4-[4-Amino-5-(4-pyrid­yl)-4H-1,2,4-triazol-3-yl]pyridinium 2,4,5-tricarboxy­benzoate

The solution reaction of 4-amino-3,5-bis­(4-pyrid­yl)-1,2,4-triazole (bpt), benzene-1,2,4,5-tetra­carboxylic acid (H₄betc) and Co(NO₃)₂·6H₂O led to the formation of the title cocrystal compound Hbpt·H₃betc or C₁₂H₁₁N₆⁺·C₁₀H₅O₈^-, in which strong hydrogen-bonding inter­actions assemble the ions into a three-dimensional supra­molecular framework.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.071
• wR factor = 0.204
• Data-to-parameter ratio = 10.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        600 Deg.
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.79
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.85
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C7     ...       1.53 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O4     ..  C10     ..       2.98 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O5     ..  C7      ..       2.97 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6     ..  O1      ..       2.61 Ang.
PLAT731_ALERT_1_C Bond    Calc     0.91(4), Rep   0.905(10) ......       4.00 su-Ra
              N5   -H5A     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.91(3), Rep   0.907(10) ......       3.00 su-Ra
              N5   -H5B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.91(4), Rep   0.905(10) ......       4.00 su-Ra
              N5   -H5A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.91(3), Rep   0.907(10) ......       3.00 su-Ra
              N5   -H5B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.91(3), Rep   0.907(10) ......       3.00 su-Ra
              N5   -H5B     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.09(5), Rep   2.091(19) ......       2.63 su-Ra
              H5A  -O7      1.555   2.666

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  16 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Organic cocrystals involving hydrogen-bonding and π-π stacking interactions are important in the areas of supramolecular chemistry, crystal engineering, and biological recognition (Wang et al., 2007). Many organic cocrystals have been assembled from N-heterocycle and polycarboxylic acids (Li et al., 2007). In our course of preparing ternary complexes containing 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole and benzene-1,2,4,5-tetracarboxylic acid (Dong et al., 2007; Guo & Du, 2002), a new cocrystal compound of Hbpt. H~3~betc was prepared unexpectedly. Herein we report the supramolecular framework of the title compound (I).

Related literature

For related literature, see: Li et al. (2007); Wang et al. (2007); Dong et al. (2007); Guo & Du (2002).

S2. Experimental

Compound (I) was synthesized in a solution reaction. H₄betc (0.1 mmol) was added to 10 ml hot ethanol solution containing bpt (0.1 mmol) and Co(NO₃)₂·6H₂O (0.1 mmol) with stirring. Then NaOH solution was added dropwise into the muddy solution to form a clear pink solution. The solution was kept at room temperature to evaporate slowly. After one week, light yellow crystals suitable for X-ray diffraction were obtained.

S3. Refinement

The H atoms of the NH₂ group were identified in difference Fourier syntheses and refined freely. The other H atoms were located geometrically, with C—H = 0.93, N—H = 0.86 and O—H = 0.82 Å and constrain to ride on their parents atoms, with U_iso = 1.2U_eq(C,N) or 1.5U_eq(O).

Computing details

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 (Sheldrick, 2000).

Figures

	Fig. 1. An ORTEP view of the title molecule, with the atom-numbersing scheme.
	Fig. 2. Packing and hydrogen bonding diagram of the title compound.

4-[4-Amino-5-(4-pyridyl)-4H-1,2,4-triazol-3-yl]pyridinium 2,4,5-tricarboxybenzoate

Crystal data

C22H16N6O8	Z = 2
Mr = 492.41	F(000) = 508
Triclinic, P1	Dx = 1.571 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.669 (4) Å	Cell parameters from 1502 reflections
b = 9.892 (4) Å	θ = 2.2–26.1°
c = 11.557 (5) Å	µ = 0.12 mm^−1
α = 78.620 (6)°	T = 296 K
β = 78.135 (6)°	Block, light-yellow
γ = 76.979 (6)°	0.30 × 0.30 × 0.20 mm
V = 1040.7 (8) Å^3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	3616 independent reflections
Radiation source: fine-focus sealed tube	2547 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ϕ and ω scans	θmax = 25.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→10
Tmin = 0.964, Tmax = 0.976	k = −11→11
5424 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.204	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.1223P)^2] where P = (Fo^2 + 2Fc^2)/3
3616 reflections	(Δ/σ)max < 0.001
336 parameters	Δρmax = 0.48 e Å^−3
2 restraints	Δρmin = −0.36 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3322 (3)	0.8520 (3)	0.1415 (3)	0.0268 (7)
C2	0.4104 (3)	0.7976 (3)	0.0394 (3)	0.0311 (8)
H2	0.3610	0.7692	−0.0097	0.037*
C3	0.5588 (3)	0.7842 (3)	0.0084 (3)	0.0288 (7)
C4	0.6323 (3)	0.8310 (3)	0.0802 (3)	0.0273 (7)
C5	0.5564 (3)	0.8803 (3)	0.1826 (3)	0.0291 (7)
H5	0.6067	0.9085	0.2313	0.035*
C6	0.4077 (3)	0.8905 (3)	0.2175 (3)	0.0260 (7)
C7	0.1694 (3)	0.8661 (3)	0.1556 (3)	0.0324 (8)
C8	0.6323 (3)	0.7232 (3)	−0.1027 (3)	0.0319 (8)
C9	0.7885 (3)	0.8363 (4)	0.0439 (3)	0.0341 (8)
C10	0.3530 (3)	0.9423 (3)	0.3371 (3)	0.0314 (8)
C11	−0.0022 (4)	0.4396 (4)	0.7227 (4)	0.0522 (10)
H11	−0.0305	0.3658	0.7794	0.063*
C12	0.1218 (4)	0.4114 (4)	0.6405 (3)	0.0466 (10)
H12	0.1766	0.3209	0.6433	0.056*
C13	0.1635 (3)	0.5187 (3)	0.5543 (3)	0.0345 (8)
C14	0.0788 (4)	0.6515 (4)	0.5562 (3)	0.0410 (9)
H14	0.1033	0.7272	0.4999	0.049*
C15	−0.0431 (4)	0.6701 (4)	0.6434 (3)	0.0447 (9)
H15	−0.0991	0.7597	0.6444	0.054*
C16	0.2958 (4)	0.5033 (3)	0.4658 (3)	0.0347 (8)
C17	0.4936 (3)	0.4228 (3)	0.3530 (3)	0.0330 (8)
C18	0.6221 (3)	0.3351 (4)	0.2942 (3)	0.0336 (8)
C19	0.6714 (3)	0.1944 (4)	0.3361 (3)	0.0401 (9)
H19	0.6186	0.1474	0.4020	0.048*
C20	0.7982 (4)	0.1261 (4)	0.2796 (3)	0.0450 (9)
H20	0.8325	0.0322	0.3077	0.054*
C21	0.8296 (4)	0.3258 (4)	0.1411 (3)	0.0478 (10)
H21	0.8852	0.3687	0.0744	0.057*
C22	0.7032 (4)	0.4010 (4)	0.1932 (3)	0.0440 (9)
H22	0.6717	0.4945	0.1619	0.053*
N1	−0.0829 (3)	0.5666 (3)	0.7248 (3)	0.0459 (8)
N2	0.3819 (3)	0.3821 (3)	0.4343 (2)	0.0303 (6)
N3	0.4787 (3)	0.5603 (3)	0.3354 (3)	0.0526 (9)
N4	0.3522 (3)	0.6111 (3)	0.4076 (3)	0.0531 (9)
N5	0.3484 (3)	0.2474 (3)	0.4713 (3)	0.0406 (7)
N6	0.8729 (3)	0.1925 (3)	0.1852 (3)	0.0457 (8)
H6A	0.9526	0.1471	0.1511	0.055*
O1	0.0868 (2)	0.9087 (3)	0.2452 (2)	0.0506 (7)
O2	0.1228 (2)	0.8334 (3)	0.0740 (2)	0.0451 (7)
O3	0.7241 (3)	0.6058 (3)	−0.0823 (2)	0.0499 (7)
H3	0.7766	0.5890	−0.1453	0.075*
O4	0.6057 (3)	0.7770 (3)	−0.2008 (2)	0.0505 (7)
O5	0.8508 (2)	0.8303 (3)	−0.0578 (2)	0.0521 (7)
O6	0.8478 (2)	0.8557 (3)	0.1290 (2)	0.0496 (7)
H6	0.9336	0.8557	0.1044	0.074*
O7	0.4391 (2)	0.9549 (2)	0.3962 (2)	0.0391 (6)
O8	0.2155 (2)	0.9750 (3)	0.3766 (2)	0.0443 (7)
H8	0.1705	0.9529	0.3328	0.066*
H5A	0.418 (4)	0.202 (5)	0.515 (4)	0.11 (2)*
H5B	0.366 (4)	0.208 (4)	0.404 (2)	0.053 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0186 (16)	0.0331 (17)	0.0240 (16)	−0.0031 (12)	0.0033 (12)	−0.0026 (13)
C2	0.0200 (17)	0.044 (2)	0.0274 (18)	−0.0047 (14)	0.0035 (13)	−0.0115 (15)
C3	0.0233 (17)	0.0357 (18)	0.0216 (16)	−0.0016 (13)	0.0046 (13)	−0.0043 (13)
C4	0.0156 (16)	0.0351 (17)	0.0262 (17)	−0.0023 (12)	0.0016 (12)	−0.0015 (13)
C5	0.0235 (17)	0.0385 (18)	0.0240 (17)	−0.0078 (13)	−0.0001 (13)	−0.0037 (14)
C6	0.0215 (16)	0.0266 (16)	0.0241 (16)	−0.0005 (12)	0.0036 (12)	−0.0030 (13)
C7	0.0207 (17)	0.043 (2)	0.0283 (18)	−0.0036 (14)	0.0032 (14)	−0.0053 (15)
C8	0.0198 (17)	0.043 (2)	0.0278 (18)	−0.0027 (14)	0.0047 (13)	−0.0065 (15)
C9	0.0260 (18)	0.044 (2)	0.0271 (19)	−0.0040 (14)	0.0033 (14)	−0.0061 (15)
C10	0.0322 (19)	0.0315 (18)	0.0257 (17)	−0.0048 (14)	0.0027 (14)	−0.0027 (14)
C11	0.047 (2)	0.048 (2)	0.048 (2)	−0.0057 (18)	0.0194 (18)	−0.0063 (18)
C12	0.039 (2)	0.041 (2)	0.046 (2)	0.0039 (16)	0.0131 (17)	−0.0085 (17)
C13	0.0274 (18)	0.0384 (19)	0.0328 (19)	0.0026 (14)	0.0018 (14)	−0.0112 (15)
C14	0.036 (2)	0.042 (2)	0.037 (2)	0.0000 (16)	0.0035 (16)	−0.0074 (16)
C15	0.033 (2)	0.045 (2)	0.049 (2)	0.0090 (16)	−0.0016 (17)	−0.0149 (19)
C16	0.033 (2)	0.0323 (18)	0.0330 (19)	−0.0002 (15)	0.0033 (15)	−0.0066 (15)
C17	0.0230 (18)	0.040 (2)	0.0269 (18)	−0.0009 (14)	0.0109 (13)	−0.0047 (15)
C18	0.0257 (18)	0.046 (2)	0.0236 (17)	−0.0036 (14)	0.0085 (13)	−0.0102 (15)
C19	0.0277 (19)	0.047 (2)	0.036 (2)	−0.0012 (16)	0.0109 (15)	−0.0080 (16)
C20	0.029 (2)	0.052 (2)	0.048 (2)	−0.0002 (16)	0.0020 (16)	−0.0136 (18)
C21	0.037 (2)	0.067 (3)	0.033 (2)	−0.0131 (19)	0.0168 (16)	−0.0134 (19)
C22	0.037 (2)	0.056 (2)	0.031 (2)	−0.0066 (17)	0.0089 (16)	−0.0059 (17)
N1	0.0358 (18)	0.051 (2)	0.0438 (19)	−0.0011 (15)	0.0075 (14)	−0.0138 (16)
N2	0.0250 (15)	0.0310 (15)	0.0282 (15)	0.0014 (11)	0.0034 (11)	−0.0051 (12)
N3	0.0407 (19)	0.0435 (19)	0.054 (2)	−0.0003 (14)	0.0238 (15)	−0.0046 (16)
N4	0.047 (2)	0.0393 (18)	0.055 (2)	−0.0005 (15)	0.0210 (16)	−0.0057 (15)
N5	0.0312 (17)	0.0373 (18)	0.048 (2)	−0.0031 (13)	0.0068 (14)	−0.0134 (15)
N6	0.0232 (16)	0.067 (2)	0.0425 (19)	−0.0008 (14)	0.0105 (13)	−0.0229 (17)
O1	0.0192 (13)	0.086 (2)	0.0429 (15)	−0.0012 (12)	0.0095 (11)	−0.0262 (14)
O2	0.0226 (13)	0.0788 (18)	0.0374 (14)	−0.0112 (11)	0.0009 (10)	−0.0216 (13)
O3	0.0452 (16)	0.0545 (16)	0.0333 (14)	0.0116 (12)	0.0100 (11)	−0.0093 (12)
O4	0.0493 (17)	0.0682 (18)	0.0256 (14)	0.0039 (13)	−0.0004 (11)	−0.0111 (12)
O5	0.0247 (14)	0.092 (2)	0.0372 (15)	−0.0150 (13)	0.0117 (11)	−0.0177 (14)
O6	0.0195 (13)	0.092 (2)	0.0395 (15)	−0.0144 (13)	0.0031 (10)	−0.0188 (14)
O7	0.0370 (14)	0.0538 (15)	0.0258 (12)	−0.0081 (11)	−0.0003 (10)	−0.0107 (11)
O8	0.0246 (13)	0.0674 (17)	0.0365 (15)	−0.0004 (11)	0.0097 (10)	−0.0231 (13)

Geometric parameters (Å, º)

C1—C2	1.397 (4)	C14—C15	1.388 (5)
C1—C6	1.404 (4)	C14—H14	0.9300
C1—C7	1.526 (4)	C15—N1	1.315 (5)
C2—C3	1.388 (4)	C15—H15	0.9300
C2—H2	0.9300	C16—N4	1.310 (4)
C3—C4	1.396 (4)	C16—N2	1.364 (4)
C3—C8	1.501 (4)	C17—N3	1.314 (4)
C4—C5	1.374 (4)	C17—N2	1.357 (4)
C4—C9	1.492 (4)	C17—C18	1.468 (4)
C5—C6	1.397 (4)	C18—C19	1.389 (5)
C5—H5	0.9300	C18—C22	1.399 (5)
C6—C10	1.520 (4)	C19—C20	1.363 (5)
C7—O2	1.248 (4)	C19—H19	0.9300
C7—O1	1.252 (4)	C20—N6	1.323 (5)
C8—O4	1.206 (4)	C20—H20	0.9300
C8—O3	1.306 (4)	C21—N6	1.322 (5)
C9—O5	1.211 (4)	C21—C22	1.369 (5)
C9—O6	1.299 (4)	C21—H21	0.9300
C10—O7	1.221 (4)	C22—H22	0.9300
C10—O8	1.302 (4)	N2—N5	1.406 (4)
C11—N1	1.323 (5)	N3—N4	1.383 (4)
C11—C12	1.380 (5)	N5—H5A	0.905 (10)
C11—H11	0.9300	N5—H5B	0.907 (10)
C12—C13	1.375 (5)	N6—H6A	0.8600
C12—H12	0.9300	O3—H3	0.8200
C13—C14	1.384 (5)	O6—H6	0.8200
C13—C16	1.464 (4)	O8—H8	0.8200
C2—C1—C6	118.4 (3)	C15—C14—H14	120.5
C2—C1—C7	114.6 (3)	N1—C15—C14	122.9 (3)
C6—C1—C7	127.0 (3)	N1—C15—H15	118.5
C3—C2—C1	122.7 (3)	C14—C15—H15	118.5
C3—C2—H2	118.6	N4—C16—N2	109.7 (3)
C1—C2—H2	118.6	N4—C16—C13	122.3 (3)
C2—C3—C4	118.5 (3)	N2—C16—C13	127.9 (3)
C2—C3—C8	118.3 (3)	N3—C17—N2	110.1 (3)
C4—C3—C8	123.1 (3)	N3—C17—C18	121.0 (3)
C5—C4—C3	118.8 (3)	N2—C17—C18	128.8 (3)
C5—C4—C9	119.8 (3)	C19—C18—C22	118.5 (3)
C3—C4—C9	121.3 (3)	C19—C18—C17	124.3 (3)
C4—C5—C6	123.5 (3)	C22—C18—C17	117.1 (3)
C4—C5—H5	118.3	C20—C19—C18	119.3 (3)
C6—C5—H5	118.3	C20—C19—H19	120.4
C5—C6—C1	117.8 (3)	C18—C19—H19	120.4
C5—C6—C10	112.4 (3)	N6—C20—C19	120.5 (4)
C1—C6—C10	129.8 (3)	N6—C20—H20	119.8
O2—C7—O1	121.8 (3)	C19—C20—H20	119.8
O2—C7—C1	117.0 (3)	N6—C21—C22	120.2 (3)
O1—C7—C1	121.2 (3)	N6—C21—H21	119.9
O4—C8—O3	123.7 (3)	C22—C21—H21	119.9
O4—C8—C3	122.6 (3)	C21—C22—C18	119.0 (4)
O3—C8—C3	113.7 (3)	C21—C22—H22	120.5
O5—C9—O6	123.8 (3)	C18—C22—H22	120.5
O5—C9—C4	122.1 (3)	C15—N1—C11	118.0 (3)
O6—C9—C4	113.9 (3)	C17—N2—C16	105.5 (3)
O7—C10—O8	119.6 (3)	C17—N2—N5	129.1 (3)
O7—C10—C6	119.6 (3)	C16—N2—N5	125.1 (3)
O8—C10—C6	120.9 (3)	C17—N3—N4	107.0 (3)
N1—C11—C12	123.2 (4)	C16—N4—N3	107.7 (3)
N1—C11—H11	118.4	N2—N5—H5A	103 (3)
C12—C11—H11	118.4	N2—N5—H5B	106 (2)
C13—C12—C11	119.2 (3)	H5A—N5—H5B	107 (4)
C13—C12—H12	120.4	C21—N6—C20	122.5 (3)
C11—C12—H12	120.4	C21—N6—H6A	118.7
C12—C13—C14	117.6 (3)	C20—N6—H6A	118.7
C12—C13—C16	124.3 (3)	C8—O3—H3	109.5
C14—C13—C16	118.0 (3)	C9—O6—H6	109.5
C13—C14—C15	119.1 (3)	C10—O8—H8	109.5
C13—C14—H14	120.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···O5^i	0.86	2.02	2.757 (4)	143
O6—H6···O1^ii	0.82	2.61	3.086 (3)	119
O3—H3···N1^iii	0.82	1.82	2.628 (4)	169
O6—H6···O2^ii	0.82	1.76	2.573 (3)	170
N6—H6A···O1^iv	0.86	2.57	3.138 (4)	124
O8—H8···O1	0.82	1.59	2.413 (3)	179
N5—H5A···O7^v	0.91 (1)	2.09 (2)	2.967 (4)	162 (5)
N5—H5B···O4^vi	0.91 (1)	2.29 (2)	3.116 (4)	152 (3)
N5—H5B···O7^vii	0.91 (1)	2.46 (3)	3.070 (4)	125 (3)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1, y, z; (iii) x+1, y, z−1; (iv) x+1, y−1, z; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y+1, −z; (vii) x, y−1, z.