catena-Poly[[triaqua­cobalt(II)]-μ-5-hydroxy­benzene-1,3-dicarboxyl­ato-κO¹:O³]

Crystals of the title compound, [Co(C₈H₄O₅)(H₂O)₃]_n, were obtained by hydro­thermal methods. Each Co^II ion is six-coordinated by two O atoms from one 5-hydroxy­benzene-1,3-dicarboxyl­ate (L) ligand, one O atom from another L ligand and three water mol­ecules [Co—O = 2.016 (3)–2.324 (3) Å]. Each ligand L, acting in a tridentate mode, bridges two Co ions, resulting in the formation of polymeric zigzag chains extending along the [110] direction. The crystal packing is stabilized by an extensive network of O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.051
• wR factor = 0.111
• Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level C
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
            identifier.
            amaranthine
CRYSC01_ALERT_1_C No recognised colour has been given for crystal colour.
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.92
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.17 Ratio

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.917
            Tmax scaled      0.651 Tmin scaled      0.559
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT793_ALERT_1_G Check the Absolute Configuration of C8     = ...          R
PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1         (9)       1.19

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

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The design and synthesis of supramolecular architectures based on Metal carboxylate coordination polymer networks has been a field of rapid growth recently due to their fascinating architectures and potential applications in functional materials (Cao et al., 2004; Chui et al., 1999; Lo et al., 2000). It is known that low dimensional coordination polymers can extend to high dimensional networks via noncovalent intermolecular forces such as hydrogen-bonding and π-π stacking interactions (Ghoshal et al., 2003; Wang et al., 2006; Holliday & Mirkin, 2001.) In this paper, we present the crystal structure of the title compound (I), obtained by hydrothermal reaction of 5-hydroxyisophthalic acid (H₂L) with cobalt acetate. The phenol hydroxy group in the ligand L in (I) remains protonated.

In the title compound, [Co(C₈H₄O₅)(H₂O)₃]_n, Co ^II ion is hexacoordinated in a distorted octahedral geometry by three O atoms from two L ligands and three water molecules (Fig. 1). The bond lengths Co1—O1, Co1—O3B, Co1—O4B and Co1—O7 are 2.016 (3) Å, 2.324 (3) Å, 2.076 (3)Å and 2.044 (3) Å, respectively. Atoms O6 and O8 occupy the axial positions with bond lengths Co1—O6 and Co1—O8 of 2.095 (3) and 2.112 (3) Å, respectively [O6—Co1—O8 172.91 (10) °]. Each ligand L acting in a tridentate mode bridges two Co ions, that results in formation of polymeric zigzag chains extended along the direction [110] (Fig. 2). The crystal packing is stabilized by extensive network of O—H···O hydrogen bonds (Table 1, Fig. 3).

Related literature

For applications of metal carboxylate coordination polymers in functional materials, see: Cao et al. (2004); Chui et al. (1999); Lo et al. (2000); For low-dimensional coordination polymers extending to high-dimensional networks via intermolecular forces, see: Ghoshal et al. (2003); Wang et al. (2006); Holliday & Mirkin (2001).

S2. Experimental

All manipulations were carried out in air. A mixture of Co(OAc)₂.6H₂O (92 mg, 0.5 mmol), Et₃ N (54 mg, 0.53 mmol), H₃hdpa (92 mg, 0.5 mmol) and water (10 cm³) were sealed in 23 cm³ Teflon-lined stainless steel parr bomb. The bomb was heated to 393 K for 4 d. Then it was cooled to room temperature to yield amaranthine sheet crystals. Yield: 99 mg (68%).

S3. Refinement

All H atoms were geometrically positioned (C—H 0.93 Å, O—H 0.82–0.89 Å), and refined as riding, with U_iso(H)=1.2U_eq(C, O).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

	Fig. 1. The ORTEP representation of the structure of the title compound showing the atomic numbering and 50% probability displacement ellipsoids [symmetry codes: (A) -1/2 + x, 1/2 + y, 1 - z; (B) 1/2 + x, -1/2 + y, 1 - z]. H atoms omitted for clarity.
	Fig. 2. A portion of polymeric zigzag chain in (I). C-bound H atoms omitted for clarity.
	Fig. 3. A packing diagram viewed down the b axis. Dashed lines indicate hydrogen bonds.

catena-Poly[[triaquacobalt(II)]-µ-5-hydroxybenzene-1,3-dicarboxylato- κO¹:O³]

Crystal data

[Co(C8H4O5)(H2O)3]	F(000) = 1192
Mr = 293.09	Dx = 1.912 Mg m^−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 882 reflections
a = 18.102 (4) Å	θ = 3.8–27.8°
b = 7.4538 (19) Å	µ = 1.72 mm^−1
c = 15.089 (4) Å	T = 293 K
V = 2035.9 (9) Å^3	Clear, amaranthine
Z = 8	0.31 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2005 independent reflections
Radiation source: fine-focus sealed tube	1494 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
φ and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→22
Tmin = 0.61, Tmax = 0.71	k = −5→9
10142 measured reflections	l = −16→18

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 1.22P] where P = (Fo^2 + 2Fc^2)/3
2005 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.58 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
Co1	1.04346 (3)	0.17886 (7)	0.37080 (4)	0.03052 (19)
O1	0.94108 (15)	0.2810 (4)	0.38571 (18)	0.0338 (7)
O2	0.91508 (16)	0.3204 (4)	0.52828 (18)	0.0359 (7)
O3	0.66360 (16)	0.5739 (4)	0.61282 (18)	0.0362 (7)
O4	0.59267 (16)	0.6600 (4)	0.50529 (18)	0.0322 (7)
O5	0.72308 (15)	0.5429 (3)	0.22300 (18)	0.0328 (6)
H9	0.7601	0.5456	0.1917	0.039*
O6	1.08354 (15)	0.4366 (4)	0.34307 (17)	0.0300 (6)
H1	1.1266	0.4413	0.3183	0.036*
H2	1.0836	0.4966	0.3886	0.036*
O7	1.03489 (15)	0.1460 (4)	0.23670 (19)	0.0341 (7)
H5	1.0238	0.2373	0.2012	0.041*
H6	1.0084	0.0595	0.2259	0.041*
O8	1.00636 (15)	−0.0888 (4)	0.38236 (17)	0.0316 (6)
H3	1.0374	−0.1590	0.4108	0.038*
H4	0.9690	−0.0914	0.4131	0.038*
C1	0.8272 (2)	0.4173 (5)	0.4220 (3)	0.0287 (9)
C2	0.7768 (2)	0.4667 (5)	0.4871 (3)	0.0313 (9)
H7	0.7881	0.4493	0.5466	0.038*
C3	0.7096 (2)	0.5416 (5)	0.4635 (3)	0.0295 (9)
C4	0.6928 (2)	0.5694 (5)	0.3739 (3)	0.0271 (8)
H8	0.6483	0.6223	0.3576	0.032*
C5	0.7433 (2)	0.5179 (5)	0.3099 (3)	0.0289 (9)
C6	0.8096 (2)	0.4427 (6)	0.3326 (3)	0.0350 (10)
H10A	0.8429	0.4080	0.2889	0.042*
C7	0.9002 (2)	0.3346 (5)	0.4477 (3)	0.0298 (9)
C8	0.6541 (2)	0.5946 (6)	0.5305 (3)	0.0323 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0279 (3)	0.0322 (3)	0.0314 (3)	0.0038 (2)	−0.0008 (2)	0.0012 (2)
O1	0.0287 (15)	0.0417 (17)	0.0311 (15)	0.0108 (12)	0.0027 (12)	−0.0030 (13)
O2	0.0370 (16)	0.0369 (16)	0.0338 (16)	0.0162 (14)	−0.0071 (13)	−0.0005 (13)
O3	0.0350 (16)	0.0449 (18)	0.0287 (16)	0.0036 (14)	−0.0007 (13)	−0.0015 (13)
O4	0.0322 (16)	0.0316 (15)	0.0329 (15)	0.0075 (12)	0.0006 (13)	−0.0019 (12)
O5	0.0339 (16)	0.0330 (15)	0.0315 (15)	0.0082 (13)	0.0016 (13)	0.0073 (12)
O6	0.0266 (14)	0.0344 (16)	0.0291 (14)	−0.0017 (13)	0.0013 (12)	−0.0052 (12)
O7	0.0356 (16)	0.0332 (15)	0.0333 (15)	0.0006 (13)	−0.0046 (13)	−0.0007 (12)
O8	0.0321 (15)	0.0383 (16)	0.0245 (15)	0.0023 (13)	0.0002 (12)	0.0032 (12)
C1	0.025 (2)	0.031 (2)	0.030 (2)	0.0022 (17)	−0.0002 (17)	0.0009 (16)
C2	0.029 (2)	0.030 (2)	0.034 (2)	0.0048 (18)	−0.0025 (18)	0.0028 (17)
C3	0.028 (2)	0.030 (2)	0.030 (2)	0.0009 (18)	0.0028 (17)	−0.0004 (16)
C4	0.0257 (19)	0.028 (2)	0.0273 (19)	0.0032 (16)	0.0020 (17)	0.0036 (16)
C5	0.027 (2)	0.027 (2)	0.033 (2)	−0.0014 (17)	0.0005 (17)	0.0039 (16)
C6	0.030 (2)	0.036 (2)	0.039 (2)	−0.0010 (19)	0.0057 (19)	0.0000 (19)
C7	0.026 (2)	0.026 (2)	0.037 (2)	−0.0021 (17)	−0.0026 (18)	0.0006 (17)
C8	0.028 (2)	0.034 (2)	0.034 (2)	−0.0020 (18)	−0.0022 (18)	−0.0002 (18)

Geometric parameters (Å, º)

Co1—O1	2.016 (3)	O7—H5	0.8889
Co1—O7	2.044 (3)	O7—H6	0.8200
Co1—O4^i	2.076 (3)	O8—H3	0.8799
Co1—O6	2.095 (3)	O8—H4	0.8200
Co1—O8	2.112 (3)	C1—C2	1.391 (6)
Co1—O3^i	2.324 (3)	C1—C6	1.399 (6)
O1—C7	1.258 (5)	C1—C7	1.510 (5)
O2—C7	1.249 (5)	C2—C3	1.384 (5)
O3—C8	1.264 (5)	C2—H7	0.9300
O3—Co1^ii	2.324 (3)	C3—C4	1.402 (5)
O4—C8	1.272 (5)	C3—C8	1.479 (6)
O4—Co1^ii	2.076 (3)	C4—C5	1.385 (6)
O5—C5	1.374 (5)	C4—H8	0.9300
O5—H9	0.8199	C5—C6	1.367 (6)
O6—H1	0.8645	C6—H10A	0.9300
O6—H2	0.8201
O1—Co1—O7	94.93 (11)	Co1—O8—H4	109.4
O1—Co1—O4^i	108.64 (11)	H3—O8—H4	103.6
O7—Co1—O4^i	156.36 (11)	C2—C1—C6	119.7 (4)
O1—Co1—O6	89.68 (12)	C2—C1—C7	120.1 (4)
O7—Co1—O6	86.47 (11)	C6—C1—C7	120.2 (4)
O4^i—Co1—O6	95.36 (11)	C3—C2—C1	120.1 (4)
O1—Co1—O8	93.16 (12)	C3—C2—H7	119.9
O7—Co1—O8	86.82 (10)	C1—C2—H7	120.0
O4^i—Co1—O8	89.89 (10)	C2—C3—C4	119.9 (4)
O6—Co1—O8	172.91 (10)	C2—C3—C8	122.0 (4)
O1—Co1—O3^i	167.23 (10)	C4—C3—C8	118.1 (4)
O7—Co1—O3^i	97.82 (10)	C5—C4—C3	119.2 (4)
O4^i—Co1—O3^i	58.66 (10)	C5—C4—H8	120.4
O6—Co1—O3^i	90.33 (11)	C3—C4—H8	120.4
O8—Co1—O3^i	88.33 (11)	C6—C5—O5	121.9 (4)
C7—O1—Co1	138.0 (3)	C6—C5—C4	121.2 (4)
C8—O3—Co1^ii	86.3 (2)	O5—C5—C4	116.9 (4)
C8—O4—Co1^ii	97.6 (2)	C5—C6—C1	119.8 (4)
C5—O5—H9	109.6	C5—C6—H10A	120.3
Co1—O6—H1	115.8	C1—C6—H10A	119.9
Co1—O6—H2	109.5	O2—C7—O1	124.8 (4)
H1—O6—H2	109.7	O2—C7—C1	118.3 (4)
Co1—O7—H5	121.5	O1—C7—C1	117.0 (4)
Co1—O7—H6	109.6	O3—C8—O4	117.4 (4)
H5—O7—H6	110.5	O3—C8—C3	123.1 (4)
Co1—O8—H3	113.5	O4—C8—C3	119.5 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H9···O3^iii	0.82	1.84	2.651 (4)	172
O6—H1···O5^iv	0.86	1.86	2.720 (4)	174
O6—H2···O2^v	0.82	1.85	2.655 (4)	166
O7—H5···O8^vi	0.89	1.89	2.773 (4)	173
O7—H6···O6^vii	0.82	2.17	2.913 (4)	151
O8—H3···O2^viii	0.88	1.74	2.612 (4)	170
O8—H4···O4^ix	0.82	1.86	2.634 (4)	158

Symmetry codes: (iii) −x+3/2, y, z−1/2; (iv) x+1/2, −y+1, −z+1/2; (v) −x+2, −y+1, −z+1; (vi) −x+2, y+1/2, −z+1/2; (vii) −x+2, y−1/2, −z+1/2; (viii) −x+2, −y, −z+1; (ix) −x+3/2, −y+1/2, z.