[TcCl(CS)(dppe)2]·C6H6

Bryan, J.C.; Burrell, A.K.; Kubas, G.J.

doi:10.1107/S1600536800019486

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[TcCl(CS)(dppe)₂]·C₆H₆

J. C. Bryan, A. K. Burrell and G. J. Kubas

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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800019486/na6007sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536800019486/na6007Isup2.hkl Contains datablock I

CCDC reference: 155840

checkCIF report

Key indicators

Single-crystal X-ray study
T = 203 K
Mean (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


 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 Tc═C 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.

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

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)]·C₆H₆	Z = 1
M_r = 1053.3	F(000) = 544
Triclinic, P1	D_x = 1.41 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.3872 (10) Å	Cell parameters from 25 reflections
b = 10.5518 (9) Å	θ = 6.7–26.0°
c = 12.8953 (11) Å	µ = 0.55 mm⁻¹
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 tube	R_int = 0.012
Graphite monochromator	θ_max = 29.0°, θ_min = 3.3°
ω scans	h = −1→13
Absorption correction: ψ scan (SHELXTL-Plus; Siemens, 1990)	k = −13→13
T_min = 0.732, T_max = 0.897	l = −17→17
7126 measured reflections	3 standard reflections every 97 reflections
6069 independent reflections	intensity decay: 1.2%

Refinement top

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters not refined
S = 1.24	w = 1/[σ²(F_o²) + (0.056P)² + 0.0349P] where P = (F_o² + 2F_c²)/3
6069 reflections	(Δ/σ)_max = 0.001
313 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −0.92 e Å⁻³
0 constraints

Crystal data top

[TcCl(C₄₆H₄₂P₄)(CS)]·C₆H₆	γ = 83.849 (8)°
M_r = 1053.3	V = 1243.3 (2) Å³
Triclinic, P1	Z = 1
a = 10.3872 (10) Å	Mo Kα radiation
b = 10.5518 (9) Å	µ = 0.55 mm⁻¹
c = 12.8953 (11) Å	T = 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)	R_int = 0.012
T_min = 0.732, T_max = 0.897	3 standard reflections every 97 reflections
7126 measured reflections	intensity decay: 1.2%
6069 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.098	H-atom parameters not refined
S = 1.24	Δρ_max = 0.74 e Å⁻³
6069 reflections	Δρ_min = −0.92 e Å⁻³
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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Tc	0.50000	0.50000	0.50000	0.0173 (1)
Cl	0.75417 (15)	0.53209 (10)	0.42117 (9)	0.0187 (3)	0.500
S	0.82814 (19)	0.54534 (14)	0.38815 (14)	0.0403 (5)	0.500
P1	0.50547 (6)	0.28557 (5)	0.66006 (4)	0.0238 (1)
P2	0.47604 (6)	0.34126 (5)	0.41108 (4)	0.0234 (1)
C1	0.6819 (6)	0.5223 (4)	0.4388 (4)	0.0217 (13)	0.500
C2	0.3945 (2)	0.1657 (2)	0.65327 (18)	0.0292 (6)
C3	0.4283 (3)	0.1669 (2)	0.52893 (19)	0.0318 (7)
C11	0.6678 (2)	0.1988 (2)	0.65647 (18)	0.0290 (6)
C12	0.7765 (3)	0.2720 (2)	0.64891 (19)	0.0328 (7)
C13	0.9039 (3)	0.2145 (3)	0.6407 (2)	0.0409 (8)
C14	0.9250 (3)	0.0846 (3)	0.6380 (2)	0.0493 (9)
C15	0.8189 (3)	0.0105 (3)	0.6456 (2)	0.0484 (9)
C16	0.6902 (3)	0.0661 (2)	0.6555 (2)	0.0383 (8)
C21	0.4395 (2)	0.2713 (2)	0.81309 (17)	0.0263 (6)
C22	0.4978 (3)	0.1849 (2)	0.90040 (19)	0.0314 (7)
C23	0.4453 (3)	0.1789 (3)	1.0151 (2)	0.0380 (7)
C24	0.3369 (3)	0.2583 (3)	1.0437 (2)	0.0400 (8)
C25	0.2783 (3)	0.3448 (3)	0.9576 (2)	0.0379 (8)
C26	0.3294 (2)	0.3510 (2)	0.84316 (18)	0.0309 (7)
C31	0.3444 (2)	0.3826 (2)	0.33554 (18)	0.0273 (6)
C32	0.2117 (3)	0.3376 (3)	0.3960 (2)	0.0379 (8)
C33	0.1093 (3)	0.3826 (3)	0.3423 (3)	0.0506 (10)
C34	0.1369 (3)	0.4723 (3)	0.2267 (3)	0.0503 (10)
C35	0.2682 (3)	0.5164 (3)	0.1640 (2)	0.0405 (8)
C36	0.3716 (3)	0.4729 (2)	0.2187 (2)	0.0306 (7)
C41	0.6189 (2)	0.2905 (2)	0.31130 (18)	0.0254 (6)
C42	0.7438 (3)	0.2744 (2)	0.3342 (2)	0.0352 (8)
C43	0.8540 (3)	0.2272 (3)	0.2669 (3)	0.0416 (8)
C44	0.8413 (3)	0.1951 (3)	0.1755 (2)	0.0411 (8)
C45	0.7178 (3)	0.2088 (3)	0.1534 (2)	0.0366 (7)
C46	0.6066 (2)	0.2554 (2)	0.22063 (19)	0.0303 (6)
C4	−0.0839 (3)	0.0777 (3)	0.9337 (2)	0.0415 (8)
C5	0.0473 (3)	0.1214 (3)	0.9081 (2)	0.0442 (8)
C6	0.1307 (3)	0.0434 (3)	0.9740 (2)	0.0412 (8)
H2A	0.40530	0.07350	0.70710	0.0350*
H2B	0.30120	0.19200	0.67710	0.0350*
H3A	0.35080	0.13270	0.52010	0.0380*
H3B	0.50240	0.10450	0.51860	0.0380*
H12	0.76340	0.36040	0.64940	0.0390*
H13	0.97530	0.26380	0.63700	0.0490*
H14	1.01080	0.04690	0.63100	0.0590*
H15	0.83340	−0.07740	0.64420	0.0580*
H16	0.61890	0.01500	0.66140	0.0460*
H22	0.57160	0.13150	0.88190	0.0380*
H23	0.48390	0.12060	1.07290	0.0460*
H24	0.30280	0.25400	1.12040	0.0480*
H25	0.20510	0.39860	0.97670	0.0450*
H26	0.28970	0.40890	0.78590	0.0370*
H32	0.19170	0.27650	0.47360	0.0460*
H33	0.02120	0.35220	0.38420	0.0610*
H34	0.06760	0.50290	0.19120	0.0600*
H35	0.28770	0.57490	0.08560	0.0490*
H36	0.45930	0.50440	0.17670	0.0370*
H42	0.75350	0.29550	0.39510	0.0420*
H43	0.93680	0.21690	0.28320	0.0500*
H44	0.91540	0.16480	0.12980	0.0490*
H45	0.70850	0.18670	0.09290	0.0440*
H46	0.52360	0.26330	0.20510	0.0360*
H4	−0.13990	0.13000	0.88870	0.0500*
H5	0.07900	0.20360	0.84620	0.0530*
H6	0.21880	0.07270	0.95620	0.0490*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tc	0.0226 (1)	0.0140 (1)	0.0156 (1)	0.0016 (1)	−0.0045 (1)	−0.0069 (1)
Cl	0.0068 (5)	0.0253 (5)	0.0216 (5)	0.0012 (4)	0.0020 (4)	−0.0111 (4)
S	0.0477 (10)	0.0352 (7)	0.0423 (8)	0.0055 (7)	−0.0184 (7)	−0.0162 (6)
P1	0.0372 (3)	0.0155 (2)	0.0180 (2)	0.0028 (2)	−0.0074 (2)	−0.0064 (2)
P2	0.0351 (3)	0.0178 (2)	0.0198 (2)	0.0020 (2)	−0.0074 (2)	−0.0104 (2)
C1	0.025 (3)	0.019 (2)	0.0167 (18)	0.0035 (18)	0.0003 (18)	−0.0075 (14)
C2	0.0439 (13)	0.0178 (10)	0.0239 (10)	−0.0027 (9)	−0.0068 (9)	−0.0069 (8)
C3	0.0531 (15)	0.0175 (10)	0.0276 (10)	−0.0014 (9)	−0.0112 (10)	−0.0110 (8)
C11	0.0421 (13)	0.0206 (10)	0.0205 (9)	0.0084 (9)	−0.0079 (9)	−0.0065 (7)
C12	0.0430 (13)	0.0277 (11)	0.0244 (10)	0.0096 (9)	−0.0088 (9)	−0.0090 (8)
C13	0.0399 (14)	0.0423 (14)	0.0330 (12)	0.0097 (11)	−0.0074 (10)	−0.0108 (10)
C14	0.0478 (16)	0.0432 (15)	0.0417 (14)	0.0215 (13)	−0.0066 (12)	−0.0099 (12)
C15	0.0648 (19)	0.0289 (13)	0.0430 (14)	0.0195 (12)	−0.0105 (13)	−0.0129 (11)
C16	0.0571 (16)	0.0217 (11)	0.0336 (12)	0.0082 (10)	−0.0141 (11)	−0.0088 (9)
C21	0.0405 (12)	0.0190 (9)	0.0192 (9)	−0.0016 (8)	−0.0074 (8)	−0.0071 (7)
C22	0.0449 (13)	0.0241 (11)	0.0245 (10)	−0.0004 (9)	−0.0110 (9)	−0.0073 (8)
C23	0.0600 (16)	0.0319 (12)	0.0233 (10)	−0.0052 (11)	−0.0150 (10)	−0.0077 (9)
C24	0.0627 (17)	0.0359 (13)	0.0217 (10)	−0.0076 (12)	−0.0062 (11)	−0.0131 (9)
C25	0.0508 (15)	0.0346 (13)	0.0276 (11)	−0.0001 (11)	−0.0030 (10)	−0.0167 (9)
C26	0.0454 (13)	0.0245 (11)	0.0227 (10)	0.0007 (9)	−0.0082 (9)	−0.0097 (8)
C31	0.0369 (12)	0.0248 (10)	0.0274 (10)	0.0031 (9)	−0.0115 (9)	−0.0163 (8)
C32	0.0433 (14)	0.0415 (14)	0.0346 (12)	−0.0055 (11)	−0.0100 (10)	−0.0194 (10)
C33	0.0409 (15)	0.069 (2)	0.0515 (16)	−0.0104 (14)	−0.0143 (13)	−0.0289 (15)
C34	0.0490 (17)	0.0590 (18)	0.0609 (18)	0.0065 (14)	−0.0316 (14)	−0.0310 (15)
C35	0.0582 (17)	0.0338 (13)	0.0401 (13)	0.0075 (11)	−0.0256 (12)	−0.0181 (10)
C36	0.0419 (13)	0.0232 (10)	0.0316 (11)	0.0027 (9)	−0.0126 (9)	−0.0142 (8)
C41	0.0363 (11)	0.0181 (9)	0.0240 (9)	0.0038 (8)	−0.0080 (8)	−0.0115 (7)
C42	0.0445 (14)	0.0334 (13)	0.0411 (13)	0.0114 (10)	−0.0201 (11)	−0.0249 (10)
C43	0.0411 (14)	0.0410 (14)	0.0580 (16)	0.0133 (11)	−0.0219 (12)	−0.0319 (13)
C44	0.0425 (14)	0.0404 (14)	0.0464 (14)	0.0100 (11)	−0.0073 (11)	−0.0289 (12)
C45	0.0480 (14)	0.0389 (13)	0.0300 (11)	0.0087 (11)	−0.0107 (10)	−0.0226 (10)
C46	0.0375 (12)	0.0303 (11)	0.0285 (10)	0.0050 (9)	−0.0107 (9)	−0.0169 (9)
C4	0.0409 (14)	0.0519 (16)	0.0345 (12)	0.0062 (12)	−0.0082 (11)	−0.0223 (11)
C5	0.0479 (15)	0.0381 (14)	0.0352 (13)	−0.0087 (11)	0.0064 (11)	−0.0127 (11)
C6	0.0330 (13)	0.0497 (16)	0.0444 (14)	−0.0056 (11)	0.0010 (11)	−0.0287 (12)

Geometric parameters (Å, º) top

Tc—Cl	2.538 (2)	C43—C44	1.390 (4)
Tc—P1	2.4091 (6)	C44—C45	1.376 (5)
Tc—P2	2.4355 (6)	C45—C46	1.392 (4)
Tc—C1	1.819 (6)	C2—H2A	0.97
S—C1	1.468 (7)	C2—H2B	0.97
P1—C2	1.842 (2)	C3—H3A	0.97
P1—C11	1.827 (2)	C3—H3B	0.97
P1—C21	1.836 (2)	C12—H12	0.93
P2—C3	1.875 (2)	C13—H13	0.93
P2—C31	1.830 (2)	C14—H14	0.93
P2—C41	1.835 (2)	C15—H15	0.93
C2—C3	1.531 (3)	C16—H16	0.93
C11—C12	1.394 (4)	C22—H22	0.93
C11—C16	1.399 (3)	C23—H23	0.93
C12—C13	1.387 (4)	C24—H24	0.93
C13—C14	1.377 (5)	C25—H25	0.93
C14—C15	1.377 (5)	C26—H26	0.93
C15—C16	1.391 (4)	C32—H32	0.93
C21—C22	1.399 (3)	C33—H33	0.93
C21—C26	1.395 (3)	C34—H34	0.93
C22—C23	1.394 (3)	C35—H35	0.93
C23—C24	1.377 (5)	C36—H36	0.93
C24—C25	1.391 (4)	C42—H42	0.93
C25—C26	1.389 (3)	C43—H43	0.93
C31—C32	1.394 (4)	C44—H44	0.93
C31—C36	1.396 (3)	C45—H45	0.93
C32—C33	1.383 (5)	C46—H46	0.93
C33—C34	1.382 (5)	C4—C5	1.388 (5)
C34—C35	1.384 (5)	C4—C6ⁱ	1.376 (4)
C35—C36	1.399 (4)	C5—C6	1.376 (4)
C41—C42	1.394 (4)	C4—H4	0.93
C41—C46	1.398 (3)	C5—H5	0.93
C42—C43	1.390 (4)	C6—H6	0.93

Cl—Tc—P1	95.43 (3)	C3—C2—H2B	109.47
Cl—Tc—P2	98.00 (3)	H2A—C2—H2B	108.14
Cl—Tc—C1ⁱⁱ	178.0 (2)	P2—C3—H3A	108.86
P1—Tc—P2	80.67 (2)	P2—C3—H3B	108.80
P1—Tc—C1	96.3 (2)	C2—C3—H3A	108.79
P2—Tc—C1	96.3 (2)	C2—C3—H3B	108.76
Tc—P1—C2	106.22 (7)	H3A—C3—H3B	107.71
Tc—P1—C11	117.08 (7)	C11—C12—H12	119.59
Tc—P1—C21	121.32 (7)	C13—C12—H12	119.65
C2—P1—C11	105.0 (1)	C12—C13—H13	119.94
C2—P1—C21	102.0 (1)	C14—C13—H13	119.88
C11—P1—C21	103.2 (1)	C13—C14—H14	120.08
Tc—P2—C3	109.02 (7)	C15—C14—H14	119.97
Tc—P2—C31	115.81 (8)	C14—C15—H15	119.73
Tc—P2—C41	122.67 (8)	C16—C15—H15	119.78
C3—P2—C31	104.9 (1)	C11—C16—H16	119.91
C3—P2—C41	98.4 (1)	C15—C16—H16	119.95
C31—P2—C41	103.5 (1)	C21—C22—H22	120.01
Tc—C1—S	178.1 (3)	C23—C22—H22	119.97
P1—C2—C3	110.8 (2)	C22—C23—H23	119.62
P2—C3—C2	113.7 (2)	C24—C23—H23	119.69
P1—C11—C12	117.7 (2)	C23—C24—H24	120.11
P1—C11—C16	123.7 (2)	C25—C24—H24	120.08
C12—C11—C16	118.5 (2)	C24—C25—H25	119.97
C11—C12—C13	120.8 (2)	C26—C25—H25	120.08
C12—C13—C14	120.2 (3)	C21—C26—H26	119.65
C13—C14—C15	119.9 (3)	C25—C26—H26	119.62
C14—C15—C16	120.5 (3)	C31—C32—H32	119.53
C11—C16—C15	120.1 (3)	C33—C32—H32	119.48
P1—C21—C22	122.1 (2)	C32—C33—H33	119.83
P1—C21—C26	119.1 (2)	C34—C33—H33	119.69
C22—C21—C26	118.8 (2)	C33—C34—H34	120.15
C21—C22—C23	120.0 (3)	C35—C34—H34	120.16
C22—C23—C24	120.7 (3)	C34—C35—H35	120.05
C23—C24—C25	119.8 (2)	C36—C35—H35	120.01
C24—C25—C26	120.0 (3)	C31—C36—H36	119.72
C21—C26—C25	120.7 (2)	C35—C36—H36	119.61
P2—C31—C32	121.1 (2)	C41—C42—H42	119.65
P2—C31—C36	120.3 (2)	C43—C42—H42	119.67
C32—C31—C36	118.2 (2)	C42—C43—H43	119.76
C31—C32—C33	121.0 (2)	C44—C43—H43	119.80
C32—C33—C34	120.5 (3)	C43—C44—H44	120.38
C33—C34—C35	119.7 (3)	C45—C44—H44	120.38
C34—C35—C36	119.9 (2)	C44—C45—H45	119.63
C31—C36—C35	120.7 (3)	C46—C45—H45	119.59
P2—C41—C42	117.7 (2)	C41—C46—H46	119.79
P2—C41—C46	123.6 (2)	C45—C46—H46	119.78
C42—C41—C46	118.4 (2)	C5—C4—C6ⁱ	119.7 (3)
C41—C42—C43	120.7 (2)	C4—C5—C6	120.2 (3)
C42—C43—C44	120.4 (3)	C4ⁱ—C6—C5	120.1 (3)
C43—C44—C45	119.2 (3)	C5—C4—H4	120.15
C44—C45—C46	120.8 (2)	C6ⁱ—C4—H4	120.15
C41—C46—C45	120.4 (2)	C4—C5—H5	119.92
P1—C2—H2A	109.49	C6—C5—H5	119.88
P1—C2—H2B	109.46	C5—C6—H6	119.94
C3—C2—H2A	109.48	C4ⁱ—C6—H6	119.96

P1—Tc—Cl—C1	114 (4)	C11—P1—C21—C22	−12.0 (2)
P2—Tc—Cl—C1	33 (4)	C2—P1—C21—C22	96.8 (2)
P1ⁱⁱ—Tc—Cl—C1	−66 (4)	C41—P2—C3—C2	137.5 (2)
P2ⁱⁱ—Tc—Cl—C1	−147 (4)	C31—P2—C41—C42	169.48 (18)
Cl—Tc—P1—C2	−130.30 (8)	Tc—P2—C41—C42	36.2 (2)
Cl—Tc—P1—C11	−13.46 (9)	Tc—P2—C3—C2	8.6 (2)
Cl—Tc—P1—C21	114.16 (9)	C31—P2—C3—C2	−116.1 (2)
P2—Tc—P1—C2	−33.05 (8)	C41—P2—C31—C32	136.0 (2)
P2—Tc—P1—C11	83.79 (8)	Tc—P2—C31—C32	−86.9 (2)
P2—Tc—P1—C21	−148.60 (9)	C3—P2—C31—C32	33.3 (2)
C1—Tc—P1—C2	−128.42 (17)	C3—P2—C41—C42	−82.9 (2)
C1—Tc—P1—C11	−11.59 (17)	Tc—P2—C31—C36	85.84 (19)
C1—Tc—P1—C21	116.03 (17)	C3—P2—C31—C36	−153.94 (19)
Clⁱⁱ—Tc—P1—C2	49.70 (8)	C3—P2—C41—C46	91.2 (2)
Clⁱⁱ—Tc—P1—C11	166.54 (9)	C41—P2—C31—C36	−51.3 (2)
Clⁱⁱ—Tc—P1—C21	−65.84 (9)	Tc—P2—C41—C46	−149.75 (16)
P2ⁱⁱ—Tc—P1—C2	146.95 (8)	C31—P2—C41—C46	−16.5 (2)
P2ⁱⁱ—Tc—P1—C11	−96.21 (8)	P1—C2—C3—P2	−37.1 (2)
P2ⁱⁱ—Tc—P1—C21	31.40 (9)	P1—C11—C12—C13	−177.19 (17)
C1ⁱⁱ—Tc—P1—C2	51.58 (17)	C12—C11—C16—C15	−0.8 (3)
C1ⁱⁱ—Tc—P1—C11	168.41 (17)	C16—C11—C12—C13	0.0 (3)
C1ⁱⁱ—Tc—P1—C21	−63.97 (17)	P1—C11—C16—C15	176.12 (17)
Cl—Tc—P2—C3	110.03 (11)	C11—C12—C13—C14	1.1 (3)
Cl—Tc—P2—C31	−132.00 (8)	C12—C13—C14—C15	−1.2 (3)
Cl—Tc—P2—C41	−3.85 (9)	C13—C14—C15—C16	0.3 (3)
P1—Tc—P2—C3	15.79 (11)	C14—C15—C16—C11	0.7 (3)
P1—Tc—P2—C31	133.76 (8)	C26—C21—C22—C23	0.4 (4)
P1—Tc—P2—C41	−98.08 (9)	P1—C21—C26—C25	−178.8 (2)
C1—Tc—P2—C3	111.14 (18)	P1—C21—C22—C23	179.1 (2)
C1—Tc—P2—C31	−130.89 (17)	C22—C21—C26—C25	−0.1 (4)
C1—Tc—P2—C41	−2.74 (17)	C21—C22—C23—C24	−0.6 (4)
Clⁱⁱ—Tc—P2—C3	−69.97 (11)	C22—C23—C24—C25	0.5 (5)
Clⁱⁱ—Tc—P2—C31	48.00 (8)	C23—C24—C25—C26	−0.1 (5)
Clⁱⁱ—Tc—P2—C41	176.15 (9)	C24—C25—C26—C21	−0.1 (4)
P1ⁱⁱ—Tc—P2—C3	−164.21 (11)	P2—C31—C32—C33	172.0 (2)
P1ⁱⁱ—Tc—P2—C31	−46.24 (8)	P2—C31—C36—C35	−173.2 (2)
P1ⁱⁱ—Tc—P2—C41	81.92 (9)	C32—C31—C36—C35	−0.2 (4)
C1ⁱⁱ—Tc—P2—C3	−68.86 (18)	C36—C31—C32—C33	−0.9 (4)
C1ⁱⁱ—Tc—P2—C31	49.11 (17)	C31—C32—C33—C34	0.7 (5)
C1ⁱⁱ—Tc—P2—C41	177.26 (18)	C32—C33—C34—C35	0.6 (5)
Tc—Cl—C1—S	164 (3)	C33—C34—C35—C36	−1.7 (5)
Tc—P1—C2—C3	49.24 (17)	C34—C35—C36—C31	1.5 (4)
C11—P1—C2—C3	−75.43 (18)	C46—C41—C42—C43	1.3 (4)
C21—P1—C2—C3	177.23 (16)	P2—C41—C42—C43	175.6 (2)
Tc—P1—C11—C16	−120.65 (17)	C42—C41—C46—C45	−1.6 (3)
C2—P1—C11—C16	−3.2 (2)	P2—C41—C46—C45	−175.57 (19)
C21—P1—C11—C16	103.4 (2)	C41—C42—C43—C44	−0.1 (4)
Tc—P1—C21—C22	−145.57 (18)	C42—C43—C44—C45	−0.9 (5)
Tc—P1—C11—C12	56.33 (18)	C43—C44—C45—C46	0.6 (4)
C2—P1—C11—C12	173.83 (17)	C44—C45—C46—C41	0.6 (4)
C21—P1—C11—C12	−79.66 (18)	C6ⁱ—C4—C5—C6	0.6 (4)
Tc—P1—C21—C26	33.1 (2)	C5—C4—C6ⁱ—C5ⁱ	−0.6 (4)
C2—P1—C21—C26	−84.51 (19)	C4—C5—C6—C4ⁱ	−0.6 (4)
C11—P1—C21—C26	166.73 (18)

Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···Clⁱⁱ	0.9702	2.7619	3.306 (3)	116.15
C2—H2B···Sⁱⁱ	0.9702	2.8746	3.591 (3)	131.41
C12—H12···Cl	0.9303	2.8195	3.198 (3)	105.65
C26—H26···Clⁱⁱ	0.9309	2.6650	3.489 (2)	147.88
C26—H26···Sⁱⁱ	0.9309	2.7282	3.574 (3)	151.50
C33—H33···Sⁱⁱⁱ	0.9303	2.7057	3.242 (4)	117.47
C42—H42···Cl	0.9296	2.6460	3.341 (3)	132.09
C42—H42···S	0.9296	2.7879	3.445 (3)	128.57

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[TcCl(C₄₆H₄₂P₄)(CS)]·C₆H₆
M_r	1053.3
Crystal system, space group	Triclinic, 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)
V (Å³)	1243.3 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.58 × 0.51 × 0.15

Data collection
Diffractometer	Siemens P4 diffractometer
Absorption correction	ψ scan (SHELXTL-Plus; Siemens, 1990)
T_min, T_max	0.732, 0.897
No. of measured, independent and observed [I > 2σ(I)] reflections	7126, 6069, 5372
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.098, 1.24
No. of reflections	6069
No. of parameters	313
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	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—Cl	2.538 (2)	Tc—C1	1.819 (6)
Tc—P1	2.4091 (6)	S—C1	1.468 (7)
Tc—P2	2.4355 (6)

Cl—Tc—P1	95.43 (3)	P1—Tc—C1	96.3 (2)
Cl—Tc—P2	98.00 (3)	P2—Tc—C1	96.3 (2)
Cl—Tc—C1ⁱ	178.0 (2)	Tc—C1—S	178.1 (3)
P1—Tc—P2	80.67 (2)	P1—C11—C16	123.7 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

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