Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010803521X/em3020sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010803521X/em3020Isup2.hkl |
CCDC reference: 684164
Single crystals of the title complex suitable for X-ray crystallographic analysis were obtained by solvothermal treatment of SmCl3 (0.05 mmol), InCl3 (0.1 mmol), Te powder (0.2 mmol) and ethylenediamine (1 ml). The reagents were placed in a thick Pyrex tube (ca 20 cm long), which was heated to 418 K for 13 d and then cooled to room temperature. Yellow block-shaped crystals of (I) were obtained (yield 26%, based on Sm).
H atoms were positioned geometrically and refined using a riding model, with C—H = 0.98 Å and N—H = 0.91 Å, and with Uiso(H) = 1.2Ueq(C,N). There was some evidence of disorder in the en ligand containing atoms N3 and N4. This was refined with geometric and displacement parameter restraints to improve the geometry using a single set of atom positions.
Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[SmCl(C2H8N2)4][In2Te4] | F(000) = 4168 |
Mr = 1166.26 | Dx = 2.869 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 15461 reflections |
a = 13.7359 (11) Å | θ = 3.2–25.4° |
b = 18.5660 (16) Å | µ = 8.18 mm−1 |
c = 21.1782 (18) Å | T = 223 K |
V = 5400.9 (8) Å3 | Block, yellow |
Z = 8 | 0.40 × 0.30 × 0.10 mm |
Rigaku Mercury CCD area-detector diffractometer | 4938 independent reflections |
Radiation source: fine-focus sealed tube | 4478 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.077 |
Detector resolution: 7.31 pixels mm-1 | θmax = 25.4°, θmin = 3.2° |
ω scans | h = −16→14 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −22→22 |
Tmin = 0.068, Tmax = 0.443 | l = −25→25 |
49875 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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.29 | w = 1/[σ2(Fo2) + (0.0187P)2 + 70.31P] where P = (Fo2 + 2Fc2)/3 |
4938 reflections | (Δ/σ)max = 0.001 |
217 parameters | Δρmax = 1.78 e Å−3 |
37 restraints | Δρmin = −1.90 e Å−3 |
[SmCl(C2H8N2)4][In2Te4] | V = 5400.9 (8) Å3 |
Mr = 1166.26 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.7359 (11) Å | µ = 8.18 mm−1 |
b = 18.5660 (16) Å | T = 223 K |
c = 21.1782 (18) Å | 0.40 × 0.30 × 0.10 mm |
Rigaku Mercury CCD area-detector diffractometer | 4938 independent reflections |
Absorption correction: multi-scan (Jacobson, 1998) | 4478 reflections with I > 2σ(I) |
Tmin = 0.068, Tmax = 0.443 | Rint = 0.077 |
49875 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 37 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.29 | w = 1/[σ2(Fo2) + (0.0187P)2 + 70.31P] where P = (Fo2 + 2Fc2)/3 |
4938 reflections | Δρmax = 1.78 e Å−3 |
217 parameters | Δρmin = −1.90 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
Sm1 | 0.70700 (4) | 0.21517 (3) | 0.43520 (2) | 0.01921 (13) | |
Cl1 | 0.8812 (2) | 0.26810 (17) | 0.49384 (14) | 0.0361 (7) | |
N1 | 0.7702 (6) | 0.1200 (5) | 0.5170 (4) | 0.033 (2) | |
H1A | 0.8339 | 0.1104 | 0.5086 | 0.040* | |
H1B | 0.7670 | 0.1395 | 0.5563 | 0.040* | |
C1 | 0.7154 (8) | 0.0521 (5) | 0.5165 (6) | 0.039 (3) | |
H1C | 0.7349 | 0.0226 | 0.5527 | 0.046* | |
H1D | 0.7304 | 0.0252 | 0.4779 | 0.046* | |
C2 | 0.6099 (8) | 0.0665 (6) | 0.5195 (5) | 0.035 (3) | |
H2C | 0.5942 | 0.0905 | 0.5595 | 0.042* | |
H2D | 0.5740 | 0.0210 | 0.5179 | 0.042* | |
N2 | 0.5805 (7) | 0.1130 (5) | 0.4659 (4) | 0.032 (2) | |
H2A | 0.5227 | 0.1342 | 0.4756 | 0.038* | |
H2B | 0.5705 | 0.0846 | 0.4315 | 0.038* | |
N3 | 0.5406 (6) | 0.2634 (5) | 0.3963 (4) | 0.032 (2) | |
H3A | 0.5011 | 0.2686 | 0.4305 | 0.038* | |
H3B | 0.5502 | 0.3080 | 0.3796 | 0.038* | |
C3 | 0.4892 (9) | 0.2199 (10) | 0.3496 (7) | 0.072 (5) | |
H3C | 0.4545 | 0.1810 | 0.3713 | 0.087* | |
H3D | 0.4407 | 0.2500 | 0.3283 | 0.087* | |
C4 | 0.5526 (10) | 0.1891 (9) | 0.3030 (7) | 0.070 (4) | |
H4C | 0.5688 | 0.2261 | 0.2717 | 0.083* | |
H4D | 0.5178 | 0.1504 | 0.2810 | 0.083* | |
N4 | 0.6427 (7) | 0.1599 (6) | 0.3289 (5) | 0.042 (3) | |
H4A | 0.6901 | 0.1653 | 0.2992 | 0.050* | |
H4B | 0.6341 | 0.1118 | 0.3348 | 0.050* | |
N5 | 0.8409 (8) | 0.1356 (6) | 0.3795 (5) | 0.047 (3) | |
H5A | 0.8700 | 0.1066 | 0.4085 | 0.057* | |
H5B | 0.8124 | 0.1070 | 0.3498 | 0.057* | |
C5 | 0.9146 (9) | 0.1818 (8) | 0.3493 (6) | 0.048 (4) | |
H5C | 0.9566 | 0.1521 | 0.3224 | 0.057* | |
H5D | 0.9553 | 0.2039 | 0.3819 | 0.057* | |
C6 | 0.8694 (10) | 0.2388 (7) | 0.3107 (7) | 0.047 (3) | |
H6C | 0.9202 | 0.2715 | 0.2954 | 0.056* | |
H6D | 0.8377 | 0.2170 | 0.2739 | 0.056* | |
N6 | 0.7975 (7) | 0.2800 (5) | 0.3467 (4) | 0.030 (2) | |
H6A | 0.7525 | 0.2971 | 0.3190 | 0.035* | |
H6B | 0.8283 | 0.3187 | 0.3638 | 0.035* | |
N7 | 0.6933 (7) | 0.3557 (5) | 0.4538 (5) | 0.033 (2) | |
H7A | 0.7542 | 0.3737 | 0.4600 | 0.040* | |
H7B | 0.6691 | 0.3764 | 0.4181 | 0.040* | |
C7 | 0.6314 (9) | 0.3771 (7) | 0.5079 (6) | 0.042 (3) | |
H7C | 0.5626 | 0.3751 | 0.4957 | 0.051* | |
H7D | 0.6467 | 0.4266 | 0.5206 | 0.051* | |
C8 | 0.6494 (9) | 0.3273 (7) | 0.5615 (6) | 0.043 (3) | |
H8C | 0.7174 | 0.3311 | 0.5750 | 0.051* | |
H8D | 0.6077 | 0.3404 | 0.5972 | 0.051* | |
N8 | 0.6283 (6) | 0.2530 (5) | 0.5418 (4) | 0.032 (2) | |
H8A | 0.5626 | 0.2476 | 0.5386 | 0.038* | |
H8B | 0.6495 | 0.2224 | 0.5724 | 0.038* | |
Te3 | 0.40385 (5) | 0.45995 (4) | 0.15792 (3) | 0.02522 (17) | |
Te1 | 0.70749 (5) | 0.57217 (4) | 0.19345 (4) | 0.02735 (18) | |
Te2 | 0.70583 (5) | 0.34483 (4) | 0.19393 (3) | 0.02606 (18) | |
Te4 | 0.51204 (5) | 0.46188 (4) | 0.34705 (3) | 0.03040 (19) | |
In1 | 0.58088 (5) | 0.45999 (4) | 0.22201 (4) | 0.02546 (19) | |
In2 | 0.33516 (5) | 0.45924 (4) | 0.28342 (4) | 0.02416 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sm1 | 0.0183 (3) | 0.0232 (3) | 0.0161 (3) | −0.0013 (2) | −0.0003 (2) | −0.0004 (2) |
Cl1 | 0.0231 (14) | 0.0534 (18) | 0.0318 (16) | −0.0042 (14) | −0.0051 (12) | −0.0067 (14) |
N1 | 0.029 (5) | 0.051 (6) | 0.019 (5) | 0.001 (5) | −0.001 (4) | 0.005 (5) |
C1 | 0.061 (9) | 0.026 (6) | 0.028 (7) | 0.006 (6) | 0.006 (6) | 0.004 (5) |
C2 | 0.044 (7) | 0.034 (6) | 0.028 (7) | −0.008 (6) | 0.000 (5) | 0.000 (5) |
N2 | 0.034 (5) | 0.037 (5) | 0.024 (5) | −0.002 (4) | 0.000 (4) | −0.002 (4) |
N3 | 0.026 (5) | 0.038 (5) | 0.032 (5) | −0.004 (4) | −0.008 (4) | 0.007 (4) |
C3 | 0.049 (8) | 0.110 (13) | 0.057 (9) | 0.011 (8) | −0.031 (7) | −0.028 (9) |
C4 | 0.062 (9) | 0.091 (11) | 0.055 (9) | 0.002 (8) | −0.030 (7) | −0.029 (8) |
N4 | 0.043 (6) | 0.051 (6) | 0.031 (6) | −0.015 (5) | 0.002 (5) | −0.005 (5) |
N5 | 0.056 (7) | 0.056 (7) | 0.030 (6) | 0.024 (6) | 0.014 (5) | 0.003 (5) |
C5 | 0.035 (7) | 0.077 (10) | 0.031 (7) | 0.008 (7) | −0.005 (6) | −0.010 (7) |
C6 | 0.052 (8) | 0.044 (8) | 0.045 (8) | −0.012 (7) | 0.015 (7) | −0.002 (7) |
N6 | 0.043 (6) | 0.029 (5) | 0.017 (5) | −0.009 (5) | 0.003 (4) | −0.001 (4) |
N7 | 0.023 (5) | 0.035 (5) | 0.042 (6) | −0.002 (4) | −0.001 (4) | 0.001 (5) |
C7 | 0.042 (7) | 0.035 (7) | 0.050 (8) | −0.004 (6) | 0.000 (6) | −0.021 (6) |
C8 | 0.033 (7) | 0.058 (8) | 0.037 (7) | −0.014 (6) | −0.001 (6) | −0.014 (7) |
N8 | 0.021 (5) | 0.046 (6) | 0.028 (5) | −0.007 (4) | −0.001 (4) | −0.005 (5) |
Te3 | 0.0236 (4) | 0.0301 (4) | 0.0219 (4) | −0.0040 (3) | −0.0010 (3) | 0.0025 (3) |
Te1 | 0.0246 (4) | 0.0244 (4) | 0.0331 (4) | 0.0002 (3) | −0.0015 (3) | 0.0035 (3) |
Te2 | 0.0293 (4) | 0.0254 (4) | 0.0235 (4) | −0.0014 (3) | −0.0044 (3) | −0.0019 (3) |
Te4 | 0.0280 (4) | 0.0395 (4) | 0.0237 (4) | −0.0005 (3) | −0.0042 (3) | 0.0039 (3) |
In1 | 0.0209 (4) | 0.0287 (4) | 0.0268 (4) | −0.0009 (3) | −0.0015 (3) | 0.0016 (3) |
In2 | 0.0199 (4) | 0.0282 (4) | 0.0244 (4) | 0.0006 (3) | 0.0011 (3) | 0.0021 (3) |
Sm1—N6 | 2.551 (8) | N5—H5A | 0.9100 |
Sm1—N3 | 2.589 (9) | N5—H5B | 0.9100 |
Sm1—N8 | 2.599 (9) | C5—C6 | 1.474 (18) |
Sm1—N1 | 2.621 (9) | C5—H5C | 0.9800 |
Sm1—N4 | 2.628 (9) | C5—H5D | 0.9800 |
Sm1—N5 | 2.638 (10) | C6—N6 | 1.462 (15) |
Sm1—N7 | 2.646 (9) | C6—H6C | 0.9800 |
Sm1—N2 | 2.653 (9) | C6—H6D | 0.9800 |
Sm1—Cl1 | 2.869 (3) | N6—H6A | 0.9100 |
N1—C1 | 1.469 (12) | N6—H6B | 0.9100 |
N1—H1A | 0.9100 | N7—C7 | 1.482 (15) |
N1—H1B | 0.9100 | N7—H7A | 0.9100 |
C1—C2 | 1.475 (15) | N7—H7B | 0.9100 |
C1—H1C | 0.9800 | C7—C8 | 1.484 (18) |
C1—H1D | 0.9800 | C7—H7C | 0.9800 |
C2—N2 | 1.483 (11) | C7—H7D | 0.9800 |
C2—H2C | 0.9800 | C8—N8 | 1.470 (15) |
C2—H2D | 0.9800 | C8—H8C | 0.9800 |
N2—H2A | 0.9100 | C8—H8D | 0.9800 |
N2—H2B | 0.9100 | N8—H8A | 0.9100 |
N3—C3 | 1.459 (12) | N8—H8B | 0.9100 |
N3—H3A | 0.9100 | Te3—In1 | 2.7848 (10) |
N3—H3B | 0.9100 | Te3—In2 | 2.8204 (11) |
C3—C4 | 1.435 (16) | Te1—In2i | 2.7769 (10) |
C3—H3C | 0.9800 | Te1—In1 | 2.7798 (10) |
C3—H3D | 0.9800 | Te2—In1 | 2.8055 (11) |
C4—N4 | 1.457 (13) | Te2—In2i | 2.8103 (10) |
C4—H4C | 0.9800 | Te4—In2 | 2.7787 (10) |
C4—H4D | 0.9800 | Te4—In1 | 2.8121 (11) |
N4—H4A | 0.9100 | In2—Te1ii | 2.7769 (10) |
N4—H4B | 0.9100 | In2—Te2ii | 2.8103 (10) |
N5—C5 | 1.473 (17) | ||
N6—Sm1—N3 | 91.9 (3) | N4—C4—H4C | 108.8 |
N6—Sm1—N8 | 135.5 (3) | C3—C4—H4D | 108.8 |
N3—Sm1—N8 | 79.4 (3) | N4—C4—H4D | 108.8 |
N6—Sm1—N1 | 129.9 (3) | H4C—C4—H4D | 107.7 |
N3—Sm1—N1 | 137.4 (3) | C4—N4—Sm1 | 117.6 (7) |
N8—Sm1—N1 | 75.3 (3) | C4—N4—H4A | 107.9 |
N6—Sm1—N4 | 73.6 (3) | Sm1—N4—H4A | 107.9 |
N3—Sm1—N4 | 64.2 (3) | C4—N4—H4B | 107.9 |
N8—Sm1—N4 | 135.2 (3) | Sm1—N4—H4B | 107.9 |
N1—Sm1—N4 | 114.5 (3) | H4A—N4—H4B | 107.2 |
N6—Sm1—N5 | 66.1 (3) | C5—N5—Sm1 | 110.3 (8) |
N3—Sm1—N5 | 131.8 (3) | C5—N5—H5A | 109.6 |
N8—Sm1—N5 | 146.1 (3) | Sm1—N5—H5A | 109.6 |
N1—Sm1—N5 | 71.8 (3) | C5—N5—H5B | 109.6 |
N4—Sm1—N5 | 68.4 (3) | Sm1—N5—H5B | 109.6 |
N6—Sm1—N7 | 71.3 (3) | H5A—N5—H5B | 108.1 |
N3—Sm1—N7 | 69.1 (3) | N5—C5—C6 | 111.7 (11) |
N8—Sm1—N7 | 64.9 (3) | N5—C5—H5C | 109.3 |
N1—Sm1—N7 | 126.2 (3) | C6—C5—H5C | 109.3 |
N4—Sm1—N7 | 119.2 (3) | N5—C5—H5D | 109.3 |
N5—Sm1—N7 | 131.9 (3) | C6—C5—H5D | 109.3 |
N6—Sm1—N2 | 146.8 (3) | H5C—C5—H5D | 107.9 |
N3—Sm1—N2 | 75.3 (3) | N6—C6—C5 | 111.8 (11) |
N8—Sm1—N2 | 73.0 (3) | N6—C6—H6C | 109.3 |
N1—Sm1—N2 | 64.7 (3) | C5—C6—H6C | 109.3 |
N4—Sm1—N2 | 73.2 (3) | N6—C6—H6D | 109.3 |
N5—Sm1—N2 | 99.5 (3) | C5—C6—H6D | 109.3 |
N7—Sm1—N2 | 128.5 (3) | H6C—C6—H6D | 107.9 |
N6—Sm1—Cl1 | 75.5 (2) | C6—N6—Sm1 | 117.8 (7) |
N3—Sm1—Cl1 | 139.1 (2) | C6—N6—H6A | 107.9 |
N8—Sm1—Cl1 | 83.0 (2) | Sm1—N6—H6A | 107.9 |
N1—Sm1—Cl1 | 70.7 (2) | C6—N6—H6B | 107.9 |
N4—Sm1—Cl1 | 141.7 (2) | Sm1—N6—H6B | 107.9 |
N5—Sm1—Cl1 | 78.7 (3) | H6A—N6—H6B | 107.2 |
N7—Sm1—Cl1 | 69.9 (2) | C7—N7—Sm1 | 114.8 (7) |
N2—Sm1—Cl1 | 133.24 (19) | C7—N7—H7A | 108.6 |
C1—N1—Sm1 | 113.9 (6) | Sm1—N7—H7A | 108.6 |
C1—N1—H1A | 108.8 | C7—N7—H7B | 108.6 |
Sm1—N1—H1A | 108.8 | Sm1—N7—H7B | 108.6 |
C1—N1—H1B | 108.8 | H7A—N7—H7B | 107.5 |
Sm1—N1—H1B | 108.8 | N7—C7—C8 | 109.2 (10) |
H1A—N1—H1B | 107.7 | N7—C7—H7C | 109.8 |
N1—C1—C2 | 110.3 (9) | C8—C7—H7C | 109.8 |
N1—C1—H1C | 109.6 | N7—C7—H7D | 109.8 |
C2—C1—H1C | 109.6 | C8—C7—H7D | 109.8 |
N1—C1—H1D | 109.6 | H7C—C7—H7D | 108.3 |
C2—C1—H1D | 109.6 | N8—C8—C7 | 109.6 (10) |
H1C—C1—H1D | 108.1 | N8—C8—H8C | 109.8 |
C1—C2—N2 | 109.9 (9) | C7—C8—H8C | 109.8 |
C1—C2—H2C | 109.7 | N8—C8—H8D | 109.8 |
N2—C2—H2C | 109.7 | C7—C8—H8D | 109.8 |
C1—C2—H2D | 109.7 | H8C—C8—H8D | 108.2 |
N2—C2—H2D | 109.7 | C8—N8—Sm1 | 114.7 (7) |
H2C—C2—H2D | 108.2 | C8—N8—H8A | 108.6 |
C2—N2—Sm1 | 115.2 (6) | Sm1—N8—H8A | 108.6 |
C2—N2—H2A | 108.5 | C8—N8—H8B | 108.6 |
Sm1—N2—H2A | 108.5 | Sm1—N8—H8B | 108.6 |
C2—N2—H2B | 108.5 | H8A—N8—H8B | 107.6 |
Sm1—N2—H2B | 108.5 | In1—Te3—In2 | 80.38 (3) |
H2A—N2—H2B | 107.5 | In2i—Te1—In1 | 77.94 (3) |
C3—N3—Sm1 | 116.8 (7) | In1—Te2—In2i | 76.97 (3) |
C3—N3—H3A | 108.1 | In2—Te4—In1 | 80.63 (3) |
Sm1—N3—H3A | 108.1 | Te1—In1—Te3 | 116.13 (3) |
C3—N3—H3B | 108.1 | Te1—In1—Te2 | 98.17 (3) |
Sm1—N3—H3B | 108.1 | Te3—In1—Te2 | 115.51 (3) |
H3A—N3—H3B | 107.3 | Te1—In1—Te4 | 113.95 (3) |
C4—C3—N3 | 113.2 (11) | Te3—In1—Te4 | 99.52 (3) |
C4—C3—H3C | 108.9 | Te2—In1—Te4 | 114.51 (3) |
N3—C3—H3C | 108.9 | Te1ii—In2—Te4 | 116.96 (4) |
C4—C3—H3D | 108.9 | Te1ii—In2—Te2ii | 98.12 (3) |
N3—C3—H3D | 108.9 | Te4—In2—Te2ii | 118.90 (3) |
H3C—C3—H3D | 107.8 | Te1ii—In2—Te3 | 111.96 (3) |
C3—C4—N4 | 113.9 (11) | Te4—In2—Te3 | 99.46 (3) |
C3—C4—H4C | 108.8 | Te2ii—In2—Te3 | 112.08 (3) |
N6—Sm1—N1—C1 | −123.8 (7) | N5—C5—C6—N6 | 52.6 (15) |
N3—Sm1—N1—C1 | 42.7 (9) | C5—C6—N6—Sm1 | −29.7 (13) |
N8—Sm1—N1—C1 | 98.3 (7) | N3—Sm1—N6—C6 | −132.3 (8) |
N4—Sm1—N1—C1 | −35.1 (8) | N8—Sm1—N6—C6 | 150.9 (8) |
N5—Sm1—N1—C1 | −90.0 (8) | N1—Sm1—N6—C6 | 38.6 (9) |
N7—Sm1—N1—C1 | 140.9 (7) | N4—Sm1—N6—C6 | −69.9 (8) |
N2—Sm1—N1—C1 | 20.4 (7) | N5—Sm1—N6—C6 | 3.3 (8) |
Cl1—Sm1—N1—C1 | −174.1 (8) | N7—Sm1—N6—C6 | 160.5 (9) |
Sm1—N1—C1—C2 | −49.3 (11) | N2—Sm1—N6—C6 | −66.6 (10) |
N1—C1—C2—N2 | 57.6 (13) | Cl1—Sm1—N6—C6 | 87.2 (8) |
C1—C2—N2—Sm1 | −38.2 (11) | N6—Sm1—N7—C7 | 175.7 (8) |
N6—Sm1—N2—C2 | 134.7 (7) | N3—Sm1—N7—C7 | 76.1 (8) |
N3—Sm1—N2—C2 | −154.9 (8) | N8—Sm1—N7—C7 | −11.7 (7) |
N8—Sm1—N2—C2 | −71.8 (7) | N1—Sm1—N7—C7 | −58.0 (8) |
N1—Sm1—N2—C2 | 9.6 (7) | N4—Sm1—N7—C7 | 117.8 (8) |
N4—Sm1—N2—C2 | 138.0 (8) | N5—Sm1—N7—C7 | −155.8 (7) |
N5—Sm1—N2—C2 | 74.2 (8) | N2—Sm1—N7—C7 | 26.6 (9) |
N7—Sm1—N2—C2 | −107.7 (8) | Cl1—Sm1—N7—C7 | −103.3 (8) |
Cl1—Sm1—N2—C2 | −9.3 (9) | Sm1—N7—C7—C8 | 40.6 (11) |
N6—Sm1—N3—C3 | 88.9 (10) | N7—C7—C8—N8 | −58.3 (13) |
N8—Sm1—N3—C3 | −135.0 (10) | C7—C8—N8—Sm1 | 48.6 (11) |
N1—Sm1—N3—C3 | −80.8 (11) | N6—Sm1—N8—C8 | −9.3 (9) |
N4—Sm1—N3—C3 | 18.2 (10) | N3—Sm1—N8—C8 | −91.1 (8) |
N5—Sm1—N3—C3 | 29.8 (11) | N1—Sm1—N8—C8 | 123.6 (8) |
N7—Sm1—N3—C3 | 158.0 (10) | N4—Sm1—N8—C8 | −126.3 (8) |
N2—Sm1—N3—C3 | −60.0 (10) | N5—Sm1—N8—C8 | 109.4 (9) |
Cl1—Sm1—N3—C3 | 158.9 (9) | N7—Sm1—N8—C8 | −19.3 (7) |
Sm1—N3—C3—C4 | −39.6 (18) | N2—Sm1—N8—C8 | −168.8 (8) |
N3—C3—C4—N4 | 43 (2) | Cl1—Sm1—N8—C8 | 51.8 (7) |
C3—C4—N4—Sm1 | −26.1 (19) | In2i—Te1—In1—Te3 | −146.16 (4) |
N6—Sm1—N4—C4 | −96.3 (11) | In2i—Te1—In1—Te2 | −22.45 (3) |
N3—Sm1—N4—C4 | 4.1 (10) | In2i—Te1—In1—Te4 | 99.04 (4) |
N8—Sm1—N4—C4 | 43.2 (12) | In2—Te3—In1—Te1 | −123.73 (4) |
N1—Sm1—N4—C4 | 136.8 (10) | In2—Te3—In1—Te2 | 122.10 (4) |
N5—Sm1—N4—C4 | −166.6 (11) | In2—Te3—In1—Te4 | −1.00 (3) |
N7—Sm1—N4—C4 | −39.5 (11) | In2i—Te2—In1—Te1 | 22.25 (3) |
N2—Sm1—N4—C4 | 85.7 (11) | In2i—Te2—In1—Te3 | 146.41 (4) |
Cl1—Sm1—N4—C4 | −133.8 (10) | In2i—Te2—In1—Te4 | −98.82 (4) |
N6—Sm1—N5—C5 | 23.2 (7) | In2—Te4—In1—Te1 | 125.28 (4) |
N3—Sm1—N5—C5 | 92.9 (9) | In2—Te4—In1—Te3 | 1.01 (3) |
N8—Sm1—N5—C5 | −114.6 (8) | In2—Te4—In1—Te2 | −122.79 (4) |
N1—Sm1—N5—C5 | −129.0 (9) | In1—Te4—In2—Te1ii | −121.67 (4) |
N4—Sm1—N5—C5 | 104.2 (8) | In1—Te4—In2—Te2ii | 120.82 (4) |
N7—Sm1—N5—C5 | −6.4 (10) | In1—Te4—In2—Te3 | −1.00 (3) |
N2—Sm1—N5—C5 | 171.7 (8) | In1—Te3—In2—Te1ii | 125.25 (4) |
Cl1—Sm1—N5—C5 | −55.8 (8) | In1—Te3—In2—Te4 | 1.01 (3) |
Sm1—N5—C5—C6 | −48.6 (12) | In1—Te3—In2—Te2ii | −125.60 (4) |
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) x−1/2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl1iii | 0.91 | 2.74 | 3.619 (10) | 164 |
N3—H3A···Cl1iii | 0.91 | 2.40 | 3.248 (10) | 156 |
N8—H8A···Cl1iii | 0.91 | 2.60 | 3.498 (9) | 169 |
N7—H7A···Cl1 | 0.91 | 2.72 | 3.166 (10) | 111 |
Symmetry code: (iii) x−1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [SmCl(C2H8N2)4][In2Te4] |
Mr | 1166.26 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 223 |
a, b, c (Å) | 13.7359 (11), 18.5660 (16), 21.1782 (18) |
V (Å3) | 5400.9 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 8.18 |
Crystal size (mm) | 0.40 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury CCD area-detector diffractometer |
Absorption correction | Multi-scan (Jacobson, 1998) |
Tmin, Tmax | 0.068, 0.443 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 49875, 4938, 4478 |
Rint | 0.077 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.101, 1.29 |
No. of reflections | 4938 |
No. of parameters | 217 |
No. of restraints | 37 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0187P)2 + 70.31P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.78, −1.90 |
Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl1i | 0.91 | 2.74 | 3.619 (10) | 163.8 |
N3—H3A···Cl1i | 0.91 | 2.40 | 3.248 (10) | 155.6 |
N8—H8A···Cl1i | 0.91 | 2.60 | 3.498 (9) | 168.9 |
N7—H7A···Cl1 | 0.91 | 2.72 | 3.166 (10) | 111.2 |
Symmetry code: (i) x−1/2, −y+1/2, −z+1. |
The number of hybrid organic–inorganic indium chalcogenides has increased rapidly in recent years, owing to their potential applications in catalysis, and in semiconductor and photoelectric chemistry (Zheng et al., 2005; Li et al., 1999; Manos et al., 2007; Ding et al., 2006; Rangan et al., 2000). These compounds have usually been prepared at moderate temperatures (room temperature or under mild hydro- or solvothermal conditions) in the presence of an organic base as a structure-directing or templating agent. In the family of indium tellurides, many related compounds with a variety of structures have been reported, as exemplified by zero-dimensional molecular K6In2Te6.4en (en is ethylenediamine) (Wang & Haushalter, 1997) and (NEt4)5[In3Te7].0.5Et2O (Park et al., 1995)}, one-dimensional {[InTe2]-}n chains built up from InTe4 tetrahedra sharing opposite edges in [(n-C4H9)4N]2[In2Te4] (Warren et al., 1994) or [Zn(taa)(µ-tren)0.5][InTe2]Cl [taa = N,N,N-tris(2-aminoethyl)amine and tren = triethylenetetramine], [M(en)3]In2Te4.en (M = Ni or Co) and [M(en)3]2[In4Te8].0.5en (M = Mn, Fe or Zn) (Zhou et al., 2007), one-dimensional chains with fused five-membered rings in [M(en)3][In2Te6] (M = Fe or Zn) and α- or β-[Mo3(en)3(µ2-Te2)3(µ3-Te)(µ3-O)][In2Te6] (Li et al., 1997), a two-dimensional layered network built of an In4Te10 supertetrahedron sharing bonds via µ2-Te, µ2-Te2 and µ6-Te3 in [Zn(en)3]4In16(Te2)4(Te3)Te22 (Chen et al., 2001), and three-dimensional frameworks constructed from the crosslinking of helical chains of corner-sharing InTe4 tetrahedra in UCR-2InTe-amine [amine = triethylenetetramine, tris(2-aminoethyl)amine or N-(2-aminoethyl)propane-1,3-diamine; UCR = University of California at Riverside] (Wang et al., 2002). The cations of these compounds are tetraalkylammonium, protonated amine, alkali metal cations or transition metal complex cations, but indium tellurides with lanthanide-containing countercations prepared under mild solvothermal conditions are rare. The only example that has been found is [LaCl(en)4]In2Te4, (II) (Chen et al., 1998), which contains one-dimensional straight {[InTe2]-}n anion chains. We report here the unusual example of the title indium telluride {[SmCl(en)4][In2Te4]}n, (I), containing sinusoidal {[InTe2]-}n anion chains with [SmCl(en)4]2+ as counterions.
In the asymmetric unit of (I), there are two In atoms, one Sm atom and four Te atoms, all of which occupy general positions. The SmIII centre is chelated by four bidentate en ligands and coordinated by one Cl- ion to form a monocapped square-antiprism geometry (Fig. 1a). The one-dimensional polymeric anion chain is built of InTe4 tetrahedra sharing opposite edges with the formula {[In2Te4]2-}n and propagates along the crystallographic a axis (Fig. 1b). All central In atoms in (I) are arranged in a sinusoidal line and the In···In···In angles are in the range 157.04 (3)–160.81 (3)°. There are two kinds of In···In distances in (I), 3.6170 (11) Å for In1···In2 and 3.4948 (11) Å for In1···In2ii [symmetry code: (ii) 1/2 + x, y, 1/2 - z]. The repeat unit consists of four edge-sharing InTe4 tetrahedra for a complete sinusoidal period of 13.7359 (11) Å, which is less than the sum of the four In···In distances [14.2236 (s.u.?) Å]. The atoms in the In1/Te3/Te4/In2 ring are almost coplanar, but the In1/Te1/Te2/In2ii ring has a butterfly structure; the dihedral angle between the wing planes In1/Te1/In2ii and In1/Te2/In2ii is 28.82 (4)°. When viewed down the one-dimensional {[InTe2]-}n chain axis, the butterfly rings display two alternating orientations (Fig. 2). A search of the Cambridge Structural Database (Version?; Allen, 2002) reveals that this sinusoidal period is rather shorter than that observed in a number of ethylenediamine transition metal-containing indium tellurides (transition metal = Mn, Fe, Co, Ni or Zn; Zhou et al., 2007), where it is in the range ca 14.2–14.6 Å.
In (I), [SmCl(en)4]2+ cations are linked into a one-dimensional sinusoidal cationic chain by way of N—H···Cl hydrogen bonds (Fig. 3) running parallel to the a axis. Pseudo-channels are constructed by the cationic chains surrounding the one-dimensional {[InTe2]-}n chains (Fig. 2). In addition, there are numerous weak N—H···Te contacts. These weak interactions seemingly contribute to the formation of the one-dimensional sinusoidal {[InTe2]-}n chains and stabilize the whole crystal structure.
Both (I) and the reported [LaCl(en)4]In2Te4, (II) (Chen et al., 1998), contain a Cl- ion which covalently coordinates to the LnIII centre to complete the coordination, but the role of this ion in the two structures is different. The [SmCl(en)4]2+ cations of (I) are assembled into a one-dimensional sinusoidal chain by N—H···Cl hydrogen bonds but, importantly, no similar hydrogen bonds exist between the [LaCl(en)4]2+ cations of (II). The ionic radius of the Sm3+ ion (1.132 Å) (Suganuma & Hori, 1999) is smaller than that of the La3+ ion (1.216 Å) (Lien et al., 2005). When the Cl- ion bonds to the Sm3+ ion of (I), its bond [2.869 (3) Å] is shorter than the La—Cl bond in (II) [2.945 (9) Å], and the electronegativity of the Cl atom in (I) should be larger than that in (II). For an N—H···Cl hydrogen bond, it is well known that the higher the electronegativity of the Cl atom, the stronger the hydrogen bond. Thus, the hydrogen-bond assembled sinusoidal cation chain in (I) affects the conformation of the anion. There is no such templating effect in (II) and the anionic chains are therefore straight. So (I) and (II) show different conformations of the polymeric anions.