In the title compound, {[Co(C7H7N2O2)2]·H2O}n, the CoII atom lies on an inversion centre and has octahedral geometry, defined by two O atoms in axial positions and four N atoms in equatorial sites from six different 3,5-diaminobenzoate ligands. Each 3,5-diaminobenzoate anion acts as a μ3-bridging ligand, linking three adjacent CoII ions through one O atom and two N atoms to form a three-dimensional coordination polymer.
Supporting information
CCDC reference: 288620
A mixture of 3,5-diaminobenzoic acid (0.15 g, 1 mmol), CoCl2·6H2O (0.12 g, 0.5 mmol), NaOH (0.04 g, 1 mmol) and water (15 ml) in a Parr Teflon-lined stainless steel vessel (25 ml) autoclave was heated at 413 K in an oven for 4 d. The autoclave was then removed from the oven and allowed to cool naturally to room temperature. Brown block crystals of (I) were obtained in 46% yield. Analysis calculated for C14H16N4O5Co: C 44.30, H 4.22, N 14.77%; found: C 44.46, H 4.20, N 14.82%. IR (KBr, ν, cm−1): 3319 (s), 3265 (m), 1555 (s), 1573 (s), 1387 (vs), 981 (s), 757 (s).
All H atoms were positioned geometrically and treated as riding, with C—H distances of 0.93 Å, N—H distances of 0.90 Å and O—H distances of 0.87 Å, and with Uiso(H) values of 1.2Ueq(C,N) or 1.5Ueq(O).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
Poly[[cobalt(II)-di-µ
3-3,5-diaminobenzoato-
κN:
κN':
κO] monohydrate]
top
Crystal data top
[Co(C7H7N2O2)2)]·H2O | F(000) = 390 |
Mr = 379.24 | Dx = 1.690 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3477 reflections |
a = 7.4666 (6) Å | θ = 2.8–27.9° |
b = 10.0219 (8) Å | µ = 1.19 mm−1 |
c = 10.3856 (8) Å | T = 294 K |
β = 106.444 (1)° | Block, brown |
V = 745.36 (10) Å3 | 0.22 × 0.20 × 0.16 mm |
Z = 2 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1771 independent reflections |
Radiation source: fine-focus sealed tube | 1646 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
ϕ and ω scans | θmax = 27.9°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −9→9 |
Tmin = 0.760, Tmax = 0.820 | k = −13→9 |
4846 measured reflections | l = −13→13 |
Refinement top
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0423P)2 + 0.6967P] where P = (Fo2 + 2Fc2)/3 |
1771 reflections | (Δ/σ)max = 0.003 |
115 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
[Co(C7H7N2O2)2)]·H2O | V = 745.36 (10) Å3 |
Mr = 379.24 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.4666 (6) Å | µ = 1.19 mm−1 |
b = 10.0219 (8) Å | T = 294 K |
c = 10.3856 (8) Å | 0.22 × 0.20 × 0.16 mm |
β = 106.444 (1)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1771 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 1646 reflections with I > 2σ(I) |
Tmin = 0.760, Tmax = 0.820 | Rint = 0.012 |
4846 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.59 e Å−3 |
1771 reflections | Δρmin = −0.35 e Å−3 |
115 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.0000 | 0.0000 | 0.0000 | 0.01493 (11) | |
O1 | 0.27215 (16) | 0.05111 (14) | 0.08842 (13) | 0.0248 (3) | |
O2 | 0.24750 (19) | 0.21828 (18) | 0.22328 (18) | 0.0469 (5) | |
N1 | 0.90098 (19) | 0.29567 (14) | 0.52129 (13) | 0.0181 (3) | |
H1A | 0.9990 | 0.2517 | 0.5749 | 0.022* | |
H1B | 0.8163 | 0.3034 | 0.5677 | 0.022* | |
N2 | 0.96145 (19) | −0.05083 (14) | 0.20216 (14) | 0.0188 (3) | |
H2A | 0.9106 | −0.1328 | 0.1962 | 0.023* | |
H2B | 1.0755 | −0.0559 | 0.2615 | 0.023* | |
C1 | 0.3394 (2) | 0.13543 (18) | 0.18033 (17) | 0.0224 (3) | |
C2 | 0.5485 (2) | 0.13008 (17) | 0.24332 (17) | 0.0203 (3) | |
C3 | 0.6293 (2) | 0.21441 (18) | 0.35034 (18) | 0.0229 (3) | |
H3 | 0.5556 | 0.2745 | 0.3808 | 0.028* | |
C4 | 0.8206 (2) | 0.20865 (16) | 0.41162 (16) | 0.0176 (3) | |
C5 | 0.9317 (2) | 0.12022 (16) | 0.36489 (15) | 0.0177 (3) | |
H5 | 1.0598 | 0.1170 | 0.4054 | 0.021* | |
C6 | 0.8502 (2) | 0.03658 (16) | 0.25718 (16) | 0.0168 (3) | |
C7 | 0.6583 (2) | 0.04102 (17) | 0.19662 (16) | 0.0186 (3) | |
H7 | 0.6039 | −0.0154 | 0.1252 | 0.022* | |
O3 | 0.3745 (11) | 0.9194 (9) | 0.3907 (7) | 0.129 (3) | 0.50 |
H3A | 0.4641 | 0.9080 | 0.4638 | 0.193* | 0.50 |
H3B | 0.4209 | 0.9342 | 0.3261 | 0.193* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.00980 (16) | 0.01681 (17) | 0.01596 (17) | 0.00037 (10) | 0.00003 (11) | −0.00137 (10) |
O1 | 0.0113 (5) | 0.0320 (7) | 0.0277 (6) | −0.0019 (5) | 0.0000 (4) | −0.0115 (5) |
O2 | 0.0171 (6) | 0.0557 (10) | 0.0584 (10) | 0.0085 (6) | −0.0047 (6) | −0.0352 (8) |
N1 | 0.0146 (6) | 0.0197 (7) | 0.0173 (6) | −0.0020 (5) | 0.0000 (5) | −0.0020 (5) |
N2 | 0.0158 (6) | 0.0196 (7) | 0.0205 (6) | 0.0025 (5) | 0.0043 (5) | −0.0003 (5) |
C1 | 0.0128 (7) | 0.0268 (8) | 0.0249 (8) | −0.0006 (6) | 0.0008 (6) | −0.0063 (7) |
C2 | 0.0125 (7) | 0.0229 (8) | 0.0230 (8) | −0.0013 (6) | 0.0010 (6) | −0.0046 (6) |
C3 | 0.0141 (7) | 0.0248 (8) | 0.0273 (8) | 0.0007 (6) | 0.0018 (6) | −0.0089 (7) |
C4 | 0.0152 (7) | 0.0176 (7) | 0.0178 (7) | −0.0036 (6) | 0.0009 (6) | −0.0012 (6) |
C5 | 0.0120 (7) | 0.0207 (7) | 0.0188 (7) | −0.0006 (6) | 0.0015 (5) | 0.0016 (6) |
C6 | 0.0151 (7) | 0.0177 (7) | 0.0178 (7) | 0.0002 (6) | 0.0052 (6) | 0.0017 (6) |
C7 | 0.0144 (7) | 0.0210 (7) | 0.0192 (7) | −0.0025 (6) | 0.0025 (6) | −0.0036 (6) |
O3 | 0.145 (6) | 0.165 (7) | 0.087 (4) | 0.003 (6) | 0.051 (4) | 0.043 (5) |
Geometric parameters (Å, º) top
Co1—O1 | 2.0441 (12) | N2—H2A | 0.9000 |
Co1—O1i | 2.0441 (12) | N2—H2B | 0.9000 |
Co1—N1ii | 2.2094 (14) | C1—C2 | 1.513 (2) |
Co1—N1iii | 2.2095 (14) | C2—C7 | 1.389 (2) |
Co1—N2iv | 2.2567 (14) | C2—C3 | 1.391 (2) |
Co1—N2v | 2.2567 (14) | C3—C4 | 1.391 (2) |
O1—C1 | 1.267 (2) | C3—H3 | 0.9300 |
O2—C1 | 1.238 (2) | C4—C5 | 1.392 (2) |
N1—C4 | 1.425 (2) | C5—C6 | 1.393 (2) |
N1—Co1vi | 2.2094 (14) | C5—H5 | 0.9300 |
N1—H1A | 0.9000 | C6—C7 | 1.393 (2) |
N1—H1B | 0.9000 | C7—H7 | 0.9300 |
N2—C6 | 1.433 (2) | O3—H3A | 0.8655 |
N2—Co1vii | 2.2567 (14) | O3—H3B | 0.8506 |
| | | |
O1—Co1—O1i | 180.0 | C6—N2—H2B | 107.7 |
O1—Co1—N1ii | 87.65 (5) | Co1vii—N2—H2B | 107.7 |
O1i—Co1—N1ii | 92.35 (5) | H2A—N2—H2B | 107.1 |
O1—Co1—N1iii | 92.35 (5) | O2—C1—O1 | 125.23 (16) |
O1i—Co1—N1iii | 87.65 (5) | O2—C1—C2 | 118.50 (15) |
N1ii—Co1—N1iii | 180.0 | O1—C1—C2 | 116.25 (15) |
O1—Co1—N2iv | 90.63 (5) | C7—C2—C3 | 120.27 (15) |
O1i—Co1—N2iv | 89.37 (5) | C7—C2—C1 | 120.70 (14) |
N1ii—Co1—N2iv | 91.05 (5) | C3—C2—C1 | 119.02 (15) |
N1iii—Co1—N2iv | 88.95 (5) | C4—C3—C2 | 119.84 (15) |
O1—Co1—N2v | 89.37 (5) | C4—C3—H3 | 120.1 |
O1i—Co1—N2v | 90.63 (5) | C2—C3—H3 | 120.1 |
N1ii—Co1—N2v | 88.95 (5) | C3—C4—C5 | 120.22 (15) |
N1iii—Co1—N2v | 91.05 (5) | C3—C4—N1 | 119.08 (15) |
N2iv—Co1—N2v | 180.00 (6) | C5—C4—N1 | 120.69 (14) |
C1—O1—Co1 | 129.57 (11) | C4—C5—C6 | 119.68 (14) |
C4—N1—Co1vi | 124.36 (10) | C4—C5—H5 | 120.2 |
C4—N1—H1A | 106.2 | C6—C5—H5 | 120.2 |
Co1vi—N1—H1A | 106.2 | C5—C6—C7 | 120.23 (15) |
C4—N1—H1B | 106.2 | C5—C6—N2 | 121.15 (14) |
Co1vi—N1—H1B | 106.2 | C7—C6—N2 | 118.55 (14) |
H1A—N1—H1B | 106.4 | C2—C7—C6 | 119.76 (15) |
C6—N2—Co1vii | 118.30 (10) | C2—C7—H7 | 120.1 |
C6—N2—H2A | 107.7 | C6—C7—H7 | 120.1 |
Co1vii—N2—H2A | 107.7 | H3A—O3—H3B | 109.2 |
| | | |
O1i—Co1—O1—C1 | 124.8 (17) | C2—C3—C4—N1 | −179.90 (15) |
N1ii—Co1—O1—C1 | −147.16 (16) | Co1vi—N1—C4—C3 | −87.68 (18) |
N1iii—Co1—O1—C1 | 32.84 (16) | Co1vi—N1—C4—C5 | 91.43 (17) |
N2iv—Co1—O1—C1 | −56.13 (16) | C3—C4—C5—C6 | −0.6 (2) |
N2v—Co1—O1—C1 | 123.87 (16) | N1—C4—C5—C6 | −179.70 (14) |
Co1—O1—C1—O2 | −10.4 (3) | C4—C5—C6—C7 | −0.2 (2) |
Co1—O1—C1—C2 | 168.03 (12) | C4—C5—C6—N2 | 176.82 (15) |
O2—C1—C2—C7 | −178.50 (19) | Co1vii—N2—C6—C5 | −107.32 (15) |
O1—C1—C2—C7 | 3.0 (3) | Co1vii—N2—C6—C7 | 69.72 (18) |
O2—C1—C2—C3 | 2.5 (3) | C3—C2—C7—C6 | −0.2 (3) |
O1—C1—C2—C3 | −176.06 (17) | C1—C2—C7—C6 | −179.19 (16) |
C7—C2—C3—C4 | −0.6 (3) | C5—C6—C7—C2 | 0.5 (2) |
C1—C2—C3—C4 | 178.44 (16) | N2—C6—C7—C2 | −176.52 (15) |
C2—C3—C4—C5 | 1.0 (3) | | |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x−1, −y+1/2, z−1/2; (iv) x−1, y, z; (v) −x+1, −y, −z; (vi) −x+1, y+1/2, −z+1/2; (vii) x+1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O3viii | 0.87 | 2.39 | 2.977 (16) | 126 |
N2—H2B···O3ix | 0.90 | 2.27 | 3.165 (8) | 173 |
N2—H2A···O2ii | 0.90 | 2.21 | 3.012 (2) | 148 |
N1—H1A···O2x | 0.90 | 2.07 | 2.8357 (19) | 142 |
Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (viii) −x+1, −y+2, −z+1; (ix) x+1, y−1, z; (x) x+1, −y+1/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Co(C7H7N2O2)2)]·H2O |
Mr | 379.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 7.4666 (6), 10.0219 (8), 10.3856 (8) |
β (°) | 106.444 (1) |
V (Å3) | 745.36 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.19 |
Crystal size (mm) | 0.22 × 0.20 × 0.16 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.760, 0.820 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4846, 1771, 1646 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.659 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.079, 1.05 |
No. of reflections | 1771 |
No. of parameters | 115 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.59, −0.35 |
Selected geometric parameters (Å, º) topCo1—O1 | 2.0441 (12) | Co1—N1iii | 2.2095 (14) |
Co1—O1i | 2.0441 (12) | Co1—N2iv | 2.2567 (14) |
Co1—N1ii | 2.2094 (14) | Co1—N2v | 2.2567 (14) |
| | | |
O1—Co1—O1i | 180.0 | N1ii—Co1—N2iv | 91.05 (5) |
O1—Co1—N1ii | 87.65 (5) | N1iii—Co1—N2iv | 88.95 (5) |
O1i—Co1—N1ii | 92.35 (5) | O1—Co1—N2v | 89.37 (5) |
O1—Co1—N1iii | 92.35 (5) | O1i—Co1—N2v | 90.63 (5) |
O1i—Co1—N1iii | 87.65 (5) | N1ii—Co1—N2v | 88.95 (5) |
N1ii—Co1—N1iii | 180.0 | N1iii—Co1—N2v | 91.05 (5) |
O1—Co1—N2iv | 90.63 (5) | N2iv—Co1—N2v | 180.00 (6) |
O1i—Co1—N2iv | 89.37 (5) | C1—O1—Co1 | 129.57 (11) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, y−1/2, −z+1/2; (iii) x−1, −y+1/2, z−1/2; (iv) x−1, y, z; (v) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O3vi | 0.87 | 2.39 | 2.977 (16) | 126 |
N2—H2B···O3vii | 0.90 | 2.27 | 3.165 (8) | 173 |
N2—H2A···O2ii | 0.90 | 2.21 | 3.012 (2) | 148 |
N1—H1A···O2viii | 0.90 | 2.07 | 2.8357 (19) | 142 |
Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (vi) −x+1, −y+2, −z+1; (vii) x+1, y−1, z; (viii) x+1, −y+1/2, z+1/2. |
In recent years, a large number of metal–organic compounds have been prepared because of the fascinating structural and topological features of these compounds and their potential applications as functional materials, such as catalysts, optical materials and molecule-based magnets (Hagrman et al., 1999; Moulton & Zaworotko, 2001; Janiak, 2003)·In this field, many organic bridging ligands, such as bipyridine, polyaromatic carboxylates and their related species, are often selected to coordinate to metal centres to obtain various types of polymeric structures, including one-, two- and three-dimensional network structures (Blake et al., 1999; Eddaoudi et al., 2001; James, 2003). 3,5-Diaminobenzoic acid, which is a polydenate organic ligand containing two amino groups and a carboxyl group, can be used as a bridging and/or terminal ligand when it coordinates to various metallic ions. Complexes of this ligand with lanthanide metals, yttrium, molybdenum and tin have been reported (Rzaczynska & Belsky, 1994; Rzaczynska & Sobolev, 1994; Rzaczynska et al., 1994; Udovic et al., 1999; Pruchnik et al., 2002, 2003). However, complexes of the first row transition metals with 3,5-diaminobenzoic acid have not yet been published. In this paper, we report the hydrothermal synthesis and structural characterization of the title complex, (I), which exhibits a three-dimensional network structure through bridging by the 3,5-diaminobenzoate anion.
In complex (I), the repeat unit is composed of one CoII atom, two 3,5-diaminobenzoate anions and a solvent water molecule. The CoII atom, lying on an inversion centre, is six-coordinated by four N atoms and two O atoms from different 3,5-diaminobenzoic acid ligands, forming a slightly distorted octahedral coordination geometry about the CoII atom (Fig. 1). The equatorial positions are occupied by the four N atoms. The N2iv—Co1—N2v and N1ii—Co1—N1iii bond angles are both 180°, and the N1ii—Co1—N2iv and N1iii —Co1—N2iv bond angles are 91.05 (5) and 88.95 (5)°, respectively [symmetry codes: (ii) x − 1, −y + 1/2, z − 1/2; (iii) −x + 1, y − 1/2, −z + 1/2; (iv) −x + 1, −y, −z; (v) x − 1, y, z]. The Co—N bond distances are 2.2094 (13) and 2.2567 (13) Å (Table 1). The axial positions are occupied by two O atoms, with the O1—Co1—O1i bond angle being 180° [symmetry code: (i) −x, −y, −z] and the Co—O bond distances being 2.0441 (11) Å. The longer Co1···O2 distance [3.339 Å] and the larger Co1—O1—C1 angle [129.57 (11)°] suggest there is no bonding interaction between atoms Co1 and O2. Thus, the carboxyl group of the 3,5-diaminobenzoate anion coordinates to the CoII atom in monodentate mode (Li et al., 2005).
In complex (I), each 3,5-diaminobenzoic acid anion ligand provides two N atoms of two amino groups and one carboxylate O atom to coordinate to three CoII atoms, thus acting as a µ3-bridging ligand. The bridging of the 3,5-diaminobenzoate anion via its O atom and an N atom links the CoII atoms into a two-dimensional network in the bc plane (Fig. 2). The distance between two adjacent CoII atoms in the plane is 9.267 Å, which is comparable with the largest of several Co···Co distances found for [Co(3,4-pyda)(H2O)2]n·H2O (9.269 Å; 3,4-pyda is the 3,4-pyridinedicarboxylate dianion; Tong et al., 2004). The large Co···Co distance in (I) indicates the absence of any interaction between the CoII atoms. The coordination of another N atom of the 3,5-diaminobenzoate anion (which is not coordinated to a CoII atom within the two-dimensional network) to a CoII ion of an adjacent two-dimensional network leads to the generation of a three-dimensional network of (I) (Fig. 3).
In the extended structure, the uncoordinated carboxyl O atoms, the solvent water molecules and the amino groups of the 3,5-diaminobenzoic acid ligand are involved in hydrogen bonding. The uncoordinated carboxyl O atoms form hydrogen bonds with the amino groups of the 3,5-diaminobenzoate anion [N2—H2A···O2iii 3.012 (2) Å and N1—H1A···O2iv 2.8357 (19) Å], and the solvent water molecules also form hydrogen bonds with the amino groups of the ligand, as well as with other solvent water molecules [N2—H2B···O3ii 3.165 (8) Å and O3—H3A···O3i 2.977 (16) Å]. The geometry of the hydrogen bonding is given in Table 2. The formation of these hydrogen bonds further stabilizes the three-dimensional structure of the complex.