1-(3-Chloro-2-pyrid-yl)-3-methyl-1H-pyrazole-5-carboxylic acid.

In the title mol-ecule, C(10)H(8)ClN(3)O(2), the dihedral angle between the pyridine and pyrazole rings is 64.01 (8)°. In the crystal structure, inter-molecular O-H⋯N hydrogen bonds link mol-ecules, forming extended chains along [001]. These chains are, in turn, linked by weak inter-molecular C-H⋯O inter-actions, 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 = 237.64

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.075

S = 1.04

1943 reflections

147 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.13 e Å−3

Absolute structure: Flack (1983 ▶) 912 Friedel pairs

Flack parameter: 0.03 (7)

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.

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043906/lh2933Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C10H8ClN3O2	F(000) = 488
Mr = 237.64	Dx = 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

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

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(Fo2) + (0.0254P)2 + 0.1923P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
1943 reflections	Δρmax = 0.14 e Å−3
147 parameters	Δρmin = −0.13 e Å−3
1 restraint	Absolute structure: Flack (1983) 912 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.03 (7)

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
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)

	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)

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)

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

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) ; (ii) .