Redetermination of catena-poly­[di­aqua­(oxy­diacetato-O,O′,O′′)­cobalt(II) monohydrate]

The structure of the title compound, catena-poly­[[[di­aqua­cobalt(II)]-μ-oxy­diacetato-κ⁴O,O′,O′′:O′′′)­cobalt(II)] monohydrate], {[Co(C₄H₄O₅)(H₂O)₂]·H₂O}_n, (I), was first de­ter­min­ed and reported by Hatfield et al. [Proc. Indian Acad. Sci. Chem. Sci. (1987), 98, 23–31]. We present here a redetermination, with appreciably improved accuracy and successful location of H atoms. In the crystal structure, oxydi­acetate plays the role of both chelating and bridging ligand, resulting in he formation of polymeric chains of complex mol­ecules along the crystallographic b axis. Water mol­ecules occupy the apical positions, thus completing the coordination octahedron of the Co^II atom. The polymeric chains are interlinked via intermolecular hydrogen bonding between carboxyl­ate and water mol­ecules, forming the three-dimensional supramolecular structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.022
• wR factor = 0.064
• Data-to-parameter ratio = 13.8

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry

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Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); 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).

(I)

Crystal data

[Co(C4H4O5)(H2O)2]·H2O	F(000) = 500
Mr = 245.05	Dx = 1.977 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
a = 7.1220 (12) Å	Cell parameters from 20 reflections
b = 10.3935 (7) Å	θ = 5.0–10.3°
c = 11.1259 (10) Å	µ = 2.10 mm^−1
β = 91.529 (10)°	T = 298 K
V = 823.27 (17) Å^3	Prism, red
Z = 4	0.40 × 0.32 × 0.32 mm

Data collection

Rigaku AFC-7S diffractometer	1458 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 26.0°, θmin = 2.7°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
Tmin = 0.451, Tmax = 0.511	l = −13→13
1757 measured reflections	3 standard reflections every 150 reflections
1624 independent reflections	intensity decay: 0.7%

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.064	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + 0.4775P] where P = (Fo^2 + 2Fc^2)/3
1624 reflections	(Δ/σ)max = 0.001
118 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.33 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	0.42776 (4)	0.39268 (2)	0.19689 (2)	0.02063 (11)
O1	0.20534 (19)	0.28219 (12)	0.26287 (13)	0.0241 (3)
O2	0.0990 (2)	0.08756 (13)	0.30293 (13)	0.0263 (3)
O3	0.5174 (2)	0.20294 (14)	0.18300 (17)	0.0409 (4)
O4	0.6875 (2)	0.40311 (12)	0.11159 (14)	0.0263 (3)
O5	0.9161 (2)	0.29292 (15)	0.02577 (14)	0.0316 (3)
O6	0.2728 (2)	0.38931 (13)	0.03141 (13)	0.0276 (3)
O7	0.5339 (2)	0.40441 (15)	0.37293 (15)	0.0342 (4)
O8	0.8955 (2)	0.33566 (17)	0.40516 (16)	0.0405 (4)
C1	0.2223 (3)	0.16117 (18)	0.26487 (17)	0.0207 (4)
C2	0.3996 (3)	0.10239 (18)	0.2181 (2)	0.0286 (5)
H2A	0.4615	0.0512	0.2804	0.034*
H2B	0.3702	0.0469	0.1501	0.034*
C3	0.6921 (3)	0.17443 (19)	0.1315 (2)	0.0268 (4)
H3A	0.6750	0.1136	0.0660	0.032*
H3B	0.7771	0.1369	0.1914	0.032*
C4	0.7718 (3)	0.29967 (19)	0.08539 (17)	0.0223 (4)
H61	0.2847	0.4578	−0.0147	0.080*
H62	0.1588	0.3667	0.0392	0.080*
H71	0.4852	0.3395	0.4235	0.080*
H72	0.6524	0.3906	0.3648	0.080*
H81	0.8712	0.2601	0.4395	0.080*
H82	0.9911	0.3221	0.3577	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.02085 (16)	0.01253 (15)	0.02889 (17)	0.00075 (9)	0.00784 (11)	0.00096 (9)
O1	0.0251 (7)	0.0135 (6)	0.0340 (8)	−0.0004 (5)	0.0083 (6)	0.0024 (6)
O2	0.0259 (7)	0.0159 (7)	0.0374 (9)	−0.0051 (6)	0.0079 (6)	0.0018 (6)
O3	0.0331 (8)	0.0140 (7)	0.0772 (12)	0.0005 (6)	0.0335 (8)	0.0020 (7)
O4	0.0273 (8)	0.0177 (7)	0.0343 (8)	0.0008 (5)	0.0100 (6)	0.0029 (6)
O5	0.0214 (7)	0.0352 (8)	0.0387 (8)	−0.0023 (6)	0.0109 (6)	−0.0056 (7)
O6	0.0265 (7)	0.0247 (8)	0.0317 (8)	−0.0055 (6)	0.0017 (6)	0.0063 (6)
O7	0.0343 (9)	0.0346 (9)	0.0337 (8)	−0.0038 (7)	0.0025 (7)	0.0056 (6)
O8	0.0353 (9)	0.0370 (9)	0.0498 (10)	0.0034 (7)	0.0122 (8)	0.0075 (8)
C1	0.0229 (9)	0.0180 (9)	0.0213 (9)	−0.0028 (7)	0.0002 (7)	0.0007 (7)
C2	0.0300 (11)	0.0150 (10)	0.0412 (12)	−0.0016 (8)	0.0113 (9)	0.0032 (8)
C3	0.0215 (10)	0.0197 (9)	0.0397 (11)	0.0053 (8)	0.0082 (8)	−0.0004 (9)
C4	0.0180 (9)	0.0254 (10)	0.0235 (9)	−0.0011 (8)	0.0003 (7)	−0.0009 (8)

Geometric parameters (Å, º)

Co—O1	2.1045 (14)	O6—H61	0.883
Co—O2^i	2.0345 (14)	O6—H62	0.852
Co—O3	2.0798 (15)	O7—H71	0.950
Co—O4	2.1041 (15)	O7—H72	0.863
Co—O6	2.1213 (15)	O8—H81	0.892
Co—O7	2.0841 (17)	O8—H82	0.884
O1—C1	1.264 (2)	C1—C2	1.508 (3)
O2—C1	1.247 (2)	C2—H2A	0.970
O3—C2	1.402 (2)	C2—H2B	0.970
O3—C3	1.415 (2)	C3—C4	1.515 (3)
O4—C4	1.269 (2)	C3—H3A	0.970
O5—C4	1.240 (2)	C3—H3B	0.970
O2^i—Co—O3	166.65 (6)	H61—O6—H62	112.81
O2^i—Co—O7	88.42 (6)	Co—O7—H71	112.70
O3—Co—O7	91.20 (7)	Co—O7—H72	102.89
O2^i—Co—O4	91.86 (6)	H71—O7—H72	108.52
O3—Co—O4	74.94 (6)	H81—O8—H82	106.06
O7—Co—O4	96.87 (6)	O2—C1—O1	123.29 (19)
O2^i—Co—O1	118.14 (6)	O2—C1—C2	118.19 (17)
O3—Co—O1	75.16 (6)	O1—C1—C2	118.52 (17)
O7—Co—O1	87.81 (6)	O3—C2—C1	107.87 (16)
O4—Co—O1	149.81 (5)	O3—C2—H2A	110.1
O2^i—Co—O6	88.32 (6)	C1—C2—H2A	110.1
O3—Co—O6	94.21 (7)	O3—C2—H2B	110.1
O7—Co—O6	169.69 (6)	C1—C2—H2B	110.1
O4—Co—O6	93.01 (6)	H2A—C2—H2B	108.4
O1—Co—O6	85.11 (6)	O3—C3—C4	107.37 (16)
C1—O1—Co	118.49 (13)	O3—C3—H3A	110.2
C1—O2—Co^ii	132.67 (14)	C4—C3—H3A	110.2
C2—O3—C3	119.72 (16)	O3—C3—H3B	110.2
C2—O3—Co	119.93 (13)	C4—C3—H3B	110.2
C3—O3—Co	120.24 (12)	H3A—C3—H3B	108.5
C4—O4—Co	119.14 (12)	O5—C4—O4	125.08 (18)
Co—O6—H61	115.82	O5—C4—C3	117.12 (17)
Co—O6—H62	113.04	O4—C4—C3	117.79 (16)
O2^i—Co—O1—C1	−178.86 (13)	O7—Co—O4—C4	92.98 (15)
O3—Co—O1—C1	0.00 (14)	O1—Co—O4—C4	−4.5 (2)
O7—Co—O1—C1	−91.82 (14)	O6—Co—O4—C4	−89.97 (15)
O4—Co—O1—C1	8.1 (2)	Co^ii—O2—C1—O1	173.05 (13)
O6—Co—O1—C1	95.67 (14)	Co^ii—O2—C1—C2	−6.5 (3)
O2^i—Co—O3—C2	176.6 (2)	Co—O1—C1—O2	179.55 (14)
O7—Co—O3—C2	88.42 (18)	Co—O1—C1—C2	−0.9 (2)
O4—Co—O3—C2	−174.79 (19)	C3—O3—C2—C1	−177.86 (18)
O1—Co—O3—C2	1.01 (17)	Co—O3—C2—C1	−1.6 (2)
O6—Co—O3—C2	−82.80 (18)	O2—C1—C2—O3	−178.82 (18)
O2^i—Co—O3—C3	−7.2 (4)	O1—C1—C2—O3	1.6 (3)
O7—Co—O3—C3	−95.37 (17)	C2—O3—C3—C4	171.17 (19)
O4—Co—O3—C3	1.41 (16)	Co—O3—C3—C4	−5.0 (2)
O1—Co—O3—C3	177.21 (18)	Co—O4—C4—O5	173.12 (15)
O6—Co—O3—C3	93.40 (17)	Co—O4—C4—C3	−7.7 (2)
O2^i—Co—O4—C4	−178.39 (15)	O3—C3—C4—O5	−172.72 (18)
O3—Co—O4—C4	3.59 (15)	O3—C3—C4—O4	8.0 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H61···O4^iii	0.88	1.82	2.700 (2)	179
O6—H62···O5^iv	0.85	1.89	2.730 (2)	167
O7—H71···O5^v	0.95	1.86	2.807 (2)	174
O7—H72···O8	0.86	1.87	2.687 (2)	158
O8—H81···O6^vi	0.89	2.00	2.876 (2)	168
O8—H82···O1^vii	0.88	1.92	2.806 (2)	176

Symmetry codes: (iii) −x+1, −y+1, −z; (iv) x−1, y, z; (v) x−1/2, −y+1/2, z+1/2; (vi) x+1/2, −y+1/2, z+1/2; (vii) x+1, y, z.