2-{(1E)-[(E)-2-(2,6-Di­chloro­benzyl­idene)hydrazin-1-yl­idene]meth­yl}phenol: crystal structure, Hirshfeld surface analysis and computational study

Manawar, R.B.; Gondaliya, M.B.; Shah, M.K.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989019012349

2-{(1E)-[(E)-2-(2,6-Dichlorobenzylidene)hydrazin-1-ylidene]methyl}phenol: crystal structure, Hirshfeld surface analysis and computational study

R. B. Manawar, M. B. Gondaliya, M. K. Shah, M. M. Jotani and E. R. T. Tiekink

An E configuration about each of the two imine bonds is found in the title molecule which, to a first approximation, is planar. The main feature of the molecular packing is π–π stacking leading to helical, supramolecular chains.

Keywords: crystal structure; Schiff base; Hirshfeld surface analysis; computational chemistry.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989019012349/hb7852sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019012349/hb7852Isup2.hkl Contains datablock I

CCDC reference: 1857868

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.044
wR factor = 0.138
Data-to-parameter ratio = 18.2

checkCIF/PLATON results

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Alert level C
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.792 Report

Alert level G
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        117 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          8 Info

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

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

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2/SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

2-{(1E)-[(E)-2-(2,6-Dichlorobenzylidene)hydrazin-1-\ ylidene]methyl}phenol top

Crystal data top

C₁₄H₁₀Cl₂N₂O	F(000) = 600
M_r = 293.14	D_x = 1.455 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.5614 (8) Å	Cell parameters from 4447 reflections
b = 15.6055 (12) Å	θ = 4.8–56.3°
c = 10.0527 (9) Å	µ = 0.48 mm⁻¹
β = 95.031 (3)°	T = 296 K
V = 1337.9 (2) Å³	Block, light-yellow
Z = 4	0.35 × 0.30 × 0.30 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2244 reflections with I > 2σ(I)
Radiation source: X-ray tube	R_int = 0.023
ω and φ scan	θ_max = 28.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→11
T_min = 0.846, T_max = 0.867	k = −15→20
10171 measured reflections	l = −11→12
3185 independent reflections

Refinement top

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)] = 0.044	Hydrogen site location: mixed
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.069P)² + 0.4482P] where P = (F_o² + 2F_c²)/3
3185 reflections	(Δ/σ)_max < 0.001
175 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.37913 (8)	−0.06610 (4)	0.23254 (7)	0.0669 (2)
Cl2	0.90894 (8)	−0.10632 (4)	0.57108 (7)	0.0646 (2)
O1	0.8423 (2)	0.25607 (11)	0.52671 (19)	0.0636 (5)
H3O	0.808 (4)	0.206 (2)	0.501 (3)	0.095*
N1	0.66249 (19)	0.14415 (10)	0.39038 (17)	0.0395 (4)
N2	0.6061 (2)	0.06313 (10)	0.34827 (19)	0.0462 (5)
C1	0.7508 (2)	0.31651 (12)	0.4623 (2)	0.0406 (5)
C2	0.6261 (2)	0.29483 (12)	0.36883 (19)	0.0343 (4)
C3	0.5366 (3)	0.36160 (13)	0.3082 (2)	0.0449 (5)
H3	0.4534	0.3486	0.2457	0.054*
C4	0.5688 (3)	0.44563 (15)	0.3390 (2)	0.0555 (6)
H4	0.5073	0.4890	0.2984	0.067*
C5	0.6932 (3)	0.46555 (14)	0.4305 (3)	0.0590 (7)
H5	0.7160	0.5226	0.4505	0.071*
C6	0.7839 (3)	0.40175 (14)	0.4924 (3)	0.0535 (6)
H6	0.8671	0.4158	0.5543	0.064*
C7	0.5859 (2)	0.20707 (12)	0.3350 (2)	0.0378 (4)
H7	0.5026	0.1960	0.2716	0.045*
C8	0.6741 (2)	0.00413 (12)	0.4161 (2)	0.0397 (5)
H8	0.7496	0.0206	0.4834	0.048*
C9	0.6461 (2)	−0.08822 (11)	0.39956 (18)	0.0333 (4)
C10	0.5215 (2)	−0.12658 (13)	0.3210 (2)	0.0389 (5)
C11	0.5039 (3)	−0.21481 (14)	0.3119 (2)	0.0453 (5)
H11	0.4196	−0.2381	0.2594	0.054*
C12	0.6111 (3)	−0.26778 (13)	0.3805 (2)	0.0487 (5)
H12	0.5998	−0.3269	0.3734	0.058*
C13	0.7354 (3)	−0.23366 (13)	0.4599 (2)	0.0459 (5)
H13	0.8080	−0.2694	0.5064	0.055*
C14	0.7504 (2)	−0.14562 (12)	0.4692 (2)	0.0387 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0580 (4)	0.0514 (4)	0.0850 (5)	−0.0036 (3)	−0.0299 (3)	0.0108 (3)
Cl2	0.0631 (4)	0.0443 (3)	0.0800 (5)	0.0068 (3)	−0.0304 (3)	−0.0017 (3)
O1	0.0630 (11)	0.0375 (8)	0.0835 (13)	0.0107 (8)	−0.0322 (9)	−0.0042 (8)
N1	0.0445 (9)	0.0262 (8)	0.0470 (10)	0.0012 (7)	−0.0009 (8)	0.0012 (7)
N2	0.0586 (11)	0.0274 (8)	0.0503 (11)	−0.0011 (8)	−0.0076 (9)	−0.0015 (7)
C1	0.0429 (11)	0.0321 (10)	0.0461 (12)	0.0060 (8)	0.0000 (9)	−0.0012 (8)
C2	0.0393 (10)	0.0284 (9)	0.0356 (10)	0.0048 (8)	0.0047 (8)	0.0015 (8)
C3	0.0543 (12)	0.0381 (11)	0.0414 (11)	0.0098 (9)	−0.0003 (10)	0.0031 (9)
C4	0.0782 (17)	0.0357 (11)	0.0520 (14)	0.0177 (11)	0.0023 (12)	0.0066 (10)
C5	0.0847 (18)	0.0287 (10)	0.0629 (15)	0.0041 (11)	0.0026 (13)	−0.0043 (10)
C6	0.0620 (15)	0.0364 (11)	0.0598 (14)	−0.0004 (10)	−0.0085 (12)	−0.0088 (10)
C7	0.0413 (10)	0.0338 (10)	0.0373 (10)	0.0012 (8)	−0.0020 (8)	0.0001 (8)
C8	0.0389 (10)	0.0315 (9)	0.0478 (12)	−0.0012 (8)	−0.0020 (9)	0.0005 (9)
C9	0.0376 (10)	0.0292 (9)	0.0333 (10)	0.0001 (7)	0.0051 (8)	0.0013 (7)
C10	0.0419 (11)	0.0359 (10)	0.0381 (10)	−0.0009 (8)	−0.0005 (8)	0.0033 (8)
C11	0.0551 (13)	0.0380 (11)	0.0424 (12)	−0.0082 (9)	0.0017 (10)	−0.0042 (9)
C12	0.0688 (15)	0.0285 (10)	0.0496 (13)	−0.0054 (10)	0.0106 (11)	−0.0019 (9)
C13	0.0608 (14)	0.0309 (10)	0.0459 (12)	0.0078 (9)	0.0041 (10)	0.0041 (9)
C14	0.0444 (11)	0.0331 (10)	0.0382 (11)	0.0016 (8)	0.0021 (9)	0.0006 (8)

Geometric parameters (Å, º) top

Cl1—C10	1.725 (2)	C5—C6	1.377 (3)
Cl2—C14	1.739 (2)	C5—H5	0.9300
O1—C1	1.354 (2)	C6—H6	0.9300
O1—H3O	0.87 (3)	C7—H7	0.9300
N1—C7	1.281 (2)	C8—C9	1.468 (3)
N1—N2	1.405 (2)	C8—H8	0.9300
N2—C8	1.258 (3)	C9—C14	1.407 (3)
C1—C6	1.388 (3)	C9—C10	1.405 (3)
C1—C2	1.401 (3)	C10—C11	1.387 (3)
C2—C3	1.401 (3)	C11—C12	1.375 (3)
C2—C7	1.445 (3)	C11—H11	0.9300
C3—C4	1.370 (3)	C12—C13	1.379 (3)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.380 (4)	C13—C14	1.382 (3)
C4—H4	0.9300	C13—H13	0.9300

C1—O1—H3O	109 (2)	C2—C7—H7	119.3
C7—N1—N2	114.17 (16)	N2—C8—C9	126.41 (18)
C8—N2—N1	111.38 (17)	N2—C8—H8	116.8
O1—C1—C6	117.72 (19)	C9—C8—H8	116.8
O1—C1—C2	121.84 (17)	C14—C9—C10	115.23 (17)
C6—C1—C2	120.44 (19)	C14—C9—C8	118.56 (17)
C3—C2—C1	117.91 (18)	C10—C9—C8	126.20 (17)
C3—C2—C7	119.52 (18)	C11—C10—C9	122.19 (18)
C1—C2—C7	122.57 (17)	C11—C10—Cl1	116.18 (16)
C4—C3—C2	121.5 (2)	C9—C10—Cl1	121.61 (15)
C4—C3—H3	119.3	C12—C11—C10	120.0 (2)
C2—C3—H3	119.3	C12—C11—H11	120.0
C3—C4—C5	119.6 (2)	C10—C11—H11	120.0
C3—C4—H4	120.2	C13—C12—C11	120.35 (18)
C5—C4—H4	120.2	C13—C12—H12	119.8
C6—C5—C4	120.7 (2)	C11—C12—H12	119.8
C6—C5—H5	119.7	C12—C13—C14	119.0 (2)
C4—C5—H5	119.7	C12—C13—H13	120.5
C5—C6—C1	119.9 (2)	C14—C13—H13	120.5
C5—C6—H6	120.1	C13—C14—C9	123.19 (19)
C1—C6—H6	120.1	C13—C14—Cl2	117.00 (16)
N1—C7—C2	121.47 (18)	C9—C14—Cl2	119.80 (14)
N1—C7—H7	119.3

C7—N1—N2—C8	−172.7 (2)	N2—C8—C9—C14	169.6 (2)
O1—C1—C2—C3	179.3 (2)	N2—C8—C9—C10	−11.4 (4)
C6—C1—C2—C3	−0.3 (3)	C14—C9—C10—C11	−0.6 (3)
O1—C1—C2—C7	0.3 (3)	C8—C9—C10—C11	−179.6 (2)
C6—C1—C2—C7	−179.4 (2)	C14—C9—C10—Cl1	178.08 (15)
C1—C2—C3—C4	−0.2 (3)	C8—C9—C10—Cl1	−0.9 (3)
C7—C2—C3—C4	178.9 (2)	C9—C10—C11—C12	−0.4 (3)
C2—C3—C4—C5	0.8 (4)	Cl1—C10—C11—C12	−179.23 (18)
C3—C4—C5—C6	−0.9 (4)	C10—C11—C12—C13	0.8 (3)
C4—C5—C6—C1	0.3 (4)	C11—C12—C13—C14	0.0 (3)
O1—C1—C6—C5	−179.4 (2)	C12—C13—C14—C9	−1.1 (3)
C2—C1—C6—C5	0.3 (4)	C12—C13—C14—Cl2	179.81 (17)
N2—N1—C7—C2	178.69 (18)	C10—C9—C14—C13	1.4 (3)
C3—C2—C7—N1	−178.4 (2)	C8—C9—C14—C13	−179.5 (2)
C1—C2—C7—N1	0.6 (3)	C10—C9—C14—Cl2	−179.53 (15)
N1—N2—C8—C9	−179.54 (19)	C8—C9—C14—Cl2	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.87 (3)	1.87 (3)	2.632 (2)	147 (3)

Summary of short interatomic contacts (Å) in (I)^a top

Contact	Distance	Symmetry operation
Cl1···H6	2.86	-1/2 + x, 1/2 - y, -1/2 + z
Cl2···H4	2.85	1/2 + x, 1/2 - y, 1/2 + z
O1···H7	2.68	1/2 + x, 1/2 - y, 1/2 + z
C2···C12	3.399 (3)	1 - x, - y, 1 - z

Note: (a) The interatomic distances were calculated using Crystal Explorer 17 (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values.

Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) top

Contact	Percentage contribution
H···H	29.4
Cl···H/H···Cl	29.1
O···H/H···O	7.4
C···H/H···C	12.0
C···C	12.0
N···H/H···N	4.5
C···N/N···C	3.9
C···Cl/Cl···C	0.6
Cl···Cl	0.4
Cl···N/N···Cl	0.4
Cl···O/O···Cl	0.1
C···O/O···C	0.1

Summary of interaction energies (kJ mol^-1) calculated for (I) top

Contact	R (Å)	E_ele	E_pol	E_dis	E_rep	E_tot
C2···C12ⁱ	4.00	-13.1	-1.4	-77.2	42.7	-55.8
Cg(C1–C6)···Cg(C9–C14)ⁱⁱ	8.58	-5.9	-0.9	-40.1	20.6	-29.2
Cl1···H6ⁱⁱⁱ +
Cl2···H4^iv +	8.53	-10.4	-1.8	-20.9	19.1	-18.7
O1···H7^iv

Symmetry codes: (i) 1 - x, -y, 1 - z; (ii) 3/2 - x, 1/2 + y, 1/2 - z; (iii) -1/2 + x, 1/2 - y, -1/2 + z; (iv) 1/2 + x, 1/2 - y, 1/2 + z.

Geometric data (°) for related 2-OH-C₆—C(H)═N—N═C(H)—C₆ molecules, i.e. R¹—C(H)═N—N═C(H)—R² top

Compound	R¹	R²	C—N—N—C	C₂N₂/R-C₆	C₂N₂/R'-C₆	R-C₆/R'-C₆	REFCODE
(I)	2-OH-C₆H₄	2,6-Cl₂-C₆H₃	-172.7 (2)	4.9 (3)	7.5 (3)	4.83 (13)	–^a
(II)	2-OH-C₆H₄	anthracen-9-yl	179.1 (2)	2.84 (13)	29.03 (16)	31.35 (8)	KOBXAD^b
(III)	2-OH-C₆H₄	2-EtOC(═O)CH₂-C₆H₄	173.32 (14)	7.25 (9)	20.02 (9)	27.26 (5)	LOSJIO^c
(IV)	2,3-(OH)₂-4,6-(t-Bu)₂-C₆H	4-Me₂NC₆H₄	-178.09 (12)	10.58 (4)	4.61 (4)	15.03 (3)	EDIQOA^d
(V)	2-naphthol	4-Me₂N-C₆H₄	-179.8 (2)	2.27 (9)	6.49 (13)	7.84 (6)	EZUYEF^e
(VI)	2-naphthol	4-OH-C₆H₄	179.30 (16)	3.93 (12)	8.44 (12)	11.91 (6)	RUTGEU^f
(VII)	2-naphthol	4-Me₂N-C₆H₄	177.98 (15)	4.90 (10)	2.32 (12)	3.82 (6)	RUTFET^g
(VIII*	2-naphthol	4-OH-3-MeO-C₆H₄	178.73 (14)	5.78 (10)	15.06 (7)	13.14 (5)	POMNIQ^h
			177.74 (15)	6.65 (9)	12.05 (11)	18.46 (6)
(IX)*	2-naphthol	pyren-1-yl	-173 (1)	2.6 (8)	4.4 (7)	6.9 (4)	APACEBⁱ
			173 (1)	5.3 (7)	4.7 (7)	7.9 (4)

* Two independent molecules in the asymmetric unit. References: (a) This work; (b) Patil & Das (2017); (c) Akkurt et al. (2015); (d) Arsenyev et al. (2016); (e) Ghosh, Adhikari et al. (2016); (f) Ghosh, Ta et al. (2016); (g) Ghosh, Ta et al. (2016); (h) Kumari et al. (2014); (i) Ghosh, Ganguly et al. (2016)

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2-{(1E)-[(E)-2-(2,6-Di­chloro­benzyl­idene)hydrazin-1-yl­idene]meth­yl}phenol: crystal structure, Hirshfeld surface analysis and computational study

Supporting information

Key indicators

checkCIF/PLATON results

2-{(1E)-[(E)-2-(2,6-Dichlorobenzylidene)hydrazin-1-ylidene]methyl}phenol: crystal structure, Hirshfeld surface analysis and computational study