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

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

doi:10.1107/S1600536809033650

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1146

doi:10.1107/S1600536809033650

Open

access

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

Ying-Jie Cai,^a Jin Li,^a Peng Huang ^a and Qing-Fu Zeng ^a ^*

^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 Co^II 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 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Co(C₁₁H₁₅N₂OS₂)₂]·H₂O
M_r = 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 ) T_min = 0.752, T_max = 0.787
13847 measured reflections
2548 independent reflections
2039 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.84 e Å⁻³
Δρ_min = −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	D⋯A	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 ); cell refinement: CAD-4 Software; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033650/hb5056sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033650/hb5056Isup2.hkl

checkCIF report

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.

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

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]·H₂O	F(000) = 1228
M_r = 587.69	D_x = 1.494 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 25 reflections
a = 12.3755 (15) Å	θ = 9–12°
b = 9.2485 (15) Å	µ = 1.01 mm⁻¹
c = 22.827 (3) Å	T = 296 K
V = 2612.7 (6) Å³	Block, red
Z = 4	0.30 × 0.25 × 0.25 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	2039 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 26.0°, θ_min = 2.4°
ω/2θ scans	h = −15→15
Absorption correction: ψ scan (North et al., 1968)	k = −11→6
T_min = 0.752, T_max = 0.787	l = −28→27
13847 measured reflections	200 standard reflections every 3 reflections
2548 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.1201P)² + 2.1692P] where P = (F_o² + 2F_c²)/3
2548 reflections	(Δ/σ)_max = 0.001
160 parameters	Δρ_max = 0.84 e Å⁻³
1 restraint	Δρ_min = −0.96 e Å⁻³

Crystal data top

[Co(C₁₁H₁₅N₂OS₂)₂]·H₂O	V = 2612.7 (6) Å³
M_r = 587.69	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 12.3755 (15) Å	µ = 1.01 mm⁻¹
b = 9.2485 (15) Å	T = 296 K
c = 22.827 (3) Å	0.30 × 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)	R_int = 0.031
T_min = 0.752, T_max = 0.787	200 standard reflections every 3 reflections
13847 measured reflections	intensity decay: 1%
2548 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	1 restraint
wR(F²) = 0.186	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.84 e Å⁻³
2548 reflections	Δρ_min = −0.96 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C3	0.2776 (3)	0.1848 (3)	0.68222 (16)	0.0417 (8)
H3	0.2082	0.2207	0.6768	0.050*
C4	0.4167 (3)	0.0107 (3)	0.64302 (14)	0.0380 (7)
C5	0.3168 (3)	0.0854 (4)	0.63802 (14)	0.0395 (7)
C6	0.4439 (3)	−0.0791 (4)	0.59437 (15)	0.0467 (9)
C7	0.2502 (3)	0.0634 (4)	0.58895 (17)	0.0524 (10)
H7	0.1846	0.1120	0.5866	0.063*
C8	0.2678 (3)	0.3286 (4)	0.76616 (19)	0.0507 (9)
H8A	0.2245	0.2739	0.7938	0.061*
H8B	0.2195	0.3881	0.7429	0.061*
C9	0.3788 (4)	−0.0974 (4)	0.54666 (16)	0.0588 (11)
H9	0.4004	−0.1560	0.5157	0.071*
C10	0.2796 (4)	−0.0272 (5)	0.54503 (18)	0.0623 (12)
C11	0.3458 (3)	0.4236 (4)	0.79892 (18)	0.0514 (9)
H11A	0.3791	0.4909	0.7718	0.062*
H11B	0.3066	0.4795	0.8279	0.062*
C14	0.5090 (4)	0.4381 (5)	0.8533 (2)	0.0673 (13)
H14A	0.5339	0.5032	0.8234	0.101*
H14B	0.5692	0.3847	0.8686	0.101*
H14C	0.4757	0.4922	0.8842	0.101*
C15	0.3836 (4)	0.2501 (5)	0.87496 (19)	0.0651 (12)
H15A	0.3375	0.3091	0.8989	0.098*
H15B	0.4402	0.2100	0.8987	0.098*
H15C	0.3421	0.1732	0.8579	0.098*
Co1	0.5000	0.18183 (7)	0.7500	0.0390 (3)
H2A	0.502 (3)	0.789 (4)	0.7815 (11)	0.059 (14)*
N1	0.4310 (2)	0.3386 (3)	0.82838 (13)	0.0431 (7)
N2	0.3272 (2)	0.2283 (3)	0.72746 (13)	0.0401 (6)
O1	0.48006 (19)	0.0189 (3)	0.68755 (11)	0.0412 (6)
O2	0.5000	0.7436 (5)	0.7500	0.0605 (11)*
S1	0.19385 (15)	−0.05824 (19)	0.48627 (6)	0.0990 (6)
H1	0.1107	0.0061	0.4937	0.148*
S2	0.56823 (10)	−0.16647 (13)	0.59645 (5)	0.0678 (4)
H2	0.5567	−0.2860	0.6159	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.0367 (18)	0.0393 (18)	0.049 (2)	−0.0001 (13)	−0.0046 (14)	0.0043 (14)
C4	0.0496 (19)	0.0308 (15)	0.0336 (16)	−0.0073 (14)	−0.0017 (14)	0.0007 (12)
C5	0.0439 (18)	0.0357 (16)	0.0391 (17)	−0.0069 (14)	−0.0053 (14)	0.0024 (13)
C6	0.062 (2)	0.0407 (18)	0.0372 (17)	−0.0006 (16)	0.0042 (16)	−0.0029 (14)
C7	0.055 (2)	0.054 (2)	0.048 (2)	−0.0105 (18)	−0.0152 (17)	0.0112 (16)
C8	0.042 (2)	0.055 (2)	0.056 (2)	0.0115 (16)	0.0015 (17)	−0.0060 (17)
C9	0.086 (3)	0.053 (2)	0.0371 (19)	−0.012 (2)	−0.0050 (19)	−0.0067 (16)
C10	0.085 (3)	0.061 (2)	0.041 (2)	−0.021 (2)	−0.022 (2)	0.0033 (18)
C11	0.057 (2)	0.0418 (19)	0.055 (2)	0.0080 (17)	0.0037 (18)	−0.0054 (16)
C14	0.056 (3)	0.068 (3)	0.078 (3)	−0.004 (2)	0.003 (2)	−0.028 (2)
C15	0.076 (3)	0.066 (3)	0.054 (2)	0.011 (2)	0.018 (2)	0.004 (2)
Co1	0.0383 (4)	0.0381 (4)	0.0406 (4)	0.000	−0.0028 (2)	0.000
N1	0.0433 (16)	0.0398 (15)	0.0462 (16)	0.0012 (12)	0.0001 (13)	−0.0065 (12)
N2	0.0376 (15)	0.0375 (14)	0.0452 (16)	0.0029 (11)	−0.0013 (12)	−0.0018 (13)
O1	0.0498 (13)	0.0367 (12)	0.0372 (12)	0.0030 (10)	−0.0080 (10)	−0.0059 (10)
S1	0.1182 (13)	0.1170 (13)	0.0616 (8)	−0.0154 (9)	−0.0498 (8)	−0.0119 (7)
S2	0.0758 (8)	0.0646 (7)	0.0629 (7)	0.0195 (6)	0.0044 (5)	−0.0196 (5)

Geometric parameters (Å, º) top

C3—N2	1.267 (5)	C11—H11A	0.9700
C3—C5	1.449 (5)	C11—H11B	0.9700
C3—H3	0.9300	C14—N1	1.449 (5)
C4—O1	1.286 (4)	C14—H14A	0.9600
C4—C5	1.421 (5)	C14—H14B	0.9600
C4—C6	1.427 (5)	C14—H14C	0.9600
C5—C7	1.406 (5)	C15—N1	1.464 (5)
C6—C9	1.366 (5)	C15—H15A	0.9600
C6—S2	1.738 (4)	C15—H15B	0.9600
C7—C10	1.356 (6)	C15—H15C	0.9600
C7—H7	0.9300	Co1—O1	2.089 (2)
C8—N2	1.477 (5)	Co1—O1ⁱ	2.089 (2)
C8—C11	1.505 (6)	Co1—N2ⁱ	2.241 (3)
C8—H8A	0.9700	Co1—N2	2.241 (3)
C8—H8B	0.9700	Co1—N1	2.456 (3)
C9—C10	1.389 (7)	Co1—N1ⁱ	2.456 (3)
C9—H9	0.9300	O2—H2A	0.832 (10)
C10—S1	1.735 (4)	S1—H1	1.2000
C11—N1	1.478 (5)	S2—H2	1.2000

N2—C3—C5	127.4 (3)	H11A—C11—H11B	107.9
N2—C3—H3	116.3	N1—C14—H14A	109.5
C5—C3—H3	116.3	N1—C14—H14B	109.5
O1—C4—C5	124.4 (3)	H14A—C14—H14B	109.5
O1—C4—C6	120.4 (3)	N1—C14—H14C	109.5
C5—C4—C6	115.2 (3)	H14A—C14—H14C	109.5
C7—C5—C4	120.2 (3)	H14B—C14—H14C	109.5
C7—C5—C3	116.8 (3)	N1—C15—H15A	109.5
C4—C5—C3	123.0 (3)	N1—C15—H15B	109.5
C9—C6—C4	123.6 (4)	H15A—C15—H15B	109.5
C9—C6—S2	119.1 (3)	N1—C15—H15C	109.5
C4—C6—S2	117.3 (3)	H15A—C15—H15C	109.5
C10—C7—C5	121.4 (4)	H15B—C15—H15C	109.5
C10—C7—H7	119.3	O1—Co1—O1ⁱ	87.65 (14)
C5—C7—H7	119.3	O1—Co1—N2ⁱ	114.06 (10)
N2—C8—C11	110.2 (3)	O1ⁱ—Co1—N2ⁱ	82.47 (10)
N2—C8—H8A	109.6	O1—Co1—N2	82.48 (10)
C11—C8—H8A	109.6	O1ⁱ—Co1—N2	114.06 (10)
N2—C8—H8B	109.6	N2ⁱ—Co1—N2	157.88 (15)
C11—C8—H8B	109.6	N1—Co1—O1	151.87 (12)
H8A—C8—H8B	108.1	N1—Co1—N2	73.88 (12)
C6—C9—C10	119.0 (4)	N1—Co1—N1ⁱ	107.64 (12)
C6—C9—H9	120.5	C14—N1—C15	109.7 (4)
C10—C9—H9	120.5	C14—N1—C11	108.4 (3)
C7—C10—C9	120.4 (4)	C15—N1—C11	110.0 (3)
C7—C10—S1	120.7 (4)	C3—N2—C8	116.5 (3)
C9—C10—S1	118.9 (3)	C3—N2—Co1	126.0 (2)
N1—C11—C8	111.9 (3)	C8—N2—Co1	117.3 (2)
N1—C11—H11A	109.2	C4—O1—Co1	130.8 (2)
C8—C11—H11A	109.2	C10—S1—H1	109.5
N1—C11—H11B	109.2	C6—S2—H2	109.5
C8—C11—H11B	109.2

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···S2ⁱⁱ	0.83 (1)	2.95 (2)	3.7001 (17)	151 (4)
O2—H2A···O1ⁱⁱ	0.83 (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
M_r	587.69
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	296
a, b, c (Å)	12.3755 (15), 9.2485 (15), 22.827 (3)
V (Å³)	2612.7 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.01
Crystal size (mm)	0.30 × 0.25 × 0.25

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.752, 0.787
No. of measured, independent and observed [I > 2σ(I)] reflections	13847, 2548, 2039
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.186, 1.06
No. of reflections	2548
No. of parameters	160
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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—O1	2.089 (2)	Co1—N1	2.456 (3)
Co1—N2	2.241 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+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

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. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Li, H.-Y., Wang, L.-J., Hou, J. & Zeng, Q.-F. (2009). Acta Cryst. E65, m1112. Web of Science CSD CrossRef IUCr Journals Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1146

doi:10.1107/S1600536809033650

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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