Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028759/at2328sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028759/at2328Isup2.hkl |
CCDC reference: 654966
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.003 Å
- R factor = 0.039
- wR factor = 0.099
- Data-to-parameter ratio = 11.0
checkCIF/PLATON results
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Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.19 PLAT432_ALERT_2_C Short Inter X...Y Contact O4 .. C9 .. 2.97 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A mixture of dtp (0.10 mmol), H4betc (0.10 mmol), ZnSO47H2O (0.20 mmol), and water (8 ml) was sealed in a Teflon-lined stainless steel vessel, which was heated at 393 K for 4 days and cooled to room temperature at a rate of 10 K/h. Light yellow crystals suitable for X-ray diffraction were obtained.
The H atoms were located geometrically, with C—H = 0.93 and O—H = 0.82 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).
Recently, there has been a growing interest in coordination polymers based on 1,2,4,5-benzenetetracarboxylate and 2,6-ditriazol-4-ylpyridine ligands (Wang, Xi, Su, Lan, Mao, You & Xie, 2007; Xia et al., 2007). In the course of preparing mixed-ligand (ternary) complexes containing such organic ligands and metal ions, a new cocrystal compound of 2,6-ditriazol-4-ylpyridine (dtp) and benzene-1,2,4,5-tetracarboxylic acid (H4Btec) was obtained which assembled by H-bonding and π-π stacking interaction. Hydrogen bonding and π-π interaction are important in the areas of supramolecular chemistry, crystal engineering, and biological recognition (Wang, Ding, Cheng, Liao & Yan, 2007). Herein we report the supramolecular framework of the title compound (C9H7N7)(C10H6O8)1/2, (I).
As shown in Fig. 1, the asymmetric structural unit contains one dtp molecule and half of H4Btec molecule. Bond lengths and angles are normal as expected. In dtp molecule, one triazole group is nearly planar with the pyridyl ring (dihedral angle of 3.1 (1)°), while the other triazole group has a dihedral angle of 33.5 (3)° with the pyridyl ring plane. Each carboxyl group of H4Btec links a triazole N atom through H-bonding interaction. The distance between the aromatic rings of adjacent dtp and H4Btec is ca 3.404 Å, which indicates the presence of some π-π stacking interaction. The intermolecular H-bonding and π-π stacking interaction assemble the molecules into a three-dimensional supramolecular framework (Fig. 2).
For related literature, see: Wang, Xi et al. (2007); Wang, Ding et al. (2007); Xia et al. (2007).
Data collection: APEX (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.
Fig. 1. View of (I), showing displacement ellipsoids drawn at the 30% probability level. | |
Fig. 2. A crystal packing diagram of compound (I). |
2C9H7N7·C10H6O8 | F(000) = 700 |
Mr = 680.58 | Dx = 1.588 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2052 reflections |
a = 9.0972 (12) Å | θ = 2.4–24.7° |
b = 15.799 (2) Å | µ = 0.12 mm−1 |
c = 10.0741 (13) Å | T = 273 K |
β = 100.523 (2)° | Block, light-yellow |
V = 1423.6 (3) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 2 |
Bruker SMART CCD diffractometer | 1971 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 25.1°, θmin = 2.3° |
ω scans | h = −10→10 |
7302 measured reflections | k = −15→18 |
2520 independent reflections | l = −10→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0408P)2 + 0.4345P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2520 reflections | Δρmax = 0.23 e Å−3 |
229 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0056 (11) |
2C9H7N7·C10H6O8 | V = 1423.6 (3) Å3 |
Mr = 680.58 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.0972 (12) Å | µ = 0.12 mm−1 |
b = 15.799 (2) Å | T = 273 K |
c = 10.0741 (13) Å | 0.20 × 0.20 × 0.10 mm |
β = 100.523 (2)° |
Bruker SMART CCD diffractometer | 1971 reflections with I > 2σ(I) |
7302 measured reflections | Rint = 0.026 |
2520 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.23 e Å−3 |
2520 reflections | Δρmin = −0.20 e Å−3 |
229 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 | ||
N1 | 0.36742 (16) | 0.16599 (9) | 0.69912 (15) | 0.0334 (4) | |
N2 | 0.61300 (16) | 0.12340 (10) | 0.75896 (15) | 0.0364 (4) | |
N5 | 0.11742 (16) | 0.19751 (10) | 0.62929 (15) | 0.0356 (4) | |
C5 | 0.49874 (19) | 0.18189 (11) | 0.77677 (18) | 0.0332 (4) | |
C8 | 0.0829 (2) | 0.12795 (12) | 0.55123 (19) | 0.0418 (5) | |
H8 | 0.1489 | 0.0842 | 0.5430 | 0.050* | |
N3 | 0.82721 (18) | 0.05862 (12) | 0.77901 (18) | 0.0501 (5) | |
C11 | 0.64839 (19) | −0.02667 (12) | 0.03665 (17) | 0.0335 (4) | |
N4 | 0.72429 (18) | 0.01326 (11) | 0.68780 (17) | 0.0476 (5) | |
C12 | 0.59825 (19) | 0.04348 (12) | 0.09964 (17) | 0.0333 (4) | |
N7 | −0.05551 (18) | 0.13098 (11) | 0.48951 (17) | 0.0470 (5) | |
C1 | 0.25722 (19) | 0.21877 (11) | 0.71126 (18) | 0.0326 (4) | |
C14 | 0.54929 (19) | −0.06941 (12) | −0.06162 (17) | 0.0349 (4) | |
H14 | 0.5824 | −0.1165 | −0.1030 | 0.042* | |
C7 | 0.5986 (2) | 0.05369 (12) | 0.67899 (19) | 0.0405 (5) | |
H7 | 0.5095 | 0.0369 | 0.6245 | 0.049* | |
N6 | −0.11620 (19) | 0.20543 (12) | 0.52764 (19) | 0.0579 (5) | |
C10 | 0.8071 (2) | −0.05768 (14) | 0.06808 (19) | 0.0401 (5) | |
C13 | 0.6961 (2) | 0.09339 (13) | 0.20797 (19) | 0.0371 (5) | |
C4 | 0.5271 (2) | 0.24769 (13) | 0.86786 (19) | 0.0400 (5) | |
H4 | 0.6202 | 0.2550 | 0.9225 | 0.048* | |
C6 | 0.7595 (2) | 0.12313 (14) | 0.8190 (2) | 0.0490 (6) | |
H6 | 0.8046 | 0.1636 | 0.8802 | 0.059* | |
C2 | 0.2718 (2) | 0.28829 (12) | 0.79400 (19) | 0.0410 (5) | |
H2 | 0.1920 | 0.3247 | 0.7965 | 0.049* | |
C3 | 0.4101 (2) | 0.30172 (13) | 0.87337 (19) | 0.0439 (5) | |
H3 | 0.4245 | 0.3480 | 0.9314 | 0.053* | |
C9 | −0.0114 (2) | 0.24308 (15) | 0.6100 (2) | 0.0529 (6) | |
H9 | −0.0225 | 0.2948 | 0.6510 | 0.064* | |
O3 | 0.72577 (16) | 0.05287 (9) | 0.32395 (13) | 0.0483 (4) | |
H3A | 0.7924 | 0.0777 | 0.3751 | 0.073* | |
O2 | 0.89983 (15) | −0.00163 (10) | 0.13212 (17) | 0.0637 (5) | |
H2A | 0.9826 | −0.0232 | 0.1549 | 0.096* | |
O4 | 0.73355 (17) | 0.16479 (10) | 0.19046 (15) | 0.0566 (4) | |
O1 | 0.84301 (16) | −0.12654 (10) | 0.03551 (17) | 0.0615 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0241 (8) | 0.0378 (9) | 0.0356 (8) | −0.0001 (7) | −0.0019 (6) | −0.0005 (7) |
N2 | 0.0213 (8) | 0.0418 (9) | 0.0426 (9) | 0.0003 (7) | −0.0032 (6) | 0.0017 (7) |
N5 | 0.0229 (8) | 0.0405 (9) | 0.0395 (9) | 0.0033 (7) | −0.0043 (6) | −0.0019 (7) |
C5 | 0.0249 (9) | 0.0364 (10) | 0.0359 (10) | −0.0018 (8) | −0.0008 (7) | 0.0059 (8) |
C8 | 0.0310 (11) | 0.0417 (12) | 0.0477 (12) | 0.0029 (9) | −0.0058 (9) | −0.0059 (10) |
N3 | 0.0244 (9) | 0.0629 (12) | 0.0597 (11) | 0.0039 (8) | −0.0012 (8) | −0.0004 (10) |
C11 | 0.0228 (9) | 0.0433 (11) | 0.0336 (10) | 0.0020 (8) | 0.0025 (8) | 0.0056 (8) |
N4 | 0.0318 (9) | 0.0533 (11) | 0.0558 (11) | 0.0051 (8) | 0.0029 (8) | 0.0003 (9) |
C12 | 0.0241 (9) | 0.0435 (11) | 0.0314 (10) | −0.0018 (8) | 0.0025 (7) | 0.0037 (8) |
N7 | 0.0323 (9) | 0.0533 (11) | 0.0498 (10) | 0.0010 (8) | −0.0074 (8) | −0.0056 (9) |
C1 | 0.0247 (9) | 0.0374 (10) | 0.0333 (10) | 0.0001 (8) | −0.0007 (7) | 0.0027 (8) |
C14 | 0.0280 (10) | 0.0415 (11) | 0.0352 (10) | 0.0025 (8) | 0.0054 (8) | 0.0004 (8) |
C7 | 0.0281 (11) | 0.0450 (12) | 0.0453 (12) | 0.0000 (9) | −0.0010 (8) | −0.0025 (10) |
N6 | 0.0323 (10) | 0.0647 (13) | 0.0680 (12) | 0.0101 (9) | −0.0137 (9) | −0.0146 (10) |
C10 | 0.0261 (10) | 0.0540 (13) | 0.0390 (11) | 0.0035 (9) | 0.0028 (8) | 0.0021 (10) |
C13 | 0.0236 (10) | 0.0454 (12) | 0.0411 (11) | −0.0012 (9) | 0.0028 (8) | 0.0015 (9) |
C4 | 0.0288 (10) | 0.0459 (12) | 0.0404 (11) | −0.0052 (9) | −0.0064 (8) | −0.0010 (9) |
C6 | 0.0257 (11) | 0.0601 (14) | 0.0563 (13) | −0.0001 (10) | −0.0050 (9) | −0.0063 (11) |
C2 | 0.0368 (11) | 0.0416 (12) | 0.0425 (11) | 0.0051 (9) | 0.0017 (9) | −0.0053 (9) |
C3 | 0.0449 (12) | 0.0440 (12) | 0.0395 (11) | −0.0044 (10) | −0.0006 (9) | −0.0076 (9) |
C9 | 0.0305 (11) | 0.0556 (14) | 0.0660 (14) | 0.0114 (10) | −0.0090 (10) | −0.0137 (11) |
O3 | 0.0453 (9) | 0.0526 (9) | 0.0406 (8) | −0.0104 (7) | −0.0091 (6) | 0.0017 (7) |
O2 | 0.0222 (7) | 0.0780 (11) | 0.0839 (11) | 0.0094 (7) | −0.0086 (8) | −0.0231 (9) |
O4 | 0.0513 (9) | 0.0497 (10) | 0.0638 (10) | −0.0160 (8) | −0.0024 (7) | 0.0079 (8) |
O1 | 0.0362 (9) | 0.0576 (10) | 0.0872 (12) | 0.0137 (7) | 0.0018 (8) | −0.0096 (9) |
N1—C1 | 1.327 (2) | N7—N6 | 1.383 (2) |
N1—C5 | 1.327 (2) | C1—C2 | 1.371 (3) |
N2—C7 | 1.357 (2) | C14—C12i | 1.389 (2) |
N2—C6 | 1.359 (2) | C14—H14 | 0.9300 |
N2—C5 | 1.426 (2) | C7—H7 | 0.9300 |
N5—C8 | 1.355 (2) | N6—C9 | 1.290 (3) |
N5—C9 | 1.359 (2) | C10—O1 | 1.199 (2) |
N5—C1 | 1.424 (2) | C10—O2 | 1.309 (2) |
C5—C4 | 1.380 (3) | C13—O4 | 1.201 (2) |
C8—N7 | 1.299 (2) | C13—O3 | 1.316 (2) |
C8—H8 | 0.9300 | C4—C3 | 1.373 (3) |
N3—C6 | 1.293 (3) | C4—H4 | 0.9300 |
N3—N4 | 1.386 (2) | C6—H6 | 0.9300 |
C11—C14 | 1.387 (2) | C2—C3 | 1.379 (3) |
C11—C12 | 1.394 (3) | C2—H2 | 0.9300 |
C11—C10 | 1.503 (2) | C3—H3 | 0.9300 |
N4—C7 | 1.299 (2) | C9—H9 | 0.9300 |
C12—C14i | 1.389 (2) | O3—H3A | 0.8200 |
C12—C13 | 1.500 (2) | O2—H2A | 0.8200 |
C1—N1—C5 | 116.15 (16) | N4—C7—N2 | 111.73 (17) |
C7—N2—C6 | 104.03 (16) | N4—C7—H7 | 124.1 |
C7—N2—C5 | 127.36 (15) | N2—C7—H7 | 124.1 |
C6—N2—C5 | 128.60 (17) | C9—N6—N7 | 106.57 (16) |
C8—N5—C9 | 104.15 (16) | O1—C10—O2 | 124.45 (18) |
C8—N5—C1 | 128.01 (16) | O1—C10—C11 | 122.52 (18) |
C9—N5—C1 | 127.83 (17) | O2—C10—C11 | 113.02 (17) |
N1—C5—C4 | 124.99 (17) | O4—C13—O3 | 124.71 (18) |
N1—C5—N2 | 113.67 (16) | O4—C13—C12 | 122.26 (17) |
C4—C5—N2 | 121.33 (16) | O3—C13—C12 | 112.86 (16) |
N7—C8—N5 | 110.47 (17) | C3—C4—C5 | 116.33 (17) |
N7—C8—H8 | 124.8 | C3—C4—H4 | 121.8 |
N5—C8—H8 | 124.8 | C5—C4—H4 | 121.8 |
C6—N3—N4 | 108.15 (16) | N3—C6—N2 | 110.38 (19) |
C14—C11—C12 | 119.20 (16) | N3—C6—H6 | 124.8 |
C14—C11—C10 | 117.78 (17) | N2—C6—H6 | 124.8 |
C12—C11—C10 | 123.01 (16) | C1—C2—C3 | 116.90 (18) |
C7—N4—N3 | 105.71 (17) | C1—C2—H2 | 121.5 |
C14i—C12—C11 | 119.27 (16) | C3—C2—H2 | 121.5 |
C14i—C12—C13 | 117.42 (17) | C4—C3—C2 | 120.86 (19) |
C11—C12—C13 | 123.31 (16) | C4—C3—H3 | 119.6 |
C8—N7—N6 | 107.43 (16) | C2—C3—H3 | 119.6 |
N1—C1—C2 | 124.69 (17) | N6—C9—N5 | 111.38 (19) |
N1—C1—N5 | 114.08 (16) | N6—C9—H9 | 124.3 |
C2—C1—N5 | 121.23 (17) | N5—C9—H9 | 124.3 |
C11—C14—C12i | 121.52 (18) | C13—O3—H3A | 109.5 |
C11—C14—H14 | 119.2 | C10—O2—H2A | 109.5 |
C12i—C14—H14 | 119.2 |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···N3ii | 0.82 | 1.82 | 2.639 (2) | 172 |
O3—H3A···N7iii | 0.82 | 1.84 | 2.656 (2) | 179 |
Symmetry codes: (ii) −x+2, −y, −z+1; (iii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | 2C9H7N7·C10H6O8 |
Mr | 680.58 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 273 |
a, b, c (Å) | 9.0972 (12), 15.799 (2), 10.0741 (13) |
β (°) | 100.523 (2) |
V (Å3) | 1423.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7302, 2520, 1971 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.099, 1.04 |
No. of reflections | 2520 |
No. of parameters | 229 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.20 |
Computer programs: APEX (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···N3i | 0.82 | 1.82 | 2.639 (2) | 172.1 |
O3—H3A···N7ii | 0.82 | 1.84 | 2.656 (2) | 178.6 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x+1, y, z. |
Recently, there has been a growing interest in coordination polymers based on 1,2,4,5-benzenetetracarboxylate and 2,6-ditriazol-4-ylpyridine ligands (Wang, Xi, Su, Lan, Mao, You & Xie, 2007; Xia et al., 2007). In the course of preparing mixed-ligand (ternary) complexes containing such organic ligands and metal ions, a new cocrystal compound of 2,6-ditriazol-4-ylpyridine (dtp) and benzene-1,2,4,5-tetracarboxylic acid (H4Btec) was obtained which assembled by H-bonding and π-π stacking interaction. Hydrogen bonding and π-π interaction are important in the areas of supramolecular chemistry, crystal engineering, and biological recognition (Wang, Ding, Cheng, Liao & Yan, 2007). Herein we report the supramolecular framework of the title compound (C9H7N7)(C10H6O8)1/2, (I).
As shown in Fig. 1, the asymmetric structural unit contains one dtp molecule and half of H4Btec molecule. Bond lengths and angles are normal as expected. In dtp molecule, one triazole group is nearly planar with the pyridyl ring (dihedral angle of 3.1 (1)°), while the other triazole group has a dihedral angle of 33.5 (3)° with the pyridyl ring plane. Each carboxyl group of H4Btec links a triazole N atom through H-bonding interaction. The distance between the aromatic rings of adjacent dtp and H4Btec is ca 3.404 Å, which indicates the presence of some π-π stacking interaction. The intermolecular H-bonding and π-π stacking interaction assemble the molecules into a three-dimensional supramolecular framework (Fig. 2).