Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035416/rz2160sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035416/rz2160Isup2.hkl |
CCDC reference: 657630
The title salt was synthesized from the reaction of 5,8-diazoniadispiro[4.2.4.2]tetradecane dibromide (0.034 g, 0.1 mmol) in methanol (5 ml) and a mixture of NiCl2 (0.013 g, 0.1 mmol) and KNCS(0.074 g, 0.4 mmol) in DMF (10 ml). The resulting mixture was set aside for the formation of green crystals (yield 40%) after several days on slow evaporation of the solvent.
The methylene H atoms were positioned geometrically with C—H = 0.97 Å and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were located from a difference Fourier map, and their positional and isotropic displacement parameters were refined.
Organo-inorganic hybrid compounds containing the hexakis(isothiocyanato)nickel(II) tetraanion have been the subject of several investigations, but the structural examples are scarce (Vicente et al., 1996; Kruger & McKee, 1996; Hoffman & Wood, 1982). In this work we present the crystal structure of a new hexakis(isothiocyanato)nickel(II) salt with the 5,8-diazoniadispiro[4.2.4.2]tetradecane dication.
The structure of the title compound (Fig. 1) comprises discrete (C12H24N2)2+ cations, [Ni(NCS)6]4- anions and water molecules in the ratio 2:1:2. The anion, which lies on an inversion centre, displays the expected N6-octahedral coordination with only minor deviations from the ideal geometry. In the cation, the six-membered ring displays a chair conformation, while the five-membered rings adopt a twist conformation. In the crystal structure, all components are linked into a three-dimensional extended network through intermolecular O—H···S, O—H···N, C—H···S, C—H···O and C—H···N hydrogen bonding interactions (Table 1, Fig. 2).
For structures containing the hexakis(isothiocyanato)nickel(II) tetraanion see: Vicente et al. (1996); Kruger & McKee (1996); Hoffman & Wood (1982).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97.
(C12H24N2)2[Ni(NCS)6]·2H2O | F(000) = 884 |
Mr = 835.89 | Dx = 1.407 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5316 reflections |
a = 9.959 (6) Å | θ = 2.6–27.3° |
b = 13.537 (8) Å | µ = 0.85 mm−1 |
c = 14.718 (9) Å | T = 273 K |
β = 96.186 (10)° | Block, green |
V = 1973 (2) Å3 | 0.30 × 0.15 × 0.15 mm |
Z = 2 |
Siemen SMART CCD diffractometer | 3660 independent reflections |
Radiation source: fine-focus sealed tube | 3220 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scan | θmax = 25.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.857, Tmax = 0.884 | k = −16→16 |
10750 measured reflections | l = −9→17 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0548P)2 + 0.9458P] where P = (Fo2 + 2Fc2)/3 |
3660 reflections | (Δ/σ)max < 0.001 |
231 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
(C12H24N2)2[Ni(NCS)6]·2H2O | V = 1973 (2) Å3 |
Mr = 835.89 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.959 (6) Å | µ = 0.85 mm−1 |
b = 13.537 (8) Å | T = 273 K |
c = 14.718 (9) Å | 0.30 × 0.15 × 0.15 mm |
β = 96.186 (10)° |
Siemen SMART CCD diffractometer | 3660 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3220 reflections with I > 2σ(I) |
Tmin = 0.857, Tmax = 0.884 | Rint = 0.024 |
10750 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.57 e Å−3 |
3660 reflections | Δρmin = −0.40 e Å−3 |
231 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 | ||
Ni1 | 1.0000 | 0.5000 | 0.0000 | 0.03897 (14) | |
S1 | 1.38818 (7) | 0.68186 (6) | 0.13836 (5) | 0.0622 (2) | |
S2 | 0.81710 (8) | 0.83015 (5) | −0.00780 (6) | 0.0666 (2) | |
S3 | 0.88411 (6) | 0.38952 (5) | 0.29815 (4) | 0.04961 (18) | |
O1 | 0.6492 (3) | 0.5411 (2) | 0.1087 (3) | 0.1166 (12) | |
N1 | 1.1787 (2) | 0.56492 (16) | 0.05640 (15) | 0.0542 (5) | |
N2 | 0.9026 (2) | 0.63532 (16) | 0.01364 (15) | 0.0535 (5) | |
N3 | 0.9581 (2) | 0.45753 (16) | 0.13052 (14) | 0.0502 (5) | |
N4 | 0.62283 (18) | 0.20076 (14) | 0.15891 (13) | 0.0422 (4) | |
N5 | 0.42206 (17) | 0.34300 (13) | 0.21603 (12) | 0.0364 (4) | |
C1 | 1.2661 (2) | 0.61201 (17) | 0.09023 (16) | 0.0439 (5) | |
C2 | 0.8688 (2) | 0.71628 (17) | 0.00460 (14) | 0.0394 (5) | |
C3 | 0.9277 (2) | 0.42916 (16) | 0.19955 (16) | 0.0387 (5) | |
C4 | 0.7825 (3) | 0.1334 (3) | 0.0665 (2) | 0.0785 (10) | |
H4A | 0.8509 | 0.0824 | 0.0663 | 0.094* | |
H4B | 0.8082 | 0.1886 | 0.0301 | 0.094* | |
C5 | 0.6463 (3) | 0.0939 (2) | 0.0289 (2) | 0.0677 (8) | |
H5A | 0.6489 | 0.0224 | 0.0242 | 0.081* | |
H5B | 0.6194 | 0.1211 | −0.0313 | 0.081* | |
C6 | 0.5482 (3) | 0.12534 (19) | 0.0955 (2) | 0.0591 (7) | |
H6A | 0.5214 | 0.0690 | 0.1300 | 0.071* | |
H6B | 0.4680 | 0.1546 | 0.0630 | 0.071* | |
C7 | 0.7685 (3) | 0.1662 (2) | 0.1626 (2) | 0.0613 (7) | |
H7A | 0.8305 | 0.2197 | 0.1807 | 0.074* | |
H7B | 0.7857 | 0.1119 | 0.2053 | 0.074* | |
C8 | 0.5808 (2) | 0.20186 (18) | 0.25351 (16) | 0.0478 (6) | |
H8A | 0.6426 | 0.2430 | 0.2923 | 0.057* | |
H8B | 0.5859 | 0.1354 | 0.2782 | 0.057* | |
C9 | 0.4389 (2) | 0.24057 (18) | 0.25463 (17) | 0.0481 (6) | |
H9A | 0.3765 | 0.1965 | 0.2194 | 0.058* | |
H9B | 0.4161 | 0.2408 | 0.3171 | 0.058* | |
C10 | 0.6074 (2) | 0.30442 (17) | 0.12066 (15) | 0.0425 (5) | |
H10A | 0.6695 | 0.3481 | 0.1565 | 0.051* | |
H10B | 0.6309 | 0.3047 | 0.0584 | 0.051* | |
C11 | 0.4657 (2) | 0.34236 (16) | 0.12166 (15) | 0.0397 (5) | |
H11A | 0.4603 | 0.4090 | 0.0972 | 0.048* | |
H11B | 0.4044 | 0.3012 | 0.0824 | 0.048* | |
C12 | 0.4972 (2) | 0.4200 (2) | 0.27791 (17) | 0.0500 (6) | |
H12A | 0.5775 | 0.3916 | 0.3110 | 0.060* | |
H12B | 0.5235 | 0.4757 | 0.2424 | 0.060* | |
C13 | 0.4000 (3) | 0.4514 (3) | 0.3420 (2) | 0.0799 (10) | |
H13A | 0.4099 | 0.4107 | 0.3966 | 0.096* | |
H13B | 0.4155 | 0.5198 | 0.3598 | 0.096* | |
C14 | 0.2636 (3) | 0.4392 (3) | 0.2928 (2) | 0.0667 (8) | |
H14A | 0.2273 | 0.5032 | 0.2732 | 0.080* | |
H14B | 0.2037 | 0.4097 | 0.3329 | 0.080* | |
C15 | 0.2732 (2) | 0.37487 (19) | 0.21222 (18) | 0.0503 (6) | |
H15A | 0.2462 | 0.4107 | 0.1562 | 0.060* | |
H15B | 0.2152 | 0.3176 | 0.2147 | 0.060* | |
H1B | 0.601 (8) | 0.604 (6) | 0.099 (5) | 0.20 (3)* | |
H1C | 0.720 (7) | 0.539 (5) | 0.061 (4) | 0.20 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0368 (2) | 0.0394 (2) | 0.0404 (2) | 0.00054 (15) | 0.00290 (17) | 0.00225 (16) |
S1 | 0.0511 (4) | 0.0662 (4) | 0.0686 (5) | −0.0110 (3) | 0.0028 (3) | −0.0142 (3) |
S2 | 0.0639 (4) | 0.0423 (4) | 0.0884 (6) | 0.0048 (3) | −0.0152 (4) | −0.0038 (3) |
S3 | 0.0476 (3) | 0.0591 (4) | 0.0417 (3) | −0.0066 (3) | 0.0031 (3) | 0.0020 (3) |
O1 | 0.0871 (19) | 0.0908 (19) | 0.183 (3) | 0.0212 (16) | 0.065 (2) | 0.043 (2) |
N1 | 0.0489 (12) | 0.0552 (12) | 0.0569 (13) | −0.0076 (10) | −0.0013 (10) | 0.0038 (10) |
N2 | 0.0581 (13) | 0.0509 (12) | 0.0510 (12) | 0.0082 (10) | 0.0033 (10) | 0.0004 (10) |
N3 | 0.0477 (11) | 0.0547 (12) | 0.0483 (12) | 0.0014 (9) | 0.0059 (9) | 0.0048 (10) |
N4 | 0.0379 (10) | 0.0412 (10) | 0.0461 (11) | 0.0066 (8) | −0.0014 (8) | −0.0067 (8) |
N5 | 0.0308 (9) | 0.0411 (9) | 0.0368 (9) | 0.0007 (7) | 0.0021 (7) | −0.0006 (7) |
C1 | 0.0434 (13) | 0.0446 (12) | 0.0445 (13) | 0.0024 (10) | 0.0080 (10) | 0.0055 (10) |
C2 | 0.0364 (11) | 0.0467 (13) | 0.0342 (11) | −0.0010 (9) | 0.0002 (9) | −0.0031 (9) |
C3 | 0.0318 (10) | 0.0378 (11) | 0.0456 (13) | 0.0006 (8) | −0.0003 (9) | −0.0036 (10) |
C4 | 0.0634 (18) | 0.100 (2) | 0.074 (2) | 0.0218 (17) | 0.0169 (16) | −0.0242 (19) |
C5 | 0.089 (2) | 0.0620 (17) | 0.0509 (16) | 0.0094 (15) | 0.0024 (15) | −0.0116 (13) |
C6 | 0.0533 (15) | 0.0458 (13) | 0.0744 (18) | 0.0057 (11) | −0.0102 (13) | −0.0163 (12) |
C7 | 0.0425 (14) | 0.0744 (18) | 0.0649 (17) | 0.0172 (12) | −0.0035 (12) | −0.0142 (14) |
C8 | 0.0520 (14) | 0.0454 (13) | 0.0451 (13) | 0.0080 (10) | 0.0016 (11) | 0.0114 (10) |
C9 | 0.0470 (13) | 0.0511 (13) | 0.0471 (13) | −0.0005 (10) | 0.0092 (10) | 0.0148 (11) |
C10 | 0.0436 (12) | 0.0501 (13) | 0.0350 (11) | −0.0039 (10) | 0.0089 (9) | −0.0003 (9) |
C11 | 0.0445 (12) | 0.0391 (11) | 0.0349 (11) | 0.0008 (9) | 0.0011 (9) | 0.0046 (9) |
C12 | 0.0400 (12) | 0.0589 (14) | 0.0504 (14) | −0.0019 (11) | 0.0016 (10) | −0.0172 (12) |
C13 | 0.0538 (16) | 0.114 (3) | 0.071 (2) | 0.0186 (17) | 0.0001 (15) | −0.0402 (19) |
C14 | 0.0437 (14) | 0.090 (2) | 0.0682 (18) | 0.0034 (14) | 0.0135 (13) | −0.0182 (16) |
C15 | 0.0319 (11) | 0.0584 (14) | 0.0593 (15) | 0.0062 (10) | −0.0004 (10) | −0.0016 (12) |
Ni1—N1 | 2.076 (2) | C5—H5A | 0.9700 |
Ni1—N1i | 2.076 (2) | C5—H5B | 0.9700 |
Ni1—N3 | 2.090 (2) | C6—H6A | 0.9700 |
Ni1—N3i | 2.090 (2) | C6—H6B | 0.9700 |
Ni1—N2 | 2.093 (2) | C7—H7A | 0.9700 |
Ni1—N2i | 2.093 (2) | C7—H7B | 0.9700 |
S1—C1 | 1.640 (3) | C8—C9 | 1.508 (3) |
S2—C2 | 1.629 (3) | C8—H8A | 0.9700 |
S3—C3 | 1.649 (3) | C8—H8B | 0.9700 |
O1—H1B | 0.99 (8) | C9—H9A | 0.9700 |
O1—H1C | 1.05 (7) | C9—H9B | 0.9700 |
N1—C1 | 1.148 (3) | C10—C11 | 1.503 (3) |
N2—C2 | 1.150 (3) | C10—H10A | 0.9700 |
N3—C3 | 1.156 (3) | C10—H10B | 0.9700 |
N4—C8 | 1.497 (3) | C11—H11A | 0.9700 |
N4—C10 | 1.514 (3) | C11—H11B | 0.9700 |
N4—C7 | 1.520 (3) | C12—C13 | 1.485 (4) |
N4—C6 | 1.522 (3) | C12—H12A | 0.9700 |
N5—C11 | 1.499 (3) | C12—H12B | 0.9700 |
N5—C9 | 1.501 (3) | C13—C14 | 1.478 (4) |
N5—C12 | 1.526 (3) | C13—H13A | 0.9700 |
N5—C15 | 1.539 (3) | C13—H13B | 0.9700 |
C4—C7 | 1.503 (4) | C14—C15 | 1.483 (4) |
C4—C5 | 1.507 (5) | C14—H14A | 0.9700 |
C4—H4A | 0.9700 | C14—H14B | 0.9700 |
C4—H4B | 0.9700 | C15—H15A | 0.9700 |
C5—C6 | 1.517 (4) | C15—H15B | 0.9700 |
N1—Ni1—N1i | 180.0 | C4—C7—H7A | 111.0 |
N1—Ni1—N3 | 89.79 (9) | N4—C7—H7A | 111.0 |
N1i—Ni1—N3 | 90.21 (9) | C4—C7—H7B | 111.0 |
N1—Ni1—N3i | 90.21 (9) | N4—C7—H7B | 111.0 |
N1i—Ni1—N3i | 89.79 (9) | H7A—C7—H7B | 109.0 |
N3—Ni1—N3i | 180.00 (11) | N4—C8—C9 | 111.71 (19) |
N1—Ni1—N2 | 88.70 (10) | N4—C8—H8A | 109.3 |
N1i—Ni1—N2 | 91.30 (10) | C9—C8—H8A | 109.3 |
N3—Ni1—N2 | 90.68 (9) | N4—C8—H8B | 109.3 |
N3i—Ni1—N2 | 89.32 (9) | C9—C8—H8B | 109.3 |
N1—Ni1—N2i | 91.30 (10) | H8A—C8—H8B | 107.9 |
N1i—Ni1—N2i | 88.70 (10) | N5—C9—C8 | 112.55 (19) |
N3—Ni1—N2i | 89.32 (9) | N5—C9—H9A | 109.1 |
N3i—Ni1—N2i | 90.68 (9) | C8—C9—H9A | 109.1 |
N2—Ni1—N2i | 180.0 | N5—C9—H9B | 109.1 |
H1B—O1—H1C | 107 (5) | C8—C9—H9B | 109.1 |
C1—N1—Ni1 | 170.2 (2) | H9A—C9—H9B | 107.8 |
C2—N2—Ni1 | 162.9 (2) | C11—C10—N4 | 111.77 (18) |
C3—N3—Ni1 | 174.8 (2) | C11—C10—H10A | 109.3 |
C8—N4—C10 | 108.03 (17) | N4—C10—H10A | 109.3 |
C8—N4—C7 | 109.36 (19) | C11—C10—H10B | 109.3 |
C10—N4—C7 | 110.9 (2) | N4—C10—H10B | 109.3 |
C8—N4—C6 | 114.2 (2) | H10A—C10—H10B | 107.9 |
C10—N4—C6 | 111.73 (19) | N5—C11—C10 | 112.15 (17) |
C7—N4—C6 | 102.51 (18) | N5—C11—H11A | 109.2 |
C11—N5—C9 | 108.28 (17) | C10—C11—H11A | 109.2 |
C11—N5—C12 | 112.61 (17) | N5—C11—H11B | 109.2 |
C9—N5—C12 | 112.18 (19) | C10—C11—H11B | 109.2 |
C11—N5—C15 | 110.00 (17) | H11A—C11—H11B | 107.9 |
C9—N5—C15 | 109.93 (18) | C13—C12—N5 | 105.3 (2) |
C12—N5—C15 | 103.79 (17) | C13—C12—H12A | 110.7 |
N1—C1—S1 | 178.5 (2) | N5—C12—H12A | 110.7 |
N2—C2—S2 | 178.5 (2) | C13—C12—H12B | 110.7 |
N3—C3—S3 | 179.6 (2) | N5—C12—H12B | 110.7 |
C7—C4—C5 | 106.2 (3) | H12A—C12—H12B | 108.8 |
C7—C4—H4A | 110.5 | C14—C13—C12 | 106.5 (2) |
C5—C4—H4A | 110.5 | C14—C13—H13A | 110.4 |
C7—C4—H4B | 110.5 | C12—C13—H13A | 110.4 |
C5—C4—H4B | 110.5 | C14—C13—H13B | 110.4 |
H4A—C4—H4B | 108.7 | C12—C13—H13B | 110.4 |
C4—C5—C6 | 106.2 (2) | H13A—C13—H13B | 108.6 |
C4—C5—H5A | 110.5 | C13—C14—C15 | 108.8 (2) |
C6—C5—H5A | 110.5 | C13—C14—H14A | 109.9 |
C4—C5—H5B | 110.5 | C15—C14—H14A | 109.9 |
C6—C5—H5B | 110.5 | C13—C14—H14B | 109.9 |
H5A—C5—H5B | 108.7 | C15—C14—H14B | 109.9 |
C5—C6—N4 | 106.2 (2) | H14A—C14—H14B | 108.3 |
C5—C6—H6A | 110.5 | C14—C15—N5 | 106.28 (19) |
N4—C6—H6A | 110.5 | C14—C15—H15A | 110.5 |
C5—C6—H6B | 110.5 | N5—C15—H15A | 110.5 |
N4—C6—H6B | 110.5 | C14—C15—H15B | 110.5 |
H6A—C6—H6B | 108.7 | N5—C15—H15B | 110.5 |
C4—C7—N4 | 104.0 (2) | H15A—C15—H15B | 108.7 |
N1—Ni1—N2—C2 | 68.3 (7) | C15—N5—C9—C8 | 175.6 (2) |
N1i—Ni1—N2—C2 | −111.7 (7) | N4—C8—C9—N5 | −58.1 (3) |
N3—Ni1—N2—C2 | 158.1 (7) | C8—N4—C10—C11 | −56.7 (2) |
N3i—Ni1—N2—C2 | −21.9 (7) | C7—N4—C10—C11 | −176.57 (19) |
C7—C4—C5—C6 | 12.4 (4) | C6—N4—C10—C11 | 69.7 (2) |
C4—C5—C6—N4 | 11.9 (3) | C9—N5—C11—C10 | −55.6 (2) |
C8—N4—C6—C5 | −149.4 (2) | C12—N5—C11—C10 | 69.0 (2) |
C10—N4—C6—C5 | 87.6 (2) | C15—N5—C11—C10 | −175.73 (18) |
C7—N4—C6—C5 | −31.2 (3) | N4—C10—C11—N5 | 58.4 (2) |
C5—C4—C7—N4 | −32.0 (3) | C11—N5—C12—C13 | 149.0 (2) |
C8—N4—C7—C4 | 160.3 (2) | C9—N5—C12—C13 | −88.6 (3) |
C10—N4—C7—C4 | −80.7 (3) | C15—N5—C12—C13 | 30.0 (3) |
C6—N4—C7—C4 | 38.7 (3) | N5—C12—C13—C14 | −29.0 (4) |
C10—N4—C8—C9 | 56.3 (2) | C12—C13—C14—C15 | 16.5 (4) |
C7—N4—C8—C9 | 177.1 (2) | C13—C14—C15—N5 | 2.7 (4) |
C6—N4—C8—C9 | −68.7 (3) | C11—N5—C15—C14 | −140.7 (2) |
C11—N5—C9—C8 | 55.4 (2) | C9—N5—C15—C14 | 100.1 (2) |
C12—N5—C9—C8 | −69.4 (3) | C12—N5—C15—C14 | −20.0 (3) |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···S3 | 0.97 | 2.88 | 3.767 (3) | 153 |
C11—H11A···O1 | 0.97 | 2.59 | 3.269 (4) | 127 |
C12—H12B···O1 | 0.97 | 2.60 | 3.463 (5) | 149 |
O1—H1C···N2 | 1.05 (7) | 2.40 (7) | 3.273 (4) | 139 (5) |
C6—H6A···S3ii | 0.97 | 2.77 | 3.587 (3) | 142 |
C6—H6B···S2iii | 0.97 | 2.88 | 3.775 (4) | 155 |
C15—H15A···N1iv | 0.97 | 2.60 | 3.507 (3) | 156 |
O1—H1B···S1iv | 0.99 (8) | 2.49 (8) | 3.290 (3) | 139 (6) |
O1—H1C···N1i | 1.05 (7) | 2.52 (7) | 3.435 (5) | 145 (5) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z; (iv) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | (C12H24N2)2[Ni(NCS)6]·2H2O |
Mr | 835.89 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 9.959 (6), 13.537 (8), 14.718 (9) |
β (°) | 96.186 (10) |
V (Å3) | 1973 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.85 |
Crystal size (mm) | 0.30 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Siemen SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.857, 0.884 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10750, 3660, 3220 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.105, 1.06 |
No. of reflections | 3660 |
No. of parameters | 231 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.57, −0.40 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1994), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···S3 | 0.97 | 2.88 | 3.767 (3) | 153.4 |
C11—H11A···O1 | 0.97 | 2.59 | 3.269 (4) | 127.4 |
C12—H12B···O1 | 0.97 | 2.60 | 3.463 (5) | 148.6 |
O1—H1C···N2 | 1.05 (7) | 2.40 (7) | 3.273 (4) | 139 (5) |
C6—H6A···S3i | 0.97 | 2.77 | 3.587 (3) | 142.0 |
C6—H6B···S2ii | 0.97 | 2.88 | 3.775 (4) | 154.7 |
C15—H15A···N1iii | 0.97 | 2.60 | 3.507 (3) | 156.0 |
O1—H1B···S1iii | 0.99 (8) | 2.49 (8) | 3.290 (3) | 139 (6) |
O1—H1C···N1iv | 1.05 (7) | 2.52 (7) | 3.435 (5) | 145 (5) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) −x+2, −y+1, −z. |
Organo-inorganic hybrid compounds containing the hexakis(isothiocyanato)nickel(II) tetraanion have been the subject of several investigations, but the structural examples are scarce (Vicente et al., 1996; Kruger & McKee, 1996; Hoffman & Wood, 1982). In this work we present the crystal structure of a new hexakis(isothiocyanato)nickel(II) salt with the 5,8-diazoniadispiro[4.2.4.2]tetradecane dication.
The structure of the title compound (Fig. 1) comprises discrete (C12H24N2)2+ cations, [Ni(NCS)6]4- anions and water molecules in the ratio 2:1:2. The anion, which lies on an inversion centre, displays the expected N6-octahedral coordination with only minor deviations from the ideal geometry. In the cation, the six-membered ring displays a chair conformation, while the five-membered rings adopt a twist conformation. In the crystal structure, all components are linked into a three-dimensional extended network through intermolecular O—H···S, O—H···N, C—H···S, C—H···O and C—H···N hydrogen bonding interactions (Table 1, Fig. 2).