metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

aEngineering Research Center for Clean Production of Textile Dyeing and Printing, Ministry of Education, Wuhan 430073, People's Republic of China
*Correspondence e-mail: qfzeng@wuse.edu.cn

(Received 20 August 2009; accepted 24 August 2009; online 29 August 2009)

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.

Related literature

For a related compound and background, see: Li et al. (2009[Li, H.-Y., Wang, L.-J., Hou, J. & Zeng, Q.-F. (2009). Acta Cryst. E65, m1112.]). For reference structural data, see: Allen et al. (1987[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.]).

[Scheme 1]

Experimental

Crystal data
  • [Co(C11H15N2OS2)2]·H2O

  • Mr = 587.69

  • Orthorhombic, P b c n

  • a = 12.3755 (15) Å

  • b = 9.2485 (15) Å

  • c = 22.827 (3) Å

  • V = 2612.7 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.01 mm−1

  • T = 296 K

  • 0.30 × 0.25 × 0.25 mm

Data collection
  • Enraf–Nonius CAD-4 diffractometer

  • Absorption correction: ψ scan (North et al., 1968[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.752, Tmax = 0.787

  • 13847 measured reflections

  • 2548 independent reflections

  • 2039 reflections with I > 2σ(I)

  • Rint = 0.031

  • 200 standard reflections every 3 reflections intensity decay: 1%

Refinement
  • R[F2 > 2σ(F2)] = 0.054

  • wR(F2) = 0.186

  • S = 1.06

  • 2548 reflections

  • 160 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.84 e Å−3

  • Δρmin = −0.96 e Å−3

Table 1
Selected bond lengths (Å)

Co1—O1 2.089 (2)
Co1—N2 2.241 (3)
Co1—N1 2.456 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2A⋯S2i 0.832 (10) 2.95 (2) 3.7001 (17) 151 (4)
O2—H2A⋯O1i 0.832 (10) 2.25 (3) 2.928 (5) 139 (4)
Symmetry code: (i) [-x+1, y+1, -z+{\script{3\over 2}}].

Data collection: CAD-4 Software (Enraf–Nonius, 1989[Enraf-Nonius (1989). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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 m3
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 mm1
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
Graphite monochromatorθmax = 26.0°, θmin = 2.4°
ω/2θ scansh = 1515
Absorption correction: ψ scan
(North et al., 1968)
k = 116
Tmin = 0.752, Tmax = 0.787l = 2827
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 Å3
1 restraintΔρmin = 0.96 e Å3
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 mm1
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 = 0.787200 standard reflections every 3 reflections
13847 measured reflections intensity decay: 1%
2548 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0541 restraint
wR(F2) = 0.186H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.84 e Å3
2548 reflectionsΔρmin = 0.96 e Å3
160 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
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)
H90.40040.15600.51570.071*
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)
H20.55670.28600.61590.102*
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)0.0000.0028 (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, º) 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 code: (i) x+1, y, z+3/2.
Hydrogen-bond geometry (Å, º) 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 code: (ii) x+1, y+1, z+3/2.

Experimental details

Crystal data
Chemical formula[Co(C11H15N2OS2)2]·H2O
Mr587.69
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)296
a, b, c (Å)12.3755 (15), 9.2485 (15), 22.827 (3)
V3)2612.7 (6)
Z4
Radiation typeMo Kα
µ (mm1)1.01
Crystal size (mm)0.30 × 0.25 × 0.25
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.752, 0.787
No. of measured, independent and
observed [I > 2σ(I)] reflections
13847, 2548, 2039
Rint0.031
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.186, 1.06
No. of reflections2548
No. of parameters160
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.84, 0.96

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
Co1—O12.089 (2)Co1—N12.456 (3)
Co1—N22.241 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···S2i0.832 (10)2.95 (2)3.7001 (17)151 (4)
O2—H2A···O1i0.832 (10)2.25 (3)2.928 (5)139 (4)
Symmetry code: (i) x+1, y+1, z+3/2.
 

Acknowledgements

The project was supported by the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, Educational Commission of Hubei Province (D20091703) and the Natural Science Foundation of Hubei Province (2008CDB038).

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationEnraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.  Google Scholar
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.  Google Scholar
First citationLi, H.-Y., Wang, L.-J., Hou, J. & Zeng, Q.-F. (2009). Acta Cryst. E65, m1112.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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