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Bis(η5-cyclo­penta­dienyl)[5,6-di­hydro-1,4-dithiine-2,3-di­selen­o­lato(2−)-κ2Se,Se′]­titanium(IV), [Ti(C5H5)2(C4H4S2Se2)], is isostructural with the all-sulfur derivative Cp2Ti(dddt) [Guyon et al. (1994). Bull. Soc. Chim. Fr. 131, 217–226] (dddt2− = 5,6-di­hydro-1,4-dithiine-2,3-di­thiol­ate). There are two molecules in the asymmetric unit, and one ethyl­ene group of the dddse2− ligand is found to be disordered in one of them. As in Cp2Ti(dddt), the TiSe2C2 ring is folded along the Se...Se axis by 49.75 (3) and 53.29 (3)° in the two independent molecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008262/fl6030sup1.cif
Contains datablocks global, 2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008262/fl60302sup2.hkl
Contains datablock 2

CCDC reference: 214572

Key indicators

  • Single-crystal X-ray study
  • T = 180 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.035
  • wR factor = 0.097
  • Data-to-parameter ratio = 12.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
DIFF_019 Alert A _diffrn_standards_number is missing Number of standards used in measurement.
Author response: see the block exptl_special_details
DIFF_020  Alert A _diffrn_standards_interval_count and
          _diffrn_standards_interval_time are missing. Number of measurements
          between standards or time (min) between standards.
Author response: see the block exptl_special_details
PLAT_724  Alert A Contact Calc     2.33953, Rep    2.30(10), Dev.      0.04 Ang.
                     H4B4 -H14A    1.555   4.565


Yellow Alert Alert Level C:
PLAT_213 Alert C Atom C13A has ADP max/min Ratio ........... 3.40 prolate General Notes
ABSTM_02 The ratio of expected to reported Tmax/Tmin(RR) is > 1.50 Tmin and Tmax reported: 0.341 0.765 Tmin and Tmax expected: 0.194 0.808 RR = 1.853 Please check that your absorption correction is appropriate.
3 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

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)°].

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. Atomic numbering scheme for Cp2Ti(dddse), with 50% probability displacement ellipsoids with one of the two disordered groups shown in light gray.
[Figure 2] Fig. 2. Projection onto the bc plane, showing the short contacts (dotted lines) between the A and B molecules (B is depicted with C3B and C4B as the ethylene group).
[Figure 3] Fig. 3. Structure of Cp2Ti(dddse) showing the short contacts between the A and B molecules (B is depicted with C3B' and C4B' as the ethylene group).
bis(η5-cyclopentadien-1-yl)[5,6-dihydro-1,4-dithiine-2,3-diselenolato(2-) –Se,Se']titanium(IV) top
Crystal data top
[Ti(C5H5)2(C4H4S2Se2)]F(000) = 1760
Mr = 452.18Dx = 2.008 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.7474 (8) ÅCell parameters from 8000 reflections
b = 10.9055 (10) Åθ = 2.8–26°
c = 21.5888 (13) ŵ = 5.70 mm1
β = 94.648 (7)°T = 180 K
V = 2991.3 (4) Å3Plate, dark green
Z = 80.33 × 0.25 × 0.04 mm
Data collection top
Stow Imaging Plate Diffraction System
diffractometer
5732 independent reflections
Radiation source: fine-focus sealed tube4603 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
ϕ scansθmax = 26.1°, θmin = 2.1°
Absorption correction: analytical
(see. N.W. Alcock (1970). Cryst. Computing, p271)
h = 1515
Tmin = 0.341, Tmax = 0.765k = 1313
26415 measured reflectionsl = 2626
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: mixed
wR(F2) = 0.097H 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 parametersΔρmax = 0.76 e Å3
0 restraintsΔρmin = 0.76 e Å3
Crystal data top
[Ti(C5H5)2(C4H4S2Se2)]V = 2991.3 (4) Å3
Mr = 452.18Z = 8
Monoclinic, P21/cMo Kα radiation
a = 12.7474 (8) ŵ = 5.70 mm1
b = 10.9055 (10) ÅT = 180 K
c = 21.5888 (13) Å0.33 × 0.25 × 0.04 mm
β = 94.648 (7)°
Data collection top
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 = 0.765Rint = 0.055
26415 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.76 e Å3
5732 reflectionsΔρmin = 0.76 e Å3
449 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ti1A0.37235 (6)0.32573 (7)0.87218 (4)0.02135 (18)
Se1A0.44696 (4)0.20155 (4)0.78622 (2)0.02446 (12)
Se2A0.20436 (4)0.31308 (4)0.80001 (2)0.02541 (12)
C1A0.3748 (4)0.2937 (4)0.7212 (2)0.0249 (10)
C2A0.2756 (4)0.3378 (4)0.7273 (2)0.0243 (10)
S3A0.19674 (10)0.42365 (11)0.67313 (6)0.0289 (3)
S4A0.44838 (11)0.30968 (12)0.65621 (6)0.0329 (3)
C3A0.2605 (5)0.4037 (5)0.6017 (2)0.0328 (11)
C4A0.3776 (5)0.4264 (5)0.6105 (3)0.0335 (12)
C5A0.3974 (4)0.5169 (5)0.8170 (3)0.0315 (11)
C6A0.3410 (4)0.5436 (5)0.8677 (3)0.0330 (12)
C9A0.4965 (4)0.4727 (4)0.8391 (3)0.0302 (11)
C8A0.5015 (4)0.4714 (5)0.9041 (2)0.0325 (12)
C7A0.4043 (5)0.5164 (5)0.9216 (3)0.0347 (12)
C12A0.3997 (7)0.2722 (6)0.9781 (3)0.058 (2)
H12A0.43510.32841.00620.070*
C10A0.3684 (5)0.1193 (5)0.9104 (3)0.0410 (14)
C11A0.4454 (5)0.1795 (5)0.9451 (3)0.0375 (13)
C13A0.2888 (7)0.2663 (7)0.9614 (4)0.063 (2)
H13A0.23610.31780.97610.076*
C14A0.2735 (5)0.1716 (7)0.9198 (4)0.054 (2)
Ti1B0.14408 (6)0.88080 (7)0.66810 (4)0.01933 (18)
Se1B0.28104 (4)0.75052 (4)0.61967 (2)0.02455 (12)
Se2B0.02242 (4)0.70804 (4)0.62819 (2)0.02281 (12)
C1B0.1894 (4)0.7172 (4)0.5481 (2)0.0230 (10)
C2B0.0842 (4)0.7009 (4)0.5511 (2)0.0213 (9)
S3B0.01012 (10)0.67595 (12)0.48877 (6)0.0309 (3)
S4B0.25818 (11)0.71289 (14)0.48091 (6)0.0358 (3)
C3B0.0754 (10)0.6130 (11)0.4308 (5)0.037 (2)0.65
H3B10.10630.53450.44650.045*0.65
H3B20.03200.59560.39170.045*0.65
C3B'0.0553 (18)0.667 (2)0.4204 (9)0.034 (4)0.35
H3B30.01240.61860.38900.041*0.35
H3B40.06320.75090.40340.041*0.35
C4B0.1632 (7)0.6999 (9)0.4173 (4)0.0366 (19)0.65
H4B10.13310.78180.40710.044*0.65
H4B20.19750.67000.38060.044*0.65
C4B'0.1631 (12)0.6088 (14)0.4320 (7)0.029 (3)0.35
H4B30.19210.59170.39180.035*0.35
H4B40.15610.52970.45390.035*0.35
C7B0.0836 (4)0.8114 (5)0.7631 (2)0.0281 (10)
C6B0.1109 (5)0.9355 (5)0.7704 (2)0.0331 (12)
C5B0.2210 (5)0.9462 (5)0.7657 (2)0.0331 (12)
C8B0.1752 (4)0.7454 (5)0.7543 (2)0.0271 (10)
C9B0.2604 (4)0.8276 (5)0.7565 (2)0.0299 (11)
C14B0.2011 (5)1.0651 (5)0.6214 (3)0.0378 (13)
C11B0.0460 (6)0.9819 (5)0.5830 (3)0.0442 (16)
C12B0.0291 (5)1.0431 (5)0.6384 (3)0.0408 (14)
C13B0.1242 (5)1.0967 (5)0.6602 (3)0.0358 (13)
C10B0.1517 (7)0.9950 (5)0.5728 (3)0.0469 (17)
H10A0.370 (8)0.045 (10)0.883 (5)0.11 (3)*
H14A0.210 (9)0.146 (10)0.903 (5)0.11 (3)*
H10B0.192 (5)0.968 (6)0.548 (3)0.042 (19)*
H9B0.330 (4)0.806 (4)0.754 (2)0.017 (12)*
H8A0.559 (5)0.445 (5)0.932 (3)0.038 (16)*
H6A0.270 (4)0.573 (5)0.864 (2)0.021 (13)*
H7B0.013 (5)0.779 (5)0.766 (3)0.036 (16)*
H5B0.264 (5)1.023 (5)0.771 (3)0.034 (15)*
H5A0.377 (5)0.531 (5)0.778 (3)0.032 (15)*
H7A0.389 (5)0.532 (6)0.961 (3)0.051 (19)*
H13B0.138 (5)1.141 (6)0.695 (3)0.040 (16)*
H9A0.546 (5)0.456 (5)0.814 (3)0.027 (14)*
H6B0.065 (6)1.001 (7)0.780 (4)0.07 (2)*
H14B0.272 (5)1.087 (6)0.626 (3)0.039 (17)*
H8B0.185 (5)0.659 (6)0.746 (3)0.044 (17)*
H11B0.014 (6)0.933 (8)0.559 (4)0.07 (2)*
H3A20.245 (4)0.319 (5)0.585 (2)0.017 (12)*
H3A10.225 (4)0.458 (5)0.573 (3)0.028 (14)*
H4A20.402 (6)0.427 (7)0.567 (4)0.06 (2)*
H11A0.510 (6)0.165 (6)0.947 (3)0.043 (18)*
H4A10.390 (5)0.501 (6)0.627 (3)0.044 (17)*
H12B0.032 (6)1.049 (7)0.657 (3)0.05 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti1A0.0201 (4)0.0249 (4)0.0190 (4)0.0003 (3)0.0016 (3)0.0004 (3)
Se1A0.0248 (2)0.0241 (2)0.0246 (2)0.00352 (18)0.00263 (19)0.00186 (17)
Se2A0.0193 (2)0.0323 (2)0.0246 (2)0.00171 (18)0.00162 (19)0.00119 (19)
C1A0.028 (2)0.020 (2)0.026 (2)0.0063 (18)0.000 (2)0.0067 (18)
C2A0.027 (2)0.023 (2)0.023 (2)0.0055 (18)0.002 (2)0.0045 (17)
S3A0.0286 (6)0.0283 (6)0.0292 (6)0.0015 (5)0.0018 (5)0.0016 (5)
S4A0.0341 (7)0.0389 (7)0.0269 (6)0.0061 (5)0.0095 (6)0.0030 (5)
C3A0.042 (3)0.030 (3)0.026 (3)0.002 (2)0.000 (2)0.005 (2)
C4A0.049 (3)0.024 (3)0.029 (3)0.001 (2)0.009 (3)0.001 (2)
C5A0.039 (3)0.026 (2)0.029 (3)0.008 (2)0.006 (2)0.001 (2)
C6A0.031 (3)0.027 (2)0.040 (3)0.005 (2)0.002 (2)0.005 (2)
C9A0.028 (3)0.022 (2)0.041 (3)0.0077 (19)0.007 (2)0.006 (2)
C8A0.033 (3)0.031 (3)0.031 (3)0.004 (2)0.011 (2)0.006 (2)
C7A0.048 (3)0.028 (3)0.029 (3)0.001 (2)0.006 (3)0.011 (2)
C12A0.112 (7)0.043 (3)0.017 (3)0.018 (4)0.007 (3)0.003 (2)
C10A0.060 (4)0.032 (3)0.031 (3)0.007 (3)0.002 (3)0.012 (2)
C11A0.026 (3)0.045 (3)0.041 (3)0.006 (2)0.002 (2)0.022 (3)
C13A0.074 (5)0.072 (5)0.052 (4)0.039 (4)0.050 (4)0.036 (4)
C14A0.034 (3)0.070 (5)0.057 (4)0.015 (3)0.006 (3)0.040 (4)
Ti1B0.0211 (4)0.0185 (4)0.0181 (4)0.0005 (3)0.0006 (3)0.0006 (3)
Se1B0.0190 (2)0.0294 (2)0.0250 (2)0.00009 (18)0.00048 (18)0.00481 (18)
Se2B0.0210 (2)0.0256 (2)0.0221 (2)0.00459 (17)0.00359 (19)0.00248 (17)
C1B0.025 (2)0.021 (2)0.023 (2)0.0029 (17)0.002 (2)0.0032 (17)
C2B0.023 (2)0.023 (2)0.018 (2)0.0003 (17)0.0058 (19)0.0021 (17)
S3B0.0263 (6)0.0410 (7)0.0244 (6)0.0041 (5)0.0031 (5)0.0046 (5)
S4B0.0303 (7)0.0538 (8)0.0248 (6)0.0028 (6)0.0106 (6)0.0033 (6)
C3B0.050 (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)
C4B0.034 (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)
C7B0.025 (2)0.042 (3)0.018 (2)0.005 (2)0.007 (2)0.003 (2)
C6B0.046 (3)0.036 (3)0.018 (2)0.010 (2)0.006 (2)0.006 (2)
C5B0.042 (3)0.035 (3)0.020 (2)0.012 (2)0.007 (2)0.004 (2)
C8B0.035 (3)0.029 (2)0.017 (2)0.001 (2)0.005 (2)0.0028 (19)
C9B0.024 (3)0.043 (3)0.022 (2)0.006 (2)0.002 (2)0.000 (2)
C14B0.042 (3)0.026 (3)0.047 (3)0.005 (2)0.013 (3)0.008 (2)
C11B0.072 (4)0.018 (2)0.038 (3)0.002 (3)0.024 (3)0.008 (2)
C12B0.041 (3)0.026 (3)0.055 (4)0.011 (2)0.001 (3)0.011 (2)
C13B0.053 (3)0.020 (2)0.033 (3)0.002 (2)0.006 (3)0.003 (2)
C10B0.092 (6)0.021 (3)0.031 (3)0.016 (3)0.021 (4)0.012 (2)
Geometric parameters (Å, º) top
Ti1A—C8A2.351 (5)Ti1B—C7B2.373 (5)
Ti1A—C7A2.357 (5)Ti1B—C8B2.383 (5)
Ti1A—C12A2.359 (6)Ti1B—C14B2.388 (5)
Ti1A—C13A2.365 (6)Ti1B—C9B2.391 (5)
Ti1A—C11A2.377 (5)Ti1B—C11B2.404 (5)
Ti1A—C14A2.383 (6)Ti1B—C10B2.414 (6)
Ti1A—C10A2.399 (5)Ti1B—Se1B2.5408 (9)
Ti1A—C9A2.402 (5)Ti1B—Se2B2.5456 (9)
Ti1A—C6A2.410 (5)Se1B—C1B1.895 (5)
Ti1A—C5A2.435 (5)Se2B—C2B1.900 (5)
Ti1A—Se1A2.5433 (10)C1B—C2B1.359 (7)
Ti1A—Se2A2.5478 (9)C1B—S4B1.755 (5)
Se1A—C1A1.902 (5)C2B—S3B1.752 (5)
Se2A—C2A1.895 (5)S3B—C3B'1.76 (2)
C1A—C2A1.370 (7)S3B—C3B1.857 (12)
C1A—S4A1.758 (5)S4B—C4B1.762 (8)
C2A—S3A1.750 (5)S4B—C4B'1.914 (14)
S3A—C3A1.814 (6)C3B—C4B1.513 (14)
S4A—C4A1.806 (5)C3B—H3B10.9900
C3A—C4A1.510 (8)C3B—H3B20.9900
C3A—H3A21.01 (5)C3B'—C4B'1.52 (2)
C3A—H3A10.94 (6)C3B'—H3B30.9900
C4A—H4A21.01 (8)C3B'—H3B40.9900
C4A—H4A10.89 (7)C4B—H4B10.9900
C5A—C6A1.388 (8)C4B—H4B20.9900
C5A—C9A1.399 (8)C4B'—H4B30.9900
C5A—H5A0.88 (6)C4B'—H4B40.9900
C6A—C7A1.393 (8)C7B—C8B1.398 (7)
C6A—H6A0.96 (5)C7B—C6B1.404 (8)
C9A—C8A1.400 (8)C7B—H7B0.97 (6)
C9A—H9A0.89 (6)C6B—C5B1.420 (8)
C8A—C7A1.412 (8)C6B—H6B0.96 (8)
C8A—H8A0.96 (6)C5B—C9B1.406 (8)
C7A—H7A0.92 (7)C5B—H5B1.00 (6)
C12A—C11A1.392 (10)C8B—C9B1.406 (8)
C12A—C13A1.432 (12)C8B—H8B0.97 (7)
C12A—H12A0.9500C9B—H9B0.92 (5)
C10A—C11A1.355 (9)C14B—C13B1.383 (9)
C10A—C14A1.367 (10)C14B—C10B1.406 (9)
C10A—H10A1.01 (11)C14B—H14B0.94 (7)
C11A—H11A0.84 (7)C11B—C10B1.390 (11)
C13A—C14A1.372 (12)C11B—C12B1.402 (9)
C13A—H13A0.9500C11B—H11B1.03 (8)
C14A—H14A0.91 (11)C12B—C13B1.393 (9)
Ti1B—C12B2.353 (5)C12B—H12B0.91 (8)
Ti1B—C6B2.358 (5)C13B—H13B0.91 (6)
Ti1B—C5B2.361 (5)C10B—H10B0.83 (7)
Ti1B—C13B2.373 (5)
H4B2···C7Bi2.827 (5)C1B···H3A12.89 (6)
H4B2···C6Bi2.790 (5)H3B3···S3Aiii2.921 (1)
H4B2···C5Bi2.823 (5)H3B4···C12Biv2.659 (6)
H4B2···C8Bi2.873 (5)H4B3···C6Bi2.754 (5)
H4B2···C9Bi2.8595 (5)H4B3···C5Bi2.806 (5)
H3B2···C6Bi2.900 (5)H4B4···C14Aii2.789 (8)
H4A2···C12Aii2.90 (8)H4B4···H14Aii2.3 (1)
Se1B···H4A13.05 (7)C4B'···C14Aii3.38 (2)
C8A—Ti1A—C7A34.9 (2)C6B—Ti1B—C7B34.52 (19)
C8A—Ti1A—C12A80.7 (2)C5B—Ti1B—C7B57.70 (18)
C7A—Ti1A—C12A76.9 (2)C13B—Ti1B—C7B109.8 (2)
C8A—Ti1A—C13A107.3 (3)C12B—Ti1B—C8B137.6 (2)
C7A—Ti1A—C13A86.9 (3)C6B—Ti1B—C8B57.10 (18)
C12A—Ti1A—C13A35.3 (3)C5B—Ti1B—C8B57.28 (18)
C8A—Ti1A—C11A91.8 (2)C13B—Ti1B—C8B132.89 (19)
C7A—Ti1A—C11A104.4 (2)C7B—Ti1B—C8B34.18 (18)
C12A—Ti1A—C11A34.2 (2)C12B—Ti1B—C14B57.0 (2)
C13A—Ti1A—C11A57.0 (2)C6B—Ti1B—C14B105.4 (2)
C8A—Ti1A—C14A137.1 (2)C5B—Ti1B—C14B90.2 (2)
C7A—Ti1A—C14A120.4 (3)C13B—Ti1B—C14B33.8 (2)
C12A—Ti1A—C14A56.6 (3)C7B—Ti1B—C14B139.9 (2)
C13A—Ti1A—C14A33.6 (3)C8B—Ti1B—C14B144.5 (2)
C11A—Ti1A—C14A55.5 (2)C12B—Ti1B—C9B137.0 (2)
C8A—Ti1A—C10A124.5 (2)C6B—Ti1B—C9B57.36 (19)
C7A—Ti1A—C10A132.8 (2)C5B—Ti1B—C9B34.42 (19)
C12A—Ti1A—C10A56.0 (2)C13B—Ti1B—C9B110.69 (19)
C13A—Ti1A—C10A55.9 (2)C7B—Ti1B—C9B57.09 (18)
C11A—Ti1A—C10A33.0 (2)C8B—Ti1B—C9B34.26 (18)
C14A—Ti1A—C10A33.2 (2)C14B—Ti1B—C9B110.5 (2)
C8A—Ti1A—C9A34.25 (19)C12B—Ti1B—C11B34.3 (2)
C7A—Ti1A—C9A56.8 (2)C6B—Ti1B—C11B118.5 (2)
C12A—Ti1A—C9A113.9 (2)C5B—Ti1B—C11B134.11 (19)
C13A—Ti1A—C9A140.9 (3)C13B—Ti1B—C11B56.25 (19)
C11A—Ti1A—C9A114.4 (2)C7B—Ti1B—C11B128.4 (2)
C14A—Ti1A—C9A169.5 (2)C8B—Ti1B—C11B157.5 (2)
C10A—Ti1A—C9A139.6 (2)C14B—Ti1B—C11B56.5 (2)
C8A—Ti1A—C6A57.02 (18)C9B—Ti1B—C11B166.2 (2)
C7A—Ti1A—C6A33.96 (18)C12B—Ti1B—C10B56.4 (2)
C12A—Ti1A—C6A107.1 (2)C6B—Ti1B—C10B133.6 (2)
C13A—Ti1A—C6A102.6 (2)C5B—Ti1B—C10B124.2 (2)
C11A—Ti1A—C6A138.0 (2)C13B—Ti1B—C10B55.8 (2)
C14A—Ti1A—C6A128.4 (3)C7B—Ti1B—C10B160.0 (2)
C10A—Ti1A—C6A158.6 (2)C8B—Ti1B—C10B165.8 (2)
C9A—Ti1A—C6A56.02 (19)C14B—Ti1B—C10B34.0 (2)
C8A—Ti1A—C5A56.51 (18)C9B—Ti1B—C10B137.8 (2)
C7A—Ti1A—C5A56.03 (19)C11B—Ti1B—C10B33.5 (3)
C12A—Ti1A—C5A132.2 (2)C12B—Ti1B—Se1B137.90 (18)
C13A—Ti1A—C5A135.9 (2)C6B—Ti1B—Se1B135.08 (14)
C11A—Ti1A—C5A146.98 (19)C5B—Ti1B—Se1B106.65 (15)
C14A—Ti1A—C5A155.5 (2)C13B—Ti1B—Se1B126.75 (16)
C10A—Ti1A—C5A168.1 (2)C7B—Ti1B—Se1B117.36 (13)
C9A—Ti1A—C5A33.61 (18)C8B—Ti1B—Se1B84.17 (13)
C6A—Ti1A—C5A33.3 (2)C14B—Ti1B—Se1B93.11 (15)
C8A—Ti1A—Se1A106.20 (15)C9B—Ti1B—Se1B77.91 (13)
C7A—Ti1A—Se1A137.61 (16)C11B—Ti1B—Se1B105.91 (18)
C12A—Ti1A—Se1A122.8 (2)C10B—Ti1B—Se1B82.03 (17)
C13A—Ti1A—Se1A131.9 (2)C12B—Ti1B—Se2B96.65 (16)
C11A—Ti1A—Se1A88.65 (16)C6B—Ti1B—Se2B110.71 (15)
C14A—Ti1A—Se1A100.4 (2)C5B—Ti1B—Se2B136.30 (14)
C10A—Ti1A—Se1A76.75 (16)C13B—Ti1B—Se2B130.67 (15)
C9A—Ti1A—Se1A81.01 (13)C7B—Ti1B—Se2B79.89 (13)
C6A—Ti1A—Se1A124.48 (15)C8B—Ti1B—Se2B82.18 (12)
C5A—Ti1A—Se1A91.56 (14)C14B—Ti1B—Se2B132.70 (16)
C8A—Ti1A—Se2A138.58 (14)C9B—Ti1B—Se2B114.33 (14)
C7A—Ti1A—Se2A115.49 (14)C11B—Ti1B—Se2B79.40 (14)
C12A—Ti1A—Se2A129.1 (2)C10B—Ti1B—Se2B99.14 (18)
C13A—Ti1A—Se2A94.1 (2)Se1B—Ti1B—Se2B82.36 (3)
C11A—Ti1A—Se2A129.30 (15)C1B—Se1B—Ti1B92.52 (15)
C14A—Ti1A—Se2A77.17 (16)C2B—Se2B—Ti1B92.43 (14)
C10A—Ti1A—Se2A96.86 (16)C2B—C1B—S4B126.6 (4)
C9A—Ti1A—Se2A113.29 (13)C2B—C1B—Se1B122.1 (4)
C6A—Ti1A—Se2A84.27 (13)S4B—C1B—Se1B111.3 (3)
C5A—Ti1A—Se2A83.35 (12)C1B—C2B—S3B127.1 (4)
Se1A—Ti1A—Se2A82.56 (3)C1B—C2B—Se2B121.1 (3)
C1A—Se1A—Ti1A94.04 (15)S3B—C2B—Se2B111.8 (2)
C2A—Se2A—Ti1A93.65 (14)C2B—S3B—C3B'108.1 (7)
C2A—C1A—S4A126.8 (4)C2B—S3B—C3B99.8 (4)
C2A—C1A—Se1A120.6 (4)C1B—S4B—C4B106.8 (3)
S4A—C1A—Se1A112.6 (3)C1B—S4B—C4B'97.7 (5)
C1A—C2A—S3A127.5 (4)C4B—C3B—S3B112.4 (7)
C1A—C2A—Se2A122.5 (4)C4B—C3B—H3B1109.1
S3A—C2A—Se2A110.0 (3)S3B—C3B—H3B1109.1
C2A—S3A—C3A103.4 (2)C4B—C3B—H3B2109.1
C1A—S4A—C4A103.3 (3)S3B—C3B—H3B2109.1
C4A—C3A—S3A112.3 (4)H3B1—C3B—H3B2107.8
C4A—C3A—H3A2111 (3)C4B'—C3B'—S3B111.6 (13)
S3A—C3A—H3A2109 (3)C4B'—C3B'—H3B3109.3
C4A—C3A—H3A1113 (3)S3B—C3B'—H3B3109.3
S3A—C3A—H3A1105 (4)C4B'—C3B'—H3B4109.3
H3A2—C3A—H3A1106 (4)S3B—C3B'—H3B4109.3
C3A—C4A—S4A113.5 (4)H3B3—C3B'—H3B4108.0
C3A—C4A—H4A2105 (4)C3B—C4B—S4B111.9 (7)
S4A—C4A—H4A2109 (4)C3B—C4B—H4B1109.2
C3A—C4A—H4A1109 (4)S4B—C4B—H4B1109.2
S4A—C4A—H4A1112 (4)C3B—C4B—H4B2109.2
H4A2—C4A—H4A1107 (6)S4B—C4B—H4B2109.2
C6A—C5A—C9A108.4 (5)H4B1—C4B—H4B2107.9
C6A—C5A—Ti1A72.4 (3)C3B'—C4B'—S4B111.5 (11)
C9A—C5A—Ti1A71.9 (3)C3B'—C4B'—H4B3109.3
C6A—C5A—H5A126 (4)S4B—C4B'—H4B3109.3
C9A—C5A—H5A125 (4)C3B'—C4B'—H4B4109.3
Ti1A—C5A—H5A125 (4)S4B—C4B'—H4B4109.3
C5A—C6A—C7A108.1 (5)H4B3—C4B'—H4B4108.0
C5A—C6A—Ti1A74.3 (3)C8B—C7B—C6B108.0 (5)
C7A—C6A—Ti1A70.9 (3)C8B—C7B—Ti1B73.3 (3)
C5A—C6A—H6A123 (3)C6B—C7B—Ti1B72.2 (3)
C7A—C6A—H6A128 (3)C8B—C7B—H7B127 (4)
Ti1A—C6A—H6A119 (3)C6B—C7B—H7B125 (4)
C5A—C9A—C8A108.2 (5)Ti1B—C7B—H7B122 (4)
C5A—C9A—Ti1A74.5 (3)C7B—C6B—C5B108.0 (5)
C8A—C9A—Ti1A70.9 (3)C7B—C6B—Ti1B73.3 (3)
C5A—C9A—H9A122 (4)C5B—C6B—Ti1B72.6 (3)
C8A—C9A—H9A129 (4)C7B—C6B—H6B126 (5)
Ti1A—C9A—H9A124 (4)C5B—C6B—H6B126 (5)
C9A—C8A—C7A107.1 (5)Ti1B—C6B—H6B124 (5)
C9A—C8A—Ti1A74.9 (3)C9B—C5B—C6B107.5 (5)
C7A—C8A—Ti1A72.8 (3)C9B—C5B—Ti1B73.9 (3)
C9A—C8A—H8A128 (4)C6B—C5B—Ti1B72.4 (3)
C7A—C8A—H8A125 (4)C9B—C5B—H5B126 (3)
Ti1A—C8A—H8A118 (4)C6B—C5B—H5B126 (3)
C6A—C7A—C8A108.2 (5)Ti1B—C5B—H5B122 (3)
C6A—C7A—Ti1A75.1 (3)C7B—C8B—C9B108.6 (5)
C8A—C7A—Ti1A72.3 (3)C7B—C8B—Ti1B72.5 (3)
C6A—C7A—H7A126 (4)C9B—C8B—Ti1B73.2 (3)
C8A—C7A—H7A125 (4)C7B—C8B—H8B131 (4)
Ti1A—C7A—H7A123 (4)C9B—C8B—H8B121 (4)
C11A—C12A—C13A106.5 (6)Ti1B—C8B—H8B118 (4)
C11A—C12A—Ti1A73.6 (3)C8B—C9B—C5B107.9 (5)
C13A—C12A—Ti1A72.6 (3)C8B—C9B—Ti1B72.6 (3)
C11A—C12A—H12A126.8C5B—C9B—Ti1B71.6 (3)
C13A—C12A—H12A126.8C8B—C9B—H9B125 (3)
Ti1A—C12A—H12A119.0C5B—C9B—H9B127 (3)
C11A—C10A—C14A109.0 (6)Ti1B—C9B—H9B124 (3)
C11A—C10A—Ti1A72.6 (3)C13B—C14B—C10B107.0 (6)
C14A—C10A—Ti1A72.7 (4)C13B—C14B—Ti1B72.5 (3)
C11A—C10A—H10A132 (6)C10B—C14B—Ti1B74.0 (3)
C14A—C10A—H10A119 (6)C13B—C14B—H14B127 (4)
Ti1A—C10A—H10A123 (6)C10B—C14B—H14B126 (4)
C10A—C11A—C12A108.7 (6)Ti1B—C14B—H14B120 (4)
C10A—C11A—Ti1A74.4 (3)C10B—C11B—C12B107.7 (5)
C12A—C11A—Ti1A72.2 (3)C10B—C11B—Ti1B73.6 (3)
C10A—C11A—H11A127 (5)C12B—C11B—Ti1B70.9 (3)
C12A—C11A—H11A124 (5)C10B—C11B—H11B131 (5)
Ti1A—C11A—H11A120 (5)C12B—C11B—H11B121 (5)
C14A—C13A—C12A106.5 (6)Ti1B—C11B—H11B118 (5)
C14A—C13A—Ti1A73.9 (4)C13B—C12B—C11B107.4 (6)
C12A—C13A—Ti1A72.1 (4)C13B—C12B—Ti1B73.6 (3)
C14A—C13A—H13A126.7C11B—C12B—Ti1B74.9 (3)
C12A—C13A—H13A126.7C13B—C12B—H12B125 (5)
Ti1A—C13A—H13A119.2C11B—C12B—H12B127 (5)
C10A—C14A—C13A109.3 (6)Ti1B—C12B—H12B118 (5)
C10A—C14A—Ti1A74.0 (3)C14B—C13B—C12B109.3 (5)
C13A—C14A—Ti1A72.5 (4)C14B—C13B—Ti1B73.7 (3)
C10A—C14A—H14A126 (7)C12B—C13B—Ti1B72.1 (3)
C13A—C14A—H14A124 (7)C14B—C13B—H13B123 (4)
Ti1A—C14A—H14A123 (7)C12B—C13B—H13B127 (4)
C12B—Ti1B—C6B84.8 (2)Ti1B—C13B—H13B118 (4)
C12B—Ti1B—C5B102.7 (2)C11B—C10B—C14B108.6 (6)
C6B—Ti1B—C5B35.0 (2)C11B—C10B—Ti1B72.8 (3)
C12B—Ti1B—C13B34.3 (2)C14B—C10B—Ti1B71.9 (3)
C6B—Ti1B—C13B77.9 (2)C11B—C10B—H10B137 (5)
C5B—Ti1B—C13B78.37 (19)C14B—C10B—H10B114 (5)
C12B—Ti1B—C7B103.7 (2)Ti1B—C10B—H10B116 (5)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y+1/2, z1/2; (iii) x, y+1, z+1; (iv) x, y+2, z+1.

Experimental details

Crystal data
Chemical formula[Ti(C5H5)2(C4H4S2Se2)]
Mr452.18
Crystal system, space groupMonoclinic, P21/c
Temperature (K)180
a, b, c (Å)12.7474 (8), 10.9055 (10), 21.5888 (13)
β (°) 94.648 (7)
V3)2991.3 (4)
Z8
Radiation typeMo Kα
µ (mm1)5.70
Crystal size (mm)0.33 × 0.25 × 0.04
Data collection
DiffractometerStow Imaging Plate Diffraction System
diffractometer
Absorption correctionAnalytical
(see. N.W. Alcock (1970). Cryst. Computing, p271)
Tmin, Tmax0.341, 0.765
No. of measured, independent and
observed [I > 2σ(I)] reflections
26415, 5732, 4603
Rint0.055
(sin θ/λ)max1)0.619
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.097, 1.05
No. of reflections5732
No. of parameters449
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Selected interatomic distances (Å) top
H4B2···C7Bi2.827 (5)C1B···H3A12.89 (6)
H4B2···C6Bi2.790 (5)H3B3···S3Aiii2.921 (1)
H4B2···C5Bi2.823 (5)H3B4···C12Biv2.659 (6)
H4B2···C8Bi2.873 (5)H4B3···C6Bi2.754 (5)
H4B2···C9Bi2.8595 (5)H4B3···C5Bi2.806 (5)
H3B2···C6Bi2.900 (5)H4B4···C14Aii2.789 (8)
H4A2···C12Aii2.90 (8)H4B4···H14Aii2.3 (1)
Se1B···H4A13.05 (7)C4B'···C14Aii3.38 (2)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y+1/2, z1/2; (iii) x, y+1, z+1; (iv) x, y+2, z+1.
 

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