
Ti1A—C6A—H6A | 119 (3) | C6B—C7B—H7B | 125 (4) |
C5A—C9A—C8A | 108.2 (5) | Ti1B—C7B—H7B | 122 (4) |
C5A—C9A—Ti1A | 74.5 (3) | C7B—C6B—C5B | 108.0 (5) |
C8A—C9A—Ti1A | 70.9 (3) | C7B—C6B—Ti1B | 73.3 (3) |
C5A—C9A—H9A | 122 (4) | C5B—C6B—Ti1B | 72.6 (3) |
C8A—C9A—H9A | 129 (4) | C7B—C6B—H6B | 126 (5) |
Ti1A—C9A—H9A | 124 (4) | C5B—C6B—H6B | 126 (5) |
C9A—C8A—C7A | 107.1 (5) | Ti1B—C6B—H6B | 124 (5) |
C9A—C8A—Ti1A | 74.9 (3) | C9B—C5B—C6B | 107.5 (5) |
C7A—C8A—Ti1A | 72.8 (3) | C9B—C5B—Ti1B | 73.9 (3) |
C9A—C8A—H8A | 128 (4) | C6B—C5B—Ti1B | 72.4 (3) |
C7A—C8A—H8A | 125 (4) | C9B—C5B—H5B | 126 (3) |
Ti1A—C8A—H8A | 118 (4) | C6B—C5B—H5B | 126 (3) |
C6A—C7A—C8A | 108.2 (5) | Ti1B—C5B—H5B | 122 (3) |
C6A—C7A—Ti1A | 75.1 (3) | C7B—C8B—C9B | 108.6 (5) |
C8A—C7A—Ti1A | 72.3 (3) | C7B—C8B—Ti1B | 72.5 (3) |
C6A—C7A—H7A | 126 (4) | C9B—C8B—Ti1B | 73.2 (3) |
C8A—C7A—H7A | 125 (4) | C7B—C8B—H8B | 131 (4) |
Ti1A—C7A—H7A | 123 (4) | C9B—C8B—H8B | 121 (4) |
C11A—C12A—C13A | 106.5 (6) | Ti1B—C8B—H8B | 118 (4) |
C11A—C12A—Ti1A | 73.6 (3) | C8B—C9B—C5B | 107.9 (5) |
C13A—C12A—Ti1A | 72.6 (3) | C8B—C9B—Ti1B | 72.6 (3) |
C11A—C12A—H12A | 126.8 | C5B—C9B—Ti1B | 71.6 (3) |
C13A—C12A—H12A | 126.8 | C8B—C9B—H9B | 125 (3) |
Ti1A—C12A—H12A | 119.0 | C5B—C9B—H9B | 127 (3) |
C11A—C10A—C14A | 109.0 (6) | Ti1B—C9B—H9B | 124 (3) |
C11A—C10A—Ti1A | 72.6 (3) | C13B—C14B—C10B | 107.0 (6) |
C14A—C10A—Ti1A | 72.7 (4) | C13B—C14B—Ti1B | 72.5 (3) |
C11A—C10A—H10A | 132 (6) | C10B—C14B—Ti1B | 74.0 (3) |
C14A—C10A—H10A | 119 (6) | C13B—C14B—H14B | 127 (4) |
Ti1A—C10A—H10A | 123 (6) | C10B—C14B—H14B | 126 (4) |
C10A—C11A—C12A | 108.7 (6) | Ti1B—C14B—H14B | 120 (4) |
C10A—C11A—Ti1A | 74.4 (3) | C10B—C11B—C12B | 107.7 (5) |
C12A—C11A—Ti1A | 72.2 (3) | C10B—C11B—Ti1B | 73.6 (3) |
C10A—C11A—H11A | 127 (5) | C12B—C11B—Ti1B | 70.9 (3) |
C12A—C11A—H11A | 124 (5) | C10B—C11B—H11B | 131 (5) |
Ti1A—C11A—H11A | 120 (5) | C12B—C11B—H11B | 121 (5) |
C14A—C13A—C12A | 106.5 (6) | Ti1B—C11B—H11B | 118 (5) |
C14A—C13A—Ti1A | 73.9 (4) | C13B—C12B—C11B | 107.4 (6) |
C12A—C13A—Ti1A | 72.1 (4) | C13B—C12B—Ti1B | 73.6 (3) |
C14A—C13A—H13A | 126.7 | C11B—C12B—Ti1B | 74.9 (3) |
C12A—C13A—H13A | 126.7 | C13B—C12B—H12B | 125 (5) |
Ti1A—C13A—H13A | 119.2 | C11B—C12B—H12B | 127 (5) |
C10A—C14A—C13A | 109.3 (6) | Ti1B—C12B—H12B | 118 (5) |
C10A—C14A—Ti1A | 74.0 (3) | C14B—C13B—C12B | 109.3 (5) |
C13A—C14A—Ti1A | 72.5 (4) | C14B—C13B—Ti1B | 73.7 (3) |
C10A—C14A—H14A | 126 (7) | C12B—C13B—Ti1B | 72.1 (3) |
C13A—C14A—H14A | 124 (7) | C14B—C13B—H13B | 123 (4) |
Ti1A—C14A—H14A | 123 (7) | C12B—C13B—H13B | 127 (4) |
C12B—Ti1B—C6B | 84.8 (2) | Ti1B—C13B—H13B | 118 (4) |
C12B—Ti1B—C5B | 102.7 (2) | C11B—C10B—C14B | 108.6 (6) |
C6B—Ti1B—C5B | 35.0 (2) | C11B—C10B—Ti1B | 72.8 (3) |
C12B—Ti1B—C13B | 34.3 (2) | C14B—C10B—Ti1B | 71.9 (3) |
C6B—Ti1B—C13B | 77.9 (2) | C11B—C10B—H10B | 137 (5) |
C5B—Ti1B—C13B | 78.37 (19) | C14B—C10B—H10B | 114 (5) |
C12B—Ti1B—C7B | 103.7 (2) | Ti1B—C10B—H10B | 116 (5) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+1/2, z−1/2; (iii) −x, −y+1, −z+1; (iv) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ti(C5H5)2(C4H4S2Se2)] |
Mr | 452.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 180 |
a, b, c (Å) | 12.7474 (8), 10.9055 (10), 21.5888 (13) |
β (°) | 94.648 (7) |
V (Å3) | 2991.3 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 5.70 |
Crystal size (mm) | 0.33 × 0.25 × 0.04 |
Data collection | |
Diffractometer | Stow Imaging Plate Diffraction System diffractometer |
Absorption correction | Analytical (see. N.W. Alcock (1970). Cryst. Computing, p271) |
Tmin, Tmax | 0.341, 0.765 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26415, 5732, 4603 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.097, 1.05 |
No. of reflections | 5732 |
No. of parameters | 449 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.76, −0.76 |
Computer programs: IPDS Software (Stoe & Cie, 1996), IPDS Software, SIR97 (Altomare, 1999), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1996) and ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
H4B2···C7Bi | 2.827 (5) | C1B···H3A1 | 2.89 (6) |
H4B2···C6Bi | 2.790 (5) | H3B3···S3Aiii | 2.921 (1) |
H4B2···C5Bi | 2.823 (5) | H3B4···C12Biv | 2.659 (6) |
H4B2···C8Bi | 2.873 (5) | H4B3···C6Bi | 2.754 (5) |
H4B2···C9Bi | 2.8595 (5) | H4B3···C5Bi | 2.806 (5) |
H3B2···C6Bi | 2.900 (5) | H4B4···C14Aii | 2.789 (8) |
H4A2···C12Aii | 2.90 (8) | H4B4···H14Aii | 2.3 (1) |
Se1B···H4A1 | 3.05 (7) | C4B'···C14Aii | 3.38 (2) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+1/2, z−1/2; (iii) −x, −y+1, −z+1; (iv) −x, −y+2, −z+1. |
The organic donor BETS [bis(ethylenedithio)tetraselenafulvalene] [(4), see Scheme] is at the origin of interesting conductive and magnetic compounds, exhibiting unusual physical properties (Brossard et al., 1998; Kobayashi et al., 2000; Uji et al., 2001). One of the key steps of the synthesis of BETS (Kato et al., 1991; Courcet et al., 1998) is the isolation of the title compound [(2), see Scheme], which easily reacts with triphosgene to give 4,5-ethylenedithio-1,3-diselenol-2-one [(3), see Scheme]. This latter provides BETS, (4), after coupling in triethylphosphite.
We report here the crystal structure of Cp2Ti(dddse) (which has never been reported to our knowledge), and compare it to its sulfur derivative, Cp2Ti(dddt), whose crystal structure has been reported in 1994 (Guyon et al., 1994). These two compounds are isostructural. The asymmetric unit (Fig. 1) contains two independent Cp2Ti(dddse) molecules (A and B) in general positions. The main difference between them is the presence of a disordered terminal ethylene group in one of the independent units of (molecule B). This disorder is probably due to the relative orientation of the B molecule versus the A molecule. Indeed, the –CH2—CH2– group of the molecule A lies between a Cp ring of another molecule A and the Se2C2S2 plane of an adjacent B molecule (see Fig. 2). Only three short contacts (smaller than the sum of the van der Walls radii; Pauling, 1960) exist between the H atoms of this ethylene group and the A and B molecules (see Table 2), leading to a stable and favourable conformation. On the opposite, the H atoms of the ethylene group of the molecule B points directly towards the Cp ring of the closest B molecule (Fig. 2), with 6 short C···H contacts (Table 2). These contacts are possibly destabilizing. As a consequence, the ethylene group flips to another position (denoted C3B'/C4B'). This new position of the ethylene group leads also to the occurrence of short contacts with neighbouring A and B molecules (Table 2). All of them, but one, involve again contacts with Cp rings. As a consequence, whatever the position, the ethylene groups of the B molecule are always connected to the Cp rings of the adjacent molecules. Despite this disorder, both –CH2—CH2– adopts a trans configuration, whereas both trans and eclipsed configurations were reported for Cp2Ti(dddt), without any disorder on the ethylene group. It should be noted here that in Cp2Ti(dddt), a disorder should also exist in the B molecule, since the equivalent displacement parameters of the C atoms are very large [0.158 (6) and 0.116 (4) Å2], and the intramolecular distance between C(3B) and C(4B) (1.267 Å) is too short for a single C—C bond. The presence of this disorder should then `remove' the eclipsed configuration. As a consequence, Cp2Ti(dddse) and Cp2Ti(dddt) exhibit the same structural features. This is also supported by the folding angle of the TiSe2C2 ring along the Se—Se axis in molecules A and B [49.75 (3) and 53.29 (3)°, respectively]. Substitution of S for Se did not affect the value of the folding angle, which are almost identical in Cp2Ti(dddt) [49.2 (1) and 51.2 (1)°].