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

The title compound, [Co(C₄H₄O₅)(C₆H₆N₄S₂)(H₂O)]·2H₂O, contains one Co^II complex and two water mol­ecules in the asymmetric unit. The tridentate oxydi­acetate dianion meridionally chelates a Co atom, and both five-membered chelate rings assume an envelope conformation. Di­amino­bi­thia­zole chelates the Co atom, in a planar configuration. Parallel thia­zole rings of neighboring complex mol­ecules are separated by 3.504 (5) Å, suggesting the existence of π–π stacking interactions.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.006 Å
• H-atom completeness 88%
• Disorder in solvent or counterion
• R factor = 0.050
• wR factor = 0.123
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT430_ALERT_2_A Short Inter D...A Contact  O8B    ..  O8C     ..       2.04 Ang.
PLAT430_ALERT_2_A Short Inter D...A Contact  O8C    ..  O8C     ..       2.11 Ang.

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.25 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....        S1'
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      25.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       <O8A
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       <O8C
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT322_ALERT_2_C Check Hybridisation of  S1'    in Main Residue .          ?
PLAT430_ALERT_2_C Short Inter D...A Contact  O8A    ..  O8C     ..       2.89 Ang.

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C10 H16 Co1 N4 O8 S2
            Atom count from the _atom_site data:  C10 H14 Co1 N4 O8 S2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C10 H16 Co N4 O8 S2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         40.00     40.00    0.00
           H         64.00     56.00    8.00
           Co         4.00      4.00    0.00
           N         16.00     16.00    0.00
           O         32.00     32.00    0.00
           S          8.00      8.00    0.00

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

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   9 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku Corporation, 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).

(I)

Crystal data

[Co(C4H4O5)(C6H6N4S2)(H2O)]·2H2O	F(000) = 908
Mr = 443.32	Dx = 1.655 Mg m^−3 Dm = 1.65 Mg m^−3 Dm measured by float by CCl4 and C2H4Br2
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 13082 reflections
a = 16.6389 (11) Å	θ = 2.5–26.0°
b = 10.1097 (8) Å	µ = 1.25 mm^−1
c = 11.205 (3) Å	T = 295 K
β = 109.247 (10)°	Prism, pink
V = 1779.5 (5) Å^3	0.42 × 0.32 × 0.30 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	4045 independent reflections
Radiation source: fine-focus sealed tube	3200 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 10.00 pixels mm^-1	θmax = 27.4°, θmin = 1.9°
ω scans	h = −19→21
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −13→13
Tmin = 0.59, Tmax = 0.69	l = −14→14
15733 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0467P)^2 + 2.3289P] where P = (Fo^2 + 2Fc^2)/3
4045 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.91 e Å^−3
0 restraints	Δρmin = −0.77 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	Occ. (<1)
Co	0.16876 (3)	0.47745 (4)	0.38724 (4)	0.04336 (14)
S1	−0.08549 (7)	0.24899 (13)	0.23464 (14)	0.0880 (4)
S1'	0.15274 (11)	0.40471 (13)	0.79181 (12)	0.0934 (4)
O1	0.15356 (15)	0.6787 (2)	0.3931 (2)	0.0538 (6)
O2	0.20832 (17)	0.8751 (2)	0.3724 (2)	0.0583 (6)
O3	0.29793 (14)	0.5581 (2)	0.4541 (2)	0.0467 (5)
O4	0.24669 (14)	0.3155 (2)	0.3977 (2)	0.0490 (5)
O5	0.37548 (15)	0.2419 (2)	0.4129 (2)	0.0623 (7)
O6	0.16993 (14)	0.5045 (2)	0.1936 (2)	0.0480 (5)
O7	0.1744 (3)	0.0876 (3)	0.5087 (3)	0.1074 (13)
O8A	0.5138 (12)	0.3613 (19)	0.3350 (15)	0.086 (5)	0.25
O8B	0.0118 (8)	0.9259 (15)	0.2410 (16)	0.178 (7)	0.50
O8C	−0.0065 (16)	−0.0324 (17)	0.408 (2)	0.163 (9)	0.25
N2	0.0101 (2)	0.3660 (4)	0.1133 (3)	0.0844 (12)
N2'	0.2729 (3)	0.5298 (4)	0.7203 (3)	0.0856 (11)
N3	0.05382 (18)	0.3777 (3)	0.3336 (3)	0.0548 (7)
N3'	0.1553 (2)	0.4389 (3)	0.5662 (3)	0.0570 (7)
C2	0.0008 (2)	0.3389 (4)	0.2230 (4)	0.0642 (10)
C2'	0.1994 (3)	0.4644 (4)	0.6841 (4)	0.0664 (10)
C4	0.0260 (3)	0.3352 (4)	0.4324 (4)	0.0633 (10)
C4'	0.0805 (3)	0.3695 (4)	0.5580 (4)	0.0642 (10)
C5	−0.0478 (3)	0.2663 (5)	0.3939 (5)	0.0877 (15)
H5	−0.0746	0.2325	0.4482	0.105*
C5'	0.0692 (4)	0.3433 (5)	0.6691 (4)	0.0846 (14)
H5'	0.0228	0.2984	0.6781	0.102*
C11	0.2135 (2)	0.7533 (3)	0.3917 (3)	0.0471 (7)
C12	0.3001 (2)	0.6909 (3)	0.4118 (3)	0.0490 (7)
H12A	0.3128	0.6915	0.3333	0.059*
H12B	0.3440	0.7407	0.4744	0.059*
C13	0.3606 (2)	0.4700 (3)	0.4359 (4)	0.0567 (9)
H13A	0.4115	0.4717	0.5097	0.068*
H13B	0.3758	0.4980	0.3634	0.068*
C14	0.3247 (2)	0.3320 (3)	0.4149 (3)	0.0481 (7)
H2A	0.0584	0.4062	0.1195	0.080*
H2B	−0.0231	0.3406	0.0321	0.080*
H2C	0.3016	0.5559	0.8001	0.080*
H2D	0.2956	0.5587	0.6681	0.080*
H6A	0.1605	0.5912	0.1665	0.080*
H6B	0.2109	0.4652	0.1698	0.080*
H7A	0.1958	0.1665	0.4916	0.080*
H7B	0.1821	0.0176	0.4634	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0454 (2)	0.0369 (2)	0.0496 (3)	−0.00081 (18)	0.01804 (18)	0.00262 (18)
S1	0.0556 (6)	0.0851 (8)	0.1246 (11)	−0.0234 (6)	0.0314 (6)	−0.0006 (7)
S1'	0.1541 (13)	0.0750 (8)	0.0715 (7)	−0.0015 (8)	0.0649 (8)	0.0110 (6)
O1	0.0565 (14)	0.0423 (12)	0.0696 (16)	0.0025 (10)	0.0301 (12)	0.0030 (11)
O2	0.0760 (16)	0.0359 (12)	0.0706 (16)	0.0019 (11)	0.0343 (13)	−0.0020 (11)
O3	0.0504 (12)	0.0355 (11)	0.0533 (13)	0.0006 (9)	0.0160 (10)	−0.0022 (9)
O4	0.0502 (13)	0.0376 (11)	0.0562 (13)	−0.0002 (9)	0.0133 (10)	−0.0007 (10)
O5	0.0533 (14)	0.0468 (13)	0.0746 (17)	0.0113 (11)	0.0044 (12)	−0.0119 (12)
O6	0.0508 (12)	0.0417 (12)	0.0516 (13)	0.0002 (9)	0.0171 (10)	0.0046 (10)
O7	0.185 (4)	0.063 (2)	0.095 (2)	0.031 (2)	0.075 (3)	0.0047 (18)
O8A	0.078 (9)	0.099 (12)	0.080 (10)	0.004 (8)	0.024 (8)	−0.039 (8)
O8B	0.123 (11)	0.184 (14)	0.257 (18)	0.055 (9)	0.103 (12)	0.111 (12)
O8C	0.22 (2)	0.070 (10)	0.166 (19)	0.014 (12)	0.011 (18)	0.023 (11)
N2	0.059 (2)	0.118 (3)	0.067 (2)	−0.034 (2)	0.0070 (17)	−0.003 (2)
N2'	0.110 (3)	0.096 (3)	0.0507 (19)	−0.014 (2)	0.0263 (19)	−0.0051 (19)
N3	0.0502 (16)	0.0498 (16)	0.071 (2)	−0.0027 (13)	0.0295 (15)	0.0027 (14)
N3'	0.078 (2)	0.0463 (16)	0.0557 (18)	0.0029 (14)	0.0343 (16)	0.0031 (13)
C2	0.0434 (19)	0.064 (2)	0.084 (3)	−0.0081 (17)	0.0186 (18)	−0.001 (2)
C2'	0.100 (3)	0.049 (2)	0.061 (2)	0.003 (2)	0.040 (2)	0.0018 (18)
C4	0.069 (2)	0.051 (2)	0.083 (3)	0.0016 (18)	0.043 (2)	0.0036 (19)
C4'	0.082 (3)	0.0434 (19)	0.086 (3)	0.0054 (18)	0.052 (2)	0.0082 (18)
C5	0.077 (3)	0.066 (3)	0.146 (5)	−0.012 (2)	0.071 (3)	0.005 (3)
C5'	0.123 (4)	0.066 (3)	0.087 (3)	−0.014 (3)	0.065 (3)	0.001 (2)
C11	0.063 (2)	0.0379 (17)	0.0450 (17)	0.0006 (14)	0.0243 (15)	−0.0044 (13)
C12	0.0557 (19)	0.0363 (16)	0.0562 (19)	−0.0068 (14)	0.0200 (15)	−0.0055 (14)
C13	0.0440 (18)	0.0465 (18)	0.075 (2)	0.0039 (15)	0.0130 (16)	−0.0090 (17)
C14	0.0490 (18)	0.0439 (17)	0.0436 (17)	0.0059 (14)	0.0049 (13)	−0.0035 (14)

Geometric parameters (Å, º)

Co—O1	2.053 (2)	N2—H2A	0.883
Co—O4	2.068 (2)	N2—H2B	0.931
Co—N3	2.068 (3)	N2'—C2'	1.330 (6)
Co—N3'	2.126 (3)	N2'—H2C	0.903
Co—O3	2.187 (2)	N2'—H2D	0.846
Co—O6	2.193 (2)	N3—C2	1.322 (5)
S1—C5	1.694 (6)	N3—C4	1.401 (5)
S1—C2	1.739 (4)	N3'—C2'	1.307 (5)
S1'—C5'	1.717 (6)	N3'—C4'	1.406 (5)
S1'—C2'	1.744 (4)	C4—C5	1.353 (6)
O1—C11	1.254 (4)	C4—C4'	1.443 (6)
O2—C11	1.249 (4)	C4'—C5'	1.345 (6)
O3—C12	1.429 (4)	C5—H5	0.9300
O3—C13	1.435 (4)	C5'—H5'	0.9300
O4—C14	1.259 (4)	C11—C12	1.520 (5)
O5—C14	1.248 (4)	C12—H12A	0.9700
O6—H6A	0.924	C12—H12B	0.9700
O6—H6B	0.902	C13—C14	1.505 (5)
O7—H7A	0.919	C13—H13A	0.9700
O7—H7B	0.904	C13—H13B	0.9700
N2—C2	1.318 (5)
O1—Co—O4	149.77 (9)	C4'—N3'—Co	113.3 (3)
O1—Co—N3	112.35 (11)	N2—C2—N3	124.4 (3)
O4—Co—N3	97.65 (10)	N2—C2—S1	122.2 (3)
O1—Co—N3'	95.68 (10)	N3—C2—S1	113.4 (3)
O4—Co—N3'	93.46 (10)	N3'—C2'—N2'	124.0 (4)
N3—Co—N3'	79.07 (12)	N3'—C2'—S1'	113.7 (3)
O1—Co—O3	74.78 (9)	N2'—C2'—S1'	122.3 (3)
O4—Co—O3	75.43 (8)	C5—C4—N3	114.0 (4)
N3—Co—O3	172.47 (10)	C5—C4—C4'	130.3 (4)
N3'—Co—O3	98.19 (11)	N3—C4—C4'	115.6 (3)
O1—Co—O6	87.09 (9)	C5'—C4'—N3'	115.4 (4)
O4—Co—O6	86.85 (9)	C5'—C4'—C4	128.4 (4)
N3—Co—O6	94.71 (10)	N3'—C4'—C4	116.2 (3)
N3'—Co—O6	173.76 (11)	C4—C5—S1	111.8 (3)
O3—Co—O6	87.93 (8)	C4—C5—H5	124.1
C5—S1—C2	89.8 (2)	S1—C5—H5	124.1
C5'—S1'—C2'	89.9 (2)	C4'—C5'—S1'	110.3 (4)
C11—O1—Co	119.2 (2)	C4'—C5'—H5'	124.8
C12—O3—C13	116.0 (3)	S1'—C5'—H5'	124.8
C12—O3—Co	111.46 (19)	O2—C11—O1	125.9 (3)
C13—O3—Co	113.44 (18)	O2—C11—C12	116.3 (3)
C14—O4—Co	120.0 (2)	O1—C11—C12	117.9 (3)
Co—O6—H6A	112.83	O3—C12—C11	108.2 (3)
Co—O6—H6B	119.45	O3—C12—H12A	110.0
H6A—O6—H6B	112.6	C11—C12—H12A	110.0
H7A—O7—H7B	115.2	O3—C12—H12B	110.0
C2—N2—H2A	114.0	C11—C12—H12B	110.0
C2—N2—H2B	129.7	H12A—C12—H12B	108.4
H2A—N2—H2B	115.8	O3—C13—C14	109.2 (3)
C2'—N2'—H2C	125.5	O3—C13—H13A	109.8
C2'—N2'—H2D	122.4	C14—C13—H13A	109.8
H2C—N2'—H2D	111.8	O3—C13—H13B	109.8
C2—N3—C4	110.9 (3)	C14—C13—H13B	109.8
C2—N3—Co	133.3 (3)	H13A—C13—H13B	108.3
C4—N3—Co	115.8 (3)	O5—C14—O4	124.8 (3)
C2'—N3'—C4'	110.8 (3)	O5—C14—C13	116.4 (3)
C2'—N3'—Co	135.9 (3)	O4—C14—C13	118.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O6	0.88	2.03	2.875 (4)	161
N2—H2B···O5^i	0.93	1.96	2.817 (4)	152
N2′—H2C···O7^ii	0.90	2.07	2.928 (5)	158
N2′—H2D···O3	0.85	2.41	3.158 (4)	148
O6—H6A···O5^iii	0.92	1.77	2.676 (3)	168
O6—H6B···O2^iv	0.90	1.81	2.711 (4)	176
O7—H7A···O4	0.92	2.16	3.048 (4)	161
O7—H7B···O2^v	0.90	1.90	2.799 (4)	175

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