supplementary materials


bg2502 scheme

Acta Cryst. (2013). E69, m252    [ doi:10.1107/S1600536813008933 ]

catena-Poly[[[diaquacobalt(II)]-bis{[mu]-2-[3-(4-carboxylatophenyl)pyridin-1-ium-1-yl]acetato}] dihydrate]

W. Gao and X.-M. Zhang

Abstract top

In the title polymeric coordination compound, {[Co(C14H10NO4)2(H2O)2]·2H2O}n, the CoII ion resides on an inversion center and exhibits a distorted octahedral coordination geometry defined by four O atoms from two pairs of equivalent monodentate carboxylate groups from 2-[3-(4-carboxylatophenyl)pyridin-1-ium-1-yl]acetate ligands and by two O atoms from two equivalent coordinating water molecules. The zwitterionic dicarboxylate ligands serve as bridges with two monodentate carboxylate and the metal ions are linked by double bridges, forming polymeric chains running along [01-1]. The chains are further stabilized and associated into layers parallel to (011) through intra- and interchain hydrogen bonding and [pi]-[pi] stacking interactions [interplanar and centroid-centroid distances of 3.658 (3) Å and 3.653 (2) Å, respectively].

Comment top

The zwitterionic ligands that contain more carboxylate groups than positive groups and hence have reduced negative charge have received little attention in crystal engineering and coordination chemistry (Zhang et al. (2010); Wang et al.. (2009)). The charge on the carboxylate ligand will certainly influence the coordination and supramolecular structures.

In this paper, we report the coordination and hydrogen-bond structure of the title CoII complex (I) derived from the zwitterionic ligand 3-carboxymethylpyridinium-4-benzoate (L).

The asymmetric unit of I contains a CoII ion on a centre of symmetry, one L ligand, one coordinated water molecule, and one lattice water molecule. Each Co atom resides in a distorted octahedral coordination geometry completed by four carboxylate O atoms from four L ligands and two O atoms from two coordinated water molecules. The Co—O distances lie in the range of 2.1031 (12)–2.1392 (14) Å. The L ligand binds two Co atoms through two monodentate carboxylate groups. Consequently, adjacent CoII centers are connected by a pair of zwitterionic ligands to give one-dimensional chains running along [011] (Fig.1). These coordination chains are further reinforced by the π-π interaction between the centrosymmetry-related phenylene groups (the interplanar and center-to-center distances are 3.658 (3) Å and 3.653 (2) Å respectively). Neighboring chains are associated via O—H···O hydrogen bonds mediated by lattice water molecules, which donate one hydrogen atom to a coordinated oxygen carboxylate from one chain and to a coordinated water molecule from another chain. Consequently, the chains are linked into layers (Fig. 2). The hydrogen bonding parameters are listed in Table 1.

Related literature top

For general background to zwitterionic ligands that contain more carboxylate groups than positive groups and hence have reduced negative charge, see: Zhang et al. (2010); Wang et al. (2009). For the synthesis of the ligand, see: Loeb et al. (2006).

Experimental top

The ligand was synthesized from 4-(3-pyridyl)benzoic acid and ethyl bromoacetate according to the procedure for similar compounds (Loeb et al., 2006). A mixture of the ligand (0.024 g, 0.10 mmol) and CoCl2.6H2O (0.010 g, 0.050 mmol) was thoroughly mixed in H2O (2 ml) and CH3OH (2 ml) in a Teflon-lined stainless steel vessel (25 ml), heated at 70°C for two days under autogenous pressure, and then cooled to room temperature. Red block crystals were harvested.

Refinement top

All the hydrogen atoms attached to carbon atoms were placed in calculated positions and refined using the riding model, and the water hydrogen atoms were located from the difference maps.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The one-dimensional coordination chain with the π-π stacking and hydrogen bonds intrachain the chains. The intrachain hydrogen bonds and π-π stacking are shown as dot lines. [Symmetry codes: (i)-x + 1, -y + 1, -z + 1 (iii) -x + 1, -y, -z + 2 (iv)x, y + 1, z - 1]
[Figure 2] Fig. 2. The two-dimensional layer assembled through hydrogen bonding interactions. [Symmetry codes: (i)-x + 1, -y + 1, -z + 1 (v)-x + 1, -y + 1, -z]
catena-Poly[[[diaquacobalt(II)]-bis{µ-2-[3-(4-carboxylatophenyl)pyridin-1-ium-1-yl]acetato}] dihydrate] top
Crystal data top
[Co(C14H10NO4)2(H2O)2]·2H2OV = 636.57 (4) Å3
Mr = 643.45Z = 1
Triclinic, P1F(000) = 333
Hall symbol: -P 1Dx = 1.679 Mg m3
a = 7.5943 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.9123 (3) ŵ = 0.75 mm1
c = 10.7673 (4) ÅT = 296 K
α = 88.769 (1)°Block, red
β = 81.681 (1)°0.10 × 0.08 × 0.06 mm
γ = 83.920 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2477 independent reflections
Radiation source: fine-focus sealed tube2449 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
phi and ω scansθmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 99
Tmin = 0.929, Tmax = 0.956k = 99
7933 measured reflectionsl = 1013
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0573P)2 + 0.4307P]
where P = (Fo2 + 2Fc2)/3
2477 reflections(Δ/σ)max < 0.001
208 parametersΔρmax = 0.42 e Å3
3 restraintsΔρmin = 0.43 e Å3
Crystal data top
[Co(C14H10NO4)2(H2O)2]·2H2Oγ = 83.920 (1)°
Mr = 643.45V = 636.57 (4) Å3
Triclinic, P1Z = 1
a = 7.5943 (3) ÅMo Kα radiation
b = 7.9123 (3) ŵ = 0.75 mm1
c = 10.7673 (4) ÅT = 296 K
α = 88.769 (1)°0.10 × 0.08 × 0.06 mm
β = 81.681 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2477 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
2449 reflections with I > 2σ(I)
Tmin = 0.929, Tmax = 0.956Rint = 0.015
7933 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.091Δρmax = 0.42 e Å3
S = 1.05Δρmin = 0.43 e Å3
2477 reflectionsAbsolute structure: ?
208 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
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
Co10.50000.00001.00000.01887 (13)
C10.1280 (2)0.2122 (2)1.01741 (17)0.0240 (4)
C20.0189 (2)0.2764 (2)0.93891 (16)0.0236 (4)
H2A0.12650.22270.96830.028*
H2B0.04680.39820.94960.028*
C30.0277 (3)0.0817 (2)0.76392 (18)0.0262 (4)
H3A0.02350.00160.81820.031*
C40.0928 (3)0.0397 (2)0.64190 (19)0.0305 (4)
H4A0.08610.06910.61310.037*
C50.1687 (3)0.1600 (2)0.56150 (18)0.0280 (4)
H5A0.21780.13030.47970.034*
C60.1715 (2)0.3251 (2)0.60302 (17)0.0218 (4)
C70.1054 (2)0.3596 (2)0.72797 (17)0.0219 (4)
H7A0.10750.46810.75900.026*
C80.2383 (2)0.4612 (2)0.51779 (16)0.0217 (4)
C90.2396 (2)0.4480 (2)0.38854 (17)0.0243 (4)
H9A0.19950.35320.35640.029*
C100.3003 (2)0.5750 (2)0.30783 (17)0.0237 (4)
H10A0.30120.56400.22190.028*
C110.3597 (2)0.7182 (2)0.35321 (16)0.0221 (4)
C120.3616 (2)0.7305 (2)0.48192 (17)0.0235 (4)
H12A0.40380.82460.51350.028*
C130.3014 (2)0.6043 (2)0.56340 (16)0.0239 (4)
H13A0.30280.61480.64910.029*
C140.4175 (2)0.8612 (2)0.26645 (17)0.0225 (4)
O10.23496 (18)0.08802 (17)0.97274 (13)0.0280 (3)
O20.1218 (2)0.2815 (2)1.12000 (14)0.0381 (4)
O30.4574 (2)0.99102 (19)0.31444 (13)0.0371 (4)
O40.41823 (18)0.83772 (17)0.14971 (12)0.0268 (3)
O50.5063 (2)0.20597 (18)0.87341 (14)0.0309 (3)
H5C0.629 (4)0.250 (4)0.867 (3)0.046*
H5B0.504 (4)0.150 (4)0.806 (3)0.046*
O60.3383 (3)0.4835 (3)0.0904 (2)0.0637 (6)
H6A0.437 (4)0.402 (3)0.100 (4)0.096*
H6B0.399 (5)0.578 (3)0.108 (4)0.096*
N10.03825 (19)0.23849 (19)0.80482 (14)0.0213 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.02626 (19)0.01584 (18)0.01403 (18)0.00255 (12)0.00149 (12)0.00310 (12)
C10.0299 (9)0.0220 (9)0.0202 (9)0.0061 (7)0.0021 (7)0.0069 (7)
C20.0257 (8)0.0247 (9)0.0185 (8)0.0008 (7)0.0008 (7)0.0034 (7)
C30.0321 (9)0.0213 (9)0.0253 (9)0.0061 (7)0.0028 (7)0.0064 (7)
C40.0403 (11)0.0208 (9)0.0299 (10)0.0037 (8)0.0029 (8)0.0005 (8)
C50.0342 (10)0.0267 (9)0.0212 (9)0.0012 (8)0.0002 (7)0.0008 (7)
C60.0225 (8)0.0227 (9)0.0196 (8)0.0007 (7)0.0023 (6)0.0046 (7)
C70.0252 (8)0.0193 (8)0.0212 (9)0.0030 (7)0.0037 (7)0.0048 (7)
C80.0217 (8)0.0227 (9)0.0189 (9)0.0004 (6)0.0003 (6)0.0056 (7)
C90.0276 (9)0.0244 (9)0.0211 (9)0.0038 (7)0.0032 (7)0.0028 (7)
C100.0255 (8)0.0283 (9)0.0164 (8)0.0003 (7)0.0022 (6)0.0049 (7)
C110.0212 (8)0.0241 (9)0.0191 (9)0.0012 (7)0.0003 (6)0.0066 (7)
C120.0277 (9)0.0220 (9)0.0202 (9)0.0018 (7)0.0021 (7)0.0025 (7)
C130.0292 (9)0.0256 (9)0.0156 (8)0.0011 (7)0.0011 (7)0.0028 (7)
C140.0250 (8)0.0226 (9)0.0183 (8)0.0007 (7)0.0003 (6)0.0043 (7)
O10.0301 (7)0.0252 (7)0.0285 (7)0.0012 (5)0.0071 (5)0.0014 (5)
O20.0499 (9)0.0381 (8)0.0265 (7)0.0040 (7)0.0121 (6)0.0041 (6)
O30.0628 (10)0.0288 (7)0.0219 (7)0.0151 (7)0.0066 (7)0.0050 (6)
O40.0387 (7)0.0241 (6)0.0173 (6)0.0066 (5)0.0011 (5)0.0055 (5)
O50.0476 (9)0.0226 (7)0.0229 (7)0.0053 (6)0.0060 (6)0.0021 (5)
O60.0462 (10)0.0515 (11)0.0891 (16)0.0104 (9)0.0100 (10)0.0085 (11)
N10.0232 (7)0.0222 (7)0.0179 (7)0.0008 (6)0.0031 (6)0.0050 (6)
Geometric parameters (Å, º) top
Co1—O4i2.1031 (12)C7—N11.346 (2)
Co1—O4ii2.1031 (12)C7—H7A0.9300
Co1—O12.1184 (13)C8—C91.396 (3)
Co1—O1iii2.1184 (13)C8—C131.400 (3)
Co1—O5iii2.1392 (14)C9—C101.387 (3)
Co1—O52.1392 (14)C9—H9A0.9300
C1—O21.236 (2)C10—C111.387 (3)
C1—O11.263 (2)C10—H10A0.9300
C1—C21.533 (3)C11—C121.394 (2)
C2—N11.474 (2)C11—C141.512 (2)
C2—H2A0.9700C12—C131.385 (3)
C2—H2B0.9700C12—H12A0.9300
C3—N11.340 (2)C13—H13A0.9300
C3—C41.370 (3)C14—O31.244 (2)
C3—H3A0.9300C14—O41.274 (2)
C4—C51.387 (3)O4—Co1iv2.1031 (12)
C4—H4A0.9300O5—H5C0.95 (3)
C5—C61.393 (3)O5—H5B0.85 (3)
C5—H5A0.9300O6—H6A0.927 (18)
C6—C71.389 (3)O6—H6B0.924 (18)
C6—C81.483 (2)
O4i—Co1—O4ii180.0C5—C6—C8122.02 (17)
O4i—Co1—O186.13 (5)N1—C7—C6120.95 (16)
O4ii—Co1—O193.87 (5)N1—C7—H7A119.5
O4i—Co1—O1iii93.87 (5)C6—C7—H7A119.5
O4ii—Co1—O1iii86.13 (5)C9—C8—C13118.49 (16)
O1—Co1—O1iii180.000 (1)C9—C8—C6119.86 (16)
O4i—Co1—O5iii88.97 (5)C13—C8—C6121.65 (16)
O4ii—Co1—O5iii91.03 (5)C10—C9—C8120.49 (17)
O1—Co1—O5iii88.79 (6)C10—C9—H9A119.8
O1iii—Co1—O5iii91.21 (6)C8—C9—H9A119.8
O4i—Co1—O591.03 (5)C11—C10—C9121.02 (16)
O4ii—Co1—O588.97 (5)C11—C10—H10A119.5
O1—Co1—O591.21 (6)C9—C10—H10A119.5
O1iii—Co1—O588.79 (6)C10—C11—C12118.66 (16)
O5iii—Co1—O5180.0C10—C11—C14121.32 (16)
O2—C1—O1127.55 (18)C12—C11—C14120.01 (17)
O2—C1—C2116.33 (17)C13—C12—C11120.78 (17)
O1—C1—C2115.98 (16)C13—C12—H12A119.6
N1—C2—C1111.06 (14)C11—C12—H12A119.6
N1—C2—H2A109.4C12—C13—C8120.54 (16)
C1—C2—H2A109.4C12—C13—H13A119.7
N1—C2—H2B109.4C8—C13—H13A119.7
C1—C2—H2B109.4O3—C14—O4125.88 (17)
H2A—C2—H2B108.0O3—C14—C11117.89 (16)
N1—C3—C4119.77 (17)O4—C14—C11116.22 (16)
N1—C3—H3A120.1C1—O1—Co1132.41 (12)
C4—C3—H3A120.1C14—O4—Co1iv127.67 (12)
C3—C4—C5119.77 (18)Co1—O5—H5C100.6 (17)
C3—C4—H4A120.1Co1—O5—H5B99.2 (19)
C5—C4—H4A120.1H5C—O5—H5B102 (2)
C4—C5—C6120.13 (18)H6A—O6—H6B98 (2)
C4—C5—H5A119.9C3—N1—C7121.83 (16)
C6—C5—H5A119.9C3—N1—C2118.73 (15)
C7—C6—C5117.43 (16)C7—N1—C2119.39 (15)
C7—C6—C8120.53 (16)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y1, z+1; (iii) x+1, y, z+2; (iv) x, y+1, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5C···O2iii0.95 (3)1.91 (3)2.835 (2)164 (3)
O5—H5B···O3i0.85 (3)1.80 (3)2.617 (2)162 (3)
O6—H6A···O4v0.93 (2)2.13 (2)3.003 (2)156 (3)
O6—H6B···O5iv0.92 (2)1.96 (2)2.880 (2)173 (4)
Symmetry codes: (i) x+1, y+1, z+1; (iii) x+1, y, z+2; (iv) x, y+1, z1; (v) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5C···O2i0.95 (3)1.91 (3)2.835 (2)164 (3)
O5—H5B···O3ii0.85 (3)1.80 (3)2.617 (2)162 (3)
O6—H6A···O4iii0.927 (18)2.13 (2)3.003 (2)156 (3)
O6—H6B···O5iv0.924 (18)1.961 (18)2.880 (2)173 (4)
Symmetry codes: (i) x+1, y, z+2; (ii) x+1, y+1, z+1; (iii) x+1, y+1, z; (iv) x, y+1, z1.
Acknowledgements top

We are thankful for financial support from the NSFC (21201069) and the Natural Science Foundation of Anhui Province (1308085QB23).

references
References top

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