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

The asymmetric unit of the title cocrystal, C(12)H(10)N(4)·2C(7)H(6)O(2), comprises a single mol-ecule of benzoic acid and one half-mol-ecule of 2-pyridine-aldazine situated about a centre of inversion. The carboxyl group is coplanar with the benzene ring to which it is connected [O-C-C-C = -172.47 (12)°] and similarly, the 2-pyridine-aldazine mol-ecule is planar (r.m.s. deviation of the 16 non-H atoms = 0.017 Å). In the crystal, mol-ecules are connected into a non-planar three-mol-ecule aggregate [dihedral angle between the benzene and pyridyl ring connected by the hydrogen bond = 61.30 (7)°] with a twisted Z-shape. Layers of 2-pyridine-aldazine mol-ecules in the ab plane are sandwiched by benzoic acid mol-ecules being connected by O-H⋯N and C-H⋯O inter-actions, the latter involving the carbonyl O atom so that each benzoic acid mol-ecule links three different 2-pyridine-aldazine mol-ecules. Inter-digitated layers stack along the c axis.

Related literature

For related studies on co-crystal formation involving the isomeric n-pyridine­aldazines, see: Broker et al. (2008 ▶); Arman et al. (2010a ▶,b ▶).

Experimental

Crystal data

C12H10N4·2C7H6O2

M = 454.48

Triclinic,

a = 4.4509 (7) Å

b = 11.3635 (17) Å

c = 12.0612 (17) Å

α = 108.985 (6)°

β = 99.830 (9)°

γ = 97.849 (10)°

V = 556.16 (14) Å3

Z = 1

Mo Kα radiation

μ = 0.09 mm−1

T = 98 K

0.40 × 0.29 × 0.12 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.759, T max = 1.000

2790 measured reflections

1935 independent reflections

1811 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.117

S = 1.00

1935 reflections

158 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.23 e Å−3

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/S1600536810040651/hg2725sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040651/hg2725Isup2.hkl

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

C12H10N4·2C7H6O2	Z = 1
Mr = 454.48	F(000) = 238
Triclinic, P1	Dx = 1.357 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.4509 (7) Å	Cell parameters from 2619 reflections
b = 11.3635 (17) Å	θ = 2.1–40.2°
c = 12.0612 (17) Å	µ = 0.09 mm−1
α = 108.985 (6)°	T = 98 K
β = 99.830 (9)°	Block, yellow
γ = 97.849 (10)°	0.40 × 0.29 × 0.12 mm
V = 556.16 (14) Å3

Rigaku AFC12K/SATURN724 diffractometer	1935 independent reflections
Radiation source: fine-focus sealed tube	1811 reflections with I > 2σ(I)
graphite	Rint = 0.022
ω scans	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −5→4
Tmin = 0.759, Tmax = 1.000	k = −13→13
2790 measured reflections	l = −14→14

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0744P)2 + 0.1759P] where P = (Fo2 + 2Fc2)/3
1935 reflections	(Δ/σ)max < 0.001
158 parameters	Δρmax = 0.20 e Å−3
1 restraint	Δρmin = −0.23 e Å−3

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
O1	0.6343 (3)	0.67141 (10)	0.18059 (9)	0.0287 (3)
H1o	0.584 (5)	0.692 (2)	0.2479 (12)	0.050 (6)*
O2	0.7598 (3)	0.88248 (10)	0.23009 (9)	0.0315 (3)
C1	0.7523 (3)	0.77587 (13)	0.16270 (12)	0.0235 (3)
C2	0.8828 (3)	0.74881 (14)	0.05272 (12)	0.0227 (3)
C3	1.0455 (3)	0.85068 (14)	0.03269 (13)	0.0278 (4)
H3	1.0702	0.9349	0.0878	0.033*
C4	1.1716 (4)	0.82926 (15)	−0.06766 (14)	0.0311 (4)
H4	1.2846	0.8987	−0.0809	0.037*
C5	1.1331 (4)	0.70640 (15)	−0.14890 (13)	0.0289 (4)
H5	1.2192	0.6919	−0.2178	0.035*
C6	0.9695 (4)	0.60477 (15)	−0.12974 (13)	0.0294 (4)
H6	0.9428	0.5208	−0.1856	0.035*
C7	0.8444 (3)	0.62603 (14)	−0.02863 (13)	0.0263 (3)
H7	0.7326	0.5564	−0.0152	0.032*
N1	0.4834 (3)	0.73022 (11)	0.39929 (10)	0.0214 (3)
N2	0.9261 (3)	0.54922 (10)	0.52702 (10)	0.0211 (3)
C8	0.6169 (3)	0.69350 (12)	0.48783 (12)	0.0190 (3)
C9	0.6033 (3)	0.75148 (13)	0.60760 (12)	0.0219 (3)
H9	0.7002	0.7236	0.6683	0.026*
C10	0.4469 (3)	0.85009 (13)	0.63643 (12)	0.0233 (3)
H10	0.4365	0.8918	0.7175	0.028*
C11	0.3052 (3)	0.88738 (13)	0.54546 (13)	0.0231 (3)
H11	0.1932	0.9541	0.5627	0.028*
C12	0.3304 (3)	0.82529 (13)	0.42883 (13)	0.0230 (3)
H12	0.2344	0.8515	0.3668	0.028*
C13	0.7833 (3)	0.58938 (13)	0.45006 (12)	0.0209 (3)
H13	0.7846	0.5516	0.3674	0.025*

	U11	U22	U33	U12	U13	U23
O1	0.0405 (6)	0.0251 (6)	0.0230 (5)	0.0084 (5)	0.0124 (5)	0.0085 (4)
O2	0.0457 (7)	0.0254 (6)	0.0247 (6)	0.0126 (5)	0.0110 (5)	0.0070 (5)
C1	0.0261 (7)	0.0244 (7)	0.0208 (7)	0.0084 (6)	0.0028 (5)	0.0093 (6)
C2	0.0231 (7)	0.0261 (7)	0.0200 (7)	0.0083 (6)	0.0018 (5)	0.0098 (6)
C3	0.0333 (8)	0.0248 (8)	0.0231 (7)	0.0064 (6)	0.0035 (6)	0.0070 (6)
C4	0.0336 (8)	0.0315 (8)	0.0299 (8)	0.0025 (7)	0.0065 (6)	0.0151 (7)
C5	0.0302 (8)	0.0372 (8)	0.0238 (7)	0.0118 (6)	0.0087 (6)	0.0135 (6)
C6	0.0349 (8)	0.0277 (8)	0.0262 (8)	0.0103 (6)	0.0091 (6)	0.0075 (6)
C7	0.0314 (8)	0.0236 (7)	0.0259 (7)	0.0084 (6)	0.0081 (6)	0.0098 (6)
N1	0.0212 (6)	0.0202 (6)	0.0235 (6)	0.0037 (5)	0.0055 (5)	0.0088 (5)
N2	0.0200 (6)	0.0203 (6)	0.0242 (6)	0.0063 (5)	0.0077 (5)	0.0073 (5)
C8	0.0165 (6)	0.0182 (6)	0.0232 (7)	0.0018 (5)	0.0060 (5)	0.0087 (5)
C9	0.0205 (7)	0.0234 (7)	0.0231 (7)	0.0037 (5)	0.0059 (5)	0.0100 (6)
C10	0.0251 (7)	0.0223 (7)	0.0230 (7)	0.0036 (6)	0.0100 (6)	0.0069 (6)
C11	0.0214 (7)	0.0183 (7)	0.0312 (8)	0.0052 (5)	0.0092 (6)	0.0091 (6)
C12	0.0220 (7)	0.0217 (7)	0.0272 (7)	0.0050 (5)	0.0040 (5)	0.0117 (6)
C13	0.0194 (6)	0.0204 (7)	0.0237 (7)	0.0036 (5)	0.0076 (5)	0.0078 (6)

O1—C1	1.3292 (18)	N1—C12	1.3381 (18)
O1—H1o	0.846 (9)	N1—C8	1.3449 (18)
O2—C1	1.2117 (17)	N2—C13	1.2757 (18)
C1—C2	1.496 (2)	N2—N2i	1.408 (2)
C2—C7	1.388 (2)	C8—C9	1.3949 (19)
C2—C3	1.391 (2)	C8—C13	1.4698 (18)
C3—C4	1.384 (2)	C9—C10	1.380 (2)
C3—H3	0.9500	C9—H9	0.9500
C4—C5	1.388 (2)	C10—C11	1.386 (2)
C4—H4	0.9500	C10—H10	0.9500
C5—C6	1.385 (2)	C11—C12	1.385 (2)
C5—H5	0.9500	C11—H11	0.9500
C6—C7	1.390 (2)	C12—H12	0.9500
C6—H6	0.9500	C13—H13	0.9500
C7—H7	0.9500
C1—O1—H1o	109.1 (15)	C6—C7—H7	120.0
O2—C1—O1	123.44 (13)	C12—N1—C8	117.83 (12)
O2—C1—C2	123.29 (14)	C13—N2—N2i	111.87 (13)
O1—C1—C2	113.26 (12)	N1—C8—C9	122.45 (12)
C7—C2—C3	119.91 (13)	N1—C8—C13	115.34 (12)
C7—C2—C1	121.78 (14)	C9—C8—C13	122.20 (12)
C3—C2—C1	118.31 (13)	C10—C9—C8	118.85 (13)
C4—C3—C2	119.96 (14)	C10—C9—H9	120.6
C4—C3—H3	120.0	C8—C9—H9	120.6
C2—C3—H3	120.0	C9—C10—C11	119.04 (12)
C3—C4—C5	120.05 (14)	C9—C10—H10	120.5
C3—C4—H4	120.0	C11—C10—H10	120.5
C5—C4—H4	120.0	C10—C11—C12	118.57 (12)
C6—C5—C4	120.19 (14)	C10—C11—H11	120.7
C6—C5—H5	119.9	C12—C11—H11	120.7
C4—C5—H5	119.9	N1—C12—C11	123.25 (13)
C5—C6—C7	119.84 (14)	N1—C12—H12	118.4
C5—C6—H6	120.1	C11—C12—H12	118.4
C7—C6—H6	120.1	N2—C13—C8	120.75 (12)
C2—C7—C6	120.06 (14)	N2—C13—H13	119.6
C2—C7—H7	120.0	C8—C13—H13	119.6
O2—C1—C2—C7	−173.81 (14)	C12—N1—C8—C9	−0.65 (19)
O1—C1—C2—C7	7.72 (19)	C12—N1—C8—C13	−179.57 (11)
O2—C1—C2—C3	6.0 (2)	N1—C8—C9—C10	0.1 (2)
O1—C1—C2—C3	−172.47 (12)	C13—C8—C9—C10	178.93 (12)
C7—C2—C3—C4	−0.7 (2)	C8—C9—C10—C11	0.8 (2)
C1—C2—C3—C4	179.52 (13)	C9—C10—C11—C12	−1.0 (2)
C2—C3—C4—C5	0.6 (2)	C8—N1—C12—C11	0.4 (2)
C3—C4—C5—C6	−0.2 (2)	C10—C11—C12—N1	0.5 (2)
C4—C5—C6—C7	−0.2 (2)	N2i—N2—C13—C8	−179.13 (12)
C3—C2—C7—C6	0.3 (2)	N1—C8—C13—N2	178.03 (12)
C1—C2—C7—C6	−179.93 (13)	C9—C8—C13—N2	−0.9 (2)
C5—C6—C7—C2	0.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1	0.85 (2)	1.88 (2)	2.7269 (16)	177 (2)
C11—H11···O2ii	0.95	2.54	3.1811 (19)	125
C12—H12···O2iii	0.95	2.59	3.4647 (19)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N1	0.85 (2)	1.88 (2)	2.7269 (16)	177 (2)
C11—H11⋯O2i	0.95	2.54	3.1811 (19)	125
C12—H12⋯O2ii	0.95	2.59	3.4647 (19)	154

Symmetry codes: (i) ; (ii) .