Bis(4-fluoro­benz­yl-κC)bis­(3-methyl­sulfanyl-1,2,4-thia­diazole-5-thiol­ato-κ2N4,S5)tin(IV)

Deng, A.-X.; Xie, Q.; Teng, M.-Y.; Fu, G.-J.

doi:10.1107/S1600536811046654

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page m1735

https://doi.org/10.1107/S1600536811046654

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Bis(4-fluorobenzyl-κC)bis(3-methylsulfanyl-1,2,4-thiadiazole-5-thiolato-κ²N⁴,S⁵)tin(IV)

Ai-Xia Deng,^a ^* Qian Xie,^a Mou-Yong Teng ^a and Guo-Jia Fu ^b

^aCollege of Materials Science and Engineering, Liaocheng University, Shandong 252059, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: dengaixia@lcu.edu.cn

(Received 2 November 2011; accepted 5 November 2011; online 9 November 2011)

The mononuclear title molecule, [Sn(C₇H₆F)₂(C₃H₃N₂S₃)₂], has 2 symmetry. The Sn^IV atom, located on a twofold rotation axis, is in a skew trapezoidal–bipyramidal geometry, with the basal plane defined by two S,N-chelating 3-methylsulfanyl-1,2,4-thiadiazole-5-thiolate ligands. The apical positions are occupied by the C atoms of two 4-fluorobenzyl groups.

Related literature

For related structures, see: Ma et al. (2005 ); Zhang et al. (2005 ); Zhang et al. (2009 ).

Experimental

Crystal data

[Sn(C₇H₆F)₂(C₃H₃N₂S₃)₂]
M_r = 663.43
Monoclinic, C 2/c
a = 13.9011 (14) Å
b = 17.769 (2) Å
c = 10.712 (1) Å
β = 104.081 (2)°
V = 2566.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.52 mm⁻¹
T = 298 K
0.46 × 0.32 × 0.22 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.542, T_max = 0.732
6371 measured reflections
2269 independent reflections
2032 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.070
S = 1.15
2269 reflections
151 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Selected bond lengths (Å)

Sn1—C4	2.155 (3)
Sn1—S2	2.4703 (8)
Sn1—N1	2.913 (3)

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811046654/xu5378sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046654/xu5378Isup2.hkl

checkCIF report

Comment top

In the title compound, from Fig.1, as far as the weak Sn—N interactions are concerned, the central Sn(IV) atom is situated in a skew-trapezoidal bipyramidal geometry, with the basal plane defined by two symmertrically chelating 3-methylmercapto-5-mercapto-1,2,4-thiadiazole ligands. The apical positions are occupied by two 4-fluorobenzyl groups. The coordination geometry of the Sn(IV) atom can also be described as distorted trans octahedral, with atoms N1, N1A, S2 and S2A occupying the equatorial positions, and atoms C4 and C4A occupying the axial positions. The molecular structure consists of a monomer with a hexa-coordinated Sn atom surrounded by two S atoms and two N atoms of the ligand, and two 4-fluorobenzyl groups.

The Sn—S bond distances and weak Sn—N bond lengths are 2.4703 (8)Å and 2.913 Å, respectively. The bite angles S2—Sn1—N1 and S2A—Sn1—N1A of title compound (59.12°) can be reconciled with a skew-trapezoidal bipyramidal geometry, although this geometry can also be considered as distorted trans octahedral. The structure of compound is close to those reported for a series of diorganotin(IV) 2-mercapto-4-methylpyrimidine derivatives (Ma et al., 2005; Zhang et al., 2005; Zhang et al. 2009). There is a good correspondence in their structure parameters: the Sn—S distances lie in the range 2.477–2.526Å and the Sn—N distances in the range 2.650–2.933 Å.

Related literature top

For related structures, see: Ma et al. (2005); Zhang et al. (2005); Zhang et al. (2009).

Experimental top

The 3-Methylmercapto-5-mercapto-1,2,4-thiadiazole (2 mmol) was added to the solution of ethanol 20 ml with sodium ethoxide (2 mmol), and the mixture was stirred for 30 minutes, then add Di(4-fluorobenzyl)dichlorotin(IV) (1 mmol) to the mixture, continuing the reaction for 12 h at 318k. After cooling down to room temperature, filtered it. The solvent of the filtrate was gradually removed by evaporation under vacuum until solid product was obtained. The solid was then recrystallized from ether-dichloromethane and colorless crystals suitable for X-ray diffraction were obtained (m.p. 410–412 K). Analysis, calculated for C₂₀H₁₈F₂N₄S₆Sn: C 36.21, H 2.73, N 8.44, F 5.73; found: C 36.17, H 2.70, N 8.50, F 5.76%.

Structure description top

For related structures, see: Ma et al. (2005); Zhang et al. (2005); Zhang et al. (2009).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The unit cell of the title compound.

Bis(4-fluorobenzyl-κC)bis(3-methylsulfanyl-1,2,4-thiadiazole-5- thiolato-κ²N⁴,S⁵)tin(IV) top

Crystal data top

[Sn(C₇H₆F)₂(C₃H₃N₂S₃)₂]	F(000) = 1320
M_r = 663.43	D_x = 1.717 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4420 reflections
a = 13.9011 (14) Å	θ = 2.5–28.2°
b = 17.769 (2) Å	µ = 1.52 mm⁻¹
c = 10.712 (1) Å	T = 298 K
β = 104.081 (2)°	Block, colourless
V = 2566.4 (5) Å³	0.46 × 0.32 × 0.22 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2269 independent reflections
Radiation source: fine-focus sealed tube	2032 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −16→16
T_min = 0.542, T_max = 0.732	k = −21→15
6371 measured reflections	l = −12→12

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0343P)² + 2.4296P] where P = (F_o² + 2F_c²)/3
2269 reflections	(Δ/σ)_max = 0.002
151 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Sn(C₇H₆F)₂(C₃H₃N₂S₃)₂]	V = 2566.4 (5) Å³
M_r = 663.43	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.9011 (14) Å	µ = 1.52 mm⁻¹
b = 17.769 (2) Å	T = 298 K
c = 10.712 (1) Å	0.46 × 0.32 × 0.22 mm
β = 104.081 (2)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2269 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2032 reflections with I > 2σ(I)
T_min = 0.542, T_max = 0.732	R_int = 0.025
6371 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.15	Δρ_max = 0.39 e Å⁻³
2269 reflections	Δρ_min = −0.55 e Å⁻³
151 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
Sn1	0.5000	0.655810 (14)	0.2500	0.03453 (11)
S1	0.62395 (8)	0.59377 (6)	−0.11579 (9)	0.0675 (3)
S2	0.56268 (6)	0.55499 (4)	0.13199 (7)	0.0467 (2)
S3	0.61389 (9)	0.82296 (6)	−0.08129 (10)	0.0711 (3)
F1	0.9231 (2)	0.50566 (15)	0.6055 (3)	0.1095 (10)
N1	0.58816 (19)	0.69118 (15)	0.0366 (2)	0.0437 (6)
N2	0.6347 (3)	0.6831 (2)	−0.1563 (3)	0.0681 (9)
C1	0.5912 (2)	0.61779 (18)	0.0233 (3)	0.0426 (7)
C2	0.6129 (3)	0.7252 (2)	−0.0662 (3)	0.0530 (8)
C3	0.6074 (3)	0.8515 (2)	0.0764 (4)	0.0667 (10)
H3A	0.5470	0.8332	0.0936	0.100*
H3B	0.6088	0.9055	0.0815	0.100*
H3C	0.6631	0.8313	0.1387	0.100*
C4	0.6259 (2)	0.71003 (17)	0.3750 (3)	0.0458 (7)
H4A	0.6534	0.7464	0.3259	0.055*
H4B	0.6041	0.7370	0.4420	0.055*
C5	0.7043 (2)	0.65510 (15)	0.4355 (3)	0.0360 (6)
C6	0.7802 (2)	0.6374 (2)	0.3788 (3)	0.0548 (8)
H6	0.7821	0.6599	0.3011	0.066*
C7	0.8538 (3)	0.5867 (3)	0.4351 (4)	0.0715 (12)
H7	0.9050	0.5751	0.3964	0.086*
C8	0.8491 (3)	0.5543 (2)	0.5482 (4)	0.0655 (10)
C9	0.7749 (3)	0.5691 (2)	0.6068 (4)	0.0612 (9)
H9	0.7729	0.5454	0.6836	0.073*
C10	0.7031 (2)	0.6196 (2)	0.5500 (3)	0.0494 (8)
H10	0.6522	0.6304	0.5897	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.03463 (17)	0.03564 (17)	0.03042 (17)	0.000	0.00231 (11)	0.000
S1	0.0884 (7)	0.0725 (6)	0.0532 (5)	−0.0119 (5)	0.0395 (5)	−0.0207 (5)
S2	0.0602 (5)	0.0405 (4)	0.0424 (4)	−0.0011 (3)	0.0183 (4)	−0.0062 (3)
S3	0.0963 (8)	0.0655 (6)	0.0573 (6)	−0.0062 (5)	0.0300 (6)	0.0142 (5)
F1	0.0829 (18)	0.0850 (17)	0.133 (2)	0.0367 (14)	−0.0270 (16)	−0.0129 (17)
N1	0.0481 (15)	0.0487 (15)	0.0385 (14)	−0.0042 (12)	0.0190 (12)	−0.0013 (11)
N2	0.084 (2)	0.081 (2)	0.0493 (18)	−0.0115 (19)	0.0362 (17)	−0.0060 (16)
C1	0.0450 (17)	0.0514 (19)	0.0333 (16)	−0.0034 (14)	0.0133 (13)	−0.0074 (13)
C2	0.0525 (19)	0.062 (2)	0.0479 (19)	−0.0058 (16)	0.0188 (16)	0.0016 (16)
C3	0.084 (3)	0.051 (2)	0.067 (3)	−0.0025 (19)	0.021 (2)	0.0029 (17)
C4	0.0427 (17)	0.0433 (17)	0.0462 (18)	−0.0074 (13)	0.0006 (14)	−0.0081 (14)
C5	0.0308 (14)	0.0436 (16)	0.0310 (15)	−0.0080 (11)	0.0027 (11)	−0.0080 (12)
C6	0.0418 (18)	0.081 (2)	0.0431 (18)	−0.0046 (17)	0.0131 (15)	−0.0049 (17)
C7	0.041 (2)	0.097 (3)	0.075 (3)	0.0132 (19)	0.0120 (19)	−0.026 (2)
C8	0.051 (2)	0.056 (2)	0.076 (3)	0.0100 (17)	−0.0116 (19)	−0.0126 (19)
C9	0.059 (2)	0.066 (2)	0.050 (2)	−0.0059 (18)	−0.0021 (17)	0.0096 (17)
C10	0.0416 (17)	0.068 (2)	0.0384 (17)	−0.0042 (15)	0.0087 (14)	−0.0011 (15)

Geometric parameters (Å, º) top

Sn1—C4	2.155 (3)	C3—H3B	0.9600
Sn1—C4ⁱ	2.155 (3)	C3—H3C	0.9600
Sn1—S2ⁱ	2.4703 (8)	C4—C5	1.489 (4)
Sn1—S2	2.4703 (8)	C4—H4A	0.9700
Sn1—N1	2.913 (3)	C4—H4B	0.9700
S1—N2	1.663 (4)	C5—C6	1.376 (4)
S1—C1	1.715 (3)	C5—C10	1.383 (4)
S2—C1	1.727 (3)	C6—C7	1.387 (5)
S3—C2	1.745 (4)	C6—H6	0.9300
S3—C3	1.786 (4)	C7—C8	1.356 (6)
F1—C8	1.370 (4)	C7—H7	0.9300
N1—C1	1.314 (4)	C8—C9	1.357 (6)
N1—C2	1.371 (4)	C9—C10	1.370 (5)
N2—C2	1.313 (4)	C9—H9	0.9300
C3—H3A	0.9600	C10—H10	0.9300

C4—Sn1—C4ⁱ	126.88 (17)	C5—C4—H4A	109.2
C4—Sn1—S2ⁱ	109.90 (9)	Sn1—C4—H4A	109.2
C4ⁱ—Sn1—S2ⁱ	107.95 (9)	C5—C4—H4B	109.2
C4—Sn1—S2	107.95 (9)	Sn1—C4—H4B	109.2
C4ⁱ—Sn1—S2	109.90 (9)	H4A—C4—H4B	107.9
S2ⁱ—Sn1—S2	87.03 (4)	C6—C5—C10	117.6 (3)
N2—S1—C1	92.81 (15)	C6—C5—C4	121.1 (3)
C1—S2—Sn1	92.51 (10)	C10—C5—C4	121.3 (3)
C2—S3—C3	101.08 (16)	C5—C6—C7	121.3 (3)
C1—N1—C2	109.2 (2)	C5—C6—H6	119.3
C2—N2—S1	107.4 (2)	C7—C6—H6	119.3
N1—C1—S1	111.3 (2)	C8—C7—C6	118.3 (3)
N1—C1—S2	123.4 (2)	C8—C7—H7	120.9
S1—C1—S2	125.31 (19)	C6—C7—H7	120.9
N2—C2—N1	119.2 (3)	C7—C8—C9	122.5 (3)
N2—C2—S3	119.3 (3)	C7—C8—F1	118.3 (4)
N1—C2—S3	121.5 (2)	C9—C8—F1	119.1 (4)
S3—C3—H3A	109.5	C8—C9—C10	118.4 (3)
S3—C3—H3B	109.5	C8—C9—H9	120.8
H3A—C3—H3B	109.5	C10—C9—H9	120.8
S3—C3—H3C	109.5	C9—C10—C5	121.9 (3)
H3A—C3—H3C	109.5	C9—C10—H10	119.1
H3B—C3—H3C	109.5	C5—C10—H10	119.1
C5—C4—Sn1	112.03 (19)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Sn(C₇H₆F)₂(C₃H₃N₂S₃)₂]
M_r	663.43
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	13.9011 (14), 17.769 (2), 10.712 (1)
β (°)	104.081 (2)
V (Å³)	2566.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.52
Crystal size (mm)	0.46 × 0.32 × 0.22

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.542, 0.732
No. of measured, independent and observed [I > 2σ(I)] reflections	6371, 2269, 2032
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.070, 1.15
No. of reflections	2269
No. of parameters	151
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.55

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Sn1—C4	2.155 (3)	Sn1—N1	2.913 (3)
Sn1—S2	2.4703 (8)

Acknowledgements

The authors thank the State Key Laboratory of Crystal Materials, Liaocheng University, China, and the School Science Foundation of Liaocheng University for financial support.

References

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Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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