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Acta Cryst. (2007). E63, m2376    [ doi:10.1107/S1600536807040238 ]

Bis{2,4-dibromo-6-[3-(cyclohexylammonio)propyliminomethyl]phenolato-[kappa]2N,O}bis(thiocyanato-[kappa]N)nickel(II) methanol disolvate

M. Liu, W.-B. Yuan, H.-W. Xu, Q. Zhang and J.-X. Li

Abstract top

The title centrosymmetric Schiff base nickel(II) complex, [Ni(NCS)2(C16H22Br2N2O)2]·2CH3OH, consists of a mononuclear complex molecule and two solvent methanol molecules. The NiII atom lies on an inversion centre and is six-coordinated by the imine N and phenolate O atoms of the two Schiff base ligands and by the N atoms of two thiocyanate ligands, in an octahedral coordination geometry. The cyclohexyl rings adopt chair conformations.

Comment top

Recently, we have reported the structures of a few Schiff base copper(II) and zinc(II) complexes (Yuan & Zhang, 2005; Yuan et al., 2007). As an extension of our investigations in this area we report herein the title new mononuclear Schiff base nickel(II) complex.

The complex consists of a mononuclear complex molecule and two lattice methanol molecules (Fig. 1). The NiII atom, lying on the inversion centre, is six-coordinated by two imine N and two phenolic O atoms from two Schiff base ligands and by two N atoms from two thiocyanate ligands, in octahedral coordination. The bond lengths and angles to the Ni(II) atom are comparable to the values in other similar complexes (Diao, 2007; Li et al., 2007; Li & Wang, 2007). The cyclohexyl rings adopt chair conformations.

Related literature top

For related structures, see: Diao (2007); Yuan & Zhang (2005); Yuan et al. (2007); Li et al. (2007); Li & Wang (2007).

Experimental top

3,5-Dibromo-2-hydroxybenzaldehyde (1.0 mmol, 280.0 mg), N-cyclohexylpropane-1,3-diamine (1.0 mmol, 156.2 mg), and nickel nitrate hexahydrate (0.5 mmol, 145.4 mg) were dissolved in a methanol solution (50 ml). The mixture was stirred at room temperature for 30 min and filtered. After keeping the filtrate in air for 12 days, green block-shaped crystals were formed.

Refinement top

All H-atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å, Uiso = 1.2Ueq (C) for aromatic 0.97 Å, Uiso = 1.2Ueq (C) for CH2, 0.96 Å, Uiso = 1.5Ueq (C) for CH3, 0.90 Å, Uiso = 1.2Ueq (N) for NH and 0.82 Å, Uiso = 1.5Ueq (O) for OH atoms.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I). Displacement ellipsoids are drawn at the 30% probability level. Labelled atoms are related to unlabelled atoms by the symmetry operation −x + 2, −y + 1, −z.
Bis{2,4-dibromo-6-[3-(cyclohexylammonio)propyliminomethyl]phenolato- κ2N,O}bis(thiocyanato-κN)nickel(II) methanol disolvate top
Crystal data top
[Ni(NCS)2(C16H22Br2N2O)2]·2CH4OZ = 1
Mr = 1075.31F000 = 542
Triclinic, P1Dx = 1.621 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 9.3410 (19) ÅCell parameters from 1932 reflections
b = 10.957 (2) Åθ = 2.3–24.9º
c = 12.210 (2) ŵ = 4.21 mm−1
α = 108.28 (3)ºT = 298 (2) K
β = 104.21 (3)ºBlock, green
γ = 100.80 (3)º0.27 × 0.23 × 0.22 mm
V = 1101.8 (4) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		4504 independent reflections
Radiation source: fine-focus sealed tube2992 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 298(2) Kθmax = 26.5º
ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→11
Tmin = 0.397, Tmax = 0.458k = −13→13
8978 measured reflectionsl = −15→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.107  w = 1/[σ2(Fo2) + (0.048P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
4504 reflectionsΔρmax = 0.60 e Å−3
243 parametersΔρmin = −0.32 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(NCS)2(C16H22Br2N2O)2]·2CH4Oγ = 100.80 (3)º
Mr = 1075.31V = 1101.8 (4) Å3
Triclinic, P1Z = 1
a = 9.3410 (19) ÅMo Kα
b = 10.957 (2) ŵ = 4.21 mm−1
c = 12.210 (2) ÅT = 298 (2) K
α = 108.28 (3)º0.27 × 0.23 × 0.22 mm
β = 104.21 (3)º
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		4504 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2992 reflections with I > 2σ(I)
Tmin = 0.397, Tmax = 0.458Rint = 0.033
8978 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045243 parameters
wR(F2) = 0.107H-atom parameters constrained
S = 1.01Δρmax = 0.60 e Å−3
4504 reflectionsΔρmin = −0.32 e Å−3
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
Ni11.00000.50000.00000.02932 (18)
Br11.51132 (5)0.62678 (5)0.30412 (4)0.05920 (18)
Br21.33026 (6)0.98998 (5)0.64540 (4)0.06664 (19)
S10.67133 (19)0.12546 (13)0.02759 (16)0.0838 (5)
O11.1701 (3)0.5367 (2)0.1599 (2)0.0343 (6)
O20.4154 (4)0.6690 (5)0.7706 (4)0.0961 (14)
H20.39100.71630.82560.144*
N10.8749 (3)0.5875 (3)0.1069 (3)0.0308 (7)
N20.7392 (4)0.6953 (3)−0.1414 (3)0.0370 (8)
H2A0.63830.6774−0.18150.044*
H2B0.75990.6164−0.15070.044*
N30.8862 (4)0.3162 (3)−0.0011 (3)0.0406 (8)
C11.0902 (5)0.6977 (4)0.2983 (3)0.0346 (9)
C21.2019 (4)0.6386 (4)0.2618 (3)0.0336 (9)
C31.3531 (5)0.6978 (4)0.3463 (4)0.0369 (10)
C41.3914 (5)0.8006 (4)0.4567 (3)0.0428 (11)
H41.49300.83590.50860.051*
C51.2775 (5)0.8511 (4)0.4899 (3)0.0402 (10)
C61.1291 (5)0.8001 (4)0.4125 (3)0.0391 (10)
H61.05270.83400.43620.047*
C70.9310 (5)0.6557 (4)0.2211 (4)0.0357 (9)
H70.86120.68170.25970.043*
C80.7085 (4)0.5674 (4)0.0512 (4)0.0361 (9)
H8A0.65240.53460.09830.043*
H8B0.67240.4997−0.03080.043*
C90.6743 (5)0.6966 (4)0.0459 (4)0.0430 (10)
H9A0.56640.6750−0.00070.052*
H9B0.68970.75630.12830.052*
C100.7701 (5)0.7713 (4)−0.0092 (4)0.0411 (10)
H10A0.74850.85670.00120.049*
H10B0.87840.78960.03440.049*
C110.8317 (5)0.7682 (4)−0.1982 (4)0.0402 (10)
H110.94030.7983−0.14720.048*
C120.7835 (9)0.8882 (6)−0.2053 (5)0.106 (3)
H12A0.79540.9484−0.12400.127*
H12B0.67550.8605−0.25400.127*
C130.8795 (9)0.9614 (5)−0.2620 (5)0.105 (3)
H13A0.84411.0377−0.26750.125*
H13B0.98640.9949−0.20990.125*
C140.8688 (6)0.8722 (5)−0.3856 (4)0.0546 (12)
H14A0.93680.9200−0.41680.066*
H14B0.76420.8467−0.44060.066*
C150.9127 (8)0.7495 (5)−0.3811 (5)0.0849 (19)
H15A1.02130.7746−0.33470.102*
H15B0.89730.6894−0.46330.102*
C160.8180 (7)0.6767 (5)−0.3229 (5)0.0758 (17)
H16A0.71060.6432−0.37400.091*
H16B0.85350.6005−0.31740.091*
C170.7955 (5)0.2382 (4)0.0099 (4)0.0410 (10)
C180.2958 (8)0.6214 (7)0.6636 (6)0.101 (2)
H18A0.26360.69500.64970.151*
H18B0.21120.56050.66830.151*
H18C0.32860.57530.59760.151*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0307 (4)0.0273 (4)0.0304 (4)0.0080 (3)0.0130 (3)0.0094 (3)
Br10.0371 (3)0.0546 (3)0.0626 (3)0.0149 (2)0.0096 (2)−0.0039 (2)
Br20.0754 (4)0.0546 (3)0.0433 (3)0.0061 (3)0.0193 (3)−0.0090 (2)
S10.0967 (11)0.0381 (8)0.1335 (14)0.0095 (7)0.0855 (11)0.0235 (8)
O10.0354 (15)0.0317 (15)0.0306 (15)0.0110 (12)0.0085 (12)0.0059 (12)
O20.073 (3)0.122 (4)0.073 (3)0.060 (3)0.012 (2)0.002 (3)
N10.0344 (18)0.0296 (18)0.0328 (18)0.0106 (14)0.0163 (15)0.0124 (15)
N20.042 (2)0.0313 (18)0.0363 (19)0.0127 (16)0.0131 (16)0.0095 (16)
N30.040 (2)0.033 (2)0.049 (2)0.0071 (17)0.0175 (17)0.0158 (17)
C10.043 (2)0.032 (2)0.031 (2)0.0103 (19)0.0155 (19)0.0130 (18)
C20.038 (2)0.030 (2)0.034 (2)0.0088 (18)0.0141 (18)0.0133 (19)
C30.034 (2)0.033 (2)0.044 (2)0.0106 (18)0.0155 (19)0.012 (2)
C40.041 (3)0.035 (2)0.035 (2)0.006 (2)0.003 (2)0.002 (2)
C50.053 (3)0.033 (2)0.028 (2)0.006 (2)0.014 (2)0.0052 (19)
C60.049 (3)0.040 (2)0.033 (2)0.016 (2)0.023 (2)0.0115 (19)
C70.039 (2)0.034 (2)0.040 (2)0.0135 (19)0.0224 (19)0.013 (2)
C80.034 (2)0.042 (2)0.036 (2)0.0140 (19)0.0178 (18)0.0133 (19)
C90.042 (2)0.050 (3)0.042 (2)0.023 (2)0.016 (2)0.016 (2)
C100.054 (3)0.032 (2)0.041 (2)0.016 (2)0.019 (2)0.014 (2)
C110.043 (2)0.037 (2)0.037 (2)0.009 (2)0.010 (2)0.013 (2)
C120.228 (8)0.070 (4)0.096 (5)0.090 (5)0.119 (5)0.054 (4)
C130.216 (8)0.050 (3)0.082 (4)0.043 (4)0.086 (5)0.039 (3)
C140.061 (3)0.062 (3)0.052 (3)0.019 (3)0.025 (2)0.030 (3)
C150.131 (6)0.064 (4)0.101 (5)0.040 (4)0.081 (4)0.045 (4)
C160.126 (5)0.047 (3)0.085 (4)0.033 (3)0.076 (4)0.028 (3)
C170.042 (3)0.035 (2)0.048 (3)0.016 (2)0.021 (2)0.011 (2)
C180.105 (5)0.101 (5)0.097 (5)0.054 (4)0.020 (4)0.034 (4)
Geometric parameters (Å, °) top
Ni1—O12.060 (3)C8—C91.525 (6)
Ni1—O1i2.060 (3)C8—H8A0.9700
Ni1—N3i2.088 (4)C8—H8B0.9700
Ni1—N32.088 (4)C9—C101.513 (6)
Ni1—N12.090 (3)C9—H9A0.9700
Ni1—N1i2.090 (3)C9—H9B0.9700
Br1—C31.900 (4)C10—H10A0.9700
Br2—C51.900 (4)C10—H10B0.9700
S1—C171.635 (5)C11—C121.488 (6)
O1—C21.306 (4)C11—C161.496 (6)
O2—C181.365 (6)C11—H110.9800
O2—H20.8200C12—C131.520 (8)
N1—C71.272 (5)C12—H12A0.9700
N1—C81.479 (5)C12—H12B0.9700
N2—C101.490 (5)C13—C141.486 (6)
N2—C111.500 (5)C13—H13A0.9700
N2—H2A0.9000C13—H13B0.9700
N2—H2B0.9000C14—C151.490 (7)
N3—C171.150 (5)C14—H14A0.9700
C1—C61.398 (5)C14—H14B0.9700
C1—C21.416 (5)C15—C161.525 (7)
C1—C71.447 (5)C15—H15A0.9700
C2—C31.415 (5)C15—H15B0.9700
C3—C41.369 (5)C16—H16A0.9700
C4—C51.376 (5)C16—H16B0.9700
C4—H40.9300C18—H18A0.9600
C5—C61.364 (6)C18—H18B0.9600
C6—H60.9300C18—H18C0.9600
C7—H70.9300
O1—Ni1—O1i180.00 (14)C10—C9—H9A108.3
O1—Ni1—N3i88.72 (12)C8—C9—H9A108.3
O1i—Ni1—N3i91.28 (12)C10—C9—H9B108.3
O1—Ni1—N391.28 (12)C8—C9—H9B108.3
O1i—Ni1—N388.72 (12)H9A—C9—H9B107.4
N3i—Ni1—N3180.00 (18)N2—C10—C9112.9 (3)
O1—Ni1—N187.62 (11)N2—C10—H10A109.0
O1i—Ni1—N192.38 (11)C9—C10—H10A109.0
N3i—Ni1—N192.76 (13)N2—C10—H10B109.0
N3—Ni1—N187.24 (13)C9—C10—H10B109.0
O1—Ni1—N1i92.38 (11)H10A—C10—H10B107.8
O1i—Ni1—N1i87.62 (11)C12—C11—C16109.7 (4)
N3i—Ni1—N1i87.24 (13)C12—C11—N2111.7 (4)
N3—Ni1—N1i92.76 (13)C16—C11—N2110.6 (3)
N1—Ni1—N1i180.00 (15)C12—C11—H11108.2
C2—O1—Ni1124.6 (2)C16—C11—H11108.2
C18—O2—H2109.5N2—C11—H11108.2
C7—N1—C8115.6 (3)C11—C12—C13110.9 (5)
C7—N1—Ni1124.4 (3)C11—C12—H12A109.5
C8—N1—Ni1120.0 (2)C13—C12—H12A109.5
C10—N2—C11113.7 (3)C11—C12—H12B109.5
C10—N2—H2A108.8C13—C12—H12B109.5
C11—N2—H2A108.8H12A—C12—H12B108.0
C10—N2—H2B108.8C14—C13—C12111.7 (5)
C11—N2—H2B108.8C14—C13—H13A109.3
H2A—N2—H2B107.7C12—C13—H13A109.3
C17—N3—Ni1159.1 (3)C14—C13—H13B109.3
C6—C1—C2121.1 (4)C12—C13—H13B109.3
C6—C1—C7116.5 (4)H13A—C13—H13B107.9
C2—C1—C7122.5 (4)C13—C14—C15110.4 (4)
O1—C2—C3121.8 (4)C13—C14—H14A109.6
O1—C2—C1123.8 (4)C15—C14—H14A109.6
C3—C2—C1114.4 (3)C13—C14—H14B109.6
C4—C3—C2124.2 (4)C15—C14—H14B109.6
C4—C3—Br1118.4 (3)H14A—C14—H14B108.1
C2—C3—Br1117.4 (3)C14—C15—C16111.7 (4)
C3—C4—C5119.1 (4)C14—C15—H15A109.3
C3—C4—H4120.5C16—C15—H15A109.3
C5—C4—H4120.5C14—C15—H15B109.3
C6—C5—C4120.1 (4)C16—C15—H15B109.3
C6—C5—Br2121.1 (3)H15A—C15—H15B107.9
C4—C5—Br2118.9 (3)C11—C16—C15111.1 (4)
C5—C6—C1121.1 (4)C11—C16—H16A109.4
C5—C6—H6119.5C15—C16—H16A109.4
C1—C6—H6119.5C11—C16—H16B109.4
N1—C7—C1127.9 (4)C15—C16—H16B109.4
N1—C7—H7116.1H16A—C16—H16B108.0
C1—C7—H7116.1N3—C17—S1178.0 (4)
N1—C8—C9112.1 (3)O2—C18—H18A109.5
N1—C8—H8A109.2O2—C18—H18B109.5
C9—C8—H8A109.2H18A—C18—H18B109.5
N1—C8—H8B109.2O2—C18—H18C109.5
C9—C8—H8B109.2H18A—C18—H18C109.5
H8A—C8—H8B107.9H18B—C18—H18C109.5
C10—C9—C8115.8 (3)
Symmetry codes: (i) −x+2, −y+1, −z.
Acknowledgements top

The authors thank the National Natural Science Foundation of Hainan Province (grant No. 20602) and the Open Fund (grant No. hnfc2006005) of Hainan Provincial Key Laboratory of Fine Chemicals for financial support.

references
References top

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