Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110033998/sq3250sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110033998/sq3250Isup2.hkl |
CCDC reference: 777430
TATP was prepared according to the method of Dickeson & Summers (1970). A mixture of Zn(NO3)2 (0.148 g, 0.5 mmol), benzotriazole-5-carboxylic acid (0.049 g, 0.3 mmol), TATP (0.068 g, 0.3 mmol), dimethylformamide (5 ml) and water (5 ml) was placed in a 23 ml Teflon reactor and stirred for 20 min in air, then heated at 453 K for 5 d, followed by cooling to room temperature at a rate of 5 K h-1. The resulting brown prismatic crystals of (I) were isolated in ca 42% yield based on Zn.
The aromatic H atoms were placed at calculated positions in the riding-model approximation, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule could not be located reliably and were omitted from the model. The presence of solvent water molecules was determined according to the IR spectrum and thermogravimetric analysis (TGA) results. The TGA results indicate that the title compound lost its lattice water molecules below 340 K, the weight loss found of 0.92% was consistent with that calculated (0.97%). The occupancy was thus fixed at 0.25.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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: SHELXTL (Sheldrick, 2008).
[Zn(C7H3N3O2)(C14H8N4)]·0.25H2O | Dx = 1.725 Mg m−3 |
Mr = 463.24 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 8475 reflections |
a = 17.3649 (9) Å | θ = 2.4–28.8° |
b = 8.6087 (4) Å | µ = 1.42 mm−1 |
c = 23.8669 (12) Å | T = 173 K |
V = 3567.8 (3) Å3 | Prismatic, brown |
Z = 8 | 0.37 × 0.32 × 0.23 mm |
F(000) = 1876 |
Bruker APEXII CCD area-detector diffractometer | 3509 independent reflections |
Radiation source: fine-focus sealed tube | 2865 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −21→20 |
Tmin = 0.623, Tmax = 0.732 | k = −9→10 |
27994 measured reflections | l = −29→29 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0427P)2] where P = (Fo2 + 2Fc2)/3 |
3509 reflections | (Δ/σ)max = 0.001 |
289 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
[Zn(C7H3N3O2)(C14H8N4)]·0.25H2O | V = 3567.8 (3) Å3 |
Mr = 463.24 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 17.3649 (9) Å | µ = 1.42 mm−1 |
b = 8.6087 (4) Å | T = 173 K |
c = 23.8669 (12) Å | 0.37 × 0.32 × 0.23 mm |
Bruker APEXII CCD area-detector diffractometer | 3509 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2865 reflections with I > 2σ(I) |
Tmin = 0.623, Tmax = 0.732 | Rint = 0.063 |
27994 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.52 e Å−3 |
3509 reflections | Δρmin = −0.36 e Å−3 |
289 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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) | |
Zn1 | 0.137594 (13) | 0.40203 (3) | 0.147600 (9) | 0.01270 (9) | |
C1 | −0.14480 (10) | 0.2372 (2) | 0.29061 (7) | 0.0125 (4) | |
C2 | −0.07543 (11) | 0.2548 (2) | 0.26116 (7) | 0.0143 (4) | |
H2A | −0.0341 | 0.1837 | 0.2659 | 0.017* | |
C3 | −0.06957 (11) | 0.3800 (2) | 0.22498 (8) | 0.0144 (4) | |
C4 | −0.13146 (11) | 0.4861 (2) | 0.21810 (8) | 0.0153 (4) | |
H4A | −0.1264 | 0.5685 | 0.1919 | 0.018* | |
C5 | −0.19828 (11) | 0.4728 (2) | 0.24835 (8) | 0.0150 (4) | |
H5A | −0.2390 | 0.5457 | 0.2441 | 0.018* | |
C6 | −0.20438 (11) | 0.3470 (2) | 0.28597 (8) | 0.0136 (4) | |
C7 | 0.00351 (12) | 0.4045 (2) | 0.19270 (8) | 0.0165 (4) | |
C8 | 0.07857 (11) | 0.0524 (2) | 0.13240 (9) | 0.0186 (5) | |
H8A | 0.0712 | 0.0546 | 0.1718 | 0.022* | |
C9 | 0.06325 (12) | −0.0853 (2) | 0.10340 (9) | 0.0209 (5) | |
H9A | 0.0453 | −0.1744 | 0.1229 | 0.025* | |
C10 | 0.07431 (12) | −0.0907 (2) | 0.04661 (9) | 0.0212 (5) | |
H10A | 0.0639 | −0.1835 | 0.0264 | 0.025* | |
C11 | 0.10110 (12) | 0.0419 (2) | 0.01858 (8) | 0.0191 (4) | |
C12 | 0.11401 (13) | 0.0476 (3) | −0.04133 (9) | 0.0216 (5) | |
C13 | 0.11589 (14) | −0.0735 (3) | −0.12602 (10) | 0.0315 (6) | |
H13A | 0.1116 | −0.1644 | −0.1484 | 0.038* | |
C14 | 0.13242 (14) | 0.0673 (3) | −0.15245 (9) | 0.0305 (6) | |
H14A | 0.1360 | 0.0699 | −0.1922 | 0.037* | |
C15 | 0.13439 (12) | 0.1868 (3) | −0.06774 (8) | 0.0223 (5) | |
C16 | 0.14820 (12) | 0.3260 (3) | −0.03436 (8) | 0.0220 (5) | |
C17 | 0.16948 (14) | 0.4670 (3) | −0.05814 (9) | 0.0276 (5) | |
H17A | 0.1735 | 0.4776 | −0.0977 | 0.033* | |
C18 | 0.18456 (14) | 0.5911 (3) | −0.02342 (9) | 0.0271 (5) | |
H18A | 0.1993 | 0.6885 | −0.0387 | 0.032* | |
C19 | 0.17802 (13) | 0.5725 (2) | 0.03418 (8) | 0.0220 (5) | |
H19A | 0.1901 | 0.6585 | 0.0576 | 0.026* | |
C20 | 0.14032 (11) | 0.3183 (2) | 0.02423 (8) | 0.0170 (4) | |
C21 | 0.11421 (11) | 0.1758 (2) | 0.05095 (8) | 0.0160 (4) | |
N1 | −0.16797 (9) | 0.13012 (18) | 0.32989 (7) | 0.0141 (4) | |
N2 | −0.23716 (9) | 0.17470 (19) | 0.34881 (6) | 0.0147 (4) | |
N3 | −0.26040 (8) | 0.30457 (18) | 0.32331 (6) | 0.0139 (4) | |
N4 | 0.10314 (9) | 0.18057 (19) | 0.10673 (6) | 0.0158 (4) | |
N5 | 0.15570 (10) | 0.4406 (2) | 0.05839 (7) | 0.0170 (4) | |
N6 | 0.10599 (12) | −0.0858 (2) | −0.07125 (7) | 0.0264 (4) | |
N7 | 0.14330 (10) | 0.1970 (2) | −0.12396 (8) | 0.0279 (5) | |
O1 | 0.06535 (8) | 0.34697 (16) | 0.21284 (6) | 0.0186 (3) | |
O2 | 0.00240 (8) | 0.47789 (17) | 0.14746 (5) | 0.0218 (3) | |
O1W | −0.0206 (8) | 0.3931 (15) | 0.0359 (6) | 0.131 (5) | 0.25 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01273 (13) | 0.01010 (14) | 0.01527 (13) | −0.00056 (9) | 0.00016 (9) | −0.00101 (9) |
C1 | 0.0156 (10) | 0.0086 (10) | 0.0133 (9) | −0.0019 (8) | −0.0015 (7) | −0.0015 (7) |
C2 | 0.0166 (10) | 0.0100 (10) | 0.0163 (10) | −0.0003 (8) | −0.0003 (8) | −0.0029 (8) |
C3 | 0.0161 (10) | 0.0117 (10) | 0.0155 (10) | −0.0032 (8) | −0.0013 (8) | −0.0031 (8) |
C4 | 0.0205 (11) | 0.0112 (11) | 0.0143 (9) | −0.0027 (8) | −0.0016 (8) | 0.0006 (8) |
C5 | 0.0174 (11) | 0.0097 (10) | 0.0179 (10) | 0.0012 (8) | −0.0032 (8) | −0.0009 (8) |
C6 | 0.0143 (10) | 0.0101 (10) | 0.0164 (10) | −0.0019 (8) | −0.0015 (8) | −0.0009 (8) |
C7 | 0.0214 (11) | 0.0090 (10) | 0.0191 (10) | −0.0040 (9) | 0.0028 (8) | −0.0065 (8) |
C8 | 0.0151 (11) | 0.0198 (11) | 0.0210 (10) | 0.0022 (9) | −0.0046 (8) | 0.0018 (8) |
C9 | 0.0197 (11) | 0.0156 (11) | 0.0275 (11) | −0.0015 (9) | −0.0077 (9) | 0.0041 (9) |
C10 | 0.0223 (12) | 0.0136 (11) | 0.0278 (11) | 0.0024 (9) | −0.0083 (9) | −0.0025 (9) |
C11 | 0.0198 (11) | 0.0153 (11) | 0.0224 (11) | 0.0017 (9) | −0.0046 (9) | −0.0024 (9) |
C12 | 0.0242 (12) | 0.0186 (12) | 0.0218 (11) | 0.0039 (9) | −0.0081 (9) | −0.0057 (9) |
C13 | 0.0397 (15) | 0.0281 (14) | 0.0267 (12) | 0.0070 (11) | −0.0094 (11) | −0.0120 (10) |
C14 | 0.0407 (15) | 0.0331 (15) | 0.0176 (11) | 0.0059 (11) | −0.0042 (10) | −0.0083 (10) |
C15 | 0.0258 (12) | 0.0218 (12) | 0.0191 (10) | 0.0036 (9) | −0.0045 (9) | −0.0030 (9) |
C16 | 0.0274 (12) | 0.0184 (12) | 0.0202 (11) | 0.0030 (9) | −0.0017 (9) | −0.0030 (9) |
C17 | 0.0411 (14) | 0.0238 (13) | 0.0179 (11) | 0.0003 (11) | 0.0007 (10) | 0.0027 (9) |
C18 | 0.0391 (14) | 0.0174 (12) | 0.0246 (11) | −0.0017 (10) | 0.0016 (10) | 0.0040 (9) |
C19 | 0.0270 (12) | 0.0152 (12) | 0.0238 (11) | −0.0001 (9) | −0.0014 (9) | −0.0008 (9) |
C20 | 0.0174 (10) | 0.0145 (11) | 0.0190 (10) | 0.0022 (8) | −0.0018 (8) | −0.0012 (8) |
C21 | 0.0159 (10) | 0.0156 (11) | 0.0166 (10) | 0.0040 (9) | −0.0038 (8) | −0.0015 (8) |
N1 | 0.0127 (8) | 0.0107 (9) | 0.0189 (8) | 0.0007 (7) | 0.0006 (7) | 0.0006 (7) |
N2 | 0.0154 (9) | 0.0098 (9) | 0.0190 (9) | 0.0007 (7) | 0.0009 (7) | 0.0014 (7) |
N3 | 0.0131 (8) | 0.0106 (9) | 0.0181 (8) | −0.0002 (7) | −0.0005 (7) | 0.0014 (7) |
N4 | 0.0130 (8) | 0.0159 (9) | 0.0184 (8) | 0.0019 (7) | −0.0037 (7) | 0.0001 (7) |
N5 | 0.0195 (9) | 0.0126 (9) | 0.0189 (9) | 0.0011 (7) | −0.0018 (7) | −0.0014 (7) |
N6 | 0.0355 (11) | 0.0203 (10) | 0.0234 (10) | 0.0043 (9) | −0.0089 (8) | −0.0075 (8) |
N7 | 0.0367 (12) | 0.0277 (12) | 0.0193 (9) | 0.0042 (9) | −0.0010 (8) | −0.0025 (9) |
O1 | 0.0158 (7) | 0.0169 (8) | 0.0231 (7) | −0.0011 (6) | 0.0030 (6) | −0.0023 (6) |
O2 | 0.0238 (8) | 0.0208 (8) | 0.0208 (8) | −0.0036 (6) | 0.0053 (6) | 0.0020 (6) |
O1W | 0.107 (10) | 0.139 (12) | 0.146 (12) | 0.033 (8) | −0.029 (9) | −0.049 (9) |
Zn1—O1 | 2.0550 (13) | C10—H10A | 0.9500 |
Zn1—N3i | 2.0793 (15) | C11—C21 | 1.406 (3) |
Zn1—N1ii | 2.1030 (16) | C11—C12 | 1.448 (3) |
Zn1—N5 | 2.1777 (17) | C12—N6 | 1.359 (3) |
Zn1—N4 | 2.2234 (16) | C12—C15 | 1.399 (3) |
Zn1—O2 | 2.4368 (15) | C13—N6 | 1.323 (3) |
Zn1—C7 | 2.565 (2) | C13—C14 | 1.396 (3) |
C1—N1 | 1.375 (2) | C13—H13A | 0.9500 |
C1—C2 | 1.403 (3) | C14—N7 | 1.321 (3) |
C1—C6 | 1.406 (3) | C14—H14A | 0.9500 |
C2—C3 | 1.384 (3) | C15—N7 | 1.354 (3) |
C2—H2A | 0.9500 | C15—C16 | 1.459 (3) |
C3—C4 | 1.420 (3) | C16—C17 | 1.390 (3) |
C3—C7 | 1.500 (3) | C16—C20 | 1.406 (3) |
C4—C5 | 1.371 (3) | C17—C18 | 1.377 (3) |
C4—H4A | 0.9500 | C17—H17A | 0.9500 |
C5—C6 | 1.411 (3) | C18—C19 | 1.389 (3) |
C5—H5A | 0.9500 | C18—H18A | 0.9500 |
C6—N3 | 1.369 (2) | C19—N5 | 1.332 (3) |
C7—O2 | 1.251 (2) | C19—H19A | 0.9500 |
C7—O1 | 1.277 (2) | C20—N5 | 1.358 (3) |
C8—N4 | 1.332 (3) | C20—C21 | 1.455 (3) |
C8—C9 | 1.398 (3) | C21—N4 | 1.346 (2) |
C8—H8A | 0.9500 | N1—N2 | 1.340 (2) |
C9—C10 | 1.370 (3) | N1—Zn1iii | 2.1030 (16) |
C9—H9A | 0.9500 | N2—N3 | 1.335 (2) |
C10—C11 | 1.403 (3) | N3—Zn1iv | 2.0793 (15) |
O1—Zn1—N3i | 100.02 (6) | C9—C10—H10A | 120.3 |
O1—Zn1—N1ii | 100.07 (6) | C11—C10—H10A | 120.3 |
N3i—Zn1—N1ii | 94.46 (6) | C10—C11—C21 | 117.32 (19) |
O1—Zn1—N5 | 149.78 (6) | C10—C11—C12 | 123.31 (19) |
N3i—Zn1—N5 | 105.37 (6) | C21—C11—C12 | 119.36 (19) |
N1ii—Zn1—N5 | 94.08 (6) | N6—C12—C15 | 120.84 (19) |
O1—Zn1—N4 | 88.30 (6) | N6—C12—C11 | 118.3 (2) |
N3i—Zn1—N4 | 91.70 (6) | C15—C12—C11 | 120.82 (19) |
N1ii—Zn1—N4 | 168.56 (6) | N6—C13—C14 | 122.9 (2) |
N5—Zn1—N4 | 74.97 (6) | N6—C13—H13A | 118.6 |
O1—Zn1—O2 | 58.32 (5) | C14—C13—H13A | 118.6 |
N3i—Zn1—O2 | 158.33 (5) | N7—C14—C13 | 122.1 (2) |
N1ii—Zn1—O2 | 89.53 (6) | N7—C14—H14A | 119.0 |
N5—Zn1—O2 | 95.56 (5) | C13—C14—H14A | 119.0 |
N4—Zn1—O2 | 88.28 (5) | N7—C15—C12 | 122.1 (2) |
O1—Zn1—C7 | 29.53 (6) | N7—C15—C16 | 118.0 (2) |
N3i—Zn1—C7 | 129.53 (6) | C12—C15—C16 | 119.94 (18) |
N1ii—Zn1—C7 | 96.47 (6) | C17—C16—C20 | 118.2 (2) |
N5—Zn1—C7 | 122.68 (6) | C17—C16—C15 | 122.56 (19) |
N4—Zn1—C7 | 86.96 (6) | C20—C16—C15 | 119.2 (2) |
O2—Zn1—C7 | 28.82 (5) | C18—C17—C16 | 118.8 (2) |
N1—C1—C2 | 131.70 (18) | C18—C17—H17A | 120.6 |
N1—C1—C6 | 106.80 (16) | C16—C17—H17A | 120.6 |
C2—C1—C6 | 121.33 (18) | C17—C18—C19 | 119.4 (2) |
C3—C2—C1 | 117.37 (18) | C17—C18—H18A | 120.3 |
C3—C2—H2A | 121.3 | C19—C18—H18A | 120.3 |
C1—C2—H2A | 121.3 | N5—C19—C18 | 123.5 (2) |
C2—C3—C4 | 121.15 (18) | N5—C19—H19A | 118.3 |
C2—C3—C7 | 119.50 (18) | C18—C19—H19A | 118.3 |
C4—C3—C7 | 119.36 (17) | N5—C20—C16 | 122.76 (19) |
C5—C4—C3 | 121.71 (18) | N5—C20—C21 | 116.85 (17) |
C5—C4—H4A | 119.1 | C16—C20—C21 | 120.38 (19) |
C3—C4—H4A | 119.1 | N4—C21—C11 | 123.08 (19) |
C4—C5—C6 | 117.56 (18) | N4—C21—C20 | 116.89 (17) |
C4—C5—H5A | 121.2 | C11—C21—C20 | 120.03 (18) |
C6—C5—H5A | 121.2 | N2—N1—C1 | 107.47 (15) |
N3—C6—C1 | 107.00 (16) | N2—N1—Zn1iii | 113.97 (12) |
N3—C6—C5 | 132.26 (18) | C1—N1—Zn1iii | 136.62 (13) |
C1—C6—C5 | 120.73 (18) | N3—N2—N1 | 110.93 (15) |
O2—C7—O1 | 122.28 (18) | N2—N3—C6 | 107.79 (15) |
O2—C7—C3 | 120.10 (18) | N2—N3—Zn1iv | 116.30 (11) |
O1—C7—C3 | 117.62 (17) | C6—N3—Zn1iv | 135.65 (13) |
O2—C7—Zn1 | 69.89 (11) | C8—N4—C21 | 118.37 (17) |
O1—C7—Zn1 | 52.51 (9) | C8—N4—Zn1 | 126.49 (13) |
C3—C7—Zn1 | 169.28 (15) | C21—N4—Zn1 | 114.95 (13) |
N4—C8—C9 | 122.38 (19) | C19—N5—C20 | 117.25 (17) |
N4—C8—H8A | 118.8 | C19—N5—Zn1 | 126.59 (14) |
C9—C8—H8A | 118.8 | C20—N5—Zn1 | 116.13 (13) |
C10—C9—C8 | 119.47 (19) | C13—N6—C12 | 115.99 (19) |
C10—C9—H9A | 120.3 | C14—N7—C15 | 116.0 (2) |
C8—C9—H9A | 120.3 | C7—O1—Zn1 | 97.96 (12) |
C9—C10—C11 | 119.37 (19) | C7—O2—Zn1 | 81.29 (12) |
N1—C1—C2—C3 | −178.15 (19) | C2—C1—N1—N2 | 174.05 (19) |
C6—C1—C2—C3 | −3.5 (3) | C6—C1—N1—N2 | −1.2 (2) |
C1—C2—C3—C4 | 0.0 (3) | C2—C1—N1—Zn1iii | −23.6 (3) |
C1—C2—C3—C7 | 179.70 (16) | C6—C1—N1—Zn1iii | 161.18 (14) |
C2—C3—C4—C5 | 2.5 (3) | C1—N1—N2—N3 | 0.7 (2) |
C7—C3—C4—C5 | −177.20 (18) | Zn1iii—N1—N2—N3 | −166.21 (11) |
C3—C4—C5—C6 | −1.5 (3) | N1—N2—N3—C6 | 0.2 (2) |
N1—C1—C6—N3 | 1.3 (2) | N1—N2—N3—Zn1iv | −174.78 (11) |
C2—C1—C6—N3 | −174.53 (16) | C1—C6—N3—N2 | −0.9 (2) |
N1—C1—C6—C5 | −179.60 (17) | C5—C6—N3—N2 | −179.9 (2) |
C2—C1—C6—C5 | 4.5 (3) | C1—C6—N3—Zn1iv | 172.60 (13) |
C4—C5—C6—N3 | 176.83 (19) | C5—C6—N3—Zn1iv | −6.3 (3) |
C4—C5—C6—C1 | −2.0 (3) | C9—C8—N4—C21 | −0.7 (3) |
C2—C3—C7—O2 | 155.12 (18) | C9—C8—N4—Zn1 | −175.42 (14) |
C4—C3—C7—O2 | −25.2 (3) | C11—C21—N4—C8 | 0.0 (3) |
C2—C3—C7—O1 | −24.2 (3) | C20—C21—N4—C8 | 179.40 (17) |
C4—C3—C7—O1 | 155.44 (18) | C11—C21—N4—Zn1 | 175.28 (15) |
C2—C3—C7—Zn1 | −2.5 (8) | C20—C21—N4—Zn1 | −5.3 (2) |
C4—C3—C7—Zn1 | 177.2 (6) | O1—Zn1—N4—C8 | −26.80 (16) |
O1—Zn1—C7—O2 | 176.12 (18) | N3i—Zn1—N4—C8 | 73.18 (16) |
N3i—Zn1—C7—O2 | 178.35 (10) | N1ii—Zn1—N4—C8 | −164.2 (3) |
N1ii—Zn1—C7—O2 | 77.10 (11) | N5—Zn1—N4—C8 | 178.64 (17) |
N5—Zn1—C7—O2 | −21.98 (13) | O2—Zn1—N4—C8 | −85.14 (16) |
N4—Zn1—C7—O2 | −91.95 (11) | C7—Zn1—N4—C8 | −56.32 (16) |
N3i—Zn1—C7—O1 | 2.22 (14) | O1—Zn1—N4—C21 | 158.33 (14) |
N1ii—Zn1—C7—O1 | −99.02 (12) | N3i—Zn1—N4—C21 | −101.70 (14) |
N5—Zn1—C7—O1 | 161.89 (11) | N1ii—Zn1—N4—C21 | 20.9 (4) |
N4—Zn1—C7—O1 | 91.93 (11) | N5—Zn1—N4—C21 | 3.76 (13) |
O2—Zn1—C7—O1 | −176.12 (18) | O2—Zn1—N4—C21 | 99.98 (13) |
O1—Zn1—C7—C3 | −24.4 (7) | C7—Zn1—N4—C21 | 128.80 (14) |
N3i—Zn1—C7—C3 | −22.2 (7) | C18—C19—N5—C20 | 1.4 (3) |
N1ii—Zn1—C7—C3 | −123.4 (7) | C18—C19—N5—Zn1 | −176.52 (17) |
N5—Zn1—C7—C3 | 137.5 (7) | C16—C20—N5—C19 | 1.0 (3) |
N4—Zn1—C7—C3 | 67.5 (7) | C21—C20—N5—C19 | −178.58 (17) |
O2—Zn1—C7—C3 | 159.5 (8) | C16—C20—N5—Zn1 | 179.10 (15) |
N4—C8—C9—C10 | 0.6 (3) | C21—C20—N5—Zn1 | −0.5 (2) |
C8—C9—C10—C11 | 0.2 (3) | O1—Zn1—N5—C19 | 117.70 (18) |
C9—C10—C11—C21 | −0.9 (3) | N3i—Zn1—N5—C19 | −96.16 (17) |
C9—C10—C11—C12 | −179.6 (2) | N1ii—Zn1—N5—C19 | −0.39 (18) |
C10—C11—C12—N6 | −5.7 (3) | N4—Zn1—N5—C19 | 176.24 (18) |
C21—C11—C12—N6 | 175.64 (19) | O2—Zn1—N5—C19 | 89.53 (17) |
C10—C11—C12—C15 | 174.4 (2) | C7—Zn1—N5—C19 | 99.98 (18) |
C21—C11—C12—C15 | −4.2 (3) | O1—Zn1—N5—C20 | −60.21 (19) |
N6—C13—C14—N7 | 3.6 (4) | N3i—Zn1—N5—C20 | 85.93 (14) |
N6—C12—C15—N7 | 3.3 (3) | N1ii—Zn1—N5—C20 | −178.31 (14) |
C11—C12—C15—N7 | −176.86 (19) | N4—Zn1—N5—C20 | −1.67 (13) |
N6—C12—C15—C16 | −175.51 (19) | O2—Zn1—N5—C20 | −88.38 (14) |
C11—C12—C15—C16 | 4.4 (3) | C7—Zn1—N5—C20 | −77.94 (15) |
N7—C15—C16—C17 | 0.4 (3) | C14—C13—N6—C12 | −1.0 (3) |
C12—C15—C16—C17 | 179.2 (2) | C15—C12—N6—C13 | −2.3 (3) |
N7—C15—C16—C20 | −179.22 (18) | C11—C12—N6—C13 | 177.8 (2) |
C12—C15—C16—C20 | −0.4 (3) | C13—C14—N7—C15 | −2.6 (3) |
C20—C16—C17—C18 | 2.3 (3) | C12—C15—N7—C14 | −0.7 (3) |
C15—C16—C17—C18 | −177.3 (2) | C16—C15—N7—C14 | 178.1 (2) |
C16—C17—C18—C19 | −0.2 (3) | O2—C7—O1—Zn1 | −4.3 (2) |
C17—C18—C19—N5 | −1.8 (4) | C3—C7—O1—Zn1 | 175.02 (14) |
C17—C16—C20—N5 | −2.8 (3) | N3i—Zn1—O1—C7 | −178.26 (11) |
C15—C16—C20—N5 | 176.79 (18) | N1ii—Zn1—O1—C7 | 85.33 (12) |
C17—C16—C20—C21 | 176.72 (19) | N5—Zn1—O1—C7 | −31.32 (18) |
C15—C16—C20—C21 | −3.7 (3) | N4—Zn1—O1—C7 | −86.83 (12) |
C10—C11—C21—N4 | 0.8 (3) | O2—Zn1—O1—C7 | 2.19 (10) |
C12—C11—C21—N4 | 179.56 (19) | O1—C7—O2—Zn1 | 3.64 (17) |
C10—C11—C21—C20 | −178.58 (18) | C3—C7—O2—Zn1 | −175.68 (17) |
C12—C11—C21—C20 | 0.1 (3) | O1—Zn1—O2—C7 | −2.24 (11) |
N5—C20—C21—N4 | 3.9 (3) | N3i—Zn1—O2—C7 | −3.5 (2) |
C16—C20—C21—N4 | −175.66 (18) | N1ii—Zn1—O2—C7 | −104.40 (12) |
N5—C20—C21—C11 | −176.63 (18) | N5—Zn1—O2—C7 | 161.54 (11) |
C16—C20—C21—C11 | 3.8 (3) | N4—Zn1—O2—C7 | 86.83 (11) |
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) x−1/2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19A···N2ii | 0.95 | 2.38 | 3.103 (3) | 132 |
Symmetry code: (ii) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C7H3N3O2)(C14H8N4)]·0.25H2O |
Mr | 463.24 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 173 |
a, b, c (Å) | 17.3649 (9), 8.6087 (4), 23.8669 (12) |
V (Å3) | 3567.8 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.42 |
Crystal size (mm) | 0.37 × 0.32 × 0.23 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.623, 0.732 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27994, 3509, 2865 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.071, 0.97 |
No. of reflections | 3509 |
No. of parameters | 289 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.52, −0.36 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19A···N2i | 0.95 | 2.38 | 3.103 (3) | 132 |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
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Considerable attention has been paid recently to the construction of inorganic–organic coordination polymers (Rosi et al., 2003; Kaye & Long, 2005; Wong-Foy et al., 2006; Lin et al., 2006; Ma, Han et al., 2007; Ma, Sun et al., 2007; Kaye et al., 2007; Han et al., 2006, 2010; Han, Deng & Goddard, 2007; Han, He et al., 2007 [Please ensure all references are cited correctly here - there was considerable ambiguity originally]) due to their interesting topological structures and potential applications as fuctional materials in molecular recognition, gas absorption, luminescence and magnetism (Ockwig et al., 2005; Rao et al., 2004; Bradshaw et al., 2005; Pan et al., 2004; Min & Suh, 2000; Deiters et al., 2005; Ishikawa et al., 2005; Lukin et al., 2003; Tezuka & Oike, 2001). The rational design and synthesis of predictable coordination polymers have been significantly influenced by choosing appropriate metal ions and organic linkers. Among the various ligands, 1,2,3-triazole and its derivatives have drawn wide attention for the construction of coordination polymers (Bai et al., 2008; Jones et al., 2002; Lu et al., 2005; Yang et al., 2007; Tabernor et al., 2004). Meanwhile, carboxylate derivatives of the 1,2,3-triazole ligand, particularly benzotriazole-5-carboxylic acid (H2btca), have been used to produce homometallic porous metal–organic frameworks (MOFs) because of their diverse coordination modes and high structural stability (Zhang et al., 2007).
With the intention of preparing btca-coordinated complexes and studying the influence of the size of the aromatic chelate ligand on the framework structure, we chose the bidentate-coordinating 1,4,8,9-tetraazatriphenylene (TATP) ligand as a second reagent (Han et al., 2009; Ma et al., 2008), and a new coordination polymer, the title compound, (I), [Zn(btca)(TATP)].0.25H2O, was successfully synthesized.
Single-crystal X-ray diffraction analysis reveals that (I) exhibits a two-dimensional layer structure in which the asymmetric unit consists of one ZnII centre, one btca ligand, one TATP ligand and 0.25 solvent water molecules (Fig. 1). Each ZnII centre is six-coordinated, with a significantly distorted ZnN4O2 octahedral coordination geometry consisting of two carboxylate O atoms (O1 and O2) from one btca ligand, two N atoms (N4 and N5) from one chelating TATP ligand and two N atoms [N3i and N1ii; symmetry codes: (i) x + 1/2, y, -z + 1/2; (ii) -x, y + 1/2, -z + 1/2] from two different btca ligands. Two of the N atoms (N1ii and N4) occupy the axial positions, with an N1ii—Zn—N4 angle of 168.56 (6)°. The other axial angles are both less than 160°.
The btca ligand of (I) coordinates to three different Zn atoms via O,O'-bidentate chelation and monodentate bridging coordination modes through two of the triazole N atoms. The latter link two adjacent ZnII centres to form a one-dimensional zigzag chain (Fig. 2). These chains are then crosslinked by the O,O'-bidentate coordination from the btca ligand to a Zn atom in a neighbouring chain to give an extended wave-like (6,3) network layer structure. Adjacent layers are connected together through C—H···N hydrogen-bonding interactions between btca and TATP ligands to help form the three-dimensional supramolecular structure (Fig. 3). The 0.25-occupancy water molecules are located between the TATP ligands of adjacent layers, where, on account of the O1W···O2 distance of 2.804 (14) Å, they probably form O—H···O hydrogen bonds with one of the carboxylate O atoms of a btca ligand.
Compound (I) is the first example of a coordination polymer constructed by btca and TATP as mixed ligands. To date, only one complex with the btca ligand, [Co3(OH)2(btca)2] (Zhang et al., 2007), has been reported, which forms a homometallic porous metal–organic framework with `sra' topology. The layered structure of (I) is quite different from that of [Co3(OH)2(btca)2], in which the btca ligands in a µ-5 mode link {Co3(OH)2} chains to yield a three-dimensional framework.
In (I), two N atoms from the secondary TATP ligand occupy two coordination positions of the ZnII atom, while the remaining coordination positions are available for btca ligands, allowing the formation of the layer structure. Clearly, the presence of secondary chelate ligands in transition metal carboxylate systems contributes to the formation of low-dimensional coordination polymers, especially one-dimensional chains and two-dimensional layers, with the metal ions acting as nodes and the carboxylate ligands as linkers. These results indicate that aromatic chelate ligands have a significant impact on the framework structures of coordination polymers.