The 2:1 cocrystal of 2,6-ditriazol-4-ylpyridine and benzene-1,2,4,5-tetra­carboxylic acid

Li, W.; Shao, M.; Liu, H.-J.; Li, M.-X.

doi:10.1107/S1600536807028759

The 2:1 cocrystal of 2,6-ditriazol-4-ylpyridine and benzene-1,2,4,5-tetracarboxylic acid

The hydrothermal reaction of 2,6-ditriazol-4-ylpyridine, benzene-1,2,4,5-tetracarboxylic acid and ZnSO₄·7H₂O led to the formation of the cocrystal compound 2,6-ditriazol-4-ylpyridine–benzene-1,2,4,5-tetracarboxylic acid (2/1), 2C₉H₇N₇·C₁₀H₆O₈, in which hydrogen-bonding and π–π stacking interactions (3.404 Å) assemble the molecules into a three-dimensional supramolecular framework. The acid molecule lies on an inversion centre.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028759/at2328sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028759/at2328Isup2.hkl Contains datablock I

CCDC reference: 654966

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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

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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
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Comment top

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).

Related literature top

For related literature, see: Wang, Xi et al. (2007); Wang, Ding et al. (2007); Xia et al. (2007).

Experimental top

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.

Structure description top

For related literature, see: Wang, Xi et al. (2007); Wang, Ding et al. (2007); Xia et al. (2007).

Computing details top

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.

Figures top

	Fig. 1. View of (I), showing displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A crystal packing diagram of compound (I).

2,6-ditriazol-4-ylpyridine–benzene-1,2,4,5-tetracarboxylic acid (2/1) top

Crystal data top

2C₉H₇N₇·C₁₀H₆O₈	F(000) = 700
M_r = 680.58	D_x = 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

Data collection top

Bruker SMART CCD diffractometer	1971 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 25.1°, θ_min = 2.3°
ω scans	h = −10→10
7302 measured reflections	k = −15→18
2520 independent reflections	l = −10→11

Refinement top

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(F_o²) + (0.0408P)² + 0.4345P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2520 reflections	Δρ_max = 0.23 e Å⁻³
229 parameters	Δρ_min = −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)

Crystal data top

2C₉H₇N₇·C₁₀H₆O₈	V = 1423.6 (3) Å³
M_r = 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)°

Data collection top

Bruker SMART CCD diffractometer	1971 reflections with I > 2σ(I)
7302 measured reflections	R_int = 0.026
2520 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.04	Δρ_max = 0.23 e Å⁻³
2520 reflections	Δρ_min = −0.20 e Å⁻³
229 parameters

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	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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
M_r	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
R_int	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
Δρ_max, Δρ_min (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.