Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105005329/gd1374sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105005329/gd1374Isup2.hkl |
CCDC reference: 269015
The title compound was synthesized by reacting stoichiometric amounts of zinc perchlorate hexahydrate with L dissolved in hot methanol, followed by crystallization by slow cooling.
The perchlorate anion exhibits very wide-amplitude displacement, indicative of partial rotational disorder that could not be resolved. The content and structure of the crystallization solvent could not be determined precisely from the diffraction data, owing to severe positional disorder and fractional occupancies at each site. The approximate unit-cell content, which best fits the diffraction data, was assessed as 1.72 molecules of methanol and 1.28 molecules of water distributed randomly in the crystal within and between the self-assembled networks. The O34/C35 and O36/C37 fragments represent methanol species with 36 and 50% occupancy, respectively. Atom O38 (nearly coinciding with the position of O34) represents a water molecule with 64% occupancy. These solvent species are located near and disordered about the inversion centre. According to this model O34/C35 (methanol) and O38 (water) are randomly distributed in the crystal at the same site in different unit cells. The coinciding position of these two species results from the hydrogen bonding of either one to the Zn-bound methanol ligand O19/H19. The apparent disorder of the solvent species seems to have a negligible effect on the precise characterization of the network structure. H atoms were placed at idealized positions; those attached to C atoms were refined using a riding model with fixed displacement parameters. The displacement parameters of the H atoms of the Zn-coordinated methanol and aqua groups were allowed to refine freely. H atoms of the water solvent molecules could not be located. The relatively high residual density should be attributed to the unresolved solvent.
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and DS ViwerPro 5.0 (Accelrys, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Zn(C12H10N4)(CH4O)2(H2O)2](ClO4)2·C12H10N4·1.72CH4O·1.28H2O | Z = 1 |
Mr = 1073.28 | F(000) = 558 |
Triclinic, P1 | Dx = 1.471 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4170 (2) Å | Cell parameters from 4290 reflections |
b = 10.8320 (2) Å | θ = 2.7–27.0° |
c = 13.1410 (3) Å | µ = 0.70 mm−1 |
α = 67.8390 (8)° | T = 110 K |
β = 81.3040 (9)° | Prism, yellow |
γ = 78.3160 (9)° | 0.30 × 0.20 × 0.15 mm |
V = 1211.56 (4) Å3 |
Nonius KappaCCD diffractometer | 5216 independent reflections |
Radiation source: fine-focus sealed tube | 4492 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 56 microns pixels mm-1 | θmax = 27.0°, θmin = 2.7° |
1° ϕ and ω scans | h = 0→12 |
Absorption correction: multi-scan (Blessing, 1995) | k = −13→13 |
Tmin = 0.818, Tmax = 0.903 | l = −16→16 |
10055 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full with fixed elements per cycle | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.053P)2 + 2.505P] where P = (Fo2 + 2Fc2)/3 |
5216 reflections | (Δ/σ)max = 0.028 |
347 parameters | Δρmax = 0.92 e Å−3 |
2 restraints | Δρmin = −1.17 e Å−3 |
[Zn(C12H10N4)(CH4O)2(H2O)2](ClO4)2·C12H10N4·1.72CH4O·1.28H2O | γ = 78.3160 (9)° |
Mr = 1073.28 | V = 1211.56 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.4170 (2) Å | Mo Kα radiation |
b = 10.8320 (2) Å | µ = 0.70 mm−1 |
c = 13.1410 (3) Å | T = 110 K |
α = 67.8390 (8)° | 0.30 × 0.20 × 0.15 mm |
β = 81.3040 (9)° |
Nonius KappaCCD diffractometer | 5216 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 4492 reflections with I > 2σ(I) |
Tmin = 0.818, Tmax = 0.903 | Rint = 0.029 |
10055 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 2 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.92 e Å−3 |
5216 reflections | Δρmin = −1.17 e Å−3 |
347 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. The perchlorate anion suffers from partial rotational disorder. Fragments O34—C35 and O36—C37 represent methanol species with 36% and 50% occupancy, respectively. Based on earlier refinement calculations, showing an occupancy of 1.0 at the O34 site, it was assumed that at this site water (O38) and methanol are randomly distributed in the crystal. O38 thus refined with occupancy of 64%. In this interpretation of the refinement calculations, the nearly coinciding positions of O34(methanol) and O38(water) result from their H-bonding to OH(19), the Zn-bound methanol ligand. O34—C35 and O38 were refined in alternating cycles of the least-squares calculations, due to very high correlations between their respective atomic parameters. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.0000 | 0.5000 | 1.0000 | 0.01552 (13) | |
N2 | 0.1802 (2) | 0.5559 (2) | 0.88446 (18) | 0.0171 (4) | |
C3 | 0.2435 (3) | 0.6585 (3) | 0.8805 (2) | 0.0190 (5) | |
H3 | 0.2119 | 0.6983 | 0.9349 | 0.023* | |
C4 | 0.3517 (3) | 0.7085 (3) | 0.8014 (2) | 0.0213 (6) | |
H4 | 0.3947 | 0.7802 | 0.8023 | 0.026* | |
C5 | 0.3975 (3) | 0.6524 (3) | 0.7197 (2) | 0.0192 (5) | |
C6 | 0.3335 (3) | 0.5446 (3) | 0.7245 (2) | 0.0208 (5) | |
H6 | 0.3630 | 0.5026 | 0.6713 | 0.025* | |
C7 | 0.2269 (3) | 0.4999 (3) | 0.8077 (2) | 0.0194 (5) | |
H7 | 0.1846 | 0.4260 | 0.8107 | 0.023* | |
C8 | 0.5078 (3) | 0.7051 (3) | 0.6298 (2) | 0.0231 (6) | |
H8 | 0.5374 | 0.6651 | 0.5754 | 0.028* | |
N9 | 0.5636 (3) | 0.8055 (3) | 0.6256 (2) | 0.0266 (5) | |
N10 | 0.6671 (3) | 0.8429 (3) | 0.5344 (2) | 0.0275 (6) | |
C11 | 0.7084 (3) | 0.9527 (3) | 0.5244 (2) | 0.0269 (6) | |
H11 | 0.6693 | 0.9959 | 0.5757 | 0.032* | |
C12 | 0.8158 (3) | 1.0129 (3) | 0.4344 (2) | 0.0224 (6) | |
C13 | 0.8697 (3) | 0.9608 (3) | 0.3514 (2) | 0.0268 (6) | |
H13 | 0.8386 | 0.8828 | 0.3513 | 0.032* | |
C14 | 0.9690 (3) | 1.0244 (3) | 0.2696 (2) | 0.0267 (6) | |
H14 | 1.0060 | 0.9874 | 0.2140 | 0.032* | |
N15 | 1.0165 (3) | 1.1359 (2) | 0.2643 (2) | 0.0246 (5) | |
C16 | 0.9650 (3) | 1.1846 (3) | 0.3445 (2) | 0.0246 (6) | |
H16 | 0.9979 | 1.2630 | 0.3424 | 0.029* | |
C17 | 0.8661 (3) | 1.1267 (3) | 0.4308 (2) | 0.0242 (6) | |
H17 | 0.8333 | 1.1642 | 0.4866 | 0.029* | |
O18 | 0.09854 (19) | 0.29692 (18) | 1.04860 (15) | 0.0189 (4) | |
H18A | 0.2019 | 0.2624 | 1.0448 | 0.069 (15)* | |
H18B | 0.0699 | 0.2410 | 1.1233 | 0.063 (14)* | |
O19 | 0.1074 (2) | 0.5314 (2) | 1.12069 (16) | 0.0226 (4) | |
H19 | 0.0802 | 0.5859 | 1.1677 | 0.075 (15)* | |
C20 | 0.2362 (3) | 0.4483 (3) | 1.1695 (3) | 0.0316 (7) | |
H20A | 0.2639 | 0.4833 | 1.2212 | 0.047* | |
H20B | 0.3154 | 0.4493 | 1.1116 | 0.047* | |
H20C | 0.2175 | 0.3556 | 1.2090 | 0.047* | |
N21 | 0.6061 (3) | 0.8020 (3) | 0.9622 (2) | 0.0250 (5) | |
C22 | 0.5713 (3) | 0.9210 (3) | 0.8823 (3) | 0.0255 (6) | |
H22 | 0.6459 | 0.9575 | 0.8283 | 0.031* | |
C23 | 0.4312 (3) | 0.9942 (3) | 0.8741 (2) | 0.0246 (6) | |
H23 | 0.4110 | 1.0786 | 0.8159 | 0.030* | |
C24 | 0.3213 (3) | 0.9416 (3) | 0.9527 (2) | 0.0218 (6) | |
C25 | 0.3576 (3) | 0.8173 (3) | 1.0367 (2) | 0.0231 (6) | |
H25 | 0.2857 | 0.7783 | 1.0922 | 0.028* | |
C26 | 0.4995 (3) | 0.7524 (3) | 1.0376 (3) | 0.0254 (6) | |
H26 | 0.5230 | 0.6678 | 1.0948 | 0.031* | |
C27 | 0.1710 (3) | 1.0152 (3) | 0.9462 (2) | 0.0245 (6) | |
H27 | 0.1506 | 1.1046 | 0.8946 | 0.029* | |
N28 | 0.0683 (3) | 0.9581 (3) | 1.0103 (2) | 0.0276 (5) | |
Cl29 | 0.34389 (10) | 0.69878 (9) | 0.35758 (7) | 0.0402 (2) | |
O30 | 0.3120 (5) | 0.6298 (4) | 0.4711 (2) | 0.0845 (13) | |
O31 | 0.4802 (6) | 0.7404 (5) | 0.3404 (4) | 0.123 (2) | |
O32 | 0.3480 (4) | 0.6154 (3) | 0.2971 (2) | 0.0593 (8) | |
O33 | 0.2406 (7) | 0.8140 (5) | 0.3142 (3) | 0.148 (3) | |
O34 | −0.0038 (7) | 0.6851 (6) | 0.2390 (7) | 0.045 (2) | 0.36 |
C35 | −0.037 (2) | 0.6052 (16) | 0.3599 (10) | 0.088 (5) | 0.36 |
H35A | 0.0167 | 0.6316 | 0.4046 | 0.132* | 0.36 |
H35B | −0.0078 | 0.5086 | 0.3735 | 0.132* | 0.36 |
H35C | −0.1417 | 0.6238 | 0.3797 | 0.132* | 0.36 |
O36 | 0.1813 (7) | 0.3859 (6) | 0.5492 (5) | 0.0616 (19) | 0.50 |
C37 | 0.0695 (14) | 0.4938 (15) | 0.5779 (12) | 0.148 (9) | 0.50 |
H37A | −0.0237 | 0.4606 | 0.6041 | 0.222* | 0.50 |
H37B | 0.0567 | 0.5759 | 0.5122 | 0.222* | 0.50 |
H37C | 0.1036 | 0.5141 | 0.6358 | 0.222* | 0.50 |
O38 | 0.0060 (4) | 0.6780 (4) | 0.2555 (3) | 0.0433 (9) | 0.64 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0122 (2) | 0.0183 (2) | 0.0138 (2) | −0.00359 (15) | 0.00155 (15) | −0.00361 (17) |
N2 | 0.0140 (10) | 0.0191 (10) | 0.0149 (10) | −0.0031 (8) | 0.0007 (8) | −0.0027 (9) |
C3 | 0.0158 (12) | 0.0227 (13) | 0.0173 (13) | −0.0041 (10) | 0.0004 (10) | −0.0058 (11) |
C4 | 0.0178 (13) | 0.0233 (13) | 0.0211 (14) | −0.0066 (10) | 0.0001 (10) | −0.0051 (11) |
C5 | 0.0126 (12) | 0.0225 (13) | 0.0151 (12) | −0.0009 (10) | −0.0007 (10) | 0.0004 (10) |
C6 | 0.0186 (13) | 0.0225 (13) | 0.0179 (13) | 0.0006 (10) | 0.0011 (10) | −0.0062 (11) |
C7 | 0.0187 (13) | 0.0184 (12) | 0.0182 (13) | −0.0027 (10) | 0.0012 (10) | −0.0046 (11) |
C8 | 0.0167 (13) | 0.0259 (14) | 0.0190 (13) | −0.0020 (11) | 0.0019 (10) | −0.0014 (11) |
N9 | 0.0192 (12) | 0.0336 (13) | 0.0183 (12) | −0.0079 (10) | 0.0054 (9) | −0.0005 (10) |
N10 | 0.0209 (12) | 0.0346 (14) | 0.0197 (12) | −0.0115 (10) | 0.0061 (10) | −0.0008 (11) |
C11 | 0.0183 (13) | 0.0333 (16) | 0.0203 (14) | −0.0037 (12) | 0.0004 (11) | −0.0007 (12) |
C12 | 0.0143 (12) | 0.0251 (14) | 0.0194 (13) | −0.0031 (10) | −0.0013 (10) | 0.0011 (11) |
C13 | 0.0270 (15) | 0.0280 (15) | 0.0229 (14) | −0.0098 (12) | −0.0005 (12) | −0.0041 (12) |
C14 | 0.0262 (15) | 0.0293 (15) | 0.0205 (14) | −0.0071 (12) | 0.0024 (11) | −0.0045 (12) |
N15 | 0.0196 (11) | 0.0244 (12) | 0.0214 (12) | −0.0053 (9) | 0.0003 (9) | 0.0015 (10) |
C16 | 0.0190 (13) | 0.0227 (13) | 0.0267 (15) | −0.0048 (11) | −0.0030 (11) | −0.0018 (12) |
C17 | 0.0188 (13) | 0.0269 (14) | 0.0211 (14) | −0.0002 (11) | −0.0019 (11) | −0.0038 (12) |
O18 | 0.0145 (9) | 0.0178 (9) | 0.0192 (9) | −0.0018 (7) | 0.0022 (7) | −0.0025 (8) |
O19 | 0.0180 (9) | 0.0316 (11) | 0.0209 (10) | −0.0012 (8) | −0.0044 (8) | −0.0128 (9) |
C20 | 0.0274 (16) | 0.0328 (16) | 0.0380 (18) | 0.0028 (13) | −0.0163 (13) | −0.0150 (14) |
N21 | 0.0159 (11) | 0.0311 (13) | 0.0306 (13) | −0.0007 (10) | −0.0004 (10) | −0.0162 (11) |
C22 | 0.0189 (13) | 0.0336 (16) | 0.0279 (15) | −0.0068 (12) | 0.0022 (11) | −0.0155 (13) |
C23 | 0.0224 (14) | 0.0279 (14) | 0.0255 (15) | −0.0043 (11) | −0.0035 (11) | −0.0109 (12) |
C24 | 0.0169 (13) | 0.0271 (14) | 0.0259 (14) | −0.0012 (11) | −0.0037 (11) | −0.0149 (12) |
C25 | 0.0161 (13) | 0.0299 (14) | 0.0239 (14) | −0.0024 (11) | −0.0006 (11) | −0.0113 (12) |
C26 | 0.0191 (13) | 0.0300 (15) | 0.0266 (15) | −0.0013 (11) | −0.0024 (11) | −0.0106 (12) |
C27 | 0.0196 (14) | 0.0283 (14) | 0.0274 (15) | 0.0004 (11) | −0.0053 (11) | −0.0127 (12) |
N28 | 0.0155 (12) | 0.0324 (13) | 0.0331 (14) | 0.0040 (10) | −0.0042 (10) | −0.0128 (11) |
Cl29 | 0.0533 (5) | 0.0366 (4) | 0.0275 (4) | 0.0104 (4) | −0.0082 (4) | −0.0149 (3) |
O30 | 0.147 (4) | 0.065 (2) | 0.0256 (15) | −0.003 (2) | −0.0041 (19) | −0.0070 (15) |
O31 | 0.178 (5) | 0.108 (3) | 0.089 (3) | −0.104 (4) | −0.061 (3) | 0.019 (3) |
O32 | 0.071 (2) | 0.081 (2) | 0.0426 (16) | −0.0272 (17) | −0.0014 (14) | −0.0352 (16) |
O33 | 0.193 (5) | 0.104 (3) | 0.056 (2) | 0.106 (4) | 0.012 (3) | −0.002 (2) |
O34 | 0.023 (3) | 0.032 (3) | 0.099 (6) | 0.002 (3) | −0.016 (3) | −0.043 (4) |
C35 | 0.105 (13) | 0.078 (10) | 0.087 (12) | −0.040 (10) | 0.035 (10) | −0.039 (10) |
O36 | 0.072 (4) | 0.051 (3) | 0.067 (4) | −0.034 (3) | 0.051 (3) | −0.035 (3) |
C37 | 0.100 (12) | 0.26 (2) | 0.068 (9) | −0.087 (15) | −0.018 (8) | −0.002 (12) |
O38 | 0.048 (2) | 0.058 (2) | 0.0291 (19) | −0.0050 (19) | 0.0029 (17) | −0.0255 (19) |
Zn1—O18 | 2.0977 (18) | O18—H18A | 0.9702 |
Zn1—O18i | 2.0977 (18) | O18—H18B | 0.9703 |
Zn1—N2i | 2.120 (2) | O19—C20 | 1.432 (4) |
Zn1—N2 | 2.120 (2) | O19—H19 | 0.9813 |
Zn1—O19i | 2.1642 (19) | C20—H20A | 0.9800 |
Zn1—O19 | 2.1642 (19) | C20—H20B | 0.9800 |
N2—C7 | 1.341 (3) | C20—H20C | 0.9800 |
N2—C3 | 1.345 (3) | N21—C22 | 1.336 (4) |
C3—C4 | 1.375 (4) | N21—C26 | 1.340 (4) |
C3—H3 | 0.9500 | C22—C23 | 1.391 (4) |
C4—C5 | 1.397 (4) | C22—H22 | 0.9500 |
C4—H4 | 0.9500 | C23—C24 | 1.391 (4) |
C5—C6 | 1.397 (4) | C23—H23 | 0.9500 |
C5—C8 | 1.470 (4) | C24—C25 | 1.398 (4) |
C6—C7 | 1.380 (4) | C24—C27 | 1.475 (4) |
C6—H6 | 0.9500 | C25—C26 | 1.378 (4) |
C7—H7 | 0.9500 | C25—H25 | 0.9500 |
C8—N9 | 1.279 (4) | C26—H26 | 0.9500 |
C8—H8 | 0.9500 | C27—N28 | 1.276 (4) |
N9—N10 | 1.412 (3) | C27—H27 | 0.9500 |
N10—C11 | 1.279 (4) | N28—N28ii | 1.415 (5) |
C11—C12 | 1.474 (4) | Cl29—O32 | 1.402 (3) |
C11—H11 | 0.9500 | Cl29—O33 | 1.403 (4) |
C12—C17 | 1.390 (4) | Cl29—O31 | 1.405 (5) |
C12—C13 | 1.395 (4) | Cl29—O30 | 1.410 (3) |
C13—C14 | 1.379 (4) | O34—C35 | 1.514 (9) |
C13—H13 | 0.9500 | C35—H35A | 0.9800 |
C14—N15 | 1.345 (4) | C35—H35B | 0.9800 |
C14—H14 | 0.9500 | C35—H35C | 0.9800 |
N15—C16 | 1.336 (4) | O36—C37 | 1.526 (9) |
C16—C17 | 1.389 (4) | C37—H37A | 0.9800 |
C16—H16 | 0.9500 | C37—H37B | 0.9800 |
C17—H17 | 0.9500 | C37—H37C | 0.9800 |
O18—Zn1—O18i | 180.0 | N15—C16—C17 | 123.4 (3) |
O18—Zn1—N2i | 89.85 (8) | N15—C16—H16 | 118.3 |
O18i—Zn1—N2i | 90.15 (8) | C17—C16—H16 | 118.3 |
O18—Zn1—N2 | 90.15 (8) | C16—C17—C12 | 119.0 (3) |
O18i—Zn1—N2 | 89.85 (8) | C16—C17—H17 | 120.5 |
N2i—Zn1—N2 | 180.00 (11) | C12—C17—H17 | 120.5 |
O18—Zn1—O19i | 88.77 (7) | Zn1—O18—H18A | 127.1 |
O18i—Zn1—O19i | 91.23 (7) | Zn1—O18—H18B | 115.2 |
N2i—Zn1—O19i | 88.80 (8) | H18A—O18—H18B | 100.1 |
N2—Zn1—O19i | 91.20 (8) | C20—O19—Zn1 | 124.83 (17) |
O18—Zn1—O19 | 91.23 (7) | C20—O19—H19 | 99.5 |
O18i—Zn1—O19 | 88.77 (7) | Zn1—O19—H19 | 134.6 |
N2i—Zn1—O19 | 91.20 (8) | O19—C20—H20A | 109.5 |
N2—Zn1—O19 | 88.80 (8) | O19—C20—H20B | 109.5 |
O19i—Zn1—O19 | 179.999 (1) | H20A—C20—H20B | 109.5 |
C7—N2—C3 | 117.7 (2) | O19—C20—H20C | 109.5 |
C7—N2—Zn1 | 122.20 (18) | H20A—C20—H20C | 109.5 |
C3—N2—Zn1 | 119.86 (18) | H20B—C20—H20C | 109.5 |
N2—C3—C4 | 123.1 (3) | C22—N21—C26 | 117.5 (2) |
N2—C3—H3 | 118.4 | N21—C22—C23 | 123.2 (3) |
C4—C3—H3 | 118.4 | N21—C22—H22 | 118.4 |
C3—C4—C5 | 119.1 (3) | C23—C22—H22 | 118.4 |
C3—C4—H4 | 120.5 | C24—C23—C22 | 118.8 (3) |
C5—C4—H4 | 120.5 | C24—C23—H23 | 120.6 |
C6—C5—C4 | 118.0 (2) | C22—C23—H23 | 120.6 |
C6—C5—C8 | 120.1 (3) | C23—C24—C25 | 118.1 (3) |
C4—C5—C8 | 121.9 (3) | C23—C24—C27 | 120.5 (3) |
C7—C6—C5 | 119.0 (3) | C25—C24—C27 | 121.4 (3) |
C7—C6—H6 | 120.5 | C26—C25—C24 | 118.8 (3) |
C5—C6—H6 | 120.5 | C26—C25—H25 | 120.6 |
N2—C7—C6 | 123.1 (3) | C24—C25—H25 | 120.6 |
N2—C7—H7 | 118.4 | N21—C26—C25 | 123.6 (3) |
C6—C7—H7 | 118.4 | N21—C26—H26 | 118.2 |
N9—C8—C5 | 119.4 (3) | C25—C26—H26 | 118.2 |
N9—C8—H8 | 120.3 | N28—C27—C24 | 119.6 (3) |
C5—C8—H8 | 120.3 | N28—C27—H27 | 120.2 |
C8—N9—N10 | 111.9 (3) | C24—C27—H27 | 120.2 |
C11—N10—N9 | 110.7 (3) | C27—N28—N28ii | 111.6 (3) |
N10—C11—C12 | 120.8 (3) | O32—Cl29—O33 | 107.4 (3) |
N10—C11—H11 | 119.6 | O32—Cl29—O31 | 108.5 (3) |
C12—C11—H11 | 119.6 | O33—Cl29—O31 | 107.8 (4) |
C17—C12—C13 | 118.0 (3) | O32—Cl29—O30 | 111.1 (2) |
C17—C12—C11 | 119.2 (3) | O33—Cl29—O30 | 112.3 (2) |
C13—C12—C11 | 122.8 (3) | O31—Cl29—O30 | 109.6 (3) |
C14—C13—C12 | 119.0 (3) | O36—C37—H37A | 109.5 |
C14—C13—H13 | 120.5 | O36—C37—H37B | 109.5 |
C12—C13—H13 | 120.5 | H37A—C37—H37B | 109.5 |
N15—C14—C13 | 123.5 (3) | O36—C37—H37C | 109.5 |
N15—C14—H14 | 118.2 | H37A—C37—H37C | 109.5 |
C13—C14—H14 | 118.2 | H37B—C37—H37C | 109.5 |
C16—N15—C14 | 117.1 (2) |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O18—H18A···N21iii | 0.97 | 1.80 | 2.773 (3) | 180 |
O18—H18B···N15iv | 0.97 | 1.83 | 2.798 (3) | 180 |
O19—H19···O34v | 0.98 | 1.69 | 2.653 (7) | 167 |
O19···O38v | ? | ? | 2.752 (7) | ? |
O36···O30 | ? | ? | 2.904 (7) | ? |
O36···O34vi | ? | ? | 2.937 (8) | ? |
O36···O38vi | ? | ? | 2.937 (7) | ? |
Symmetry codes: (iii) −x+1, −y+1, −z+2; (iv) x−1, y−1, z+1; (v) x, y, z+1; (vi) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C12H10N4)(CH4O)2(H2O)2](ClO4)2·C12H10N4·1.72CH4O·1.28H2O |
Mr | 1073.28 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 110 |
a, b, c (Å) | 9.4170 (2), 10.8320 (2), 13.1410 (3) |
α, β, γ (°) | 67.8390 (8), 81.3040 (9), 78.3160 (9) |
V (Å3) | 1211.56 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.70 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.818, 0.903 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10055, 5216, 4492 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.132, 1.04 |
No. of reflections | 5216 |
No. of parameters | 347 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.92, −1.17 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), DENZO, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and DS ViwerPro 5.0 (Accelrys, 2002).
Zn1—O18 | 2.0977 (18) | Zn1—O19 | 2.1642 (19) |
Zn1—N2 | 2.120 (2) | ||
O18—Zn1—N2 | 90.15 (8) | O18i—Zn1—O19 | 88.77 (7) |
O18i—Zn1—N2 | 89.85 (8) | N2i—Zn1—O19 | 91.20 (8) |
O18—Zn1—O19 | 91.23 (7) | N2—Zn1—O19 | 88.80 (8) |
Symmetry code: (i) −x, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O18—H18A···N21ii | 0.97 | 1.80 | 2.773 (3) | 180 |
O18—H18B···N15iii | 0.97 | 1.83 | 2.798 (3) | 180 |
O19—H19···O34iv | 0.98 | 1.69 | 2.653 (7) | 167 |
O19···O38iv | ? | ? | 2.752 (7) | ? |
O36···O30 | ? | ? | 2.904 (7) | ? |
O36···O34v | ? | ? | 2.937 (8) | ? |
O36···O38v | ? | ? | 2.937 (7) | ? |
Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) x−1, y−1, z+1; (iv) x, y, z+1; (v) −x, −y+1, −z+1. |
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We have been exploring the coordination chemistry of a large series of polyimine ligands with transition metal ions (Patra & Goldberg, 2002, 2003a,b) and with metalloporphyrins (Diskin-Posner, Patra & Goldberg, 2002, 2001). Tailored derivatives of the 4,4'-bipyridyl-type ligands with various spacers between the bipyridyl functions are very effective in the formation of diverse architectures via coordination through metal ion connectors (e.g. Co, Ni, Mn, Zn, Ag and Pb). Such ligands are also excellent proton acceptors in hydrogen bonding (through their N-atom sites), in the presence of strong proton-donating agents.
We refer here to the 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene ligand (L), and its hydrogen bonding and coordination to [Zn(H2O)2(MeOH)2]2+ cations, affording self-assembled two-dimensional networks. Another important feature of L is its aromatic nature, with delocalized π electrons, preserving the planar geometry of this ligand both in its coordination polymers or oligomers with various transition metals and as a free non-coordinated species in its protonated or base forms (Kennedy & Waterson, 2003; Ciurtin et al., 2001).
The title compound, (I) (Fig. 1), consists of the octahedral [Zn(H2O)2(MeOH)2(L)2]2+ dication, two perchlorate anions and another ligand species hydrogen bonded to the water ligands. The dication and the extended bipyridyl moieties reside on crystallographic inversion centres. The crystal structure is a solvate incorporating additional molecules of methanol and water, not bound to the metal centre, in the unit cell.
The solvated zinc ion [labelled hereafter as Zn(s)] coordinates at trans-related sites to two molecules of the ligand [Zn—N = 2.120 (2) Å], forming a linear L–Zn(s)–L oligomer. Adjacent units of the latter are aligned parallel to one another in an offset manner along the long molecular axis, in such a way that the pyridyl ends of one trimer hydrogen bond to the Zn-bound water ligands of two adjacent L–Zn(s)–L trimers [O···N = 2.798 (3) Å; Fig. 2]. The double chains thus formed propagate along the [11–1] axis through the crystal. The overlapping planar ligand segments of neighbouring oligomers in these double chains further interact with one another through π–π interactions, as indicated by the very close interligand spacing. The mean interplanar distance between the parallel stacked pyridyl rings [N2/C3–C7 and C12–C14/N15/C16/C17 at (1 − x, 2 − y, 1 − z)] is 3.369 (7) Å, the shortest atom-to-atom distance between these two rings being 3.252 (3) Å (Fig. 3). The overlapping pyridyl rings are nearly parallel to each other, the angle between their normals being 5.6 (2)°. The third ligand moiety provides a bridging unit between different double chains by hydrogen bonding through its N-atom sites on both sides, accepting the second H atom of the zinc-bound water ligands [O···N = 2.773 (3) Å].
The binding pattern described above results in a supramolecularly assembled network in the form of a nearly square grid (Fig. 2). The van der Waals width of the void space in the grid is about 8 Å, sizeable enough to accommodate the perchlorate anions and additional methanol and water solvent molecules. The zinc-bound methanol ligands hydrogen bond to the lattice-occluded solvent [represented by O34, O36 (methanol) and O38 (water) in Table 2], the latter lying also within a hydrogen-bonding distances from the perchlorate anions. The network arrays stack in the crystal along the [111] axis. The crystal packing of (I) viewed down the a axis is shown in Fig. 4, illustrating the inclusion of the perchlorate anions and disordered solvent molecules in channel voids propagating through the crystal. A space-filling illustration of the channel structure down a, excluding these species, is presented in Fig. 5. This structure illustrates nicely the high versatility of bipyridyl ligands in the construction of hybrid organic–inorganic supramolecular assemblies.