1-(3-Chloro-2-pyrid­yl)-3-methyl-1H-pyrazole-5-carboxylic acid

Cai, H.; Guo, Y.; Li, J.-G.; Wu, Y.

doi:10.1107/S1600536809043906

organic compounds

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Volume 65| Part 11| November 2009| Page o2876

https://doi.org/10.1107/S1600536809043906

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1-(3-Chloro-2-pyridyl)-3-methyl-1H-pyrazole-5-carboxylic acid

Hua Cai,^a ^* Ying Guo,^a Jian-Gang Li ^a and Yao Wu ^a

^aCollege of Science, Civil Aviation University of China, Tianjin 300300, People's Republic of China
^*Correspondence e-mail: caihua-1109@163.com

(Received 18 October 2009; accepted 23 October 2009; online 28 October 2009)

In the title molecule, C₁₀H₈ClN₃O₂, the dihedral angle between the pyridine and pyrazole rings is 64.01 (8)°. In the crystal structure, intermolecular O—H⋯N hydrogen bonds link molecules, forming extended chains along [001]. These chains are, in turn, linked by weak intermolecular C—H⋯O interactions, forming a two-dimensional network perpendicular to the b axis.

Related literature

The title compound was prepared adventitiously as part of our research program related to metal-organic frameworks. See: Lehn (1995 ) for background information. For the topologies of metal-organic frameworks, see: Kitakawa et al. (2004 ); Rosi et al. (2005 ); Subramanian & Zaworotko (1994 ).

Experimental

Crystal data

C₁₀H₈ClN₃O₂
M_r = 237.64
Orthorhombic, P c a 2₁
a = 8.250 (6) Å
b = 11.232 (8) Å
c = 11.942 (8) Å
V = 1106.6 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.582, T_max = 1.000
5084 measured reflections
1943 independent reflections
1754 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.075
S = 1.04
1943 reflections
147 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³
Absolute structure: Flack (1983 ) 912 Friedel pairs
Flack parameter: 0.03 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1ⁱ	0.82	1.93	2.755 (3)	180
C2—H2A⋯O1ⁱⁱ	0.93	2.36	3.258 (4)	161
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y, z]$ .

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2001 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009 ) and DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809043906/lh2933sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043906/lh2933Isup2.hkl

checkCIF report

Comment top

Recently, metal-organic frameworks (MOFs) have attracted great attention (Lehn et al., 1995) because of their intriguing topologies (Subramanian et al., 1994; Kitakawa et al., 2004; Rosi et al., 2005). During our efforts to investigate the assembly of metal-organic coordination frameworks, a new compound, (I), was accidentally generated under hydrothermal conditions and the crystal structure of the title compound (I) is described in this paper. The molecular structure of (I) is shown in Fig. 1. The dihedral angle between the pyridine and pyrazole rings is 64.01 (8)°. The dihedral angle between the mean plane of the pyrazole ring and the plane formed by the atoms C10/O1/O2 is 7.47 (18)°. In the crystal structure, O—H···N hydrogen bonds involving the carboxylic acid O atoms and the 3-chloropyridin-2-yl group N atoms, form one-dimensional chains along [001] (Fig. 2). These chains, are in turn, linked by weak intermolecular C—H···O interactions forming a two-dimensional network perpendicular to the b-axis (Fig. 3).

Related literature top

The title compound was prepared adventitiously as part of our research program related to metal-organic frameworks. See: Lehn et al. (1995) for background information. For the topologies of metal-organic frameworks, see: Kitakawa et al. (2004); Rosi et al. (2005); Subramanian & Zaworotko (1994).

Experimental top

A mixture of Zn(OAc)₂.4H₂O (21.8 mg, 0.1 mmol), 1-(3-chloropyridin-2-yl)-3- methyl-pyrazole-5-carboxylic acid (23.8 mg, 0.1 mmol) in water (10 ml) was heated at 433 K for 3 d in a sealed Teflon-lined stainless steel vessel (20 ml) under autogenous pressure. After the reaction mixture was slowly cooled to room temperature at a rate of 5 K h^-1, pale-yellow lamellar single crystals suitable for X-ray diffraction were produced.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2003); 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), PLATON (Spek, 2009) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) showing 30% probability ellipsoids.
	Fig. 2. The one-dimensional chain structure of (I), showing O—H···N hydrogen bonds as red dashed lines.
	Fig. 3. Part of the crystal structure with hydrogen bonds shown as dashed lines.

1-(3-Chloro-2-pyridyl)-3-methyl-1H-pyrazole-5-carboxylic acid top

Crystal data top

C₁₀H₈ClN₃O₂	F(000) = 488
M_r = 237.64	D_x = 1.426 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2602 reflections
a = 8.250 (6) Å	θ = 3.1–27.5°
b = 11.232 (8) Å	µ = 0.33 mm⁻¹
c = 11.942 (8) Å	T = 296 K
V = 1106.6 (13) Å³	Block, colourless
Z = 4	0.24 × 0.20 × 0.18 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	1943 independent reflections
Radiation source: fine-focus sealed tube	1754 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
T_min = 0.582, T_max = 1.000	k = −11→13
5084 measured reflections	l = −14→14

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)] = 0.033	H-atom parameters constrained
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0254P)² + 0.1923P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1943 reflections	Δρ_max = 0.14 e Å⁻³
147 parameters	Δρ_min = −0.13 e Å⁻³
1 restraint	Absolute structure: Flack (1983) 912 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (7)

Crystal data top

C₁₀H₈ClN₃O₂	V = 1106.6 (13) Å³
M_r = 237.64	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 8.250 (6) Å	µ = 0.33 mm⁻¹
b = 11.232 (8) Å	T = 296 K
c = 11.942 (8) Å	0.24 × 0.20 × 0.18 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	1943 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1754 reflections with I > 2σ(I)
T_min = 0.582, T_max = 1.000	R_int = 0.032
5084 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.075	Δρ_max = 0.14 e Å⁻³
S = 1.04	Δρ_min = −0.13 e Å⁻³
1943 reflections	Absolute structure: Flack (1983) 912 Friedel pairs
147 parameters	Absolute structure parameter: 0.03 (7)
1 restraint

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
Cl1	1.19679 (9)	0.18938 (6)	0.13597 (6)	0.0748 (2)
O1	0.7978 (2)	0.17726 (13)	0.1372 (2)	0.0622 (5)
O2	0.6983 (2)	0.34151 (14)	0.05851 (17)	0.0664 (5)
H2	0.6504	0.2936	0.0186	0.100*
N1	0.9622 (2)	0.18043 (16)	0.42451 (15)	0.0446 (5)
N2	0.9738 (2)	0.33015 (15)	0.29058 (16)	0.0414 (4)
N3	1.0231 (2)	0.42331 (17)	0.35467 (17)	0.0490 (5)
C1	1.1171 (3)	0.1403 (2)	0.26170 (19)	0.0484 (6)
C2	1.1532 (3)	0.0288 (2)	0.3012 (2)	0.0606 (7)
H2A	1.2178	−0.0224	0.2594	0.073*
C3	1.0928 (3)	−0.0067 (2)	0.4034 (3)	0.0625 (7)
H3	1.1145	−0.0823	0.4314	0.075*
C4	0.9994 (3)	0.0727 (2)	0.4629 (2)	0.0544 (6)
H4	0.9607	0.0501	0.5329	0.065*
C5	1.0179 (2)	0.21361 (19)	0.32469 (18)	0.0396 (5)
C6	0.9573 (3)	0.5193 (2)	0.3074 (2)	0.0502 (6)
C7	0.8657 (3)	0.4882 (2)	0.2137 (2)	0.0508 (6)
H7	0.8092	0.5395	0.1668	0.061*
C8	0.8758 (3)	0.36675 (19)	0.20469 (19)	0.0421 (5)
C9	0.9834 (4)	0.6389 (2)	0.3575 (3)	0.0786 (9)
H9A	1.0755	0.6363	0.4066	0.118*
H9B	0.8889	0.6617	0.3992	0.118*
H9C	1.0026	0.6958	0.2991	0.118*
C10	0.7890 (3)	0.28386 (18)	0.1310 (2)	0.0435 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0825 (5)	0.0840 (5)	0.0578 (4)	0.0041 (4)	0.0284 (4)	−0.0126 (4)
O1	0.0816 (12)	0.0439 (10)	0.0612 (10)	−0.0104 (8)	−0.0217 (10)	0.0019 (10)
O2	0.0833 (13)	0.0539 (10)	0.0618 (12)	−0.0028 (9)	−0.0294 (11)	0.0010 (9)
N1	0.0460 (11)	0.0480 (11)	0.0399 (11)	−0.0015 (8)	0.0012 (9)	0.0004 (8)
N2	0.0477 (11)	0.0391 (10)	0.0376 (10)	−0.0016 (8)	0.0009 (9)	−0.0041 (8)
N3	0.0497 (11)	0.0477 (11)	0.0496 (11)	−0.0037 (9)	−0.0004 (10)	−0.0108 (9)
C1	0.0471 (13)	0.0541 (14)	0.0441 (13)	0.0011 (11)	0.0002 (10)	−0.0101 (11)
C2	0.0564 (14)	0.0555 (15)	0.0701 (17)	0.0155 (12)	−0.0069 (14)	−0.0158 (13)
C3	0.0659 (17)	0.0482 (13)	0.0734 (18)	0.0074 (14)	−0.0155 (15)	0.0052 (13)
C4	0.0598 (15)	0.0549 (16)	0.0484 (13)	−0.0030 (13)	−0.0059 (11)	0.0096 (11)
C5	0.0368 (11)	0.0429 (12)	0.0391 (12)	−0.0007 (9)	−0.0034 (9)	−0.0053 (9)
C6	0.0511 (13)	0.0416 (13)	0.0578 (15)	−0.0040 (11)	0.0021 (12)	−0.0096 (11)
C7	0.0562 (14)	0.0425 (13)	0.0539 (13)	0.0012 (11)	−0.0029 (12)	0.0017 (11)
C8	0.0451 (12)	0.0438 (13)	0.0373 (11)	−0.0019 (10)	0.0012 (9)	−0.0007 (10)
C9	0.088 (2)	0.0546 (16)	0.093 (2)	0.0004 (16)	−0.0138 (19)	−0.0207 (16)
C10	0.0493 (12)	0.0425 (12)	0.0386 (11)	−0.0034 (10)	0.0030 (11)	0.0035 (12)

Geometric parameters (Å, º) top

Cl1—C1	1.729 (3)	C2—H2A	0.9300
O1—C10	1.202 (2)	C3—C4	1.376 (4)
O2—C10	1.314 (3)	C3—H3	0.9300
O2—H2	0.8200	C4—H4	0.9300
N1—C4	1.330 (3)	C6—C7	1.394 (4)
N1—C5	1.331 (3)	C6—C9	1.486 (4)
N2—N3	1.359 (2)	C7—C8	1.371 (3)
N2—C8	1.369 (3)	C7—H7	0.9300
N2—C5	1.418 (3)	C8—C10	1.468 (3)
N3—C6	1.333 (3)	C9—H9A	0.9600
C1—C2	1.371 (4)	C9—H9B	0.9600
C1—C5	1.383 (3)	C9—H9C	0.9600
C2—C3	1.377 (4)

C10—O2—H2	109.5	C1—C5—N2	123.0 (2)
C4—N1—C5	118.9 (2)	N3—C6—C7	111.0 (2)
N3—N2—C8	111.56 (16)	N3—C6—C9	120.1 (2)
N3—N2—C5	118.17 (18)	C7—C6—C9	128.9 (2)
C8—N2—C5	130.08 (18)	C8—C7—C6	106.2 (2)
C6—N3—N2	105.21 (18)	C8—C7—H7	126.9
C2—C1—C5	119.0 (2)	C6—C7—H7	126.9
C2—C1—Cl1	120.47 (19)	N2—C8—C7	106.01 (19)
C5—C1—Cl1	120.49 (18)	N2—C8—C10	123.1 (2)
C1—C2—C3	119.4 (2)	C7—C8—C10	130.4 (2)
C1—C2—H2A	120.3	C6—C9—H9A	109.5
C3—C2—H2A	120.3	C6—C9—H9B	109.5
C4—C3—C2	118.2 (2)	H9A—C9—H9B	109.5
C4—C3—H3	120.9	C6—C9—H9C	109.5
C2—C3—H3	120.9	H9A—C9—H9C	109.5
N1—C4—C3	122.7 (3)	H9B—C9—H9C	109.5
N1—C4—H4	118.6	O1—C10—O2	124.5 (2)
C3—C4—H4	118.6	O1—C10—C8	124.4 (3)
N1—C5—C1	121.6 (2)	O2—C10—C8	111.10 (19)
N1—C5—N2	115.29 (19)

C8—N2—N3—C6	−0.9 (2)	C8—N2—C5—C1	69.0 (3)
C5—N2—N3—C6	−176.4 (2)	N2—N3—C6—C7	0.2 (3)
C5—C1—C2—C3	−1.3 (3)	N2—N3—C6—C9	178.8 (2)
Cl1—C1—C2—C3	177.8 (2)	N3—C6—C7—C8	0.6 (3)
C1—C2—C3—C4	−0.8 (4)	C9—C6—C7—C8	−177.9 (3)
C5—N1—C4—C3	−0.4 (4)	N3—N2—C8—C7	1.3 (2)
C2—C3—C4—N1	1.7 (4)	C5—N2—C8—C7	176.0 (2)
C4—N1—C5—C1	−1.9 (3)	N3—N2—C8—C10	−172.2 (2)
C4—N1—C5—N2	−179.44 (19)	C5—N2—C8—C10	2.6 (4)
C2—C1—C5—N1	2.8 (3)	C6—C7—C8—N2	−1.1 (2)
Cl1—C1—C5—N1	−176.29 (17)	C6—C7—C8—C10	171.7 (2)
C2—C1—C5—N2	−179.9 (2)	N2—C8—C10—O1	−1.5 (4)
Cl1—C1—C5—N2	1.0 (3)	C7—C8—C10—O1	−173.2 (3)
N3—N2—C5—N1	60.9 (3)	N2—C8—C10—O2	177.4 (2)
C8—N2—C5—N1	−113.5 (3)	C7—C8—C10—O2	5.7 (4)
N3—N2—C5—C1	−116.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1ⁱ	0.82	1.93	2.755 (3)	180
C2—H2A···O1ⁱⁱ	0.93	2.36	3.258 (4)	161

Symmetry codes: (i) −x+3/2, y, z−1/2; (ii) x+1/2, −y, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₈ClN₃O₂
M_r	237.64
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	296
a, b, c (Å)	8.250 (6), 11.232 (8), 11.942 (8)
V (Å³)	1106.6 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.582, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5084, 1943, 1754
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.075, 1.04
No. of reflections	1943
No. of parameters	147
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.13
Absolute structure	Flack (1983) 912 Friedel pairs
Absolute structure parameter	0.03 (7)

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and DIAMOND (Brandenburg & Berndt, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1ⁱ	0.82	1.93	2.755 (3)	179.9
C2—H2A···O1ⁱⁱ	0.93	2.36	3.258 (4)	161.2

Symmetry codes: (i) −x+3/2, y, z−1/2; (ii) x+1/2, −y, z.

Acknowledgements

We acknowledge financial support by the Scientific Research Foundation of the Civil Aviation University of China (No. 08CAUC-S01) and the Natural Science Foundation of Tianjin (09JCYBJC04200).

References

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