In the title compound, {[Zn(C10H8N2)(H2O)4](C6H5O4S)2·3H2O}n, the Zn atom, the bipyridine ligand and one of water molecules are located on twofold rotation axes. The Zn atom is coordinated by four O atoms from four water molecules and two N atoms from two 4,4′-bipyridine molecules in a distorted octahedral geometry. The Zn2+ ions are linked by the 4,4′-bipyridine molecules to form a one-dimensional straight chain propagating along the c axis. The 4-hydroxybenzenesulfonate counter-ions are bridged by the solvent water molecules through hydrogen bonds to generate a two-dimensional layer featuring large pores. In the crystal packing, the intralayer pores form one-dimensional channels along the c axis, in which the one-dimensional [Zn(C10H8N2)(H2O)4]2+ chains are encapsulated. Electrostatic interactions between cations and anions and extensive hydrogen bonds result in a three-dimensional supramolecular structure.
Supporting information
CCDC reference: 628498
The title compound was synthesized by hydrothermal methods under autogenous pressure. A mixture of Zn(NO3)2·6H2O (148 mg, 0.5 mmol), sodium 4-hydroxybenzenesulfonate dihydrate (116 mg, 0.5 mmol), 4, 4'-bipyridine (78 mg, 0.5 mmol) and distilled water (15 ml) was stirred under ambient conditions. The final mixture was sealed in a 25 ml Teflon-lined steel autoclave, heated at 438 K for 3 d and then cooled to room temperature. Colorless prism-like crystals of (I) were obtained, and these were recovered by filtration, washed with distilled water and dried in air (yield 33%). Analysis calculated for C22H32N2O15S2Zn: C 38.15, H 4.66, N, 4.05%; found: C 38.10, H 4.61, N, 4.03%.
Aromatic H atoms were placed in calculated positions and treated using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)]. H atoms bonded to O atoms were visible in a difference map and were refined with a DFIX (SHELXL97; Sheldrick, 1997a) restraint [O—H = 0.90 (1) Å and Uiso(H) = 1.5Ueq(O)].
Data collection: CrystalClear (Rigaku Corporation & Molecular Structure Corporation,
2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97.
catena-Poly[[[tetraaquazinc(II)]-µ-4,4'-bipyridine] bis(4-hydroxybenzenesulfonate) trihydrate]
top
Crystal data top
[Zn(C10H8N2)(H2O)4](C6H5O4S)2·3H2O) | F(000) = 720 |
Mr = 693.99 | Dx = 1.584 Mg m−3 |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 4741 reflections |
a = 17.623 (1) Å | θ = 2.1–27.5° |
b = 7.2451 (6) Å | µ = 1.06 mm−1 |
c = 11.3957 (8) Å | T = 293 K |
V = 1455.00 (19) Å3 | Prism, colorless |
Z = 2 | 0.35 × 0.30 × 0.25 mm |
Data collection top
Rigaku Mercury70 (2x2 bin mode) diffractometer | 3337 independent reflections |
Radiation source: fine-focus sealed tube | 3066 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | h = −22→22 |
Tmin = 0.698, Tmax = 0.768 | k = −9→7 |
11370 measured reflections | l = −14→14 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0394P)2 + 0.17P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.074 | (Δ/σ)max = 0.001 |
S = 1.00 | Δρmax = 0.46 e Å−3 |
3337 reflections | Δρmin = −0.39 e Å−3 |
218 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
10 restraints | Extinction coefficient: 0.0250 (16) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 1401 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.030 (12) |
Crystal data top
[Zn(C10H8N2)(H2O)4](C6H5O4S)2·3H2O) | V = 1455.00 (19) Å3 |
Mr = 693.99 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 17.623 (1) Å | µ = 1.06 mm−1 |
b = 7.2451 (6) Å | T = 293 K |
c = 11.3957 (8) Å | 0.35 × 0.30 × 0.25 mm |
Data collection top
Rigaku Mercury70 (2x2 bin mode) diffractometer | 3337 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 3066 reflections with I > 2σ(I) |
Tmin = 0.698, Tmax = 0.768 | Rint = 0.030 |
11370 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.074 | Δρmax = 0.46 e Å−3 |
S = 1.00 | Δρmin = −0.39 e Å−3 |
3337 reflections | Absolute structure: Flack (1983), with 1401 Friedel pairs |
218 parameters | Absolute structure parameter: 0.030 (12) |
10 restraints | |
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 | |
Zn1 | 1.0000 | 0.0000 | −0.47429 (3) | 0.02876 (12) | |
S1 | 0.80032 (3) | 0.46768 (8) | −0.64587 (5) | 0.03371 (15) | |
N1 | 1.0000 | 0.0000 | −0.66070 (19) | 0.0313 (5) | |
N2 | 1.0000 | 0.0000 | −1.28440 (19) | 0.0295 (5) | |
O1 | 0.95289 (12) | 0.2660 (3) | −0.46385 (18) | 0.0496 (5) | |
H1B | 0.9676 (17) | 0.339 (4) | −0.405 (2) | 0.074* | |
H1A | 0.9132 (13) | 0.314 (4) | −0.501 (3) | 0.074* | |
O1W | 1.0000 | 0.5000 | −0.2851 (2) | 0.0463 (6) | |
H1W | 1.0398 (12) | 0.469 (5) | −0.240 (2) | 0.069* | |
O2 | 0.89034 (10) | −0.1163 (3) | −0.47600 (19) | 0.0507 (5) | |
H2A | 0.8495 (12) | −0.067 (4) | −0.442 (3) | 0.076* | |
H2B | 0.8787 (19) | −0.224 (3) | −0.510 (3) | 0.076* | |
O2W | 0.76026 (17) | 0.4406 (3) | −1.2966 (2) | 0.0740 (7) | |
H2W | 0.7685 (18) | 0.337 (4) | −1.339 (3) | 0.111* | |
H3W | 0.760 (2) | 0.545 (4) | −1.339 (3) | 0.111* | |
O3 | 0.78828 (15) | 0.2749 (3) | −0.61725 (19) | 0.0628 (6) | |
O4 | 0.73210 (10) | 0.5752 (3) | −0.62770 (17) | 0.0476 (5) | |
O5 | 0.86574 (10) | 0.5419 (3) | −0.58612 (16) | 0.0557 (6) | |
O6 | 0.86675 (10) | 0.5232 (4) | −1.15198 (16) | 0.0526 (5) | |
H6A | 0.8357 (16) | 0.458 (4) | −1.196 (2) | 0.079* | |
C1 | 0.93978 (13) | 0.0570 (4) | −0.7220 (2) | 0.0408 (7) | |
H1C | 0.8969 | 0.0959 | −0.6814 | 0.049* | |
C2 | 0.93837 (13) | 0.0608 (4) | −0.8431 (2) | 0.0389 (7) | |
H2C | 0.8956 | 0.1047 | −0.8818 | 0.047* | |
C3 | 1.0000 | 0.0000 | −0.9073 (2) | 0.0256 (5) | |
C4 | 1.0000 | 0.0000 | −1.0379 (2) | 0.0253 (5) | |
C5 | 0.93584 (13) | 0.0466 (4) | −1.10231 (19) | 0.0367 (6) | |
H5 | 0.8913 | 0.0787 | −1.0637 | 0.044* | |
C6 | 0.93802 (13) | 0.0454 (4) | −1.22321 (19) | 0.0363 (7) | |
H6B | 0.8943 | 0.0777 | −1.2641 | 0.044* | |
C7 | 0.82075 (12) | 0.4792 (4) | −0.79747 (19) | 0.0316 (5) | |
C8 | 0.88698 (14) | 0.5633 (3) | −0.8375 (2) | 0.0402 (6) | |
H8 | 0.9215 | 0.6116 | −0.7840 | 0.048* | |
C9 | 0.90142 (15) | 0.5749 (4) | −0.9554 (2) | 0.0428 (6) | |
H9 | 0.9459 | 0.6305 | −0.9815 | 0.051* | |
C10 | 0.85002 (13) | 0.5042 (4) | −1.0361 (2) | 0.0384 (5) | |
C11 | 0.78438 (14) | 0.4168 (3) | −0.9965 (2) | 0.0390 (6) | |
H11 | 0.7503 | 0.3664 | −1.0500 | 0.047* | |
C12 | 0.77019 (13) | 0.4056 (4) | −0.8782 (2) | 0.0360 (6) | |
H12 | 0.7262 | 0.3479 | −0.8519 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.02908 (17) | 0.0401 (2) | 0.01711 (16) | 0.00100 (17) | 0.000 | 0.000 |
S1 | 0.0327 (3) | 0.0363 (3) | 0.0321 (3) | 0.0021 (3) | 0.0008 (2) | 0.0001 (2) |
N1 | 0.0311 (12) | 0.0444 (15) | 0.0185 (11) | 0.0035 (15) | 0.000 | 0.000 |
N2 | 0.0306 (12) | 0.0389 (14) | 0.0189 (11) | −0.0015 (16) | 0.000 | 0.000 |
O1 | 0.0632 (13) | 0.0453 (11) | 0.0403 (11) | 0.0192 (9) | −0.0196 (10) | −0.0056 (9) |
O1W | 0.0465 (13) | 0.0545 (15) | 0.0379 (13) | −0.0042 (16) | 0.000 | 0.000 |
O2 | 0.0330 (9) | 0.0676 (13) | 0.0515 (12) | −0.0101 (9) | 0.0097 (9) | −0.0194 (11) |
O2W | 0.0991 (19) | 0.0532 (15) | 0.0696 (17) | 0.0009 (13) | −0.0237 (15) | 0.0000 (12) |
O3 | 0.0979 (18) | 0.0379 (11) | 0.0524 (13) | 0.0030 (11) | 0.0209 (12) | 0.0104 (9) |
O4 | 0.0389 (9) | 0.0611 (13) | 0.0428 (11) | 0.0142 (8) | 0.0047 (8) | −0.0023 (9) |
O5 | 0.0438 (10) | 0.0818 (17) | 0.0415 (10) | −0.0068 (11) | −0.0104 (8) | −0.0029 (10) |
O6 | 0.0531 (11) | 0.0691 (14) | 0.0356 (9) | −0.0038 (12) | 0.0084 (8) | 0.0029 (12) |
C1 | 0.0323 (12) | 0.068 (2) | 0.0220 (11) | 0.0123 (12) | 0.0022 (9) | −0.0029 (11) |
C2 | 0.0301 (11) | 0.0630 (19) | 0.0238 (11) | 0.0135 (11) | −0.0039 (9) | −0.0028 (11) |
C3 | 0.0279 (13) | 0.0298 (15) | 0.0192 (12) | 0.0003 (17) | 0.000 | 0.000 |
C4 | 0.0284 (12) | 0.0271 (14) | 0.0205 (12) | −0.0001 (15) | 0.000 | 0.000 |
C5 | 0.0303 (11) | 0.0575 (19) | 0.0222 (10) | 0.0092 (11) | 0.0026 (8) | −0.0028 (10) |
C6 | 0.0294 (11) | 0.058 (2) | 0.0214 (10) | 0.0091 (12) | −0.0033 (8) | 0.0011 (11) |
C7 | 0.0319 (10) | 0.0286 (12) | 0.0343 (11) | 0.0029 (11) | 0.0033 (9) | 0.0002 (11) |
C8 | 0.0388 (13) | 0.0405 (14) | 0.0412 (14) | −0.0100 (10) | −0.0009 (11) | −0.0049 (11) |
C9 | 0.0384 (13) | 0.0442 (15) | 0.0458 (16) | −0.0118 (11) | 0.0092 (11) | 0.0024 (11) |
C10 | 0.0405 (11) | 0.0376 (13) | 0.0373 (12) | 0.0023 (13) | 0.0062 (10) | −0.0015 (17) |
C11 | 0.0367 (12) | 0.0444 (14) | 0.0358 (15) | −0.0007 (10) | −0.0012 (10) | −0.0041 (10) |
C12 | 0.0279 (11) | 0.0405 (14) | 0.0395 (14) | −0.0029 (10) | 0.0045 (10) | −0.0007 (11) |
Geometric parameters (Å, º) top
Zn1—O1i | 2.102 (2) | O6—H6A | 0.88 (3) |
Zn1—O1 | 2.102 (2) | C1—C2 | 1.380 (3) |
Zn1—O2i | 2.108 (2) | C1—H1C | 0.9300 |
Zn1—O2 | 2.108 (2) | C2—C3 | 1.382 (3) |
Zn1—N1 | 2.124 (2) | C2—H2C | 0.9300 |
Zn1—N2ii | 2.164 (2) | C3—C2i | 1.382 (3) |
S1—O5 | 1.443 (2) | C3—C4 | 1.488 (3) |
S1—O4 | 1.447 (2) | C4—C5 | 1.390 (3) |
S1—O3 | 1.450 (2) | C4—C5i | 1.390 (3) |
S1—C7 | 1.767 (2) | C5—C6 | 1.378 (3) |
N1—C1 | 1.336 (3) | C5—H5 | 0.9300 |
N1—C1i | 1.336 (3) | C6—H6B | 0.9300 |
N2—C6 | 1.337 (2) | C7—C12 | 1.387 (3) |
N2—C6i | 1.337 (2) | C7—C8 | 1.393 (3) |
N2—Zn1iii | 2.164 (2) | C8—C9 | 1.370 (4) |
O1—H1B | 0.89 (3) | C8—H8 | 0.9300 |
O1—H1A | 0.89 (3) | C9—C10 | 1.389 (3) |
O1W—H1W | 0.89 (1) | C9—H9 | 0.9300 |
O2—H2A | 0.89 (3) | C10—C11 | 1.393 (3) |
O2—H2B | 0.90 (1) | C11—C12 | 1.374 (4) |
O2W—H2W | 0.90 (3) | C11—H11 | 0.9300 |
O2W—H3W | 0.90 (3) | C12—H12 | 0.9300 |
O6—C10 | 1.360 (3) | | |
| | | |
O1i—Zn1—O1 | 173.51 (11) | N1—C1—H1C | 118.5 |
O1i—Zn1—O2i | 90.29 (9) | C2—C1—H1C | 118.5 |
O1—Zn1—O2i | 89.77 (9) | C1—C2—C3 | 120.6 (2) |
O1i—Zn1—O2 | 89.77 (9) | C1—C2—H2C | 119.7 |
O1—Zn1—O2 | 90.29 (9) | C3—C2—H2C | 119.7 |
O2i—Zn1—O2 | 178.94 (12) | C2i—C3—C2 | 116.0 (3) |
O1i—Zn1—N1 | 93.24 (6) | C2i—C3—C4 | 121.98 (13) |
O1—Zn1—N1 | 93.24 (6) | C2—C3—C4 | 121.98 (13) |
O2i—Zn1—N1 | 89.47 (6) | C5—C4—C5i | 116.2 (3) |
O2—Zn1—N1 | 89.47 (6) | C5—C4—C3 | 121.90 (13) |
O1i—Zn1—N2ii | 86.76 (6) | C5i—C4—C3 | 121.90 (13) |
O1—Zn1—N2ii | 86.76 (6) | C6—C5—C4 | 120.3 (2) |
O2i—Zn1—N2ii | 90.53 (6) | C6—C5—H5 | 119.9 |
O2—Zn1—N2ii | 90.53 (6) | C4—C5—H5 | 119.9 |
N1—Zn1—N2ii | 180.0 | N2—C6—C5 | 123.1 (2) |
O5—S1—O4 | 113.31 (12) | N2—C6—H6B | 118.5 |
O5—S1—O3 | 111.70 (14) | C5—C6—H6B | 118.5 |
O4—S1—O3 | 111.39 (14) | C12—C7—C8 | 119.3 (2) |
O5—S1—C7 | 106.31 (11) | C12—C7—S1 | 119.95 (17) |
O4—S1—C7 | 106.48 (11) | C8—C7—S1 | 120.76 (18) |
O3—S1—C7 | 107.18 (12) | C9—C8—C7 | 120.2 (2) |
C1—N1—C1i | 116.9 (3) | C9—C8—H8 | 119.9 |
C1—N1—Zn1 | 121.54 (13) | C7—C8—H8 | 119.9 |
C1i—N1—Zn1 | 121.54 (13) | C8—C9—C10 | 120.4 (2) |
C6—N2—C6i | 117.1 (2) | C8—C9—H9 | 119.8 |
C6—N2—Zn1iii | 121.43 (12) | C10—C9—H9 | 119.8 |
C6i—N2—Zn1iii | 121.43 (12) | O6—C10—C9 | 117.7 (2) |
Zn1—O1—H1B | 118 (2) | O6—C10—C11 | 122.7 (2) |
Zn1—O1—H1A | 130 (2) | C9—C10—C11 | 119.6 (2) |
H1B—O1—H1A | 110 (3) | C12—C11—C10 | 119.7 (2) |
Zn1—O2—H2A | 125 (2) | C12—C11—H11 | 120.1 |
Zn1—O2—H2B | 124 (2) | C10—C11—H11 | 120.1 |
H2A—O2—H2B | 111 (3) | C11—C12—C7 | 120.7 (2) |
H2W—O2W—H3W | 115 (4) | C11—C12—H12 | 119.6 |
C10—O6—H6A | 111 (2) | C7—C12—H12 | 119.6 |
N1—C1—C2 | 122.9 (2) | | |
| | | |
O1i—Zn1—N1—C1 | 134.58 (16) | C6i—N2—C6—C5 | −0.1 (2) |
O1—Zn1—N1—C1 | −45.42 (16) | Zn1iii—N2—C6—C5 | 179.9 (2) |
O2i—Zn1—N1—C1 | −135.16 (16) | C4—C5—C6—N2 | 0.3 (4) |
O2—Zn1—N1—C1 | 44.84 (16) | O5—S1—C7—C12 | 175.6 (2) |
O1i—Zn1—N1—C1i | −45.42 (16) | O4—S1—C7—C12 | −63.3 (2) |
O1—Zn1—N1—C1i | 134.58 (16) | O3—S1—C7—C12 | 56.0 (2) |
O2i—Zn1—N1—C1i | 44.84 (16) | O5—S1—C7—C8 | −5.0 (2) |
O2—Zn1—N1—C1i | −135.16 (16) | O4—S1—C7—C8 | 116.1 (2) |
C1i—N1—C1—C2 | −0.8 (2) | O3—S1—C7—C8 | −124.6 (2) |
Zn1—N1—C1—C2 | 179.2 (2) | C12—C7—C8—C9 | 0.8 (4) |
N1—C1—C2—C3 | 1.6 (4) | S1—C7—C8—C9 | −178.6 (2) |
C1—C2—C3—C2i | −0.77 (19) | C7—C8—C9—C10 | 0.4 (4) |
C1—C2—C3—C4 | 179.23 (19) | C8—C9—C10—O6 | 178.7 (3) |
C2i—C3—C4—C5 | 174.55 (19) | C8—C9—C10—C11 | −1.6 (4) |
C2—C3—C4—C5 | −5.45 (19) | O6—C10—C11—C12 | −178.7 (3) |
C2i—C3—C4—C5i | −5.45 (19) | C9—C10—C11—C12 | 1.6 (4) |
C2—C3—C4—C5i | 174.55 (19) | C10—C11—C12—C7 | −0.4 (4) |
C5i—C4—C5—C6 | −0.13 (19) | C8—C7—C12—C11 | −0.8 (4) |
C3—C4—C5—C6 | 179.87 (19) | S1—C7—C12—C11 | 178.59 (19) |
Symmetry codes: (i) −x+2, −y, z; (ii) x, y, z+1; (iii) x, y, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O5 | 0.89 (3) | 2.09 (2) | 2.880 (3) | 148 (3) |
O1—H1B···O1W | 0.89 (3) | 1.89 (3) | 2.777 (3) | 178 (3) |
O2—H2A···O4iv | 0.89 (3) | 1.94 (3) | 2.824 (3) | 172 (3) |
O2—H2B···O5v | 0.90 (1) | 1.92 (3) | 2.810 (3) | 174 (3) |
O1W—H1W···O6vi | 0.89 (1) | 1.93 (1) | 2.801 (2) | 163 (3) |
O2W—H3W···O3vii | 0.90 (3) | 1.94 (2) | 2.750 (3) | 149 (4) |
O2W—H2W···O4viii | 0.90 (3) | 1.93 (2) | 2.788 (3) | 157 (4) |
O6—H6A···O2W | 0.88 (3) | 1.76 (2) | 2.568 (3) | 152 (3) |
Symmetry codes: (iv) −x+3/2, y−1/2, −z−1; (v) x, y−1, z; (vi) −x+2, −y+1, z+1; (vii) −x+3/2, y+1/2, −z−2; (viii) −x+3/2, y−1/2, −z−2. |
Experimental details
Crystal data |
Chemical formula | [Zn(C10H8N2)(H2O)4](C6H5O4S)2·3H2O) |
Mr | 693.99 |
Crystal system, space group | Orthorhombic, P21212 |
Temperature (K) | 293 |
a, b, c (Å) | 17.623 (1), 7.2451 (6), 11.3957 (8) |
V (Å3) | 1455.00 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 |
|
Data collection |
Diffractometer | Rigaku Mercury70 (2x2 bin mode) diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2000) |
Tmin, Tmax | 0.698, 0.768 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11370, 3337, 3066 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.074, 1.00 |
No. of reflections | 3337 |
No. of parameters | 218 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.46, −0.39 |
Absolute structure | Flack (1983), with 1401 Friedel pairs |
Absolute structure parameter | 0.030 (12) |
Selected geometric parameters (Å, º) topZn1—O1 | 2.102 (2) | S1—O5 | 1.443 (2) |
Zn1—O2 | 2.108 (2) | S1—O4 | 1.447 (2) |
Zn1—N1 | 2.124 (2) | S1—O3 | 1.450 (2) |
Zn1—N2i | 2.164 (2) | | |
| | | |
O1ii—Zn1—O1 | 173.51 (11) | O2—Zn1—N1 | 89.47 (6) |
O1—Zn1—O2ii | 89.77 (9) | O1—Zn1—N2i | 86.76 (6) |
O1—Zn1—O2 | 90.29 (9) | O2—Zn1—N2i | 90.53 (6) |
O2ii—Zn1—O2 | 178.94 (12) | N1—Zn1—N2i | 180.0 |
O1—Zn1—N1 | 93.24 (6) | | |
Symmetry codes: (i) x, y, z+1; (ii) −x+2, −y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O5 | 0.89 (3) | 2.09 (2) | 2.880 (3) | 148 (3) |
O1—H1B···O1W | 0.89 (3) | 1.89 (3) | 2.777 (3) | 178 (3) |
O2—H2A···O4iii | 0.89 (3) | 1.94 (3) | 2.824 (3) | 172 (3) |
O2—H2B···O5iv | 0.90 (1) | 1.92 (3) | 2.810 (3) | 174 (3) |
O1W—H1W···O6v | 0.89 (1) | 1.93 (1) | 2.801 (2) | 163 (3) |
O2W—H3W···O3vi | 0.90 (3) | 1.94 (2) | 2.750 (3) | 149 (4) |
O2W—H2W···O4vii | 0.90 (3) | 1.93 (2) | 2.788 (3) | 157 (4) |
O6—H6A···O2W | 0.88 (3) | 1.76 (2) | 2.568 (3) | 152 (3) |
Symmetry codes: (iii) −x+3/2, y−1/2, −z−1; (iv) x, y−1, z; (v) −x+2, −y+1, z+1; (vi) −x+3/2, y+1/2, −z−2; (vii) −x+3/2, y−1/2, −z−2. |
Supramolecular chemistry and crystal engineering are active fields of chemistry owing to the intriguing structural topologies examined and potential applications in host–guest chemistry, catalysis and electrical conductivity (Biradha & Zaworotko, 1998; Yaghi et al., 1995; Conn & Rebek, 1997). The key to successful construction of supramolecular architecture is the control and manipulation of coordination bonds and non-covalent interactions by carefully selecting the coordination geometry of the metal centers and the organic ligands containing appropriate functional groups (such as carboxylic acid and pyridine) (Tong et al., 1999; Dong et al., 2000). In the past few years, much effort has so far been devoted to the study of carboxylate-based supramolecular assemblies (Prior & Rosseinsky, 2001; Sun et al., 2003). However, relatively little attention has been paid to the sulfonate-based supramolecular assemblies, despite the fact that the sulfonate-containing ligand can provide three potential hydrogen-bond acceptors (Evans et al., 1999). Recently, the combination of the sulfonate-containing ligand with metal ions in our laboratory has produced several complexes with diverse structural topologies (Liu & Xu, 2005a,b). The hydrothermal reaction of Zn(NO3)2 with sodium 4-hydroxybenzenesulfonate (HBSNa) and 4, 4'-bipyridine (bpy) yields the title complex, (I). We present its structure here.
The asymmetric unit of (I) consists of a half-occupied [Zn(bpy)(H2O)4] cation, an HBS anion, and one and a half solvent water molecules. The cation is located on a twofold rotation axis that passes through atoms Zn1, N1, N2, C3 and C4. The Zn atom is six-coordinated by four O atoms from four water molecules in a distorted square-planar geometry, with two N atoms from two bpy molecules in apical positions (Fig. 1). The ZnO4N2 octahedron is slightly elongated (Table 1). The bond lengths involving Zn are normal, and are comparable to the values in related zinc(II) complexes (Zhang & Zhu, 2005; Huang et al., 1998). As depicted in Fig. 2, the Zn ions are linked by the bpy molecules to produce a one-dimensional straight chain propagating along the c axis. The chain is repeated by translation about every 11.4 Å along the c direction, comparable with the length of the c axis. The two pyridine rings of the bpy system are not coplanar but make a dihedral angle of 5.1 (2)°, which is smaller than the corresponding angles of 39.2 (1)° in [Zn(bpy)Cl2]n (Hu & Englert, 2005).
The HBS− anion is not involved in coordination but is hydrogen-bonded to the [Zn(bpy)(H2O)4] cation and solvent water molecules. As depicted in Fig. 3, the HBS− anions are linked by the solvent water molecules (O2W) through hydrogen bonds between (a) water molecules and sulfonate O atoms and (b) hydroxy groups and water O atoms (Table 2) to form a one-dimensional ladder struture propagating along the b axis. In the one-dimensional ladder structure, the HBS− anion adopts two types of conformations based on the orientations of the sulfonate group (up and down in the Fig. 3). It is interesting that the benzene rings of the HBS− anions with the same conformation are parallel and are twisted with respect to the benzene rings of the other type of HBS− anions, with a dihedral angle of 57.4 (1). The one-dimensional ladders are further linked by O1W—H1W···O6vi (symmetry code see Table 2) hydrogen bonds to produce a two-dimensional layered structure featuring large pores as illustrated in Fig. 4. In the crystal packing, the intralayer pores form one-dimensional channel along the c axis. A noteworthy feature of this compound is that the one-dimensional [Zn(C10H8N2)(H2O)4]2+ chains are encapsulated in the host channels. The encapsulated cations interact with the negative layers via electrostatic interactions and hydrogen bonds between (a) coordinated water molecules and sulfonate O atoms and (b) coordinated water molecules and solvent water molecules (Fig. 5 and Table 2). These interactions are responsible for the three-dimensional supramolecular framework structure (Fig. 6).