2-Amino-5-chloro-pyridine-benzoic acid (1/1).

In the title compound, C(5)H(5)ClN(2)·C(7)H(6)O(2), the carboxyl group of the benzoic acid mol-ecule is twisted away from the attached ring by 14.22 (7)°. In the crystal, the 2-amino-5-chloro-pyridine mol-ecules inter-act with the carboxyl groups of benzoic acid mol-ecules through N-H⋯O and O-H⋯N hydrogen bonds, forming cyclic R(2) (2)(8) hydrogen-bonded motifs, and linking the mol-ecules into chains parallel to the [001] direction. Neighbouring 2-amino-5-chloro-pyridine mol-ecules are also centrosymmetrically paired through C-H⋯Cl hydrogen bonds, forming another R(2) (2)(8) motif. The crystal structure is further stabilized by weak C-H⋯O hydrogen bonds.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶); For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Lynch & Jones (2004 ▶). For reference bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C5H5ClN2·C7H6O2

M = 250.68

Monoclinic,

a = 17.6114 (19) Å

b = 5.3442 (6) Å

c = 12.4774 (13) Å

β = 100.161 (2)°

V = 1155.9 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 100 K

0.55 × 0.25 × 0.07 mm

Data collection

Bruker SMART APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.844, T max = 0.979

11852 measured reflections

3331 independent reflections

2802 reflections with > 2(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.111

S = 1.12

3331 reflections

198 parameters

All H-atom parameters refined

Δρmax = 0.46 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004447/wn2376sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004447/wn2376Isup2.hkl

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

C5H5ClN2·C7H6O2	F(000) = 520
Mr = 250.68	Dx = 1.440 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5100 reflections
a = 17.6114 (19) Å	θ = 2.4–30.0°
b = 5.3442 (6) Å	µ = 0.32 mm−1
c = 12.4774 (13) Å	T = 100 K
β = 100.161 (2)°	Plate, colourless
V = 1155.9 (2) Å3	0.55 × 0.25 × 0.07 mm
Z = 4

Bruker SMART APEX DUO CCD area-detector diffractometer	3331 independent reflections
Radiation source: fine-focus sealed tube	2802 reflections with > 2(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 30.0°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −24→24
Tmin = 0.844, Tmax = 0.979	k = −7→7
11852 measured reflections	l = −17→17

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	All H-atom parameters refined
S = 1.12	w = 1/[σ2(Fo2) + (0.0596P)2 + 0.2767P] where P = (Fo2 + 2Fc2)/3
3331 reflections	(Δ/σ)max < 0.001
198 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.029115 (18)	0.29660 (7)	0.17435 (3)	0.02611 (11)
N1	0.17431 (6)	−0.2004 (2)	0.08617 (9)	0.0197 (2)
N2	0.22948 (8)	−0.2526 (3)	−0.06737 (10)	0.0270 (3)
C1	0.12668 (7)	−0.0733 (2)	0.14079 (10)	0.0202 (2)
C2	0.08720 (7)	0.1356 (2)	0.09858 (10)	0.0203 (2)
C3	0.09605 (8)	0.2235 (3)	−0.00426 (11)	0.0232 (3)
C4	0.14399 (8)	0.0960 (3)	−0.06017 (11)	0.0229 (3)
C5	0.18308 (7)	−0.1193 (2)	−0.01300 (10)	0.0199 (2)
O1	0.30023 (6)	0.33873 (19)	0.06701 (7)	0.0235 (2)
O2	0.25316 (5)	0.46305 (18)	0.21358 (7)	0.0202 (2)
C6	0.35843 (7)	0.1449 (3)	0.34708 (10)	0.0194 (2)
C7	0.40642 (7)	−0.0304 (3)	0.40807 (10)	0.0226 (3)
C8	0.44122 (8)	−0.2180 (3)	0.35634 (12)	0.0232 (3)
C9	0.42870 (8)	−0.2295 (3)	0.24289 (12)	0.0227 (3)
C10	0.38163 (7)	−0.0544 (2)	0.18193 (10)	0.0202 (2)
C11	0.34623 (7)	0.1339 (2)	0.23375 (10)	0.0170 (2)
C12	0.29775 (7)	0.3214 (2)	0.16423 (10)	0.0173 (2)
H1	0.1213 (10)	−0.132 (3)	0.2126 (14)	0.028 (4)*
H3	0.0695 (11)	0.375 (4)	−0.0377 (16)	0.040 (5)*
H4	0.1539 (10)	0.154 (4)	−0.1271 (15)	0.032 (5)*
H6	0.3370 (10)	0.270 (4)	0.3810 (14)	0.026 (4)*
H7	0.4150 (10)	−0.018 (4)	0.4848 (14)	0.032 (5)*
H8	0.4762 (10)	−0.344 (3)	0.4016 (14)	0.026 (4)*
H9	0.4506 (10)	−0.362 (3)	0.2061 (14)	0.029 (4)*
H10	0.3722 (9)	−0.058 (3)	0.1028 (13)	0.024 (4)*
H1O2	0.2262 (13)	0.590 (5)	0.1647 (19)	0.061 (7)*
H1N2	0.2563 (11)	−0.378 (4)	−0.0353 (16)	0.039 (5)*
H2N2	0.2443 (11)	−0.186 (4)	−0.1250 (16)	0.033 (5)*

	U11	U22	U33	U12	U13	U23
Cl1	0.02624 (17)	0.02425 (18)	0.02760 (18)	0.00709 (12)	0.00407 (12)	0.00036 (12)
N1	0.0220 (5)	0.0181 (5)	0.0187 (5)	0.0018 (4)	0.0026 (4)	0.0026 (4)
N2	0.0345 (6)	0.0266 (6)	0.0217 (5)	0.0075 (5)	0.0096 (5)	0.0059 (5)
C1	0.0208 (5)	0.0187 (6)	0.0208 (6)	0.0005 (5)	0.0025 (4)	0.0021 (5)
C2	0.0185 (5)	0.0186 (6)	0.0228 (6)	0.0008 (5)	0.0011 (4)	−0.0009 (5)
C3	0.0232 (6)	0.0200 (6)	0.0240 (6)	0.0016 (5)	−0.0028 (5)	0.0040 (5)
C4	0.0249 (6)	0.0229 (6)	0.0193 (6)	0.0005 (5)	−0.0006 (5)	0.0049 (5)
C5	0.0208 (5)	0.0189 (6)	0.0193 (5)	−0.0018 (5)	0.0012 (4)	0.0010 (5)
O1	0.0320 (5)	0.0243 (5)	0.0148 (4)	0.0045 (4)	0.0059 (3)	0.0020 (4)
O2	0.0225 (4)	0.0211 (4)	0.0178 (4)	0.0043 (4)	0.0055 (3)	0.0031 (4)
C6	0.0207 (5)	0.0203 (6)	0.0182 (5)	0.0006 (5)	0.0063 (4)	0.0022 (5)
C7	0.0219 (6)	0.0267 (7)	0.0191 (6)	0.0010 (5)	0.0037 (4)	0.0056 (5)
C8	0.0197 (6)	0.0206 (6)	0.0291 (7)	0.0010 (5)	0.0034 (5)	0.0065 (5)
C9	0.0210 (6)	0.0182 (6)	0.0289 (7)	0.0010 (5)	0.0044 (5)	−0.0018 (5)
C10	0.0210 (5)	0.0195 (6)	0.0200 (5)	−0.0013 (5)	0.0033 (4)	−0.0026 (5)
C11	0.0165 (5)	0.0158 (5)	0.0187 (5)	−0.0029 (4)	0.0030 (4)	0.0015 (4)
C12	0.0179 (5)	0.0167 (6)	0.0172 (5)	−0.0025 (4)	0.0027 (4)	0.0001 (4)

Cl1—C2	1.7382 (13)	O2—C12	1.3190 (15)
N1—C5	1.3454 (16)	O2—H1O2	0.98 (2)
N1—C1	1.3532 (17)	C6—C11	1.3936 (17)
N2—C5	1.3530 (18)	C6—C7	1.3946 (18)
N2—H1N2	0.88 (2)	C6—H6	0.907 (18)
N2—H2N2	0.881 (19)	C7—C8	1.392 (2)
C1—C2	1.3705 (18)	C7—H7	0.945 (17)
C1—H1	0.970 (18)	C8—C9	1.395 (2)
C2—C3	1.4006 (19)	C8—H8	1.015 (18)
C3—C4	1.368 (2)	C9—C10	1.3854 (19)
C3—H3	0.99 (2)	C9—H9	0.962 (18)
C4—C5	1.4149 (18)	C10—C11	1.4005 (18)
C4—H4	0.936 (18)	C10—H10	0.972 (16)
O1—C12	1.2250 (15)	C11—C12	1.4913 (17)
C5—N1—C1	118.92 (11)	C11—C6—H6	120.1 (11)
C5—N2—H1N2	120.0 (13)	C7—C6—H6	120.1 (11)
C5—N2—H2N2	119.3 (13)	C8—C7—C6	120.33 (12)
H1N2—N2—H2N2	117.8 (18)	C8—C7—H7	120.9 (11)
N1—C1—C2	122.21 (12)	C6—C7—H7	118.7 (11)
N1—C1—H1	118.2 (11)	C7—C8—C9	119.92 (12)
C2—C1—H1	119.5 (11)	C7—C8—H8	119.6 (10)
C1—C2—C3	119.61 (12)	C9—C8—H8	120.5 (10)
C1—C2—Cl1	120.10 (10)	C10—C9—C8	119.96 (12)
C3—C2—Cl1	120.25 (10)	C10—C9—H9	119.2 (11)
C4—C3—C2	118.61 (12)	C8—C9—H9	120.8 (11)
C4—C3—H3	118.7 (11)	C9—C10—C11	120.26 (12)
C2—C3—H3	122.6 (11)	C9—C10—H10	121.5 (10)
C3—C4—C5	119.45 (12)	C11—C10—H10	118.3 (10)
C3—C4—H4	121.2 (11)	C6—C11—C10	119.82 (12)
C5—C4—H4	119.3 (11)	C6—C11—C12	122.12 (11)
N1—C5—N2	117.98 (12)	C10—C11—C12	118.04 (11)
N1—C5—C4	121.20 (12)	O1—C12—O2	123.17 (11)
N2—C5—C4	120.81 (12)	O1—C12—C11	120.66 (11)
C12—O2—H1O2	111.7 (14)	O2—C12—C11	116.17 (10)
C11—C6—C7	119.69 (12)
C5—N1—C1—C2	−0.16 (19)	C6—C7—C8—C9	0.6 (2)
N1—C1—C2—C3	−0.2 (2)	C7—C8—C9—C10	0.0 (2)
N1—C1—C2—Cl1	−178.03 (10)	C8—C9—C10—C11	−0.3 (2)
C1—C2—C3—C4	0.34 (19)	C7—C6—C11—C10	0.60 (19)
Cl1—C2—C3—C4	178.12 (10)	C7—C6—C11—C12	−177.84 (11)
C2—C3—C4—C5	−0.04 (19)	C9—C10—C11—C6	−0.01 (19)
C1—N1—C5—N2	−178.39 (12)	C9—C10—C11—C12	178.49 (11)
C1—N1—C5—C4	0.47 (19)	C6—C11—C12—O1	165.21 (12)
C3—C4—C5—N1	−0.37 (19)	C10—C11—C12—O1	−13.25 (18)
C3—C4—C5—N2	178.46 (13)	C6—C11—C12—O2	−14.87 (17)
C11—C6—C7—C8	−0.9 (2)	C10—C11—C12—O2	166.67 (11)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···N1i	0.98 (2)	1.65 (2)	2.629 (1)	175 (2)
N2—H1N2···O1ii	0.88 (2)	2.04 (2)	2.898 (2)	165.4 (18)
N2—H2N2···O2iii	0.88 (2)	2.37 (2)	3.231 (2)	165.8 (17)
C3—H3···Cl1iv	0.99 (2)	2.82 (2)	3.780 (2)	163.4 (16)
C6—H6···O1v	0.91 (2)	2.58 (2)	3.095 (2)	116.3 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯N1i	0.98 (2)	1.65 (2)	2.629 (1)	175 (2)
N2—H1N2⋯O1ii	0.88 (2)	2.04 (2)	2.898 (2)	165.4 (18)
N2—H2N2⋯O2iii	0.88 (2)	2.37 (2)	3.231 (2)	165.8 (17)
C3—H3⋯Cl1iv	0.99 (2)	2.82 (2)	3.780 (2)	163.4 (16)
C6—H6⋯O1v	0.91 (2)	2.58 (2)	3.095 (2)	116.3 (15)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .