metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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 SnIV 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[Ma, C.-L., Zhang, J.-H., Tian, G.-R. & Zhang, R.-F. (2005). J. Organomet. Chem. pp. 519-533.]); Zhang et al. (2005[Zhang, J.-H., Zhang, R.-F., Ma, C.-L. & Wang, D.-Q. (2005). Acta Cryst. E61, m2075-m2077.]); Zhang et al. (2009[Zhang, J., Zhang, R., Ma, C., Wang, H. & Wang, D. (2009). Acta Cryst. E65, m1030.]).

[Scheme 1]

Experimental

Crystal data
  • [Sn(C7H6F)2(C3H3N2S3)2]

  • Mr = 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[Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.542, Tmax = 0.732

  • 6371 measured reflections

  • 2269 independent reflections

  • 2032 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.025

  • wR(F2) = 0.070

  • S = 1.15

  • 2269 reflections

  • 151 parameters

  • H-atom parameters constrained

  • Δρmax = 0.39 e Å−3

  • Δρmin = −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[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information


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%.

Refinement top

All H atoms were placed geometrically and treated as riding on their parent atoms, with methylene C—H distances of 0.97 Å, methyl and thiadiazole C—H distances of 0.96 Å.

Structure description 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.

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
[Figure 1] Fig. 1. The molecular structure of the compound, showing 30% probability displacement ellipsoids.
[Figure 2] 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
Mr = 663.43Dx = 1.717 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4420 reflections
a = 13.9011 (14) Åθ = 2.5–28.2°
b = 17.769 (2) ŵ = 1.52 mm1
c = 10.712 (1) ÅT = 298 K
β = 104.081 (2)°Block, colourless
V = 2566.4 (5) Å30.46 × 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 tube2032 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
φ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1616
Tmin = 0.542, Tmax = 0.732k = 2115
6371 measured reflectionsl = 1212
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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070H-atom parameters constrained
S = 1.15 w = 1/[σ2(Fo2) + (0.0343P)2 + 2.4296P]
where P = (Fo2 + 2Fc2)/3
2269 reflections(Δ/σ)max = 0.002
151 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.55 e Å3
Crystal data top
[Sn(C7H6F)2(C3H3N2S3)2]V = 2566.4 (5) Å3
Mr = 663.43Z = 4
Monoclinic, C2/cMo Kα radiation
a = 13.9011 (14) ŵ = 1.52 mm1
b = 17.769 (2) ÅT = 298 K
c = 10.712 (1) Å0.46 × 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)
Tmin = 0.542, Tmax = 0.732Rint = 0.025
6371 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.070H-atom parameters constrained
S = 1.15Δρmax = 0.39 e Å3
2269 reflectionsΔρmin = 0.55 e Å3
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
xyzUiso*/Ueq
Sn10.50000.655810 (14)0.25000.03453 (11)
S10.62395 (8)0.59377 (6)0.11579 (9)0.0675 (3)
S20.56268 (6)0.55499 (4)0.13199 (7)0.0467 (2)
S30.61389 (9)0.82296 (6)0.08129 (10)0.0711 (3)
F10.9231 (2)0.50566 (15)0.6055 (3)0.1095 (10)
N10.58816 (19)0.69118 (15)0.0366 (2)0.0437 (6)
N20.6347 (3)0.6831 (2)0.1563 (3)0.0681 (9)
C10.5912 (2)0.61779 (18)0.0233 (3)0.0426 (7)
C20.6129 (3)0.7252 (2)0.0662 (3)0.0530 (8)
C30.6074 (3)0.8515 (2)0.0764 (4)0.0667 (10)
H3A0.54700.83320.09360.100*
H3B0.60880.90550.08150.100*
H3C0.66310.83130.13870.100*
C40.6259 (2)0.71003 (17)0.3750 (3)0.0458 (7)
H4A0.65340.74640.32590.055*
H4B0.60410.73700.44200.055*
C50.7043 (2)0.65510 (15)0.4355 (3)0.0360 (6)
C60.7802 (2)0.6374 (2)0.3788 (3)0.0548 (8)
H60.78210.65990.30110.066*
C70.8538 (3)0.5867 (3)0.4351 (4)0.0715 (12)
H70.90500.57510.39640.086*
C80.8491 (3)0.5543 (2)0.5482 (4)0.0655 (10)
C90.7749 (3)0.5691 (2)0.6068 (4)0.0612 (9)
H90.77290.54540.68360.073*
C100.7031 (2)0.6196 (2)0.5500 (3)0.0494 (8)
H100.65220.63040.58970.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.03463 (17)0.03564 (17)0.03042 (17)0.0000.00231 (11)0.000
S10.0884 (7)0.0725 (6)0.0532 (5)0.0119 (5)0.0395 (5)0.0207 (5)
S20.0602 (5)0.0405 (4)0.0424 (4)0.0011 (3)0.0183 (4)0.0062 (3)
S30.0963 (8)0.0655 (6)0.0573 (6)0.0062 (5)0.0300 (6)0.0142 (5)
F10.0829 (18)0.0850 (17)0.133 (2)0.0367 (14)0.0270 (16)0.0129 (17)
N10.0481 (15)0.0487 (15)0.0385 (14)0.0042 (12)0.0190 (12)0.0013 (11)
N20.084 (2)0.081 (2)0.0493 (18)0.0115 (19)0.0362 (17)0.0060 (16)
C10.0450 (17)0.0514 (19)0.0333 (16)0.0034 (14)0.0133 (13)0.0074 (13)
C20.0525 (19)0.062 (2)0.0479 (19)0.0058 (16)0.0188 (16)0.0016 (16)
C30.084 (3)0.051 (2)0.067 (3)0.0025 (19)0.021 (2)0.0029 (17)
C40.0427 (17)0.0433 (17)0.0462 (18)0.0074 (13)0.0006 (14)0.0081 (14)
C50.0308 (14)0.0436 (16)0.0310 (15)0.0080 (11)0.0027 (11)0.0080 (12)
C60.0418 (18)0.081 (2)0.0431 (18)0.0046 (17)0.0131 (15)0.0049 (17)
C70.041 (2)0.097 (3)0.075 (3)0.0132 (19)0.0120 (19)0.026 (2)
C80.051 (2)0.056 (2)0.076 (3)0.0100 (17)0.0116 (19)0.0126 (19)
C90.059 (2)0.066 (2)0.050 (2)0.0059 (18)0.0021 (17)0.0096 (17)
C100.0416 (17)0.068 (2)0.0384 (17)0.0042 (15)0.0087 (14)0.0011 (15)
Geometric parameters (Å, º) top
Sn1—C42.155 (3)C3—H3B0.9600
Sn1—C4i2.155 (3)C3—H3C0.9600
Sn1—S2i2.4703 (8)C4—C51.489 (4)
Sn1—S22.4703 (8)C4—H4A0.9700
Sn1—N12.913 (3)C4—H4B0.9700
S1—N21.663 (4)C5—C61.376 (4)
S1—C11.715 (3)C5—C101.383 (4)
S2—C11.727 (3)C6—C71.387 (5)
S3—C21.745 (4)C6—H60.9300
S3—C31.786 (4)C7—C81.356 (6)
F1—C81.370 (4)C7—H70.9300
N1—C11.314 (4)C8—C91.357 (6)
N1—C21.371 (4)C9—C101.370 (5)
N2—C21.313 (4)C9—H90.9300
C3—H3A0.9600C10—H100.9300
C4—Sn1—C4i126.88 (17)C5—C4—H4A109.2
C4—Sn1—S2i109.90 (9)Sn1—C4—H4A109.2
C4i—Sn1—S2i107.95 (9)C5—C4—H4B109.2
C4—Sn1—S2107.95 (9)Sn1—C4—H4B109.2
C4i—Sn1—S2109.90 (9)H4A—C4—H4B107.9
S2i—Sn1—S287.03 (4)C6—C5—C10117.6 (3)
N2—S1—C192.81 (15)C6—C5—C4121.1 (3)
C1—S2—Sn192.51 (10)C10—C5—C4121.3 (3)
C2—S3—C3101.08 (16)C5—C6—C7121.3 (3)
C1—N1—C2109.2 (2)C5—C6—H6119.3
C2—N2—S1107.4 (2)C7—C6—H6119.3
N1—C1—S1111.3 (2)C8—C7—C6118.3 (3)
N1—C1—S2123.4 (2)C8—C7—H7120.9
S1—C1—S2125.31 (19)C6—C7—H7120.9
N2—C2—N1119.2 (3)C7—C8—C9122.5 (3)
N2—C2—S3119.3 (3)C7—C8—F1118.3 (4)
N1—C2—S3121.5 (2)C9—C8—F1119.1 (4)
S3—C3—H3A109.5C8—C9—C10118.4 (3)
S3—C3—H3B109.5C8—C9—H9120.8
H3A—C3—H3B109.5C10—C9—H9120.8
S3—C3—H3C109.5C9—C10—C5121.9 (3)
H3A—C3—H3C109.5C9—C10—H10119.1
H3B—C3—H3C109.5C5—C10—H10119.1
C5—C4—Sn1112.03 (19)
Symmetry code: (i) x+1, y, z+1/2.

Experimental details

Crystal data
Chemical formula[Sn(C7H6F)2(C3H3N2S3)2]
Mr663.43
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)13.9011 (14), 17.769 (2), 10.712 (1)
β (°) 104.081 (2)
V3)2566.4 (5)
Z4
Radiation typeMo Kα
µ (mm1)1.52
Crystal size (mm)0.46 × 0.32 × 0.22
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.542, 0.732
No. of measured, independent and
observed [I > 2σ(I)] reflections
6371, 2269, 2032
Rint0.025
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.070, 1.15
No. of reflections2269
No. of parameters151
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.55

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

Selected bond lengths (Å) top
Sn1—C42.155 (3)Sn1—N12.913 (3)
Sn1—S22.4703 (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

First citationBruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationMa, C.-L., Zhang, J.-H., Tian, G.-R. & Zhang, R.-F. (2005). J. Organomet. Chem. pp. 519–533.  Web of Science CSD CrossRef Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhang, J.-H., Zhang, R.-F., Ma, C.-L. & Wang, D.-Q. (2005). Acta Cryst. E61, m2075–m2077.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationZhang, J., Zhang, R., Ma, C., Wang, H. & Wang, D. (2009). Acta Cryst. E65, m1030.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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