Co-crystallization of N′-benzyl­idene­pyridine-4-carbohydrazide and benzoic acid via autoxidation of benzaldehyde

The 1:1 co-crystal N′-[(2-methyl­phen­yl)methyl­idene]pyridine-4-carbohydrazide–benzoic acid (1/1) formed unexpectedly after autoxidation of benzaldehyde during the slow evaporation process of a solution of isoniazid in benzaldehyde. The original intent of the synthesis was to modify isoniazid with benzaldehyde and crystallize the product in order to improve efficacy against Mycobacteria species, but benzoic acid formed spontaneously and co-crystallized with the intended product, N′-benzyl­idene­pyridine-4-carbohydrazide.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.054
• wR factor = 0.112
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      6.421 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         10 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          8 Note

Alert level G
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          4 Note
PLAT933_ALERT_2_G Number of HKL-OMIT Records in Embedded .res File          4 Note
PLAT967_ALERT_5_G Note: Two-Theta Cutoff Value in Embedded .res ..       56.0 Degree
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         20 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT-Plus (Bruker, 2016); data reduction: SAINT-Plus and XPREP (Bruker 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

N'-[(2-methylphenyl)methylidene]pyridine-4-carbohydrazide; benzoic acid

Crystal data

C13H11N3O·C7H6O2	Dx = 1.312 Mg m^−3
Mr = 347.36	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9857 reflections
a = 11.7044 (17) Å	θ = 2.8–28.1°
b = 7.8531 (10) Å	µ = 0.09 mm^−1
c = 38.253 (5) Å	T = 173 K
V = 3516.1 (8) Å^3	Block, colourless
Z = 8	0.30 × 0.22 × 0.16 mm
F(000) = 1456

Data collection

Bruker D8 Venture Microfocus with Photon III CCD area-detector diffractometer	3902 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 28.0°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −15→15
Tmin = 0.709, Tmax = 0.746	k = −8→10
73794 measured reflections	l = −49→50
4239 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: mixed
wR(F^2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0274P)^2 + 2.3245P] where P = (Fo^2 + 2Fc^2)/3
4239 reflections	(Δ/σ)max = 0.001
243 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3
0 constraints

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

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. The crystal structure was solved through direct methods using SHELXT. Non-hydrogen atoms were first refined isotropically followed by anisotropic refinement by full matrix least-squares calculations based on F² using SHELXL.

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

	x	y	z	Uiso*/Ueq
C1	0.63979 (12)	0.05245 (18)	0.40684 (4)	0.0224 (3)
C2	0.71809 (13)	0.15589 (19)	0.42397 (4)	0.0252 (3)
H2A	0.79074	0.178612	0.413922	0.03*
C3	0.68809 (13)	0.2256 (2)	0.45612 (4)	0.0278 (3)
H3	0.742184	0.295037	0.467926	0.033*
C4	0.51195 (13)	0.0976 (2)	0.45471 (4)	0.0294 (3)
H4	0.439948	0.077268	0.465382	0.035*
C5	0.53502 (13)	0.0207 (2)	0.42278 (4)	0.0273 (3)
H5	0.48046	−0.052042	0.412045	0.033*
C6	0.66282 (12)	−0.03373 (18)	0.37245 (4)	0.0217 (3)
C7	0.83497 (12)	0.04298 (19)	0.29981 (4)	0.0241 (3)
H7	0.875011	0.138628	0.308817	0.029*
C8	0.85942 (12)	−0.01869 (18)	0.26424 (4)	0.0225 (3)
C9	0.78697 (13)	−0.13366 (19)	0.24744 (4)	0.0275 (3)
H9	0.72116	−0.175227	0.259209	0.033*
C10	0.81045 (14)	−0.1876 (2)	0.21367 (4)	0.0325 (3)
H10	0.761097	−0.266749	0.202491	0.039*
C11	0.90585 (15)	−0.1264 (2)	0.19618 (4)	0.0329 (4)
H11	0.921511	−0.16284	0.17299	0.039*
C12	0.97809 (14)	−0.0121 (2)	0.21258 (4)	0.0330 (4)
H12	1.043564	0.029452	0.200633	0.04*
C13	0.95532 (13)	0.0423 (2)	0.24649 (4)	0.0288 (3)
H13	1.005101	0.121063	0.257586	0.035*
N1	0.73940 (11)	0.04239 (16)	0.35104 (3)	0.0243 (3)
N2	0.58653 (11)	0.19911 (17)	0.47113 (3)	0.0284 (3)
N3	0.75993 (11)	−0.03198 (16)	0.31860 (3)	0.0235 (3)
O1	0.61404 (9)	−0.16790 (13)	0.36487 (3)	0.0264 (2)
H1	0.7778 (16)	0.136 (3)	0.3562 (5)	0.035 (5)*
C14	0.62773 (13)	0.54692 (19)	0.57434 (4)	0.0255 (3)
C15	0.71251 (13)	0.6581 (2)	0.58553 (4)	0.0296 (3)
H15	0.776244	0.680985	0.570885	0.036*
C16	0.70449 (15)	0.7358 (2)	0.61798 (4)	0.0359 (4)
H16	0.762819	0.81133	0.625584	0.043*
C17	0.61171 (16)	0.7034 (3)	0.63923 (4)	0.0415 (4)
H17	0.605726	0.757686	0.661344	0.05*
C18	0.52751 (16)	0.5920 (3)	0.62834 (5)	0.0463 (5)
H18	0.463906	0.569504	0.643068	0.056*
C19	0.53547 (14)	0.5127 (2)	0.59597 (4)	0.0365 (4)
H19	0.477851	0.435326	0.588664	0.044*
C20	0.63940 (13)	0.4638 (2)	0.53921 (4)	0.0281 (3)
O2	0.55589 (10)	0.35567 (16)	0.53235 (3)	0.0357 (3)
O3	0.71911 (11)	0.49208 (17)	0.51992 (3)	0.0428 (3)
H2	0.565 (2)	0.303 (3)	0.5101 (6)	0.070 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0269 (7)	0.0212 (6)	0.0192 (6)	0.0038 (6)	−0.0001 (5)	0.0006 (5)
C2	0.0264 (7)	0.0278 (7)	0.0212 (6)	−0.0004 (6)	0.0014 (5)	0.0009 (6)
C3	0.0313 (8)	0.0302 (8)	0.0220 (7)	−0.0009 (6)	−0.0012 (6)	−0.0021 (6)
C4	0.0280 (7)	0.0339 (8)	0.0261 (7)	0.0010 (6)	0.0051 (6)	0.0002 (6)
C5	0.0266 (7)	0.0280 (7)	0.0273 (7)	−0.0013 (6)	0.0017 (6)	−0.0017 (6)
C6	0.0229 (7)	0.0218 (6)	0.0205 (6)	0.0042 (5)	−0.0018 (5)	−0.0001 (5)
C7	0.0262 (7)	0.0235 (7)	0.0226 (7)	−0.0011 (6)	−0.0010 (5)	−0.0012 (5)
C8	0.0258 (7)	0.0214 (6)	0.0203 (6)	0.0027 (6)	0.0007 (5)	0.0017 (5)
C9	0.0296 (7)	0.0304 (7)	0.0226 (7)	−0.0043 (6)	0.0001 (6)	0.0015 (6)
C10	0.0383 (8)	0.0353 (8)	0.0240 (7)	−0.0029 (7)	−0.0047 (6)	−0.0032 (6)
C11	0.0403 (9)	0.0392 (9)	0.0192 (7)	0.0088 (7)	0.0023 (6)	−0.0003 (6)
C12	0.0298 (8)	0.0415 (9)	0.0276 (8)	0.0025 (7)	0.0075 (6)	0.0043 (7)
C13	0.0267 (7)	0.0317 (8)	0.0279 (7)	−0.0022 (6)	0.0018 (6)	−0.0009 (6)
N1	0.0289 (6)	0.0238 (6)	0.0201 (5)	−0.0027 (5)	0.0019 (5)	−0.0051 (5)
N2	0.0340 (7)	0.0300 (7)	0.0212 (6)	0.0026 (5)	0.0023 (5)	−0.0012 (5)
N3	0.0266 (6)	0.0254 (6)	0.0185 (5)	0.0017 (5)	0.0003 (5)	−0.0031 (5)
O1	0.0295 (5)	0.0244 (5)	0.0252 (5)	−0.0022 (4)	0.0007 (4)	−0.0028 (4)
C14	0.0261 (7)	0.0264 (7)	0.0240 (7)	0.0016 (6)	−0.0001 (6)	0.0018 (6)
C15	0.0294 (7)	0.0300 (8)	0.0294 (7)	−0.0038 (6)	0.0006 (6)	0.0032 (6)
C16	0.0382 (9)	0.0349 (8)	0.0348 (8)	−0.0053 (7)	−0.0086 (7)	−0.0029 (7)
C17	0.0439 (10)	0.0542 (11)	0.0263 (8)	0.0004 (9)	−0.0018 (7)	−0.0125 (8)
C18	0.0338 (9)	0.0726 (14)	0.0324 (9)	−0.0093 (9)	0.0096 (7)	−0.0118 (9)
C19	0.0277 (8)	0.0499 (10)	0.0318 (8)	−0.0110 (7)	0.0037 (6)	−0.0070 (7)
C20	0.0312 (7)	0.0282 (7)	0.0250 (7)	−0.0002 (6)	0.0023 (6)	0.0016 (6)
O2	0.0366 (6)	0.0436 (7)	0.0271 (6)	−0.0091 (5)	0.0055 (5)	−0.0098 (5)
O3	0.0474 (8)	0.0493 (7)	0.0316 (6)	−0.0129 (6)	0.0156 (5)	−0.0054 (6)

Geometric parameters (Å, º)

C1—C2	1.389 (2)	C11—C12	1.384 (2)
C1—C5	1.392 (2)	C11—H11	0.95
C1—C6	1.5039 (19)	C12—C13	1.391 (2)
C2—C3	1.391 (2)	C12—H12	0.95
C2—H2A	0.95	C13—H13	0.95
C3—N2	1.336 (2)	N1—N3	1.3922 (16)
C3—H3	0.95	N1—H1	0.89 (2)
C4—N2	1.338 (2)	C14—C19	1.387 (2)
C4—C5	1.389 (2)	C14—C15	1.389 (2)
C4—H4	0.95	C14—C20	1.500 (2)
C5—H5	0.95	C15—C16	1.386 (2)
C6—O1	1.2328 (17)	C15—H15	0.95
C6—N1	1.3533 (19)	C16—C17	1.380 (2)
C7—N3	1.2784 (19)	C16—H16	0.95
C7—C8	1.4725 (19)	C17—C18	1.382 (3)
C7—H7	0.95	C17—H17	0.95
C8—C9	1.395 (2)	C18—C19	1.389 (2)
C8—C13	1.397 (2)	C18—H18	0.95
C9—C10	1.387 (2)	C19—H19	0.95
C9—H9	0.95	C20—O3	1.2101 (19)
C10—C11	1.388 (2)	C20—O2	1.3210 (19)
C10—H10	0.95	O2—H2	0.95 (2)
C2—C1—C5	118.66 (13)	C11—C12—C13	120.31 (15)
C2—C1—C6	123.89 (13)	C11—C12—H12	119.8
C5—C1—C6	117.41 (13)	C13—C12—H12	119.8
C3—C2—C1	118.72 (14)	C12—C13—C8	120.14 (15)
C3—C2—H2A	120.6	C12—C13—H13	119.9
C1—C2—H2A	120.6	C8—C13—H13	119.9
N2—C3—C2	122.90 (14)	C6—N1—N3	117.93 (12)
N2—C3—H3	118.6	C6—N1—H1	124.6 (12)
C2—C3—H3	118.6	N3—N1—H1	117.5 (12)
N2—C4—C5	123.01 (14)	C3—N2—C4	118.11 (13)
N2—C4—H4	118.5	C7—N3—N1	115.24 (12)
C5—C4—H4	118.5	C19—C14—C15	119.61 (14)
C4—C5—C1	118.57 (14)	C19—C14—C20	121.40 (14)
C4—C5—H5	120.7	C15—C14—C20	118.98 (14)
C1—C5—H5	120.7	C16—C15—C14	120.27 (15)
O1—C6—N1	122.82 (13)	C16—C15—H15	119.9
O1—C6—C1	120.47 (13)	C14—C15—H15	119.9
N1—C6—C1	116.70 (12)	C17—C16—C15	119.97 (16)
N3—C7—C8	120.11 (13)	C17—C16—H16	120
N3—C7—H7	119.9	C15—C16—H16	120
C8—C7—H7	119.9	C16—C17—C18	120.03 (16)
C9—C8—C13	119.10 (13)	C16—C17—H17	120
C9—C8—C7	121.35 (13)	C18—C17—H17	120
C13—C8—C7	119.53 (13)	C17—C18—C19	120.28 (16)
C10—C9—C8	120.42 (14)	C17—C18—H18	119.9
C10—C9—H9	119.8	C19—C18—H18	119.9
C8—C9—H9	119.8	C14—C19—C18	119.84 (16)
C9—C10—C11	120.16 (15)	C14—C19—H19	120.1
C9—C10—H10	119.9	C18—C19—H19	120.1
C11—C10—H10	119.9	O3—C20—O2	124.57 (15)
C12—C11—C10	119.87 (14)	O3—C20—C14	122.44 (15)
C12—C11—H11	120.1	O2—C20—C14	112.98 (13)
C10—C11—H11	120.1	C20—O2—H2	112.0 (15)
C5—C1—C2—C3	−0.9 (2)	C7—C8—C13—C12	−178.61 (14)
C6—C1—C2—C3	−178.49 (13)	O1—C6—N1—N3	2.5 (2)
C1—C2—C3—N2	−0.8 (2)	C1—C6—N1—N3	−178.20 (11)
N2—C4—C5—C1	−1.0 (2)	C2—C3—N2—C4	1.6 (2)
C2—C1—C5—C4	1.7 (2)	C5—C4—N2—C3	−0.7 (2)
C6—C1—C5—C4	179.49 (13)	C8—C7—N3—N1	−176.72 (12)
C2—C1—C6—O1	152.30 (14)	C6—N1—N3—C7	−178.41 (13)
C5—C1—C6—O1	−25.3 (2)	C19—C14—C15—C16	−0.6 (2)
C2—C1—C6—N1	−27.0 (2)	C20—C14—C15—C16	−179.49 (15)
C5—C1—C6—N1	155.35 (13)	C14—C15—C16—C17	−0.3 (3)
N3—C7—C8—C9	13.8 (2)	C15—C16—C17—C18	0.8 (3)
N3—C7—C8—C13	−167.96 (14)	C16—C17—C18—C19	−0.3 (3)
C13—C8—C9—C10	0.5 (2)	C15—C14—C19—C18	1.1 (3)
C7—C8—C9—C10	178.77 (14)	C20—C14—C19—C18	179.94 (17)
C8—C9—C10—C11	−0.6 (2)	C17—C18—C19—C14	−0.7 (3)
C9—C10—C11—C12	0.5 (3)	C19—C14—C20—O3	179.85 (17)
C10—C11—C12—C13	−0.3 (3)	C15—C14—C20—O3	−1.3 (2)
C11—C12—C13—C8	0.2 (2)	C19—C14—C20—O2	−1.6 (2)
C9—C8—C13—C12	−0.3 (2)	C15—C14—C20—O2	177.25 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.89 (2)	2.02 (2)	2.8981 (17)	171 (2)
O2—H2···N2	0.95 (2)	1.72 (3)	2.6693 (17)	176 (2)
C3—H3···O3	0.95	2.53	3.236 (2)	131

Symmetry code: (i) −x+3/2, y+1/2, z.