Aqua­(2,2′-diamino-4,4′-bi-1,3-thia­zole-κ²N,N′)(thio­diacetato-κ³O,S,O′)cobalt(II) dihydrate

The title Co^II complex, [Co(C₆H₆N₄S₂)(C₄H₄O₄S)(H₂O)]·2H₂O, assumes a distorted octa­hedral coordination geometry formed by a diamino­bithia­zole (DABT) ligand, a thio­diacetate dianion (TDA) and a water mol­ecule. The TDA dianion chelates to the Co^II atom with a facial configuration. Within the chelating DABT ligand, the two thia­zole rings are twisted with respect to each other [dihedral angle = 12.04 (9)°].

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.042
• wR factor = 0.102
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT411_ALERT_2_B Short Inter H...H Contact  H8B    ..  H8B     ..       2.06 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co     -   S3      ..       7.97 su
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT322_ALERT_2_C Check Hybridisation of  S2     in Main Residue .          ?

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Transition metal complexes of diaminobithiazole (DABT) have shown potential application in some fields (Waring, 1981; Fisher et al., 1985). As part of our ongoing investigation of metal complexes incorporating the DABT ligand (Liu et al., 2001), the title Co^II compound, (I), was prepared and its X-ray crystal structure is reported here.

The molecular structure of (I) is shown in Fig. 1. The Co^II complex assumes a distorted octahedral coordination geometry formed by a DABT ligand, a thiodiacetate dianion (TDA) and a coordinated water molecule. The tridentate TDA dianion chelates to the Co^II atom with a facial configuration. Both chelating five-membered rings display an envelope configuration, which is consistent with that found in an Ni^II complex with a chelating TDA ligand (Pan et al., 2005). The DABT ligand chelates to the Co^II atom with an average Co—N bond distance of 2.110 (3) Å (Table 1), which is comparable with the value of 2.097 (3) Å found in a corresponding compound, [Co(DABT)(ODA)(H₂O)] (ODA is oxydiacetate; Shen et al., 2004). The two thiazole rings of the DABT ligand are twisted with respect to each other around the C3—C4 bond, with a dihedral angle of 12.04 (9)°. This conformation is also found in [Cd(DABT)₂Cl₂] (Liu et al., 2003), but it differs from the planar configuration of DABT found in [Cu(DABT)Cl₂] (Liu et al., 2001).

A partially overlapping arrangement of parallel thiazole rings related by an inversion centre is observed (Fig. 2). The face-to-face separation between the mean planes of the S1-thiazole and S1^vi-thiazole rings is 3.558 (18) Å [symmetry code (vi): −x, 1 − y, 1 − z], which is significantly shorter than the thickness of the aromatic ring (3.7 Å) and suggests the existence of π–π stacking. There is extensive hydrogen bonding in the crystal structure of (I) (Table 2).

S2. Experimental

An aqueous solution (20 ml) containing DABT (0.20 g, 1 mmol) and CoCl₂·6H₂O (0.24 g, 1 mmol) was mixed with an aqueous solution (10 ml) of H₂TDA (0.15 g, 1 mmol) and NaOH(0.08 g, 2 mmol). The mixture was refluxed for 5 h. The solution was cooled to room temperature and then filtered. Single crystals of (I) were obtained from the filtrate after 3 d.

S3. Refinement

H atoms bonded to O and N atoms were located in a difference Fourier map and refined as riding on their parent atoms, with U_iso(H) = 1.5U_eq(O,N). H atoms bonded to C atoms were placed in calculated positions with C—H = 0.97 (methylene) or 0.93 Å (aromatic), and were included in the final cycles of refinement in a riding mode, with U_iso(H) = 1.2U_eq(C).

Computing details

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

	Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). Dashed lines indicate the hydrogen bonding.
	Fig. 2. A unit-cell packing diagram for (I), showing π–π stacking between the S1-thiazole and S1^vi-thiazole rings [symmetry code: (vi) −x, 1 − y, 1 − z]. H atoms have been omitted for clarity.

Aqua(2,2'-diamino-4,4'-bi-1,3-thiazole-κ²N,N')(thiodiacetato- κ³O,S,O')cobalt(II) dihydrate

Crystal data

[Co(C6H6N4S2)(C4H4O4S)(H2O)]·2H2O	F(000) = 940
Mr = 459.38	Dx = 1.798 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6855 reflections
a = 10.6918 (11) Å	θ = 3.0–24.0°
b = 7.1329 (7) Å	µ = 1.42 mm^−1
c = 22.794 (2) Å	T = 295 K
β = 102.538 (2)°	Prism, pink
V = 1696.9 (3) Å^3	0.30 × 0.20 × 0.15 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	3003 independent reflections
Radiation source: fine-focus sealed tube	2513 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 10.00 pixels mm^-1	θmax = 25.0°, θmin = 1.8°
ω scans	h = −9→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −8→8
Tmin = 0.665, Tmax = 0.802	l = −27→19
8649 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0449P)^2 + 1.2046P] where P = (Fo^2 + 2Fc^2)/3
3003 reflections	(Δ/σ)max = 0.001
226 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co	0.26840 (4)	0.72267 (6)	0.622648 (18)	0.02734 (15)
O1	0.2811 (2)	1.0045 (3)	0.60165 (11)	0.0400 (6)
O2	0.3663 (3)	1.2332 (3)	0.55773 (12)	0.0512 (7)
O3	0.3389 (2)	0.7742 (4)	0.71193 (10)	0.0413 (6)
O4	0.4930 (2)	0.8607 (5)	0.78787 (11)	0.0584 (8)
O5	0.2792 (2)	0.4345 (3)	0.64243 (10)	0.0367 (6)
H5A	0.3449	0.4206	0.6691	0.055*
H5B	0.2916	0.3792	0.6109	0.055*
N1	0.1748 (3)	0.6768 (4)	0.53176 (11)	0.0302 (6)
N2	0.3336 (3)	0.6030 (5)	0.47892 (12)	0.0446 (8)
H2A	0.3445	0.5959	0.4402	0.067*
H2B	0.3816	0.5263	0.5074	0.067*
N3	0.0754 (3)	0.7418 (4)	0.62842 (12)	0.0327 (7)
N4	0.0705 (3)	0.7351 (5)	0.73050 (14)	0.0563 (10)
H4A	0.1557	0.7302	0.7420	0.084*
H4B	0.0288	0.7309	0.7584	0.084*
O1W	0.1367 (3)	0.1883 (5)	0.70383 (14)	0.0720 (9)
H1C	0.1435	0.2897	0.6831	0.108*
H1D	0.1775	0.1017	0.6834	0.108*
O2W	0.3075 (3)	0.8286 (6)	0.84951 (13)	0.0840 (11)
H2C	0.2234	0.8496	0.8517	0.126*
H2D	0.3380	0.8576	0.8175	0.126*
S1	0.10075 (10)	0.72328 (13)	0.41805 (4)	0.0425 (3)
S2	−0.15024 (9)	0.77706 (15)	0.64843 (5)	0.0476 (3)
S3	0.50173 (8)	0.74037 (11)	0.61952 (4)	0.0314 (2)
C1	0.2153 (3)	0.6608 (5)	0.48164 (14)	0.0315 (8)
C2	−0.0058 (4)	0.7701 (5)	0.46259 (16)	0.0387 (9)
H2	−0.0892	0.8123	0.4484	0.050*
C3	0.0476 (3)	0.7375 (4)	0.52079 (16)	0.0321 (8)
C4	−0.0097 (3)	0.7561 (4)	0.57284 (16)	0.0315 (8)
C5	−0.1329 (4)	0.7772 (5)	0.57527 (17)	0.0413 (9)
H5	−0.2000	0.7902	0.5419	0.050*
C6	0.0148 (3)	0.7475 (5)	0.67259 (17)	0.0380 (9)
C7	0.3688 (3)	1.0734 (5)	0.57931 (14)	0.0361 (8)
C8	0.4846 (4)	0.9525 (5)	0.57599 (16)	0.0415 (9)
H8A	0.5613	1.0273	0.5892	0.050*
H8B	0.4797	0.9195	0.5343	0.050*
C9	0.5526 (3)	0.8267 (6)	0.69543 (15)	0.0398 (9)
H9A	0.6265	0.7543	0.7154	0.048*
H9B	0.5805	0.9556	0.6936	0.048*
C10	0.4539 (3)	0.8206 (5)	0.73385 (15)	0.0351 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0191 (3)	0.0367 (3)	0.0250 (3)	−0.00001 (18)	0.00215 (17)	−0.00213 (18)
O1	0.0277 (13)	0.0359 (13)	0.0550 (16)	0.0018 (11)	0.0056 (11)	0.0012 (11)
O2	0.063 (2)	0.0417 (16)	0.0455 (17)	0.0050 (13)	0.0047 (14)	0.0116 (12)
O3	0.0232 (13)	0.0723 (18)	0.0282 (13)	−0.0090 (12)	0.0052 (10)	−0.0101 (11)
O4	0.0328 (15)	0.109 (2)	0.0313 (15)	−0.0191 (15)	0.0024 (11)	−0.0236 (15)
O5	0.0310 (14)	0.0415 (14)	0.0337 (13)	0.0007 (10)	−0.0020 (10)	0.0032 (10)
N1	0.0267 (15)	0.0344 (15)	0.0280 (15)	0.0020 (12)	0.0026 (11)	−0.0014 (12)
N2	0.0387 (19)	0.065 (2)	0.0313 (16)	0.0063 (15)	0.0094 (13)	−0.0020 (14)
N3	0.0205 (15)	0.0410 (17)	0.0361 (17)	0.0005 (12)	0.0049 (12)	−0.0028 (12)
N4	0.0300 (18)	0.103 (3)	0.039 (2)	−0.0022 (17)	0.0123 (15)	0.0003 (17)
O1W	0.068 (2)	0.079 (2)	0.079 (2)	−0.0111 (18)	0.0395 (18)	−0.0050 (18)
O2W	0.074 (2)	0.131 (3)	0.056 (2)	−0.023 (2)	0.0328 (17)	−0.015 (2)
S1	0.0474 (6)	0.0484 (6)	0.0277 (5)	0.0074 (4)	−0.0005 (4)	0.0024 (4)
S2	0.0225 (5)	0.0646 (7)	0.0577 (7)	0.0013 (4)	0.0130 (4)	−0.0047 (5)
S3	0.0255 (5)	0.0395 (5)	0.0297 (5)	0.0047 (3)	0.0072 (3)	0.0026 (3)
C1	0.0320 (19)	0.0351 (18)	0.0258 (18)	−0.0015 (15)	0.0028 (14)	0.0010 (14)
C2	0.034 (2)	0.039 (2)	0.037 (2)	0.0048 (15)	−0.0058 (16)	−0.0010 (15)
C3	0.0269 (19)	0.0290 (17)	0.037 (2)	0.0001 (13)	0.0003 (15)	−0.0014 (14)
C4	0.0248 (18)	0.0294 (17)	0.038 (2)	−0.0020 (13)	0.0009 (14)	−0.0010 (14)
C5	0.027 (2)	0.046 (2)	0.047 (2)	0.0036 (16)	−0.0013 (16)	0.0014 (17)
C6	0.0238 (19)	0.044 (2)	0.047 (2)	−0.0047 (15)	0.0096 (16)	−0.0054 (16)
C7	0.033 (2)	0.039 (2)	0.0304 (19)	0.0017 (16)	−0.0043 (15)	−0.0001 (15)
C8	0.041 (2)	0.047 (2)	0.039 (2)	−0.0002 (18)	0.0143 (16)	0.0099 (17)
C9	0.0240 (19)	0.061 (2)	0.0332 (19)	−0.0044 (17)	0.0039 (14)	−0.0019 (17)
C10	0.029 (2)	0.043 (2)	0.0314 (19)	−0.0032 (16)	0.0028 (15)	−0.0022 (16)

Geometric parameters (Å, º)

Co—S3	2.5143 (10)	O1W—H1C	0.8751
Co—O1	2.078 (2)	O1W—H1D	0.9358
Co—O3	2.044 (2)	O2W—H2C	0.9237
Co—O5	2.102 (2)	O2W—H2D	0.8849
Co—N1	2.121 (3)	S1—C2	1.716 (4)
Co—N3	2.100 (3)	S1—C1	1.741 (3)
O1—C7	1.260 (4)	S2—C5	1.717 (4)
O2—C7	1.239 (4)	S2—C6	1.744 (4)
O3—C10	1.266 (4)	S3—C8	1.797 (3)
O4—C10	1.245 (4)	S3—C9	1.806 (3)
O5—H5A	0.8291	C2—C3	1.346 (5)
O5—H5B	0.8541	C2—H2	0.9300
N1—C1	1.312 (4)	C3—C4	1.455 (5)
N1—C3	1.397 (4)	C4—C5	1.339 (5)
N2—C1	1.345 (4)	C5—H5	0.9300
N2—H2A	0.9157	C7—C8	1.525 (5)
N2—H2B	0.9166	C8—H8A	0.9700
N3—C6	1.311 (5)	C8—H8B	0.9700
N3—C4	1.394 (4)	C9—C10	1.512 (5)
N4—C6	1.328 (5)	C9—H9A	0.9700
N4—H4A	0.8924	C9—H9B	0.9700
N4—H4B	0.8533
O3—Co—O1	91.55 (10)	C9—S3—Co	94.85 (11)
O3—Co—N3	94.66 (10)	N1—C1—N2	124.0 (3)
O1—Co—N3	93.77 (10)	N1—C1—S1	113.4 (3)
O3—Co—O5	88.34 (10)	N2—C1—S1	122.6 (2)
O1—Co—O5	172.83 (9)	C3—C2—S1	110.8 (3)
N3—Co—O5	93.39 (10)	C3—C2—H2	124.6
O3—Co—N1	173.61 (10)	S1—C2—H2	124.6
O1—Co—N1	87.99 (10)	C2—C3—N1	114.7 (3)
N3—Co—N1	79.02 (10)	C2—C3—C4	128.6 (3)
O5—Co—N1	92.91 (10)	N1—C3—C4	116.6 (3)
O3—Co—S3	82.26 (7)	C5—C4—N3	115.2 (3)
O1—Co—S3	80.22 (7)	C5—C4—C3	129.5 (3)
N3—Co—S3	173.13 (8)	N3—C4—C3	115.3 (3)
O5—Co—S3	92.66 (7)	C4—C5—S2	110.8 (3)
N1—Co—S3	103.93 (8)	C4—C5—H5	124.6
C7—O1—Co	124.2 (2)	S2—C5—H5	124.6
C10—O3—Co	123.8 (2)	N3—C6—N4	124.9 (3)
Co—O5—H5A	105.8	N3—C6—S2	113.4 (3)
Co—O5—H5B	106.4	N4—C6—S2	121.7 (3)
H5A—O5—H5B	107.5	O2—C7—O1	124.4 (3)
C1—N1—C3	111.3 (3)	O2—C7—C8	116.6 (3)
C1—N1—Co	133.5 (2)	O1—C7—C8	118.9 (3)
C3—N1—Co	111.2 (2)	C7—C8—S3	115.8 (2)
C1—N2—H2A	112.3	C7—C8—H8A	108.3
C1—N2—H2B	122.5	S3—C8—H8A	108.3
H2A—N2—H2B	118.8	C7—C8—H8B	108.3
C6—N3—C4	111.2 (3)	S3—C8—H8B	108.3
C6—N3—Co	134.9 (2)	H8A—C8—H8B	107.4
C4—N3—Co	113.9 (2)	C10—C9—S3	116.2 (2)
C6—N4—H4A	120.2	C10—C9—H9A	108.2
C6—N4—H4B	123.4	S3—C9—H9A	108.2
H4A—N4—H4B	116.4	C10—C9—H9B	108.2
H1C—O1W—H1D	100.1	S3—C9—H9B	108.2
H2C—O2W—H2D	122.9	H9A—C9—H9B	107.4
C2—S1—C1	89.69 (16)	O4—C10—O3	122.6 (3)
C5—S2—C6	89.52 (18)	O4—C10—C9	116.1 (3)
C8—S3—C9	102.43 (18)	O3—C10—C9	121.3 (3)
C8—S3—Co	94.31 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2W^i	0.92	2.09	2.943 (4)	154
N2—H2B···O2^ii	0.92	2.41	3.168 (4)	140
N4—H4A···O3	0.89	2.23	3.003 (4)	144
N4—H4B···O1W^iii	0.85	2.15	2.950 (5)	156
O5—H5A···O4^iv	0.83	1.85	2.656 (3)	165
O5—H5B···O2^ii	0.86	1.90	2.727 (3)	162
O1W—H1C···O5	0.88	2.15	2.879 (4)	141
O1W—H1D···O1^ii	0.94	2.46	3.330 (4)	154
O2W—H2C···S1^v	0.92	2.27	2.994 (3)	135
O2W—H2D···O3	0.89	2.48	3.249 (4)	145
O2W—H2D···O4	0.89	1.92	2.678 (4)	142

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, y−1, z; (iii) −x, y+1/2, −z+3/2; (iv) −x+1, y−1/2, −z+3/2; (v) x, −y+3/2, z+1/2.