Download citation
Download citation
link to html
The NiII centre in the cation of the title compound, [Ni(C6H12S3)2]Br2·4H2O, occupies a crystallographic inversion centre and is octahedrally coordinated by six S-donors from two [9]­aneS3 ligands. Ni-S distances range from 2.3749 (16) to 2.4077 (15) Å and S-Ni-S angles where both thia donors belong to the same ligand lie in a narrow range between 88.09 (5) and 88.67 (6)°. The water mol­ecules participate in extensive hydrogen bonding with each other and with the Br- anions to form double chains with eight- and 12-membered hydrogen-bonded rings running along the crystallographic a direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011187/na6089sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011187/na6089Isup2.hkl
Contains datablock I

CCDC reference: 170878

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](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








Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of two asymmetric units of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view along the b axis of part of one double chain of water molecules and Br- ions running along the a direction. The double chain has alternating smaller and larger hydrogen-bonded rings denoted by the graph-set symbols R24(8) and R46(12). [Symmetry codes: (i) -x, 1 - y, 1 - z; (iii) -x, 1 - y, -z; (iv) 1 + x, y, 1 + z; (v) 1 - x, 1 - y, 1 - z.
Bis(1,4,7-trithiacyclononane-S,S',S")nickel(II) dibromide tetrahydrate top
Crystal data top
[Ni(C6H12S3)2]Br2·4H2OZ = 1
Mr = 651.27F(000) = 330
Triclinic, P1Dx = 1.873 Mg m3
a = 7.654 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.972 (4) ÅCell parameters from 16 reflections
c = 9.132 (5) Åθ = 12–14°
α = 93.34 (4)°µ = 4.86 mm1
β = 102.63 (4)°T = 150 K
γ = 107.79 (4)°Tablet, purple
V = 577.4 (5) Å30.23 × 0.12 × 0.08 mm
Data collection top
Stoe Stadi-4 four-circle
diffractometer
1985 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.054
Graphite monochromatorθmax = 26.2°, θmin = 2.9°
ω/θ scansh = 99
Absorption correction: numerical
(X-RED; Stoe & Cie, 1997)
k = 1111
Tmin = 0.551, Tmax = 0.725l = 1011
2771 measured reflections3 standard reflections every 60 min
2252 independent reflections intensity decay: random variation: +2.6%
Refinement top
Refinement on F2Primary atom site location: direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier synthesis
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: see text
wR(F2) = 0.092H 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 parametersΔρmax = 0.68 e Å3
6 restraintsΔρmin = 0.88 e Å3
Crystal data top
[Ni(C6H12S3)2]Br2·4H2Oγ = 107.79 (4)°
Mr = 651.27V = 577.4 (5) Å3
Triclinic, P1Z = 1
a = 7.654 (3) ÅMo Kα radiation
b = 8.972 (4) ŵ = 4.86 mm1
c = 9.132 (5) ÅT = 150 K
α = 93.34 (4)°0.23 × 0.12 × 0.08 mm
β = 102.63 (4)°
Data collection top
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 = 0.7253 standard reflections every 60 min
2771 measured reflections intensity decay: random variation: +2.6%
2252 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0386 restraints
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.68 e Å3
2252 reflectionsΔρmin = 0.88 e Å3
131 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni0.00000.00000.00000.01327 (18)
Br0.24112 (7)0.39105 (5)0.65592 (5)0.02586 (15)
S10.06612 (15)0.01729 (12)0.24151 (11)0.0173 (2)
C20.0798 (7)0.2163 (5)0.2712 (5)0.0222 (9)
H2A0.04670.28990.32540.027*
H2B0.16830.21660.33570.027*
C30.1465 (6)0.2738 (5)0.1230 (5)0.0202 (9)
H3A0.28060.20990.07770.024*
H3B0.14140.38470.14480.024*
S40.01066 (15)0.26420 (12)0.01535 (12)0.0169 (2)
C50.2292 (6)0.3874 (5)0.0858 (5)0.0198 (9)
H5A0.23480.40770.19470.024*
H5B0.26050.49030.04650.024*
C60.3740 (6)0.3086 (5)0.0673 (5)0.0184 (9)
H6A0.37900.30230.04020.022*
H6B0.50000.37700.12810.022*
S70.33104 (15)0.11275 (12)0.12214 (11)0.0163 (2)
C80.3370 (6)0.1498 (5)0.3224 (5)0.0203 (9)
H8A0.33980.25960.34670.024*
H8B0.45410.13830.38500.024*
C90.1650 (6)0.0358 (5)0.3615 (5)0.0197 (9)
H9A0.17950.07030.35830.024*
H9B0.16680.06960.46710.024*
O100.2084 (6)0.6328 (5)0.4009 (5)0.0405 (10)
H10A0.234 (7)0.578 (7)0.470 (5)0.05 (2)*
H10B0.090 (2)0.612 (7)0.383 (7)0.044 (19)*
O110.4594 (6)0.1750 (5)0.2588 (5)0.0442 (10)
H11A0.551 (4)0.211 (5)0.278 (6)0.020 (13)*
H11B0.379 (6)0.232 (6)0.301 (7)0.047 (19)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0133 (4)0.0138 (4)0.0120 (4)0.0035 (3)0.0038 (3)0.0006 (3)
Br0.0288 (3)0.0251 (3)0.0214 (2)0.0109 (2)0.00003 (19)0.00202 (18)
S10.0188 (5)0.0190 (5)0.0141 (5)0.0048 (4)0.0064 (4)0.0010 (4)
C20.025 (2)0.023 (2)0.022 (2)0.013 (2)0.0082 (19)0.0001 (18)
C30.020 (2)0.025 (2)0.018 (2)0.0122 (19)0.0046 (17)0.0014 (17)
S40.0177 (5)0.0168 (5)0.0166 (5)0.0064 (4)0.0038 (4)0.0013 (4)
C50.021 (2)0.016 (2)0.019 (2)0.0022 (18)0.0037 (17)0.0002 (16)
C60.017 (2)0.015 (2)0.018 (2)0.0028 (17)0.0037 (17)0.0020 (16)
S70.0153 (5)0.0180 (5)0.0148 (5)0.0050 (4)0.0033 (4)0.0001 (4)
C80.020 (2)0.026 (2)0.012 (2)0.0050 (19)0.0029 (17)0.0019 (17)
C90.024 (2)0.021 (2)0.014 (2)0.0063 (18)0.0068 (17)0.0042 (17)
O100.036 (2)0.053 (3)0.039 (2)0.017 (2)0.0139 (18)0.0232 (19)
O110.036 (2)0.046 (2)0.061 (3)0.019 (2)0.024 (2)0.024 (2)
Geometric parameters (Å, º) top
Ni—S12.3749 (16)C2—H2A0.9900
Ni—S42.4077 (15)C2—H2B0.9900
Ni—S72.3987 (17)C3—H3A0.9900
S1—C91.820 (5)C3—H3B0.9900
S1—C21.829 (5)C5—H5A0.9900
C2—C31.516 (6)C5—H5B0.9900
C3—S41.817 (4)C6—H6A0.9900
S4—C51.829 (5)C6—H6B0.9900
C5—C61.517 (6)C8—H8A0.9900
C6—S71.808 (4)C8—H8B0.9900
S7—C81.828 (4)C9—H9A0.9900
C8—C91.527 (6)C9—H9B0.9900
S1—Ni—S488.09 (5)S4—C3—H3A108.6
S1—Ni—S788.67 (6)C2—C3—H3B108.6
S4—Ni—S788.25 (6)S4—C3—H3B108.6
S1i—Ni—S491.91 (5)H3A—C3—H3B107.5
S1i—Ni—S791.33 (6)C6—C5—H5A109.3
S7i—Ni—S491.75 (6)S4—C5—H5A109.3
C9—S1—C2103.0 (2)C6—C5—H5B109.3
C9—S1—Ni99.67 (15)S4—C5—H5B109.3
C2—S1—Ni104.11 (15)H5A—C5—H5B108.0
C3—C2—S1111.9 (3)C5—C6—H6A108.4
C2—C3—S4114.8 (3)S7—C6—H6A108.4
C3—S4—C5102.6 (2)C5—C6—H6B108.4
C3—S4—Ni99.00 (15)S7—C6—H6B108.4
C5—S4—Ni103.04 (15)H6A—C6—H6B107.4
C6—C5—S4111.4 (3)C9—C8—H8A109.3
C5—C6—S7115.7 (3)S7—C8—H8A109.3
C6—S7—C8101.8 (2)C9—C8—H8B109.3
C6—S7—Ni99.32 (15)S7—C8—H8B109.3
C8—S7—Ni104.07 (16)H8A—C8—H8B108.0
C9—C8—S7111.6 (3)C8—C9—H9A108.1
C8—C9—S1116.7 (3)S1—C9—H9A108.1
C3—C2—H2A109.2C8—C9—H9B108.1
S1—C2—H2A109.2S1—C9—H9B108.1
C3—C2—H2B109.2H9A—C9—H9B107.3
S1—C2—H2B109.2H10A—O10—H10B105 (6)
H2A—C2—H2B107.9H11A—O11—H11B104 (5)
C2—C3—H3A108.6
S1—C2—C3—S453.8 (4)C6—S7—C8—C9130.4 (3)
C2—C3—S4—C558.5 (4)S7—C8—C9—S150.7 (4)
C3—S4—C5—C6134.4 (3)C2—S1—C9—C862.5 (4)
S4—C5—C6—S755.2 (4)C9—S1—C2—C3132.9 (3)
C5—C6—S7—C860.5 (4)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O10—H10A···Br0.85 (5)2.46 (5)3.295 (5)169 (5)
O10—H10B···Br0.84 (3)2.47 (3)3.303 (5)168 (5)
O11—H11A···Br0.85 (4)2.60 (4)3.425 (5)164 (4)
O11—H11B···O100.85 (5)1.92 (5)2.770 (7)176 (5)

Experimental details

Crystal data
Chemical formula[Ni(C6H12S3)2]Br2·4H2O
Mr651.27
Crystal system, space groupTriclinic, 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)
V3)577.4 (5)
Z1
Radiation typeMo Kα
µ (mm1)4.86
Crystal size (mm)0.23 × 0.12 × 0.08
Data collection
DiffractometerStoe Stadi-4 four-circle
diffractometer
Absorption correctionNumerical
(X-RED; Stoe & Cie, 1997)
Tmin, Tmax0.551, 0.725
No. of measured, independent and
observed [I > 2σ(I)] reflections
2771, 2252, 1985
Rint0.054
(sin θ/λ)max1)0.620
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.092, 1.09
No. of reflections2252
No. of parameters131
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds