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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2813.
Published online 2010 October 20. doi:  10.1107/S1600536810040651
PMCID: PMC3009141

Benzoic acid–2-{(E)-[(E)-2-(2-pyridyl­methyl­idene)hydrazin-1-yl­idene]meth­yl}pyridine (2/1)

Abstract

The asymmetric unit of the title cocrystal, C12H10N4·2C7H6O2, comprises a single mol­ecule of benzoic acid and one half-mol­ecule of 2-pyridine­aldazine 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-pyridine­aldazine mol­ecule is planar (r.m.s. deviation of the 16 non-H atoms = 0.017 Å). In the crystal, mol­ecules are connected into a non-planar three-mol­ecule 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-pyridine­aldazine mol­ecules in the ab plane are sandwiched by benzoic acid mol­ecules being connected by O—H(...)N and C—H(...)O inter­actions, the latter involving the carbonyl O atom so that each benzoic acid mol­ecule links three different 2-pyridine­aldazine mol­ecules. Inter­digitated 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 [triangle]); Arman et al. (2010a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2813-scheme1.jpg

Experimental

Crystal data

  • C12H10N4·2C7H6O2
  • M r = 454.48
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2813-efi1.jpg
  • 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 [triangle]) 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 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

supplementary crystallographic information

Comment

Co-crystallization experiments with the isomeric n-pyridinealdazines have led to the characterization of several co-crystals (Broker et al., 2008; Arman et al., 2010a; Arman et al., 2010b), and in continuation of these studies, the co-crystallization of benzoic acid and 2-pyridinealdazine was investigated. This lead to the isolation of the title 2/1 co-crystal, (I).

The asymmetric unit in (I) comprises a molecule of benzoic acid, Fig. 1, and half a molecule of 2-pyridinealdazine, with the latter disposed about a centre of inversion, Fig. 2. The constituents of (I) are connected by O—H···N hydrogen bonds, Table 1, to generate a centrosymmetric three molecule aggregate, Fig. 3. The benzoic acid molecule is planar as seen in the value of the O1—C1—C2—C3 torsion angle of -172.47 (12) °. Similarly, the 2-pyridinealdazine molecule is planar with the r.m.s. deviation of the 16 non-hydrogen atoms being 0.017 Å. However, the three molecule aggregate is not planar as the benzene ring forms a dihedral angle of 61.30 (7) ° with the pyridyl ring to which it is hydrogen bonded. Overall, when viewed normal to the plane through 2-pyridinealdazine, the aggregate has the shape of a twisted letter Z.

In the crystal packing, the 2-pyridinealdazine molecules pack in the ab plane with the benzoic acid molecules sandwiching these, Fig. 4. The connections are mediated by the aforementioned O—H···N hydrogen bond as well as C—H···O interactions formed by the carbonyl-O atom; each benzoic acid molecule links three distinct 2-pyridinealdazine molecules. Inter-digitated layers stack along the c axis.

Experimental

Yellow crystals of (I) were isolated from the 2/1 co-crystallization of benzoic acid (Sigma Aldrich, 0.24 mmol) and 2-[(E)-[(E)-2-(pyridin-2-ylmethylidene)hydrazin-1-ylidene]methyl]pyridine (Sigma Aldrich, 0.12 mmol) in ethanol, m. pt. 351–353 K.

IR assignment (cm-1): 2600 (br) ν(O—H); 1691 ν(C=O); 1627 ν(C═N); 1469, 1451, 1416 ν(C–C(aromatic)); 1627 ν(C—N); 777 δ(C—H).

Refinement

C-bound H-atoms were placed in calculated positions (C–H 0.95–0.99 Å) and were included in the refinement in the riding model approximation with Uiso(H) set to 1.2Ueq(C). The O-bound H-atom was located in a difference Fourier map and was refined with a distance restraint of O–H 0.84±0.01 Å, and with Uiso(H) = 1.5Ueq(O). In the final refinement a low angle reflection evidently effected by the beam stop was omitted, i.e. (0 1 1).

Figures

Fig. 1.
Molecular structure of benzoic acid found in the structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level
Fig. 2.
Molecular structure of 2-pyridinealdazine found in the structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level. The molecule is disposed about a centre of inversion and i = 2 - x, 1 - y, 1 - z.
Fig. 3.
The three molecule aggregate in (I) highlighting the extended chair conformation. The O—H···N hydrogen bonds are shown as orange dashed lines.
Fig. 4.
A view of the supramolecular layer in (I) whereby 2-pyridinealdazine molecules are sandwiched by benzoic acid molecules. The O—H···N hydrogen bonds and C—H···O contacts are shown as orange ...
Fig. 5.
A view in projection down the a axis showing the stacking of layers comprising three molecule aggregates along c. The O—H···N hydrogen bonds and C—H···O contacts are shown as orange and blue ...

Crystal data

C12H10N4·2C7H6O2Z = 1
Mr = 454.48F(000) = 238
Triclinic, P1Dx = 1.357 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.4509 (7) ÅCell parameters from 2619 reflections
b = 11.3635 (17) Åθ = 2.1–40.2°
c = 12.0612 (17) ŵ = 0.09 mm1
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

Data collection

Rigaku AFC12K/SATURN724 diffractometer1935 independent reflections
Radiation source: fine-focus sealed tube1811 reflections with I > 2σ(I)
graphiteRint = 0.022
ω scansθmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −5→4
Tmin = 0.759, Tmax = 1.000k = −13→13
2790 measured reflectionsl = −14→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H atoms treated by a mixture of independent and constrained refinement
S = 1.00w = 1/[σ2(Fo2) + (0.0744P)2 + 0.1759P] where P = (Fo2 + 2Fc2)/3
1935 reflections(Δ/σ)max < 0.001
158 parametersΔρmax = 0.20 e Å3
1 restraintΔρmin = −0.23 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.6343 (3)0.67141 (10)0.18059 (9)0.0287 (3)
H1o0.584 (5)0.692 (2)0.2479 (12)0.050 (6)*
O20.7598 (3)0.88248 (10)0.23009 (9)0.0315 (3)
C10.7523 (3)0.77587 (13)0.16270 (12)0.0235 (3)
C20.8828 (3)0.74881 (14)0.05272 (12)0.0227 (3)
C31.0455 (3)0.85068 (14)0.03269 (13)0.0278 (4)
H31.07020.93490.08780.033*
C41.1716 (4)0.82926 (15)−0.06766 (14)0.0311 (4)
H41.28460.8987−0.08090.037*
C51.1331 (4)0.70640 (15)−0.14890 (13)0.0289 (4)
H51.21920.6919−0.21780.035*
C60.9695 (4)0.60477 (15)−0.12974 (13)0.0294 (4)
H60.94280.5208−0.18560.035*
C70.8444 (3)0.62603 (14)−0.02863 (13)0.0263 (3)
H70.73260.5564−0.01520.032*
N10.4834 (3)0.73022 (11)0.39929 (10)0.0214 (3)
N20.9261 (3)0.54922 (10)0.52702 (10)0.0211 (3)
C80.6169 (3)0.69350 (12)0.48783 (12)0.0190 (3)
C90.6033 (3)0.75148 (13)0.60760 (12)0.0219 (3)
H90.70020.72360.66830.026*
C100.4469 (3)0.85009 (13)0.63643 (12)0.0233 (3)
H100.43650.89180.71750.028*
C110.3052 (3)0.88738 (13)0.54546 (13)0.0231 (3)
H110.19320.95410.56270.028*
C120.3304 (3)0.82529 (13)0.42883 (13)0.0230 (3)
H120.23440.85150.36680.028*
C130.7833 (3)0.58938 (13)0.45006 (12)0.0209 (3)
H130.78460.55160.36740.025*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0405 (6)0.0251 (6)0.0230 (5)0.0084 (5)0.0124 (5)0.0085 (4)
O20.0457 (7)0.0254 (6)0.0247 (6)0.0126 (5)0.0110 (5)0.0070 (5)
C10.0261 (7)0.0244 (7)0.0208 (7)0.0084 (6)0.0028 (5)0.0093 (6)
C20.0231 (7)0.0261 (7)0.0200 (7)0.0083 (6)0.0018 (5)0.0098 (6)
C30.0333 (8)0.0248 (8)0.0231 (7)0.0064 (6)0.0035 (6)0.0070 (6)
C40.0336 (8)0.0315 (8)0.0299 (8)0.0025 (7)0.0065 (6)0.0151 (7)
C50.0302 (8)0.0372 (8)0.0238 (7)0.0118 (6)0.0087 (6)0.0135 (6)
C60.0349 (8)0.0277 (8)0.0262 (8)0.0103 (6)0.0091 (6)0.0075 (6)
C70.0314 (8)0.0236 (7)0.0259 (7)0.0084 (6)0.0081 (6)0.0098 (6)
N10.0212 (6)0.0202 (6)0.0235 (6)0.0037 (5)0.0055 (5)0.0088 (5)
N20.0200 (6)0.0203 (6)0.0242 (6)0.0063 (5)0.0077 (5)0.0073 (5)
C80.0165 (6)0.0182 (6)0.0232 (7)0.0018 (5)0.0060 (5)0.0087 (5)
C90.0205 (7)0.0234 (7)0.0231 (7)0.0037 (5)0.0059 (5)0.0100 (6)
C100.0251 (7)0.0223 (7)0.0230 (7)0.0036 (6)0.0100 (6)0.0069 (6)
C110.0214 (7)0.0183 (7)0.0312 (8)0.0052 (5)0.0092 (6)0.0091 (6)
C120.0220 (7)0.0217 (7)0.0272 (7)0.0050 (5)0.0040 (5)0.0117 (6)
C130.0194 (6)0.0204 (7)0.0237 (7)0.0036 (5)0.0076 (5)0.0078 (6)

Geometric parameters (Å, °)

O1—C11.3292 (18)N1—C121.3381 (18)
O1—H1o0.846 (9)N1—C81.3449 (18)
O2—C11.2117 (17)N2—C131.2757 (18)
C1—C21.496 (2)N2—N2i1.408 (2)
C2—C71.388 (2)C8—C91.3949 (19)
C2—C31.391 (2)C8—C131.4698 (18)
C3—C41.384 (2)C9—C101.380 (2)
C3—H30.9500C9—H90.9500
C4—C51.388 (2)C10—C111.386 (2)
C4—H40.9500C10—H100.9500
C5—C61.385 (2)C11—C121.385 (2)
C5—H50.9500C11—H110.9500
C6—C71.390 (2)C12—H120.9500
C6—H60.9500C13—H130.9500
C7—H70.9500
C1—O1—H1o109.1 (15)C6—C7—H7120.0
O2—C1—O1123.44 (13)C12—N1—C8117.83 (12)
O2—C1—C2123.29 (14)C13—N2—N2i111.87 (13)
O1—C1—C2113.26 (12)N1—C8—C9122.45 (12)
C7—C2—C3119.91 (13)N1—C8—C13115.34 (12)
C7—C2—C1121.78 (14)C9—C8—C13122.20 (12)
C3—C2—C1118.31 (13)C10—C9—C8118.85 (13)
C4—C3—C2119.96 (14)C10—C9—H9120.6
C4—C3—H3120.0C8—C9—H9120.6
C2—C3—H3120.0C9—C10—C11119.04 (12)
C3—C4—C5120.05 (14)C9—C10—H10120.5
C3—C4—H4120.0C11—C10—H10120.5
C5—C4—H4120.0C10—C11—C12118.57 (12)
C6—C5—C4120.19 (14)C10—C11—H11120.7
C6—C5—H5119.9C12—C11—H11120.7
C4—C5—H5119.9N1—C12—C11123.25 (13)
C5—C6—C7119.84 (14)N1—C12—H12118.4
C5—C6—H6120.1C11—C12—H12118.4
C7—C6—H6120.1N2—C13—C8120.75 (12)
C2—C7—C6120.06 (14)N2—C13—H13119.6
C2—C7—H7120.0C8—C13—H13119.6
O2—C1—C2—C7−173.81 (14)C12—N1—C8—C9−0.65 (19)
O1—C1—C2—C77.72 (19)C12—N1—C8—C13−179.57 (11)
O2—C1—C2—C36.0 (2)N1—C8—C9—C100.1 (2)
O1—C1—C2—C3−172.47 (12)C13—C8—C9—C10178.93 (12)
C7—C2—C3—C4−0.7 (2)C8—C9—C10—C110.8 (2)
C1—C2—C3—C4179.52 (13)C9—C10—C11—C12−1.0 (2)
C2—C3—C4—C50.6 (2)C8—N1—C12—C110.4 (2)
C3—C4—C5—C6−0.2 (2)C10—C11—C12—N10.5 (2)
C4—C5—C6—C7−0.2 (2)N2i—N2—C13—C8−179.13 (12)
C3—C2—C7—C60.3 (2)N1—C8—C13—N2178.03 (12)
C1—C2—C7—C6−179.93 (13)C9—C8—C13—N2−0.9 (2)
C5—C6—C7—C20.2 (2)

Symmetry codes: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1o···N10.85 (2)1.88 (2)2.7269 (16)177 (2)
C11—H11···O2ii0.952.543.1811 (19)125
C12—H12···O2iii0.952.593.4647 (19)154

Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2725).

References

  • Arman, H. D., Kaulgud, T. & Tiekink, E. R. T. (2010a). Acta Cryst. E66, o2356. [PMC free article] [PubMed]
  • Arman, H. D., Kaulgud, T. & Tiekink, E. R. T. (2010b). Acta Cryst. E66, o2629. [PMC free article] [PubMed]
  • Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Broker, G. A., Bettens, R. P. A. & Tiekink, E. R. T. (2008). CrystEngComm, 10, 879–887.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Molecular Structure Corporation & Rigaku (2005). CrystalClear MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

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