Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112044393/fn3119sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112044393/fn3119Isup2.hkl |
CCDC reference: 915089
For related literature, see: Abbasi et al. (2012); Bhattacharya & Saha (2011); Cao et al. (2009); Evans & Lin (2002); Fu et al. (2005); Ishikawa et al. (2005); Lee et al. (2009); Lin et al. (2009); Ma et al. (2009); Mircea & Long (2008); Teo & Hor (2011); Tiekink et al. (2010); Yang et al. (2006).
All chemicals were purchased from commercial sources and were used as received. The bix ligand was synthesized following the literature method of Yang et al. (2006). Ni(NO3)2 (0.1168 g, 0.4 mmol), H3BTC (0.0846 g, 0.4 mmol) and bix (0.0927 g, 0.4 mmol) were mixed in an H2O—C2H5OH (7 ml, 1:2.5 v/v) binary solvent. The reaction mixture was then heated to 453 K and kept for 3 d in a sealed 18 ml Teflon-lined stainless steel vessel under autogenous pressure. After slow cooling to room temperature, green block-shaped crystals of (I) were filtered off and washed with distilled water and ethanol (yield 58%, based on Ni). Analysis calculated for C23H20N4NiO7: C 52.80, H 3.85, N 10.71%; found: C 52.64, H 3.97, N 10.92%.
H atoms bonded to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93—0.97 Å and Uiso(H) = 1.2Ueq(C). The carboxy H atom was located in a difference Fourier map and refined with the restraint O—H = 0.858 (10) Å [Value amended to match CIF - OK?]. The water H atoms were initially found in a difference Fourier map and subsequently treated as riding on their parent atoms, with O—H = 0.85 Å and Uiso(H) = 1.5Ueq(O). [Added text OK?] The water molecule was refined as partially occupied with an occupancy of 0.415 (7) because of the large displacement ellipsoids. It is possible that some of the water may have evaporated from the crystal, and this agrees with the TG analysis.
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Ni(C9H4O6)(C14H14N4)]·0.41H2O | F(000) = 1056 |
Mr = 512.49 | Dx = 1.558 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 16428 reflections |
a = 7.8106 (16) Å | θ = 3.1–27.6° |
b = 16.929 (3) Å | µ = 0.94 mm−1 |
c = 17.144 (5) Å | T = 293 K |
β = 105.48 (3)° | Block, green |
V = 2184.6 (9) Å3 | 0.29 × 0.24 × 0.22 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 4929 independent reflections |
Radiation source: fine-focus sealed tube | 3999 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −10→9 |
Tmin = 0.772, Tmax = 0.818 | k = −21→21 |
20085 measured reflections | l = −22→22 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.044P)2 + 0.5113P] where P = (Fo2 + 2Fc2)/3 |
4929 reflections | (Δ/σ)max = 0.001 |
321 parameters | Δρmax = 0.35 e Å−3 |
7 restraints | Δρmin = −0.21 e Å−3 |
[Ni(C9H4O6)(C14H14N4)]·0.41H2O | V = 2184.6 (9) Å3 |
Mr = 512.49 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.8106 (16) Å | µ = 0.94 mm−1 |
b = 16.929 (3) Å | T = 293 K |
c = 17.144 (5) Å | 0.29 × 0.24 × 0.22 mm |
β = 105.48 (3)° |
Rigaku R-AXIS RAPID diffractometer | 4929 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3999 reflections with I > 2σ(I) |
Tmin = 0.772, Tmax = 0.818 | Rint = 0.038 |
20085 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 7 restraints |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.35 e Å−3 |
4929 reflections | Δρmin = −0.21 e Å−3 |
321 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. |
Refinement. DFIX 0.85 0.01 o6 h61 isor 0.01 o7 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.0868 (3) | 0.98611 (13) | 0.23406 (13) | 0.0356 (5) | |
H1 | 0.1952 | 0.9988 | 0.2244 | 0.043* | |
C2 | −0.0295 (3) | 1.03873 (13) | 0.25062 (13) | 0.0370 (5) | |
H2 | −0.0162 | 1.0933 | 0.2545 | 0.044* | |
C3 | −0.1352 (3) | 0.91945 (12) | 0.25001 (13) | 0.0330 (4) | |
H3 | −0.2104 | 0.8779 | 0.2538 | 0.040* | |
C4 | −0.3254 (3) | 1.02498 (13) | 0.28569 (13) | 0.0372 (5) | |
H4A | −0.4318 | 0.9981 | 0.2550 | 0.045* | |
H4B | −0.3403 | 1.0810 | 0.2742 | 0.045* | |
C5 | −0.3010 (3) | 1.01105 (12) | 0.37488 (13) | 0.0328 (4) | |
C6 | −0.2167 (3) | 1.06650 (13) | 0.43240 (14) | 0.0401 (5) | |
H6 | −0.1778 | 1.1140 | 0.4160 | 0.048* | |
C7 | −0.1908 (3) | 1.05096 (15) | 0.51355 (15) | 0.0467 (6) | |
H7 | −0.1355 | 1.0884 | 0.5517 | 0.056* | |
C8 | −0.2466 (3) | 0.98011 (15) | 0.53886 (14) | 0.0435 (5) | |
H8 | −0.2280 | 0.9702 | 0.5938 | 0.052* | |
C9 | −0.3299 (3) | 0.92409 (13) | 0.48280 (13) | 0.0363 (5) | |
C10 | −0.3572 (3) | 0.94042 (13) | 0.40075 (13) | 0.0355 (5) | |
H10 | −0.4142 | 0.9033 | 0.3626 | 0.043* | |
C11 | −0.3986 (3) | 0.84580 (15) | 0.50568 (16) | 0.0475 (6) | |
H11A | −0.5228 | 0.8520 | 0.5044 | 0.057* | |
H11B | −0.3917 | 0.8067 | 0.4653 | 0.057* | |
C12 | −0.3550 (3) | 0.81812 (15) | 0.65550 (16) | 0.0479 (6) | |
H12 | −0.4594 | 0.8399 | 0.6623 | 0.058* | |
C13 | −0.2267 (3) | 0.78261 (13) | 0.71262 (15) | 0.0415 (5) | |
H13 | −0.2280 | 0.7755 | 0.7662 | 0.050* | |
C14 | −0.1445 (3) | 0.77928 (13) | 0.60296 (13) | 0.0337 (4) | |
H14 | −0.0797 | 0.7698 | 0.5656 | 0.040* | |
C15 | 0.3727 (2) | 0.67887 (11) | 0.41504 (11) | 0.0271 (4) | |
C16 | 0.3100 (3) | 0.68329 (11) | 0.48368 (12) | 0.0293 (4) | |
H16 | 0.2089 | 0.7130 | 0.4821 | 0.035* | |
C17 | 0.3953 (3) | 0.64435 (11) | 0.55408 (11) | 0.0282 (4) | |
C18 | 0.5481 (3) | 0.60083 (12) | 0.55714 (11) | 0.0301 (4) | |
H18 | 0.6063 | 0.5743 | 0.6043 | 0.036* | |
C19 | 0.6134 (3) | 0.59721 (12) | 0.48901 (12) | 0.0301 (4) | |
C20 | 0.5256 (3) | 0.63564 (12) | 0.41807 (11) | 0.0297 (4) | |
H20 | 0.5690 | 0.6325 | 0.3727 | 0.036* | |
C21 | 0.2826 (3) | 0.72423 (12) | 0.34093 (12) | 0.0284 (4) | |
C22 | 0.3235 (3) | 0.65098 (12) | 0.62762 (11) | 0.0294 (4) | |
C23 | 0.7821 (3) | 0.55387 (13) | 0.49284 (12) | 0.0357 (5) | |
N1 | 0.0193 (2) | 0.91090 (10) | 0.23369 (10) | 0.0304 (4) | |
N2 | −0.1705 (2) | 0.99559 (10) | 0.26044 (10) | 0.0316 (4) | |
N3 | −0.0922 (2) | 0.75817 (10) | 0.67968 (10) | 0.0317 (4) | |
N4 | −0.3029 (2) | 0.81615 (11) | 0.58500 (12) | 0.0397 (4) | |
Ni1 | 0.13384 (3) | 0.805870 (14) | 0.224375 (14) | 0.02599 (9) | |
O1 | 0.3176 (2) | 0.71167 (9) | 0.27453 (8) | 0.0349 (3) | |
O2 | 0.1706 (2) | 0.77737 (10) | 0.34571 (9) | 0.0420 (4) | |
O3 | 0.1779 (2) | 0.68850 (9) | 0.61615 (9) | 0.0399 (4) | |
O4 | 0.4030 (2) | 0.62242 (10) | 0.69351 (9) | 0.0413 (4) | |
O5 | 0.8556 (2) | 0.56209 (13) | 0.43742 (10) | 0.0645 (6) | |
O6 | 0.8409 (2) | 0.51034 (11) | 0.55490 (10) | 0.0484 (4) | |
H61 | 0.939 (3) | 0.489 (2) | 0.553 (3) | 0.136 (17)* | |
O7 | 0.8747 (6) | 0.7522 (3) | 0.4139 (3) | 0.069 (2) | 0.415 (7) |
H71 | 0.8488 | 0.7034 | 0.4079 | 0.103* | 0.415 (7) |
H72 | 0.9492 | 0.7622 | 0.3870 | 0.103* | 0.415 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0351 (10) | 0.0343 (11) | 0.0370 (11) | −0.0043 (9) | 0.0086 (9) | 0.0017 (9) |
C2 | 0.0438 (12) | 0.0273 (10) | 0.0393 (12) | −0.0035 (9) | 0.0102 (10) | −0.0013 (9) |
C3 | 0.0375 (11) | 0.0266 (10) | 0.0353 (11) | 0.0003 (8) | 0.0103 (9) | 0.0019 (8) |
C4 | 0.0359 (11) | 0.0343 (11) | 0.0419 (12) | 0.0088 (9) | 0.0114 (10) | 0.0024 (9) |
C5 | 0.0280 (9) | 0.0319 (10) | 0.0389 (11) | 0.0079 (8) | 0.0095 (9) | −0.0020 (9) |
C6 | 0.0380 (11) | 0.0323 (11) | 0.0500 (14) | 0.0013 (9) | 0.0116 (10) | −0.0032 (10) |
C7 | 0.0457 (13) | 0.0425 (13) | 0.0463 (14) | 0.0030 (10) | 0.0027 (11) | −0.0129 (11) |
C8 | 0.0404 (12) | 0.0519 (14) | 0.0361 (12) | 0.0132 (10) | 0.0065 (10) | 0.0021 (10) |
C9 | 0.0299 (10) | 0.0358 (11) | 0.0425 (12) | 0.0079 (8) | 0.0083 (9) | 0.0049 (9) |
C10 | 0.0332 (10) | 0.0339 (11) | 0.0376 (12) | 0.0042 (8) | 0.0061 (9) | −0.0036 (9) |
C11 | 0.0340 (11) | 0.0503 (14) | 0.0545 (15) | 0.0028 (10) | 0.0054 (11) | 0.0160 (12) |
C12 | 0.0448 (13) | 0.0478 (14) | 0.0610 (16) | 0.0161 (11) | 0.0312 (12) | 0.0103 (11) |
C13 | 0.0485 (13) | 0.0381 (12) | 0.0462 (13) | 0.0066 (10) | 0.0272 (11) | 0.0023 (10) |
C14 | 0.0310 (10) | 0.0357 (11) | 0.0373 (11) | 0.0043 (8) | 0.0143 (9) | 0.0056 (9) |
C15 | 0.0284 (9) | 0.0285 (10) | 0.0241 (9) | 0.0024 (7) | 0.0066 (8) | 0.0004 (7) |
C16 | 0.0283 (9) | 0.0306 (10) | 0.0298 (10) | 0.0065 (8) | 0.0094 (8) | 0.0006 (8) |
C17 | 0.0294 (9) | 0.0322 (10) | 0.0249 (9) | 0.0034 (8) | 0.0106 (8) | −0.0011 (8) |
C18 | 0.0316 (10) | 0.0347 (11) | 0.0228 (9) | 0.0070 (8) | 0.0052 (8) | 0.0009 (8) |
C19 | 0.0275 (9) | 0.0350 (11) | 0.0277 (10) | 0.0070 (8) | 0.0072 (8) | −0.0027 (8) |
C20 | 0.0304 (10) | 0.0361 (11) | 0.0251 (9) | 0.0055 (8) | 0.0116 (8) | −0.0011 (8) |
C21 | 0.0304 (10) | 0.0293 (9) | 0.0256 (10) | 0.0007 (8) | 0.0076 (8) | −0.0003 (8) |
C22 | 0.0330 (10) | 0.0321 (10) | 0.0254 (10) | 0.0013 (8) | 0.0120 (8) | −0.0010 (8) |
C23 | 0.0337 (10) | 0.0433 (12) | 0.0291 (11) | 0.0127 (9) | 0.0066 (9) | −0.0022 (9) |
N1 | 0.0339 (9) | 0.0297 (9) | 0.0266 (8) | 0.0006 (7) | 0.0065 (7) | 0.0015 (7) |
N2 | 0.0345 (9) | 0.0281 (8) | 0.0320 (9) | 0.0027 (7) | 0.0087 (7) | 0.0003 (7) |
N3 | 0.0332 (9) | 0.0289 (9) | 0.0358 (9) | 0.0031 (7) | 0.0142 (7) | 0.0016 (7) |
N4 | 0.0313 (9) | 0.0405 (10) | 0.0489 (11) | 0.0071 (8) | 0.0135 (8) | 0.0135 (9) |
Ni1 | 0.02930 (14) | 0.02844 (14) | 0.02108 (13) | 0.00116 (10) | 0.00819 (10) | 0.00002 (10) |
O1 | 0.0436 (8) | 0.0381 (8) | 0.0253 (7) | 0.0081 (6) | 0.0132 (6) | 0.0038 (6) |
O2 | 0.0528 (9) | 0.0467 (9) | 0.0275 (8) | 0.0246 (8) | 0.0125 (7) | 0.0068 (7) |
O3 | 0.0389 (8) | 0.0556 (10) | 0.0298 (8) | 0.0145 (7) | 0.0170 (7) | 0.0019 (7) |
O4 | 0.0462 (9) | 0.0517 (10) | 0.0269 (8) | 0.0059 (7) | 0.0115 (7) | 0.0080 (7) |
O5 | 0.0533 (10) | 0.1024 (16) | 0.0460 (10) | 0.0438 (11) | 0.0278 (9) | 0.0212 (10) |
O6 | 0.0420 (9) | 0.0612 (11) | 0.0422 (9) | 0.0261 (8) | 0.0115 (8) | 0.0106 (8) |
O7 | 0.056 (3) | 0.103 (4) | 0.054 (3) | 0.005 (3) | 0.027 (2) | 0.008 (3) |
C1—C2 | 1.355 (3) | C15—C20 | 1.390 (3) |
C1—N1 | 1.377 (3) | C15—C16 | 1.392 (3) |
C1—H1 | 0.9300 | C15—C21 | 1.491 (3) |
C2—N2 | 1.369 (3) | C16—C17 | 1.381 (3) |
C2—H2 | 0.9300 | C16—H16 | 0.9300 |
C3—N1 | 1.318 (3) | C17—C18 | 1.392 (3) |
C3—N2 | 1.340 (3) | C17—C22 | 1.515 (2) |
C3—H3 | 0.9300 | C18—C19 | 1.395 (3) |
C4—N2 | 1.476 (2) | C18—H18 | 0.9300 |
C4—C5 | 1.508 (3) | C19—C20 | 1.388 (3) |
C4—H4A | 0.9700 | C19—C23 | 1.495 (3) |
C4—H4B | 0.9700 | C20—H20 | 0.9300 |
C5—C10 | 1.387 (3) | C21—O1 | 1.258 (2) |
C5—C6 | 1.393 (3) | C21—O2 | 1.272 (2) |
C6—C7 | 1.377 (3) | C21—Ni1 | 2.452 (2) |
C6—H6 | 0.9300 | C22—O4 | 1.233 (2) |
C7—C8 | 1.385 (3) | C22—O3 | 1.271 (2) |
C7—H7 | 0.9300 | C22—Ni1i | 2.6057 (18) |
C8—C9 | 1.383 (3) | C23—O5 | 1.242 (2) |
C8—H8 | 0.9300 | C23—O6 | 1.275 (3) |
C9—C10 | 1.393 (3) | Ni1—N1 | 2.0157 (17) |
C9—C11 | 1.520 (3) | N3—Ni1i | 2.0390 (17) |
C10—H10 | 0.9300 | Ni1—O3ii | 1.9775 (15) |
C11—N4 | 1.455 (3) | Ni1—N3ii | 2.0390 (17) |
C11—H11A | 0.9700 | Ni1—O2 | 2.0794 (15) |
C11—H11B | 0.9700 | Ni1—O1 | 2.1642 (15) |
C12—C13 | 1.342 (3) | Ni1—O4ii | 2.6013 (16) |
C12—N4 | 1.375 (3) | Ni1—C22ii | 2.6057 (19) |
C12—H12 | 0.9300 | O3—Ni1i | 1.9775 (15) |
C13—N3 | 1.382 (3) | O4—Ni1i | 2.6013 (16) |
C13—H13 | 0.9300 | O6—H61 | 0.858 (10) |
C14—N3 | 1.318 (3) | O7—H71 | 0.8500 |
C14—N4 | 1.346 (3) | O7—H72 | 0.8501 |
C14—H14 | 0.9300 | ||
C2—C1—N1 | 109.39 (18) | C19—C20—H20 | 120.1 |
C2—C1—H1 | 125.3 | C15—C20—H20 | 120.1 |
N1—C1—H1 | 125.3 | O1—C21—O2 | 119.81 (18) |
C1—C2—N2 | 106.34 (19) | O1—C21—C15 | 121.14 (17) |
C1—C2—H2 | 126.8 | O2—C21—C15 | 119.05 (17) |
N2—C2—H2 | 126.8 | O1—C21—Ni1 | 61.83 (10) |
N1—C3—N2 | 111.52 (18) | O2—C21—Ni1 | 57.98 (10) |
N1—C3—H3 | 124.2 | C15—C21—Ni1 | 176.47 (14) |
N2—C3—H3 | 124.2 | O4—C22—O3 | 123.28 (17) |
N2—C4—C5 | 110.68 (17) | O4—C22—C17 | 121.69 (17) |
N2—C4—H4A | 109.5 | O3—C22—C17 | 115.03 (17) |
C5—C4—H4A | 109.5 | O4—C22—Ni1i | 76.10 (11) |
N2—C4—H4B | 109.5 | O3—C22—Ni1i | 47.27 (9) |
C5—C4—H4B | 109.5 | C17—C22—Ni1i | 161.87 (14) |
H4A—C4—H4B | 108.1 | O5—C23—O6 | 124.48 (19) |
C10—C5—C6 | 119.0 (2) | O5—C23—C19 | 119.57 (19) |
C10—C5—C4 | 119.60 (19) | O6—C23—C19 | 115.95 (17) |
C6—C5—C4 | 121.3 (2) | C3—N1—C1 | 105.56 (17) |
C7—C6—C5 | 120.0 (2) | C3—N1—Ni1 | 124.38 (14) |
C7—C6—H6 | 120.0 | C1—N1—Ni1 | 129.70 (13) |
C5—C6—H6 | 120.0 | C3—N2—C2 | 107.20 (17) |
C6—C7—C8 | 120.6 (2) | C3—N2—C4 | 125.27 (17) |
C6—C7—H7 | 119.7 | C2—N2—C4 | 127.28 (17) |
C8—C7—H7 | 119.7 | C14—N3—C13 | 105.04 (18) |
C9—C8—C7 | 120.3 (2) | C14—N3—Ni1i | 121.73 (13) |
C9—C8—H8 | 119.8 | C13—N3—Ni1i | 132.99 (15) |
C7—C8—H8 | 119.8 | C14—N4—C12 | 106.24 (19) |
C8—C9—C10 | 118.9 (2) | C14—N4—C11 | 125.84 (19) |
C8—C9—C11 | 123.5 (2) | C12—N4—C11 | 127.90 (19) |
C10—C9—C11 | 117.7 (2) | O3ii—Ni1—N1 | 102.93 (7) |
C5—C10—C9 | 121.2 (2) | O3ii—Ni1—N3ii | 91.32 (7) |
C5—C10—H10 | 119.4 | N1—Ni1—N3ii | 98.09 (7) |
C9—C10—H10 | 119.4 | O3ii—Ni1—O2 | 159.66 (6) |
N4—C11—C9 | 114.4 (2) | N1—Ni1—O2 | 94.08 (6) |
N4—C11—H11A | 108.7 | N3ii—Ni1—O2 | 97.30 (7) |
C9—C11—H11A | 108.7 | O3ii—Ni1—O1 | 98.36 (6) |
N4—C11—H11B | 108.7 | N1—Ni1—O1 | 151.61 (6) |
C9—C11—H11B | 108.7 | N3ii—Ni1—O1 | 99.98 (7) |
H11A—C11—H11B | 107.6 | O2—Ni1—O1 | 62.07 (6) |
C13—C12—N4 | 106.96 (19) | O3ii—Ni1—C21 | 128.94 (7) |
C13—C12—H12 | 126.5 | N1—Ni1—C21 | 123.80 (6) |
N4—C12—H12 | 126.5 | N3ii—Ni1—C21 | 100.42 (7) |
C12—C13—N3 | 109.7 (2) | O2—Ni1—C21 | 31.25 (6) |
C12—C13—H13 | 125.2 | O1—Ni1—C21 | 30.82 (5) |
N3—C13—H13 | 125.2 | O3ii—Ni1—O4ii | 55.55 (6) |
N3—C14—N4 | 112.05 (17) | N1—Ni1—O4ii | 90.24 (6) |
N3—C14—H14 | 124.0 | N3ii—Ni1—O4ii | 146.87 (6) |
N4—C14—H14 | 124.0 | O2—Ni1—O4ii | 114.10 (6) |
C20—C15—C16 | 119.29 (18) | O1—Ni1—O4ii | 86.47 (6) |
C20—C15—C21 | 120.58 (16) | C21—Ni1—O4ii | 101.30 (6) |
C16—C15—C21 | 120.02 (17) | O3ii—Ni1—C22ii | 28.18 (6) |
C17—C16—C15 | 121.13 (17) | N1—Ni1—C22ii | 98.21 (6) |
C17—C16—H16 | 119.4 | N3ii—Ni1—C22ii | 119.48 (7) |
C15—C16—H16 | 119.4 | O2—Ni1—C22ii | 138.73 (7) |
C16—C17—C18 | 119.64 (17) | O1—Ni1—C22ii | 91.73 (6) |
C16—C17—C22 | 119.53 (17) | C21—Ni1—C22ii | 116.78 (6) |
C18—C17—C22 | 120.82 (18) | O4ii—Ni1—C22ii | 27.41 (5) |
C17—C18—C19 | 119.56 (18) | C21—O1—Ni1 | 87.34 (12) |
C17—C18—H18 | 120.2 | C21—O2—Ni1 | 90.77 (12) |
C19—C18—H18 | 120.2 | C22—O3—Ni1i | 104.55 (12) |
C20—C19—C18 | 120.49 (17) | C22—O4—Ni1i | 76.49 (11) |
C20—C19—C23 | 119.48 (17) | C23—O6—H61 | 110 (3) |
C18—C19—C23 | 120.00 (18) | H71—O7—H72 | 107.7 |
C19—C20—C15 | 119.88 (17) |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H61···O5iii | 0.86 (1) | 1.79 (1) | 2.641 (2) | 171 (4) |
O7—H71···O5 | 0.85 | 2.44 | 3.251 (6) | 159 |
O7—H72···O2iv | 0.85 | 2.05 | 2.887 (4) | 167 |
Symmetry codes: (iii) −x+2, −y+1, −z+1; (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C9H4O6)(C14H14N4)]·0.41H2O |
Mr | 512.49 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.8106 (16), 16.929 (3), 17.144 (5) |
β (°) | 105.48 (3) |
V (Å3) | 2184.6 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.94 |
Crystal size (mm) | 0.29 × 0.24 × 0.22 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.772, 0.818 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20085, 4929, 3999 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.088, 1.06 |
No. of reflections | 4929 |
No. of parameters | 321 |
No. of restraints | 7 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.21 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Ni1—N1 | 2.0157 (17) | Ni1—O2 | 2.0794 (15) |
N3—Ni1i | 2.0390 (17) | Ni1—O1 | 2.1642 (15) |
Ni1—O3ii | 1.9775 (15) | Ni1—O4ii | 2.6013 (16) |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H61···O5iii | 0.858 (10) | 1.789 (12) | 2.641 (2) | 171 (4) |
O7—H71···O5 | 0.85 | 2.44 | 3.251 (6) | 159.2 |
O7—H72···O2iv | 0.85 | 2.05 | 2.887 (4) | 166.8 |
Symmetry codes: (iii) −x+2, −y+1, −z+1; (iv) x+1, y, z. |
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In the last two decades, impressive progress has been made in the design and synthesis of metal–organic frameworks (MOFs) and coordination polymers in diverse structures with different dimensionalities and topologies. The interest lies in their potential applications, such as heterogeneous catalysis (Ma et al., 2009; Lee et al., 2009), luminescence (Fu et al., 2005), nonlinear optical activity (Evans & Lin, 2002), magnetism (Ishikawa et al., 2005) and as microporous materials (Mircea & Long, 2008). From a crystal engineering point of view, the synthesis of such species is often based on the self-assembly of appropriate bridging ligands containing O- or N-donor groups (Teo & Hor, 2011), giving supramolecular networks assembled by metal coordinate bonds, covalent bonds or intermolecular weak interactions. The study of utilizing intermolecular interactions, such as hydrogen bonds, π–π or C—H···π stackings, van der Waals contacts or a combination of these, to control the solid-state formation of a compound is at the heart of crystal engineering (Tiekink et al., 2010). Such noncovalent bonds are capable of assembling repeating units, giving rise to polymeric structures (Abbasi et al., 2012).
As an excellent hydrogen-bond donor and acceptor for building intriguing architectures, trimesic acid (H3BTC) is an outstanding ligand which has attracted much attention (Cao et al., 2009; Bhattacharya & Saha, 2011). Herein, we report the synthesis and structure of the title three-dimensional supramolecular framework, {[Ni(HBTC)(bix)].0.42H2O}n [bix is 1,3-bis(imidazol-l-ylmethyl)benzene], (I), which was obtained from the hydrothermal reaction of nickel nitrate, bix and H3BTC.
Compound (I) crystallizes in the monoclinic space group P21/c. The asymmetric unit is composed of one NiII cation, one bix ligand, one dianionic HBTC ligand and one partially occupied solvent water molecule, as shown in Fig. 1. The NiII cation is six-coordinated in a distorted triangular prism, defined by two N atoms from two bix ligands [Ni—N = 2.019 (2)–2.039 (2) Å] and four O atoms from two HBTC ligands [Ni—O = 1.980 (2)–2.602 (3) Å]. Selected bond lengths are listed in Table 1. In (I), the bix molecule and HBTC anions both act as bidentate ligands, connecting the NiII cations to form chains. Pairs of chains wind around each other, with an Ni···Ni separation of 8.78 (3) Å along [001] (Fig. 2). The solvent water molecules are located between these chains through O7—H72···O2 hydrogen bonds (Table 2). A related compound with a similar composition (bix, BTC and an NiII cation) has also been reported, which exhibits a two-dimensional coordination layer structure (Lin et al., 2009).
Adjacent chains are linked by O6—H61···O5 [O···O = 2.639 (3) Å] hydrogen bonds to form a wave-like layer (Fig. 3). When the O7—H71···O5 [O···O = 3.263 (10) Å] hydrogen bond is considered, a three-dimensional framework is built up (Fig. 4).
We also carried out a powder X-ray diffraction (PXRD) experiment and a thermogravimetric (TG) analysis to investigate the purity and stability of (I). The PXRD results (Fig. 5) showed that the peak positions and their intensities are consistent with the simulated pattern from the single-crystal XRD data, showing that the powder sample is a single phase.
TG analysis experiments were carried out to determine the thermal stability of (I) (Fig. 6). The TG curve reveals that there is a small weight loss (2.9%) below 373 K, arising from the loss of the water molecules (calculated 3.4%). The difference between these two values may be attributed to the evaporation of some of the water molecules in storage and during the experiment. A sharp weight-loss step occurs in the range 636–731 K, which may be assigned as the decomposition of the two types of ligand, with a weight loss of 82.7% (calculated 82.3%). The observed final mass remnant of 14.2% can likely be ascribed to the deposition of NiO (calculated 14.3%).
In summary, a new nickel coordination polymer with a three-dimensional supramolecular structure has been hydrothermally synthesized by reacting bix, H3BTC and Ni(NO3)2. The results reveal that hydrogen bonding in (I) plays an important role in both the formation of the stacking structure and the stability of the crystal.