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Acta Cryst. (2007). E63, m2311    [ doi:10.1107/S1600536807038573 ]

catena-Poly[[diaquabis(methanol)cobalt(II)]-[mu]-phthalato]

C.-Q. Liu, X.-T. Yang, L.-L. An, R. Li and J.-M. Shi

Abstract top

In the crystal structure of the polymeric title compound, [Co([mu]-C8H4O4)(CH3OH)2(H2O)2]n, two independent CoII atoms both occupy special positions with \overline{1} site symmetry. Each CoII atom assumes a distorted octahedral coordination geometry. The phthalate anion acts as a bridging ligand and leads to the formation of a zigzag chain running along the c axis. O-H...O and C-H...O hydrogen bonds connect the chains and result in the formation of a three-dimensional structure.

Comment top

Phthalate anion is a versatile ligand and a large number of multi-nuclear complexes with it as a bridging ligand have been reported (Baca et al., 2003, 2006). Here we report the crystal structure of a novel coordination polymer dealing with phthalate anion, (I).

Fig. 1 shows the asymmetric unit and the symmetry-related fragment of (I). Atoms Co1 and Co2 lie in an inversion centre and are in a distorted octahedral CoO6 coordination geometry (Table 1). Each phthalate anion as a µ2-bridging ligand joins two adjacent CoII atoms with separation of 6.6367 (6) Å and it results in the formation of a zigzag one-dimensional chain along the c axis. The overall crystal structure of (I) is a super-molecular three-dimensional network, which attributes to the connection between chains by the O—H···O and C—H···O hydrogen bonds (Table 2 and Fig. 2).

Related literature top

For related crystal structures, see: Baca et al. (2003, 2006).

Experimental top

A methanol solution (50 ml) containing phthalic acid (3.32 g, 0.02 mol) and cobalt acetate (1.77 g, 0.01 mol) was refluxed for 50 min and the reaction solid was separated and dried. The dried solid (0.2 g) was dissolved in H2O (20 ml) and pink single crystals were obtained after the solution had been allowed to stand at room temperature for about a month.

Refinement top

H atoms of water molecules and hydroxyl groups were located in a difference Fourier map and were refined with distance restraints of O—H = 0.85 (2) Å for water molecules and 0.82 (2) Å for hydroxyl groups, and with Uiso(H) = 1.5Ueq(O). Other H atoms were placed in calculated positions (C—H = 0.93 or 0.96 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The coordination structure of (I), with the atom numbering scheme and thermal ellipsoids drawn at the 30% probability level [symmetry codes: (i) −x + 1, −y, −z + 2; (ii) −x + 1, −y, −z + 1].
[Figure 2] Fig. 2. A packing diagram of (I), showing hydrogen bonds (dashed lines).
catena-Poly[[diaquabis(methanol)cobalt(II)]-µ-phthalato] top
Crystal data top
[Co(C8H4O4)(CH4O)2(H2O)2]F000 = 668
Mr = 323.16Dx = 1.613 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2648 reflections
a = 10.0810 (9) Åθ = 2.6–27.6º
b = 9.9429 (9) ŵ = 1.32 mm−1
c = 13.2735 (12) ÅT = 293 (2) K
β = 90.300 (2)ºPrism, pink
V = 1330.4 (2) Å30.20 × 0.20 × 0.15 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		2351 independent reflections
Radiation source: fine-focus sealed tube2172 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
T = 293(2) Kθmax = 25.1º
φ and ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −6→12
Tmin = 0.778, Tmax = 0.826k = −11→11
5378 measured reflectionsl = −15→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.077H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.133  w = 1/[σ2(Fo2) + (0.0199P)2 + 5.7387P]
where P = (Fo2 + 2Fc2)/3
S = 1.27(Δ/σ)max < 0.001
2351 reflectionsΔρmax = 0.49 e Å−3
193 parametersΔρmin = −0.30 e Å−3
8 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Co(C8H4O4)(CH4O)2(H2O)2]V = 1330.4 (2) Å3
Mr = 323.16Z = 4
Monoclinic, P21/cMo Kα
a = 10.0810 (9) ŵ = 1.32 mm−1
b = 9.9429 (9) ÅT = 293 (2) K
c = 13.2735 (12) Å0.20 × 0.20 × 0.15 mm
β = 90.300 (2)º
Data collection top
Bruker SMART APEX CCD
diffractometer		2351 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2172 reflections with I > 2σ(I)
Tmin = 0.778, Tmax = 0.826Rint = 0.026
5378 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0778 restraints
wR(F2) = 0.133H atoms treated by a mixture of
independent and constrained refinement
S = 1.27Δρmax = 0.49 e Å−3
2351 reflectionsΔρmin = −0.30 e Å−3
193 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Co10.50000.00001.00000.0270 (3)
Co20.50000.00000.50000.0291 (3)
O10.3636 (3)0.1108 (3)0.9162 (3)0.0247 (8)
O20.1792 (4)−0.0057 (4)0.9467 (3)0.0421 (10)
O30.4035 (4)0.1133 (4)0.6087 (3)0.0316 (9)
O40.3505 (4)−0.0417 (3)0.7224 (3)0.0304 (9)
O50.6557 (4)0.1154 (4)0.9317 (3)0.0352 (9)
H20.717 (5)0.087 (7)0.966 (4)0.053*
O60.5027 (5)0.1347 (4)1.1156 (3)0.0374 (10)
H6C0.553 (5)0.120 (6)1.166 (3)0.056*
H6D0.471 (6)0.214 (3)1.117 (4)0.056*
O70.6667 (4)0.1246 (4)0.5157 (4)0.0459 (11)
H10.661 (8)0.198 (4)0.488 (5)0.069*
O80.4320 (4)0.1280 (4)0.3867 (3)0.0343 (10)
H8A0.412 (6)0.210 (3)0.388 (5)0.051*
H8B0.499 (4)0.115 (5)0.349 (4)0.051*
C10.2433 (5)0.0782 (5)0.8981 (4)0.0250 (12)
C20.1755 (5)0.1554 (5)0.8149 (4)0.0273 (12)
C30.0660 (6)0.2309 (6)0.8391 (5)0.0417 (15)
H3A0.03140.22500.90370.050*
C40.0059 (6)0.3155 (7)0.7695 (5)0.0482 (18)
H4A−0.06820.36580.78710.058*
C50.0578 (6)0.3241 (6)0.6739 (5)0.0460 (17)
H5A0.02000.38220.62700.055*
C60.1661 (6)0.2462 (6)0.6475 (5)0.0400 (14)
H6B0.19960.25120.58250.048*
C70.2251 (5)0.1606 (5)0.7175 (4)0.0267 (12)
C80.3358 (5)0.0702 (5)0.6825 (4)0.0236 (12)
C90.6831 (7)0.1107 (7)0.8252 (5)0.0537 (18)
H9A0.75660.16870.81040.080*
H9B0.60640.14000.78820.080*
H9C0.70470.02020.80620.080*
C100.7954 (9)0.0949 (10)0.5518 (8)0.098 (4)
H10A0.84930.17430.54890.147*
H10B0.83410.02590.51080.147*
H10C0.79020.06420.62020.147*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0288 (6)0.0185 (5)0.0336 (6)−0.0006 (5)−0.0035 (4)0.0013 (5)
Co20.0353 (6)0.0198 (5)0.0321 (6)0.0021 (5)0.0001 (5)−0.0005 (5)
O10.0189 (19)0.0197 (18)0.035 (2)−0.0017 (15)−0.0050 (15)0.0037 (16)
O20.037 (2)0.043 (2)0.045 (2)−0.012 (2)−0.0051 (19)0.015 (2)
O30.044 (2)0.0190 (19)0.032 (2)0.0042 (18)0.0052 (18)−0.0024 (16)
O40.051 (3)0.0164 (19)0.0236 (19)0.0067 (17)0.0021 (18)0.0000 (15)
O50.032 (2)0.034 (2)0.040 (2)−0.0033 (19)−0.0020 (18)0.0073 (19)
O60.055 (3)0.022 (2)0.035 (2)0.011 (2)−0.011 (2)−0.0040 (18)
O70.039 (3)0.022 (2)0.076 (3)−0.002 (2)−0.011 (2)0.005 (2)
O80.041 (3)0.023 (2)0.038 (2)0.0115 (19)0.0017 (19)0.0029 (18)
C10.029 (3)0.021 (3)0.025 (3)0.002 (2)−0.002 (2)−0.004 (2)
C20.023 (3)0.024 (3)0.035 (3)0.000 (2)−0.003 (2)−0.003 (2)
C30.032 (3)0.046 (4)0.046 (4)0.013 (3)0.003 (3)−0.002 (3)
C40.032 (3)0.050 (4)0.063 (5)0.021 (3)−0.002 (3)−0.005 (3)
C50.043 (4)0.038 (4)0.057 (4)0.011 (3)−0.012 (3)0.010 (3)
C60.042 (4)0.034 (3)0.043 (3)0.002 (3)−0.005 (3)0.009 (3)
C70.026 (3)0.017 (3)0.037 (3)−0.001 (2)−0.002 (2)−0.002 (2)
C80.037 (3)0.019 (3)0.014 (2)−0.001 (2)−0.007 (2)0.004 (2)
C90.057 (5)0.037 (4)0.067 (5)−0.002 (3)0.008 (4)0.009 (4)
C100.074 (6)0.102 (8)0.118 (8)−0.039 (6)−0.034 (6)0.048 (7)
Geometric parameters (Å, °) top
Co1—O1i2.080 (3)O7—H10.82 (5)
Co1—O12.080 (3)O8—H8A0.84 (3)
Co1—O5i2.148 (4)O8—H8B0.85 (4)
Co1—O52.148 (4)C1—C21.506 (7)
Co1—O62.037 (4)C2—C31.374 (8)
Co1—O6i2.037 (4)C2—C71.389 (8)
Co2—O32.077 (4)C3—C41.386 (9)
Co2—O3ii2.077 (4)C3—H3A0.9300
Co2—O72.098 (4)C4—C51.377 (9)
Co2—O7ii2.098 (4)C4—H4A0.9300
Co2—O8ii2.083 (4)C5—C61.385 (9)
Co2—O82.083 (4)C5—H5A0.9300
O1—C11.277 (6)C6—C71.392 (8)
O2—C11.239 (6)C6—H6B0.9300
O3—C81.271 (6)C7—C81.508 (7)
O4—C81.240 (6)C9—H9A0.9600
O5—C91.443 (8)C9—H9B0.9600
O5—H20.82 (5)C9—H9C0.9600
O6—H6C0.85 (4)C10—H10A0.9600
O6—H6D0.85 (5)C10—H10B0.9600
O7—C101.411 (9)C10—H10C0.9600
O6—Co1—O6i180.000 (1)Co2—O7—H1115 (5)
O6—Co1—O1i86.52 (15)Co2—O8—H8A131 (4)
O6i—Co1—O1i93.48 (15)Co2—O8—H8B94 (4)
O6—Co1—O193.48 (15)H8A—O8—H8B110 (3)
O6i—Co1—O186.52 (15)O2—C1—O1124.8 (5)
O1i—Co1—O1180.000 (1)O2—C1—C2119.3 (5)
O6—Co1—O5i92.29 (17)O1—C1—C2115.8 (5)
O6i—Co1—O5i87.71 (17)C3—C2—C7119.4 (5)
O1i—Co1—O5i88.50 (14)C3—C2—C1118.0 (5)
O1—Co1—O5i91.50 (14)C7—C2—C1122.4 (5)
O6—Co1—O587.71 (17)C2—C3—C4121.6 (6)
O6i—Co1—O592.29 (17)C2—C3—H3A119.2
O1i—Co1—O591.50 (14)C4—C3—H3A119.2
O1—Co1—O588.50 (14)C5—C4—C3119.0 (6)
O5i—Co1—O5180.0C5—C4—H4A120.5
O3—Co2—O3ii180.00 (14)C3—C4—H4A120.5
O3—Co2—O8ii89.05 (15)C4—C5—C6120.2 (6)
O3ii—Co2—O8ii90.95 (15)C4—C5—H5A119.9
O3—Co2—O890.95 (15)C6—C5—H5A119.9
O3ii—Co2—O889.05 (15)C5—C6—C7120.5 (6)
O8ii—Co2—O8180.00 (15)C5—C6—H6B119.8
O3—Co2—O789.33 (17)C7—C6—H6B119.8
O3ii—Co2—O790.67 (17)C2—C7—C6119.3 (5)
O8ii—Co2—O791.63 (17)C2—C7—C8122.4 (5)
O8—Co2—O788.37 (17)C6—C7—C8118.2 (5)
O3—Co2—O7ii90.67 (17)O4—C8—O3124.6 (5)
O3ii—Co2—O7ii89.33 (17)O4—C8—C7119.3 (5)
O8ii—Co2—O7ii88.37 (17)O3—C8—C7115.9 (4)
O8—Co2—O7ii91.63 (17)O5—C9—H9A109.5
O7—Co2—O7ii180.00 (18)O5—C9—H9B109.5
C1—O1—Co1126.2 (3)H9A—C9—H9B109.5
C8—O3—Co2127.4 (3)O5—C9—H9C109.5
C9—O5—Co1122.7 (4)H9A—C9—H9C109.5
C9—O5—H2113 (5)H9B—C9—H9C109.5
Co1—O5—H298 (5)O7—C10—H10A109.5
Co1—O6—H6C119 (4)O7—C10—H10B109.5
Co1—O6—H6D128 (4)H10A—C10—H10B109.5
H6C—O6—H6D112 (3)O7—C10—H10C109.5
C10—O7—Co2130.1 (5)H10A—C10—H10C109.5
C10—O7—H1114 (6)H10B—C10—H10C109.5
O6—Co1—O1—C1−110.5 (4)O2—C1—C2—C7−126.5 (6)
O6i—Co1—O1—C169.5 (4)O1—C1—C2—C756.9 (7)
O5i—Co1—O1—C1−18.1 (4)C7—C2—C3—C4−2.0 (9)
O5—Co1—O1—C1161.9 (4)C1—C2—C3—C4173.3 (6)
O8ii—Co2—O3—C8−43.5 (4)C2—C3—C4—C5−0.1 (10)
O8—Co2—O3—C8136.5 (4)C3—C4—C5—C61.7 (10)
O7—Co2—O3—C8−135.1 (4)C4—C5—C6—C7−1.2 (10)
O7ii—Co2—O3—C844.9 (4)C3—C2—C7—C62.6 (8)
O6—Co1—O5—C9−158.0 (4)C1—C2—C7—C6−172.6 (5)
O6i—Co1—O5—C922.0 (4)C3—C2—C7—C8−173.6 (5)
O1i—Co1—O5—C9115.6 (4)C1—C2—C7—C811.3 (8)
O1—Co1—O5—C9−64.4 (4)C5—C6—C7—C2−1.0 (9)
O3—Co2—O7—C10114.6 (7)C5—C6—C7—C8175.3 (5)
O3ii—Co2—O7—C10−65.4 (7)Co2—O3—C8—O425.4 (7)
O8ii—Co2—O7—C1025.6 (7)Co2—O3—C8—C7−150.5 (4)
O8—Co2—O7—C10−154.4 (7)C2—C7—C8—O428.2 (8)
Co1—O1—C1—O218.8 (8)C6—C7—C8—O4−148.0 (5)
Co1—O1—C1—C2−164.9 (3)C2—C7—C8—O3−155.7 (5)
O2—C1—C2—C358.3 (7)C6—C7—C8—O328.1 (7)
O1—C1—C2—C3−118.3 (6)
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H2···O2i0.82 (5)1.75 (6)2.557 (5)167 (7)
O7—H1···O5iii0.82 (5)2.00 (5)2.817 (6)175 (8)
O6—H6C···O4i0.85 (5)1.93 (5)2.764 (5)165 (6)
O6—H6D···O3iv0.85 (4)1.85 (4)2.699 (5)176 (6)
O8—H8A···O1iii0.84 (3)1.88 (3)2.716 (5)170 (6)
O8—H8B···O4ii0.85 (4)1.94 (5)2.770 (5)166 (5)
C5—H5A···O2v0.932.493.331 (7)150
Symmetry codes: (i) −x+1, −y, −z+2; (iii) x, −y+1/2, z−1/2; (iv) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (v) −x, y+1/2, −z+3/2.
Table 1
Selected geometric parameters (Å) top
Co1—O12.080 (3)Co2—O32.077 (4)
Co1—O52.148 (4)Co2—O72.098 (4)
Co1—O62.037 (4)Co2—O82.083 (4)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H2···O2i0.82 (5)1.75 (6)2.557 (5)167 (7)
O7—H1···O5ii0.82 (5)2.00 (5)2.817 (6)175 (8)
O6—H6C···O4i0.85 (5)1.93 (5)2.764 (5)165 (6)
O6—H6D···O3iii0.85 (4)1.85 (4)2.699 (5)176 (6)
O8—H8A···O1ii0.84 (3)1.88 (3)2.716 (5)170 (6)
O8—H8B···O4iv0.85 (4)1.94 (5)2.770 (5)166 (5)
C5—H5A···O2v0.932.493.331 (7)150
Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, −y+1/2, z−1/2; (iii) x, −y+1/2, z+1/2; (iv) −x+1, −y, −z+1; (v) −x, y+1/2, −z+3/2.
Acknowledgements top

The authors thank the Science Foundation of Xinzhou Teachers' University (grant No. 200501).

references
References top

Baca, S. G., Filippovab, I. G., Gerbeleua, N. V., Simonovb, Y. A., Gdaniecc, M., Timcoa, G. A., Ghercob, O. A. & Malaesteana, Y. L. (2003). Inorg. Chim. Acta, 344, 109–116.

Baca, S. G., Reetz, M. T., Goddard, R., Filippova, I. G., Simonov, Y. A., Gdanied, M. & Gerebeleu, N. (2006). Polyhedron, 25, 1215–1222.

Bruker (1997). SMART (Version 5.6) and SAINT (Version 5.A06). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2001). SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS (Version 2.10). University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.