metal-organic compounds
4-(Dimethylamino)pyridinium dibromidotriphenylstannate(IV)
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
The anion in the title salt, (C7H11N2)[SnBr2(C6H5)3], lies on a twofold rotation axis that passes through the metal atom as well as the Cipso—Cpara atoms of one of the aromatic rings. The metal center is five-coordinate in a trans-Br2SnC3 trigonal bipyramidal geometry. The cation is disordered about a center of inversion.
Related literature
For the crystal structures of dibromidotriorganostannates, see: Aslanov et al. (1977); Spek et al. (2004); Wharf & Simard (1991).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); 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, 2008).
Supporting information
10.1107/S1600536808011094/sg2227sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011094/sg2227Isup2.hkl
Tetraphenyltin (2 g, 4.7 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (1.7 g, 4.6 mmol) were heated in chloroform (100 ml) for 6 h. The solution was filtered and the solvent allow to evaporate to give yellow crystals (m.p. 455–457 K, 80% yield).
The cation is disordered over a center-of-inversion, and was allowed to refine over this
as a half-occupancy cation. For the aromatic ring, 1,2-related distances were restrained to 1.39±0.01 Å and 1,3-related ones to 2.78±0.01 Å. For the dimethylamino group, the N–C distances were restrained to 1.50±0.01 Å. Anisotropic temperature factors of the carbon and nitrogen atoms were restrained to be nearly isotropic.Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the
in the riding model approximation, with U(H) set to 1.2 to 1.5U(C). The ammonium H-atom was similarly treated (N–H 0.86 Å; U(H) = 1.2U(B).The final difference Fourier map had a large peak at 1 Å from Br1.
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 2008).(C7H11N2)[SnBr2(C6H5)3] | F(000) = 1240 |
Mr = 632.99 | Dx = 1.706 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 7191 reflections |
a = 15.5955 (2) Å | θ = 2.3–24.8° |
b = 10.6897 (1) Å | µ = 4.29 mm−1 |
c = 14.8204 (2) Å | T = 100 K |
β = 93.924 (1)° | Block, yellow |
V = 2464.93 (5) Å3 | 0.3 × 0.2 × 0.1 mm |
Z = 4 |
Bruker SMART APEXII diffractometer | 2840 independent reflections |
Radiation source: fine-focus sealed tube | 2328 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −20→20 |
Tmin = 0.368, Tmax = 0.651 | k = −13→13 |
24740 measured reflections | l = −19→19 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0352P)2 + 2.1489P] where P = (Fo2 + 2Fc2)/3 |
2840 reflections | (Δ/σ)max = 0.001 |
180 parameters | Δρmax = 0.34 e Å−3 |
69 restraints | Δρmin = −1.16 e Å−3 |
(C7H11N2)[SnBr2(C6H5)3] | V = 2464.93 (5) Å3 |
Mr = 632.99 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.5955 (2) Å | µ = 4.29 mm−1 |
b = 10.6897 (1) Å | T = 100 K |
c = 14.8204 (2) Å | 0.3 × 0.2 × 0.1 mm |
β = 93.924 (1)° |
Bruker SMART APEXII diffractometer | 2840 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2328 reflections with I > 2σ(I) |
Tmin = 0.368, Tmax = 0.651 | Rint = 0.033 |
24740 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 69 restraints |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.34 e Å−3 |
2840 reflections | Δρmin = −1.16 e Å−3 |
180 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Sn1 | 0.5000 | 0.76516 (2) | 0.7500 | 0.03975 (9) | |
Br1 | 0.56766 (2) | 0.76825 (3) | 0.928473 (19) | 0.05538 (10) | |
C1 | 0.60873 (15) | 0.8708 (2) | 0.71394 (16) | 0.0377 (5) | |
C2 | 0.69169 (17) | 0.8273 (3) | 0.73324 (19) | 0.0504 (6) | |
H2 | 0.7004 | 0.7512 | 0.7629 | 0.061* | |
C3 | 0.76163 (18) | 0.8960 (3) | 0.7087 (2) | 0.0613 (8) | |
H3 | 0.8169 | 0.8647 | 0.7206 | 0.074* | |
C4 | 0.7501 (2) | 1.0094 (3) | 0.6672 (2) | 0.0647 (9) | |
H4 | 0.7974 | 1.0557 | 0.6515 | 0.078* | |
C5 | 0.6686 (2) | 1.0548 (3) | 0.6489 (2) | 0.0648 (8) | |
H5 | 0.6603 | 1.1322 | 0.6210 | 0.078* | |
C6 | 0.59864 (18) | 0.9851 (3) | 0.6720 (2) | 0.0518 (7) | |
H6 | 0.5435 | 1.0162 | 0.6588 | 0.062* | |
C7 | 0.5000 | 0.5641 (3) | 0.7500 | 0.0372 (7) | |
C8 | 0.51067 (16) | 0.4971 (3) | 0.67160 (19) | 0.0461 (6) | |
H8 | 0.5173 | 0.5399 | 0.6179 | 0.055* | |
C9 | 0.51168 (18) | 0.3672 (3) | 0.6717 (2) | 0.0557 (7) | |
H9 | 0.5203 | 0.3239 | 0.6187 | 0.067* | |
C10 | 0.5000 | 0.3029 (4) | 0.7500 | 0.0595 (11) | |
H10 | 0.5000 | 0.2159 | 0.7500 | 0.071* | |
N1 | 0.3033 (4) | 0.9766 (5) | 1.0723 (4) | 0.0750 (16) | 0.50 |
H1 | 0.3207 | 1.0468 | 1.0950 | 0.090* | 0.50 |
C11 | 0.3619 (5) | 0.8914 (9) | 1.0461 (4) | 0.065 (4) | 0.50 |
H11 | 0.4203 | 0.9101 | 1.0530 | 0.078* | 0.50 |
C12 | 0.3361 (4) | 0.7792 (6) | 1.0100 (4) | 0.0548 (14) | 0.50 |
H12 | 0.3757 | 0.7209 | 0.9920 | 0.066* | 0.50 |
C13 | 0.2490 (6) | 0.7552 (8) | 1.0011 (6) | 0.0454 (9) | 0.50 |
C14 | 0.1886 (3) | 0.8397 (5) | 1.0268 (4) | 0.0547 (14) | 0.50 |
H14 | 0.1302 | 0.8215 | 1.0199 | 0.066* | 0.50 |
C15 | 0.2171 (6) | 0.9515 (9) | 1.0628 (6) | 0.091 (9) | 0.50 |
H15 | 0.1778 | 1.0104 | 1.0808 | 0.109* | 0.50 |
N2 | 0.2210 (3) | 0.6420 (4) | 0.9598 (3) | 0.0512 (11) | 0.50 |
C16 | 0.2813 (5) | 0.5487 (7) | 0.9338 (7) | 0.059 (6) | 0.50 |
H16A | 0.3126 | 0.5803 | 0.8850 | 0.089* | 0.50 |
H16B | 0.2508 | 0.4744 | 0.9145 | 0.089* | 0.50 |
H16C | 0.3208 | 0.5295 | 0.9844 | 0.089* | 0.50 |
C17 | 0.1314 (6) | 0.6173 (12) | 0.9365 (9) | 0.077 (4) | 0.50 |
H17A | 0.0998 | 0.6239 | 0.9897 | 0.116* | 0.50 |
H17B | 0.1250 | 0.5345 | 0.9119 | 0.116* | 0.50 |
H17C | 0.1096 | 0.6772 | 0.8924 | 0.116* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.03660 (13) | 0.03341 (14) | 0.04972 (15) | 0.000 | 0.00641 (10) | 0.000 |
Br1 | 0.05950 (19) | 0.0641 (2) | 0.04166 (16) | −0.00651 (13) | −0.00302 (13) | −0.00418 (12) |
C1 | 0.0366 (12) | 0.0376 (13) | 0.0393 (12) | −0.0018 (10) | 0.0044 (10) | −0.0026 (10) |
C2 | 0.0446 (14) | 0.0523 (17) | 0.0544 (16) | 0.0075 (12) | 0.0036 (12) | 0.0014 (13) |
C3 | 0.0356 (14) | 0.085 (2) | 0.0640 (19) | −0.0006 (14) | 0.0056 (13) | −0.0193 (17) |
C4 | 0.0598 (19) | 0.073 (2) | 0.0630 (19) | −0.0290 (17) | 0.0163 (15) | −0.0189 (17) |
C5 | 0.078 (2) | 0.0459 (17) | 0.070 (2) | −0.0193 (15) | 0.0078 (17) | 0.0074 (15) |
C6 | 0.0485 (15) | 0.0409 (15) | 0.0651 (18) | −0.0002 (12) | −0.0021 (13) | 0.0052 (13) |
C7 | 0.0311 (16) | 0.0348 (17) | 0.0456 (19) | 0.000 | 0.0023 (14) | 0.000 |
C8 | 0.0429 (14) | 0.0454 (14) | 0.0503 (15) | −0.0012 (11) | 0.0056 (11) | −0.0031 (12) |
C9 | 0.0529 (16) | 0.0472 (16) | 0.0668 (19) | 0.0020 (13) | 0.0029 (14) | −0.0157 (14) |
C10 | 0.055 (2) | 0.038 (2) | 0.085 (3) | 0.000 | −0.001 (2) | 0.000 |
N1 | 0.080 (4) | 0.075 (4) | 0.070 (3) | −0.024 (3) | 0.002 (3) | −0.017 (3) |
C11 | 0.057 (5) | 0.077 (7) | 0.061 (5) | −0.010 (5) | −0.003 (4) | −0.002 (4) |
C12 | 0.050 (3) | 0.066 (4) | 0.049 (3) | 0.000 (3) | 0.003 (2) | 0.004 (3) |
C13 | 0.051 (2) | 0.050 (2) | 0.0354 (18) | −0.0006 (18) | 0.0071 (16) | 0.0045 (17) |
C14 | 0.050 (3) | 0.058 (3) | 0.057 (3) | −0.004 (3) | 0.009 (3) | −0.007 (3) |
C15 | 0.096 (12) | 0.091 (12) | 0.088 (12) | −0.004 (8) | 0.017 (8) | −0.006 (8) |
N2 | 0.061 (3) | 0.046 (2) | 0.047 (3) | −0.002 (2) | 0.003 (2) | −0.001 (2) |
C16 | 0.068 (8) | 0.049 (7) | 0.061 (8) | 0.005 (5) | 0.014 (5) | −0.018 (5) |
C17 | 0.073 (7) | 0.068 (6) | 0.088 (6) | −0.018 (5) | −0.005 (5) | −0.006 (5) |
Sn1—C1 | 2.135 (2) | C10—C9i | 1.372 (4) |
Sn1—C1i | 2.135 (2) | C10—H10 | 0.9300 |
Sn1—C7 | 2.149 (3) | N1—C11 | 1.366 (9) |
Sn1—Br1i | 2.7801 (3) | N1—C15 | 1.369 (9) |
Sn1—Br1 | 2.7801 (3) | N1—H1 | 0.8600 |
C1—C6 | 1.375 (4) | C11—C12 | 1.363 (9) |
C1—C2 | 1.386 (3) | C11—H11 | 0.9300 |
C2—C3 | 1.384 (4) | C12—C13 | 1.379 (9) |
C2—H2 | 0.9300 | C12—H12 | 0.9300 |
C3—C4 | 1.365 (5) | C13—C14 | 1.378 (9) |
C3—H3 | 0.9300 | C13—N2 | 1.412 (8) |
C4—C5 | 1.371 (5) | C14—C15 | 1.370 (9) |
C4—H4 | 0.9300 | C14—H14 | 0.9300 |
C5—C6 | 1.383 (4) | C15—H15 | 0.9300 |
C5—H5 | 0.9300 | N2—C16 | 1.441 (7) |
C6—H6 | 0.9300 | N2—C17 | 1.441 (8) |
C7—C8 | 1.384 (3) | C16—H16A | 0.9600 |
C7—C8i | 1.384 (3) | C16—H16B | 0.9600 |
C8—C9 | 1.389 (4) | C16—H16C | 0.9600 |
C8—H8 | 0.9300 | C17—H17A | 0.9600 |
C9—C10 | 1.372 (4) | C17—H17B | 0.9600 |
C9—H9 | 0.9300 | C17—H17C | 0.9600 |
C1—Sn1—C1i | 116.17 (13) | C9—C8—C7 | 121.2 (3) |
C1—Sn1—C7 | 121.92 (6) | C9—C8—H8 | 119.4 |
C1i—Sn1—C7 | 121.92 (6) | C7—C8—H8 | 119.4 |
C1—Sn1—Br1 | 88.61 (6) | C10—C9—C8 | 120.0 (3) |
C1—Sn1—Br1i | 90.68 (6) | C10—C9—H9 | 120.0 |
C1i—Sn1—Br1i | 88.61 (6) | C8—C9—H9 | 120.0 |
C7—Sn1—Br1 | 90.68 (1) | C9—C10—C9i | 119.8 (4) |
C7—Sn1—Br1i | 90.68 (1) | C9—C10—H10 | 120.1 |
C1i—Sn1—Br1 | 90.68 (6) | C9i—C10—H10 | 120.1 |
Br1—Sn1—Br1i | 178.64 (2) | C11—N1—C15 | 120.8 (7) |
C6—C1—C2 | 117.9 (2) | C11—N1—H1 | 119.6 |
C6—C1—Sn1 | 120.98 (18) | C15—N1—H1 | 119.6 |
C2—C1—Sn1 | 121.13 (19) | C12—C11—N1 | 120.8 (7) |
C3—C2—C1 | 120.6 (3) | C12—C11—H11 | 119.6 |
C3—C2—H2 | 119.7 | N1—C11—H11 | 119.6 |
C1—C2—H2 | 119.7 | C11—C12—C13 | 117.7 (6) |
C4—C3—C2 | 120.5 (3) | C11—C12—H12 | 121.2 |
C4—C3—H3 | 119.7 | C13—C12—H12 | 121.2 |
C2—C3—H3 | 119.7 | C14—C13—C12 | 122.6 (7) |
C3—C4—C5 | 119.7 (3) | C14—C13—N2 | 119.0 (7) |
C3—C4—H4 | 120.2 | C12—C13—N2 | 118.3 (7) |
C5—C4—H4 | 120.2 | C15—C14—C13 | 118.0 (7) |
C4—C5—C6 | 119.8 (3) | C15—C14—H14 | 121.0 |
C4—C5—H5 | 120.1 | C13—C14—H14 | 121.0 |
C6—C5—H5 | 120.1 | C14—C15—N1 | 120.1 (7) |
C1—C6—C5 | 121.5 (3) | C14—C15—H15 | 120.0 |
C1—C6—H6 | 119.2 | N1—C15—H15 | 120.0 |
C5—C6—H6 | 119.2 | C13—N2—C16 | 121.4 (6) |
C8—C7—C8i | 117.7 (3) | C13—N2—C17 | 121.8 (7) |
C8—C7—Sn1 | 121.13 (17) | C16—N2—C17 | 116.7 (7) |
C8i—C7—Sn1 | 121.13 (17) | ||
C1i—Sn1—C1—C6 | −32.12 (19) | C1—Sn1—C7—C8i | 119.08 (14) |
C7—Sn1—C1—C6 | 147.88 (19) | C1i—Sn1—C7—C8i | −60.92 (14) |
Br1i—Sn1—C1—C6 | 56.7 (2) | Br1i—Sn1—C7—C8i | −149.70 (12) |
Br1—Sn1—C1—C6 | −122.2 (2) | Br1—Sn1—C7—C8i | 30.30 (12) |
C1i—Sn1—C1—C2 | 146.9 (2) | C8i—C7—C8—C9 | −0.75 (19) |
C7—Sn1—C1—C2 | −33.1 (2) | Sn1—C7—C8—C9 | 179.25 (19) |
Br1i—Sn1—C1—C2 | −124.3 (2) | C7—C8—C9—C10 | 1.5 (4) |
Br1—Sn1—C1—C2 | 56.9 (2) | C8—C9—C10—C9i | −0.74 (18) |
C6—C1—C2—C3 | −1.6 (4) | C15—N1—C11—C12 | −0.1 (3) |
Sn1—C1—C2—C3 | 179.4 (2) | N1—C11—C12—C13 | −0.1 (3) |
C1—C2—C3—C4 | 1.8 (5) | C11—C12—C13—C14 | 0.2 (7) |
C2—C3—C4—C5 | −0.7 (5) | C11—C12—C13—N2 | 177.0 (7) |
C3—C4—C5—C6 | −0.4 (5) | C12—C13—C14—C15 | −0.2 (10) |
C2—C1—C6—C5 | 0.4 (4) | N2—C13—C14—C15 | −177.0 (7) |
Sn1—C1—C6—C5 | 179.5 (2) | C13—C14—C15—N1 | 0.1 (9) |
C4—C5—C6—C1 | 0.6 (5) | C11—N1—C15—C14 | 0.1 (7) |
C1—Sn1—C7—C8 | −60.92 (14) | C14—C13—N2—C16 | −178.4 (7) |
C1i—Sn1—C7—C8 | 119.08 (14) | C12—C13—N2—C16 | 4.7 (11) |
Br1i—Sn1—C7—C8 | 30.30 (12) | C14—C13—N2—C17 | 5.7 (12) |
Br1—Sn1—C7—C8 | −149.70 (12) | C12—C13—N2—C17 | −171.2 (9) |
Symmetry code: (i) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | (C7H11N2)[SnBr2(C6H5)3] |
Mr | 632.99 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 15.5955 (2), 10.6897 (1), 14.8204 (2) |
β (°) | 93.924 (1) |
V (Å3) | 2464.93 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.29 |
Crystal size (mm) | 0.3 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Bruker SMART APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.368, 0.651 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24740, 2840, 2328 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.069, 1.06 |
No. of reflections | 2840 |
No. of parameters | 180 |
No. of restraints | 69 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −1.16 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).
Sn1—C1 | 2.135 (2) | Sn1—Br1 | 2.7801 (3) |
Sn1—C7 | 2.149 (3) | ||
C1—Sn1—C1i | 116.17 (13) | C1—Sn1—Br1i | 90.68 (6) |
C1—Sn1—C7 | 121.92 (6) | C7—Sn1—Br1 | 90.68 (1) |
C1—Sn1—Br1 | 88.61 (6) | Br1—Sn1—Br1i | 178.64 (2) |
Symmetry code: (i) −x+1, y, −z+3/2. |
Acknowledgements
We thank the University of Malaya for funding this study (FR155/2007 A) and also for the purchase of the diffractometer.
References
Aslanov, L. A., Attiya, V. M., Ionov, V. M., Permin, A. B. & Petrosyan, V. S. (1977). Zh. Strukt. Khim. 18, 1113–1118. CAS Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L., Wijkens, P. & van Koten, G. (2004). Private communication (refcode CSIGOC). CCDC, Cambridge, England. Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar
Wharf, I. & Simard, M. G. (1991). Acta Cryst. C47, 1605–1609. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
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The aqueous solubility of biocidal triorganotin halides can be improved by converting them to their ionic salts through treatment with an ammonium halide. A small number of ammonium dihalogenotriorganostannates are known; tetraethylammonium dibromidotriphenylstannate, who crystal structure is known, is synthesized in this manner (Wharf & Simard, 1991).
The present synthesis uses the mild brominating agent, 4-dimethylaminopyridine hydrobromide perbromide, which cleaves one of the four tin-carbon bonds of tetraphenyltin to yield the bromidotriphenylstannate anion. In the title compound (I), the anion lies about a twofold rotation axis that passes through the metal atom as well as the Cipso–Cpara atoms of one of the aromatic rings. The metal center is five-coordinate in a trans-C3SnBr2 trigonal bipyramidal geometry. The cation and anion exist as two non-interacting species (Fig. 1).