1-(6-Chloro­pyridin-3-ylmeth­yl)-3-phenyl-1H-pyrazole-5-carboxylic acid

In the title compound, C₁₆H₁₂ClN₃O₂, the pyrazole ring makes dihedral angles of 4.6 (1) and 67.1 (1)° with the phenyl and pyridine rings, respectively. The structure displays O—H...N hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.044
• wR factor = 0.095
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.49
           From the CIF: _reflns_number_total               3276
           Count of symmetry unique reflns         1834
           Completeness (_total/calc)            178.63%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1442
           Fraction of Friedel pairs measured     0.786
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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

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S1. Comment

Pyrazole framework plays an essential role in biologically active compounds. Many pyrazole derivatives are known to exhibit a wide range of biological properties such as anticoagulant (Jia et al., 2004), antipyretic, antibacterial, hypoglycaemic, antihyperglycaemic, analgesic, anti-inflammatory, sedative-hypnotic (Cottineau et al., 2002; Finn et al., 2003), and antitumour (Wei et al., 2006) activities. We report here the crystal structure of the title compound, (I).

Related literature

For related literature, see: Cottineau et al. (2002); Finn et al. (2003); Jia et al. (2004); Wei et al. (2006); Xia et al. (2007).

S2. Experimental

A mixture of ethyl 1-((6-chloropyridin-3-yl)methyl)-3-phenyl-1H-pyrazole-5-carboxylate (0.01 mol) that was synthesized according to the literature procedure (Xia et al., 2007) and potassium hydroxide (0.02 mol) in ethanol (40 ml) was heated to reflux for 1 h. The solvent was removed under reduced pressure and the residue was dissolved in water and acidified with hydrochloric acid (10%). The precipitate was filtered and dried to give a white solid (yield 86%). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in acetone at room temperature for 6 d.

S3. Refinement

All H atoms were placed at geometrically calculated positions and allowed to ride with C—H = 0.97 Å (for CH₂ groups), and O—H = 0.82 Å; their isotropic displacement parameters were set to 1.2 times (CH₂ groups) or 1.5 times (O—H groups) the equivalent displacement parameter of their parent atoms.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular strure of (I), showing displacement ellipsoids drawn at 50% probability level.
	Fig. 2. Packing view of (I), shown down the c axis. Hydrogen bonds leading to columns units are drawn as dashed lines.

1-(6-Chloropyridin-3-ylmethyl)-3-phenyl-1H-pyrazole-5-carboxylic acid

Crystal data

C16H12ClN3O2	F(000) = 2592
Mr = 313.74	Dx = 1.454 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 1585 reflections
a = 20.5430 (5) Å	θ = 2.5–21.4°
b = 54.5902 (15) Å	µ = 0.28 mm^−1
c = 5.1134 (1) Å	T = 293 K
V = 5734.4 (2) Å^3	Plate, colourless
Z = 16	0.26 × 0.14 × 0.04 mm

Data collection

Bruker APEX2 CCD area-detector diffractometer	3276 independent reflections
Radiation source: fine-focus sealed tube	2193 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
φ and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −25→26
Tmin = 0.931, Tmax = 0.989	k = −67→70
11476 measured reflections	l = −6→6

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0367P)^2 + 0.3657P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3276 reflections	Δρmax = 0.20 e Å^−3
200 parameters	Δρmin = −0.16 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (7)

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	0.59781 (18)	0.25213 (5)	−0.3934 (7)	0.0630 (9)
H1	0.5909	0.2643	−0.5178	0.076*
C2	0.65305 (18)	0.25237 (6)	−0.2456 (7)	0.0635 (9)
H2	0.6840	0.2646	−0.2708	0.076*
C3	0.66326 (15)	0.23443 (5)	−0.0576 (6)	0.0544 (8)
H3	0.7009	0.2348	0.0437	0.065*
C4	0.61805 (12)	0.21602 (5)	−0.0195 (5)	0.0383 (6)
C5	0.56229 (13)	0.21617 (5)	−0.1724 (6)	0.0500 (7)
H5	0.5310	0.2040	−0.1489	0.060*
C6	0.55259 (15)	0.23404 (6)	−0.3588 (6)	0.0618 (9)
H6	0.5152	0.2338	−0.4612	0.074*
C7	0.62922 (12)	0.19686 (4)	0.1782 (5)	0.0348 (6)
C8	0.67929 (11)	0.19464 (4)	0.3623 (5)	0.0367 (6)
H8	0.7142	0.2052	0.3862	0.044*
C9	0.66637 (11)	0.17366 (4)	0.5004 (5)	0.0332 (6)
C10	0.70235 (12)	0.16293 (5)	0.7217 (5)	0.0359 (6)
C11	0.57428 (11)	0.14209 (4)	0.4677 (6)	0.0380 (6)
H11A	0.5281	0.1450	0.4422	0.046*
H11B	0.5811	0.1386	0.6517	0.046*
C12	0.59414 (11)	0.11997 (4)	0.3095 (5)	0.0350 (6)
C13	0.64818 (12)	0.10619 (4)	0.3792 (6)	0.0416 (7)
H13	0.6730	0.1106	0.5238	0.050*
C14	0.66494 (13)	0.08599 (5)	0.2343 (6)	0.0467 (7)
H14	0.7012	0.0766	0.2769	0.056*
C15	0.55921 (11)	0.11244 (4)	0.0930 (5)	0.0377 (6)
H15	0.5232	0.1216	0.0431	0.045*
C16	0.62635 (13)	0.08010 (5)	0.0246 (5)	0.0421 (7)
Cl1	0.64398 (4)	0.054295 (13)	−0.16079 (18)	0.0733 (3)
N1	0.58700 (9)	0.17805 (4)	0.2025 (4)	0.0373 (5)
N2	0.60997 (9)	0.16434 (3)	0.3997 (4)	0.0357 (5)
N3	0.57445 (10)	0.09264 (4)	−0.0486 (4)	0.0415 (6)
O1	0.75219 (8)	0.17705 (3)	0.7891 (4)	0.0445 (5)
H1A	0.7717	0.1708	0.9117	0.067*
O2	0.69003 (8)	0.14364 (3)	0.8283 (4)	0.0480 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.091 (2)	0.0468 (17)	0.051 (2)	0.0154 (17)	0.009 (2)	0.0181 (18)
C2	0.088 (2)	0.0406 (16)	0.062 (2)	−0.0096 (16)	0.008 (2)	0.0083 (16)
C3	0.0670 (19)	0.0435 (16)	0.053 (2)	−0.0087 (15)	−0.0061 (15)	0.0055 (15)
C4	0.0491 (16)	0.0328 (13)	0.0330 (15)	0.0067 (12)	0.0070 (13)	−0.0013 (12)
C5	0.0477 (16)	0.0501 (16)	0.0523 (19)	0.0053 (13)	−0.0031 (15)	0.0144 (16)
C6	0.0642 (19)	0.067 (2)	0.054 (2)	0.0120 (17)	−0.0065 (16)	0.0159 (19)
C7	0.0401 (14)	0.0307 (13)	0.0337 (16)	0.0017 (11)	0.0022 (12)	−0.0031 (11)
C8	0.0392 (14)	0.0322 (13)	0.0386 (17)	−0.0012 (10)	0.0008 (13)	−0.0034 (13)
C9	0.0344 (13)	0.0351 (13)	0.0300 (14)	0.0031 (11)	0.0007 (11)	−0.0010 (12)
C10	0.0338 (14)	0.0411 (15)	0.0327 (14)	0.0051 (12)	0.0011 (11)	−0.0048 (13)
C11	0.0324 (13)	0.0408 (15)	0.0409 (16)	−0.0010 (11)	0.0017 (12)	0.0065 (13)
C12	0.0323 (12)	0.0349 (13)	0.0379 (15)	−0.0066 (11)	−0.0018 (12)	0.0110 (13)
C13	0.0380 (14)	0.0449 (15)	0.0420 (18)	−0.0028 (12)	−0.0123 (13)	0.0027 (14)
C14	0.0486 (16)	0.0434 (15)	0.0481 (18)	0.0103 (13)	−0.0116 (15)	0.0010 (14)
C15	0.0334 (13)	0.0412 (14)	0.0386 (16)	0.0004 (11)	−0.0016 (13)	0.0139 (14)
C16	0.0533 (17)	0.0368 (14)	0.0361 (17)	0.0018 (13)	−0.0048 (13)	0.0031 (12)
Cl1	0.1066 (7)	0.0495 (4)	0.0638 (6)	0.0242 (4)	−0.0260 (5)	−0.0104 (4)
N1	0.0408 (12)	0.0361 (11)	0.0350 (12)	0.0030 (10)	−0.0042 (10)	0.0054 (10)
N2	0.0351 (11)	0.0342 (11)	0.0376 (14)	−0.0008 (9)	−0.0044 (10)	0.0044 (10)
N3	0.0405 (12)	0.0432 (12)	0.0408 (14)	−0.0010 (10)	−0.0076 (10)	0.0066 (12)
O1	0.0438 (10)	0.0461 (10)	0.0436 (13)	0.0002 (9)	−0.0131 (9)	−0.0006 (9)
O2	0.0544 (11)	0.0449 (10)	0.0446 (12)	−0.0011 (9)	−0.0081 (10)	0.0098 (10)

Geometric parameters (Å, º)

C1—C2	1.363 (5)	C10—O2	1.212 (3)
C1—C6	1.367 (4)	C10—O1	1.327 (3)
C1—H1	0.9300	C11—N2	1.460 (3)
C2—C3	1.388 (4)	C11—C12	1.510 (3)
C2—H2	0.9300	C11—H11A	0.9700
C3—C4	1.382 (3)	C11—H11B	0.9700
C3—H3	0.9300	C12—C15	1.382 (4)
C4—C5	1.387 (4)	C12—C13	1.388 (3)
C4—C7	1.473 (3)	C13—C14	1.373 (4)
C5—C6	1.378 (4)	C13—H13	0.9300
C5—H5	0.9300	C14—C16	1.372 (4)
C6—H6	0.9300	C14—H14	0.9300
C7—N1	1.350 (3)	C15—N3	1.338 (3)
C7—C8	1.400 (3)	C15—H15	0.9300
C8—C9	1.371 (3)	C16—N3	1.321 (3)
C8—H8	0.9300	C16—Cl1	1.736 (3)
C9—N2	1.366 (3)	N1—N2	1.342 (3)
C9—C10	1.473 (4)	O1—H1A	0.8200
C2—C1—C6	120.0 (3)	O1—C10—C9	110.8 (2)
C2—C1—H1	120.0	N2—C11—C12	113.7 (2)
C6—C1—H1	120.0	N2—C11—H11A	108.8
C1—C2—C3	120.2 (3)	C12—C11—H11A	108.8
C1—C2—H2	119.9	N2—C11—H11B	108.8
C3—C2—H2	119.9	C12—C11—H11B	108.8
C4—C3—C2	120.6 (3)	H11A—C11—H11B	107.7
C4—C3—H3	119.7	C15—C12—C13	117.4 (3)
C2—C3—H3	119.7	C15—C12—C11	121.8 (2)
C3—C4—C5	118.1 (3)	C13—C12—C11	120.8 (2)
C3—C4—C7	120.6 (2)	C14—C13—C12	119.8 (3)
C5—C4—C7	121.3 (2)	C14—C13—H13	120.1
C6—C5—C4	120.9 (3)	C12—C13—H13	120.1
C6—C5—H5	119.6	C16—C14—C13	117.7 (2)
C4—C5—H5	119.6	C16—C14—H14	121.1
C1—C6—C5	120.2 (3)	C13—C14—H14	121.1
C1—C6—H6	119.9	N3—C15—C12	123.5 (2)
C5—C6—H6	119.9	N3—C15—H15	118.2
N1—C7—C8	110.2 (2)	C12—C15—H15	118.2
N1—C7—C4	120.2 (2)	N3—C16—C14	124.5 (3)
C8—C7—C4	129.6 (2)	N3—C16—Cl1	115.7 (2)
C9—C8—C7	106.0 (2)	C14—C16—Cl1	119.8 (2)
C9—C8—H8	127.0	N2—N1—C7	105.52 (19)
C7—C8—H8	127.0	N1—N2—C9	111.93 (19)
N2—C9—C8	106.3 (2)	N1—N2—C11	117.81 (19)
N2—C9—C10	124.5 (2)	C9—N2—C11	130.2 (2)
C8—C9—C10	129.1 (2)	C16—N3—C15	117.0 (2)
O2—C10—O1	123.3 (2)	C10—O1—H1A	109.5
O2—C10—C9	125.9 (2)
C6—C1—C2—C3	−0.7 (5)	N2—C11—C12—C13	83.1 (3)
C1—C2—C3—C4	0.6 (5)	C15—C12—C13—C14	0.1 (4)
C2—C3—C4—C5	−0.6 (4)	C11—C12—C13—C14	179.3 (2)
C2—C3—C4—C7	179.4 (3)	C12—C13—C14—C16	−0.6 (4)
C3—C4—C5—C6	0.6 (4)	C13—C12—C15—N3	0.7 (4)
C7—C4—C5—C6	−179.3 (2)	C11—C12—C15—N3	−178.5 (2)
C2—C1—C6—C5	0.8 (5)	C13—C14—C16—N3	0.5 (4)
C4—C5—C6—C1	−0.7 (5)	C13—C14—C16—Cl1	−178.4 (2)
C3—C4—C7—N1	−175.6 (2)	C8—C7—N1—N2	0.4 (3)
C5—C4—C7—N1	4.3 (4)	C4—C7—N1—N2	−178.8 (2)
C3—C4—C7—C8	5.4 (4)	C7—N1—N2—C9	−0.9 (3)
C5—C4—C7—C8	−174.7 (3)	C7—N1—N2—C11	−178.79 (19)
N1—C7—C8—C9	0.2 (3)	C8—C9—N2—N1	1.0 (3)
C4—C7—C8—C9	179.3 (2)	C10—C9—N2—N1	178.7 (2)
C7—C8—C9—N2	−0.7 (3)	C8—C9—N2—C11	178.6 (2)
C7—C8—C9—C10	−178.3 (2)	C10—C9—N2—C11	−3.7 (4)
N2—C9—C10—O2	6.5 (4)	C12—C11—N2—N1	86.5 (3)
C8—C9—C10—O2	−176.4 (3)	C12—C11—N2—C9	−90.9 (3)
N2—C9—C10—O1	−174.9 (2)	C14—C16—N3—C15	0.2 (4)
C8—C9—C10—O1	2.2 (3)	Cl1—C16—N3—C15	179.12 (18)
N2—C11—C12—C15	−97.8 (3)	C12—C15—N3—C16	−0.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3^i	0.82	1.98	2.794 (3)	176

Symmetry code: (i) x+1/4, −y+1/4, z+5/4.