catena-Poly[[dimethyl­bis­(thio­cyanato-κN)tin(IV)]-μ-(4,4′-bipyridine-κ2N:N′)]

Najafi, E.; Amini, M.M.; Ng, S.W.

doi:10.1107/S1600536811005459

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page m350

doi:10.1107/S1600536811005459

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catena-Poly[[dimethylbis(thiocyanato-κN)tin(IV)]-μ-(4,4′-bipyridine-κ²N:N′)]

Ezzatollah Najafi,^a Mostafa M. Amini ^a and Seik Weng Ng ^b ^*

^aDepartment of Chemistry, General Campus, Shahid Beheshti University, Tehran 1983963113, Iran, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 5 February 2011; accepted 14 February 2011; online 19 February 2011)

The title dimethyltin diisothiocyanate adduct of 4,4′-bipyridine, [Sn(CH₃)₂(NCS)₂(C₁₀H₈N₂)]_n, adopts a chain motif in which the N-heterocycle functions as a bridge to adjacent all-trans octahedrally coordinated tin atoms. The Sn^IV atom lies on a special position of 2/m site symmetry, the methyl C atom on a special position of 2 site symmetry, and the thiocyanate and 4,4′-bipyridine on a special position of m site symmetry.

Related literature

For the 4,4′-bipyridine adducts of diorganotin dichlorides, see: Ma et al. (2004 ); Ng (1998 ). For the dimethyltin di(isothiocyanate) adduct of 1,10-phenanthroline, see: Najafi et al. (2011 ).

Experimental

Crystal data

[Sn(CH₃)₂(NCS)₂(C₁₀H₈N₂)]
M_r = 421.10
Monoclinic, C 2/m
a = 10.8697 (8) Å
b = 7.7741 (6) Å
c = 11.3979 (8) Å
β = 115.817 (1)°
V = 867.0 (1) Å³
Z = 2
Mo Kα radiation
μ = 1.71 mm⁻¹
T = 295 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.628, T_max = 0.847
4033 measured reflections
1066 independent reflections
1064 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.061
S = 1.08
1066 reflections
64 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005459/si2334sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005459/si2334Isup2.hkl

checkCIF report

Comment top

The 4,4'-bipyridine ligand forms a number of adducts with diorganotin dihalides; the adducts adopt linear chain structures as the ligand functions in a bridging mode. The organotin dihalides include dimethyltin dichloride (Ng, 1998), dibutyltin dichloride and dibenzyltin dichloride (Ma et al., 2004); no pseudohalides have been reported. The dimethyltin diisothiocyanate adduct similarly adopts a chain motif (Scheme I, Fig. 1). Polymeric [Sn(NCS)₂(CH₃)₂(C₁₀H₈N₂)₂]_n has the N-heterocycle functioning as a bridging to adjacent all-trans octahedrally coordinated tin atoms. The tin atom lies on a special position of 2/m site symmetry, the methyl carbon on a special position of 2 site symmetry, and the isothiocyanate and 4,4'-bipyridine on a special position of m site symmetry. The geometry of the tin atom in the dimethyltin di(isothiocyanate) adduct with 1,10-phenanthroline is a cis-octahedron (Najafi et al., 2011).

Related literature top

For the 4,4'-bipyridine adducts of diorganotin dichlorides, see: Ma et al. (2004); Ng (1998). For the dimethyltin di(isothiocyanate) adduct of 1,10-phenanthroline, see: Najafi et al. (2011).

Experimental top

Dimethyltin diisothiocyanate (1 mmol, 0.26 g) and 4,4'-bipyridine (1 mmol, 0.16 g) were loaded into a convection tube. The tube was filled with acetonitrile and methanol (v:v / 9:1) and kept at 333 K. Colorless crystals were collected from the side arm after several days.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of a portion of the Sn(NCS)₂(CH₃)₂(C₁₀H₈N₂) chain at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

catena-Poly[[dimethylbis(thiocyanato-κN)tin(IV)]- µ-(4,4'-bipyridine-κ²N:N')] top

Crystal data top

[Sn(CH₃)₂(NCS)₂(C₁₀H₈N₂)]	F(000) = 416
M_r = 421.10	D_x = 1.613 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 3765 reflections
a = 10.8697 (8) Å	θ = 3.8–28.3°
b = 7.7741 (6) Å	µ = 1.71 mm⁻¹
c = 11.3979 (8) Å	T = 295 K
β = 115.817 (1)°	Prism, colorless
V = 867.0 (1) Å³	0.30 × 0.20 × 0.10 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	1066 independent reflections
Radiation source: fine-focus sealed tube	1064 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
T_min = 0.628, T_max = 0.847	k = −10→10
4033 measured reflections	l = −14→14

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.048P)² + 0.1158P] where P = (F_o² + 2F_c²)/3
1066 reflections	(Δ/σ)_max = 0.001
64 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.82 e Å⁻³

Crystal data top

[Sn(CH₃)₂(NCS)₂(C₁₀H₈N₂)]	V = 867.0 (1) Å³
M_r = 421.10	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 10.8697 (8) Å	µ = 1.71 mm⁻¹
b = 7.7741 (6) Å	T = 295 K
c = 11.3979 (8) Å	0.30 × 0.20 × 0.10 mm
β = 115.817 (1)°

Data collection top

Bruker SMART APEX diffractometer	1066 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1064 reflections with I > 2σ(I)
T_min = 0.628, T_max = 0.847	R_int = 0.021
4033 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.08	Δρ_max = 0.49 e Å⁻³
1066 reflections	Δρ_min = −0.82 e Å⁻³
64 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Sn1	0.5000	0.5000	0.5000	0.03309 (11)
S1	0.6834 (2)	0.5000	0.18029 (16)	0.0967 (5)
N1	0.3011 (3)	0.5000	0.2981 (2)	0.0404 (5)
N2	0.6379 (4)	0.5000	0.3960 (4)	0.0763 (12)
C1	0.5000	0.2290 (5)	0.5000	0.0713 (12)
H1A	0.5254	0.1878	0.5869	0.107*	0.50
H1B	0.5644	0.1878	0.4697	0.107*	0.50
H1C	0.4103	0.1878	0.4434	0.107*	0.50
C2	0.1780 (4)	0.5000	0.2946 (3)	0.0713 (14)
H2	0.1717	0.5000	0.3734	0.086*
C3	0.0584 (4)	0.5000	0.1812 (3)	0.0721 (15)
H3	−0.0254	0.5000	0.1849	0.087*
C4	0.0628 (3)	0.5000	0.0623 (3)	0.0388 (6)
C5	0.1893 (4)	0.5000	0.0663 (4)	0.102 (3)
H5	0.1985	0.5000	−0.0112	0.122*
C6	0.3047 (4)	0.5000	0.1840 (4)	0.099 (2)
H6	0.3896	0.5000	0.1826	0.119*
C7	0.6565 (3)	0.5000	0.3071 (4)	0.0501 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.02266 (15)	0.04968 (17)	0.02072 (15)	0.000	0.00366 (10)	0.000
S1	0.1031 (11)	0.1490 (14)	0.0594 (8)	0.000	0.0554 (8)	0.000
N1	0.0246 (11)	0.0643 (15)	0.0225 (11)	0.000	0.0011 (9)	0.000
N2	0.0413 (17)	0.146 (4)	0.0449 (19)	0.000	0.0216 (16)	0.000
C1	0.064 (3)	0.0532 (19)	0.068 (3)	0.000	0.002 (2)	0.000
C2	0.0298 (16)	0.154 (5)	0.0201 (15)	0.000	0.0018 (13)	0.000
C3	0.0252 (16)	0.157 (5)	0.0280 (17)	0.000	0.0057 (14)	0.000
C4	0.0231 (13)	0.0624 (16)	0.0215 (13)	0.000	0.0009 (12)	0.000
C5	0.0260 (17)	0.253 (8)	0.0205 (17)	0.000	0.0053 (14)	0.000
C6	0.0210 (16)	0.244 (8)	0.0231 (17)	0.000	0.0016 (14)	0.000
C7	0.0300 (15)	0.077 (2)	0.0387 (17)	0.000	0.0110 (13)	0.000

Geometric parameters (Å, º) top

Sn1—C1ⁱ	2.107 (4)	C1—H1B	0.9600
Sn1—C1	2.107 (4)	C1—H1C	0.9600
Sn1—N2ⁱ	2.280 (3)	C2—C3	1.378 (5)
Sn1—N2	2.280 (3)	C2—H2	0.9300
Sn1—N1ⁱ	2.374 (2)	C3—C4	1.376 (4)
Sn1—N1	2.374 (2)	C3—H3	0.9300
S1—C7	1.595 (4)	C4—C5	1.356 (5)
N1—C6	1.318 (5)	C4—C4ⁱⁱ	1.480 (5)
N1—C2	1.321 (5)	C5—C6	1.381 (5)
N2—C7	1.116 (5)	C5—H5	0.9300
C1—H1A	0.9600	C6—H6	0.9300

C1ⁱ—Sn1—C1	180.0	H1A—C1—H1B	109.5
C1ⁱ—Sn1—N2ⁱ	90.0	Sn1—C1—H1C	109.5
C1—Sn1—N2ⁱ	90.000 (1)	H1A—C1—H1C	109.5
C1ⁱ—Sn1—N2	90.000 (1)	H1B—C1—H1C	109.5
C1—Sn1—N2	90.0	N1—C2—C3	123.9 (3)
N2ⁱ—Sn1—N2	180.000 (1)	N1—C2—H2	118.1
C1ⁱ—Sn1—N1ⁱ	90.000 (1)	C3—C2—H2	118.1
C1—Sn1—N1ⁱ	90.000 (1)	C4—C3—C2	120.0 (3)
N2ⁱ—Sn1—N1ⁱ	91.34 (12)	C4—C3—H3	120.0
N2—Sn1—N1ⁱ	88.66 (12)	C2—C3—H3	120.0
C1ⁱ—Sn1—N1	90.0	C5—C4—C3	115.9 (3)
C1—Sn1—N1	90.000 (1)	C5—C4—C4ⁱⁱ	122.0 (3)
N2ⁱ—Sn1—N1	88.66 (12)	C3—C4—C4ⁱⁱ	122.1 (4)
N2—Sn1—N1	91.34 (12)	C4—C5—C6	120.7 (3)
N1ⁱ—Sn1—N1	180.0	C4—C5—H5	119.6
C6—N1—C2	115.8 (3)	C6—C5—H5	119.6
C6—N1—Sn1	123.4 (2)	N1—C6—C5	123.6 (3)
C2—N1—Sn1	120.8 (2)	N1—C6—H6	118.2
C7—N2—Sn1	153.1 (3)	C5—C6—H6	118.2
Sn1—C1—H1A	109.5	N2—C7—S1	179.8 (4)
Sn1—C1—H1B	109.5

C1ⁱ—Sn1—N1—C6	90.0	N1—Sn1—N2—C7	0.000 (2)
C1—Sn1—N1—C6	−90.0	C6—N1—C2—C3	0.0
N2ⁱ—Sn1—N1—C6	180.0	Sn1—N1—C2—C3	180.0
N2—Sn1—N1—C6	0.0	N1—C2—C3—C4	0.0
C1ⁱ—Sn1—N1—C2	−90.0	C2—C3—C4—C5	0.0
C1—Sn1—N1—C2	90.0	C2—C3—C4—C4ⁱⁱ	180.0
N2ⁱ—Sn1—N1—C2	0.0	C3—C4—C5—C6	0.0
N2—Sn1—N1—C2	180.0	C4ⁱⁱ—C4—C5—C6	180.0
C1ⁱ—Sn1—N2—C7	−90.000 (1)	C2—N1—C6—C5	0.0
C1—Sn1—N2—C7	90.000 (1)	Sn1—N1—C6—C5	180.0
N1ⁱ—Sn1—N2—C7	180.000 (2)	C4—C5—C6—N1	0.0

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

Experimental details

Crystal data
Chemical formula	[Sn(CH₃)₂(NCS)₂(C₁₀H₈N₂)]
M_r	421.10
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	295
a, b, c (Å)	10.8697 (8), 7.7741 (6), 11.3979 (8)
β (°)	115.817 (1)
V (Å³)	867.0 (1)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.71
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.628, 0.847
No. of measured, independent and observed [I > 2σ(I)] reflections	4033, 1066, 1064
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.061, 1.08
No. of reflections	1066
No. of parameters	64
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.82

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank Shahid Beheshti University and the University of Malaya for supporting this study.

References

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