metal-organic compounds
[μ-1,2,3,4-Tetrakis(pyridin-4-yl)butane-κ2N1:N4]bis[trimethyl(thiocyanato-κN)tin(IV)]
aDepartment of Chemistry, General Campus, Shahid Beheshti University, Tehran 1983963113, Iran, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: seikweng@um.edu.my
In the title compound, [Sn2(CH3)6(NCS)2(C24H22N4)], the 1,2,3,4-tetrakis(pyridin-4-yl)butane ligand uses the pyridine N atoms at the ends of the butyl chain to coordinate to two trimethylthiocyanatotin(IV) units, forming a dinuclear structure. The SnIV atom in the molecule shows a distorted trans-trigonal–bipyramidal coordination with the methyl groups in equatorial positions. The molecule lies on a center of inversion, with the mid-point of the butyl chain coinciding with this In the crystal, weak C—H⋯π interactions occur between pyridine rings of adjacent molecules.
Experimental
Crystal data
|
Refinement
|
Data collection: CrysAlis PRO (Agilent, 2012); cell CrysAlis PRO; data reduction: CrysAlis PRO; 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
10.1107/S160053681204737X/xu5652sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681204737X/xu5652Isup2.hkl
Trimethyltin thiocyanate (0.19 g, 1 mmol) and 4-[1,3,4-tris(pyridin-4-yl)butan-2-yl]pyridine (0.73 g, 2 mmol) were loaded into a convection tube; the tube was filled with ethyl alcohol andkept at 333 K. Colorless crystals were collected from the side arm after several days.
Carbon-bound H atoms were placed in calculated positions [C–H 0.93 to 0.96 Å, Uiso(H) 1.2 to 1.5Ueq(C)] and were included in the
in the riding model approximation.Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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).Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [(CH3)3Sn(NCS)]2(C24H22N4) at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. |
[Sn2(CH3)6(NCS)2(C24H22N4)] | Z = 1 |
Mr = 810.20 | F(000) = 406 |
Triclinic, P1 | Dx = 1.500 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2959 (8) Å | Cell parameters from 3676 reflections |
b = 9.7210 (7) Å | θ = 2.9–27.5° |
c = 10.2448 (9) Å | µ = 1.54 mm−1 |
α = 90.388 (7)° | T = 295 K |
β = 94.381 (7)° | Prism, colorless |
γ = 103.646 (7)° | 0.25 × 0.25 × 0.05 mm |
V = 896.72 (13) Å3 |
Agilent SuperNova Dual diffractometer with an Atlas detector | 4153 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 3645 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.030 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 27.6°, θmin = 2.9° |
ω scan | h = −10→12 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | k = −12→12 |
Tmin = 0.700, Tmax = 0.927 | l = −12→13 |
8527 measured reflections |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0324P)2 + 0.1997P] where P = (Fo2 + 2Fc2)/3 |
4153 reflections | (Δ/σ)max = 0.001 |
190 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.52 e Å−3 |
[Sn2(CH3)6(NCS)2(C24H22N4)] | γ = 103.646 (7)° |
Mr = 810.20 | V = 896.72 (13) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.2959 (8) Å | Mo Kα radiation |
b = 9.7210 (7) Å | µ = 1.54 mm−1 |
c = 10.2448 (9) Å | T = 295 K |
α = 90.388 (7)° | 0.25 × 0.25 × 0.05 mm |
β = 94.381 (7)° |
Agilent SuperNova Dual diffractometer with an Atlas detector | 4153 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 3645 reflections with I > 2σ(I) |
Tmin = 0.700, Tmax = 0.927 | Rint = 0.030 |
8527 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.50 e Å−3 |
4153 reflections | Δρmin = −0.52 e Å−3 |
190 parameters |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.76200 (2) | 0.553034 (18) | 0.347974 (18) | 0.03890 (8) | |
S1 | 1.20140 (12) | 0.90346 (10) | 0.55879 (11) | 0.0742 (3) | |
N1 | 0.9749 (3) | 0.7032 (3) | 0.4286 (3) | 0.0656 (9) | |
N2 | 0.5239 (3) | 0.3899 (2) | 0.2637 (2) | 0.0347 (5) | |
N3 | 0.3574 (3) | −0.2627 (3) | 0.0683 (3) | 0.0566 (7) | |
C1 | 0.6775 (5) | 0.7271 (3) | 0.2837 (4) | 0.0666 (11) | |
H1A | 0.7503 | 0.8136 | 0.3056 | 0.100* | |
H1B | 0.5888 | 0.7273 | 0.3259 | 0.100* | |
H1C | 0.6549 | 0.7193 | 0.1906 | 0.100* | |
C2 | 0.7196 (4) | 0.4771 (3) | 0.5374 (3) | 0.0531 (8) | |
H2A | 0.7987 | 0.5248 | 0.5993 | 0.080* | |
H2B | 0.7133 | 0.3771 | 0.5381 | 0.080* | |
H2C | 0.6275 | 0.4948 | 0.5608 | 0.080* | |
C3 | 0.8759 (4) | 0.4507 (4) | 0.2210 (3) | 0.0579 (9) | |
H3A | 0.9803 | 0.4938 | 0.2321 | 0.087* | |
H3B | 0.8397 | 0.4597 | 0.1319 | 0.087* | |
H3C | 0.8592 | 0.3522 | 0.2414 | 0.087* | |
C4 | 1.0677 (4) | 0.7876 (3) | 0.4841 (3) | 0.0458 (7) | |
C5 | 0.4359 (3) | 0.4259 (3) | 0.1683 (3) | 0.0382 (6) | |
H5 | 0.4698 | 0.5106 | 0.1264 | 0.046* | |
C6 | 0.2962 (3) | 0.3436 (3) | 0.1280 (3) | 0.0403 (6) | |
H6 | 0.2388 | 0.3734 | 0.0606 | 0.048* | |
C7 | 0.2420 (3) | 0.2165 (3) | 0.1887 (3) | 0.0351 (6) | |
C8 | 0.3340 (3) | 0.1789 (3) | 0.2859 (3) | 0.0437 (7) | |
H8 | 0.3030 | 0.0944 | 0.3290 | 0.052* | |
C9 | 0.4726 (3) | 0.2655 (3) | 0.3204 (3) | 0.0439 (7) | |
H9 | 0.5332 | 0.2365 | 0.3857 | 0.053* | |
C10 | 0.0880 (3) | 0.1277 (3) | 0.1497 (3) | 0.0427 (7) | |
H10A | 0.0202 | 0.1894 | 0.1367 | 0.051* | |
H10B | 0.0551 | 0.0649 | 0.2203 | 0.051* | |
C11 | 0.0817 (3) | 0.0381 (2) | 0.0226 (3) | 0.0315 (5) | |
H11 | 0.1201 | 0.1030 | −0.0463 | 0.038* | |
C12 | 0.1783 (3) | −0.0664 (3) | 0.0395 (2) | 0.0314 (5) | |
C13 | 0.2892 (3) | −0.0683 (3) | −0.0411 (3) | 0.0373 (6) | |
H13 | 0.3068 | −0.0037 | −0.1079 | 0.045* | |
C14 | 0.3750 (4) | −0.1665 (3) | −0.0230 (3) | 0.0483 (7) | |
H14 | 0.4498 | −0.1644 | −0.0789 | 0.058* | |
C15 | 0.2501 (5) | −0.2597 (4) | 0.1456 (4) | 0.0619 (10) | |
H15 | 0.2353 | −0.3257 | 0.2115 | 0.074* | |
C16 | 0.1589 (4) | −0.1668 (3) | 0.1362 (3) | 0.0510 (8) | |
H16 | 0.0854 | −0.1712 | 0.1939 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.03404 (13) | 0.03835 (12) | 0.04120 (12) | 0.00409 (8) | −0.00196 (8) | −0.00293 (8) |
S1 | 0.0695 (7) | 0.0535 (5) | 0.0823 (7) | −0.0110 (5) | −0.0211 (5) | −0.0118 (4) |
N1 | 0.0449 (18) | 0.0651 (18) | 0.076 (2) | −0.0031 (15) | −0.0090 (15) | −0.0174 (15) |
N2 | 0.0307 (12) | 0.0330 (11) | 0.0389 (12) | 0.0063 (9) | −0.0018 (9) | −0.0036 (9) |
N3 | 0.0480 (18) | 0.0529 (16) | 0.072 (2) | 0.0224 (13) | −0.0095 (15) | −0.0021 (14) |
C1 | 0.071 (3) | 0.0364 (16) | 0.086 (3) | 0.0074 (16) | −0.018 (2) | 0.0022 (15) |
C2 | 0.056 (2) | 0.066 (2) | 0.0380 (16) | 0.0187 (16) | −0.0005 (14) | −0.0060 (14) |
C3 | 0.0422 (19) | 0.070 (2) | 0.058 (2) | 0.0038 (16) | 0.0117 (15) | −0.0171 (16) |
C4 | 0.0440 (18) | 0.0423 (15) | 0.0475 (17) | 0.0043 (14) | −0.0004 (14) | −0.0002 (12) |
C5 | 0.0411 (16) | 0.0313 (13) | 0.0384 (14) | 0.0028 (11) | −0.0019 (12) | 0.0001 (10) |
C6 | 0.0413 (17) | 0.0400 (14) | 0.0388 (15) | 0.0126 (12) | −0.0102 (12) | −0.0044 (11) |
C7 | 0.0282 (14) | 0.0332 (13) | 0.0416 (14) | 0.0035 (11) | 0.0010 (11) | −0.0113 (10) |
C8 | 0.0444 (18) | 0.0332 (13) | 0.0480 (16) | −0.0003 (12) | −0.0025 (13) | 0.0029 (11) |
C9 | 0.0397 (17) | 0.0365 (14) | 0.0511 (17) | 0.0053 (12) | −0.0116 (13) | 0.0025 (12) |
C10 | 0.0279 (15) | 0.0472 (15) | 0.0509 (17) | 0.0054 (12) | 0.0017 (12) | −0.0149 (12) |
C11 | 0.0221 (13) | 0.0306 (12) | 0.0394 (13) | 0.0020 (10) | 0.0011 (10) | −0.0032 (10) |
C12 | 0.0245 (13) | 0.0342 (12) | 0.0333 (13) | 0.0048 (10) | −0.0038 (10) | −0.0044 (10) |
C13 | 0.0323 (15) | 0.0351 (13) | 0.0438 (15) | 0.0065 (11) | 0.0041 (12) | 0.0003 (11) |
C14 | 0.0366 (17) | 0.0446 (16) | 0.065 (2) | 0.0120 (13) | 0.0039 (14) | −0.0089 (14) |
C15 | 0.068 (3) | 0.0549 (19) | 0.064 (2) | 0.0211 (18) | −0.0032 (19) | 0.0193 (16) |
C16 | 0.050 (2) | 0.0559 (18) | 0.0497 (18) | 0.0151 (15) | 0.0096 (15) | 0.0136 (14) |
Sn1—C1 | 2.116 (3) | C6—C7 | 1.390 (4) |
Sn1—C3 | 2.119 (3) | C6—H6 | 0.9300 |
Sn1—C2 | 2.113 (3) | C7—C8 | 1.371 (4) |
Sn1—N1 | 2.258 (3) | C7—C10 | 1.509 (4) |
Sn1—N2 | 2.489 (2) | C8—C9 | 1.381 (4) |
S1—C4 | 1.606 (3) | C8—H8 | 0.9300 |
N1—C4 | 1.152 (4) | C9—H9 | 0.9300 |
N2—C5 | 1.328 (3) | C10—C11 | 1.551 (4) |
N2—C9 | 1.344 (3) | C10—H10A | 0.9700 |
N3—C14 | 1.319 (4) | C10—H10B | 0.9700 |
N3—C15 | 1.326 (5) | C11—C12 | 1.509 (4) |
C1—H1A | 0.9600 | C11—C11i | 1.557 (5) |
C1—H1B | 0.9600 | C11—H11 | 0.9800 |
C1—H1C | 0.9600 | C12—C13 | 1.373 (4) |
C2—H2A | 0.9600 | C12—C16 | 1.388 (4) |
C2—H2B | 0.9600 | C13—C14 | 1.385 (4) |
C2—H2C | 0.9600 | C13—H13 | 0.9300 |
C3—H3A | 0.9600 | C14—H14 | 0.9300 |
C3—H3B | 0.9600 | C15—C16 | 1.376 (5) |
C3—H3C | 0.9600 | C15—H15 | 0.9300 |
C5—C6 | 1.386 (4) | C16—H16 | 0.9300 |
C5—H5 | 0.9300 | ||
C1—Sn1—C3 | 120.57 (17) | C5—C6—H6 | 120.1 |
C1—Sn1—C2 | 118.37 (16) | C7—C6—H6 | 120.1 |
C3—Sn1—C2 | 120.97 (15) | C8—C7—C6 | 116.6 (2) |
C1—Sn1—N1 | 90.01 (13) | C8—C7—C10 | 122.7 (2) |
C3—Sn1—N1 | 92.20 (13) | C6—C7—C10 | 120.7 (3) |
C2—Sn1—N1 | 90.71 (12) | C7—C8—C9 | 120.5 (2) |
C1—Sn1—N2 | 89.41 (11) | C7—C8—H8 | 119.8 |
C3—Sn1—N2 | 89.29 (10) | C9—C8—H8 | 119.8 |
C2—Sn1—N2 | 88.33 (10) | N2—C9—C8 | 123.0 (3) |
N1—Sn1—N2 | 178.49 (10) | N2—C9—H9 | 118.5 |
C4—N1—Sn1 | 168.1 (3) | C8—C9—H9 | 118.5 |
C5—N2—C9 | 116.8 (2) | C7—C10—C11 | 112.5 (2) |
C5—N2—Sn1 | 121.93 (16) | C7—C10—H10A | 109.1 |
C9—N2—Sn1 | 121.08 (18) | C11—C10—H10A | 109.1 |
C14—N3—C15 | 115.2 (3) | C7—C10—H10B | 109.1 |
Sn1—C1—H1A | 109.5 | C11—C10—H10B | 109.1 |
Sn1—C1—H1B | 109.5 | H10A—C10—H10B | 107.8 |
H1A—C1—H1B | 109.5 | C12—C11—C10 | 111.5 (2) |
Sn1—C1—H1C | 109.5 | C12—C11—C11i | 111.1 (2) |
H1A—C1—H1C | 109.5 | C10—C11—C11i | 110.7 (3) |
H1B—C1—H1C | 109.5 | C12—C11—H11 | 107.8 |
Sn1—C2—H2A | 109.5 | C10—C11—H11 | 107.8 |
Sn1—C2—H2B | 109.5 | C11i—C11—H11 | 107.8 |
H2A—C2—H2B | 109.5 | C13—C12—C16 | 116.3 (3) |
Sn1—C2—H2C | 109.5 | C13—C12—C11 | 121.8 (2) |
H2A—C2—H2C | 109.5 | C16—C12—C11 | 121.9 (3) |
H2B—C2—H2C | 109.5 | C12—C13—C14 | 120.1 (3) |
Sn1—C3—H3A | 109.5 | C12—C13—H13 | 119.9 |
Sn1—C3—H3B | 109.5 | C14—C13—H13 | 119.9 |
H3A—C3—H3B | 109.5 | N3—C14—C13 | 124.2 (3) |
Sn1—C3—H3C | 109.5 | N3—C14—H14 | 117.9 |
H3A—C3—H3C | 109.5 | C13—C14—H14 | 117.9 |
H3B—C3—H3C | 109.5 | N3—C15—C16 | 125.3 (3) |
N1—C4—S1 | 178.0 (3) | N3—C15—H15 | 117.4 |
N2—C5—C6 | 123.3 (2) | C16—C15—H15 | 117.4 |
N2—C5—H5 | 118.3 | C15—C16—C12 | 119.0 (3) |
C6—C5—H5 | 118.3 | C15—C16—H16 | 120.5 |
C5—C6—C7 | 119.8 (3) | C12—C16—H16 | 120.5 |
C1—Sn1—N1—C4 | 64.3 (14) | C7—C8—C9—N2 | 1.0 (5) |
C3—Sn1—N1—C4 | −175.1 (14) | C8—C7—C10—C11 | −101.4 (3) |
C2—Sn1—N1—C4 | −54.0 (14) | C6—C7—C10—C11 | 79.9 (3) |
C1—Sn1—N2—C5 | 24.7 (2) | C7—C10—C11—C12 | 62.2 (3) |
C3—Sn1—N2—C5 | −95.9 (2) | C7—C10—C11—C11i | −173.6 (3) |
C2—Sn1—N2—C5 | 143.1 (2) | C10—C11—C12—C13 | −123.3 (3) |
C1—Sn1—N2—C9 | −149.7 (3) | C11i—C11—C12—C13 | 112.7 (3) |
C3—Sn1—N2—C9 | 89.7 (2) | C10—C11—C12—C16 | 57.5 (3) |
C2—Sn1—N2—C9 | −31.3 (2) | C11i—C11—C12—C16 | −66.6 (4) |
C9—N2—C5—C6 | 1.3 (4) | C16—C12—C13—C14 | −0.3 (4) |
Sn1—N2—C5—C6 | −173.4 (2) | C11—C12—C13—C14 | −179.6 (2) |
N2—C5—C6—C7 | 0.1 (4) | C15—N3—C14—C13 | −0.6 (5) |
C5—C6—C7—C8 | −1.0 (4) | C12—C13—C14—N3 | 0.5 (4) |
C5—C6—C7—C10 | 177.9 (3) | C14—N3—C15—C16 | 0.5 (5) |
C6—C7—C8—C9 | 0.4 (4) | N3—C15—C16—C12 | −0.3 (6) |
C10—C7—C8—C9 | −178.4 (3) | C13—C12—C16—C15 | 0.2 (4) |
C5—N2—C9—C8 | −1.8 (4) | C11—C12—C16—C15 | 179.5 (3) |
Sn1—N2—C9—C8 | 172.9 (2) |
Symmetry code: (i) −x, −y, −z. |
Cg is the centroid of the N2-pyridine ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···Cgii | 0.93 | 2.79 | 3.631 (4) | 151 |
Symmetry code: (ii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Sn2(CH3)6(NCS)2(C24H22N4)] |
Mr | 810.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 9.2959 (8), 9.7210 (7), 10.2448 (9) |
α, β, γ (°) | 90.388 (7), 94.381 (7), 103.646 (7) |
V (Å3) | 896.72 (13) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.54 |
Crystal size (mm) | 0.25 × 0.25 × 0.05 |
Data collection | |
Diffractometer | Agilent SuperNova Dual diffractometer with an Atlas detector |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.700, 0.927 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8527, 4153, 3645 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.076, 1.05 |
No. of reflections | 4153 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.52 |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
Cg is the centroid of the N2-pyridine ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···Cgi | 0.93 | 2.7905 | 3.631 (4) | 151 |
Symmetry code: (i) −x+1, −y, −z. |
Acknowledgements
The authors thank Shahid Beheshti University and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.
References
Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Forder, R. A. & Sheldrick, G. M. (1970). J. Organomet. Chem. 21, 115–120. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Unlike trimethyltin chloride, the pseudohalide, trimethyltin thiocyanate, furnishes only few coordination compounds with aromatic amines. Trimethyltin thiocyanate itself exists as a zigzag chain in which the thiocyanate unit bridges adjacent trimethyltin cations (Forder & Sheldrick, 1970). The title adduct (Scheme I, Fig. 1) is the first crystal structure report of such an adduct. The tetrapyridyl-substitutent butane ligand, C24H22N4, uses the pyridine N-atoms at the either ends of the butyl chain to coordinate to a trimethylthiocyanatotin unit. The dinuclear molecule lies on a center-of-inversion, with the mid-point of the butyl chain coinciding with this symmetry element.
The Sn atom is displaced out of the trigonal plane, in the direction of the thiocyanate ion, by 0.036 (2) Å.