Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102017754/av1121sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017754/av1121Isup2.hkl |
CCDC reference: 199405
Compound (I) was obtained in nearly 30% yield by the reaction of [Ni(tren)2]Cl2 (Ellermeier et al., 2002) (0.211 g, 0.5 mmol), Sb (0.121 g, 1 mmol) and S (0.096 g, 3 mmol) in an aqueous solution of PA (5 ml; 99%, Merck Chemical). The mixture was heated in a Teflon-lined steel autoclave with an inner volume of 30 ml for 6 d at 413 K, and then cooled to room temperature within 3 h. After washing with water and drying under vacuum, turquoise crystals of (I) were obtained. The compound is stable in air and in water.
The H atoms were positioned with idealized geometry and refined with fixed isotropic displacement parameters [Uiso(H) = 1.2Ueq(Namine, Cmethylene) and 1.5Ueq(Nammonium, Cmethyl) Please check added text] using a riding model, with C—H distances of 0.97 Å and N—H distances in the range 0.89–0.90 Å.
Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: CIFTAB in SHELXL97.
(C3H10N)[NiSbS4(C6H18N4)] | Z = 2 |
Mr = 515.06 | F(000) = 520 |
Triclinic, P1 | Dx = 1.782 Mg m−3 |
a = 7.5707 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.303 (2) Å | Cell parameters from 24 reflections |
c = 12.605 (3) Å | θ = 20–29° |
α = 63.98 (3)° | µ = 2.82 mm−1 |
β = 84.49 (3)° | T = 293 K |
γ = 82.26 (3)° | Polyhedron, turquoise |
V = 959.7 (3) Å3 | 0.5 × 0.2 × 0.1 mm |
Philips PW1100 four-circle diffractometer | 3940 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 28.0°, θmin = 2.7° |
ω/θ scans | h = 0→9 |
Absorption correction: ψ scan [X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998)] | k = −14→14 |
Tmin = 0.513, Tmax = 0.720 | l = −16→16 |
4967 measured reflections | 3 standard reflections every 120 min |
4625 independent reflections | intensity decay: none |
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)] = 0.019 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.050 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0217P)2 + 0.3866P] where P = (Fo2 + 2Fc2)/3 |
4625 reflections | (Δ/σ)max = 0.002 |
181 parameters | Δρmax = 0.71 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
(C3H10N)[NiSbS4(C6H18N4)] | γ = 82.26 (3)° |
Mr = 515.06 | V = 959.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5707 (15) Å | Mo Kα radiation |
b = 11.303 (2) Å | µ = 2.82 mm−1 |
c = 12.605 (3) Å | T = 293 K |
α = 63.98 (3)° | 0.5 × 0.2 × 0.1 mm |
β = 84.49 (3)° |
Philips PW1100 four-circle diffractometer | 3940 reflections with I > 2σ(I) |
Absorption correction: ψ scan [X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998)] | Rint = 0.013 |
Tmin = 0.513, Tmax = 0.720 | 3 standard reflections every 120 min |
4967 measured reflections | intensity decay: none |
4625 independent reflections |
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.050 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.71 e Å−3 |
4625 reflections | Δρmin = −0.47 e Å−3 |
181 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 | ||
Sb | 0.742414 (18) | 0.688104 (13) | 0.664750 (12) | 0.02788 (4) | |
S1 | 0.50536 (7) | 0.66644 (5) | 0.56963 (5) | 0.03326 (11) | |
S2 | 0.74095 (9) | 0.48688 (6) | 0.83310 (5) | 0.04205 (14) | |
S3 | 0.66770 (8) | 0.87578 (6) | 0.69651 (6) | 0.03942 (13) | |
S4 | 1.00701 (9) | 0.70430 (7) | 0.55436 (7) | 0.05046 (17) | |
Ni | 0.48115 (4) | 0.44435 (3) | 0.72600 (2) | 0.02841 (6) | |
N1 | 0.4546 (3) | 0.24846 (18) | 0.85448 (16) | 0.0336 (4) | |
N2 | 0.2759 (2) | 0.40871 (19) | 0.64784 (17) | 0.0343 (4) | |
H1N2 | 0.1987 | 0.4821 | 0.6174 | 0.041* | |
H2N2 | 0.3215 | 0.3884 | 0.5885 | 0.041* | |
N3 | 0.3009 (3) | 0.4915 (2) | 0.8435 (2) | 0.0454 (5) | |
H1N3 | 0.3493 | 0.5449 | 0.8661 | 0.055* | |
H2N3 | 0.2000 | 0.5353 | 0.8065 | 0.055* | |
N4 | 0.6884 (3) | 0.34876 (19) | 0.65835 (17) | 0.0356 (4) | |
H1N4 | 0.6678 | 0.3682 | 0.5830 | 0.043* | |
H2N4 | 0.7927 | 0.3784 | 0.6589 | 0.043* | |
N5 | 0.2448 (3) | 0.9160 (2) | 0.5848 (2) | 0.0554 (6) | |
H1N5 | 0.2436 | 0.9855 | 0.5145 | 0.083* | |
H2N5 | 0.1862 | 0.8541 | 0.5822 | 0.083* | |
H3N5 | 0.3570 | 0.8833 | 0.6036 | 0.083* | |
C1 | 0.3142 (3) | 0.1939 (2) | 0.8194 (2) | 0.0407 (5) | |
H1A | 0.2497 | 0.1374 | 0.8900 | 0.049* | |
H1B | 0.3713 | 0.1393 | 0.7816 | 0.049* | |
C2 | 0.1819 (3) | 0.2989 (2) | 0.7360 (2) | 0.0403 (5) | |
H2C | 0.1202 | 0.2606 | 0.6965 | 0.048* | |
H2D | 0.0938 | 0.3317 | 0.7805 | 0.048* | |
C3 | 0.4072 (4) | 0.2608 (3) | 0.9662 (2) | 0.0495 (6) | |
H3C | 0.5111 | 0.2798 | 0.9932 | 0.059* | |
H3D | 0.3703 | 0.1777 | 1.0264 | 0.059* | |
C4 | 0.2577 (4) | 0.3703 (3) | 0.9490 (2) | 0.0537 (7) | |
H4C | 0.1468 | 0.3432 | 0.9387 | 0.064* | |
H4D | 0.2428 | 0.3878 | 1.0182 | 0.064* | |
C5 | 0.6309 (3) | 0.1740 (2) | 0.8547 (2) | 0.0435 (6) | |
H5A | 0.6207 | 0.0798 | 0.8979 | 0.052* | |
H5B | 0.7145 | 0.1974 | 0.8943 | 0.052* | |
C6 | 0.7005 (3) | 0.2050 (2) | 0.7291 (2) | 0.0434 (6) | |
H6A | 0.8237 | 0.1675 | 0.7298 | 0.052* | |
H6B | 0.6307 | 0.1659 | 0.6946 | 0.052* | |
C7 | 0.1582 (4) | 0.9571 (3) | 0.6741 (2) | 0.0458 (6) | |
H7A | 0.0365 | 0.9941 | 0.6527 | 0.055* | |
H7B | 0.2209 | 1.0256 | 0.6757 | 0.055* | |
C8 | 0.1566 (4) | 0.8429 (3) | 0.7949 (3) | 0.0546 (7) | |
H8A | 0.2784 | 0.8075 | 0.8170 | 0.066* | |
H8B | 0.0968 | 0.7735 | 0.7926 | 0.066* | |
C9 | 0.0626 (5) | 0.8839 (4) | 0.8875 (3) | 0.0732 (10) | |
H9A | 0.0643 | 0.8086 | 0.9632 | 0.110* | |
H9B | −0.0588 | 0.9175 | 0.8667 | 0.110* | |
H9C | 0.1228 | 0.9515 | 0.8911 | 0.110* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sb | 0.02684 (7) | 0.02500 (7) | 0.03242 (8) | −0.00593 (5) | −0.00283 (5) | −0.01175 (5) |
S1 | 0.0359 (3) | 0.0306 (3) | 0.0342 (3) | −0.0063 (2) | −0.0094 (2) | −0.0124 (2) |
S2 | 0.0574 (4) | 0.0314 (3) | 0.0347 (3) | −0.0092 (3) | −0.0119 (3) | −0.0086 (2) |
S3 | 0.0431 (3) | 0.0343 (3) | 0.0478 (3) | −0.0044 (2) | −0.0035 (3) | −0.0236 (3) |
S4 | 0.0350 (3) | 0.0443 (3) | 0.0669 (4) | −0.0051 (3) | 0.0136 (3) | −0.0222 (3) |
Ni | 0.03015 (14) | 0.02492 (13) | 0.03024 (14) | −0.00574 (10) | −0.00185 (11) | −0.01107 (11) |
N1 | 0.0397 (10) | 0.0288 (9) | 0.0316 (9) | −0.0091 (8) | −0.0022 (8) | −0.0107 (8) |
N2 | 0.0328 (9) | 0.0335 (9) | 0.0380 (10) | −0.0033 (7) | −0.0045 (8) | −0.0161 (8) |
N3 | 0.0497 (12) | 0.0418 (11) | 0.0533 (13) | −0.0079 (9) | 0.0037 (10) | −0.0286 (10) |
N4 | 0.0349 (10) | 0.0368 (10) | 0.0364 (10) | −0.0048 (8) | −0.0002 (8) | −0.0168 (8) |
N5 | 0.0561 (14) | 0.0413 (12) | 0.0570 (14) | −0.0014 (10) | 0.0110 (11) | −0.0140 (11) |
C1 | 0.0445 (13) | 0.0332 (12) | 0.0484 (14) | −0.0152 (10) | −0.0007 (11) | −0.0183 (11) |
C2 | 0.0333 (12) | 0.0431 (13) | 0.0512 (14) | −0.0117 (10) | 0.0000 (10) | −0.0248 (11) |
C3 | 0.0708 (18) | 0.0461 (14) | 0.0300 (12) | −0.0207 (13) | 0.0038 (12) | −0.0121 (11) |
C4 | 0.0690 (19) | 0.0578 (17) | 0.0445 (15) | −0.0209 (14) | 0.0175 (13) | −0.0315 (13) |
C5 | 0.0455 (14) | 0.0281 (11) | 0.0473 (14) | −0.0008 (10) | −0.0117 (11) | −0.0063 (10) |
C6 | 0.0407 (13) | 0.0329 (12) | 0.0564 (15) | 0.0035 (10) | −0.0029 (11) | −0.0208 (11) |
C7 | 0.0493 (14) | 0.0362 (12) | 0.0507 (15) | −0.0046 (11) | −0.0056 (12) | −0.0169 (11) |
C8 | 0.0427 (14) | 0.0486 (15) | 0.0565 (17) | −0.0048 (12) | −0.0064 (12) | −0.0072 (13) |
C9 | 0.091 (3) | 0.078 (2) | 0.0515 (18) | −0.038 (2) | 0.0005 (17) | −0.0218 (17) |
Sb—S1 | 2.3467 (8) | N5—H3N5 | 0.8900 |
Sb—S2 | 2.3333 (12) | C1—C2 | 1.518 (4) |
Sb—S3 | 2.3150 (8) | C1—H1A | 0.9700 |
Sb—S4 | 2.3071 (10) | C1—H1B | 0.9700 |
S1—Ni | 2.4359 (12) | C2—H2C | 0.9700 |
S2—Ni | 2.6936 (9) | C2—H2D | 0.9700 |
Ni—N1 | 2.116 (2) | C3—C4 | 1.514 (4) |
Ni—N2 | 2.0876 (19) | C3—H3C | 0.9700 |
Ni—N3 | 2.109 (2) | C3—H3D | 0.9700 |
Ni—N4 | 2.110 (2) | C4—H4C | 0.9700 |
N1—C5 | 1.478 (3) | C4—H4D | 0.9700 |
N1—C3 | 1.482 (3) | C5—C6 | 1.520 (4) |
N1—C1 | 1.487 (3) | C5—H5A | 0.9700 |
N2—C2 | 1.469 (3) | C5—H5B | 0.9700 |
N2—H1N2 | 0.9000 | C6—H6A | 0.9700 |
N2—H2N2 | 0.9000 | C6—H6B | 0.9700 |
N3—C4 | 1.480 (4) | C7—C8 | 1.504 (4) |
N3—H1N3 | 0.9000 | C7—H7A | 0.9700 |
N3—H2N3 | 0.9000 | C7—H7B | 0.9700 |
N4—C6 | 1.466 (3) | C8—C9 | 1.520 (5) |
N4—H1N4 | 0.9000 | C8—H8A | 0.9700 |
N4—H2N4 | 0.9000 | C8—H8B | 0.9700 |
N5—C7 | 1.465 (3) | C9—H9A | 0.9600 |
N5—H1N5 | 0.8900 | C9—H9B | 0.9600 |
N5—H2N5 | 0.8900 | C9—H9C | 0.9600 |
S1—Sb—S2 | 98.54 (4) | N1—C1—H1A | 108.8 |
S1—Sb—S3 | 107.58 (3) | C2—C1—H1A | 108.8 |
S1—Sb—S4 | 111.90 (3) | N1—C1—H1B | 108.8 |
S2—Sb—S3 | 115.66 (3) | C2—C1—H1B | 108.8 |
S2—Sb—S4 | 112.23 (4) | H1A—C1—H1B | 107.7 |
S3—Sb—S4 | 110.31 (4) | N2—C2—C1 | 109.87 (19) |
Sb—S1—Ni | 89.83 (4) | N2—C2—H2C | 109.7 |
Sb—S2—Ni | 84.10 (4) | C1—C2—H2C | 109.7 |
N1—Ni—N2 | 83.09 (8) | N2—C2—H2D | 109.7 |
N1—Ni—N3 | 82.47 (9) | C1—C2—H2D | 109.7 |
N1—Ni—N4 | 82.55 (8) | H2C—C2—H2D | 108.2 |
N2—Ni—N3 | 92.28 (8) | N1—C3—C4 | 110.8 (2) |
N2—Ni—N4 | 95.54 (8) | N1—C3—H3C | 109.5 |
N3—Ni—N4 | 162.13 (9) | C4—C3—H3C | 109.5 |
N1—Ni—S1 | 176.65 (5) | N1—C3—H3D | 109.5 |
N2—Ni—S1 | 93.94 (6) | C4—C3—H3D | 109.5 |
N3—Ni—S1 | 99.24 (7) | H3C—C3—H3D | 108.1 |
N4—Ni—S1 | 96.23 (6) | N3—C4—C3 | 109.4 (2) |
N1—Ni—S2 | 95.67 (6) | N3—C4—H4C | 109.8 |
N2—Ni—S2 | 178.31 (6) | C3—C4—H4C | 109.8 |
N3—Ni—S2 | 86.41 (7) | N3—C4—H4D | 109.8 |
N4—Ni—S2 | 85.43 (6) | C3—C4—H4D | 109.8 |
S1—Ni—S2 | 87.33 (4) | H4C—C4—H4D | 108.2 |
C5—N1—C3 | 113.3 (2) | N1—C5—C6 | 110.57 (19) |
C5—N1—C1 | 110.91 (19) | N1—C5—H5A | 109.5 |
C3—N1—C1 | 112.9 (2) | C6—C5—H5A | 109.5 |
C5—N1—Ni | 105.42 (14) | N1—C5—H5B | 109.5 |
C3—N1—Ni | 104.69 (14) | C6—C5—H5B | 109.5 |
C1—N1—Ni | 109.13 (14) | H5A—C5—H5B | 108.1 |
C2—N2—Ni | 110.05 (14) | N4—C6—C5 | 109.6 (2) |
C2—N2—H1N2 | 109.6 | N4—C6—H6A | 109.7 |
Ni—N2—H1N2 | 109.6 | C5—C6—H6A | 109.7 |
C2—N2—H2N2 | 109.6 | N4—C6—H6B | 109.7 |
Ni—N2—H2N2 | 109.6 | C5—C6—H6B | 109.7 |
H1N2—N2—H2N2 | 108.2 | H6A—C6—H6B | 108.2 |
C4—N3—Ni | 110.89 (16) | N5—C7—C8 | 111.6 (2) |
C4—N3—H1N3 | 109.5 | N5—C7—H7A | 109.3 |
Ni—N3—H1N3 | 109.5 | C8—C7—H7A | 109.3 |
C4—N3—H2N3 | 109.5 | N5—C7—H7B | 109.3 |
Ni—N3—H2N3 | 109.5 | C8—C7—H7B | 109.3 |
H1N3—N3—H2N3 | 108.0 | H7A—C7—H7B | 108.0 |
C6—N4—Ni | 110.73 (15) | C7—C8—C9 | 112.0 (3) |
C6—N4—H1N4 | 109.5 | C7—C8—H8A | 109.2 |
Ni—N4—H1N4 | 109.5 | C9—C8—H8A | 109.2 |
C6—N4—H2N4 | 109.5 | C7—C8—H8B | 109.2 |
Ni—N4—H2N4 | 109.5 | C9—C8—H8B | 109.2 |
H1N4—N4—H2N4 | 108.1 | H8A—C8—H8B | 107.9 |
C7—N5—H1N5 | 109.5 | C8—C9—H9A | 109.5 |
C7—N5—H2N5 | 109.5 | C8—C9—H9B | 109.5 |
H1N5—N5—H2N5 | 109.5 | H9A—C9—H9B | 109.5 |
C7—N5—H3N5 | 109.5 | C8—C9—H9C | 109.5 |
H1N5—N5—H3N5 | 109.5 | H9A—C9—H9C | 109.5 |
H2N5—N5—H3N5 | 109.5 | H9B—C9—H9C | 109.5 |
N1—C1—C2 | 113.89 (19) | ||
S4—Sb—S1—S1 | 0.00 (6) | S1—Ni—N1—C3 | −147.5 (9) |
S3—Sb—S1—S1 | 0.00 (5) | S1—Ni—N1—C3 | −147.5 (9) |
S3—Sb—S1—S1 | 0.00 (5) | S2—Ni—N1—C3 | 59.04 (16) |
S2—Sb—S1—S1 | 0.00 (5) | N2—Ni—N1—C1 | 1.25 (15) |
S4—Sb—S1—Ni | 114.50 (4) | N3—Ni—N1—C1 | 94.48 (16) |
S3—Sb—S1—Ni | −124.17 (3) | N4—Ni—N1—C1 | −95.29 (16) |
S3—Sb—S1—Ni | −124.17 (3) | S1—Ni—N1—C1 | −26.5 (11) |
S2—Sb—S1—Ni | −3.71 (2) | S1—Ni—N1—C1 | −26.5 (11) |
S1—Sb—S1—Ni | 0 (6) | S2—Ni—N1—C1 | −179.91 (14) |
S4—Sb—S2—Ni | −114.59 (3) | N3—Ni—N2—C2 | −61.63 (16) |
S3—Sb—S2—Ni | 117.64 (3) | N4—Ni—N2—C2 | 102.28 (16) |
S3—Sb—S2—Ni | 117.64 (3) | N1—Ni—N2—C2 | 20.50 (15) |
S1—Sb—S2—Ni | 3.37 (2) | S1—Ni—N2—C2 | −161.06 (14) |
S1—Sb—S2—Ni | 3.37 (2) | S1—Ni—N2—C2 | −161.06 (14) |
S4—Sb—S3—S3 | 0.00 (19) | S2—Ni—N2—C2 | −22.4 (19) |
S2—Sb—S3—S3 | 0.00 (18) | N2—Ni—N3—C4 | 84.27 (19) |
S1—Sb—S3—S3 | 0.00 (17) | N4—Ni—N3—C4 | −31.7 (4) |
S1—Sb—S3—S3 | 0.00 (17) | N1—Ni—N3—C4 | 1.54 (18) |
S1—S1—Ni—N2 | 0.00 (7) | S1—Ni—N3—C4 | 178.63 (17) |
Sb—S1—Ni—N2 | −177.94 (6) | S1—Ni—N3—C4 | 178.63 (17) |
S1—S1—Ni—N3 | 0.00 (7) | S2—Ni—N3—C4 | −94.66 (18) |
Sb—S1—Ni—N3 | 89.10 (7) | N2—Ni—N4—C6 | −80.39 (17) |
S1—S1—Ni—N4 | 0.00 (7) | N3—Ni—N4—C6 | 35.1 (3) |
Sb—S1—Ni—N4 | −81.92 (6) | N1—Ni—N4—C6 | 1.88 (16) |
S1—S1—Ni—N1 | 0.0 (2) | S1—Ni—N4—C6 | −174.98 (15) |
Sb—S1—Ni—N1 | −150.3 (10) | S1—Ni—N4—C6 | −174.98 (15) |
Sb—S1—Ni—S1 | 0 (6) | S2—Ni—N4—C6 | 98.21 (16) |
S1—S1—Ni—S2 | 0.00 (7) | C5—N1—C1—C2 | −138.4 (2) |
Sb—S1—Ni—S2 | 3.18 (2) | C3—N1—C1—C2 | 93.2 (3) |
Sb—S2—Ni—N2 | −142.0 (19) | Ni—N1—C1—C2 | −22.7 (2) |
Sb—S2—Ni—N3 | −102.66 (7) | Ni—N2—C2—C1 | −37.8 (2) |
Sb—S2—Ni—N4 | 93.25 (6) | N1—C1—C2—N2 | 40.7 (3) |
Sb—S2—Ni—N1 | 175.28 (6) | C5—N1—C3—C4 | 162.6 (2) |
Sb—S2—Ni—S1 | −3.22 (2) | C1—N1—C3—C4 | −70.3 (3) |
Sb—S2—Ni—S1 | −3.22 (2) | Ni—N1—C3—C4 | 48.2 (2) |
N2—Ni—N1—C5 | 120.43 (15) | Ni—N3—C4—C3 | 23.9 (3) |
N3—Ni—N1—C5 | −146.34 (16) | N1—C3—C4—N3 | −49.2 (3) |
N4—Ni—N1—C5 | 23.89 (15) | C3—N1—C5—C6 | −160.0 (2) |
S1—Ni—N1—C5 | 92.7 (10) | C1—N1—C5—C6 | 71.9 (2) |
S1—Ni—N1—C5 | 92.7 (10) | Ni—N1—C5—C6 | −46.1 (2) |
S2—Ni—N1—C5 | −60.73 (15) | Ni—N4—C6—C5 | −27.1 (2) |
N2—Ni—N1—C3 | −119.81 (17) | N1—C5—C6—N4 | 50.0 (3) |
N3—Ni—N1—C3 | −26.57 (16) | N5—C7—C8—C9 | −178.5 (3) |
N4—Ni—N1—C3 | 143.65 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···S4i | 0.90 | 2.56 | 3.445 (2) | 170 |
N2—H2N2···S1ii | 0.90 | 2.54 | 3.431 (2) | 172 |
N4—H1N4···S1ii | 0.90 | 2.62 | 3.428 (2) | 150 |
N5—H1N5···S3iii | 0.89 | 2.50 | 3.347 (3) | 159 |
N5—H2N5···S4i | 0.89 | 2.46 | 3.348 (3) | 173 |
N5—H3N5···S3 | 0.89 | 2.70 | 3.515 (3) | 152 |
N5—H3N5···S1 | 0.89 | 2.75 | 3.284 (3) | 120 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C3H10N)[NiSbS4(C6H18N4)] |
Mr | 515.06 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.5707 (15), 11.303 (2), 12.605 (3) |
α, β, γ (°) | 63.98 (3), 84.49 (3), 82.26 (3) |
V (Å3) | 959.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.82 |
Crystal size (mm) | 0.5 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Philips PW1100 four-circle diffractometer |
Absorption correction | ψ scan [X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998)] |
Tmin, Tmax | 0.513, 0.720 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4967, 4625, 3940 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.050, 1.02 |
No. of reflections | 4625 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.71, −0.47 |
Computer programs: DIF4 (Stoe & Cie, 1992), DIF4, REDU4 (Stoe & Cie, 1992), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), CIFTAB in SHELXL97.
Sb—S1 | 2.3467 (8) | Ni—N1 | 2.116 (2) |
Sb—S2 | 2.3333 (12) | Ni—N2 | 2.0876 (19) |
Sb—S3 | 2.3150 (8) | Ni—N3 | 2.109 (2) |
Sb—S4 | 2.3071 (10) | Ni—N4 | 2.110 (2) |
S1—Ni | 2.4359 (12) | N5—C7 | 1.465 (3) |
S2—Ni | 2.6936 (9) | ||
S1—Sb—S2 | 98.54 (4) | N2—Ni—N4 | 95.54 (8) |
S1—Sb—S3 | 107.58 (3) | N3—Ni—N4 | 162.13 (9) |
S1—Sb—S4 | 111.90 (3) | N1—Ni—S1 | 176.65 (5) |
S2—Sb—S3 | 115.66 (3) | N2—Ni—S1 | 93.94 (6) |
S2—Sb—S4 | 112.23 (4) | N3—Ni—S1 | 99.24 (7) |
S3—Sb—S4 | 110.31 (4) | N4—Ni—S1 | 96.23 (6) |
Sb—S1—Ni | 89.83 (4) | N1—Ni—S2 | 95.67 (6) |
Sb—S2—Ni | 84.10 (4) | N2—Ni—S2 | 178.31 (6) |
N1—Ni—N2 | 83.09 (8) | N3—Ni—S2 | 86.41 (7) |
N1—Ni—N3 | 82.47 (9) | N4—Ni—S2 | 85.43 (6) |
N1—Ni—N4 | 82.55 (8) | S1—Ni—S2 | 87.33 (4) |
N2—Ni—N3 | 92.28 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···S4i | 0.90 | 2.56 | 3.445 (2) | 170 |
N2—H2N2···S1ii | 0.90 | 2.54 | 3.431 (2) | 172 |
N4—H1N4···S1ii | 0.90 | 2.62 | 3.428 (2) | 150 |
N5—H1N5···S3iii | 0.89 | 2.50 | 3.347 (3) | 159 |
N5—H2N5···S4i | 0.89 | 2.46 | 3.348 (3) | 173 |
N5—H3N5···S3 | 0.89 | 2.70 | 3.515 (3) | 152 |
N5—H3N5···S1 | 0.89 | 2.75 | 3.284 (3) | 120 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+2, −z+1. |
Thioantimonates(III) exhibit a rich structural diversity, due to the very flexible coordination behaviour of the SbIII atom, with coordination numbers ranging from 3 to 6 (Sheldrick & Wachhold, 1997; Wang & Liebau, 1996). The thioantimonate(III) anions occur as isolated units, chains, layers or three-dimensional frameworks (Sheldrick & Wachhold, 1998). On the other hand, thioantimonates(V) are often isolated (Graf & Schäfer, 1976; Schur et al., 1998). Compounds in which the SbVS4 tetrahedron is interconnected to transition metal cations are A2AuSbS4 (A is Rb or Cs; Hanko & Kanatzidis, 1998), MAg2SbS4 and M2AgSbS4 (M is K or Rb; Schimek et al., 1996), or [(H2O)9Mo3S4SbS4Mo3(H2O)9](CH3C6H4SO3)8.24H2O (Sakane et al., 1998).
A way of connecting SbVS4 tetrahedra to transition metal cations (TMC), based on our results obtained recently with thioantimonates(III), has been established Added text OK?. Using the tetradentate ligand tren [tren is tris(2-aminoethyl)amine], together with Co and Ni, we have prepared neutral compounds such as [Co(tren)]Sb2S5 and [Co(tren)]Sb4S8 (Stähler & Bensch, 2001a), the chain-like [Sb2S42-] anion in [Ni(tren)]Sb2S4 and a layered compound, [Co(tren)]Sb2S4 (Stähler & Bensch, 2001b). In these compounds, the tetradentate ligand leaves one or two sites at the TMC free, and these sites are used to form bonds to S atoms of the thioantimonate(III) anions. Applying the very successful method presented for thioantimonates(III), we synthesized the title new and unusual thioantimonate(V) compound, [PAH][Ni(tren)SbS4], (I), with an [SbVS4]3- anion acting as a bidentate ligand. \sch
The structure of (I) is composed of PAH+ cations and [Ni(tren)SbS4]- anions (Fig. 1). The Ni2+ ion is surrounded by four N atoms of the tren ligand and two S atoms of the [SbVS4]3- anion, to form a distorted octahedron (NiN4S2). The Ni—N distances range from 2.0876 (19) to 2.116 (2) Å, with N—Ni—N angles between 82.47 (9) and 162.13 (9)° (Table 1). The two Ni—S distances of 2.4359 (12) and 2.6936 (9) Å are significantly different. It can be assumed that geometrical reasons are responsible for the long Ni—S2 bond. The S1—Ni—N1 [176.65 (5)°] and S2—Ni—N2 [178.31 (6)°] angles deviate slightly from the ideal value of 180°. The SbVS4 tetrahedron is only moderately distorted, with Sb—S distances and S—Sb—S angles in the ranges 2.3071 (10)–2.3467 (8) Å and 98.54 (4)–115.66 (3)°, respectively (see Table 1). These values are in the normal range for [SbVS4]3- anions (Mereiter et al., 1979; Hanko & Kanatzidis, 1998; Sakane et al., 1998).
The anionic part of the structure of (I) may be viewed as being composed of an [NiN4]2+ cation sharing two S atoms with the [SbVS4]3- anion, thus yielding the final [Ni(tren)SbS4]- anion. These anions are stacked along the a axis (Fig. 2) and the PAH+ cations are located near the [SbVS4]3- anion. The C—N bond distance in PAH+ is in the normal range for a primary amine [C7—N5 1.465 (3) Å].
In (I), a hydrogen-bond network (Table 2) is observed which may contribute significantly to the stability of the compound. There are three short intermolecular contacts, involving atoms S1 [H2N2···S1i and H1N4···S1i; symmetry code: (i) 1 - x, 1 - y, 1 - z Please check added symmetry code] and S4 [H1N2···S4iii; symmetry code: (iii) x - 1, y, z Please check added symmetry code] of the [SbVS4]3- tetrahedron and the H atoms of the tren ligand, with H···S distances in the range 2.54–2.62 Å. Four H···S contacts are observed between the PAH+ cation and atoms S1, S3, S3ii and S4iii [symmetry code: (ii) 1 - x, 2 - y, 1 - z Please check added symmetry code], with H···S distances in the range 2.46–2.75 Å; the corresponding angles are in the range 120.2–173.2°.