Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104031671/ta1477sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104031671/ta1477Isup2.hkl |
CCDC reference: 264785
All chemicals and solvents were of reagent grade and were used without further purification. The title compound was synthesized from a hydrothermal reaction of ZnO (0.600 g), 4-cyanopyridine (0.770 g), H3PO4 (85 w%, 1.00 ml) and H2O (12.0 ml) in a 25 ml Teflon-lined stainless steel Parr bomb at 413 K for 3 d. Colorless block-like crystals were isolated and washed, in turn, with water, ethanol and anhydrous ether. IR (KBr disc, cm−1): 3253.40 (w), 3104.20 (s), 2425.06 (w), 1609.01 (s), 1498.67 (w), 1403.81 (s), 1247.75 (m), 1200.04 (w), 1141.98 (s), 1072.69 (s), 1018.50 (s), 911.04 (m), 856.05 (w), 821.15 (w), 752.01 (m), 684.01 (m), 595.50 (s), 573.82 (m), 543.86 (w), 431.24 (m).
H atoms attached to N and O atoms were located from difference Fourier maps, and other H atoms were positioned geometrically. H atoms attached to N and C atoms were refined using a riding model, and those attached to O atoms were refined in fixed positions.
Data collection: SMART (Bruker, 1997–2000); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens 1990); software used to prepare material for publication: SHELXL97.
[Zn2(C6H5NO2)2(HPO4)2] | F(000) = 1136 |
Mr = 568.92 | Dx = 2.096 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4415 reflections |
a = 20.560 (4) Å | θ = 2.6–31.9° |
b = 8.5138 (17) Å | µ = 2.91 mm−1 |
c = 10.387 (2) Å | T = 292 K |
β = 97.46 (3)° | Block, colourless |
V = 1802.8 (6) Å3 | 0.20 × 0.20 × 0.15 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 6748 independent reflections |
Radiation source: fine-focus sealed tube | 5343 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 15X15 microns pixels mm-1 | θmax = 33.5°, θmin = 2.0° |
ϕ and ω scans | h = −31→27 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick 1996) | k = −13→10 |
Tmin = 0.564, Tmax = 0.646 | l = −14→15 |
17073 measured reflections |
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)] = 0.040 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0485P)2] where P = (Fo2 + 2Fc2)/3 |
6748 reflections | (Δ/σ)max = 0.001 |
271 parameters | Δρmax = 0.84 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Zn2(C6H5NO2)2(HPO4)2] | V = 1802.8 (6) Å3 |
Mr = 568.92 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.560 (4) Å | µ = 2.91 mm−1 |
b = 8.5138 (17) Å | T = 292 K |
c = 10.387 (2) Å | 0.20 × 0.20 × 0.15 mm |
β = 97.46 (3)° |
Bruker SMART CCD area-detector diffractometer | 6748 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick 1996) | 5343 reflections with I > 2σ(I) |
Tmin = 0.564, Tmax = 0.646 | Rint = 0.033 |
17073 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.84 e Å−3 |
6748 reflections | Δρmin = −0.41 e Å−3 |
271 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. 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 | ||
Zn1 | 0.060200 (11) | 0.41855 (3) | 0.34836 (2) | 0.01953 (7) | |
Zn2 | 0.435373 (11) | 0.69146 (3) | 0.07294 (2) | 0.01955 (7) | |
P1 | −0.02186 (3) | 0.70972 (6) | 0.39118 (5) | 0.01833 (10) | |
P2 | 0.52407 (2) | 0.40639 (6) | 0.18276 (5) | 0.01830 (10) | |
O1 | 0.34028 (7) | 0.7064 (2) | 0.07722 (19) | 0.0344 (4) | |
O2 | 0.31375 (10) | 0.5333 (3) | −0.0817 (3) | 0.0645 (8) | |
O3 | 0.15645 (8) | 0.4049 (2) | 0.3655 (2) | 0.0413 (5) | |
O4 | 0.19065 (9) | 0.3779 (3) | 0.5782 (2) | 0.0481 (5) | |
O6 | 0.04142 (7) | 0.63901 (19) | 0.35893 (17) | 0.0266 (3) | |
O8 | 0.45938 (7) | 0.48255 (19) | 0.13070 (16) | 0.0250 (3) | |
O11 | −0.07813 (8) | 0.59388 (19) | 0.33297 (18) | 0.0310 (4) | |
H1O | −0.1141 | 0.6178 | 0.3603 | 0.037* | |
O12 | 0.57966 (7) | 0.53603 (19) | 0.18968 (17) | 0.0270 (3) | |
H2O | 0.6107 | 0.5067 | 0.1487 | 0.032* | |
N1 | 0.10409 (9) | 0.6353 (3) | 0.0813 (2) | 0.0365 (5) | |
H1N | 0.0642 | 0.6365 | 0.0978 | 0.044* | |
N2 | 0.39507 (9) | 0.3894 (2) | 0.3794 (2) | 0.0299 (4) | |
H2N | 0.4349 | 0.3894 | 0.3623 | 0.036* | |
C1 | 0.22999 (10) | 0.6299 (3) | 0.0309 (2) | 0.0279 (5) | |
C2 | 0.18270 (11) | 0.5379 (3) | −0.0416 (3) | 0.0337 (5) | |
H2 | 0.1940 | 0.4737 | −0.1077 | 0.040* | |
C3 | 0.11913 (11) | 0.5430 (3) | −0.0141 (3) | 0.0375 (6) | |
H3 | 0.0869 | 0.4824 | −0.0617 | 0.045* | |
C4 | 0.14772 (12) | 0.7257 (4) | 0.1523 (3) | 0.0403 (6) | |
H4 | 0.1349 | 0.7891 | 0.2174 | 0.048* | |
C5 | 0.21197 (11) | 0.7246 (3) | 0.1286 (3) | 0.0356 (6) | |
H5 | 0.2430 | 0.7869 | 0.1778 | 0.043* | |
C6 | 0.30083 (11) | 0.6217 (3) | 0.0039 (3) | 0.0325 (5) | |
C7 | 0.26933 (10) | 0.3911 (3) | 0.4331 (2) | 0.0249 (4) | |
C8 | 0.32127 (11) | 0.4059 (3) | 0.5320 (3) | 0.0308 (5) | |
H8 | 0.3135 | 0.4175 | 0.6177 | 0.037* | |
C9 | 0.38429 (11) | 0.4029 (3) | 0.5018 (3) | 0.0335 (5) | |
H9 | 0.4195 | 0.4105 | 0.5675 | 0.040* | |
C10 | 0.34640 (11) | 0.3756 (3) | 0.2816 (3) | 0.0333 (5) | |
H10 | 0.3559 | 0.3668 | 0.1967 | 0.040* | |
C11 | 0.28256 (11) | 0.3745 (3) | 0.3062 (3) | 0.0320 (5) | |
H11 | 0.2485 | 0.3627 | 0.2386 | 0.038* | |
C12 | 0.19919 (11) | 0.3916 (3) | 0.4632 (3) | 0.0290 (5) | |
O5 | −0.03256 (8) | 0.87138 (18) | 0.33143 (16) | 0.0274 (3) | |
O7 | −0.02299 (7) | 0.72513 (18) | 0.53739 (15) | 0.0240 (3) | |
O9 | 0.51956 (7) | 0.35507 (18) | 0.32299 (15) | 0.0228 (3) | |
O10 | 0.54235 (8) | 0.27031 (18) | 0.10061 (15) | 0.0248 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01798 (11) | 0.02530 (13) | 0.01586 (12) | 0.00091 (8) | 0.00427 (9) | 0.00038 (8) |
Zn2 | 0.01591 (11) | 0.02595 (13) | 0.01677 (12) | −0.00076 (8) | 0.00198 (8) | −0.00141 (9) |
P1 | 0.0192 (2) | 0.0209 (2) | 0.0156 (2) | 0.00032 (18) | 0.00509 (18) | −0.00047 (18) |
P2 | 0.0174 (2) | 0.0245 (3) | 0.0132 (2) | 0.00088 (18) | 0.00266 (18) | 0.00170 (18) |
O1 | 0.0161 (7) | 0.0441 (10) | 0.0431 (11) | −0.0007 (7) | 0.0036 (7) | −0.0052 (8) |
O2 | 0.0284 (10) | 0.0802 (16) | 0.089 (2) | −0.0124 (10) | 0.0245 (11) | −0.0482 (15) |
O3 | 0.0163 (7) | 0.0692 (14) | 0.0385 (11) | 0.0056 (8) | 0.0042 (7) | 0.0050 (9) |
O4 | 0.0223 (8) | 0.0885 (16) | 0.0357 (12) | −0.0027 (10) | 0.0122 (8) | 0.0010 (11) |
O6 | 0.0214 (7) | 0.0261 (8) | 0.0344 (10) | −0.0004 (6) | 0.0110 (6) | −0.0036 (6) |
O8 | 0.0197 (7) | 0.0307 (8) | 0.0240 (8) | 0.0036 (6) | −0.0001 (6) | 0.0065 (6) |
O11 | 0.0239 (8) | 0.0383 (10) | 0.0321 (10) | −0.0061 (7) | 0.0079 (7) | −0.0126 (7) |
O12 | 0.0236 (7) | 0.0304 (8) | 0.0286 (9) | −0.0061 (6) | 0.0099 (6) | −0.0043 (6) |
N1 | 0.0152 (8) | 0.0512 (13) | 0.0440 (14) | 0.0002 (8) | 0.0073 (8) | 0.0147 (10) |
N2 | 0.0174 (8) | 0.0377 (11) | 0.0361 (12) | −0.0011 (7) | 0.0088 (8) | −0.0023 (9) |
C1 | 0.0164 (9) | 0.0320 (11) | 0.0358 (14) | 0.0003 (8) | 0.0054 (9) | 0.0024 (9) |
C2 | 0.0225 (10) | 0.0366 (13) | 0.0417 (15) | −0.0018 (9) | 0.0035 (10) | −0.0025 (11) |
C3 | 0.0217 (11) | 0.0429 (14) | 0.0472 (17) | −0.0072 (10) | 0.0015 (10) | 0.0067 (12) |
C4 | 0.0272 (12) | 0.0511 (17) | 0.0452 (17) | 0.0048 (11) | 0.0142 (11) | −0.0020 (13) |
C5 | 0.0222 (11) | 0.0434 (15) | 0.0424 (16) | −0.0004 (10) | 0.0084 (10) | −0.0050 (11) |
C6 | 0.0180 (9) | 0.0370 (13) | 0.0437 (16) | 0.0010 (9) | 0.0080 (9) | −0.0016 (11) |
C7 | 0.0162 (9) | 0.0291 (11) | 0.0298 (12) | 0.0013 (8) | 0.0048 (8) | 0.0008 (8) |
C8 | 0.0223 (10) | 0.0456 (14) | 0.0255 (12) | −0.0008 (9) | 0.0062 (9) | −0.0050 (10) |
C9 | 0.0192 (10) | 0.0480 (15) | 0.0323 (14) | −0.0029 (9) | 0.0000 (9) | −0.0066 (11) |
C10 | 0.0265 (11) | 0.0466 (14) | 0.0282 (13) | 0.0007 (10) | 0.0089 (9) | −0.0009 (10) |
C11 | 0.0195 (10) | 0.0484 (14) | 0.0278 (13) | −0.0002 (9) | 0.0023 (9) | 0.0028 (10) |
C12 | 0.0190 (9) | 0.0350 (12) | 0.0340 (13) | −0.0003 (8) | 0.0066 (9) | −0.0024 (10) |
O5 | 0.0413 (9) | 0.0240 (8) | 0.0175 (8) | 0.0057 (7) | 0.0063 (7) | 0.0022 (6) |
O7 | 0.0274 (7) | 0.0300 (8) | 0.0149 (7) | −0.0016 (6) | 0.0046 (6) | 0.0018 (6) |
O9 | 0.0210 (7) | 0.0326 (8) | 0.0156 (7) | 0.0046 (6) | 0.0051 (6) | 0.0045 (6) |
O10 | 0.0315 (8) | 0.0266 (8) | 0.0176 (8) | 0.0020 (6) | 0.0075 (6) | −0.0001 (6) |
Zn1—O6 | 1.9222 (16) | N2—C9 | 1.323 (3) |
Zn1—O5i | 1.9226 (17) | N2—C10 | 1.336 (3) |
Zn1—O7ii | 1.9303 (16) | N2—H2N | 0.8600 |
Zn1—O3 | 1.9671 (17) | C1—C5 | 1.384 (4) |
Zn2—O8 | 1.9210 (16) | C1—C2 | 1.392 (3) |
Zn2—O9iii | 1.9255 (15) | C1—C6 | 1.520 (3) |
Zn2—O10iv | 1.9442 (16) | C2—C3 | 1.374 (3) |
Zn2—O1 | 1.9656 (16) | C2—H2 | 0.9300 |
P1—O6 | 1.5103 (16) | C3—H3 | 0.9300 |
P1—O5 | 1.5140 (16) | C4—C5 | 1.375 (3) |
P1—O7 | 1.5275 (16) | C4—H4 | 0.9300 |
P1—O11 | 1.5796 (16) | C5—H5 | 0.9300 |
P2—O10 | 1.5149 (16) | C7—C11 | 1.388 (3) |
P2—O8 | 1.5150 (15) | C7—C8 | 1.388 (3) |
P2—O9 | 1.5350 (16) | C7—C12 | 1.515 (3) |
P2—O12 | 1.5837 (16) | C8—C9 | 1.372 (3) |
O1—C6 | 1.264 (3) | C8—H8 | 0.9300 |
O2—C6 | 1.220 (3) | C9—H9 | 0.9300 |
O3—C12 | 1.258 (3) | C10—C11 | 1.369 (3) |
O4—C12 | 1.236 (3) | C10—H10 | 0.9300 |
O11—H1O | 0.8504 | C11—H11 | 0.9300 |
O12—H2O | 0.8495 | O5—Zn1v | 1.9226 (17) |
N1—C4 | 1.330 (4) | O7—Zn1ii | 1.9303 (16) |
N1—C3 | 1.332 (4) | O9—Zn2vi | 1.9255 (15) |
N1—H1N | 0.8600 | O10—Zn2iv | 1.9442 (16) |
O6—Zn1—O5i | 102.90 (7) | C2—C1—C6 | 119.5 (2) |
O6—Zn1—O7ii | 119.02 (7) | C3—C2—C1 | 119.1 (3) |
O5i—Zn1—O7ii | 111.97 (7) | C3—C2—H2 | 120.4 |
O6—Zn1—O3 | 105.05 (8) | C1—C2—H2 | 120.4 |
O5i—Zn1—O3 | 104.05 (8) | N1—C3—C2 | 119.5 (2) |
O7ii—Zn1—O3 | 112.40 (8) | N1—C3—H3 | 120.3 |
O8—Zn2—O9iii | 114.15 (7) | C2—C3—H3 | 120.3 |
O8—Zn2—O10iv | 111.27 (7) | N1—C4—C5 | 119.4 (3) |
O9iii—Zn2—O10iv | 104.20 (7) | N1—C4—H4 | 120.3 |
O8—Zn2—O1 | 105.59 (7) | C5—C4—H4 | 120.3 |
O9iii—Zn2—O1 | 110.38 (7) | C4—C5—C1 | 119.3 (2) |
O10iv—Zn2—O1 | 111.40 (8) | C4—C5—H5 | 120.3 |
O6—P1—O5 | 110.79 (10) | C1—C5—H5 | 120.3 |
O6—P1—O7 | 112.30 (10) | O2—C6—O1 | 127.4 (2) |
O5—P1—O7 | 108.02 (9) | O2—C6—C1 | 117.9 (2) |
O6—P1—O11 | 105.99 (9) | O1—C6—C1 | 114.7 (2) |
O5—P1—O11 | 110.52 (10) | C11—C7—C8 | 119.0 (2) |
O7—P1—O11 | 109.23 (10) | C11—C7—C12 | 120.4 (2) |
O10—P2—O8 | 113.38 (9) | C8—C7—C12 | 120.5 (2) |
O10—P2—O9 | 111.52 (9) | C9—C8—C7 | 119.2 (2) |
O8—P2—O9 | 107.58 (9) | C9—C8—H8 | 120.4 |
O10—P2—O12 | 109.16 (9) | C7—C8—H8 | 120.4 |
O8—P2—O12 | 108.23 (9) | N2—C9—C8 | 120.1 (2) |
O9—P2—O12 | 106.71 (9) | N2—C9—H9 | 119.9 |
C6—O1—Zn2 | 120.79 (16) | C8—C9—H9 | 119.9 |
C12—O3—Zn1 | 131.88 (18) | N2—C10—C11 | 120.0 (2) |
P1—O6—Zn1 | 125.95 (10) | N2—C10—H10 | 120.0 |
P2—O8—Zn2 | 133.30 (10) | C11—C10—H10 | 120.0 |
P1—O11—H1O | 110.4 | C10—C11—C7 | 119.2 (2) |
P2—O12—H2O | 110.9 | C10—C11—H11 | 120.4 |
C4—N1—C3 | 123.3 (2) | C7—C11—H11 | 120.4 |
C4—N1—H1N | 118.4 | O4—C12—O3 | 128.0 (2) |
C3—N1—H1N | 118.4 | O4—C12—C7 | 117.3 (2) |
C9—N2—C10 | 122.4 (2) | O3—C12—C7 | 114.7 (2) |
C9—N2—H2N | 118.8 | P1—O5—Zn1v | 126.65 (10) |
C10—N2—H2N | 118.8 | P1—O7—Zn1ii | 127.97 (10) |
C5—C1—C2 | 119.4 (2) | P2—O9—Zn2vi | 130.89 (9) |
C5—C1—C6 | 121.1 (2) | P2—O10—Zn2iv | 119.99 (9) |
O8—Zn2—O1—C6 | −64.3 (2) | C2—C1—C6—O2 | 0.0 (4) |
O9iii—Zn2—O1—C6 | 171.9 (2) | C5—C1—C6—O1 | 0.3 (4) |
O10iv—Zn2—O1—C6 | 56.6 (2) | C2—C1—C6—O1 | −178.1 (2) |
O6—Zn1—O3—C12 | 89.4 (2) | C11—C7—C8—C9 | −0.3 (4) |
O5i—Zn1—O3—C12 | −162.8 (2) | C12—C7—C8—C9 | 179.2 (2) |
O7ii—Zn1—O3—C12 | −41.4 (3) | C10—N2—C9—C8 | −1.1 (4) |
O5—P1—O6—Zn1 | −153.17 (12) | C7—C8—C9—N2 | 1.3 (4) |
O7—P1—O6—Zn1 | 85.94 (14) | C9—N2—C10—C11 | −0.3 (4) |
O11—P1—O6—Zn1 | −33.25 (16) | N2—C10—C11—C7 | 1.4 (4) |
O5i—Zn1—O6—P1 | 90.95 (14) | C8—C7—C11—C10 | −1.1 (4) |
O7ii—Zn1—O6—P1 | −33.51 (16) | C12—C7—C11—C10 | 179.5 (2) |
O3—Zn1—O6—P1 | −160.42 (13) | Zn1—O3—C12—O4 | 2.8 (4) |
O10—P2—O8—Zn2 | −119.85 (14) | Zn1—O3—C12—C7 | −177.88 (16) |
O9—P2—O8—Zn2 | 116.36 (14) | C11—C7—C12—O4 | 167.1 (2) |
O12—P2—O8—Zn2 | 1.40 (17) | C8—C7—C12—O4 | −12.3 (4) |
O9iii—Zn2—O8—P2 | −40.16 (16) | C11—C7—C12—O3 | −12.3 (3) |
O10iv—Zn2—O8—P2 | 77.42 (15) | C8—C7—C12—O3 | 168.3 (2) |
O1—Zn2—O8—P2 | −161.58 (13) | O6—P1—O5—Zn1v | 75.36 (15) |
C5—C1—C2—C3 | −0.1 (4) | O7—P1—O5—Zn1v | −161.25 (11) |
C6—C1—C2—C3 | 178.3 (2) | O11—P1—O5—Zn1v | −41.81 (15) |
C4—N1—C3—C2 | 0.6 (4) | O6—P1—O7—Zn1ii | −95.66 (13) |
C1—C2—C3—N1 | −0.2 (4) | O5—P1—O7—Zn1ii | 141.87 (12) |
C3—N1—C4—C5 | −0.6 (4) | O11—P1—O7—Zn1ii | 21.62 (15) |
N1—C4—C5—C1 | 0.3 (4) | O10—P2—O9—Zn2vi | 29.23 (16) |
C2—C1—C5—C4 | 0.1 (4) | O8—P2—O9—Zn2vi | 154.15 (11) |
C6—C1—C5—C4 | −178.3 (3) | O12—P2—O9—Zn2vi | −89.89 (14) |
Zn2—O1—C6—O2 | −5.9 (4) | O8—P2—O10—Zn2iv | 67.88 (13) |
Zn2—O1—C6—C1 | 172.05 (16) | O9—P2—O10—Zn2iv | −170.51 (9) |
C5—C1—C6—O2 | 178.4 (3) | O12—P2—O10—Zn2iv | −52.85 (13) |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1, −y+1, −z; (v) −x, y+1/2, −z+1/2; (vi) −x+1, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H1O···O4ii | 0.85 | 1.77 | 2.610 (2) | 167.3 |
O12—H2O···O2iv | 0.85 | 1.81 | 2.655 (3) | 169.6 |
N2—H2N···O8 | 0.86 | 2.64 | 3.153 (3) | 119 |
Symmetry codes: (ii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C6H5NO2)2(HPO4)2] |
Mr | 568.92 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 292 |
a, b, c (Å) | 20.560 (4), 8.5138 (17), 10.387 (2) |
β (°) | 97.46 (3) |
V (Å3) | 1802.8 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.91 |
Crystal size (mm) | 0.20 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick 1996) |
Tmin, Tmax | 0.564, 0.646 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17073, 6748, 5343 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.776 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.097, 1.02 |
No. of reflections | 6748 |
No. of parameters | 271 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.84, −0.41 |
Computer programs: SMART (Bruker, 1997–2000), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Siemens 1990), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H1O···O4i | 0.85 | 1.77 | 2.610 (2) | 167.3 |
O12—H2O···O2ii | 0.85 | 1.81 | 2.655 (3) | 169.6 |
N2—H2N···O8 | 0.86 | 2.64 | 3.153 (3) | 119.2 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
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Because of the potential applications in catalysis, medicine and host–guest chemistry, inorganic metal oxides and salts structurally directed by polydentate organic ligands have attracted much attention (Leininger et al., 2000; Hagrman et al., 1999; Zhang et al., 2002; Yuan et al., 2002). In recent years, organically templated zinc phosphates have become a focus of much interest as a result of their rich structural and compositional diversity. A number of zinc phosphates with zero-, one-, two- and three-dimensional architectures have been constructed by employing solvothermal methods (Wang et al., 2003; Xing et al., 2004). In this paper, we report the hydrothermal synthesis and structural characterization of Zn2(C6H5NO2)2(HPO4)2, (C6H5NO2 = isonicotinate = ina), a novel organic–inorganic hybrid compound.
The asymmetric unit contains two crystallographically nonequivalent, but chemically identical, [Zn(ina)(HPO4)] groups. Each of these groups is bonded to another via a centrosymmetric junction to form two different dimers that can be regarded as the secondary building units of the structure (Fig. 1). These secondary building units are bonded to like units to form two distinct inorganic two-dimensional networks, a Zn1 layer and a Zn2 layer (Fig. 2). The centrosymmetric junctions are eight-membered rings comprising four tetrahedral centres (two Zn and two P) and four corner-shared bridging O atoms (Fig. 1). The Zn2O4 unit is considerably distorted from a regular tetrahedron (Table 1). Each dimer is connected to four others in the same layer via an O bridging atom of PO4 (O5 for the Zn1 layer and O9 for the Zn2 layer; Fig. 1) to form the two-dimensional inorganic networks composed of the eight-membered rings and larger 16-membered rings (4Zn, 4P and 8O; Fig. 2). The ina ligands are coordinated to Zn via one carboxylate O atom and extend on both sides of the networks (Figs. 2 and 3). There are strong intradimer hydorgen bonds between the HPO4 units and the free carboxyl O atom of ina (Table 2). These bonds help control the steric relationship between the pyridine rings and the eight-membered inorganic rings.
The main difference between the two layers is that in the Zn1 layer all pyridine rings are parallel to one another (face-to-face arrangement), while in the Zn2 layer they have two orientations that are perpendicular to one another (face-to-edge arrangement). The Zn1 and Zn2 layers stack alternately in an.. ABAB.. fashion along the a axis to give rise to a three-dimensional structure (Fig. 3). The adjacent layers are interdigitated through ina rings to result in a tight packing. They are also connected via interlayer hydrogen bonding (Table 2).
The title compound contains N-protonated isonicotinate, [(H)NC5H4CO2], which was not a starting reactant. It has been demonstrated that 4-cyanopyridine can be hydrolized slowly to yield isonicotinic acid under hydrothermal conditions (Evens et al., 1999). It is therefore very likely that the formation and crystal growth of the title compound was controlled by the hydrolyzation of 4-cyanopyridine.