Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049288/cv2314sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049288/cv2314Isup2.hkl |
CCDC reference: 667154
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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).
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%).
All H atoms were geometrically positioned (C—H 0.93 Å, O—H 0.82–0.89 Å), and refined as riding, with Uiso(H)=1.2Ueq(C, O).
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).
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).
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).
[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) Å3 | Clear, amaranthine |
Z = 8 | 0.31 × 0.30 × 0.25 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.05P)2 + 1.22P] where P = (Fo2 + 2Fc2)/3 |
2005 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
[Co(C8H4O5)(H2O)3] | V = 2035.9 (9) Å3 |
Mr = 293.09 | Z = 8 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 18.102 (4) Å | µ = 1.72 mm−1 |
b = 7.4538 (19) Å | T = 293 K |
c = 15.089 (4) Å | 0.31 × 0.30 × 0.25 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2005 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1494 reflections with I > 2σ(I) |
Tmin = 0.61, Tmax = 0.71 | Rint = 0.061 |
10142 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.45 e Å−3 |
2005 reflections | Δρmin = −0.58 e Å−3 |
154 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Co1—O1 | 2.016 (3) | O7—H5 | 0.8889 |
Co1—O7 | 2.044 (3) | O7—H6 | 0.8200 |
Co1—O4i | 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—O3i | 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—Co1ii | 2.324 (3) | C3—C4 | 1.402 (5) |
O4—C8 | 1.272 (5) | C3—C8 | 1.479 (6) |
O4—Co1ii | 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—O4i | 108.64 (11) | H3—O8—H4 | 103.6 |
O7—Co1—O4i | 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) |
O4i—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 |
O4i—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—O3i | 167.23 (10) | C4—C3—C8 | 118.1 (4) |
O7—Co1—O3i | 97.82 (10) | C5—C4—C3 | 119.2 (4) |
O4i—Co1—O3i | 58.66 (10) | C5—C4—H8 | 120.4 |
O6—Co1—O3i | 90.33 (11) | C3—C4—H8 | 120.4 |
O8—Co1—O3i | 88.33 (11) | C6—C5—O5 | 121.9 (4) |
C7—O1—Co1 | 138.0 (3) | C6—C5—C4 | 121.2 (4) |
C8—O3—Co1ii | 86.3 (2) | O5—C5—C4 | 116.9 (4) |
C8—O4—Co1ii | 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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H9···O3iii | 0.82 | 1.84 | 2.651 (4) | 172 |
O6—H1···O5iv | 0.86 | 1.86 | 2.720 (4) | 174 |
O6—H2···O2v | 0.82 | 1.85 | 2.655 (4) | 166 |
O7—H5···O8vi | 0.89 | 1.89 | 2.773 (4) | 173 |
O7—H6···O6vii | 0.82 | 2.17 | 2.913 (4) | 151 |
O8—H3···O2viii | 0.88 | 1.74 | 2.612 (4) | 170 |
O8—H4···O4ix | 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. |
Experimental details
Crystal data | |
Chemical formula | [Co(C8H4O5)(H2O)3] |
Mr | 293.09 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 293 |
a, b, c (Å) | 18.102 (4), 7.4538 (19), 15.089 (4) |
V (Å3) | 2035.9 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.72 |
Crystal size (mm) | 0.31 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.61, 0.71 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10142, 2005, 1494 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.111, 1.03 |
No. of reflections | 2005 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.58 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H9···O3i | 0.82 | 1.84 | 2.651 (4) | 172.4 |
O6—H1···O5ii | 0.86 | 1.86 | 2.720 (4) | 173.9 |
O6—H2···O2iii | 0.82 | 1.85 | 2.655 (4) | 165.7 |
O7—H5···O8iv | 0.89 | 1.89 | 2.773 (4) | 173.1 |
O7—H6···O6v | 0.82 | 2.17 | 2.913 (4) | 151.4 |
O8—H3···O2vi | 0.88 | 1.74 | 2.612 (4) | 169.8 |
O8—H4···O4vii | 0.82 | 1.86 | 2.634 (4) | 158.0 |
Symmetry codes: (i) −x+3/2, y, z−1/2; (ii) x+1/2, −y+1, −z+1/2; (iii) −x+2, −y+1, −z+1; (iv) −x+2, y+1/2, −z+1/2; (v) −x+2, y−1/2, −z+1/2; (vi) −x+2, −y, −z+1; (vii) −x+3/2, −y+1/2, z. |
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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).