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Acta Cryst. (2009). E65, m1146    [ doi:10.1107/S1600536809033650 ]

Bis{2-[2-(dimethylamino)ethyliminomethyl]-4,6-disulfanylphenolato}cobalt(II) monohydrate

Y.-J. Cai, J. Li, P. Huang and Q.-F. Zeng

Abstract top

In the title hydrated complex, [Co(C11H15N2OS2)2]·H2O, the CoII atom (site symmetry 2) is coordinated by two O,N,N'-tridentate Schiff base ligands, resulting in a very distorted cis-CoO2N4 octahedral geometry for the metal ion. In the crystal, the water molecule (O-atom site symmetry 2) interacts with nearby complex molecules by way of bifurcated O-H...(O,S) hydrogen bonds.

Comment top

As part of our onging studies of this family of compounds (Li et al., 2009), 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 Co(II) is six-coordinated in a distorted octhaedral coordination by two N,N,O-tridentate Schiff base ligands.

Related literature top

For a related compound and background, see: Li 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), N,N-dimethylethane-1,2-diamine (176 mg, 2 mmol) and CoCl2.6H2O (1 mmol, 238 mg) in methanol (10 ml) was stirred for 1 h. After keeping the filtrate in air for 7 d, red blocks of (I) were formed.

Refinement top

The water H atom was located in a difference map and its position was freely refined. All other H atoms were positioned geometrically (C—H = 0.93–0.97Å, S—H = 1.2Å) 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. Atoms with the suffix A are generated by the symmetry operation (1–x, y, 3/2–z).
Bis{2-[2-(dimethylamino)ethyliminomethyl]-4,6-disulfanylphenolato}cobalt(II) monohydrate top
Crystal data top
[Co(C11H15N2OS2)2]·H2OF(000) = 1228
Mr = 587.69Dx = 1.494 Mg m−3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 25 reflections
a = 12.3755 (15) Åθ = 9–12°
b = 9.2485 (15) ŵ = 1.01 mm−1
c = 22.827 (3) ÅT = 296 K
V = 2612.7 (6) Å3Block, red
Z = 40.30 × 0.25 × 0.25 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		2039 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
graphiteθmax = 26.0°, θmin = 2.4°
ω/2θ scansh = −15→15
Absorption correction: ψ scan
(North et al., 1968)		k = −11→6
Tmin = 0.752, Tmax = 0.787l = −28→27
13847 measured reflections200 standard reflections every 3 reflections
2548 independent reflections intensity decay: 1%
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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.186H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.1201P)2 + 2.1692P]
where P = (Fo2 + 2Fc2)/3
2548 reflections(Δ/σ)max = 0.001
160 parametersΔρmax = 0.84 e Å−3
1 restraintΔρmin = −0.96 e Å−3
Crystal data top
[Co(C11H15N2OS2)2]·H2OV = 2612.7 (6) Å3
Mr = 587.69Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 12.3755 (15) ŵ = 1.01 mm−1
b = 9.2485 (15) ÅT = 296 K
c = 22.827 (3) Å0.30 × 0.25 × 0.25 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		2039 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.031
Tmin = 0.752, Tmax = 0.787θmax = 26.0°
13847 measured reflections200 standard reflections every 3 reflections
2548 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.186Δρmax = 0.84 e Å−3
S = 1.06Δρmin = −0.96 e Å−3
2548 reflectionsAbsolute structure: ?
160 parametersFlack parameter: ?
1 restraintRogers 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
C30.2776 (3)0.1848 (3)0.68222 (16)0.0417 (8)
H30.20820.22070.67680.050*
C40.4167 (3)0.0107 (3)0.64302 (14)0.0380 (7)
C50.3168 (3)0.0854 (4)0.63802 (14)0.0395 (7)
C60.4439 (3)−0.0791 (4)0.59437 (15)0.0467 (9)
C70.2502 (3)0.0634 (4)0.58895 (17)0.0524 (10)
H70.18460.11200.58660.063*
C80.2678 (3)0.3286 (4)0.76616 (19)0.0507 (9)
H8A0.22450.27390.79380.061*
H8B0.21950.38810.74290.061*
C90.3788 (4)−0.0974 (4)0.54666 (16)0.0588 (11)
H90.4004−0.15600.51570.071*
C100.2796 (4)−0.0272 (5)0.54503 (18)0.0623 (12)
C110.3458 (3)0.4236 (4)0.79892 (18)0.0514 (9)
H11A0.37910.49090.77180.062*
H11B0.30660.47950.82790.062*
C140.5090 (4)0.4381 (5)0.8533 (2)0.0673 (13)
H14A0.53390.50320.82340.101*
H14B0.56920.38470.86860.101*
H14C0.47570.49220.88420.101*
C150.3836 (4)0.2501 (5)0.87496 (19)0.0651 (12)
H15A0.33750.30910.89890.098*
H15B0.44020.21000.89870.098*
H15C0.34210.17320.85790.098*
Co10.50000.18183 (7)0.75000.0390 (3)
H2A0.502 (3)0.789 (4)0.7815 (11)0.059 (14)*
N10.4310 (2)0.3386 (3)0.82838 (13)0.0431 (7)
N20.3272 (2)0.2283 (3)0.72746 (13)0.0401 (6)
O10.48006 (19)0.0189 (3)0.68755 (11)0.0412 (6)
O20.50000.7436 (5)0.75000.0605 (11)*
S10.19385 (15)−0.05824 (19)0.48627 (6)0.0990 (6)
H10.11070.00610.49370.148*
S20.56823 (10)−0.16647 (13)0.59645 (5)0.0678 (4)
H20.5567−0.28600.61590.102*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C30.0367 (18)0.0393 (18)0.049 (2)−0.0001 (13)−0.0046 (14)0.0043 (14)
C40.0496 (19)0.0308 (15)0.0336 (16)−0.0073 (14)−0.0017 (14)0.0007 (12)
C50.0439 (18)0.0357 (16)0.0391 (17)−0.0069 (14)−0.0053 (14)0.0024 (13)
C60.062 (2)0.0407 (18)0.0372 (17)−0.0006 (16)0.0042 (16)−0.0029 (14)
C70.055 (2)0.054 (2)0.048 (2)−0.0105 (18)−0.0152 (17)0.0112 (16)
C80.042 (2)0.055 (2)0.056 (2)0.0115 (16)0.0015 (17)−0.0060 (17)
C90.086 (3)0.053 (2)0.0371 (19)−0.012 (2)−0.0050 (19)−0.0067 (16)
C100.085 (3)0.061 (2)0.041 (2)−0.021 (2)−0.022 (2)0.0033 (18)
C110.057 (2)0.0418 (19)0.055 (2)0.0080 (17)0.0037 (18)−0.0054 (16)
C140.056 (3)0.068 (3)0.078 (3)−0.004 (2)0.003 (2)−0.028 (2)
C150.076 (3)0.066 (3)0.054 (2)0.011 (2)0.018 (2)0.004 (2)
Co10.0383 (4)0.0381 (4)0.0406 (4)0.000−0.0028 (2)0.000
N10.0433 (16)0.0398 (15)0.0462 (16)0.0012 (12)0.0001 (13)−0.0065 (12)
N20.0376 (15)0.0375 (14)0.0452 (16)0.0029 (11)−0.0013 (12)−0.0018 (13)
O10.0498 (13)0.0367 (12)0.0372 (12)0.0030 (10)−0.0080 (10)−0.0059 (10)
S10.1182 (13)0.1170 (13)0.0616 (8)−0.0154 (9)−0.0498 (8)−0.0119 (7)
S20.0758 (8)0.0646 (7)0.0629 (7)0.0195 (6)0.0044 (5)−0.0196 (5)
Geometric parameters (Å, °) top
C3—N21.267 (5)C11—H11A0.9700
C3—C51.449 (5)C11—H11B0.9700
C3—H30.9300C14—N11.449 (5)
C4—O11.286 (4)C14—H14A0.9600
C4—C51.421 (5)C14—H14B0.9600
C4—C61.427 (5)C14—H14C0.9600
C5—C71.406 (5)C15—N11.464 (5)
C6—C91.366 (5)C15—H15A0.9600
C6—S21.738 (4)C15—H15B0.9600
C7—C101.356 (6)C15—H15C0.9600
C7—H70.9300Co1—O12.089 (2)
C8—N21.477 (5)Co1—O1i2.089 (2)
C8—C111.505 (6)Co1—N2i2.241 (3)
C8—H8A0.9700Co1—N22.241 (3)
C8—H8B0.9700Co1—N12.456 (3)
C9—C101.389 (7)Co1—N1i2.456 (3)
C9—H90.9300O2—H2A0.832 (10)
C10—S11.735 (4)S1—H11.2000
C11—N11.478 (5)S2—H21.2000
N2—C3—C5127.4 (3)H11A—C11—H11B107.9
N2—C3—H3116.3N1—C14—H14A109.5
C5—C3—H3116.3N1—C14—H14B109.5
O1—C4—C5124.4 (3)H14A—C14—H14B109.5
O1—C4—C6120.4 (3)N1—C14—H14C109.5
C5—C4—C6115.2 (3)H14A—C14—H14C109.5
C7—C5—C4120.2 (3)H14B—C14—H14C109.5
C7—C5—C3116.8 (3)N1—C15—H15A109.5
C4—C5—C3123.0 (3)N1—C15—H15B109.5
C9—C6—C4123.6 (4)H15A—C15—H15B109.5
C9—C6—S2119.1 (3)N1—C15—H15C109.5
C4—C6—S2117.3 (3)H15A—C15—H15C109.5
C10—C7—C5121.4 (4)H15B—C15—H15C109.5
C10—C7—H7119.3O1—Co1—O1i87.65 (14)
C5—C7—H7119.3O1—Co1—N2i114.06 (10)
N2—C8—C11110.2 (3)O1i—Co1—N2i82.47 (10)
N2—C8—H8A109.6O1—Co1—N282.48 (10)
C11—C8—H8A109.6O1i—Co1—N2114.06 (10)
N2—C8—H8B109.6N2i—Co1—N2157.88 (15)
C11—C8—H8B109.6N1—Co1—O1151.87 (12)
H8A—C8—H8B108.1N1—Co1—N273.88 (12)
C6—C9—C10119.0 (4)N1—Co1—N1i107.64 (12)
C6—C9—H9120.5C14—N1—C15109.7 (4)
C10—C9—H9120.5C14—N1—C11108.4 (3)
C7—C10—C9120.4 (4)C15—N1—C11110.0 (3)
C7—C10—S1120.7 (4)C3—N2—C8116.5 (3)
C9—C10—S1118.9 (3)C3—N2—Co1126.0 (2)
N1—C11—C8111.9 (3)C8—N2—Co1117.3 (2)
N1—C11—H11A109.2C4—O1—Co1130.8 (2)
C8—C11—H11A109.2C10—S1—H1109.5
N1—C11—H11B109.2C6—S2—H2109.5
C8—C11—H11B109.2
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···S2ii0.83 (1)2.95 (2)3.7001 (17)151 (4)
O2—H2A···O1ii0.83 (1)2.25 (3)2.928 (5)139 (4)
Symmetry codes: (ii) −x+1, y+1, −z+3/2.
Table 1
Selected geometric parameters (Å) top
Co1—O12.089 (2)Co1—N12.456 (3)
Co1—N22.241 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···S2i0.83 (1)2.95 (2)3.7001 (17)151 (4)
O2—H2A···O1i0.83 (1)2.25 (3)2.928 (5)139 (4)
Symmetry codes: (i) −x+1, y+1, −z+3/2.
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.

Li, H.-Y., Wang, L.-J., Hou, J. & Zeng, Q.-F. (2009). Acta Cryst. E65, m1112.

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.