catena-Poly[[dimethyl­bis­(thio­cyanato-κN)tin(IV)]-μ-(4,4′-bipyridine-κ² N:N′)]

Abstract

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,

• a = 10.8697 (8) Å

• b = 7.7741 (6) Å

• c = 11.3979 (8) Å

• β = 115.817 (1)°

• V = 867.0 (1) ų

• 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[F ² > 2σ(F ²)] = 0.023

• wR(F ²) = 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Hydrogen atoms were placed in calculated positions (C–H 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_eq(C).

Figures

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.

Crystal data

[Sn(CH3)2(NCS)2(C10H8N2)]	F(000) = 416
Mr = 421.10	Dx = 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

Bruker SMART APEX diffractometer	1066 independent reflections
Radiation source: fine-focus sealed tube	1064 reflections with I > 2σ(I)
graphite	Rint = 0.021
ω scans	θmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
Tmin = 0.628, Tmax = 0.847	k = −10→10
4033 measured reflections	l = −14→14

Refinement

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(Fo2) + (0.048P)2 + 0.1158P] where P = (Fo2 + 2Fc2)/3
1066 reflections	(Δ/σ)max = 0.001
64 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.82 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	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, °)

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.