2-(4-Chloro-phen-yl)acetic acid-2-{(E)-[(E)-2-(2-pyridyl-methyl-idene)hydrazin-1-yl-idene]meth-yl}pyridine (1/1).

In the crystal of the title 1:1 adduct, C(8)H(7)ClO(2)·C(12)H(10)N(4), the components are linked by an O-H⋯N hydrogen bond between the carb-oxy-lic acid and one of the pyridine N atoms. In the acid, the carb-oxy-lic acid group is approximately normal to [dihedral angle = 72.9 (2)°] but twisted with respect to the plane through the benzene ring [C-C-C-O torsion angle = 25.4 (5)°]. The base is roughly planar [dihedral angle between rings = 12.66 (15)°; r.m.s. deviation of the 16 non-H atoms = 0.107 Å] and the conformations about both imine bonds are E. The dimeric aggregates are linked into a supra-molecular layer in the ab plane by C-H⋯O inter-actions.

Related literature

For related studies on co-crystal formation, see: Broker & Tiekink (2007 ▶); Broker et al. (2008 ▶); Arman et al. (2010 ▶).

Experimental

Crystal data

C8H7ClO2·C12H10N4

M = 380.83

Orthorhombic,

a = 11.740 (6) Å

b = 4.641 (2) Å

c = 33.451 (15) Å

V = 1822.6 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 98 K

0.22 × 0.19 × 0.09 mm

Data collection

Rigaku Saturn724 diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.625, T max = 1.000

7554 measured reflections

4091 independent reflections

3661 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.113

S = 1.14

4091 reflections

247 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.24 e Å−3

Absolute structure: Flack (1983 ▶), 1973 Friedel pairs

Flack parameter: 0.09 (8)

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810032721/hb5608sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032721/hb5608Isup2.hkl

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

C8H7ClO2·C12H10N4	F(000) = 792
Mr = 380.83	Dx = 1.388 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 4996 reflections
a = 11.740 (6) Å	θ = 2.1–40.3°
b = 4.641 (2) Å	µ = 0.23 mm−1
c = 33.451 (15) Å	T = 98 K
V = 1822.6 (15) Å3	Prism, yellow
Z = 4	0.22 × 0.19 × 0.09 mm

Rigaku Saturn724 diffractometer	4091 independent reflections
Radiation source: sealed tube	3661 reflections with I > 2σ(I)
graphite	Rint = 0.046
Detector resolution: 28.5714 pixels mm-1	θmax = 27.5°, θmin = 2.4°
ω scans	h = −4→15
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −4→6
Tmin = 0.625, Tmax = 1.000	l = −43→42
7554 measured reflections

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)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.113	w = 1/[σ2(Fo2) + (0.0265P)2 + 0.6335P] where P = (Fo2 + 2Fc2)/3
S = 1.14	(Δ/σ)max = 0.001
4091 reflections	Δρmax = 0.28 e Å−3
247 parameters	Δρmin = −0.24 e Å−3
2 restraints	Absolute structure: Flack (1983), 1973 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.09 (8)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.54028 (7)	1.20255 (16)	0.67877 (3)	0.03461 (19)
O1	0.2462 (2)	0.4385 (5)	0.86536 (7)	0.0339 (6)
H1o	0.201 (3)	0.542 (7)	0.8788 (10)	0.051*
O2	0.2010 (2)	0.7655 (5)	0.81878 (7)	0.0349 (6)
N1	0.0916 (2)	0.7320 (5)	0.91096 (8)	0.0273 (6)
N2	0.0996 (2)	0.3341 (5)	1.00194 (8)	0.0256 (6)
N3	0.1807 (2)	0.1275 (5)	1.01538 (8)	0.0249 (6)
N4	0.1708 (2)	−0.3295 (6)	1.10056 (8)	0.0278 (6)
C1	0.3916 (3)	0.5966 (7)	0.77127 (10)	0.0273 (7)
C2	0.4965 (3)	0.7262 (7)	0.77713 (10)	0.0311 (7)
H2	0.5380	0.6864	0.8009	0.037*
C3	0.5427 (3)	0.9140 (7)	0.74890 (10)	0.0308 (7)
H3	0.6146	1.0022	0.7533	0.037*
C4	0.4823 (3)	0.9690 (6)	0.71456 (10)	0.0261 (7)
C5	0.3768 (3)	0.8454 (7)	0.70749 (10)	0.0291 (7)
H5	0.3354	0.8872	0.6838	0.035*
C6	0.3332 (3)	0.6583 (7)	0.73615 (10)	0.0297 (7)
H6	0.2613	0.5701	0.7316	0.036*
C7	0.3417 (3)	0.4012 (7)	0.80335 (10)	0.0319 (8)
H7A	0.3044	0.2341	0.7904	0.038*
H7B	0.4040	0.3272	0.8204	0.038*
C8	0.2559 (3)	0.5567 (7)	0.82911 (10)	0.0276 (7)
C9	0.0329 (3)	0.9348 (7)	0.89091 (10)	0.0284 (7)
H9	0.0593	0.9934	0.8653	0.034*
C10	−0.0646 (3)	1.0608 (7)	0.90619 (10)	0.0302 (7)
H10	−0.1038	1.2045	0.8914	0.036*
C11	−0.1048 (3)	0.9744 (7)	0.94373 (10)	0.0263 (7)
H11	−0.1721	1.0564	0.9547	0.032*
C12	−0.0443 (3)	0.7666 (6)	0.96461 (10)	0.0255 (6)
H12	−0.0696	0.7024	0.9901	0.031*
C13	0.0548 (3)	0.6533 (6)	0.94746 (10)	0.0245 (6)
C14	0.1254 (3)	0.4354 (6)	0.96765 (9)	0.0252 (7)
H14	0.1924	0.3680	0.9547	0.030*
C15	0.1501 (3)	0.0090 (6)	1.04822 (9)	0.0250 (7)
H15	0.0799	0.0642	1.0601	0.030*
C16	0.2202 (3)	−0.2089 (6)	1.06803 (9)	0.0220 (6)
C17	0.3292 (3)	−0.2836 (6)	1.05470 (10)	0.0265 (7)
H17	0.3609	−0.1966	1.0315	0.032*
C18	0.3902 (3)	−0.4885 (7)	1.07626 (10)	0.0287 (7)
H18	0.4648	−0.5416	1.0682	0.034*
C19	0.3413 (3)	−0.6131 (7)	1.10929 (10)	0.0306 (7)
H19	0.3815	−0.7537	1.1244	0.037*
C20	0.2316 (3)	−0.5292 (7)	1.12030 (10)	0.0299 (7)
H20	0.1980	−0.6182	1.1430	0.036*

	U11	U22	U33	U12	U13	U23
Cl1	0.0384 (4)	0.0313 (4)	0.0342 (4)	−0.0011 (3)	0.0090 (4)	0.0029 (4)
O1	0.0357 (14)	0.0361 (13)	0.0299 (14)	0.0045 (10)	0.0061 (10)	0.0038 (10)
O2	0.0357 (14)	0.0371 (13)	0.0320 (14)	0.0084 (11)	0.0047 (11)	0.0067 (11)
N1	0.0269 (14)	0.0267 (13)	0.0281 (14)	−0.0008 (11)	−0.0003 (11)	−0.0001 (12)
N2	0.0238 (13)	0.0274 (13)	0.0255 (14)	0.0036 (10)	−0.0027 (11)	0.0004 (11)
N3	0.0215 (13)	0.0276 (13)	0.0256 (14)	0.0015 (11)	−0.0025 (10)	−0.0002 (11)
N4	0.0273 (14)	0.0276 (14)	0.0285 (15)	−0.0005 (12)	−0.0004 (12)	0.0022 (11)
C1	0.0304 (17)	0.0263 (16)	0.0254 (16)	0.0081 (13)	0.0056 (13)	0.0002 (13)
C2	0.0298 (17)	0.0371 (18)	0.0263 (17)	0.0060 (14)	−0.0028 (13)	0.0000 (14)
C3	0.0238 (16)	0.0304 (16)	0.038 (2)	−0.0023 (13)	0.0010 (14)	−0.0014 (15)
C4	0.0313 (16)	0.0210 (14)	0.0259 (16)	0.0018 (13)	0.0058 (14)	−0.0032 (12)
C5	0.0296 (17)	0.0312 (16)	0.0266 (17)	0.0036 (13)	−0.0031 (13)	−0.0024 (14)
C6	0.0268 (16)	0.0287 (16)	0.0337 (19)	−0.0007 (13)	0.0005 (14)	−0.0039 (14)
C7	0.0338 (18)	0.0256 (16)	0.036 (2)	0.0058 (14)	0.0059 (15)	0.0021 (14)
C8	0.0264 (16)	0.0275 (16)	0.0288 (17)	−0.0079 (13)	−0.0023 (14)	0.0020 (14)
C9	0.0296 (17)	0.0298 (17)	0.0256 (17)	0.0004 (13)	−0.0025 (13)	0.0038 (14)
C10	0.0327 (17)	0.0265 (15)	0.0313 (19)	0.0019 (14)	−0.0106 (15)	0.0006 (14)
C11	0.0220 (16)	0.0257 (15)	0.0314 (17)	0.0007 (12)	−0.0035 (13)	0.0005 (14)
C12	0.0244 (15)	0.0250 (15)	0.0270 (16)	−0.0056 (12)	0.0015 (13)	0.0003 (13)
C13	0.0235 (15)	0.0226 (14)	0.0273 (17)	−0.0033 (12)	−0.0025 (13)	−0.0032 (12)
C14	0.0212 (15)	0.0249 (16)	0.0294 (17)	−0.0006 (12)	−0.0001 (13)	−0.0020 (13)
C15	0.0244 (16)	0.0244 (15)	0.0263 (16)	0.0006 (12)	−0.0038 (13)	−0.0026 (12)
C16	0.0243 (15)	0.0193 (13)	0.0223 (15)	−0.0027 (12)	−0.0019 (12)	−0.0013 (12)
C17	0.0253 (17)	0.0273 (16)	0.0269 (17)	−0.0021 (13)	0.0002 (13)	0.0018 (14)
C18	0.0193 (15)	0.0299 (16)	0.037 (2)	−0.0005 (13)	−0.0029 (13)	−0.0037 (14)
C19	0.0378 (18)	0.0256 (16)	0.0283 (18)	0.0004 (14)	−0.0123 (14)	0.0019 (14)
C20	0.0383 (19)	0.0292 (16)	0.0222 (16)	−0.0014 (14)	−0.0031 (14)	0.0020 (13)

Cl1—C4	1.753 (3)	C7—H7A	0.9900
O1—C8	1.336 (4)	C7—H7B	0.9900
O1—H1o	0.85 (3)	C9—C10	1.383 (5)
O2—C8	1.214 (4)	C9—H9	0.9500
N1—C13	1.346 (4)	C10—C11	1.400 (5)
N1—C9	1.346 (4)	C10—H10	0.9500
N2—C14	1.276 (4)	C11—C12	1.387 (4)
N2—N3	1.424 (3)	C11—H11	0.9500
N3—C15	1.280 (4)	C12—C13	1.399 (4)
N4—C20	1.343 (4)	C12—H12	0.9500
N4—C16	1.354 (4)	C13—C14	1.472 (4)
C1—C2	1.385 (5)	C14—H14	0.9500
C1—C6	1.391 (5)	C15—C16	1.463 (4)
C1—C7	1.522 (4)	C15—H15	0.9500
C2—C3	1.394 (5)	C16—C17	1.399 (4)
C2—H2	0.9500	C17—C18	1.391 (4)
C3—C4	1.373 (5)	C17—H17	0.9500
C3—H3	0.9500	C18—C19	1.373 (5)
C4—C5	1.386 (4)	C18—H18	0.9500
C5—C6	1.391 (5)	C19—C20	1.396 (5)
C5—H5	0.9500	C19—H19	0.9500
C6—H6	0.9500	C20—H20	0.9500
C7—C8	1.509 (4)
C8—O1—H1o	108 (3)	C10—C9—H9	118.8
C13—N1—C9	118.5 (3)	C9—C10—C11	119.3 (3)
C14—N2—N3	111.9 (3)	C9—C10—H10	120.4
C15—N3—N2	111.9 (3)	C11—C10—H10	120.4
C20—N4—C16	116.9 (3)	C12—C11—C10	118.6 (3)
C2—C1—C6	118.0 (3)	C12—C11—H11	120.7
C2—C1—C7	120.1 (3)	C10—C11—H11	120.7
C6—C1—C7	121.9 (3)	C11—C12—C13	118.7 (3)
C1—C2—C3	121.4 (3)	C11—C12—H12	120.6
C1—C2—H2	119.3	C13—C12—H12	120.6
C3—C2—H2	119.3	N1—C13—C12	122.5 (3)
C4—C3—C2	118.8 (3)	N1—C13—C14	115.0 (3)
C4—C3—H3	120.6	C12—C13—C14	122.5 (3)
C2—C3—H3	120.6	N2—C14—C13	122.1 (3)
C3—C4—C5	121.8 (3)	N2—C14—H14	118.9
C3—C4—Cl1	119.1 (2)	C13—C14—H14	118.9
C5—C4—Cl1	119.1 (3)	N3—C15—C16	121.9 (3)
C4—C5—C6	118.0 (3)	N3—C15—H15	119.1
C4—C5—H5	121.0	C16—C15—H15	119.1
C6—C5—H5	121.0	N4—C16—C17	123.1 (3)
C1—C6—C5	122.0 (3)	N4—C16—C15	114.1 (3)
C1—C6—H6	119.0	C17—C16—C15	122.8 (3)
C5—C6—H6	119.0	C18—C17—C16	118.3 (3)
C8—C7—C1	112.0 (3)	C18—C17—H17	120.8
C8—C7—H7A	109.2	C16—C17—H17	120.8
C1—C7—H7A	109.2	C19—C18—C17	119.4 (3)
C8—C7—H7B	109.2	C19—C18—H18	120.3
C1—C7—H7B	109.2	C17—C18—H18	120.3
H7A—C7—H7B	107.9	C18—C19—C20	118.7 (3)
O2—C8—O1	122.7 (3)	C18—C19—H19	120.6
O2—C8—C7	125.0 (3)	C20—C19—H19	120.6
O1—C8—C7	112.3 (3)	N4—C20—C19	123.6 (3)
N1—C9—C10	122.4 (3)	N4—C20—H20	118.2
N1—C9—H9	118.8	C19—C20—H20	118.2
C14—N2—N3—C15	−174.8 (3)	C9—N1—C13—C12	2.4 (5)
C6—C1—C2—C3	0.2 (5)	C9—N1—C13—C14	−178.6 (3)
C7—C1—C2—C3	−177.8 (3)	C11—C12—C13—N1	−2.1 (5)
C1—C2—C3—C4	−0.3 (5)	C11—C12—C13—C14	179.0 (3)
C2—C3—C4—C5	0.6 (5)	N3—N2—C14—C13	−179.8 (2)
C2—C3—C4—Cl1	−179.5 (2)	N1—C13—C14—N2	−178.1 (3)
C3—C4—C5—C6	−0.9 (5)	C12—C13—C14—N2	0.9 (5)
Cl1—C4—C5—C6	179.3 (2)	N2—N3—C15—C16	−179.6 (3)
C2—C1—C6—C5	−0.4 (5)	C20—N4—C16—C17	0.0 (4)
C7—C1—C6—C5	177.5 (3)	C20—N4—C16—C15	−179.3 (3)
C4—C5—C6—C1	0.7 (5)	N3—C15—C16—N4	−174.6 (3)
C2—C1—C7—C8	98.4 (4)	N3—C15—C16—C17	6.0 (5)
C6—C1—C7—C8	−79.5 (4)	N4—C16—C17—C18	−0.9 (5)
C1—C7—C8—O2	25.4 (5)	C15—C16—C17—C18	178.4 (3)
C1—C7—C8—O1	−154.6 (3)	C16—C17—C18—C19	0.9 (5)
C13—N1—C9—C10	−1.1 (5)	C17—C18—C19—C20	−0.1 (5)
N1—C9—C10—C11	−0.5 (5)	C16—N4—C20—C19	0.8 (5)
C9—C10—C11—C12	0.8 (5)	C18—C19—C20—N4	−0.8 (5)
C10—C11—C12—C13	0.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1	0.85 (3)	1.89 (3)	2.734 (4)	173 (3)
C9—H9···O2	0.95	2.51	3.215 (4)	131
C10—H10···O1i	0.95	2.57	3.493 (4)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N1	0.85 (3)	1.89 (3)	2.734 (4)	173 (3)
C9—H9⋯O2	0.95	2.51	3.215 (4)	131
C10—H10⋯O1i	0.95	2.57	3.493 (4)	164

Symmetry code: (i) .