supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, m1113    [ doi:10.1107/S1600536809032425 ]

Bis(2-cyclohexyliminomethyl-4,6-disulfanylphenolato)nickel(II) acetonitrile solvate

Q. Wang, J. Hou, P. Huang and Q.-F. Zeng

Abstract top

In the title compound, [Ni(C13H16NOS2)2]·CH3CN, the NiII atom is four-coordinated by two N,O-bidentate Schiff base ligands, resulting in a distorted tetrahedral coordination for the metal ion.

Comment top

There has been much research interest in Schiff base metal complexes due to their molecular architectures and biological activities (Shi et al., 2008; Xu et al., 2009). In this work, we report here the crystal structure of the title compound, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). The NiII is four-coordinated in a distort tetrahedral configuration by two N atoms and two O atoms of the Schiff base ligands.

Related literature top

For background, see: Shi et al. (2008); Xu et al. (2009). For reference structural data, see: Allen et al. (1987).

Experimental top

A mixture of 2-hydroxy-3,5-dimercaptobenzaldehyde (372 mg, 2 mmol), cyclohexanamine (198 mg, 2 mmol) and NiCl2.6H2O (1 mmol, 236 mg) in acetonitrile (10 ml) was stirred for 1 h. After keeping the filtrate in air for 9 d, green blocks of (I) were formed.

Refinement top

The H atoms were positioned geometrically (C—H = 0.93–0.97Å, S—H = 1.20Å) and refined as riding, with Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl C).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids.
Bis(2-cyclohexyliminomethyl-4,6-disulfanylphenolato)nickel(II) acetonitrile solvate top
Crystal data top
[Ni(C13H16NOS2)2]·C2H3NF(000) = 1328
Mr = 632.54Dx = 1.376 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 9.483 (2) Åθ = 9–12°
b = 15.879 (4) ŵ = 0.94 mm−1
c = 20.335 (4) ÅT = 296 K
β = 94.10 (1)°Block, green
V = 3054.2 (12) Å30.35 × 0.27 × 0.22 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		5366 independent reflections
Radiation source: fine-focus sealed tube3750 reflections with I > 2σ(I)
graphiteRint = 0.027
ω/2θ scansθmax = 25.0°, θmin = 1.6°
Absorption correction: ψ scan
(North et al., 1968)		h = −11→11
Tmin = 0.735, Tmax = 0.820k = −13→18
15868 measured reflectionsl = −24→22
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.166H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.099P)2 + 1.0949P]
where P = (Fo2 + 2Fc2)/3
5366 reflections(Δ/σ)max = 0.001
348 parametersΔρmax = 0.47 e Å−3
0 restraintsΔρmin = −0.60 e Å−3
Crystal data top
[Ni(C13H16NOS2)2]·C2H3NV = 3054.2 (12) Å3
Mr = 632.54Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.483 (2) ŵ = 0.94 mm−1
b = 15.879 (4) ÅT = 296 K
c = 20.335 (4) Å0.35 × 0.27 × 0.22 mm
β = 94.10 (1)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		3750 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.027
Tmin = 0.735, Tmax = 0.820θmax = 25.0°
15868 measured reflectionsStandard reflections: 0
5366 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.166Δρmax = 0.47 e Å−3
S = 1.02Δρmin = −0.60 e Å−3
5366 reflectionsAbsolute structure: ?
348 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Ni10.71327 (5)0.75018 (3)0.18476 (2)0.05582 (19)
S20.26353 (13)0.63623 (8)0.12076 (7)0.0863 (4)
H20.33440.62060.17050.129*
S31.23712 (14)0.60737 (8)0.43291 (7)0.0908 (4)
H31.32750.58510.39840.136*
S40.79783 (18)0.81852 (8)0.40833 (6)0.0977 (5)
H40.67620.79700.40380.147*
S10.13179 (17)0.90908 (12)−0.02558 (9)0.1251 (6)
H10.16600.9015−0.08100.188*
O10.5238 (3)0.72316 (17)0.15565 (13)0.0613 (6)
N10.8485 (3)0.65868 (19)0.16717 (14)0.0536 (7)
N20.7138 (3)0.86444 (18)0.14541 (15)0.0557 (7)
O20.7561 (3)0.75360 (16)0.27700 (13)0.0637 (7)
C60.4421 (4)0.7675 (2)0.11519 (18)0.0536 (9)
C70.8643 (4)0.7192 (2)0.30842 (18)0.0545 (9)
C80.6061 (4)0.8918 (2)0.10958 (19)0.0629 (10)
H80.61320.94630.09350.076*
C90.9529 (4)0.6585 (2)0.28132 (17)0.0525 (8)
C100.4764 (4)0.8483 (2)0.09145 (18)0.0563 (9)
C110.9349 (4)0.6301 (2)0.21331 (18)0.0533 (8)
H110.99280.58600.20190.064*
C121.0666 (4)0.6232 (2)0.32019 (19)0.0605 (9)
H121.12330.58270.30220.073*
C130.8493 (4)0.6203 (2)0.10085 (18)0.0606 (9)
H130.94170.59410.09630.073*
C140.3781 (4)0.8914 (3)0.0477 (2)0.0724 (11)
H140.40040.94440.03200.087*
C150.2163 (4)0.7773 (3)0.0500 (2)0.0734 (12)
H150.12990.75340.03590.088*
C160.2523 (5)0.8559 (3)0.0285 (2)0.0796 (13)
C170.8334 (4)0.9231 (3)0.1596 (2)0.0653 (10)
H170.83400.96420.12370.078*
C180.3084 (4)0.7349 (3)0.0923 (2)0.0626 (10)
C191.0113 (5)0.7079 (3)0.4122 (2)0.0705 (11)
H191.03050.72470.45580.085*
C201.0944 (4)0.6480 (2)0.3841 (2)0.0651 (10)
C210.8255 (5)0.6871 (3)0.04867 (19)0.0704 (11)
H21A0.89940.72920.05440.084*
H21B0.73570.71470.05380.084*
C220.9003 (5)0.7419 (2)0.3745 (2)0.0652 (11)
C230.7365 (6)0.5537 (3)0.0916 (2)0.0792 (13)
H23A0.64510.57840.09830.095*
H23B0.75440.50960.12410.095*
C240.7174 (7)0.5820 (3)−0.0312 (2)0.0996 (17)
H24A0.72720.5560−0.07380.119*
H24B0.62360.6063−0.03160.119*
C250.8253 (6)0.6502 (3)−0.0205 (2)0.0934 (16)
H25A0.80560.6945−0.05260.112*
H25B0.91820.6276−0.02720.112*
C270.8141 (5)0.9695 (3)0.2230 (3)0.0917 (16)
H27A0.80950.92940.25880.110*
H27B0.72581.00050.21910.110*
C280.9709 (4)0.8773 (3)0.1640 (3)0.0867 (15)
H28A0.98350.84940.12240.104*
H28B0.96990.83440.19800.104*
C260.7338 (7)0.5155 (3)0.0220 (2)0.1025 (17)
H26A0.82090.48470.01750.123*
H26B0.65600.47590.01630.123*
C291.0753 (5)0.9852 (4)0.2428 (3)0.1024 (17)
H29A1.07890.94630.27960.123*
H29B1.15161.02540.25050.123*
C300.9370 (6)1.0306 (4)0.2386 (3)0.118 (2)
H30A0.93701.07320.20440.141*
H30B0.92461.05870.28010.141*
C311.0947 (5)0.9375 (4)0.1802 (3)0.113 (2)
H31A1.18210.90570.18490.135*
H31B1.10150.97700.14410.135*
C320.4297 (7)0.8572 (5)0.2992 (4)0.118 (2)
C330.4114 (8)0.7686 (4)0.3059 (4)0.136 (3)
H33A0.41860.75380.35180.204*
H33B0.48320.73960.28380.204*
H33C0.31990.75270.28660.204*
N30.4466 (8)0.9245 (5)0.2955 (5)0.202 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0539 (3)0.0583 (3)0.0548 (3)0.0049 (2)0.0010 (2)0.0045 (2)
S20.0703 (7)0.0812 (8)0.1054 (10)−0.0226 (6)−0.0069 (6)0.0092 (7)
S30.0947 (9)0.0854 (8)0.0856 (8)0.0120 (7)−0.0396 (7)0.0045 (6)
S40.1485 (13)0.0862 (8)0.0582 (7)0.0428 (8)0.0060 (7)−0.0134 (6)
S10.0975 (10)0.1409 (14)0.1285 (13)0.0185 (9)−0.0514 (9)0.0419 (11)
O10.0512 (14)0.0626 (15)0.0692 (17)0.0009 (12)−0.0019 (12)0.0147 (13)
N10.0524 (17)0.0566 (17)0.0514 (17)0.0010 (13)0.0013 (14)−0.0010 (13)
N20.0549 (18)0.0538 (17)0.0583 (18)−0.0018 (14)0.0027 (14)0.0042 (14)
O20.0707 (17)0.0704 (17)0.0496 (15)0.0234 (13)0.0009 (13)0.0020 (11)
C60.0460 (19)0.064 (2)0.051 (2)0.0031 (16)0.0047 (16)0.0011 (16)
C70.065 (2)0.0505 (19)0.048 (2)−0.0004 (18)0.0033 (17)0.0033 (16)
C80.071 (3)0.056 (2)0.061 (2)0.0054 (19)0.0038 (19)0.0138 (18)
C90.057 (2)0.0480 (19)0.052 (2)−0.0005 (16)0.0026 (16)0.0027 (15)
C100.053 (2)0.059 (2)0.057 (2)0.0036 (17)−0.0011 (16)0.0051 (17)
C110.050 (2)0.051 (2)0.058 (2)0.0045 (16)0.0020 (16)−0.0027 (16)
C120.059 (2)0.057 (2)0.063 (2)0.0004 (18)−0.0066 (18)0.0019 (18)
C130.066 (2)0.063 (2)0.052 (2)0.0069 (19)0.0013 (17)−0.0074 (17)
C140.069 (3)0.075 (3)0.071 (3)0.009 (2)−0.009 (2)0.016 (2)
C150.050 (2)0.100 (3)0.069 (3)0.005 (2)−0.0070 (19)−0.001 (2)
C160.069 (3)0.094 (3)0.073 (3)0.022 (2)−0.014 (2)0.009 (2)
C170.065 (2)0.061 (2)0.070 (3)−0.0159 (19)0.0038 (19)0.0089 (19)
C180.054 (2)0.074 (3)0.059 (2)0.0018 (18)0.0033 (18)−0.0036 (18)
C190.098 (3)0.057 (2)0.053 (2)−0.004 (2)−0.015 (2)0.0020 (19)
C200.069 (2)0.057 (2)0.067 (3)−0.0027 (19)−0.0175 (19)0.0079 (19)
C210.088 (3)0.067 (3)0.057 (2)−0.013 (2)0.011 (2)−0.0008 (19)
C220.092 (3)0.053 (2)0.050 (2)0.006 (2)0.002 (2)−0.0014 (16)
C230.116 (4)0.060 (2)0.059 (2)−0.018 (2)−0.005 (2)0.0038 (19)
C240.155 (5)0.075 (3)0.064 (3)−0.009 (3)−0.027 (3)−0.005 (2)
C250.142 (5)0.083 (3)0.057 (3)−0.002 (3)0.019 (3)0.004 (2)
C270.068 (3)0.077 (3)0.131 (4)−0.008 (2)0.017 (3)−0.041 (3)
C280.060 (3)0.097 (3)0.105 (4)−0.015 (2)0.021 (2)−0.041 (3)
C260.168 (5)0.062 (3)0.074 (3)−0.014 (3)−0.015 (3)−0.010 (2)
C290.078 (3)0.119 (4)0.110 (4)−0.035 (3)0.008 (3)−0.037 (3)
C300.101 (4)0.096 (4)0.158 (6)−0.029 (3)0.028 (4)−0.062 (4)
C310.065 (3)0.130 (5)0.148 (5)−0.036 (3)0.031 (3)−0.061 (4)
C320.093 (4)0.105 (5)0.159 (6)−0.015 (4)0.020 (4)0.009 (4)
C330.178 (7)0.111 (5)0.130 (6)−0.026 (4)0.081 (5)−0.016 (4)
N30.146 (6)0.105 (5)0.350 (13)−0.024 (4)−0.011 (6)0.050 (6)
Geometric parameters (Å, °) top
Ni1—O21.891 (3)C17—C271.507 (6)
Ni1—O11.900 (3)C17—H170.9800
Ni1—N21.983 (3)C19—C221.368 (6)
Ni1—N11.987 (3)C19—C201.386 (6)
S2—C181.734 (4)C19—H190.9300
S2—H21.2000C21—C251.523 (6)
S3—C201.744 (4)C21—H21A0.9700
S3—H31.2000C21—H21B0.9700
S4—C221.731 (4)C23—C261.537 (6)
S4—H41.2000C23—H23A0.9700
S1—C161.746 (4)C23—H23B0.9700
S1—H11.2000C24—C251.495 (7)
O1—C61.297 (4)C24—C261.513 (7)
N1—C111.283 (4)C24—H24A0.9700
N1—C131.481 (5)C24—H24B0.9700
N2—C81.287 (5)C25—H25A0.9700
N2—C171.480 (5)C25—H25B0.9700
O2—C71.291 (4)C27—C301.532 (6)
C6—C101.417 (5)C27—H27A0.9700
C6—C181.417 (5)C27—H27B0.9700
C7—C221.409 (5)C28—C311.531 (6)
C7—C91.415 (5)C28—H28A0.9700
C8—C101.436 (5)C28—H28B0.9700
C8—H80.9300C26—H26A0.9700
C9—C121.407 (5)C26—H26B0.9700
C9—C111.453 (5)C29—C301.493 (8)
C10—C141.418 (5)C29—C311.504 (7)
C11—H110.9300C29—H29A0.9700
C12—C201.365 (5)C29—H29B0.9700
C12—H120.9300C30—H30A0.9700
C13—C231.505 (6)C30—H30B0.9700
C13—C211.506 (6)C31—H31A0.9700
C13—H130.9800C31—H31B0.9700
C14—C161.351 (6)C32—N31.085 (8)
C14—H140.9300C32—C331.424 (9)
C15—C181.358 (6)C33—H33A0.9600
C15—C161.374 (7)C33—H33B0.9600
C15—H150.9300C33—H33C0.9600
C17—C281.490 (6)
O2—Ni1—O1116.53 (12)C13—C21—H21A109.3
O2—Ni1—N2111.55 (12)C25—C21—H21A109.3
O1—Ni1—N296.35 (12)C13—C21—H21B109.3
O2—Ni1—N195.97 (11)C25—C21—H21B109.3
O1—Ni1—N1112.76 (12)H21A—C21—H21B107.9
N2—Ni1—N1125.16 (12)C19—C22—C7124.0 (4)
C18—S2—H2109.5C19—C22—S4119.0 (3)
C20—S3—H3109.5C7—C22—S4117.0 (3)
C22—S4—H4109.5C13—C23—C26110.9 (4)
C16—S1—H1109.5C13—C23—H23A109.4
C6—O1—Ni1125.7 (2)C26—C23—H23A109.4
C11—N1—C13118.4 (3)C13—C23—H23B109.4
C11—N1—Ni1120.9 (2)C26—C23—H23B109.4
C13—N1—Ni1120.7 (2)H23A—C23—H23B108.0
C8—N2—C17117.7 (3)C25—C24—C26111.5 (4)
C8—N2—Ni1120.8 (3)C25—C24—H24A109.3
C17—N2—Ni1121.4 (2)C26—C24—H24A109.3
C7—O2—Ni1125.8 (2)C25—C24—H24B109.3
O1—C6—C10124.5 (3)C26—C24—H24B109.3
O1—C6—C18119.4 (3)H24A—C24—H24B108.0
C10—C6—C18116.1 (3)C24—C25—C21111.6 (4)
O2—C7—C22119.6 (3)C24—C25—H25A109.3
O2—C7—C9124.7 (3)C21—C25—H25A109.3
C22—C7—C9115.8 (3)C24—C25—H25B109.3
N2—C8—C10127.9 (3)C21—C25—H25B109.3
N2—C8—H8116.1H25A—C25—H25B108.0
C10—C8—H8116.1C17—C27—C30110.4 (4)
C12—C9—C7120.3 (3)C17—C27—H27A109.6
C12—C9—C11116.4 (3)C30—C27—H27A109.6
C7—C9—C11123.3 (3)C17—C27—H27B109.6
C6—C10—C14119.6 (3)C30—C27—H27B109.6
C6—C10—C8124.2 (3)H27A—C27—H27B108.1
C14—C10—C8116.2 (4)C17—C28—C31111.2 (4)
N1—C11—C9127.7 (3)C17—C28—H28A109.4
N1—C11—H11116.1C31—C28—H28A109.4
C9—C11—H11116.1C17—C28—H28B109.4
C20—C12—C9120.6 (4)C31—C28—H28B109.4
C20—C12—H12119.7H28A—C28—H28B108.0
C9—C12—H12119.7C24—C26—C23112.1 (4)
N1—C13—C23110.7 (3)C24—C26—H26A109.2
N1—C13—C21109.9 (3)C23—C26—H26A109.2
C23—C13—C21109.7 (3)C24—C26—H26B109.2
N1—C13—H13108.8C23—C26—H26B109.2
C23—C13—H13108.8H26A—C26—H26B107.9
C21—C13—H13108.8C30—C29—C31110.8 (5)
C16—C14—C10120.5 (4)C30—C29—H29A109.5
C16—C14—H14119.8C31—C29—H29A109.5
C10—C14—H14119.8C30—C29—H29B109.5
C18—C15—C16119.2 (4)C31—C29—H29B109.5
C18—C15—H15120.4H29A—C29—H29B108.1
C16—C15—H15120.4C29—C30—C27111.0 (4)
C14—C16—C15121.4 (4)C29—C30—H30A109.4
C14—C16—S1120.3 (4)C27—C30—H30A109.4
C15—C16—S1118.3 (4)C29—C30—H30B109.4
N2—C17—C28111.1 (3)C27—C30—H30B109.4
N2—C17—C27109.7 (3)H30A—C30—H30B108.0
C28—C17—C27110.3 (4)C29—C31—C28111.0 (4)
N2—C17—H17108.6C29—C31—H31A109.4
C28—C17—H17108.6C28—C31—H31A109.4
C27—C17—H17108.6C29—C31—H31B109.4
C15—C18—C6123.2 (4)C28—C31—H31B109.4
C15—C18—S2119.8 (3)H31A—C31—H31B108.0
C6—C18—S2117.1 (3)N3—C32—C33178.0 (10)
C22—C19—C20118.4 (4)C32—C33—H33A109.5
C22—C19—H19120.8C32—C33—H33B109.5
C20—C19—H19120.8H33A—C33—H33B109.5
C12—C20—C19120.9 (4)C32—C33—H33C109.5
C12—C20—S3121.7 (3)H33A—C33—H33C109.5
C19—C20—S3117.4 (3)H33B—C33—H33C109.5
C13—C21—C25111.7 (4)
Table 1
Selected geometric parameters (Å, °) top
Ni1—O21.891 (3)Ni1—N21.983 (3)
Ni1—O11.900 (3)Ni1—N11.987 (3)
O1—Ni1—N296.35 (12)O2—Ni1—N195.97 (11)
references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.

Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Shi, L., Fang, R.-Q., Xue, J.-Y., Xiao, Z.-P., Tan, S.-H. & Zhu, H.-L. (2008). Aust. J. Chem. 61, 288-296

Xu, S.-P., Shi, L., Lv, P.-C., Fang, R.-Q. & Zhu, H.-L. (2009). J. Coord. Chem. 62, 2048-2057.