Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109010956/sf3102sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109010956/sf3102Isup2.hkl |
CCDC reference: 735099
For related literature, see: Ahari et al. (1995a); Bedard et al. (1989); Li et al. (1999, 2000); Parise et al. (1994); Wendland et al. (1998).
A mixture of Sn power (0.0594 g, 0.5 mmol) and Se (0.0789 g, 1.0 mmol) with MnCl2.4H2O (0.1980 g, 1.0 mmol) in 3.0 ml of teta/glycol (v/v 1:2) was stirred for 30 min in a 17.0 ml Teflon-lined stainless steel vessel. The vessel was sealed and heated at 463 K for one week. Orange block crystals were isolated by washing with ethanol and water.
All H atoms bound to C atoms were refined using a riding model with C—H distances of 0.97 Å and Uiso(H) values of 1.2Ueq(C). The imine H atoms were refined using a riding model with N—H distances of 0.91 Å and Uiso(H) set at 1.2Ueq(N). The amine H atoms were located in a difference Fourier map and refined isotropically with Uiso(H) set at 1.5Ueq(N).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Mn(C10H28N6)][Sn3Se7] | F(000) = 2172 |
Mr = 1196.11 | Dx = 2.953 Mg m−3 |
Monoclinic, P21/n | Melting point: not measured K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71069 Å |
a = 11.893 (5) Å | θ = 1.9–26.1° |
b = 13.322 (5) Å | µ = 12.69 mm−1 |
c = 17.097 (5) Å | T = 207 K |
β = 96.659 (5)° | Block, orange |
V = 2690.5 (17) Å3 | 0.12 × 0.12 × 0.08 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 5291 independent reflections |
Radiation source: fine-focus sealed tube | 3945 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ω scan | θmax = 26.1°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→14 |
Tmin = 0.230, Tmax = 0.308 | k = −16→16 |
14868 measured reflections | l = −15→21 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0273P)2] where P = (Fo2 + 2Fc2)/3 |
5291 reflections | (Δ/σ)max = 0.001 |
256 parameters | Δρmax = 1.20 e Å−3 |
6 restraints | Δρmin = −0.88 e Å−3 |
[Mn(C10H28N6)][Sn3Se7] | V = 2690.5 (17) Å3 |
Mr = 1196.11 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.893 (5) Å | µ = 12.69 mm−1 |
b = 13.322 (5) Å | T = 207 K |
c = 17.097 (5) Å | 0.12 × 0.12 × 0.08 mm |
β = 96.659 (5)° |
Bruker SMART APEX CCD diffractometer | 5291 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3945 reflections with I > 2σ(I) |
Tmin = 0.230, Tmax = 0.308 | Rint = 0.055 |
14868 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 6 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 1.20 e Å−3 |
5291 reflections | Δρmin = −0.88 e Å−3 |
256 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.0151 (8) | 0.2378 (7) | −0.0479 (6) | 0.041 (3) | |
H1A | 1.0381 | 0.2501 | −0.0996 | 0.049* | |
H1B | 1.0701 | 0.1929 | −0.0199 | 0.049* | |
C2 | 1.0141 (8) | 0.3334 (7) | −0.0047 (6) | 0.041 (3) | |
H2A | 1.0910 | 0.3581 | 0.0071 | 0.049* | |
H2B | 0.9711 | 0.3829 | −0.0373 | 0.049* | |
C3 | 0.9266 (10) | 0.4091 (8) | 0.0970 (6) | 0.058 (3) | |
H3A | 0.8718 | 0.4397 | 0.0577 | 0.070* | |
H3B | 0.9899 | 0.4550 | 0.1074 | 0.070* | |
C4 | 0.8715 (9) | 0.3929 (9) | 0.1737 (7) | 0.058 (3) | |
H4A | 0.8388 | 0.4552 | 0.1897 | 0.069* | |
H4B | 0.9283 | 0.3712 | 0.2157 | 0.069* | |
C5 | 0.7640 (9) | 0.2531 (7) | 0.2305 (6) | 0.046 (3) | |
H5A | 0.7641 | 0.2990 | 0.2746 | 0.055* | |
H5B | 0.6926 | 0.2171 | 0.2248 | 0.055* | |
C6 | 0.8566 (8) | 0.1832 (7) | 0.2453 (5) | 0.038 (2) | |
H6A | 0.8450 | 0.1423 | 0.2906 | 0.046* | |
H6B | 0.9264 | 0.2204 | 0.2579 | 0.046* | |
C7 | 0.7910 (9) | 0.0288 (7) | 0.1775 (6) | 0.046 (3) | |
H7A | 0.8147 | −0.0144 | 0.2221 | 0.056* | |
H7B | 0.7143 | 0.0513 | 0.1816 | 0.056* | |
C8 | 0.7955 (10) | −0.0257 (7) | 0.1040 (6) | 0.052 (3) | |
H8A | 0.7460 | −0.0837 | 0.1025 | 0.062* | |
H8B | 0.8720 | −0.0492 | 0.1009 | 0.062* | |
C9 | 0.6359 (9) | 0.0475 (7) | 0.0148 (5) | 0.045 (3) | |
H9A | 0.5993 | 0.0600 | 0.0617 | 0.054* | |
H9B | 0.6076 | −0.0157 | −0.0079 | 0.054* | |
C10 | 0.6074 (8) | 0.1318 (7) | −0.0442 (6) | 0.041 (3) | |
H10A | 0.6415 | 0.1186 | −0.0921 | 0.050* | |
H10B | 0.5261 | 0.1365 | −0.0576 | 0.050* | |
N1 | 0.9061 (8) | 0.1906 (7) | −0.0563 (5) | 0.046 (2) | |
H11 | 0.910 (8) | 0.1237 (17) | −0.058 (5) | 0.069* | |
H12 | 0.869 (8) | 0.232 (5) | −0.092 (4) | 0.069* | |
N2 | 0.9642 (8) | 0.3202 (6) | 0.0677 (5) | 0.046 (2) | |
H2 | 1.0205 | 0.2975 | 0.1040 | 0.055* | |
N3 | 0.7761 (8) | 0.3099 (7) | 0.1578 (5) | 0.062 (3) | |
H3 | 0.7091 | 0.3403 | 0.1409 | 0.074* | |
N4 | 0.8683 (6) | 0.1165 (5) | 0.1773 (5) | 0.037 (2) | |
H4 | 0.9410 | 0.0943 | 0.1801 | 0.045* | |
N5 | 0.7596 (7) | 0.0408 (5) | 0.0362 (5) | 0.040 (2) | |
H5 | 0.7909 | 0.0173 | −0.0063 | 0.048* | |
N6 | 0.6527 (7) | 0.2277 (6) | −0.0075 (5) | 0.041 (2) | |
H13 | 0.607 (7) | 0.237 (6) | 0.031 (4) | 0.062* | |
H14 | 0.656 (8) | 0.273 (5) | −0.047 (4) | 0.062* | |
Mn1 | 0.82375 (12) | 0.20223 (10) | 0.06120 (8) | 0.0321 (4) | |
Se1 | 0.15410 (7) | 0.07534 (6) | 0.13339 (5) | 0.0223 (2) | |
Se2 | 0.44058 (7) | 0.07885 (6) | 0.24427 (6) | 0.0274 (2) | |
Se3 | 0.34580 (8) | 0.26259 (6) | 0.03677 (5) | 0.0239 (2) | |
Se4 | 0.45946 (7) | 0.37623 (6) | 0.22809 (5) | 0.0202 (2) | |
Se5 | 0.16816 (7) | 0.30535 (6) | 0.24788 (5) | 0.0242 (2) | |
Se6 | 0.26315 (8) | 0.55473 (6) | 0.11141 (5) | 0.0253 (2) | |
Se7 | 0.61897 (8) | 0.50332 (7) | 0.07738 (5) | 0.0266 (2) | |
Sn1 | 0.32590 (5) | 0.22048 (4) | 0.18025 (3) | 0.01988 (15) | |
Sn2 | 0.41900 (5) | 0.44057 (4) | 0.07331 (3) | 0.01951 (15) | |
Sn3 | 0.25791 (5) | 0.47987 (4) | 0.24775 (3) | 0.02007 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.036 (6) | 0.050 (7) | 0.035 (7) | −0.004 (5) | −0.002 (5) | −0.001 (5) |
C2 | 0.035 (6) | 0.043 (7) | 0.045 (7) | 0.001 (5) | 0.007 (5) | 0.014 (5) |
C3 | 0.066 (9) | 0.057 (8) | 0.053 (8) | 0.004 (6) | 0.012 (7) | 0.005 (6) |
C4 | 0.053 (8) | 0.060 (8) | 0.058 (8) | 0.010 (6) | −0.002 (6) | −0.017 (6) |
C5 | 0.066 (8) | 0.036 (6) | 0.038 (7) | 0.006 (5) | 0.019 (6) | −0.001 (5) |
C6 | 0.043 (6) | 0.045 (6) | 0.024 (6) | −0.005 (5) | −0.004 (5) | 0.007 (5) |
C7 | 0.063 (8) | 0.033 (6) | 0.043 (7) | −0.001 (5) | 0.004 (6) | 0.013 (5) |
C8 | 0.095 (10) | 0.016 (5) | 0.046 (7) | 0.005 (5) | 0.019 (7) | 0.010 (5) |
C9 | 0.074 (8) | 0.038 (6) | 0.027 (6) | −0.014 (6) | 0.025 (6) | −0.004 (5) |
C10 | 0.040 (6) | 0.050 (7) | 0.036 (7) | −0.003 (5) | 0.011 (5) | −0.008 (5) |
N1 | 0.047 (6) | 0.050 (6) | 0.044 (6) | −0.016 (5) | 0.016 (5) | −0.004 (5) |
N2 | 0.074 (7) | 0.029 (5) | 0.031 (5) | −0.009 (5) | −0.007 (5) | −0.003 (4) |
N3 | 0.085 (8) | 0.045 (6) | 0.055 (7) | 0.028 (6) | 0.002 (6) | −0.008 (5) |
N4 | 0.033 (5) | 0.028 (4) | 0.051 (6) | 0.009 (4) | 0.004 (4) | 0.008 (4) |
N5 | 0.058 (6) | 0.028 (5) | 0.037 (5) | −0.002 (4) | 0.023 (4) | −0.007 (4) |
N6 | 0.047 (6) | 0.032 (5) | 0.048 (6) | −0.004 (4) | 0.019 (4) | 0.005 (4) |
Mn1 | 0.0464 (9) | 0.0240 (8) | 0.0273 (9) | −0.0057 (7) | 0.0100 (7) | −0.0008 (6) |
Se1 | 0.0312 (5) | 0.0165 (4) | 0.0198 (5) | −0.0024 (4) | 0.0046 (4) | 0.0000 (4) |
Se2 | 0.0234 (5) | 0.0192 (5) | 0.0405 (6) | 0.0015 (4) | 0.0068 (4) | 0.0103 (4) |
Se3 | 0.0363 (5) | 0.0168 (4) | 0.0198 (5) | −0.0045 (4) | 0.0085 (4) | −0.0017 (4) |
Se4 | 0.0254 (5) | 0.0168 (4) | 0.0187 (5) | 0.0011 (4) | 0.0045 (4) | 0.0025 (4) |
Se5 | 0.0266 (5) | 0.0163 (4) | 0.0320 (6) | −0.0012 (4) | 0.0131 (4) | −0.0021 (4) |
Se6 | 0.0341 (5) | 0.0208 (5) | 0.0219 (5) | 0.0102 (4) | 0.0071 (4) | 0.0047 (4) |
Se7 | 0.0298 (5) | 0.0309 (5) | 0.0193 (5) | −0.0080 (4) | 0.0031 (4) | 0.0053 (4) |
Sn1 | 0.0274 (3) | 0.0127 (3) | 0.0212 (3) | 0.0026 (2) | 0.0096 (3) | 0.0027 (2) |
Sn2 | 0.0268 (3) | 0.0144 (3) | 0.0189 (3) | −0.0004 (2) | 0.0092 (3) | 0.0016 (2) |
Sn3 | 0.0293 (3) | 0.0140 (3) | 0.0183 (3) | 0.0006 (2) | 0.0085 (3) | −0.0010 (2) |
C1—N1 | 1.433 (12) | C10—H10B | 0.9700 |
C1—C2 | 1.474 (12) | N1—Mn1 | 2.340 (9) |
C1—H1A | 0.9700 | N1—H11 | 0.89 (2) |
C1—H1B | 0.9700 | N1—H12 | 0.90 (2) |
C2—N2 | 1.444 (11) | N2—Mn1 | 2.287 (8) |
C2—H2A | 0.9700 | N2—H2 | 0.9100 |
C2—H2B | 0.9700 | N3—Mn1 | 2.308 (8) |
C3—N2 | 1.381 (12) | N3—H3 | 0.9100 |
C3—C4 | 1.547 (14) | N4—Mn1 | 2.299 (8) |
C3—H3A | 0.9700 | N4—H4 | 0.9100 |
C3—H3B | 0.9700 | N5—Mn1 | 2.306 (7) |
C4—N3 | 1.585 (13) | N5—H5 | 0.9100 |
C4—H4A | 0.9700 | N6—Mn1 | 2.254 (9) |
C4—H4B | 0.9700 | N6—H13 | 0.91 (2) |
C5—C6 | 1.442 (12) | N6—H14 | 0.91 (2) |
C5—N3 | 1.476 (12) | Se1—Sn3i | 2.5197 (12) |
C5—H5A | 0.9700 | Se1—Sn1 | 2.8592 (13) |
C5—H5B | 0.9700 | Se2—Sn1 | 2.5044 (12) |
C6—N4 | 1.481 (11) | Se2—Sn3i | 2.7211 (14) |
C6—H6A | 0.9700 | Se3—Sn1 | 2.5540 (12) |
C6—H6B | 0.9700 | Se3—Sn2 | 2.5776 (13) |
C7—C8 | 1.458 (13) | Se4—Sn1 | 2.6826 (12) |
C7—N4 | 1.487 (11) | Se4—Sn2 | 2.7701 (12) |
C7—H7A | 0.9700 | Se4—Sn3 | 2.8200 (13) |
C7—H7B | 0.9700 | Se5—Sn3 | 2.5584 (13) |
C8—N5 | 1.482 (11) | Se5—Sn1 | 2.5764 (12) |
C8—H8A | 0.9700 | Se6—Sn2 | 2.5402 (12) |
C8—H8B | 0.9700 | Se6—Sn3 | 2.5429 (12) |
C9—N5 | 1.477 (12) | Se7—Sn2 | 2.5142 (14) |
C9—C10 | 1.521 (13) | Se7—Sn2ii | 2.6703 (13) |
C9—H9A | 0.9700 | Sn2—Se7ii | 2.6703 (13) |
C9—H9B | 0.9700 | Sn3—Se1iii | 2.5197 (12) |
C10—N6 | 1.496 (12) | Sn3—Se2iii | 2.7211 (14) |
C10—H10A | 0.9700 | ||
N1—C1—C2 | 111.7 (8) | C5—N3—H3 | 109.1 |
N1—C1—H1A | 109.3 | C4—N3—H3 | 109.1 |
C2—C1—H1A | 109.3 | Mn1—N3—H3 | 109.1 |
N1—C1—H1B | 109.3 | C6—N4—C7 | 110.8 (7) |
C2—C1—H1B | 109.3 | C6—N4—Mn1 | 110.2 (5) |
H1A—C1—H1B | 107.9 | C7—N4—Mn1 | 108.2 (6) |
N2—C2—C1 | 110.6 (8) | C6—N4—H4 | 109.2 |
N2—C2—H2A | 109.5 | C7—N4—H4 | 109.2 |
C1—C2—H2A | 109.5 | Mn1—N4—H4 | 109.2 |
N2—C2—H2B | 109.5 | C9—N5—C8 | 114.7 (8) |
C1—C2—H2B | 109.5 | C9—N5—Mn1 | 106.8 (6) |
H2A—C2—H2B | 108.1 | C8—N5—Mn1 | 110.7 (6) |
N2—C3—C4 | 112.0 (9) | C9—N5—H5 | 108.2 |
N2—C3—H3A | 109.2 | C8—N5—H5 | 108.2 |
C4—C3—H3A | 109.2 | Mn1—N5—H5 | 108.2 |
N2—C3—H3B | 109.2 | C10—N6—Mn1 | 110.4 (6) |
C4—C3—H3B | 109.2 | C10—N6—H13 | 101 (6) |
H3A—C3—H3B | 107.9 | Mn1—N6—H13 | 103 (6) |
C3—C4—N3 | 108.5 (9) | C10—N6—H14 | 108 (6) |
C3—C4—H4A | 110.0 | Mn1—N6—H14 | 112 (6) |
N3—C4—H4A | 110.0 | H13—N6—H14 | 122 (4) |
C3—C4—H4B | 110.0 | N6—Mn1—N2 | 122.1 (3) |
N3—C4—H4B | 110.0 | N6—Mn1—N4 | 128.9 (3) |
H4A—C4—H4B | 108.4 | N2—Mn1—N4 | 101.9 (3) |
C6—C5—N3 | 109.3 (8) | N6—Mn1—N5 | 77.5 (3) |
C6—C5—H5A | 109.8 | N2—Mn1—N5 | 151.0 (3) |
N3—C5—H5A | 109.8 | N4—Mn1—N5 | 74.6 (3) |
C6—C5—H5B | 109.8 | N6—Mn1—N3 | 89.9 (3) |
N3—C5—H5B | 109.8 | N2—Mn1—N3 | 77.1 (3) |
H5A—C5—H5B | 108.3 | N4—Mn1—N3 | 75.0 (3) |
C5—C6—N4 | 113.0 (8) | N5—Mn1—N3 | 127.5 (3) |
C5—C6—H6A | 109.0 | N6—Mn1—N1 | 90.3 (3) |
N4—C6—H6A | 109.0 | N2—Mn1—N1 | 73.2 (3) |
C5—C6—H6B | 109.0 | N4—Mn1—N1 | 129.1 (3) |
N4—C6—H6B | 109.0 | N5—Mn1—N1 | 86.6 (3) |
H6A—C6—H6B | 107.8 | N3—Mn1—N1 | 144.9 (3) |
C8—C7—N4 | 107.7 (8) | Sn3i—Se1—Sn1 | 84.20 (4) |
C8—C7—H7A | 110.2 | Sn1—Se2—Sn3i | 87.44 (4) |
N4—C7—H7A | 110.2 | Sn1—Se3—Sn2 | 92.04 (3) |
C8—C7—H7B | 110.2 | Sn1—Se4—Sn2 | 85.24 (3) |
N4—C7—H7B | 110.2 | Sn1—Se4—Sn3 | 86.19 (4) |
H7A—C7—H7B | 108.5 | Sn2—Se4—Sn3 | 84.64 (3) |
C7—C8—N5 | 109.9 (8) | Sn3—Se5—Sn1 | 94.18 (4) |
C7—C8—H8A | 109.7 | Sn2—Se6—Sn3 | 95.54 (4) |
N5—C8—H8A | 109.7 | Sn2—Se7—Sn2ii | 90.73 (3) |
C7—C8—H8B | 109.7 | Se2—Sn1—Se3 | 118.61 (4) |
N5—C8—H8B | 109.7 | Se2—Sn1—Se5 | 121.50 (4) |
H8A—C8—H8B | 108.2 | Se3—Sn1—Se5 | 119.21 (4) |
N5—C9—C10 | 110.3 (8) | Se2—Sn1—Se4 | 100.15 (4) |
N5—C9—H9A | 109.6 | Se3—Sn1—Se4 | 90.31 (3) |
C10—C9—H9A | 109.6 | Se5—Sn1—Se4 | 87.71 (4) |
N5—C9—H9B | 109.6 | Se2—Sn1—Se1 | 87.04 (4) |
C10—C9—H9B | 109.6 | Se3—Sn1—Se1 | 91.27 (3) |
H9A—C9—H9B | 108.1 | Se5—Sn1—Se1 | 83.61 (4) |
N6—C10—C9 | 108.1 (8) | Se4—Sn1—Se1 | 170.79 (3) |
N6—C10—H10A | 110.1 | Se7—Sn2—Se6 | 120.65 (4) |
C9—C10—H10A | 110.1 | Se7—Sn2—Se3 | 127.18 (4) |
N6—C10—H10B | 110.1 | Se6—Sn2—Se3 | 112.14 (4) |
C9—C10—H10B | 110.1 | Se7—Sn2—Se7ii | 89.27 (3) |
H10A—C10—H10B | 108.4 | Se6—Sn2—Se7ii | 91.89 (4) |
C1—N1—Mn1 | 110.4 (6) | Se3—Sn2—Se7ii | 90.52 (4) |
C1—N1—H11 | 113 (7) | Se7—Sn2—Se4 | 91.00 (3) |
Mn1—N1—H11 | 97 (7) | Se6—Sn2—Se4 | 89.51 (3) |
C1—N1—H12 | 100 (7) | Se3—Sn2—Se4 | 87.90 (3) |
Mn1—N1—H12 | 108 (7) | Se7ii—Sn2—Se4 | 178.20 (3) |
H11—N1—H12 | 128 (4) | Se1iii—Sn3—Se6 | 119.30 (4) |
C3—N2—C2 | 112.9 (8) | Se1iii—Sn3—Se5 | 126.32 (4) |
C3—N2—Mn1 | 110.0 (7) | Se6—Sn3—Se5 | 114.31 (4) |
C2—N2—Mn1 | 114.4 (6) | Se1iii—Sn3—Se2iii | 89.81 (4) |
C3—N2—H2 | 106.3 | Se6—Sn3—Se2iii | 88.25 (3) |
C2—N2—H2 | 106.3 | Se5—Sn3—Se2iii | 94.35 (4) |
Mn1—N2—H2 | 106.3 | Se1iii—Sn3—Se4 | 93.67 (4) |
C5—N3—C4 | 110.5 (9) | Se6—Sn3—Se4 | 88.35 (3) |
C5—N3—Mn1 | 109.9 (6) | Se5—Sn3—Se4 | 85.16 (4) |
C4—N3—Mn1 | 109.0 (6) | Se2iii—Sn3—Se4 | 176.02 (4) |
N1—C1—C2—N2 | 50.4 (11) | C4—N3—Mn1—N1 | −36.8 (10) |
N2—C3—C4—N3 | −53.5 (12) | C1—N1—Mn1—N6 | 141.8 (7) |
N3—C5—C6—N4 | −54.2 (11) | C1—N1—Mn1—N2 | 18.1 (7) |
N4—C7—C8—N5 | −59.6 (11) | C1—N1—Mn1—N4 | −73.7 (8) |
N5—C9—C10—N6 | −59.0 (10) | C1—N1—Mn1—N5 | −140.7 (7) |
C2—C1—N1—Mn1 | −42.2 (10) | C1—N1—Mn1—N3 | 51.6 (10) |
C4—C3—N2—C2 | 179.0 (9) | Sn3i—Se2—Sn1—Se3 | −113.77 (4) |
C4—C3—N2—Mn1 | 49.9 (11) | Sn3i—Se2—Sn1—Se5 | 56.71 (5) |
C1—C2—N2—C3 | −159.7 (9) | Sn3i—Se2—Sn1—Se4 | 150.27 (3) |
C1—C2—N2—Mn1 | −32.9 (10) | Sn3i—Se2—Sn1—Se1 | −23.94 (3) |
C6—C5—N3—C4 | −76.0 (10) | Sn2—Se3—Sn1—Se2 | −118.49 (5) |
C6—C5—N3—Mn1 | 44.3 (10) | Sn2—Se3—Sn1—Se5 | 70.80 (5) |
C3—C4—N3—C5 | 149.6 (8) | Sn2—Se3—Sn1—Se4 | −16.74 (3) |
C3—C4—N3—Mn1 | 28.7 (10) | Sn2—Se3—Sn1—Se1 | 154.19 (3) |
C5—C6—N4—C7 | −84.0 (10) | Sn3—Se5—Sn1—Se2 | 121.22 (4) |
C5—C6—N4—Mn1 | 35.7 (9) | Sn3—Se5—Sn1—Se3 | −68.35 (5) |
C8—C7—N4—C6 | 172.3 (8) | Sn3—Se5—Sn1—Se4 | 20.72 (3) |
C8—C7—N4—Mn1 | 51.4 (9) | Sn3—Se5—Sn1—Se1 | −156.23 (4) |
C10—C9—N5—C8 | 169.1 (8) | Sn2—Se4—Sn1—Se2 | 134.76 (3) |
C10—C9—N5—Mn1 | 46.1 (8) | Sn3—Se4—Sn1—Se2 | −140.31 (3) |
C7—C8—N5—C9 | −83.6 (10) | Sn2—Se4—Sn1—Se3 | 15.59 (3) |
C7—C8—N5—Mn1 | 37.2 (10) | Sn3—Se4—Sn1—Se3 | 100.52 (3) |
C9—C10—N6—Mn1 | 39.9 (9) | Sn2—Se4—Sn1—Se5 | −103.63 (3) |
C10—N6—Mn1—N2 | 144.6 (6) | Sn3—Se4—Sn1—Se5 | −18.71 (3) |
C10—N6—Mn1—N4 | −70.3 (7) | Sn2—Se4—Sn1—Se1 | −84.3 (2) |
C10—N6—Mn1—N5 | −12.1 (6) | Sn3—Se4—Sn1—Se1 | 0.6 (2) |
C10—N6—Mn1—N3 | −140.8 (6) | Sn3i—Se1—Sn1—Se2 | 26.10 (3) |
C10—N6—Mn1—N1 | 74.4 (6) | Sn3i—Se1—Sn1—Se3 | 144.69 (3) |
C3—N2—Mn1—N6 | 57.1 (8) | Sn3i—Se1—Sn1—Se5 | −96.05 (4) |
C2—N2—Mn1—N6 | −71.2 (7) | Sn3i—Se1—Sn1—Se4 | −115.5 (2) |
C3—N2—Mn1—N4 | −95.9 (7) | Sn2ii—Se7—Sn2—Se6 | −91.77 (4) |
C2—N2—Mn1—N4 | 135.9 (6) | Sn2ii—Se7—Sn2—Se3 | 90.10 (5) |
C3—N2—Mn1—N5 | −175.5 (7) | Sn2ii—Se7—Sn2—Se7ii | 0.0 |
C2—N2—Mn1—N5 | 56.2 (10) | Sn2ii—Se7—Sn2—Se4 | 178.22 (3) |
C3—N2—Mn1—N3 | −24.5 (7) | Sn3—Se6—Sn2—Se7 | −102.10 (4) |
C2—N2—Mn1—N3 | −152.7 (7) | Sn3—Se6—Sn2—Se3 | 76.29 (4) |
C3—N2—Mn1—N1 | 136.5 (7) | Sn3—Se6—Sn2—Se7ii | 167.63 (3) |
C2—N2—Mn1—N1 | 8.3 (6) | Sn3—Se6—Sn2—Se4 | −11.23 (3) |
C6—N4—Mn1—N6 | −85.2 (7) | Sn1—Se3—Sn2—Se7 | 105.86 (4) |
C7—N4—Mn1—N6 | 36.0 (7) | Sn1—Se3—Sn2—Se6 | −72.40 (4) |
C6—N4—Mn1—N2 | 65.1 (6) | Sn1—Se3—Sn2—Se7ii | −164.66 (3) |
C7—N4—Mn1—N2 | −173.6 (6) | Sn1—Se3—Sn2—Se4 | 16.21 (3) |
C6—N4—Mn1—N5 | −144.6 (6) | Sn1—Se4—Sn2—Se7 | −142.63 (3) |
C7—N4—Mn1—N5 | −23.3 (6) | Sn3—Se4—Sn2—Se7 | 130.76 (4) |
C6—N4—Mn1—N3 | −7.9 (6) | Sn1—Se4—Sn2—Se6 | 96.73 (4) |
C7—N4—Mn1—N3 | 113.4 (6) | Sn3—Se4—Sn2—Se6 | 10.11 (3) |
C6—N4—Mn1—N1 | 143.0 (6) | Sn1—Se4—Sn2—Se3 | −15.46 (3) |
C7—N4—Mn1—N1 | −95.7 (6) | Sn3—Se4—Sn2—Se3 | −102.07 (4) |
C9—N5—Mn1—N6 | −18.0 (5) | Sn1—Se4—Sn2—Se7ii | −44.2 (11) |
C8—N5—Mn1—N6 | −143.5 (7) | Sn3—Se4—Sn2—Se7ii | −130.8 (11) |
C9—N5—Mn1—N2 | −154.5 (6) | Sn2—Se6—Sn3—Se1iii | 104.32 (5) |
C8—N5—Mn1—N2 | 80.0 (8) | Sn2—Se6—Sn3—Se5 | −72.90 (5) |
C9—N5—Mn1—N4 | 118.7 (6) | Sn2—Se6—Sn3—Se2iii | −166.88 (3) |
C8—N5—Mn1—N4 | −6.8 (6) | Sn2—Se6—Sn3—Se4 | 11.04 (3) |
C9—N5—Mn1—N3 | 62.0 (7) | Sn1—Se5—Sn3—Se1iii | −110.73 (5) |
C8—N5—Mn1—N3 | −63.5 (8) | Sn1—Se5—Sn3—Se6 | 66.27 (4) |
C9—N5—Mn1—N1 | −109.1 (6) | Sn1—Se5—Sn3—Se2iii | 156.31 (3) |
C8—N5—Mn1—N1 | 125.4 (7) | Sn1—Se5—Sn3—Se4 | −19.72 (3) |
C5—N3—Mn1—N6 | 111.6 (7) | Sn1—Se4—Sn3—Se1iii | 145.08 (3) |
C4—N3—Mn1—N6 | −127.1 (7) | Sn2—Se4—Sn3—Se1iii | −129.36 (3) |
C5—N3—Mn1—N2 | −125.3 (8) | Sn1—Se4—Sn3—Se6 | −95.67 (4) |
C4—N3—Mn1—N2 | −4.0 (6) | Sn2—Se4—Sn3—Se6 | −10.11 (3) |
C5—N3—Mn1—N4 | −19.0 (7) | Sn1—Se4—Sn3—Se5 | 18.90 (3) |
C4—N3—Mn1—N4 | 102.2 (7) | Sn2—Se4—Sn3—Se5 | 104.46 (3) |
C5—N3—Mn1—N5 | 37.5 (9) | Sn1—Se4—Sn3—Se2iii | −64.2 (5) |
C4—N3—Mn1—N5 | 158.8 (6) | Sn2—Se4—Sn3—Se2iii | 21.4 (5) |
C5—N3—Mn1—N1 | −158.1 (7) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) −x+1/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H11···Se1iv | 0.89 (2) | 3.01 (5) | 3.818 (9) | 152 (7) |
N5—H5···Se1iv | 0.91 | 2.65 | 3.542 (7) | 168 |
N4—H4···Se1v | 0.91 | 2.76 | 3.607 (8) | 156 |
N3—H3···Se7 | 0.91 | 2.60 | 3.380 (9) | 144 |
N2—H2···Se5v | 0.91 | 2.85 | 3.699 (8) | 155 |
Symmetry codes: (iv) −x+1, −y, −z; (v) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C10H28N6)][Sn3Se7] |
Mr | 1196.11 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 207 |
a, b, c (Å) | 11.893 (5), 13.322 (5), 17.097 (5) |
β (°) | 96.659 (5) |
V (Å3) | 2690.5 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 12.69 |
Crystal size (mm) | 0.12 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.230, 0.308 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14868, 5291, 3945 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.079, 0.99 |
No. of reflections | 5291 |
No. of parameters | 256 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.20, −0.88 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).
N1—Mn1 | 2.340 (9) | Se4—Sn1 | 2.6826 (12) |
N2—Mn1 | 2.287 (8) | Se4—Sn2 | 2.7701 (12) |
N3—Mn1 | 2.308 (8) | Se4—Sn3 | 2.8200 (13) |
N4—Mn1 | 2.299 (8) | Se5—Sn3 | 2.5584 (13) |
N5—Mn1 | 2.306 (7) | Se5—Sn1 | 2.5764 (12) |
N6—Mn1 | 2.254 (9) | Se6—Sn2 | 2.5402 (12) |
Se1—Sn3i | 2.5197 (12) | Se6—Sn3 | 2.5429 (12) |
Se1—Sn1 | 2.8592 (13) | Se7—Sn2 | 2.5142 (14) |
Se2—Sn1 | 2.5044 (12) | Se7—Sn2ii | 2.6703 (13) |
Se2—Sn3i | 2.7211 (14) | Sn2—Se7ii | 2.6703 (13) |
Se3—Sn1 | 2.5540 (12) | Sn3—Se1iii | 2.5197 (12) |
Se3—Sn2 | 2.5776 (13) | Sn3—Se2iii | 2.7211 (14) |
N6—Mn1—N2 | 122.1 (3) | N5—Mn1—N3 | 127.5 (3) |
N6—Mn1—N4 | 128.9 (3) | N6—Mn1—N1 | 90.3 (3) |
N2—Mn1—N4 | 101.9 (3) | N2—Mn1—N1 | 73.2 (3) |
N6—Mn1—N5 | 77.5 (3) | N4—Mn1—N1 | 129.1 (3) |
N2—Mn1—N5 | 151.0 (3) | N5—Mn1—N1 | 86.6 (3) |
N4—Mn1—N5 | 74.6 (3) | N3—Mn1—N1 | 144.9 (3) |
N6—Mn1—N3 | 89.9 (3) | Se4—Sn1—Se1 | 170.79 (3) |
N2—Mn1—N3 | 77.1 (3) | Se7ii—Sn2—Se4 | 178.20 (3) |
N4—Mn1—N3 | 75.0 (3) | Se2iii—Sn3—Se4 | 176.02 (4) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) −x+1/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H11···Se1iv | 0.89 (2) | 3.01 (5) | 3.818 (9) | 152 (7) |
N5—H5···Se1iv | 0.91 | 2.65 | 3.542 (7) | 168.4 |
N4—H4···Se1v | 0.91 | 2.76 | 3.607 (8) | 156.2 |
N3—H3···Se7 | 0.91 | 2.60 | 3.380 (9) | 143.7 |
N2—H2···Se5v | 0.91 | 2.85 | 3.699 (8) | 155.0 |
Symmetry codes: (iv) −x+1, −y, −z; (v) x+1, y, z. |
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Since the extension of established synthetic methodologies for zeolites to metal sulfides (Bedard et al., 1989), chalcogenidometalates have been of considerable interest because of the combination of the microporous features of zeolites and their intrinsic semiconducting behaviour. Organic amines play an important role in the formation of these materials by acting as templates and charge-balancing counter-ions. Synthesis of organic–inorganic hybrid tin chalcogenides is generally performed in the presence of nonchelating organic amines, and a series of dimeric anions with general formula [Sn2Q6]4- (Q = S, Se and Te; Li et al., 1999) have been prepared with in-situ-generated metal–amine complexes. However, little (Li et al., 2000) is known about the incorporation of metal complexes into two-dimensional or three-dimensional networks of tin chalcogenides. It is known that the tendancy of SnIV to extend its coordination number from 4 to 5 or 6 allows the formation of a variety of two- and three-dimensional anionic structures. The most important feature of metal complexes is the integration of their electronic, optical and magnetic properties with the host inorganic frameworks, which helps to provide complementary properties and synergistic effects. We report here the crystal structure of such a compound, {[Mn(peha)][Sn3Se7]}n {peha is pentaethylenehexamine; [-CH2(NHCH2CH2)2NH2]2}.
As shown in Figs. 1 and 2, compound (I) consists of anionic ∞[Sn3Se7]2- layers with metal complexes [Mn(peha)]2+ accommodated between adjacent layers. Within the ∞[Sn3Se7]2- layer, semicubic cluster units (Sn3Se4) are connected by edge sharing of five-coordinated tin polyhedra to form a 63 net with cavities surrounded by 12 Sn–Se polyhedra (Fig. 3). While all Sn atoms are coordinated in a trigonal-bipyramidal fashion, the Se atom located intermediately between three Sn atoms (Sn1, Sn2 and Sn3) is trigonally coordinated, and the remaining Se atoms are bicoordinated. In the metal complex [Mn(peha)]2+, the Mn centre is six-coordinated by N atoms from the peha molecule, displaying a distorted octahedral configuration. Atoms N1, N2 and N3 are meridional, as are the other three N atoms (N4, N5 and N6). The peha molecules are generated from the decomposition and rearrangement of triethylenetetramine {teta; [–CH2NH(CH2)2NH2]2}.
Each Sn atom of (I) adopts a coordination environment with the µ3-Se atoms in axial (ax) positions [the opposite axial atoms are Se1 for Sn1, Se7ii for Sn2 and Se2iii for Sn3; symmetry codes: (ii) -x + 1, -y + 1, -z; (iii) -x + 1/2, y + 1/2, -z + 1/2]. The axial Se—Sn bond lengths are significantly longer than those for equatorial sites, which are similar to the distances found in the literature (Parise et al., 1994). The Seax—Sn—Seax angles are 170.79 (3) (Se4—Sn1—Se1), 178.20 (3) (Se4—Sn2—Se7ii) and 176.02 (4)° (Se4—Sn3—Se2iii), so the structures can be described as slightly distorted trigonal bipyramids.
In [Mn(peha)]2+, the Mn—N distances range from 2.254 (9) to 2.340 (9) Å and are in the normal range (Wendland et al., 1998). The heavy distortion of the octahedral environment in the metal centre is manifested by the trans angles, which range from 128.9 (3) to 151.0 (3)°, and the cis angles, which lie in the range 73.2 (3)–129.1 (3)°.
As shown in Fig. 2 and Table 2, the title compound forms a three-dimensional network via weak N—H···Se interactions between N atoms of peha molecules and µ2-Se atoms from two adjacent polyanion layers. The layers are oriented normal to the b axis and along the ac direction. All Sn atoms within each layer are nearly coplanar (the mean deviation from the plane is 0.0597 Å). The average interlayer separation as measured between the tin planes is 9.23 Å. Both (I) and the previously reported compound TMA–SnSe (TMA is trimethyl amine; Ahari, Ozin et al., 1995; Ahari, Bowes et al., 1995) contain anionic ∞[Sn3Se7]2- layers, but the steric requirements of charge-balancing cations in the two structures are different. The flexibility of the Sn3Se7 framework has been verified by varying the organic template or including molecular guests in the two structures. It is obvious that the distortion of the cavities in the title compound is a result of the bulk of the Mn complexes. On the basis of the Se···Se distances (Fig. 3), the holes have the approximate dimensions of 8.74 × 13.87 Å and are significantly distorted from a regular hexagonal shape. Therefore, the incorporation of metal complexes into such structures not only explores its flexibility [please clarify what this means] but may be able to introduce new properties into semiconductors.