Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011187/na6089sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011187/na6089Isup2.hkl |
CCDC reference: 170878
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.007 Å
- R factor = 0.038
- wR factor = 0.091
- Data-to-parameter ratio = 17.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound was prepared by reaction of NiBr2·3H2O with 1,4,7-trithiacyclononane in MeOH. The resulting precipitate was washed with Et2O, dissolved in MeOH and Et2O vapour was then diffused into the solution to afford a purple microcrystalline solid. A crystal grew spontaneously by evaporation of the solvent while the solution was being examined on the microscope slide. This crystal was mounted in a film of RS3000 perfluoropolyether oil (Hoechst) and transferred into the cold stream of an Oxford Cryosystems open-flow cryostat (Cosier & Glazer, 1986) operating at 150 (2) K.
The structure was solved by direct methods (Sheldrick, 1997) and developed through iterative cycles of least-squares refinement and difference Fourier syntheses. Water H atoms were found from a ΔF synthesis, while others were placed geometrically; these were then refined as a rigid H2O group [O—H 0.85 (1) Å and H···H 1.34 (2) Å], using a riding model with C—H distances of 0.99 Å.
Data collection: STADI-4 (Stoe & Cie, 1997); cell refinement: STADI-4; data reduction: X-RED (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2001).
[Ni(C6H12S3)2]Br2·4H2O | Z = 1 |
Mr = 651.27 | F(000) = 330 |
Triclinic, P1 | Dx = 1.873 Mg m−3 |
a = 7.654 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.972 (4) Å | Cell parameters from 16 reflections |
c = 9.132 (5) Å | θ = 12–14° |
α = 93.34 (4)° | µ = 4.86 mm−1 |
β = 102.63 (4)° | T = 150 K |
γ = 107.79 (4)° | Tablet, purple |
V = 577.4 (5) Å3 | 0.23 × 0.12 × 0.08 mm |
Stoe Stadi-4 four-circle diffractometer | 1985 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.054 |
Graphite monochromator | θmax = 26.2°, θmin = 2.9° |
ω/θ scans | h = −9→9 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1997) | k = −11→11 |
Tmin = 0.551, Tmax = 0.725 | l = −10→11 |
2771 measured reflections | 3 standard reflections every 60 min |
2252 independent reflections | intensity decay: random variation: +−2.6% |
Refinement on F2 | Primary atom site location: direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier synthesis |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: see text |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0294P)2 + 3.122P] where P = (Fo2 + 2Fc2)/3 |
2252 reflections | (Δ/σ)max = 0.001 |
131 parameters | Δρmax = 0.68 e Å−3 |
6 restraints | Δρmin = −0.88 e Å−3 |
[Ni(C6H12S3)2]Br2·4H2O | γ = 107.79 (4)° |
Mr = 651.27 | V = 577.4 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.654 (3) Å | Mo Kα radiation |
b = 8.972 (4) Å | µ = 4.86 mm−1 |
c = 9.132 (5) Å | T = 150 K |
α = 93.34 (4)° | 0.23 × 0.12 × 0.08 mm |
β = 102.63 (4)° |
Stoe Stadi-4 four-circle diffractometer | 1985 reflections with I > 2σ(I) |
Absorption correction: numerical (X-RED; Stoe & Cie, 1997) | Rint = 0.054 |
Tmin = 0.551, Tmax = 0.725 | 3 standard reflections every 60 min |
2771 measured reflections | intensity decay: random variation: +−2.6% |
2252 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 6 restraints |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.68 e Å−3 |
2252 reflections | Δρmin = −0.88 e Å−3 |
131 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 | ||
Ni | 0.0000 | 0.0000 | 0.0000 | 0.01327 (18) | |
Br | 0.24112 (7) | 0.39105 (5) | 0.65592 (5) | 0.02586 (15) | |
S1 | 0.06612 (15) | −0.01729 (12) | −0.24151 (11) | 0.0173 (2) | |
C2 | 0.0798 (7) | −0.2163 (5) | −0.2712 (5) | 0.0222 (9) | |
H2A | −0.0467 | −0.2899 | −0.3254 | 0.027* | |
H2B | 0.1683 | −0.2166 | −0.3357 | 0.027* | |
C3 | 0.1465 (6) | −0.2738 (5) | −0.1230 (5) | 0.0202 (9) | |
H3A | 0.2806 | −0.2099 | −0.0777 | 0.024* | |
H3B | 0.1414 | −0.3847 | −0.1448 | 0.024* | |
S4 | 0.01066 (15) | −0.26420 (12) | 0.01535 (12) | 0.0169 (2) | |
C5 | −0.2292 (6) | −0.3874 (5) | −0.0858 (5) | 0.0198 (9) | |
H5A | −0.2348 | −0.4077 | −0.1947 | 0.024* | |
H5B | −0.2605 | −0.4903 | −0.0465 | 0.024* | |
C6 | −0.3740 (6) | −0.3086 (5) | −0.0673 (5) | 0.0184 (9) | |
H6A | −0.3790 | −0.3023 | 0.0402 | 0.022* | |
H6B | −0.5000 | −0.3770 | −0.1281 | 0.022* | |
S7 | −0.33104 (15) | −0.11275 (12) | −0.12214 (11) | 0.0163 (2) | |
C8 | −0.3370 (6) | −0.1498 (5) | −0.3224 (5) | 0.0203 (9) | |
H8A | −0.3398 | −0.2596 | −0.3467 | 0.024* | |
H8B | −0.4541 | −0.1383 | −0.3850 | 0.024* | |
C9 | −0.1650 (6) | −0.0358 (5) | −0.3615 (5) | 0.0197 (9) | |
H9A | −0.1795 | 0.0703 | −0.3583 | 0.024* | |
H9B | −0.1668 | −0.0696 | −0.4671 | 0.024* | |
O10 | 0.2084 (6) | 0.6328 (5) | 0.4009 (5) | 0.0405 (10) | |
H10A | 0.234 (7) | 0.578 (7) | 0.470 (5) | 0.05 (2)* | |
H10B | 0.090 (2) | 0.612 (7) | 0.383 (7) | 0.044 (19)* | |
O11 | −0.4594 (6) | 0.1750 (5) | −0.2588 (5) | 0.0442 (10) | |
H11A | −0.551 (4) | 0.211 (5) | −0.278 (6) | 0.020 (13)* | |
H11B | −0.379 (6) | 0.232 (6) | −0.301 (7) | 0.047 (19)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0133 (4) | 0.0138 (4) | 0.0120 (4) | 0.0035 (3) | 0.0038 (3) | −0.0006 (3) |
Br | 0.0288 (3) | 0.0251 (3) | 0.0214 (2) | 0.0109 (2) | 0.00003 (19) | −0.00202 (18) |
S1 | 0.0188 (5) | 0.0190 (5) | 0.0141 (5) | 0.0048 (4) | 0.0064 (4) | 0.0010 (4) |
C2 | 0.025 (2) | 0.023 (2) | 0.022 (2) | 0.013 (2) | 0.0082 (19) | −0.0001 (18) |
C3 | 0.020 (2) | 0.025 (2) | 0.018 (2) | 0.0122 (19) | 0.0046 (17) | −0.0014 (17) |
S4 | 0.0177 (5) | 0.0168 (5) | 0.0166 (5) | 0.0064 (4) | 0.0038 (4) | 0.0013 (4) |
C5 | 0.021 (2) | 0.016 (2) | 0.019 (2) | 0.0022 (18) | 0.0037 (17) | −0.0002 (16) |
C6 | 0.017 (2) | 0.015 (2) | 0.018 (2) | −0.0028 (17) | 0.0037 (17) | 0.0020 (16) |
S7 | 0.0153 (5) | 0.0180 (5) | 0.0148 (5) | 0.0050 (4) | 0.0033 (4) | −0.0001 (4) |
C8 | 0.020 (2) | 0.026 (2) | 0.012 (2) | 0.0050 (19) | 0.0029 (17) | 0.0019 (17) |
C9 | 0.024 (2) | 0.021 (2) | 0.014 (2) | 0.0063 (18) | 0.0068 (17) | 0.0042 (17) |
O10 | 0.036 (2) | 0.053 (3) | 0.039 (2) | 0.017 (2) | 0.0139 (18) | 0.0232 (19) |
O11 | 0.036 (2) | 0.046 (2) | 0.061 (3) | 0.019 (2) | 0.024 (2) | 0.024 (2) |
Ni—S1 | 2.3749 (16) | C2—H2A | 0.9900 |
Ni—S4 | 2.4077 (15) | C2—H2B | 0.9900 |
Ni—S7 | 2.3987 (17) | C3—H3A | 0.9900 |
S1—C9 | 1.820 (5) | C3—H3B | 0.9900 |
S1—C2 | 1.829 (5) | C5—H5A | 0.9900 |
C2—C3 | 1.516 (6) | C5—H5B | 0.9900 |
C3—S4 | 1.817 (4) | C6—H6A | 0.9900 |
S4—C5 | 1.829 (5) | C6—H6B | 0.9900 |
C5—C6 | 1.517 (6) | C8—H8A | 0.9900 |
C6—S7 | 1.808 (4) | C8—H8B | 0.9900 |
S7—C8 | 1.828 (4) | C9—H9A | 0.9900 |
C8—C9 | 1.527 (6) | C9—H9B | 0.9900 |
S1—Ni—S4 | 88.09 (5) | S4—C3—H3A | 108.6 |
S1—Ni—S7 | 88.67 (6) | C2—C3—H3B | 108.6 |
S4—Ni—S7 | 88.25 (6) | S4—C3—H3B | 108.6 |
S1i—Ni—S4 | 91.91 (5) | H3A—C3—H3B | 107.5 |
S1i—Ni—S7 | 91.33 (6) | C6—C5—H5A | 109.3 |
S7i—Ni—S4 | 91.75 (6) | S4—C5—H5A | 109.3 |
C9—S1—C2 | 103.0 (2) | C6—C5—H5B | 109.3 |
C9—S1—Ni | 99.67 (15) | S4—C5—H5B | 109.3 |
C2—S1—Ni | 104.11 (15) | H5A—C5—H5B | 108.0 |
C3—C2—S1 | 111.9 (3) | C5—C6—H6A | 108.4 |
C2—C3—S4 | 114.8 (3) | S7—C6—H6A | 108.4 |
C3—S4—C5 | 102.6 (2) | C5—C6—H6B | 108.4 |
C3—S4—Ni | 99.00 (15) | S7—C6—H6B | 108.4 |
C5—S4—Ni | 103.04 (15) | H6A—C6—H6B | 107.4 |
C6—C5—S4 | 111.4 (3) | C9—C8—H8A | 109.3 |
C5—C6—S7 | 115.7 (3) | S7—C8—H8A | 109.3 |
C6—S7—C8 | 101.8 (2) | C9—C8—H8B | 109.3 |
C6—S7—Ni | 99.32 (15) | S7—C8—H8B | 109.3 |
C8—S7—Ni | 104.07 (16) | H8A—C8—H8B | 108.0 |
C9—C8—S7 | 111.6 (3) | C8—C9—H9A | 108.1 |
C8—C9—S1 | 116.7 (3) | S1—C9—H9A | 108.1 |
C3—C2—H2A | 109.2 | C8—C9—H9B | 108.1 |
S1—C2—H2A | 109.2 | S1—C9—H9B | 108.1 |
C3—C2—H2B | 109.2 | H9A—C9—H9B | 107.3 |
S1—C2—H2B | 109.2 | H10A—O10—H10B | 105 (6) |
H2A—C2—H2B | 107.9 | H11A—O11—H11B | 104 (5) |
C2—C3—H3A | 108.6 | ||
S1—C2—C3—S4 | 53.8 (4) | C6—S7—C8—C9 | −130.4 (3) |
C2—C3—S4—C5 | 58.5 (4) | S7—C8—C9—S1 | 50.7 (4) |
C3—S4—C5—C6 | −134.4 (3) | C2—S1—C9—C8 | 62.5 (4) |
S4—C5—C6—S7 | 55.2 (4) | C9—S1—C2—C3 | −132.9 (3) |
C5—C6—S7—C8 | 60.5 (4) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10A···Br | 0.85 (5) | 2.46 (5) | 3.295 (5) | 169 (5) |
O10—H10B···Br | 0.84 (3) | 2.47 (3) | 3.303 (5) | 168 (5) |
O11—H11A···Br | 0.85 (4) | 2.60 (4) | 3.425 (5) | 164 (4) |
O11—H11B···O10 | 0.85 (5) | 1.92 (5) | 2.770 (7) | 176 (5) |
Experimental details
Crystal data | |
Chemical formula | [Ni(C6H12S3)2]Br2·4H2O |
Mr | 651.27 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 7.654 (3), 8.972 (4), 9.132 (5) |
α, β, γ (°) | 93.34 (4), 102.63 (4), 107.79 (4) |
V (Å3) | 577.4 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 4.86 |
Crystal size (mm) | 0.23 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Stoe Stadi-4 four-circle diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1997) |
Tmin, Tmax | 0.551, 0.725 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2771, 2252, 1985 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.620 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.092, 1.09 |
No. of reflections | 2252 |
No. of parameters | 131 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.68, −0.88 |
Computer programs: STADI-4 (Stoe & Cie, 1997), STADI-4, X-RED (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1994), SHELXL97 and PLATON (Spek, 2001).
The NiII centre occupies a crystallographic inversion centre and is octahedrally coordinated by six S-donors from two [9]aneS3 ligands (Fig. 1). The Ni—S distances range from 2.3749 (16) to 2.4077 (15) Å, while cis-S—Ni—S angles lie in a narrow range between 88.09 (5) and 88.67 (6)°. Fig. 2 shows a view along the b axis of part of one double chain of paired water molecules and Br- ions running along the a direction. Each double chain has alternating smaller and larger hydrogen bonded rings denoted by the graph-set symbols R24(8) and R46(12).