Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026359/bh2098sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026359/bh2098Isup2.hkl |
CCDC reference: 654772
An aqueous solution (20 ml) of benzene-1,3,5-tricarboxylic acid (H3BTC) (0.96 g, 0.5 mmol) and NaOH (0.04 g, 1 mmol) was added into an aqueous solution (10 ml) of Ni(CH3CO2)2.2H2O (0.12 g, 0.5 mmol) under stirring. The resulting solution was filtered and a solution of 4,4'-bipy (0.05 g, 0.5 mmol in 15 ml e thanol) was added dropwise. After 15 days, green crystals suitable for X-ray single-crystal diffraction studies were collected by filtration and washed with ethanol. Yield: 68%.
A lattice water molecule with occupancy 1/2 is disordered over two sites, O13w and O14w, with 1/4 occupancy for each. The C-bonded H atoms were placed geometrically and refined with C—H bond lengths constrained to 0.93 Å and Uiso(H) = 1.2Ueq(carrier C). H atoms of water molecules and hydroxy group were clearly visible in a difference map, and were included in the refinement as riding atoms after regularizing some bond lengths [O—H in the range 0.82 to 0.97 Å] and with fixed isotropic displacement parameters: Uiso(H) = 1.2Ueq(carrier O).
Benzenetricarboxylate (BTC) ligands are universal bridging ligands in the construction of a number of coordination networks (Yaghi et al., 1996; Wei & Han, 2005; Guo et al., 2006; Eddaoudi et al., 2001). In this paper, we present the synthesis and structural characterization of a new coordination polymer of trinuclear NiII units bridged by BTC ligands, {[Ni3Na(OH)(C9H3O6)2(H2O)11].1.5H2O}n, (I), which was synthesized by the reaction of nickel(II) salt with H3BTC in basic conditions. The title compound is isomorphous with the CoII complex published by Cheng et al. (2004).
As shown in Fig. 1, the asymmetric unit contains three crystallographically independent NiII centers, which are all octahedrally coordinated by six O atoms, which are from two BTC carboxylate groups, one OH- unit and three aqua ligands (Table 2). The three NiII ions are bridged by three bidentate carboxylates of three BTC ligands, two aqua ligands and one OH- anion, to form a new trinuclear metal cluster. The NaI ion is coordinated by six water molecules, and the distorted octahedron is attached to the trinuclear unit though two bridging aqua ligands.
The BTC ligands exhibit two different coordination modes in (I). In the first one, the BTC ligand acts as a bidentate ligand bridging two NiII centers, while another one acts as a tetradentate ligand linking four NiII centers of neighboring trinuclear units to form a one-dimensional zigzag chain (Fig. 2). The chains are further connected into a three-dimensional framework through a complex hydrogen bonding scheme involving water molecules and carboxylate groups of BTC (Table 3 and Fig. 3). The hydrogen bonds D···A separations range from 2.597 to 3.437 Å.
For related literature, see: Guo et al. (2006) Yaghi et al. (1996); Wei & Han (2005); Eddaoudi et al. (2001); Cheng et al. (2004).
Data collection: SMART (Siemens, 1994); cell refinement: SMART; data reduction: XPREP (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.
[Ni3Na(OH)(C9H3O6)2(H2O)11]·1.5H2O | F(000) = 3472 |
Mr = 855.56 | Dx = 1.921 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | θ = 3.2–27.5° |
a = 18.842 (5) Å | µ = 2.03 mm−1 |
b = 14.557 (4) Å | T = 293 K |
c = 21.343 (6) Å | Prism, green |
V = 5854 (3) Å3 | 0.18 × 0.12 × 0.10 mm |
Z = 8 |
Siemens SMART CCD area-detector diffractometer | 6693 independent reflections |
Radiation source: fine-focus sealed tube | 2994 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.133 |
φ and ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1995) | h = −24→17 |
Tmin = 0.712, Tmax = 0.820 | k = −18→18 |
43629 measured reflections | l = −27→27 |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0069P)2] where P = (Fo2 + 2Fc2)/3 |
6693 reflections | (Δ/σ)max = 0.003 |
442 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
[Ni3Na(OH)(C9H3O6)2(H2O)11]·1.5H2O | V = 5854 (3) Å3 |
Mr = 855.56 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 18.842 (5) Å | µ = 2.03 mm−1 |
b = 14.557 (4) Å | T = 293 K |
c = 21.343 (6) Å | 0.18 × 0.12 × 0.10 mm |
Siemens SMART CCD area-detector diffractometer | 6693 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1995) | 2994 reflections with I > 2σ(I) |
Tmin = 0.712, Tmax = 0.820 | Rint = 0.133 |
43629 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.67 e Å−3 |
6693 reflections | Δρmin = −0.64 e Å−3 |
442 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.30004 (5) | 0.96049 (7) | 0.12261 (4) | 0.0209 (2) | |
Ni2 | 0.46166 (5) | 0.96371 (7) | 0.21056 (4) | 0.0221 (2) | |
Ni3 | 0.43621 (5) | 0.85216 (7) | 0.09272 (4) | 0.0203 (2) | |
Na1 | 0.4108 (2) | 1.2046 (2) | 0.12750 (16) | 0.0479 (10) | |
O1 | 0.4066 (2) | 0.9715 (3) | 0.1299 (2) | 0.0177 (11) | |
H1A | 0.4240 | 1.0227 | 0.1043 | 0.021* | |
O1W | 0.4691 (3) | 0.8171 (3) | 0.1864 (2) | 0.0231 (12) | |
H1WA | 0.5168 | 0.7924 | 0.1890 | 0.028* | |
H1WB | 0.4356 | 0.7785 | 0.2088 | 0.028* | |
O2W | 0.5213 (3) | 0.9412 (4) | 0.2905 (2) | 0.0386 (16) | |
H2WB | 0.5444 | 0.9874 | 0.2987 | 0.046* | |
H2WA | 0.4947 | 0.9292 | 0.3198 | 0.046* | |
O3W | 0.4550 (3) | 0.7222 (3) | 0.0684 (2) | 0.0298 (13) | |
H3WB | 0.4190 | 0.6916 | 0.0737 | 0.036* | |
H3WA | 0.4961 | 0.7169 | 0.0563 | 0.036* | |
O4W | 0.2878 (3) | 1.1036 (3) | 0.1260 (2) | 0.0302 (14) | |
H4B | 0.2642 | 1.1176 | 0.1568 | 0.036* | |
H4A | 0.2685 | 1.1279 | 0.1019 | 0.036* | |
O5W | 0.4611 (3) | 1.1076 (3) | 0.2207 (2) | 0.0246 (13) | |
H5WA | 0.5016 | 1.1258 | 0.2271 | 0.030* | |
H5WB | 0.4339 | 1.1225 | 0.2579 | 0.030* | |
O6W | 0.3608 (4) | 1.2973 (5) | 0.2047 (3) | 0.072 (2) | |
H6WA | 0.3423 | 1.3423 | 0.1883 | 0.087* | |
H6WB | 0.3846 | 1.2941 | 0.2368 | 0.087* | |
O7W | 0.3552 (3) | 1.2859 (4) | 0.0450 (2) | 0.0418 (16) | |
H7WA | 0.3798 | 1.2827 | 0.0134 | 0.050* | |
H7WB | 0.3161 | 1.2630 | 0.0383 | 0.050* | |
O8W | 0.4635 (3) | 1.1087 (4) | 0.0522 (2) | 0.0359 (15) | |
H8WB | 0.4396 | 1.1093 | 0.0201 | 0.043* | |
H8WA | 0.5037 | 1.1268 | 0.0445 | 0.043* | |
O9W | 0.5163 (4) | 1.2981 (5) | 0.1248 (3) | 0.087 (3) | |
H9WA | 0.5434 | 1.2818 | 0.1527 | 0.105* | |
H9WB | 0.5359 | 1.2926 | 0.0907 | 0.105* | |
O10W | 0.9046 (4) | 0.5735 (5) | 0.3553 (3) | 0.081 (3) | |
H10A | 0.8738 | 0.5572 | 0.3800 | 0.097* | |
H10B | 0.8799 | 0.6114 | 0.3355 | 0.097* | |
O11 | 0.4002 (3) | 0.8816 (4) | 0.0019 (2) | 0.0244 (13) | |
O11W | 0.3286 (3) | 0.8147 (3) | 0.1170 (2) | 0.0216 (12) | |
H11A | 0.3248 | 0.7825 | 0.1567 | 0.026* | |
H11B | 0.3040 | 0.7817 | 0.0841 | 0.026* | |
O12 | 0.3000 (3) | 0.9568 (4) | 0.0280 (2) | 0.0255 (12) | |
O12W | 0.1917 (3) | 0.9377 (4) | 0.1137 (2) | 0.0382 (15) | |
H12B | 0.1780 | 0.9051 | 0.1426 | 0.046* | |
H12C | 0.1826 | 0.9074 | 0.0746 | 0.046* | |
O13 | 0.0850 (3) | 0.8013 (4) | −0.1728 (2) | 0.0396 (16) | |
O14 | 0.0847 (3) | 0.8387 (4) | −0.0716 (2) | 0.0366 (15) | |
O15 | 0.3123 (3) | 0.7961 (4) | −0.2849 (2) | 0.0501 (19) | |
O16 | 0.4126 (3) | 0.7897 (4) | −0.2299 (2) | 0.0346 (15) | |
O21 | 0.5430 (3) | 0.8863 (3) | 0.0806 (2) | 0.0200 (11) | |
O22 | 0.5552 (3) | 0.9755 (3) | 0.1659 (2) | 0.0225 (12) | |
O23 | 0.8758 (3) | 0.8365 (4) | 0.0208 (2) | 0.0412 (17) | |
O24 | 0.7754 (3) | 0.7999 (3) | −0.0298 (2) | 0.0241 (13) | |
O25 | 0.8776 (3) | 0.9416 (4) | 0.2330 (2) | 0.0346 (15) | |
O26 | 0.7764 (3) | 0.9579 (4) | 0.2863 (2) | 0.0328 (14) | |
C11 | 0.3022 (4) | 0.8840 (5) | −0.0699 (3) | 0.0214 (17) | |
C12 | 0.2288 (4) | 0.8807 (5) | −0.0723 (3) | 0.0202 (17) | |
H12A | 0.2027 | 0.9008 | −0.0379 | 0.024* | |
C13 | 0.1934 (4) | 0.8482 (5) | −0.1249 (3) | 0.0220 (17) | |
C14 | 0.2331 (4) | 0.8259 (5) | −0.1778 (3) | 0.0243 (18) | |
H14A | 0.2100 | 0.8074 | −0.2142 | 0.029* | |
C15 | 0.3057 (5) | 0.8311 (5) | −0.1770 (3) | 0.0244 (18) | |
C16 | 0.3418 (4) | 0.8565 (5) | −0.1224 (3) | 0.0231 (17) | |
H16A | 0.3911 | 0.8552 | −0.1209 | 0.028* | |
C17 | 0.3378 (5) | 0.9104 (5) | −0.0088 (3) | 0.0238 (18) | |
C18 | 0.1150 (5) | 0.8302 (6) | −0.1236 (4) | 0.030 (2) | |
C19 | 0.3468 (5) | 0.8048 (5) | −0.2348 (4) | 0.032 (2) | |
C21 | 0.6585 (4) | 0.9124 (4) | 0.1226 (3) | 0.0140 (15) | |
C22 | 0.6952 (4) | 0.8773 (5) | 0.0710 (3) | 0.0198 (17) | |
H22A | 0.6701 | 0.8592 | 0.0356 | 0.024* | |
C23 | 0.7686 (4) | 0.8689 (5) | 0.0717 (3) | 0.0173 (16) | |
C24 | 0.8055 (4) | 0.8929 (4) | 0.1251 (3) | 0.0170 (16) | |
H24A | 0.8547 | 0.8884 | 0.1255 | 0.020* | |
C25 | 0.7701 (4) | 0.9238 (5) | 0.1788 (3) | 0.0188 (17) | |
C26 | 0.6972 (4) | 0.9336 (5) | 0.1762 (3) | 0.0182 (16) | |
H26A | 0.6733 | 0.9550 | 0.2114 | 0.022* | |
C27 | 0.5799 (4) | 0.9255 (5) | 0.1228 (3) | 0.0183 (16) | |
C28 | 0.8090 (5) | 0.8336 (5) | 0.0160 (3) | 0.0253 (19) | |
C29 | 0.8120 (4) | 0.9432 (5) | 0.2376 (3) | 0.0231 (18) | |
O13W | 0.5621 (14) | 0.9796 (16) | 0.4849 (11) | 0.071 (7) | 0.25 |
H13A | 0.5628 | 0.9379 | 0.5108 | 0.086* | 0.25 |
H13B | 0.5850 | 0.9712 | 0.4574 | 0.086* | 0.25 |
O14W | 0.4786 (16) | 0.975 (2) | 0.4410 (12) | 0.088 (9) | 0.25 |
H14B | 0.4782 | 0.9293 | 0.4187 | 0.105* | 0.25 |
H14C | 0.5106 | 0.9997 | 0.4106 | 0.105* | 0.25 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0187 (6) | 0.0275 (5) | 0.0165 (5) | 0.0014 (5) | 0.0001 (4) | −0.0005 (4) |
Ni2 | 0.0183 (6) | 0.0295 (6) | 0.0186 (5) | −0.0004 (5) | 0.0007 (4) | −0.0014 (4) |
Ni3 | 0.0170 (5) | 0.0255 (5) | 0.0184 (5) | −0.0001 (5) | −0.0008 (4) | −0.0022 (4) |
Na1 | 0.049 (3) | 0.055 (2) | 0.040 (2) | 0.015 (2) | −0.0016 (19) | −0.0046 (18) |
O1 | 0.015 (3) | 0.023 (3) | 0.016 (2) | −0.002 (2) | −0.005 (2) | 0.000 (2) |
O1W | 0.018 (3) | 0.025 (3) | 0.026 (3) | −0.002 (2) | 0.000 (2) | 0.007 (2) |
O2W | 0.040 (4) | 0.053 (4) | 0.022 (3) | −0.008 (3) | −0.006 (3) | 0.000 (3) |
O3W | 0.016 (3) | 0.033 (3) | 0.041 (3) | −0.004 (3) | −0.002 (3) | −0.008 (2) |
O4W | 0.038 (4) | 0.027 (3) | 0.026 (3) | 0.016 (3) | 0.001 (3) | −0.001 (2) |
O5W | 0.018 (3) | 0.030 (3) | 0.026 (3) | −0.004 (3) | 0.004 (2) | −0.011 (2) |
O6W | 0.100 (7) | 0.070 (5) | 0.047 (4) | 0.024 (5) | 0.022 (4) | 0.013 (4) |
O7W | 0.035 (4) | 0.055 (4) | 0.035 (3) | 0.002 (3) | 0.003 (3) | −0.008 (3) |
O8W | 0.027 (4) | 0.053 (4) | 0.027 (3) | −0.008 (3) | 0.003 (3) | 0.007 (3) |
O9W | 0.066 (6) | 0.111 (7) | 0.085 (5) | −0.013 (5) | 0.012 (5) | −0.043 (5) |
O10W | 0.092 (7) | 0.067 (5) | 0.083 (6) | −0.010 (5) | 0.021 (5) | −0.011 (4) |
O11 | 0.017 (3) | 0.041 (3) | 0.015 (3) | 0.001 (3) | −0.004 (2) | −0.003 (2) |
O11W | 0.025 (3) | 0.020 (3) | 0.021 (3) | −0.002 (2) | −0.002 (2) | −0.001 (2) |
O12 | 0.027 (3) | 0.031 (3) | 0.018 (3) | 0.009 (3) | −0.003 (2) | −0.003 (2) |
O12W | 0.025 (4) | 0.056 (4) | 0.034 (3) | −0.004 (3) | 0.001 (3) | −0.009 (3) |
O13 | 0.026 (4) | 0.066 (4) | 0.027 (3) | −0.011 (3) | −0.008 (3) | 0.014 (3) |
O14 | 0.021 (3) | 0.050 (4) | 0.039 (3) | −0.004 (3) | 0.003 (3) | −0.002 (3) |
O15 | 0.048 (5) | 0.081 (5) | 0.021 (3) | 0.018 (4) | −0.012 (3) | −0.014 (3) |
O16 | 0.030 (4) | 0.045 (4) | 0.029 (3) | 0.006 (3) | 0.005 (3) | −0.013 (3) |
O21 | 0.012 (3) | 0.027 (3) | 0.021 (3) | −0.003 (2) | 0.000 (2) | −0.004 (2) |
O22 | 0.017 (3) | 0.029 (3) | 0.021 (3) | −0.002 (2) | 0.006 (2) | −0.007 (2) |
O23 | 0.019 (3) | 0.068 (5) | 0.037 (3) | −0.001 (3) | 0.007 (3) | −0.024 (3) |
O24 | 0.027 (3) | 0.029 (3) | 0.017 (3) | 0.003 (3) | −0.002 (2) | −0.007 (2) |
O25 | 0.020 (3) | 0.064 (4) | 0.020 (3) | 0.000 (3) | −0.005 (3) | −0.004 (3) |
O26 | 0.023 (3) | 0.059 (4) | 0.017 (3) | 0.009 (3) | 0.002 (2) | −0.003 (3) |
C11 | 0.019 (4) | 0.027 (4) | 0.018 (4) | −0.007 (4) | 0.001 (3) | 0.005 (3) |
C12 | 0.020 (5) | 0.027 (4) | 0.014 (3) | 0.000 (3) | 0.001 (3) | 0.000 (3) |
C13 | 0.019 (4) | 0.023 (4) | 0.024 (4) | 0.005 (4) | 0.000 (4) | 0.004 (3) |
C14 | 0.025 (5) | 0.022 (4) | 0.025 (4) | −0.003 (4) | −0.010 (4) | 0.001 (3) |
C15 | 0.032 (5) | 0.026 (4) | 0.015 (4) | −0.004 (4) | −0.002 (4) | −0.004 (3) |
C16 | 0.020 (5) | 0.026 (4) | 0.023 (4) | 0.000 (4) | −0.006 (3) | −0.001 (3) |
C17 | 0.030 (5) | 0.021 (4) | 0.021 (4) | −0.007 (4) | 0.003 (4) | 0.001 (3) |
C18 | 0.024 (5) | 0.041 (5) | 0.024 (4) | −0.004 (4) | 0.002 (4) | 0.008 (4) |
C19 | 0.042 (6) | 0.026 (5) | 0.027 (4) | 0.006 (4) | 0.006 (4) | −0.003 (4) |
C21 | 0.011 (4) | 0.016 (4) | 0.015 (3) | 0.005 (3) | 0.000 (3) | −0.002 (3) |
C22 | 0.016 (4) | 0.024 (4) | 0.019 (4) | 0.003 (3) | −0.002 (3) | −0.003 (3) |
C23 | 0.012 (4) | 0.023 (4) | 0.017 (3) | −0.004 (3) | 0.000 (3) | 0.005 (3) |
C24 | 0.015 (4) | 0.020 (4) | 0.015 (3) | 0.003 (3) | −0.005 (3) | −0.004 (3) |
C25 | 0.025 (5) | 0.019 (4) | 0.012 (3) | 0.000 (3) | 0.000 (3) | 0.000 (3) |
C26 | 0.015 (4) | 0.026 (4) | 0.013 (3) | −0.004 (3) | 0.008 (3) | −0.001 (3) |
C27 | 0.017 (4) | 0.025 (4) | 0.013 (3) | −0.006 (3) | 0.004 (3) | 0.004 (3) |
C28 | 0.026 (5) | 0.031 (5) | 0.019 (4) | −0.001 (4) | 0.011 (4) | −0.001 (3) |
C29 | 0.021 (5) | 0.022 (4) | 0.027 (4) | 0.000 (4) | −0.006 (4) | 0.001 (3) |
O13W | 0.127 (19) | 0.028 (17) | 0.059 (16) | −0.004 (15) | 0.020 (15) | 0.029 (13) |
O14W | 0.08 (3) | 0.03 (2) | 0.16 (2) | −0.005 (19) | 0.038 (18) | 0.035 (17) |
Ni1—O26i | 1.995 (5) | O11W—H11A | 0.9700 |
Ni1—O12 | 2.021 (4) | O11W—H11B | 0.9700 |
Ni1—O1 | 2.021 (5) | O12—C17 | 1.257 (8) |
Ni1—O12W | 2.077 (5) | O12W—H12B | 0.8200 |
Ni1—O4W | 2.098 (5) | O12W—H12C | 0.9595 |
Ni1—O11W | 2.193 (5) | O13—C18 | 1.265 (9) |
Ni2—O22 | 2.011 (5) | O14—C18 | 1.253 (8) |
Ni2—O1 | 2.013 (4) | O15—C19 | 1.260 (9) |
Ni2—O25i | 2.016 (5) | O16—C19 | 1.263 (10) |
Ni2—O2W | 2.069 (5) | O21—C27 | 1.273 (8) |
Ni2—O5W | 2.106 (5) | O22—C27 | 1.262 (8) |
Ni2—O1W | 2.200 (5) | O23—C28 | 1.262 (9) |
Ni3—O1 | 1.989 (5) | O24—C28 | 1.265 (8) |
Ni3—O3W | 1.993 (5) | O25—C29 | 1.241 (9) |
Ni3—O21 | 2.088 (5) | O25—Ni2ii | 2.016 (5) |
Ni3—O11 | 2.099 (5) | O26—C29 | 1.255 (8) |
Ni3—O1W | 2.155 (4) | O26—Ni1ii | 1.995 (5) |
Ni3—O11W | 2.162 (5) | C11—C12 | 1.385 (10) |
Na1—O6W | 2.329 (7) | C11—C16 | 1.403 (10) |
Na1—O8W | 2.348 (6) | C11—C17 | 1.516 (10) |
Na1—O7W | 2.367 (6) | C12—C13 | 1.388 (9) |
Na1—O9W | 2.410 (8) | C12—H12A | 0.9300 |
Na1—O5W | 2.616 (6) | C13—C14 | 1.394 (10) |
Na1—O4W | 2.744 (7) | C13—C18 | 1.500 (10) |
O1—H1A | 0.9800 | C14—C15 | 1.370 (11) |
O1W—H1WA | 0.9700 | C14—H14A | 0.9300 |
O1W—H1WB | 0.9700 | C15—C16 | 1.401 (9) |
O2W—H2WB | 0.8200 | C15—C19 | 1.505 (10) |
O2W—H2WA | 0.8201 | C16—H16A | 0.9300 |
O3W—H3WB | 0.8200 | C21—C26 | 1.392 (9) |
O3W—H3WA | 0.8201 | C21—C22 | 1.397 (9) |
O4W—H4B | 0.8200 | C21—C27 | 1.494 (10) |
O4W—H4A | 0.7223 | C22—C23 | 1.389 (10) |
O5W—H5WA | 0.8200 | C22—H22A | 0.9300 |
O5W—H5WB | 0.9699 | C23—C24 | 1.379 (9) |
O6W—H6WA | 0.8200 | C23—C28 | 1.502 (9) |
O6W—H6WB | 0.8194 | C24—C25 | 1.400 (9) |
O7W—H7WA | 0.8200 | C24—H24A | 0.9300 |
O7W—H7WB | 0.8199 | C25—C26 | 1.382 (10) |
O8W—H8WB | 0.8200 | C25—C29 | 1.510 (9) |
O8W—H8WA | 0.8200 | C26—H26A | 0.9300 |
O9W—H9WA | 0.8200 | O13W—O14W | 1.83 (4) |
O9W—H9WB | 0.8197 | O13W—H13A | 0.8200 |
O10W—H10A | 0.8200 | O13W—H13B | 0.7389 |
O10W—H10B | 0.8363 | O14W—H14B | 0.8200 |
O11—C17 | 1.267 (9) | O14W—H14C | 0.9557 |
O26i—Ni1—O12 | 166.8 (2) | H5WA—O5W—H5WB | 106.5 |
O26i—Ni1—O1 | 98.6 (2) | Na1—O6W—H6WA | 108.9 |
O12—Ni1—O1 | 94.5 (2) | Na1—O6W—H6WB | 109.6 |
O26i—Ni1—O12W | 82.3 (2) | H6WA—O6W—H6WB | 129.8 |
O12—Ni1—O12W | 84.5 (2) | Na1—O7W—H7WA | 109.4 |
O1—Ni1—O12W | 175.3 (2) | Na1—O7W—H7WB | 108.9 |
O26i—Ni1—O4W | 87.7 (2) | H7WA—O7W—H7WB | 109.9 |
O12—Ni1—O4W | 93.5 (2) | Na1—O8W—H8WB | 109.5 |
O1—Ni1—O4W | 91.6 (2) | Na1—O8W—H8WA | 109.7 |
O12W—Ni1—O4W | 93.1 (2) | H8WB—O8W—H8WA | 109.6 |
O26i—Ni1—O11W | 95.1 (2) | Na1—O9W—H9WA | 109.5 |
O12—Ni1—O11W | 85.39 (19) | Na1—O9W—H9WB | 109.8 |
O1—Ni1—O11W | 80.59 (18) | H9WA—O9W—H9WB | 109.7 |
O12W—Ni1—O11W | 94.7 (2) | H10A—O10W—H10B | 97.0 |
O4W—Ni1—O11W | 172.0 (2) | C17—O11—Ni3 | 122.3 (5) |
O22—Ni2—O1 | 92.37 (19) | Ni3—O11W—Ni1 | 89.96 (17) |
O22—Ni2—O25i | 170.2 (2) | Ni3—O11W—H11A | 113.7 |
O1—Ni2—O25i | 96.6 (2) | Ni1—O11W—H11A | 113.7 |
O22—Ni2—O2W | 85.9 (2) | Ni3—O11W—H11B | 113.6 |
O1—Ni2—O2W | 173.7 (2) | Ni1—O11W—H11B | 113.6 |
O25i—Ni2—O2W | 84.7 (2) | H11A—O11W—H11B | 110.9 |
O22—Ni2—O5W | 88.2 (2) | C17—O12—Ni1 | 129.7 (5) |
O1—Ni2—O5W | 91.67 (19) | Ni1—O12W—H12B | 109.4 |
O25i—Ni2—O5W | 95.4 (2) | Ni1—O12W—H12C | 109.2 |
O2W—Ni2—O5W | 94.4 (2) | H12B—O12W—H12C | 109.4 |
O22—Ni2—O1W | 85.17 (19) | C27—O21—Ni3 | 123.1 (4) |
O1—Ni2—O1W | 83.52 (18) | C27—O22—Ni2 | 128.3 (5) |
O25i—Ni2—O1W | 92.0 (2) | C29—O25—Ni2ii | 137.1 (5) |
O2W—Ni2—O1W | 90.26 (19) | C29—O26—Ni1ii | 133.7 (5) |
O5W—Ni2—O1W | 171.62 (18) | C12—C11—C16 | 119.5 (7) |
O1—Ni3—O3W | 169.2 (2) | C12—C11—C17 | 118.8 (7) |
O1—Ni3—O21 | 96.40 (19) | C16—C11—C17 | 121.5 (7) |
O3W—Ni3—O21 | 91.3 (2) | C11—C12—C13 | 121.4 (7) |
O1—Ni3—O11 | 95.68 (19) | C11—C12—H12A | 119.3 |
O3W—Ni3—O11 | 90.6 (2) | C13—C12—H12A | 119.3 |
O21—Ni3—O11 | 98.54 (19) | C12—C13—C14 | 118.5 (7) |
O1—Ni3—O1W | 85.27 (18) | C12—C13—C18 | 121.2 (7) |
O3W—Ni3—O1W | 88.06 (18) | C14—C13—C18 | 120.1 (7) |
O21—Ni3—O1W | 83.95 (19) | C15—C14—C13 | 120.8 (7) |
O11—Ni3—O1W | 177.2 (2) | C15—C14—H14A | 119.6 |
O1—Ni3—O11W | 82.07 (18) | C13—C14—H14A | 119.6 |
O3W—Ni3—O11W | 89.4 (2) | C14—C15—C16 | 120.7 (7) |
O21—Ni3—O11W | 173.16 (18) | C14—C15—C19 | 119.3 (7) |
O11—Ni3—O11W | 88.26 (19) | C16—C15—C19 | 119.9 (8) |
O1W—Ni3—O11W | 89.27 (18) | C15—C16—C11 | 118.8 (7) |
O6W—Na1—O8W | 178.1 (3) | C15—C16—H16A | 120.6 |
O6W—Na1—O7W | 93.3 (2) | C11—C16—H16A | 120.6 |
O8W—Na1—O7W | 88.6 (2) | O12—C17—O11 | 126.2 (7) |
O6W—Na1—O9W | 91.3 (3) | O12—C17—C11 | 115.0 (7) |
O8W—Na1—O9W | 88.3 (2) | O11—C17—C11 | 118.8 (7) |
O7W—Na1—O9W | 93.7 (3) | O14—C18—O13 | 124.3 (8) |
O6W—Na1—O5W | 85.5 (2) | O14—C18—C13 | 116.6 (7) |
O8W—Na1—O5W | 92.6 (2) | O13—C18—C13 | 118.9 (7) |
O7W—Na1—O5W | 174.8 (3) | O15—C19—O16 | 124.0 (8) |
O9W—Na1—O5W | 91.4 (3) | O15—C19—C15 | 117.1 (8) |
O6W—Na1—O4W | 88.7 (2) | O16—C19—C15 | 118.8 (7) |
O8W—Na1—O4W | 91.7 (2) | C26—C21—C22 | 118.1 (7) |
O7W—Na1—O4W | 83.4 (2) | C26—C21—C27 | 119.3 (6) |
O9W—Na1—O4W | 177.1 (3) | C22—C21—C27 | 122.6 (6) |
O5W—Na1—O4W | 91.47 (19) | C23—C22—C21 | 121.1 (7) |
Ni3—O1—Ni2 | 98.5 (2) | C23—C22—H22A | 119.5 |
Ni3—O1—Ni1 | 100.3 (2) | C21—C22—H22A | 119.5 |
Ni2—O1—Ni1 | 125.0 (2) | C24—C23—C22 | 119.3 (7) |
Ni3—O1—H1A | 110.4 | C24—C23—C28 | 119.0 (7) |
Ni2—O1—H1A | 110.4 | C22—C23—C28 | 121.7 (6) |
Ni1—O1—H1A | 110.4 | C23—C24—C25 | 121.2 (7) |
Ni3—O1W—Ni2 | 88.23 (17) | C23—C24—H24A | 119.4 |
Ni3—O1W—H1WA | 114.0 | C25—C24—H24A | 119.4 |
Ni2—O1W—H1WA | 114.0 | C26—C25—C24 | 118.3 (6) |
Ni3—O1W—H1WB | 113.9 | C26—C25—C29 | 122.2 (6) |
Ni2—O1W—H1WB | 113.9 | C24—C25—C29 | 119.5 (7) |
H1WA—O1W—H1WB | 111.1 | C25—C26—C21 | 122.0 (6) |
Ni2—O2W—H2WB | 109.5 | C25—C26—H26A | 119.0 |
Ni2—O2W—H2WA | 109.3 | C21—C26—H26A | 119.0 |
H2WB—O2W—H2WA | 109.7 | O22—C27—O21 | 124.9 (7) |
Ni3—O3W—H3WB | 109.5 | O22—C27—C21 | 116.1 (6) |
Ni3—O3W—H3WA | 109.8 | O21—C27—C21 | 118.9 (6) |
H3WB—O3W—H3WA | 140.7 | O23—C28—O24 | 125.0 (7) |
Ni1—O4W—Na1 | 116.1 (2) | O23—C28—C23 | 115.5 (7) |
Ni1—O4W—H4B | 109.4 | O24—C28—C23 | 119.4 (7) |
Na1—O4W—H4B | 108.5 | O25—C29—O26 | 127.0 (7) |
Ni1—O4W—H4A | 121.1 | O25—C29—C25 | 116.8 (7) |
Na1—O4W—H4A | 99.9 | O26—C29—C25 | 116.2 (7) |
H4B—O4W—H4A | 100.2 | O14W—O13W—H13A | 108.6 |
Ni2—O5W—Na1 | 117.4 (2) | O14W—O13W—H13B | 95.1 |
Ni2—O5W—H5WA | 109.5 | H13A—O13W—H13B | 114.0 |
Na1—O5W—H5WA | 106.9 | O13W—O14W—H14B | 109.5 |
Ni2—O5W—H5WB | 108.0 | O13W—O14W—H14C | 78.0 |
Na1—O5W—H5WB | 108.0 | H14B—O14W—H14C | 85.1 |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x+1/2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O8W | 0.98 | 1.83 | 2.807 (7) | 173 |
O1W—H1WA···O13iii | 0.97 | 1.90 | 2.797 (8) | 152 |
O1W—H1WB···O16iv | 0.97 | 1.70 | 2.596 (7) | 152 |
O1W—H1WB···O15iv | 0.97 | 2.57 | 3.438 (8) | 149 |
O2W—H2WB···O10Wv | 0.82 | 1.99 | 2.752 (9) | 155 |
O2W—H2WA···O9Wvi | 0.82 | 2.26 | 2.848 (8) | 130 |
O3W—H3WB···O10Wi | 0.82 | 2.31 | 2.872 (8) | 126 |
O3W—H3WA···O14iii | 0.82 | 1.88 | 2.601 (8) | 145 |
O4W—H4B···O15vii | 0.82 | 2.28 | 3.049 (8) | 157 |
O4W—H4A···O24viii | 0.72 | 2.04 | 2.757 (7) | 174 |
O5W—H5WA···O16viii | 0.82 | 2.03 | 2.818 (8) | 160 |
O5W—H5WB···O13vii | 0.97 | 1.88 | 2.772 (7) | 151 |
O6W—H6WB···O13vii | 0.82 | 2.45 | 3.153 (9) | 145 |
O7W—H7WA···O14ix | 0.82 | 2.10 | 2.841 (8) | 150 |
O7W—H7WB···O24viii | 0.82 | 1.96 | 2.778 (8) | 174 |
O8W—H8WB···O21viii | 0.82 | 2.17 | 2.838 (7) | 138 |
O8W—H8WA···O11viii | 0.82 | 2.07 | 2.821 (8) | 153 |
O9W—H9WA···O16viii | 0.82 | 2.12 | 2.909 (10) | 162 |
O9W—H9WB···O23v | 0.82 | 2.32 | 3.062 (9) | 150 |
O10W—H10A···O12Wvi | 0.82 | 2.14 | 2.764 (9) | 133 |
O10W—H10B···O15iii | 0.84 | 2.14 | 2.981 (10) | 177 |
O11W—H11A···O15iv | 0.97 | 1.71 | 2.659 (7) | 166 |
O11W—H11B···O24x | 0.97 | 1.74 | 2.693 (6) | 165 |
O12W—H12C···O7Wxi | 0.96 | 2.01 | 2.795 (7) | 138 |
O13W—H13A···O14ii | 0.82 | 1.99 | 2.79 (2) | 168 |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x+1/2, y, −z+1/2; (iii) x+1/2, −y+3/2, −z; (iv) x, −y+3/2, z+1/2; (v) −x+3/2, y+1/2, z; (vi) −x+1, y−1/2, −z+1/2; (vii) −x+1/2, −y+2, z+1/2; (viii) −x+1, −y+2, −z; (ix) −x+1/2, y+1/2, z; (x) x−1/2, −y+3/2, −z; (xi) −x+1/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Ni3Na(OH)(C9H3O6)2(H2O)11]·1.5H2O |
Mr | 855.56 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 18.842 (5), 14.557 (4), 21.343 (6) |
V (Å3) | 5854 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.03 |
Crystal size (mm) | 0.18 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1995) |
Tmin, Tmax | 0.712, 0.820 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 43629, 6693, 2994 |
Rint | 0.133 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.127, 0.89 |
No. of reflections | 6693 |
No. of parameters | 442 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.64 |
Computer programs: SMART (Siemens, 1994), SMART, XPREP (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O8W | 0.98 | 1.83 | 2.807 (7) | 173.3 |
O1W—H1WA···O13i | 0.97 | 1.90 | 2.797 (8) | 151.7 |
O1W—H1WB···O16ii | 0.97 | 1.70 | 2.596 (7) | 152.0 |
O2W—H2WB···O10Wiii | 0.82 | 1.99 | 2.752 (9) | 154.5 |
O4W—H4B···O15iv | 0.82 | 2.28 | 3.049 (8) | 156.5 |
O4W—H4A···O24v | 0.72 | 2.04 | 2.757 (7) | 173.7 |
O5W—H5WA···O16v | 0.82 | 2.03 | 2.818 (8) | 160.3 |
O5W—H5WB···O13iv | 0.97 | 1.88 | 2.772 (7) | 151.0 |
O7W—H7WA···O14vi | 0.82 | 2.10 | 2.841 (8) | 150.4 |
O7W—H7WB···O24v | 0.82 | 1.96 | 2.778 (8) | 174.0 |
O8W—H8WA···O11v | 0.82 | 2.07 | 2.821 (8) | 152.5 |
O9W—H9WA···O16v | 0.82 | 2.12 | 2.909 (10) | 162.0 |
O9W—H9WB···O23iii | 0.82 | 2.32 | 3.062 (9) | 150.0 |
O10W—H10B···O15i | 0.84 | 2.14 | 2.981 (10) | 177.2 |
O11W—H11A···O15ii | 0.97 | 1.71 | 2.659 (7) | 166.0 |
O11W—H11B···O24vii | 0.97 | 1.74 | 2.693 (6) | 165.1 |
O13W—H13A···O14viii | 0.82 | 1.99 | 2.79 (2) | 167.8 |
Symmetry codes: (i) x+1/2, −y+3/2, −z; (ii) x, −y+3/2, z+1/2; (iii) −x+3/2, y+1/2, z; (iv) −x+1/2, −y+2, z+1/2; (v) −x+1, −y+2, −z; (vi) −x+1/2, y+1/2, z; (vii) x−1/2, −y+3/2, −z; (viii) x+1/2, y, −z+1/2. |
Benzenetricarboxylate (BTC) ligands are universal bridging ligands in the construction of a number of coordination networks (Yaghi et al., 1996; Wei & Han, 2005; Guo et al., 2006; Eddaoudi et al., 2001). In this paper, we present the synthesis and structural characterization of a new coordination polymer of trinuclear NiII units bridged by BTC ligands, {[Ni3Na(OH)(C9H3O6)2(H2O)11].1.5H2O}n, (I), which was synthesized by the reaction of nickel(II) salt with H3BTC in basic conditions. The title compound is isomorphous with the CoII complex published by Cheng et al. (2004).
As shown in Fig. 1, the asymmetric unit contains three crystallographically independent NiII centers, which are all octahedrally coordinated by six O atoms, which are from two BTC carboxylate groups, one OH- unit and three aqua ligands (Table 2). The three NiII ions are bridged by three bidentate carboxylates of three BTC ligands, two aqua ligands and one OH- anion, to form a new trinuclear metal cluster. The NaI ion is coordinated by six water molecules, and the distorted octahedron is attached to the trinuclear unit though two bridging aqua ligands.
The BTC ligands exhibit two different coordination modes in (I). In the first one, the BTC ligand acts as a bidentate ligand bridging two NiII centers, while another one acts as a tetradentate ligand linking four NiII centers of neighboring trinuclear units to form a one-dimensional zigzag chain (Fig. 2). The chains are further connected into a three-dimensional framework through a complex hydrogen bonding scheme involving water molecules and carboxylate groups of BTC (Table 3 and Fig. 3). The hydrogen bonds D···A separations range from 2.597 to 3.437 Å.