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The title compound, chloro­bis­[1,2-ethanediyl­bis­(di­phenyl­phos­phine)-P,P'](thio­carbonyl-C)­technetium benzene sol­vate, [TcCl(C46H42P4)(CS)]·C6H6, was obtained as one of two Tc-containing products isolated from the reaction between CS2 and the electron-deficient complex [TcCl(dppe)2], where dppe is 1,2-ethane­diyl­bis­(di­phenyl­phosphine). The structure exhibits an unusually short Tc-C distance [1.819 (6) Å], suggesting some multiple-bond character.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800019486/na6007sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800019486/na6007Isup2.hkl
Contains datablock I

CCDC reference: 155840

Key indicators

  • Single-crystal X-ray study
  • T = 203 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in main residue
  • R factor = 0.032
  • wR factor = 0.098
  • Data-to-parameter ratio = 19.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 29.00 From the CIF: _reflns_number_total 6069 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 6622 Completeness (_total/calc) 91.65% Alert C: < 95% complete PLAT_301 Alert C Main residue disorder ........................ 5.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

Two new compounds were prepared during an examination of the reactivity of the 16-electron complex [TcCl(dppe)2], where dppe is 1,2-ethanediylbis(diphenylphosphine) (Burrell, Kubas & Bryan, 1994). Both a dithioformate complex, [Tc(S2CH)(dppe)2] (Bryan et al., 2001) and a thiocarbonyl complex [TcCl(CS)(dppe)2] were formed. The latter, (I), is the topic of this paper and is the first reported example of a Tc–thiocarbonyl complex.

The structure can be solved in P1 with Z = 1, but a high degree of correlation is observed, and the Cl and CS ligands are disordered (50:50) superimposed on each other. There is an apparent inversion centre at Tc, strongly suggesting that the correct space group is P1. When solved in P1, only half of the molecule makes up the asymmetric unit, with the metal ion located at the crystallographic inversion centre. The chloride and thiocarbonyl ligands are modeled with equal occupancy factors (50:50) at the same site of ligation on Tc, but are assumed to be different on either side of the inversion centre, as illustrated in Fig. 1. The Tc—C bond length is apparently quite short at 1.819 (6) Å, and may indicate some level of multiple bonding, although this bond distance may be affected by the disorder. The only published example of a TcC is the closely related [TcCl(CCHPh)Cl(dppe)2] (Burrell, Bryan & Kubas, 1994), which is 1.861 (9) Å. For comparison, Tc—CO bond lengths typically range from 1.88 to 2.00 Å, with a mean value of 1.93 Å (Allen & Kennard, 1993). Otherwise, the title complex is structurally quite similar to the isoelectronic [ReCl(CO)(dppe)2] (da Silva et al., 1998).

Experimental top

[TcCl(dppe)2] (100 mg) was added to a benzene (50 ml) solution containing CS2 (0.2 ml) and triphenylphosphine (50 mg). This mixture was heated to reflux for 2 min and then allowed to cool. Hexane was added to the solution and then the mixture was allowed to stand. Over time, a mixture of orange and yellow crystals were deposited. The yellow crystals proved to be [TcCl(CS)(dppe)2]·C6H6.

Refinement top

All H atoms were placed in calculated positions, refined using a riding model, and given an isotropic displacement parameters equal to 1.2 times the equivalent isotropic displacement parameter of the atom to which they were attached.

Computing details top

Data collection: XSCANS; cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2000).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids. The benzene solvate and all H atoms have been omitted for clarity.
(I) top
Crystal data top
[TcCl(C46H42P4)(CS)]·C6H6Z = 1
Mr = 1053.3F(000) = 544
Triclinic, P1Dx = 1.41 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.3872 (10) ÅCell parameters from 25 reflections
b = 10.5518 (9) Åθ = 6.7–26.0°
c = 12.8953 (11) ŵ = 0.55 mm1
α = 67.185 (6)°T = 203 K
β = 72.620 (9)°Plate, yellow
γ = 83.849 (8)°0.58 × 0.51 × 0.15 mm
V = 1243.3 (2) Å3
Data collection top
Siemens P4
diffractometer
5372 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.012
Graphite monochromatorθmax = 29.0°, θmin = 3.3°
ω scansh = 113
Absorption correction: ψ scan
(SHELXTL-Plus; Siemens, 1990)
k = 1313
Tmin = 0.732, Tmax = 0.897l = 1717
7126 measured reflections3 standard reflections every 97 reflections
6069 independent reflections intensity decay: 1.2%
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters not refined
S = 1.24 w = 1/[σ2(Fo2) + (0.056P)2 + 0.0349P]
where P = (Fo2 + 2Fc2)/3
6069 reflections(Δ/σ)max = 0.001
313 parametersΔρmax = 0.74 e Å3
0 restraintsΔρmin = 0.92 e Å3
0 constraints
Crystal data top
[TcCl(C46H42P4)(CS)]·C6H6γ = 83.849 (8)°
Mr = 1053.3V = 1243.3 (2) Å3
Triclinic, P1Z = 1
a = 10.3872 (10) ÅMo Kα radiation
b = 10.5518 (9) ŵ = 0.55 mm1
c = 12.8953 (11) ÅT = 203 K
α = 67.185 (6)°0.58 × 0.51 × 0.15 mm
β = 72.620 (9)°
Data collection top
Siemens P4
diffractometer
5372 reflections with I > 2σ(I)
Absorption correction: ψ scan
(SHELXTL-Plus; Siemens, 1990)
Rint = 0.012
Tmin = 0.732, Tmax = 0.8973 standard reflections every 97 reflections
7126 measured reflections intensity decay: 1.2%
6069 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.098H-atom parameters not refined
S = 1.24Δρmax = 0.74 e Å3
6069 reflectionsΔρmin = 0.92 e Å3
313 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Tc0.500000.500000.500000.0173 (1)
Cl0.75417 (15)0.53209 (10)0.42117 (9)0.0187 (3)0.500
S0.82814 (19)0.54534 (14)0.38815 (14)0.0403 (5)0.500
P10.50547 (6)0.28557 (5)0.66006 (4)0.0238 (1)
P20.47604 (6)0.34126 (5)0.41108 (4)0.0234 (1)
C10.6819 (6)0.5223 (4)0.4388 (4)0.0217 (13)0.500
C20.3945 (2)0.1657 (2)0.65327 (18)0.0292 (6)
C30.4283 (3)0.1669 (2)0.52893 (19)0.0318 (7)
C110.6678 (2)0.1988 (2)0.65647 (18)0.0290 (6)
C120.7765 (3)0.2720 (2)0.64891 (19)0.0328 (7)
C130.9039 (3)0.2145 (3)0.6407 (2)0.0409 (8)
C140.9250 (3)0.0846 (3)0.6380 (2)0.0493 (9)
C150.8189 (3)0.0105 (3)0.6456 (2)0.0484 (9)
C160.6902 (3)0.0661 (2)0.6555 (2)0.0383 (8)
C210.4395 (2)0.2713 (2)0.81309 (17)0.0263 (6)
C220.4978 (3)0.1849 (2)0.90040 (19)0.0314 (7)
C230.4453 (3)0.1789 (3)1.0151 (2)0.0380 (7)
C240.3369 (3)0.2583 (3)1.0437 (2)0.0400 (8)
C250.2783 (3)0.3448 (3)0.9576 (2)0.0379 (8)
C260.3294 (2)0.3510 (2)0.84316 (18)0.0309 (7)
C310.3444 (2)0.3826 (2)0.33554 (18)0.0273 (6)
C320.2117 (3)0.3376 (3)0.3960 (2)0.0379 (8)
C330.1093 (3)0.3826 (3)0.3423 (3)0.0506 (10)
C340.1369 (3)0.4723 (3)0.2267 (3)0.0503 (10)
C350.2682 (3)0.5164 (3)0.1640 (2)0.0405 (8)
C360.3716 (3)0.4729 (2)0.2187 (2)0.0306 (7)
C410.6189 (2)0.2905 (2)0.31130 (18)0.0254 (6)
C420.7438 (3)0.2744 (2)0.3342 (2)0.0352 (8)
C430.8540 (3)0.2272 (3)0.2669 (3)0.0416 (8)
C440.8413 (3)0.1951 (3)0.1755 (2)0.0411 (8)
C450.7178 (3)0.2088 (3)0.1534 (2)0.0366 (7)
C460.6066 (2)0.2554 (2)0.22063 (19)0.0303 (6)
C40.0839 (3)0.0777 (3)0.9337 (2)0.0415 (8)
C50.0473 (3)0.1214 (3)0.9081 (2)0.0442 (8)
C60.1307 (3)0.0434 (3)0.9740 (2)0.0412 (8)
H2A0.405300.073500.707100.0350*
H2B0.301200.192000.677100.0350*
H3A0.350800.132700.520100.0380*
H3B0.502400.104500.518600.0380*
H120.763400.360400.649400.0390*
H130.975300.263800.637000.0490*
H141.010800.046900.631000.0590*
H150.833400.077400.644200.0580*
H160.618900.015000.661400.0460*
H220.571600.131500.881900.0380*
H230.483900.120601.072900.0460*
H240.302800.254001.120400.0480*
H250.205100.398600.976700.0450*
H260.289700.408900.785900.0370*
H320.191700.276500.473600.0460*
H330.021200.352200.384200.0610*
H340.067600.502900.191200.0600*
H350.287700.574900.085600.0490*
H360.459300.504400.176700.0370*
H420.753500.295500.395100.0420*
H430.936800.216900.283200.0500*
H440.915400.164800.129800.0490*
H450.708500.186700.092900.0440*
H460.523600.263300.205100.0360*
H40.139900.130000.888700.0500*
H50.079000.203600.846200.0530*
H60.218800.072700.956200.0490*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Tc0.0226 (1)0.0140 (1)0.0156 (1)0.0016 (1)0.0045 (1)0.0069 (1)
Cl0.0068 (5)0.0253 (5)0.0216 (5)0.0012 (4)0.0020 (4)0.0111 (4)
S0.0477 (10)0.0352 (7)0.0423 (8)0.0055 (7)0.0184 (7)0.0162 (6)
P10.0372 (3)0.0155 (2)0.0180 (2)0.0028 (2)0.0074 (2)0.0064 (2)
P20.0351 (3)0.0178 (2)0.0198 (2)0.0020 (2)0.0074 (2)0.0104 (2)
C10.025 (3)0.019 (2)0.0167 (18)0.0035 (18)0.0003 (18)0.0075 (14)
C20.0439 (13)0.0178 (10)0.0239 (10)0.0027 (9)0.0068 (9)0.0069 (8)
C30.0531 (15)0.0175 (10)0.0276 (10)0.0014 (9)0.0112 (10)0.0110 (8)
C110.0421 (13)0.0206 (10)0.0205 (9)0.0084 (9)0.0079 (9)0.0065 (7)
C120.0430 (13)0.0277 (11)0.0244 (10)0.0096 (9)0.0088 (9)0.0090 (8)
C130.0399 (14)0.0423 (14)0.0330 (12)0.0097 (11)0.0074 (10)0.0108 (10)
C140.0478 (16)0.0432 (15)0.0417 (14)0.0215 (13)0.0066 (12)0.0099 (12)
C150.0648 (19)0.0289 (13)0.0430 (14)0.0195 (12)0.0105 (13)0.0129 (11)
C160.0571 (16)0.0217 (11)0.0336 (12)0.0082 (10)0.0141 (11)0.0088 (9)
C210.0405 (12)0.0190 (9)0.0192 (9)0.0016 (8)0.0074 (8)0.0071 (7)
C220.0449 (13)0.0241 (11)0.0245 (10)0.0004 (9)0.0110 (9)0.0073 (8)
C230.0600 (16)0.0319 (12)0.0233 (10)0.0052 (11)0.0150 (10)0.0077 (9)
C240.0627 (17)0.0359 (13)0.0217 (10)0.0076 (12)0.0062 (11)0.0131 (9)
C250.0508 (15)0.0346 (13)0.0276 (11)0.0001 (11)0.0030 (10)0.0167 (9)
C260.0454 (13)0.0245 (11)0.0227 (10)0.0007 (9)0.0082 (9)0.0097 (8)
C310.0369 (12)0.0248 (10)0.0274 (10)0.0031 (9)0.0115 (9)0.0163 (8)
C320.0433 (14)0.0415 (14)0.0346 (12)0.0055 (11)0.0100 (10)0.0194 (10)
C330.0409 (15)0.069 (2)0.0515 (16)0.0104 (14)0.0143 (13)0.0289 (15)
C340.0490 (17)0.0590 (18)0.0609 (18)0.0065 (14)0.0316 (14)0.0310 (15)
C350.0582 (17)0.0338 (13)0.0401 (13)0.0075 (11)0.0256 (12)0.0181 (10)
C360.0419 (13)0.0232 (10)0.0316 (11)0.0027 (9)0.0126 (9)0.0142 (8)
C410.0363 (11)0.0181 (9)0.0240 (9)0.0038 (8)0.0080 (8)0.0115 (7)
C420.0445 (14)0.0334 (13)0.0411 (13)0.0114 (10)0.0201 (11)0.0249 (10)
C430.0411 (14)0.0410 (14)0.0580 (16)0.0133 (11)0.0219 (12)0.0319 (13)
C440.0425 (14)0.0404 (14)0.0464 (14)0.0100 (11)0.0073 (11)0.0289 (12)
C450.0480 (14)0.0389 (13)0.0300 (11)0.0087 (11)0.0107 (10)0.0226 (10)
C460.0375 (12)0.0303 (11)0.0285 (10)0.0050 (9)0.0107 (9)0.0169 (9)
C40.0409 (14)0.0519 (16)0.0345 (12)0.0062 (12)0.0082 (11)0.0223 (11)
C50.0479 (15)0.0381 (14)0.0352 (13)0.0087 (11)0.0064 (11)0.0127 (11)
C60.0330 (13)0.0497 (16)0.0444 (14)0.0056 (11)0.0010 (11)0.0287 (12)
Geometric parameters (Å, º) top
Tc—Cl2.538 (2)C43—C441.390 (4)
Tc—P12.4091 (6)C44—C451.376 (5)
Tc—P22.4355 (6)C45—C461.392 (4)
Tc—C11.819 (6)C2—H2A0.97
S—C11.468 (7)C2—H2B0.97
P1—C21.842 (2)C3—H3A0.97
P1—C111.827 (2)C3—H3B0.97
P1—C211.836 (2)C12—H120.93
P2—C31.875 (2)C13—H130.93
P2—C311.830 (2)C14—H140.93
P2—C411.835 (2)C15—H150.93
C2—C31.531 (3)C16—H160.93
C11—C121.394 (4)C22—H220.93
C11—C161.399 (3)C23—H230.93
C12—C131.387 (4)C24—H240.93
C13—C141.377 (5)C25—H250.93
C14—C151.377 (5)C26—H260.93
C15—C161.391 (4)C32—H320.93
C21—C221.399 (3)C33—H330.93
C21—C261.395 (3)C34—H340.93
C22—C231.394 (3)C35—H350.93
C23—C241.377 (5)C36—H360.93
C24—C251.391 (4)C42—H420.93
C25—C261.389 (3)C43—H430.93
C31—C321.394 (4)C44—H440.93
C31—C361.396 (3)C45—H450.93
C32—C331.383 (5)C46—H460.93
C33—C341.382 (5)C4—C51.388 (5)
C34—C351.384 (5)C4—C6i1.376 (4)
C35—C361.399 (4)C5—C61.376 (4)
C41—C421.394 (4)C4—H40.93
C41—C461.398 (3)C5—H50.93
C42—C431.390 (4)C6—H60.93
Cl—Tc—P195.43 (3)C3—C2—H2B109.47
Cl—Tc—P298.00 (3)H2A—C2—H2B108.14
Cl—Tc—C1ii178.0 (2)P2—C3—H3A108.86
P1—Tc—P280.67 (2)P2—C3—H3B108.80
P1—Tc—C196.3 (2)C2—C3—H3A108.79
P2—Tc—C196.3 (2)C2—C3—H3B108.76
Tc—P1—C2106.22 (7)H3A—C3—H3B107.71
Tc—P1—C11117.08 (7)C11—C12—H12119.59
Tc—P1—C21121.32 (7)C13—C12—H12119.65
C2—P1—C11105.0 (1)C12—C13—H13119.94
C2—P1—C21102.0 (1)C14—C13—H13119.88
C11—P1—C21103.2 (1)C13—C14—H14120.08
Tc—P2—C3109.02 (7)C15—C14—H14119.97
Tc—P2—C31115.81 (8)C14—C15—H15119.73
Tc—P2—C41122.67 (8)C16—C15—H15119.78
C3—P2—C31104.9 (1)C11—C16—H16119.91
C3—P2—C4198.4 (1)C15—C16—H16119.95
C31—P2—C41103.5 (1)C21—C22—H22120.01
Tc—C1—S178.1 (3)C23—C22—H22119.97
P1—C2—C3110.8 (2)C22—C23—H23119.62
P2—C3—C2113.7 (2)C24—C23—H23119.69
P1—C11—C12117.7 (2)C23—C24—H24120.11
P1—C11—C16123.7 (2)C25—C24—H24120.08
C12—C11—C16118.5 (2)C24—C25—H25119.97
C11—C12—C13120.8 (2)C26—C25—H25120.08
C12—C13—C14120.2 (3)C21—C26—H26119.65
C13—C14—C15119.9 (3)C25—C26—H26119.62
C14—C15—C16120.5 (3)C31—C32—H32119.53
C11—C16—C15120.1 (3)C33—C32—H32119.48
P1—C21—C22122.1 (2)C32—C33—H33119.83
P1—C21—C26119.1 (2)C34—C33—H33119.69
C22—C21—C26118.8 (2)C33—C34—H34120.15
C21—C22—C23120.0 (3)C35—C34—H34120.16
C22—C23—C24120.7 (3)C34—C35—H35120.05
C23—C24—C25119.8 (2)C36—C35—H35120.01
C24—C25—C26120.0 (3)C31—C36—H36119.72
C21—C26—C25120.7 (2)C35—C36—H36119.61
P2—C31—C32121.1 (2)C41—C42—H42119.65
P2—C31—C36120.3 (2)C43—C42—H42119.67
C32—C31—C36118.2 (2)C42—C43—H43119.76
C31—C32—C33121.0 (2)C44—C43—H43119.80
C32—C33—C34120.5 (3)C43—C44—H44120.38
C33—C34—C35119.7 (3)C45—C44—H44120.38
C34—C35—C36119.9 (2)C44—C45—H45119.63
C31—C36—C35120.7 (3)C46—C45—H45119.59
P2—C41—C42117.7 (2)C41—C46—H46119.79
P2—C41—C46123.6 (2)C45—C46—H46119.78
C42—C41—C46118.4 (2)C5—C4—C6i119.7 (3)
C41—C42—C43120.7 (2)C4—C5—C6120.2 (3)
C42—C43—C44120.4 (3)C4i—C6—C5120.1 (3)
C43—C44—C45119.2 (3)C5—C4—H4120.15
C44—C45—C46120.8 (2)C6i—C4—H4120.15
C41—C46—C45120.4 (2)C4—C5—H5119.92
P1—C2—H2A109.49C6—C5—H5119.88
P1—C2—H2B109.46C5—C6—H6119.94
C3—C2—H2A109.48C4i—C6—H6119.96
P1—Tc—Cl—C1114 (4)C11—P1—C21—C2212.0 (2)
P2—Tc—Cl—C133 (4)C2—P1—C21—C2296.8 (2)
P1ii—Tc—Cl—C166 (4)C41—P2—C3—C2137.5 (2)
P2ii—Tc—Cl—C1147 (4)C31—P2—C41—C42169.48 (18)
Cl—Tc—P1—C2130.30 (8)Tc—P2—C41—C4236.2 (2)
Cl—Tc—P1—C1113.46 (9)Tc—P2—C3—C28.6 (2)
Cl—Tc—P1—C21114.16 (9)C31—P2—C3—C2116.1 (2)
P2—Tc—P1—C233.05 (8)C41—P2—C31—C32136.0 (2)
P2—Tc—P1—C1183.79 (8)Tc—P2—C31—C3286.9 (2)
P2—Tc—P1—C21148.60 (9)C3—P2—C31—C3233.3 (2)
C1—Tc—P1—C2128.42 (17)C3—P2—C41—C4282.9 (2)
C1—Tc—P1—C1111.59 (17)Tc—P2—C31—C3685.84 (19)
C1—Tc—P1—C21116.03 (17)C3—P2—C31—C36153.94 (19)
Clii—Tc—P1—C249.70 (8)C3—P2—C41—C4691.2 (2)
Clii—Tc—P1—C11166.54 (9)C41—P2—C31—C3651.3 (2)
Clii—Tc—P1—C2165.84 (9)Tc—P2—C41—C46149.75 (16)
P2ii—Tc—P1—C2146.95 (8)C31—P2—C41—C4616.5 (2)
P2ii—Tc—P1—C1196.21 (8)P1—C2—C3—P237.1 (2)
P2ii—Tc—P1—C2131.40 (9)P1—C11—C12—C13177.19 (17)
C1ii—Tc—P1—C251.58 (17)C12—C11—C16—C150.8 (3)
C1ii—Tc—P1—C11168.41 (17)C16—C11—C12—C130.0 (3)
C1ii—Tc—P1—C2163.97 (17)P1—C11—C16—C15176.12 (17)
Cl—Tc—P2—C3110.03 (11)C11—C12—C13—C141.1 (3)
Cl—Tc—P2—C31132.00 (8)C12—C13—C14—C151.2 (3)
Cl—Tc—P2—C413.85 (9)C13—C14—C15—C160.3 (3)
P1—Tc—P2—C315.79 (11)C14—C15—C16—C110.7 (3)
P1—Tc—P2—C31133.76 (8)C26—C21—C22—C230.4 (4)
P1—Tc—P2—C4198.08 (9)P1—C21—C26—C25178.8 (2)
C1—Tc—P2—C3111.14 (18)P1—C21—C22—C23179.1 (2)
C1—Tc—P2—C31130.89 (17)C22—C21—C26—C250.1 (4)
C1—Tc—P2—C412.74 (17)C21—C22—C23—C240.6 (4)
Clii—Tc—P2—C369.97 (11)C22—C23—C24—C250.5 (5)
Clii—Tc—P2—C3148.00 (8)C23—C24—C25—C260.1 (5)
Clii—Tc—P2—C41176.15 (9)C24—C25—C26—C210.1 (4)
P1ii—Tc—P2—C3164.21 (11)P2—C31—C32—C33172.0 (2)
P1ii—Tc—P2—C3146.24 (8)P2—C31—C36—C35173.2 (2)
P1ii—Tc—P2—C4181.92 (9)C32—C31—C36—C350.2 (4)
C1ii—Tc—P2—C368.86 (18)C36—C31—C32—C330.9 (4)
C1ii—Tc—P2—C3149.11 (17)C31—C32—C33—C340.7 (5)
C1ii—Tc—P2—C41177.26 (18)C32—C33—C34—C350.6 (5)
Tc—Cl—C1—S164 (3)C33—C34—C35—C361.7 (5)
Tc—P1—C2—C349.24 (17)C34—C35—C36—C311.5 (4)
C11—P1—C2—C375.43 (18)C46—C41—C42—C431.3 (4)
C21—P1—C2—C3177.23 (16)P2—C41—C42—C43175.6 (2)
Tc—P1—C11—C16120.65 (17)C42—C41—C46—C451.6 (3)
C2—P1—C11—C163.2 (2)P2—C41—C46—C45175.57 (19)
C21—P1—C11—C16103.4 (2)C41—C42—C43—C440.1 (4)
Tc—P1—C21—C22145.57 (18)C42—C43—C44—C450.9 (5)
Tc—P1—C11—C1256.33 (18)C43—C44—C45—C460.6 (4)
C2—P1—C11—C12173.83 (17)C44—C45—C46—C410.6 (4)
C21—P1—C11—C1279.66 (18)C6i—C4—C5—C60.6 (4)
Tc—P1—C21—C2633.1 (2)C5—C4—C6i—C5i0.6 (4)
C2—P1—C21—C2684.51 (19)C4—C5—C6—C4i0.6 (4)
C11—P1—C21—C26166.73 (18)
Symmetry codes: (i) x, y, z+2; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2B···Clii0.97022.76193.306 (3)116.15
C2—H2B···Sii0.97022.87463.591 (3)131.41
C12—H12···Cl0.93032.81953.198 (3)105.65
C26—H26···Clii0.93092.66503.489 (2)147.88
C26—H26···Sii0.93092.72823.574 (3)151.50
C33—H33···Siii0.93032.70573.242 (4)117.47
C42—H42···Cl0.92962.64603.341 (3)132.09
C42—H42···S0.92962.78793.445 (3)128.57
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x1, y, z.

Experimental details

Crystal data
Chemical formula[TcCl(C46H42P4)(CS)]·C6H6
Mr1053.3
Crystal system, space groupTriclinic, P1
Temperature (K)203
a, b, c (Å)10.3872 (10), 10.5518 (9), 12.8953 (11)
α, β, γ (°)67.185 (6), 72.620 (9), 83.849 (8)
V3)1243.3 (2)
Z1
Radiation typeMo Kα
µ (mm1)0.55
Crystal size (mm)0.58 × 0.51 × 0.15
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionψ scan
(SHELXTL-Plus; Siemens, 1990)
Tmin, Tmax0.732, 0.897
No. of measured, independent and
observed [I > 2σ(I)] reflections
7126, 6069, 5372
Rint0.012
(sin θ/λ)max1)0.682
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.098, 1.24
No. of reflections6069
No. of parameters313
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.74, 0.92

Computer programs: XSCANS, SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2000).

Selected geometric parameters (Å, º) top
Tc—Cl2.538 (2)Tc—C11.819 (6)
Tc—P12.4091 (6)S—C11.468 (7)
Tc—P22.4355 (6)
Cl—Tc—P195.43 (3)P1—Tc—C196.3 (2)
Cl—Tc—P298.00 (3)P2—Tc—C196.3 (2)
Cl—Tc—C1i178.0 (2)Tc—C1—S178.1 (3)
P1—Tc—P280.67 (2)P1—C11—C16123.7 (2)
Symmetry code: (i) x+1, y+1, z+1.
 

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