Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023446/fj2023sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023446/fj2023Isup2.hkl |
CCDC reference: 650691
An aqueous solution (10 ml) of CoCl2.6H2O (0.0238 g, 1 mmol) and a mixture of disodium 1,5-naphthalenedisulfonate (0.0332 g, 1 mmol) and dpp (0.0398 g, 2 mmol) in distilled water (10 ml) were placed in two tubes of an H-tube. Slow diffusion of the two solutions into joint aqueous solution produced deep purple crystals after 1 month (ca 10% yield based on Co).
The atoms C7 and C8 are disordered over two positions. H atoms attached to C atoms were placed in geometrically idealized positions, with Csp3—H = 0.97 Å and Csp2—H= 0.93 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). H atoms attached to O atoms were located in difference Fourier maps and refined with a global Uiso(H) value. The O—H distances are in the range 0.599 (14)–0.947 (15) Å.
As a bipyridine-type ligand with a flexible –CH2CH2CH2– spacer, 1,3-di-4-pyridylpropane (dpp) has been employed to construct novel metal-organic coordination polymers with intriguing structural topologies (Plater et al., 2000; Pan et al., 2001; Biradha et al., 2002; Fu et al., 2003; Wu et al., 2005; Carlucci et al., 2000, 2002; Luan et al., 2005). The 1,5-naphthalenedisulfonate dianion (NDS2-), which possesses six O atoms, has been also employed either as a ligand with multiple binding sites available to construct coordination polymers with varying dimensionalities, or as a counter ion, forming extensive hydrogen-bonding interaction with the water molecules (Cai et al., 2001; Chandrasekhar et al., 2003; Côtê & Shimizu, 2003; Cai, 2004; Gao et al., 2005; Voogt & Blanch, 2005). In the present work, we report a cobalt(II) complex, [Co(C13H14N2)2(H2O)4].(C10H6O6S2).H2O, (I), with a three-dimensional H-bonding network structure created by the sulfonate dianions acting as hydrogen-bond acceptors.
As shown in Fig. 1, four water molecules coordinate to Co(II) ion in the equatorial positions with Co—O bonds (2.1022 (8)–2.1230 (7) Å), while the two dpp ligands coordinate to Co(II) through N atoms [Co—N = 2.1294 (8) Å] in the long axial direction to complete a distorted octahedral coordination (Table 1). The dihedral angle is 58.76 (5)° between the two pyridyl planes, and the N···N distance is 9.121 (5) Å in the same dpp ligand. The NDS dianion, which lies about an inversion site, does not coordinate to the Co(II) ion, but balances the charge.
Hydrogen bonds play an important role for enhancing the stability of the solid-state structure (Table 2). Two intermolecular hydrogen bonds are formed between O atoms of the two coordinated water molecules and two O atoms of sulfonate groups, respectively. An additional intermolecular hydrogen bond is formed between atom O3 of the uncoordinated water molecule and the sulfonate atom O6. All these intermolecular hydrogen bonds result in a two-dimensional structure (Fig. 2). The two-dimensional structures are further linked via another hydrogen bond between uncoordinated N atom of dpp and coordinated O1 atom to give rise to a three-dimensional network (Fig. 3).
For related literature, see: Biradha et al. (2002); Côtê & Shimizu (2003); Cai (2004); Cai et al. (2001); Carlucci et al. (2000, 2002); Chandrasekhar et al. (2003); Fu et al. (2003); Gao et al. (2005); Luan et al. (2005); Pan et al. (2001); Plater et al. (2000); Voogt & Blanch (2005); Wu et al. (2005).
Data collection: RAPID-AUTO (Rigaku 2001); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).
[Co(C13H14N2)2(H2O)4](C10H6O6S2)·H2O | F(000) = 890 |
Mr = 849.82 | Dx = 1.43 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 17625 reflections |
a = 11.844 (2) Å | θ = 1.7–27.5° |
b = 8.3912 (17) Å | µ = 0.61 mm−1 |
c = 20.035 (4) Å | T = 298 K |
β = 97.56 (3)° | Block, pink |
V = 1973.9 (7) Å3 | 0.51 × 0.44 × 0.37 mm |
Z = 2 |
Rigaku R-axis Rapid IP area-detector diffractometer | 3259 reflections with I > 2σ(I) |
ω Oscillation scans | Rint = 0.041 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | θmax = 27.5°, θmin = 1.7° |
Tmin = 0.747, Tmax = 0.807 | h = 0→15 |
17625 measured reflections | k = 0→10 |
4418 independent reflections | l = −25→25 |
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)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0633P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.002 |
4418 reflections | Δρmax = 0.39 e Å−3 |
283 parameters | Δρmin = −0.26 e Å−3 |
0 restraints |
[Co(C13H14N2)2(H2O)4](C10H6O6S2)·H2O | V = 1973.9 (7) Å3 |
Mr = 849.82 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.844 (2) Å | µ = 0.61 mm−1 |
b = 8.3912 (17) Å | T = 298 K |
c = 20.035 (4) Å | 0.51 × 0.44 × 0.37 mm |
β = 97.56 (3)° |
Rigaku R-axis Rapid IP area-detector diffractometer | 4418 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3259 reflections with I > 2σ(I) |
Tmin = 0.747, Tmax = 0.807 | Rint = 0.041 |
17625 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.39 e Å−3 |
4418 reflections | Δρmin = −0.26 e Å−3 |
283 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Co1 | 0 | 0 | 0 | 0.03243 (4) | |
S1 | 0.747491 (16) | 0.35189 (3) | 0.086588 (11) | 0.04424 (6) | |
N1 | 0.05768 (5) | 0.16358 (9) | 0.07838 (3) | 0.03629 (17) | |
N2 | 0.71693 (6) | 0.35709 (11) | 0.35647 (4) | 0.0559 (2) | |
O1 | 0.09129 (4) | −0.18980 (7) | 0.05235 (3) | 0.04155 (16) | |
O2 | −0.14437 (5) | −0.05367 (8) | 0.04662 (3) | 0.04633 (17) | |
O6 | 0.76383 (6) | 0.47271 (9) | 0.13864 (3) | 0.0592 (2) | |
O4 | 0.76400 (5) | 0.19127 (8) | 0.11191 (4) | 0.0585 (2) | |
O5 | 0.81263 (5) | 0.38569 (8) | 0.03177 (3) | 0.05015 (18) | |
C1 | 0.04884 (7) | 0.12998 (12) | 0.14243 (4) | 0.0447 (2) | |
H1 | 0.0158 | 0.0337 | 0.1523 | 0.054* | |
C2 | 0.08631 (7) | 0.23099 (13) | 0.19450 (5) | 0.0498 (3) | |
H2 | 0.0775 | 0.203 | 0.2384 | 0.06* | |
C3 | 0.13715 (6) | 0.37430 (12) | 0.18186 (4) | 0.0434 (2) | |
C4 | 0.14654 (7) | 0.40891 (12) | 0.11582 (5) | 0.0459 (2) | |
H4 | 0.1805 | 0.5036 | 0.1048 | 0.055* | |
C5 | 0.10545 (7) | 0.30265 (11) | 0.06603 (4) | 0.0423 (2) | |
H5 | 0.1113 | 0.3292 | 0.0216 | 0.051* | |
C6 | 0.18164 (8) | 0.48559 (13) | 0.23797 (5) | 0.0579 (3) | 0.5 |
H6A | 0.1227 | 0.5047 | 0.2664 | 0.069* | 0.5 |
H6B | 0.2013 | 0.5869 | 0.2192 | 0.069* | 0.5 |
C7 | 0.28932 (14) | 0.4136 (3) | 0.28140 (9) | 0.0529 (5) | 0.5103 (12) |
H7A | 0.3116 | 0.4813 | 0.3201 | 0.063* | 0.5103 (12) |
H7B | 0.2712 | 0.309 | 0.2976 | 0.063* | 0.5103 (12) |
C8 | 0.38620 (15) | 0.4003 (2) | 0.24030 (10) | 0.0507 (4)* | 0.5103 (12) |
H8A | 0.3953 | 0.4995 | 0.2168 | 0.061* | 0.5103 (12) |
H8B | 0.3711 | 0.3159 | 0.2072 | 0.061* | 0.5103 (12) |
C6' | 0.18164 (8) | 0.48559 (13) | 0.23797 (5) | 0.0579 (3) | 0.5 |
H6'A | 0.1556 | 0.449 | 0.2793 | 0.069* | 0.5 |
H6'B | 0.1496 | 0.5907 | 0.228 | 0.069* | 0.5 |
C7' | 0.31428 (14) | 0.4992 (2) | 0.24959 (10) | 0.0461 (5) | 0.4897 (12) |
H7'A | 0.3413 | 0.5425 | 0.2097 | 0.055* | 0.4897 (12) |
H7'B | 0.3376 | 0.5707 | 0.2869 | 0.055* | 0.4897 (12) |
C8' | 0.36579 (16) | 0.3346 (3) | 0.26491 (11) | 0.0546 (5)* | 0.4897 (12) |
H8'A | 0.3555 | 0.2683 | 0.2249 | 0.066* | 0.4897 (12) |
H8'B | 0.3299 | 0.2828 | 0.3 | 0.066* | 0.4897 (12) |
C9 | 0.49568 (8) | 0.36248 (15) | 0.28889 (6) | 0.0698 (3) | |
C10 | 0.51811 (9) | 0.31754 (17) | 0.35430 (6) | 0.0756 (4) | |
H10 | 0.4588 | 0.2874 | 0.3777 | 0.091* | |
C11 | 0.62792 (9) | 0.31639 (16) | 0.38596 (6) | 0.0682 (4) | |
H11 | 0.6405 | 0.2851 | 0.4309 | 0.082* | |
C12 | 0.69455 (9) | 0.39956 (14) | 0.29287 (5) | 0.0620 (3) | |
H12 | 0.7553 | 0.4277 | 0.2703 | 0.074* | |
C13 | 0.58737 (9) | 0.40483 (16) | 0.25804 (6) | 0.0714 (4) | |
H13 | 0.5769 | 0.4373 | 0.2133 | 0.086* | |
C14 | 0.53333 (7) | 0.23713 (12) | 0.06039 (5) | 0.0537 (3) | |
H14 | 0.5629 | 0.1496 | 0.0853 | 0.064* | |
C15 | 0.60165 (6) | 0.36363 (11) | 0.05135 (4) | 0.0416 (2) | |
C16 | 0.55874 (6) | 0.50062 (10) | 0.01431 (4) | 0.0402 (2) | |
C17 | 0.62546 (7) | 0.63484 (12) | 0.00435 (5) | 0.0509 (3) | |
H17 | 0.7014 | 0.6369 | 0.0233 | 0.061* | |
C18 | 0.58165 (8) | 0.76140 (13) | −0.03229 (6) | 0.0604 (3) | |
H18 | 0.6281 | 0.8479 | −0.0389 | 0.072* | |
O3 | 0.91963 (6) | 0.70891 (10) | 0.13413 (4) | 0.0646 (2) | |
H1B | 0.1124 (8) | −0.2462 (12) | 0.0288 (5) | 0.056 (3)* | |
H2B | −0.1361 (8) | −0.1205 (13) | 0.0732 (5) | 0.069 (3)* | |
H1A | 0.1499 (9) | −0.1651 (14) | 0.0826 (6) | 0.079 (4)* | |
H3A | 0.9564 (10) | 0.6867 (17) | 0.1185 (7) | 0.091 (4)* | |
H2A | −0.1742 (8) | 0.0219 (12) | 0.0639 (5) | 0.054 (3)* | |
H3B | 0.8764 (11) | 0.6151 (19) | 0.1378 (7) | 0.105 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.02614 (5) | 0.04243 (8) | 0.02745 (6) | −0.00126 (6) | −0.00123 (5) | −0.00051 (7) |
S1 | 0.03892 (9) | 0.05174 (12) | 0.04334 (11) | 0.00923 (9) | 0.01024 (8) | 0.00641 (10) |
N1 | 0.0296 (3) | 0.0474 (4) | 0.0306 (3) | −0.0017 (3) | −0.0007 (2) | −0.0010 (3) |
N2 | 0.0445 (3) | 0.0709 (5) | 0.0487 (4) | −0.0011 (4) | −0.0072 (3) | 0.0056 (4) |
O1 | 0.0343 (2) | 0.0515 (3) | 0.0367 (3) | 0.0046 (3) | −0.0036 (2) | −0.0015 (3) |
O2 | 0.0389 (3) | 0.0546 (3) | 0.0462 (3) | −0.0026 (3) | 0.0083 (2) | 0.0012 (3) |
O6 | 0.0601 (3) | 0.0717 (5) | 0.0471 (3) | −0.0018 (3) | 0.0124 (3) | −0.0068 (3) |
O4 | 0.0535 (3) | 0.0603 (4) | 0.0631 (4) | 0.0170 (3) | 0.0132 (3) | 0.0197 (3) |
O5 | 0.0426 (3) | 0.0606 (4) | 0.0503 (3) | 0.0114 (3) | 0.0171 (2) | 0.0075 (3) |
C1 | 0.0445 (4) | 0.0541 (5) | 0.0346 (4) | −0.0113 (4) | 0.0022 (3) | 0.0006 (4) |
C2 | 0.0483 (4) | 0.0692 (6) | 0.0309 (4) | −0.0042 (5) | 0.0019 (3) | −0.0018 (4) |
C3 | 0.0302 (3) | 0.0571 (5) | 0.0413 (4) | 0.0078 (4) | −0.0007 (3) | −0.0121 (4) |
C4 | 0.0426 (4) | 0.0447 (5) | 0.0486 (5) | −0.0033 (4) | −0.0013 (4) | −0.0019 (4) |
C5 | 0.0408 (4) | 0.0521 (5) | 0.0330 (4) | −0.0034 (4) | 0.0014 (3) | 0.0012 (4) |
C6 | 0.0428 (4) | 0.0712 (6) | 0.0564 (5) | 0.0090 (5) | −0.0057 (4) | −0.0288 (5) |
C7 | 0.0462 (8) | 0.0649 (11) | 0.0454 (9) | −0.0040 (9) | −0.0018 (7) | −0.0238 (9) |
C6' | 0.0428 (4) | 0.0712 (6) | 0.0564 (5) | 0.0090 (5) | −0.0057 (4) | −0.0288 (5) |
C7' | 0.0417 (8) | 0.0449 (9) | 0.0483 (9) | −0.0019 (8) | −0.0071 (7) | −0.0075 (9) |
C9 | 0.0473 (4) | 0.0830 (7) | 0.0721 (6) | 0.0170 (5) | −0.0184 (4) | −0.0303 (6) |
C10 | 0.0463 (5) | 0.1014 (9) | 0.0795 (7) | −0.0036 (6) | 0.0099 (5) | −0.0072 (7) |
C11 | 0.0552 (5) | 0.0993 (9) | 0.0486 (5) | 0.0038 (6) | 0.0013 (4) | 0.0113 (6) |
C12 | 0.0591 (5) | 0.0731 (7) | 0.0515 (6) | −0.0039 (6) | −0.0013 (5) | 0.0091 (5) |
C13 | 0.0754 (6) | 0.0836 (8) | 0.0482 (6) | 0.0172 (6) | −0.0180 (5) | −0.0014 (6) |
C14 | 0.0490 (4) | 0.0438 (5) | 0.0695 (6) | 0.0063 (4) | 0.0123 (4) | 0.0179 (5) |
C15 | 0.0371 (3) | 0.0437 (5) | 0.0460 (4) | 0.0070 (4) | 0.0131 (3) | 0.0044 (4) |
C16 | 0.0373 (3) | 0.0387 (4) | 0.0473 (4) | 0.0053 (4) | 0.0151 (3) | 0.0029 (4) |
C17 | 0.0368 (4) | 0.0489 (5) | 0.0680 (6) | 0.0003 (4) | 0.0106 (4) | 0.0100 (5) |
C18 | 0.0460 (4) | 0.0468 (5) | 0.0892 (7) | −0.0055 (4) | 0.0122 (5) | 0.0173 (5) |
O3 | 0.0722 (4) | 0.0668 (5) | 0.0584 (4) | −0.0010 (4) | 0.0218 (3) | 0.0022 (4) |
Co1—O2i | 2.1022 (8) | C7—H7A | 0.97 |
Co1—O2 | 2.1022 (8) | C7—H7B | 0.97 |
Co1—O1 | 2.1230 (7) | C8—C9 | 1.548 (2) |
Co1—O1i | 2.1230 (7) | C8—H8A | 0.97 |
Co1—N1i | 2.1294 (8) | C8—H8B | 0.97 |
Co1—N1 | 2.1294 (8) | C7'—C8' | 1.525 (3) |
S1—O4 | 1.4444 (8) | C7'—H7'A | 0.97 |
S1—O6 | 1.4491 (8) | C7'—H7'B | 0.97 |
S1—O5 | 1.4508 (8) | C8'—C9 | 1.568 (2) |
S1—C15 | 1.7807 (9) | C8'—H8'A | 0.97 |
N1—C1 | 1.3314 (11) | C8'—H8'B | 0.97 |
N1—C5 | 1.3341 (12) | C9—C10 | 1.3559 (17) |
N2—C12 | 1.3161 (13) | C9—C13 | 1.3654 (17) |
N2—C11 | 1.3193 (14) | C10—C11 | 1.3700 (15) |
O1—H1B | 0.735 (10) | C10—H10 | 0.93 |
O1—H1A | 0.884 (10) | C11—H11 | 0.93 |
O2—H2B | 0.771 (11) | C12—C13 | 1.3665 (15) |
O2—H2A | 0.823 (10) | C12—H12 | 0.93 |
C1—C2 | 1.3718 (13) | C13—H13 | 0.93 |
C1—H1 | 0.93 | C14—C15 | 1.3612 (13) |
C2—C3 | 1.3831 (14) | C14—C18ii | 1.4036 (13) |
C2—H2 | 0.93 | C14—H14 | 0.93 |
C3—C4 | 1.3732 (13) | C15—C16 | 1.4252 (12) |
C3—C6 | 1.5026 (13) | C16—C17 | 1.4051 (13) |
C4—C5 | 1.3782 (13) | C16—C16ii | 1.4336 (15) |
C4—H4 | 0.93 | C17—C18 | 1.3549 (14) |
C5—H5 | 0.93 | C17—H17 | 0.93 |
C6—C7 | 1.567 (2) | C18—C14ii | 1.4036 (13) |
C6—H6A | 0.97 | C18—H18 | 0.93 |
C6—H6B | 0.97 | O3—H3A | 0.599 (14) |
C7—C8 | 1.502 (3) | O3—H3B | 0.947 (15) |
O2i—Co1—O2 | 180.00 (3) | C8—C7—H7A | 109.6 |
O2i—Co1—O1 | 89.37 (3) | C6—C7—H7A | 109.6 |
O2—Co1—O1 | 90.63 (3) | C8—C7—H7B | 109.6 |
O2i—Co1—O1i | 90.63 (3) | C6—C7—H7B | 109.6 |
O2—Co1—O1i | 89.37 (3) | H7A—C7—H7B | 108.1 |
O1—Co1—O1i | 180.00 (4) | C7—C8—C9 | 107.91 (14) |
O2i—Co1—N1i | 90.64 (3) | C7—C8—H8A | 110.1 |
O2—Co1—N1i | 89.36 (3) | C9—C8—H8A | 110.1 |
O1—Co1—N1i | 88.50 (3) | C7—C8—H8B | 110.1 |
O1i—Co1—N1i | 91.50 (3) | C9—C8—H8B | 110.1 |
O2i—Co1—N1 | 89.36 (3) | H8A—C8—H8B | 108.4 |
O2—Co1—N1 | 90.64 (3) | C8'—C7'—H7'A | 109.8 |
O1—Co1—N1 | 91.50 (3) | C8'—C7'—H7'B | 109.8 |
O1i—Co1—N1 | 88.50 (3) | H7'A—C7'—H7'B | 108.3 |
N1i—Co1—N1 | 180.00 (4) | C7'—C8'—C9 | 106.09 (15) |
O4—S1—O6 | 113.64 (5) | C7'—C8'—H8'A | 110.5 |
O4—S1—O5 | 112.80 (4) | C9—C8'—H8'A | 110.5 |
O6—S1—O5 | 111.97 (4) | C7'—C8'—H8'B | 110.5 |
O4—S1—C15 | 105.68 (4) | C9—C8'—H8'B | 110.5 |
O6—S1—C15 | 106.11 (5) | H8'A—C8'—H8'B | 108.7 |
O5—S1—C15 | 105.89 (4) | C10—C9—C13 | 116.33 (10) |
C1—N1—C5 | 116.94 (7) | C10—C9—C8 | 134.91 (12) |
C1—N1—Co1 | 121.07 (6) | C13—C9—C8 | 108.20 (12) |
C5—N1—Co1 | 121.99 (6) | C10—C9—C8' | 108.32 (12) |
C12—N2—C11 | 115.63 (9) | C13—C9—C8' | 134.99 (13) |
Co1—O1—H1B | 111.1 (7) | C9—C10—C11 | 120.18 (11) |
Co1—O1—H1A | 117.8 (7) | C9—C10—H10 | 119.9 |
H1B—O1—H1A | 106.7 (10) | C11—C10—H10 | 119.9 |
Co1—O2—H2B | 115.2 (8) | N2—C11—C10 | 123.83 (11) |
Co1—O2—H2A | 116.1 (7) | N2—C11—H11 | 118.1 |
H2B—O2—H2A | 107.0 (11) | C10—C11—H11 | 118.1 |
N1—C1—C2 | 122.92 (9) | N2—C12—C13 | 123.95 (11) |
N1—C1—H1 | 118.5 | N2—C12—H12 | 118 |
C2—C1—H1 | 118.5 | C13—C12—H12 | 118 |
C1—C2—C3 | 120.20 (9) | C9—C13—C12 | 120.08 (11) |
C1—C2—H2 | 119.9 | C9—C13—H13 | 120 |
C3—C2—H2 | 119.9 | C12—C13—H13 | 120 |
C4—C3—C2 | 116.92 (8) | C15—C14—C18ii | 120.14 (9) |
C4—C3—C6 | 121.64 (9) | C15—C14—H14 | 119.9 |
C2—C3—C6 | 121.44 (8) | C18ii—C14—H14 | 119.9 |
C3—C4—C5 | 119.66 (9) | C14—C15—C16 | 121.39 (7) |
C3—C4—H4 | 120.2 | C14—C15—S1 | 117.82 (7) |
C5—C4—H4 | 120.2 | C16—C15—S1 | 120.79 (6) |
N1—C5—C4 | 123.34 (8) | C17—C16—C15 | 123.49 (7) |
N1—C5—H5 | 118.3 | C17—C16—C16ii | 118.91 (10) |
C4—C5—H5 | 118.3 | C15—C16—C16ii | 117.60 (10) |
C3—C6—C7 | 110.84 (11) | C18—C17—C16 | 121.52 (8) |
C3—C6—H6A | 109.5 | C18—C17—H17 | 119.2 |
C7—C6—H6A | 109.5 | C16—C17—H17 | 119.2 |
C3—C6—H6B | 109.5 | C17—C18—C14ii | 120.42 (9) |
C7—C6—H6B | 109.5 | C17—C18—H18 | 119.8 |
H6A—C6—H6B | 108.1 | C14ii—C18—H18 | 119.8 |
C8—C7—C6 | 110.43 (14) | H3A—O3—H3B | 102.7 (16) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O6 | 0.947 (15) | 1.792 (14) | 2.7176 (11) | 164.8 (13) |
O3—H3A···O1iii | 0.599 (14) | 2.436 (14) | 2.9013 (12) | 136.6 (16) |
O2—H2A···O4iv | 0.823 (10) | 1.916 (10) | 2.7363 (11) | 174.6 (10) |
O1—H1B···O5v | 0.735 (10) | 1.979 (10) | 2.7096 (10) | 173.1 (10) |
O1—H1A···N2vi | 0.884 (10) | 1.872 (10) | 2.7495 (12) | 171.3 (11) |
O2—H2B···O3vii | 0.771 (11) | 1.940 (11) | 2.6959 (11) | 166.8 (11) |
Symmetry codes: (iii) x+1, y+1, z; (iv) x−1, y, z; (v) −x+1, −y, −z; (vi) −x+1, y−1/2, −z+1/2; (vii) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C13H14N2)2(H2O)4](C10H6O6S2)·H2O |
Mr | 849.82 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 11.844 (2), 8.3912 (17), 20.035 (4) |
β (°) | 97.56 (3) |
V (Å3) | 1973.9 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.61 |
Crystal size (mm) | 0.51 × 0.44 × 0.37 |
Data collection | |
Diffractometer | Rigaku R-axis Rapid IP area-detector |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.747, 0.807 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17625, 4418, 3259 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.108, 1.02 |
No. of reflections | 4418 |
No. of parameters | 283 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.39, −0.26 |
Computer programs: RAPID-AUTO (Rigaku 2001), RAPID-AUTO, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b) and Mercury (Macrae et al., 2006), SHELXL97 and WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O6 | 0.947 (15) | 1.792 (14) | 2.7176 (11) | 164.8 (13) |
O3—H3A···O1i | 0.599 (14) | 2.436 (14) | 2.9013 (12) | 136.6 (16) |
O2—H2A···O4ii | 0.823 (10) | 1.916 (10) | 2.7363 (11) | 174.6 (10) |
O1—H1B···O5iii | 0.735 (10) | 1.979 (10) | 2.7096 (10) | 173.1 (10) |
O1—H1A···N2iv | 0.884 (10) | 1.872 (10) | 2.7495 (12) | 171.3 (11) |
O2—H2B···O3v | 0.771 (11) | 1.940 (11) | 2.6959 (11) | 166.8 (11) |
Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y, z; (iii) −x+1, −y, −z; (iv) −x+1, y−1/2, −z+1/2; (v) x−1, y−1, z. |
As a bipyridine-type ligand with a flexible –CH2CH2CH2– spacer, 1,3-di-4-pyridylpropane (dpp) has been employed to construct novel metal-organic coordination polymers with intriguing structural topologies (Plater et al., 2000; Pan et al., 2001; Biradha et al., 2002; Fu et al., 2003; Wu et al., 2005; Carlucci et al., 2000, 2002; Luan et al., 2005). The 1,5-naphthalenedisulfonate dianion (NDS2-), which possesses six O atoms, has been also employed either as a ligand with multiple binding sites available to construct coordination polymers with varying dimensionalities, or as a counter ion, forming extensive hydrogen-bonding interaction with the water molecules (Cai et al., 2001; Chandrasekhar et al., 2003; Côtê & Shimizu, 2003; Cai, 2004; Gao et al., 2005; Voogt & Blanch, 2005). In the present work, we report a cobalt(II) complex, [Co(C13H14N2)2(H2O)4].(C10H6O6S2).H2O, (I), with a three-dimensional H-bonding network structure created by the sulfonate dianions acting as hydrogen-bond acceptors.
As shown in Fig. 1, four water molecules coordinate to Co(II) ion in the equatorial positions with Co—O bonds (2.1022 (8)–2.1230 (7) Å), while the two dpp ligands coordinate to Co(II) through N atoms [Co—N = 2.1294 (8) Å] in the long axial direction to complete a distorted octahedral coordination (Table 1). The dihedral angle is 58.76 (5)° between the two pyridyl planes, and the N···N distance is 9.121 (5) Å in the same dpp ligand. The NDS dianion, which lies about an inversion site, does not coordinate to the Co(II) ion, but balances the charge.
Hydrogen bonds play an important role for enhancing the stability of the solid-state structure (Table 2). Two intermolecular hydrogen bonds are formed between O atoms of the two coordinated water molecules and two O atoms of sulfonate groups, respectively. An additional intermolecular hydrogen bond is formed between atom O3 of the uncoordinated water molecule and the sulfonate atom O6. All these intermolecular hydrogen bonds result in a two-dimensional structure (Fig. 2). The two-dimensional structures are further linked via another hydrogen bond between uncoordinated N atom of dpp and coordinated O1 atom to give rise to a three-dimensional network (Fig. 3).