4-(1H-Pyrazol-3-yl)pyridine–terephthalic acid–water (2/1/2)

Tan, Z.-D.; Tan, F.-J.; Tan, B.; Zhang, C.-M.

doi:10.1107/S1600536812021599

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1942

doi:10.1107/S1600536812021599

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4-(1H-Pyrazol-3-yl)pyridine–terephthalic acid–water (2/1/2)

Zheng-De Tan,^a ^* Feng-Jiao Tan,^b Bo Tan ^b and Cheng-Ming Zhang ^a

^aCollege of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiang Tan 411104, People's Republic of China, and ^bThe People's Hospital of Xiangtan County, Xiang Tan 411104, People's Republic of China
^*Correspondence e-mail: tzd0517@163.com

(Received 8 March 2012; accepted 13 May 2012; online 31 May 2012)

In the title compound, 2C₈H₇N₃·C₈H₆O₄·2H₂O, the pyridine and pyrazole rings are approximately coplanar, the dihedral angle between them being 4.69 (9)°. The asymmetric unit consists of half of the terephthalic acid (an inversion centre generates the other half of the molecule), one 4-(1H-pyrazol-3-yl)pyridine (4pp) molecule and one water molecule. In the crystal, two 4pp and one terephthalic acid molecules form a linear three-molecule unit as a result of O—H⋯N hydrogen bonds. These units are further assembled into a three-dimensional network by two types of hydrogen bonds, viz. O—H⋯O and N—H⋯O.

Related literature

For the synthesis of 4-(1H-pyrazol-3-yl)-pyridine, see: Davies et al. (2003 ).

Experimental

Crystal data

2C₈H₇N₃·C₈H₆O₄·2H₂O
M_r = 492.49
Triclinic, $[P \overline 1]$
a = 6.8364 (14) Å
b = 9.5308 (19) Å
c = 10.131 (2) Å
α = 67.52 (3)°
β = 71.22 (3)°
γ = 78.10 (3)°
V = 574.9 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.32 × 0.25 × 0.18 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.967, T_max = 0.981
5041 measured reflections
2024 independent reflections
1254 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.128
S = 1.21
2024 reflections
172 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1Wⁱ	0.86	1.98	2.829 (3)	170
O1W—H1W⋯O2ⁱⁱ	0.84 (1)	1.99 (1)	2.811 (3)	167 (2)
O1W—H2W⋯O1ⁱⁱⁱ	0.84 (1)	2.06 (1)	2.864 (3)	161 (2)
O1—H11⋯N3	0.82 (1)	1.80 (1)	2.614 (3)	170 (3)
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z; (iii) -x+1, -y+1, -z.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812021599/nk2153sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021599/nk2153Isup2.hkl

checkCIF report

Comment top

In the title compound, the pyridine ring and the pyrazole ring are approximately coplanar with the dihedral angles between them being 4.69 (9)°. Two 4pp and one terephthalic acid form a linear three-molecule unit as a result of O—H···N hydrogen bonds (Fig.2 and Table 1), which the N atom is from the ring of pyridine.There is a hydrogen interaction between N1 from pyrazol as the hydrogen bond donor and O1w as the hydrogen bond acceptor.At the same time, O1w as the hydrogen bond donor interacts with two O2 atoms from different terephthalic acid (Fig.3). These supermolecules are assembled into a three-dimensional network by two types of hydrogen bonding including O—H···O and N—H···O.

Related literature top

For the synthesis of 4-(1H-pyrazol-3-yl)-pyridine, see: Davies et al. (2003).

Experimental top

4-(1H-pyrazol-3-yl)-pyridine was prepared according to the published method of Davies et al. (2003). An aqueous solution (20 mL) containing terephthalic acid( 0.1 mmol,16 mg), NaOH (0.2 mmol,8 mg) and 4-(1H-pyrazol-3-yl)-pyridine (0.2 mmol,29 mg) was stirred for 20 minutes in air, and left to stand at room temperature for about four weeks, then the colorless crystals were obtained.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, with 30% probability displacement ellipsoids [Symmetry codes: i = -x, -y, -z].
	Fig. 2. A view of the supermolecule unit of the title compound. Hydrogen bonds are shown as dashed lines.
	Fig. 3. Three types hydrogen bonds in the stucture. Hydrogen bonds are shown as dashed lines.

4-(1H-Pyrazol-3-yl)pyridine–terephthalic acid–water (2/1/2) top

Crystal data top

2C₈H₇N₃·C₈H₆O₄·2H₂O	Z = 1
M_r = 492.49	F(000) = 258
Triclinic, P1	D_x = 1.423 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8364 (14) Å	Cell parameters from 4645 reflections
b = 9.5308 (19) Å	θ = 3.2–27.5°
c = 10.131 (2) Å	µ = 0.11 mm⁻¹
α = 67.52 (3)°	T = 293 K
β = 71.22 (3)°	Block, colourless
γ = 78.10 (3)°	0.32 × 0.25 × 0.18 mm
V = 574.9 (2) Å³

Data collection top

Rigaku SCXmini diffractometer	2024 independent reflections
Radiation source: sealed tube	1254 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
T_min = 0.967, T_max = 0.981	k = −11→11
5041 measured reflections	l = −12→12

Refinement top

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ²(F_o²) + (0.0423P)²] where P = (F_o² + 2F_c²)/3
2024 reflections	(Δ/σ)_max = 0.002
172 parameters	Δρ_max = 0.32 e Å⁻³
4 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

2C₈H₇N₃·C₈H₆O₄·2H₂O	γ = 78.10 (3)°
M_r = 492.49	V = 574.9 (2) Å³
Triclinic, P1	Z = 1
a = 6.8364 (14) Å	Mo Kα radiation
b = 9.5308 (19) Å	µ = 0.11 mm⁻¹
c = 10.131 (2) Å	T = 293 K
α = 67.52 (3)°	0.32 × 0.25 × 0.18 mm
β = 71.22 (3)°

Data collection top

Rigaku SCXmini diffractometer	2024 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1254 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.981	R_int = 0.054
5041 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	4 restraints
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	Δρ_max = 0.32 e Å⁻³
2024 reflections	Δρ_min = −0.28 e Å⁻³
172 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
C1	1.0188 (4)	0.3344 (3)	0.3605 (3)	0.0315 (7)
H1W	0.422 (4)	0.7787 (14)	0.275 (3)	0.047*
N1	1.2378 (3)	0.4525 (3)	0.3732 (3)	0.0425 (7)
H1	1.3209	0.5197	0.3507	0.051*
O1	0.3502 (3)	0.2110 (2)	0.0458 (2)	0.0473 (6)
O1W	0.4882 (3)	0.6952 (2)	0.2700 (2)	0.0513 (6)
C2	1.0696 (4)	0.2524 (3)	0.4943 (3)	0.0420 (8)
H2	1.0189	0.1622	0.5651	0.050*
H2W	0.553 (4)	0.702 (3)	0.1821 (10)	0.063*
N2	1.1240 (4)	0.4575 (3)	0.2854 (2)	0.0400 (7)
O2	0.3105 (3)	−0.0044 (2)	0.2397 (2)	0.0475 (6)
C3	1.2093 (5)	0.3327 (4)	0.4991 (3)	0.0444 (8)
H3	1.2723	0.3089	0.5749	0.053*
N3	0.6010 (3)	0.2457 (3)	0.1765 (3)	0.0396 (6)
C4	0.6356 (4)	0.1461 (3)	0.3035 (3)	0.0449 (8)
H4	0.5675	0.0577	0.3498	0.054*
C5	0.7685 (4)	0.1702 (3)	0.3678 (3)	0.0418 (8)
H5	0.7896	0.0987	0.4563	0.050*
C6	0.8716 (4)	0.3018 (3)	0.3005 (3)	0.0311 (7)
C7	0.8296 (4)	0.4054 (3)	0.1688 (3)	0.0421 (8)
H7	0.8919	0.4962	0.1210	0.050*
C8	0.6973 (4)	0.3730 (3)	0.1105 (3)	0.0451 (8)
H8	0.6734	0.4420	0.0218	0.054*
C9	0.1342 (4)	0.0404 (3)	0.0568 (3)	0.0303 (7)
C10	0.0548 (4)	0.1468 (3)	−0.0570 (3)	0.0362 (7)
H10	0.0913	0.2463	−0.0964	0.043*
C11	0.2749 (4)	0.0835 (3)	0.1202 (3)	0.0365 (7)
H11	0.427 (3)	0.212 (3)	0.093 (2)	0.044*
C12	0.0774 (4)	−0.1067 (3)	0.1123 (3)	0.0368 (7)
H12	0.1291	−0.1799	0.1882	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0348 (17)	0.0340 (17)	0.0324 (17)	−0.0076 (14)	−0.0138 (14)	−0.0124 (15)
N1	0.0410 (16)	0.0508 (17)	0.0497 (17)	−0.0133 (12)	−0.0191 (13)	−0.0218 (15)
O1	0.0540 (14)	0.0522 (14)	0.0513 (14)	−0.0250 (11)	−0.0301 (11)	−0.0111 (12)
O1W	0.0522 (16)	0.0496 (14)	0.0540 (14)	−0.0137 (11)	−0.0216 (12)	−0.0092 (12)
C2	0.0446 (19)	0.0435 (19)	0.0449 (19)	−0.0102 (15)	−0.0174 (16)	−0.0152 (16)
N2	0.0418 (15)	0.0459 (16)	0.0419 (15)	−0.0168 (12)	−0.0179 (12)	−0.0134 (13)
O2	0.0631 (15)	0.0476 (14)	0.0426 (13)	−0.0174 (11)	−0.0317 (12)	−0.0065 (12)
C3	0.050 (2)	0.050 (2)	0.043 (2)	−0.0045 (16)	−0.0243 (16)	−0.0161 (18)
N3	0.0368 (15)	0.0468 (16)	0.0402 (16)	−0.0107 (12)	−0.0117 (12)	−0.0156 (14)
C4	0.045 (2)	0.049 (2)	0.048 (2)	−0.0232 (16)	−0.0101 (16)	−0.0169 (18)
C5	0.0507 (19)	0.0396 (18)	0.0389 (18)	−0.0182 (15)	−0.0195 (15)	−0.0043 (15)
C6	0.0322 (17)	0.0341 (17)	0.0327 (17)	−0.0028 (14)	−0.0119 (14)	−0.0149 (15)
C7	0.0468 (19)	0.0375 (18)	0.048 (2)	−0.0141 (14)	−0.0211 (16)	−0.0090 (16)
C8	0.049 (2)	0.048 (2)	0.0427 (19)	−0.0108 (17)	−0.0227 (16)	−0.0090 (17)
C9	0.0263 (16)	0.0353 (18)	0.0329 (16)	−0.0078 (13)	−0.0074 (13)	−0.0134 (15)
C10	0.0382 (18)	0.0311 (16)	0.0435 (18)	−0.0124 (14)	−0.0149 (15)	−0.0094 (15)
C11	0.0349 (17)	0.0402 (19)	0.0439 (19)	−0.0119 (15)	−0.0123 (15)	−0.0190 (17)
C12	0.0381 (18)	0.0401 (18)	0.0364 (17)	−0.0093 (14)	−0.0177 (14)	−0.0081 (15)

Geometric parameters (Å, º) top

C1—N2	1.336 (3)	C4—C5	1.373 (4)
C1—C2	1.397 (4)	C4—H4	0.9300
C1—C6	1.465 (3)	C5—C6	1.391 (3)
N1—C3	1.337 (3)	C5—H5	0.9300
N1—N2	1.340 (3)	C6—C7	1.400 (4)
N1—H1	0.8600	C7—C8	1.364 (4)
O1—C11	1.272 (3)	C7—H7	0.9300
O1—H11	0.8202 (11)	C8—H8	0.9300
O1W—H1W	0.8400 (11)	C9—C12	1.383 (3)
O1W—H2W	0.8400 (11)	C9—C10	1.391 (4)
C2—C3	1.364 (4)	C9—C11	1.506 (4)
C2—H2	0.9300	C10—C12ⁱ	1.382 (4)
O2—C11	1.247 (3)	C10—H10	0.9300
C3—H3	0.9300	C12—C10ⁱ	1.382 (4)
N3—C8	1.333 (3)	C12—H12	0.9300
N3—C4	1.335 (4)

N2—C1—C2	110.9 (2)	C5—C6—C7	116.8 (3)
N2—C1—C6	120.5 (2)	C5—C6—C1	123.3 (2)
C2—C1—C6	128.6 (3)	C7—C6—C1	120.0 (2)
C3—N1—N2	113.3 (2)	C8—C7—C6	120.0 (3)
C3—N1—H1	123.3	C8—C7—H7	120.0
N2—N1—H1	123.3	C6—C7—H7	120.0
C11—O1—H11	102.3 (19)	N3—C8—C7	122.2 (3)
H1W—O1W—H2W	111.1 (12)	N3—C8—H8	118.9
C3—C2—C1	105.4 (3)	C7—C8—H8	118.9
C3—C2—H2	127.3	C12—C9—C10	118.0 (2)
C1—C2—H2	127.3	C12—C9—C11	120.6 (3)
C1—N2—N1	104.1 (2)	C10—C9—C11	121.4 (2)
N1—C3—C2	106.3 (3)	C12ⁱ—C10—C9	120.9 (3)
N1—C3—H3	126.8	C12ⁱ—C10—H10	119.5
C2—C3—H3	126.8	C9—C10—H10	119.5
C8—N3—C4	119.1 (2)	O2—C11—O1	124.0 (3)
N3—C4—C5	122.0 (3)	O2—C11—C9	119.7 (3)
N3—C4—H4	119.0	O1—C11—C9	116.3 (3)
C5—C4—H4	119.0	C9—C12—C10ⁱ	121.1 (3)
C4—C5—C6	120.0 (3)	C9—C12—H12	119.4
C4—C5—H5	120.0	C10ⁱ—C12—H12	119.4
C6—C5—H5	120.0

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1Wⁱⁱ	0.86	1.98	2.829 (3)	170
O1W—H1W···O2ⁱⁱⁱ	0.84 (1)	1.99 (1)	2.811 (3)	167 (2)
O1W—H2W···O1^iv	0.84 (1)	2.06 (1)	2.864 (3)	161 (2)
O1—H11···N3	0.82 (1)	1.80 (1)	2.614 (3)	170 (3)

Symmetry codes: (ii) x+1, y, z; (iii) x, y+1, z; (iv) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	2C₈H₇N₃·C₈H₆O₄·2H₂O
M_r	492.49
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.8364 (14), 9.5308 (19), 10.131 (2)
α, β, γ (°)	67.52 (3), 71.22 (3), 78.10 (3)
V (Å³)	574.9 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.32 × 0.25 × 0.18

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.967, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	5041, 2024, 1254
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.128, 1.21
No. of reflections	2024
No. of parameters	172
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.28

Computer programs: PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1Wⁱ	0.86	1.98	2.829 (3)	170
O1W—H1W···O2ⁱⁱ	0.8400 (11)	1.986 (7)	2.811 (3)	167 (2)
O1W—H2W···O1ⁱⁱⁱ	0.8400 (11)	2.058 (9)	2.864 (3)	161 (2)
O1—H11···N3	0.8202 (11)	1.801 (5)	2.614 (3)	170 (3)

Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z; (iii) −x+1, −y+1, −z.

Acknowledgements

The authors acknowledge Hunan Provincial Department of Education for the Xiang Norimichi Foundation (2010 243).

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Davies, G. M., Jeffery, J. C. & Ward, M. D. (2003). New J. Chem. 27, 1550–1553. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Americas Corporation, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar