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Acta Cryst. (2007). E63, m1964-m1965    [ doi:10.1107/S1600536807029595 ]

Aqua(2,2'-diamino-4,4'-bi-1,3-thiazole-[kappa]2N,N')(pyridine-2,6-dicarboxylato-[kappa]3O,N,O')cobalt(II) tetrahydrate

C.-E. Wei, G.-H. Chen and B.-X. Liu

Abstract top

The structure of the title complex, [Co(C7H3NO4)(C6H6N4S2)(H2O)]·4H2O, displays a distorted octahedral coordination geometry around the CoII center, formed by a diaminobithiazole molecule (DABT), one pyridine-2,6-dicarboxylate anion and one water molecule. The pyridine-2,6-dicarboxylate anion chelates the CoII ion with a facial configuration. Within the chelating DABT ligand, the thiazole rings are twisted with respect to each other [dihedral angle 15.10 (5)°]. Uncoordinated water molecules are involved in O-H...O and N-H...O hydrogen bonds, with H...O separations in the range 1.88-2.17 Å, stabilizing the crystal structure.

Comment top

Transition metal complexes of 2,2'-diamino-4,4'-bi-1,3-thiazole (DABT) have shown potential applications in the field of soft magnetic materials (Sun et al., 1997). As a part of a serial structural investigation of metal complexes with DABT (Liu et al., 2003), the title CoII complex was recently prepared and its X-ray structure is presented here.

The molecular structure of the title compound is shown in Fig. 1. The complex has a distorted octahedral coordination geometry formed by one DABT ligand, one pyridine-2,6-dicarboxylate anion and one water molecule. The asymmetric unit is completed with four lattice water molecules.

Thiazole rings of DABT are not coplanar, as observed in other complexes we have reported. The dihedral angle between thiazole rings is 15.10 (5) °, the rings being defined as C11/C12/C13/S11/N11 and C14/C15/C16/S12/N13. This angle is similar to the dihedral angle of 17.23 (7)° found in [Cr(C4H5NO4)(C6H6N4S2)(H2O)]Cl·H2O, (Liu & Xu, 2004). Bond lengths C16—N14 [1.335 (4) Å] and C16—N13 [1.324 (4) Å] imply the existence of electron delocalization between thiazole rings and amino groups. This feature for DABT can be found in other DABT complexes based on MnII (Liu & Xu, 2005) and CoII (Liu, Yu & Xu, 2005) we have reported. Other DABT complexes have been reported (Liu et al., 2006; Zhang et al., 2006).

The tridentate pyridine-2,6-dicarboxylate anion chelates to the CoII ion with a facial configuration (Ma et al., 2002). The maximum deviation from the mean plane defined by C21···C27/N21/O21···O24 is 0.082 (3) Å, for atom N21.

The extensive hydrogen bonding scheme involving lattice water molecules and complex helps to stabilize the crystal structure, as shown in Fig. 1. and Table reporting intermolecular contacts..

Related literature top

For general background, see Liu et al. (2006); For synthesis see Zhang et al. (2006). For related structures see: Liu & Xu (2004, 2005); Liu et al. (2003, 2005); Sun et al. (1997), Ma et al. (2002).

Experimental top

The complex was prepared following a procedure similar to that previously used for a NiII compound (Zhang et al., 2006). An aqueous solution (20 ml) containing DABT (1 mmol) and CoCl2 (1 mmol) was mixed with an aqueous solution (10 ml) of pyridine-2,6-dicarboxylic acid (1 mmol) and NaOH (2 mmol). The mixture was refluxed for 5 h. After cooling to room temperature the solution was filtered. Red single crystals of the title complex were obtained from the filtrate after 30 d.

Refinement top

C-bonded H atoms were placed in calculated positions, and were included in the refinement in riding mode with C—H distances constrained to 0.93 Å and Uiso(H) = 1.2Ueq(carrier C atom). H atoms of amino groups of DABT were located in a difference map and included in the refinement with fixed positions and isotropic displacement parameters Uiso(H) = 0.05 Å2. Finally, H atoms of water molecules were located in a difference map and included in the refinement as riding with O—H bond lengths constrained to the found distances and Uiso(H) = 1.5Ueq(carrier O atom).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). Dashed lines show the hydrogen bonds [symmetry code: (i) x − 1, y, z].
Aqua(2,2'-diamino-4,4'-bi-1,3-thiazole-κ2N,N')(pyridine- 2,6-dicarboxylato-κ3O,N,O')cobalt(II) tetrahydrate top
Crystal data top
[Co(C7H3NO4)(C6H6N4S2)(H2O)]·4H2OF000 = 1052
Mr = 512.38Dx = 1.734 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4380 reflections
a = 10.0259 (15) Åθ = 2.0–27.5º
b = 7.0956 (11) ŵ = 1.15 mm−1
c = 27.648 (4) ÅT = 295 (2) K
β = 93.528 (2)ºPrism, red
V = 1963.2 (5) Å30.26 × 0.20 × 0.15 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		4488 independent reflections
Radiation source: fine-focus sealed tube2781 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.058
Detector resolution: 10.0 pixels mm-1θmax = 27.5º
T = 295(2) Kθmin = 2.0º
ω scansh = −12→13
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −7→9
Tmin = 0.76, Tmax = 0.84l = −34→35
11819 measured reflections
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)] = 0.048H-atom parameters constrained
wR(F2) = 0.112  w = 1/[σ2(Fo2) + (0.041P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
4488 reflectionsΔρmax = 0.39 e Å−3
271 parametersΔρmin = −0.53 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Co(C7H3NO4)(C6H6N4S2)(H2O)]·4H2OV = 1963.2 (5) Å3
Mr = 512.38Z = 4
Monoclinic, P21/cMo Kα
a = 10.0259 (15) ŵ = 1.15 mm−1
b = 7.0956 (11) ÅT = 295 (2) K
c = 27.648 (4) Å0.26 × 0.20 × 0.15 mm
β = 93.528 (2)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		4488 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2781 reflections with I > 2σ(I)
Tmin = 0.76, Tmax = 0.84Rint = 0.058
11819 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.048271 parameters
wR(F2) = 0.112H-atom parameters constrained
S = 1.01Δρmax = 0.39 e Å−3
4488 reflectionsΔρmin = −0.53 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co0.70981 (5)0.52542 (7)0.673116 (16)0.02505 (15)
N110.5102 (3)0.5782 (4)0.69340 (9)0.0249 (7)
N120.3703 (3)0.5793 (5)0.62170 (11)0.0416 (9)
H12A0.42060.58890.59640.050*
H12B0.28430.57560.61360.050*
N130.7381 (3)0.5238 (4)0.74861 (9)0.0246 (7)
N140.9684 (3)0.4777 (5)0.76659 (11)0.0393 (8)
H14A0.97780.42650.73940.050*
H14B1.03170.46370.79000.050*
N210.7092 (3)0.6023 (4)0.60086 (9)0.0238 (7)
O10.9027 (2)0.3886 (3)0.66627 (8)0.0322 (6)
H1A0.95710.44460.65110.048*
H1B0.89620.28370.65630.048*
O210.8075 (2)0.8037 (3)0.67166 (8)0.0318 (6)
O220.8782 (2)1.0307 (3)0.62364 (9)0.0349 (6)
O230.6270 (2)0.2834 (3)0.63337 (8)0.0315 (6)
O240.5645 (3)0.1782 (4)0.55884 (9)0.0449 (7)
O1W0.4090 (3)−0.1295 (4)0.54364 (10)0.0501 (8)
H1WA0.4614−0.04380.55350.075*
H1WB0.4072−0.12940.51340.075*
O2W0.9974 (3)0.2014 (4)0.55043 (9)0.0520 (8)
H2WA0.95440.19870.52320.078*
H2WB0.94750.16320.57170.078*
O3W1.0712 (3)0.5351 (4)0.59782 (10)0.0482 (7)
H3WA1.07340.63250.58280.072*
H3WB1.04650.45090.57990.072*
O4W1.1338 (3)0.8492 (4)0.54165 (9)0.0470 (7)
H4WA1.21530.86010.54430.070*
H4WB1.09930.95070.54990.070*
S110.26088 (9)0.55446 (15)0.70815 (4)0.0358 (3)
S120.80820 (10)0.54847 (16)0.83941 (3)0.0378 (3)
C110.4991 (4)0.5664 (5)0.74335 (12)0.0263 (8)
C120.3732 (4)0.5532 (5)0.75708 (13)0.0329 (9)
H120.35020.54460.78910.039*
C130.3914 (4)0.5722 (5)0.67035 (13)0.0293 (8)
C140.6233 (3)0.5582 (5)0.77352 (12)0.0268 (8)
C150.6420 (4)0.5770 (5)0.82163 (13)0.0332 (9)
H150.57480.60200.84250.040*
C160.8444 (4)0.5117 (5)0.77936 (12)0.0274 (8)
C210.7622 (3)0.7664 (5)0.58793 (12)0.0246 (8)
C220.7694 (4)0.8154 (5)0.53997 (12)0.0324 (9)
H220.80620.93020.53150.039*
C230.7210 (4)0.6913 (6)0.50479 (13)0.0363 (9)
H230.72310.72250.47220.044*
C240.6693 (4)0.5201 (5)0.51834 (13)0.0332 (9)
H240.63810.43370.49500.040*
C250.6647 (3)0.4792 (5)0.56717 (12)0.0249 (8)
C260.6130 (4)0.2984 (5)0.58774 (13)0.0298 (8)
C270.8201 (3)0.8784 (5)0.63080 (13)0.0269 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0258 (3)0.0284 (3)0.0209 (3)−0.0019 (2)0.00102 (19)0.0000 (2)
N110.0250 (17)0.0282 (18)0.0219 (15)−0.0007 (12)0.0037 (12)0.0019 (13)
N120.0281 (18)0.069 (3)0.0275 (17)0.0025 (16)−0.0039 (14)−0.0014 (17)
N130.0236 (16)0.0279 (17)0.0222 (15)−0.0020 (13)0.0008 (12)0.0033 (13)
N140.0272 (18)0.063 (2)0.0273 (17)0.0008 (16)−0.0065 (13)−0.0040 (16)
N210.0253 (16)0.0238 (17)0.0221 (15)−0.0044 (12)−0.0006 (12)−0.0020 (13)
O10.0344 (15)0.0291 (15)0.0330 (14)0.0013 (11)0.0023 (11)−0.0048 (12)
O210.0390 (16)0.0353 (16)0.0209 (13)−0.0092 (12)−0.0005 (11)−0.0014 (12)
O220.0403 (16)0.0300 (15)0.0341 (15)−0.0124 (12)0.0012 (12)−0.0024 (12)
O230.0394 (16)0.0256 (14)0.0295 (14)−0.0043 (11)0.0039 (11)0.0027 (12)
O240.0606 (19)0.0334 (16)0.0397 (16)−0.0197 (14)−0.0044 (14)−0.0087 (14)
O1W0.062 (2)0.0436 (18)0.0450 (17)−0.0232 (15)0.0053 (14)−0.0062 (15)
O2W0.058 (2)0.060 (2)0.0384 (16)−0.0206 (16)0.0055 (14)−0.0009 (15)
O3W0.0499 (18)0.0456 (18)0.0491 (18)−0.0084 (14)0.0023 (14)0.0041 (15)
O4W0.0489 (18)0.0468 (18)0.0451 (17)−0.0039 (14)0.0018 (14)0.0022 (14)
S110.0258 (5)0.0401 (6)0.0420 (6)−0.0004 (4)0.0045 (4)−0.0018 (5)
S120.0423 (6)0.0492 (7)0.0214 (5)−0.0010 (5)−0.0027 (4)−0.0007 (5)
C110.032 (2)0.0211 (19)0.0265 (19)−0.0015 (15)0.0054 (15)0.0001 (15)
C120.032 (2)0.037 (2)0.030 (2)0.0015 (17)0.0068 (16)0.0007 (18)
C130.028 (2)0.033 (2)0.027 (2)0.0002 (16)0.0000 (16)−0.0020 (17)
C140.031 (2)0.025 (2)0.0254 (19)−0.0041 (16)0.0038 (15)0.0015 (16)
C150.033 (2)0.040 (2)0.027 (2)0.0002 (17)0.0027 (16)−0.0010 (18)
C160.031 (2)0.027 (2)0.0235 (18)−0.0018 (16)−0.0027 (15)0.0025 (16)
C210.0219 (18)0.024 (2)0.0277 (19)−0.0013 (15)0.0001 (15)−0.0019 (16)
C220.040 (2)0.029 (2)0.028 (2)−0.0080 (17)−0.0019 (17)0.0065 (17)
C230.049 (3)0.041 (2)0.0189 (19)−0.0058 (19)−0.0007 (17)0.0024 (18)
C240.043 (2)0.033 (2)0.0228 (19)−0.0084 (18)0.0011 (16)−0.0070 (17)
C250.0285 (19)0.0220 (19)0.0237 (18)−0.0005 (15)−0.0006 (14)−0.0003 (15)
C260.029 (2)0.031 (2)0.029 (2)−0.0037 (16)0.0025 (16)0.0000 (17)
C270.025 (2)0.026 (2)0.029 (2)−0.0039 (15)0.0016 (15)−0.0050 (17)
Geometric parameters (Å, °) top
Co—N212.070 (3)O1W—H1WB0.8346
Co—N132.089 (3)O2W—H2WA0.8437
Co—N112.144 (3)O2W—H2WB0.8397
Co—O232.176 (2)O3W—H3WA0.8077
Co—O12.182 (2)O3W—H3WB0.8042
Co—O212.206 (2)O4W—H4WA0.8198
N11—C131.316 (4)O4W—H4WB0.8369
N11—C111.395 (4)S11—C121.706 (4)
N12—C131.350 (4)S11—C131.729 (4)
N12—H12A0.8902S12—C151.720 (4)
N12—H12B0.8774S12—C161.741 (3)
N13—C161.324 (4)C11—C121.344 (5)
N13—C141.399 (4)C11—C141.457 (5)
N14—C161.335 (4)C12—H120.9300
N14—H14A0.8454C14—C151.338 (5)
N14—H14B0.8832C15—H150.9300
N21—C251.334 (4)C21—C221.377 (4)
N21—C211.338 (4)C21—C271.513 (4)
O1—H1A0.8126C22—C231.379 (5)
O1—H1B0.7954C22—H220.9300
O21—C271.261 (4)C23—C241.381 (5)
O22—C271.250 (4)C23—H230.9300
O23—C261.265 (4)C24—C251.385 (5)
O24—C261.247 (4)C24—H240.9300
O1W—H1WA0.8383C25—C261.508 (5)
N21—Co—N13163.25 (11)C15—S12—C1690.01 (17)
N21—Co—N11105.01 (11)C12—C11—N11114.7 (3)
N13—Co—N1179.13 (10)C12—C11—C14128.3 (3)
N21—Co—O2375.06 (10)N11—C11—C14116.8 (3)
N13—Co—O23121.63 (10)C11—C12—S11111.2 (3)
N11—Co—O2386.38 (10)C11—C12—H12124.4
N21—Co—O189.05 (10)S11—C12—H12124.4
N13—Co—O191.00 (10)N11—C13—N12124.3 (3)
N11—Co—O1161.20 (10)N11—C13—S11113.9 (3)
O23—Co—O185.27 (9)N12—C13—S11121.8 (3)
N21—Co—O2173.83 (10)C15—C14—N13116.0 (3)
N13—Co—O2189.42 (10)C15—C14—C11128.9 (3)
N11—Co—O21105.71 (10)N13—C14—C11115.2 (3)
O23—Co—O21148.60 (9)C14—C15—S12110.2 (3)
O1—Co—O2190.00 (9)C14—C15—H15124.9
C13—N11—C11110.6 (3)S12—C15—H15124.9
C13—N11—Co134.3 (2)N13—C16—N14124.6 (3)
C11—N11—Co112.4 (2)N13—C16—S12113.3 (3)
C13—N12—H12A136.5N14—C16—S12122.1 (3)
C13—N12—H12B110.3N21—C21—C22121.5 (3)
H12A—N12—H12B113.3N21—C21—C27112.8 (3)
C16—N13—C14110.4 (3)C22—C21—C27125.6 (3)
C16—N13—Co134.1 (2)C21—C22—C23118.7 (3)
C14—N13—Co115.2 (2)C21—C22—H22120.6
C16—N14—H14A118.0C23—C22—H22120.6
C16—N14—H14B117.7C22—C23—C24119.5 (3)
H14A—N14—H14B119.3C22—C23—H23120.3
C25—N21—C21120.3 (3)C24—C23—H23120.3
C25—N21—Co118.8 (2)C23—C24—C25119.0 (3)
C21—N21—Co120.6 (2)C23—C24—H24120.5
Co—O1—H1A117.0C25—C24—H24120.5
Co—O1—H1B113.1N21—C25—C24120.9 (3)
H1A—O1—H1B108.7N21—C25—C26113.7 (3)
C27—O21—Co117.5 (2)C24—C25—C26125.4 (3)
C26—O23—Co116.9 (2)O24—C26—O23126.6 (3)
H1WA—O1W—H1WB107.5O24—C26—C25118.0 (3)
H2WA—O2W—H2WB108.8O23—C26—C25115.3 (3)
H3WA—O3W—H3WB109.6O22—C27—O21125.4 (3)
H4WA—O4W—H4WB108.7O22—C27—C21119.4 (3)
C12—S11—C1389.57 (17)O21—C27—C21115.3 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O3W0.812.022.812 (4)163
O1—H1B···O22i0.802.012.804 (3)174
O1W—H1WA···O240.841.882.701 (4)164
O1W—H1WB···O24ii0.842.062.883 (4)167
O2W—H2WA···O4Wiii0.841.982.816 (4)171
O2W—H2WB···O22i0.841.882.700 (4)163
O3W—H3WA···O4W0.812.032.809 (4)163
O3W—H3WB···O2W0.812.002.784 (4)165
O4W—H4WA···O1Wiv0.821.942.760 (4)173
O4W—H4WB···O2Wv0.842.052.866 (4)164
N12—H12A···O1Wv0.892.473.030 (4)121
N12—H12B···O3Wvi0.882.173.047 (4)173
N14—H14A···O10.852.132.881 (4)148
N14—H14B···O21vii0.882.193.003 (4)152
N14—H14B···O22vii0.882.553.338 (4)150
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z+1; (iii) −x+2, −y+1, −z+1; (iv) x+1, y+1, z; (v) x, y+1, z; (vi) x−1, y, z; (vii) −x+2, y−1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O3W0.812.022.812 (4)163
O1—H1B···O22i0.802.012.804 (3)174
O1W—H1WA···O240.841.882.701 (4)164
O1W—H1WB···O24ii0.842.062.883 (4)167
O2W—H2WA···O4Wiii0.841.982.816 (4)171
O2W—H2WB···O22i0.841.882.700 (4)163
O3W—H3WA···O4W0.812.032.809 (4)163
O3W—H3WB···O2W0.812.002.784 (4)165
O4W—H4WA···O1Wiv0.821.942.760 (4)173
O4W—H4WB···O2Wv0.842.052.866 (4)164
N12—H12B···O3Wvi0.882.173.047 (4)173
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z+1; (iii) −x+2, −y+1, −z+1; (iv) x+1, y+1, z; (v) x, y+1, z; (vi) x−1, y, z.
Acknowledgements top

The project was supported by the Educational Development Foundation of Shanghai Educational Committee, China (AB0448).

references
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