Experimental and theoretical studies of the products of addition–elimination reactions between benzil dihydrazone and three isomeric chloro­benz­aldehydes

Liu, Y.-N.; Cheng, S.-S.; Wang, C.; Xing, D.-X.; Liu, Y.; Tan, X.-J.

doi:10.1107/S2053229615010682

Experimental and theoretical studies of the products of addition–elimination reactions between benzil dihydrazone and three isomeric chlorobenzaldehydes

Y.-N. Liu, S.-S. Cheng, C. Wang, D.-X. Xing, Y. Liu and X.-J. Tan

A series of mono- and di-Schiff bases formed between benzil dihydrazone {BDH; systematic name: (1Z)-[(2E)-2-hydrazinylidene-1,2-diphenylethylidene]hydrazine} and three isomeric chlorobenzaldehydes were designed and synthesized to be used as model compounds to help to explain the reaction mechanisms for the formation of Schiff bases. These compounds are 1-(2-chlorobenzylidene)-2-{2-[2-(2-chlorobenzylidene)hydrazin-1-ylidene]-1,2-diphenylethylidene}hydrazine (BDHOCB), and the 3-chloro (BDHMCB) and 4-chloro (BDHPCB) analogues, all having the formula C₂₈H₂₀Cl₂N₄. Surprisingly, only di-Schiff bases were obtained; our attempts to push the reaction in favour of the mono-Schiff bases all failed. Density functional theory (DFT) calculations were performed to explain the trend in the experimental results. In the case of the systems studied, the type of Schiff base produced exhibits a clear dependence on the HOMO–LUMO energy gaps (ΔE_HOMO–LUMO), i.e. the product is mainly governed by its stability. The compounds were characterized by single-crystal X-ray diffractometry, elemental analysis, melting point, ¹H NMR and ¹³C NMR spectroscopy. The structural features of the three new Schiff bases are similar. For instance, they have the same chemical formula, all the molecules have a symmetrical double helix structure, with each Ph—C=N—N=C—Ph arm exhibiting an anti conformation, and their supramolecular interactions include intermolecular π–π and weak C—H

π stacking interactions. The crystal systems are different, however, viz. triclinic (space group P $\overline{1}$ ) for BDHPCB, monoclinic (space group P2₁/n) for BDHOCB and orthorhombic (space group Pnna) for BDHMCB.

Keywords: addition–elimination; di-Schiff base; synthesis; characterization; benzil dihydrazone; crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615010682/lf3010sup1.cif Contains datablocks BDHOCB, BDHMCB, BDHPCB, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229615010682/lf3010BDHOCBsup2.hkl Contains datablock BDHOCB
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615010682/lf3010BDHOCBsup5.cml Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229615010682/lf3010BDHMCBsup3.hkl Contains datablock BDHMCB
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615010682/lf3010BDHMCBsup6.cml Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229615010682/lf3010BDHPCBsup4.hkl Contains datablock BDHPCB
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615010682/lf3010BDHPCBsup7.cml Supplementary material

CCDC references: 1404627; 1404626; 1404625

Computing details top

For all compounds, data collection: SMART (Bruker, 2001). Cell refinement: SMART (Bruker, 2001) for BDHOCB, BDHPCB; SMART for BDHMCB. For all compounds, data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 2001), PLATON (Spek, 2009) and DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

(BDHOCB) 1-(2-Chlorobenzylidene)-2-{2-[2-(2-chlorobenzylidene)hydrazin-1-ylidene]-1,2-diphenylethylidene}hydrazine top

Crystal data top

C₂₈H₂₀Cl₂N₄	F(000) = 1000
M_r = 483.38	D_x = 1.293 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 380 reflections
a = 9.271 (3) Å	θ = 2.5–26.0°
b = 15.786 (5) Å	µ = 0.29 mm⁻¹
c = 17.035 (6) Å	T = 298 K
β = 95.322 (5)°	Block, yellow
V = 2482.4 (14) Å³	0.55 × 0.50 × 0.32 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	5492 independent reflections
Radiation source: fine-focus sealed tube	3106 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
phi and ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→10
T_min = 0.852, T_max = 0.915	k = −19→20
14572 measured reflections	l = −21→21

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)] = 0.050	Hydrogen site location: difference Fourier map
wR(F²) = 0.150	All H-atom parameters refined
S = 0.95	w = 1/[σ²(F_o²) + (0.0828P)²] where P = (F_o² + 2F_c²)/3
5492 reflections	(Δ/σ)_max = 0.001
387 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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) top

	x	y	z	U_iso*/U_eq
C1	0.2031 (3)	0.23878 (17)	0.70015 (14)	0.0692 (6)
C2	0.1559 (3)	0.2309 (2)	0.62107 (16)	0.0864 (8)
C3	0.0460 (3)	0.1775 (2)	0.59691 (19)	0.0877 (9)
C4	−0.0187 (3)	0.13020 (19)	0.65161 (18)	0.0836 (8)
C5	0.0258 (3)	0.13836 (15)	0.73091 (16)	0.0669 (6)
C6	0.13700 (19)	0.19350 (12)	0.75645 (12)	0.0519 (5)
C7	0.18144 (18)	0.20286 (11)	0.84089 (12)	0.0472 (5)
C8	0.0868 (2)	0.14054 (13)	1.01586 (13)	0.0541 (5)
C9	0.1350 (2)	0.13633 (11)	1.09981 (12)	0.0517 (5)
C10	0.0487 (2)	0.10266 (13)	1.15489 (15)	0.0659 (6)
C11	0.0999 (4)	0.09847 (19)	1.23475 (17)	0.0883 (8)
C12	0.2363 (4)	0.1268 (2)	1.25811 (19)	0.0932 (9)
C13	0.3234 (3)	0.15985 (17)	1.20556 (17)	0.0817 (7)
C14	0.2727 (3)	0.16413 (14)	1.12724 (15)	0.0636 (6)
C15	0.4309 (3)	0.09363 (15)	0.88704 (17)	0.0744 (7)
C16	0.5477 (3)	0.03943 (18)	0.9015 (2)	0.0942 (9)
C17	0.6852 (3)	0.07083 (19)	0.90641 (19)	0.0926 (9)
C18	0.7087 (3)	0.1552 (2)	0.89774 (18)	0.0878 (8)
C19	0.5926 (2)	0.20920 (16)	0.88542 (15)	0.0667 (6)
C20	0.45228 (19)	0.17922 (11)	0.87971 (11)	0.0480 (5)
C21	0.32974 (18)	0.23870 (11)	0.86653 (11)	0.0444 (4)
C22	0.2490 (2)	0.43873 (12)	0.89966 (13)	0.0546 (5)
C23	0.1406 (2)	0.50573 (12)	0.89255 (13)	0.0558 (5)
C24	0.1317 (3)	0.56503 (13)	0.95207 (15)	0.0709 (7)
C25	0.0276 (4)	0.62802 (18)	0.9463 (3)	0.1018 (10)
C26	−0.0639 (4)	0.63357 (19)	0.8797 (3)	0.1193 (15)
C27	−0.0564 (3)	0.57727 (19)	0.8184 (3)	0.1014 (11)
C28	0.0447 (3)	0.51328 (16)	0.82488 (17)	0.0744 (7)
N1	0.09605 (16)	0.17574 (11)	0.89066 (10)	0.0550 (4)
N2	0.15540 (17)	0.18352 (11)	0.96920 (10)	0.0575 (4)
N3	0.35533 (16)	0.31738 (10)	0.87708 (10)	0.0519 (4)
N4	0.23339 (17)	0.37024 (10)	0.86230 (10)	0.0566 (4)
Cl1	−0.12354 (7)	0.06504 (5)	1.12484 (5)	0.0983 (3)
Cl2	0.25019 (11)	0.56054 (5)	1.03667 (4)	0.1100 (3)
H1	0.281 (3)	0.2780 (14)	0.7172 (13)	0.071 (7)*
H2	0.200 (3)	0.267 (2)	0.5844 (19)	0.123 (11)*
H3	0.010 (3)	0.1689 (17)	0.5460 (16)	0.096 (9)*
H4	−0.091 (3)	0.0920 (17)	0.6367 (16)	0.096 (9)*
H5	−0.017 (2)	0.1095 (15)	0.7678 (14)	0.069 (7)*
H6	−0.001 (3)	0.1085 (15)	0.9945 (14)	0.081 (7)*
H7	0.035 (3)	0.0692 (18)	1.2690 (19)	0.111 (10)*
H8	0.279 (3)	0.1251 (19)	1.313 (2)	0.123 (11)*
H9	0.432 (3)	0.1795 (17)	1.2252 (15)	0.097 (8)*
H10	0.334 (3)	0.1880 (15)	1.0871 (14)	0.082 (7)*
H11	0.343 (3)	0.0724 (14)	0.8842 (14)	0.080 (8)*
H12	0.526 (3)	−0.019 (2)	0.9092 (16)	0.109 (9)*
H13	0.770 (3)	0.0319 (18)	0.9167 (15)	0.106 (8)*
H14	0.804 (3)	0.1780 (19)	0.8968 (16)	0.114 (10)*
H15	0.607 (2)	0.2663 (15)	0.8792 (13)	0.074 (7)*
H16	0.330 (2)	0.4493 (13)	0.9328 (13)	0.071 (7)*
H17	0.030 (3)	0.6658 (19)	0.9909 (18)	0.105 (9)*
H18	−0.132 (4)	0.677 (2)	0.8754 (19)	0.138 (12)*
H19	−0.119 (4)	0.5799 (18)	0.7749 (19)	0.108 (11)*
H20	0.056 (2)	0.4698 (17)	0.7830 (13)	0.082 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0622 (14)	0.0893 (17)	0.0556 (15)	−0.0065 (13)	0.0024 (11)	−0.0042 (12)
C2	0.0882 (19)	0.112 (2)	0.0582 (17)	−0.0042 (17)	0.0051 (14)	−0.0057 (16)
C3	0.0851 (19)	0.116 (2)	0.0590 (18)	0.0143 (17)	−0.0114 (15)	−0.0235 (17)
C4	0.0725 (17)	0.0904 (19)	0.083 (2)	−0.0022 (15)	−0.0179 (15)	−0.0250 (16)
C5	0.0625 (14)	0.0688 (15)	0.0676 (16)	−0.0061 (12)	−0.0031 (12)	−0.0073 (13)
C6	0.0434 (10)	0.0565 (12)	0.0546 (13)	0.0075 (9)	−0.0012 (9)	−0.0068 (9)
C7	0.0389 (9)	0.0462 (10)	0.0561 (12)	0.0064 (8)	0.0027 (9)	−0.0030 (9)
C8	0.0463 (11)	0.0497 (12)	0.0666 (14)	0.0023 (9)	0.0069 (10)	0.0018 (10)
C9	0.0576 (12)	0.0398 (10)	0.0586 (13)	0.0066 (9)	0.0099 (10)	0.0033 (9)
C10	0.0746 (14)	0.0505 (12)	0.0751 (17)	0.0061 (10)	0.0206 (12)	0.0015 (11)
C11	0.120 (2)	0.0798 (18)	0.0700 (19)	0.0135 (17)	0.0343 (19)	0.0127 (14)
C12	0.119 (3)	0.092 (2)	0.066 (2)	0.0101 (19)	−0.0030 (19)	−0.0006 (15)
C13	0.097 (2)	0.0730 (16)	0.0724 (19)	0.0054 (15)	−0.0081 (16)	0.0014 (14)
C14	0.0701 (14)	0.0553 (13)	0.0646 (16)	0.0027 (11)	0.0021 (12)	0.0047 (11)
C15	0.0574 (14)	0.0561 (14)	0.110 (2)	0.0061 (11)	0.0121 (13)	−0.0006 (13)
C16	0.087 (2)	0.0569 (16)	0.139 (3)	0.0230 (15)	0.0140 (18)	0.0067 (16)
C17	0.0669 (17)	0.083 (2)	0.124 (3)	0.0342 (15)	−0.0071 (16)	−0.0052 (16)
C18	0.0472 (14)	0.090 (2)	0.123 (2)	0.0150 (13)	−0.0089 (14)	−0.0095 (16)
C19	0.0466 (12)	0.0604 (14)	0.0915 (18)	0.0038 (10)	−0.0019 (11)	−0.0042 (12)
C20	0.0429 (10)	0.0475 (11)	0.0533 (12)	0.0056 (8)	0.0025 (8)	−0.0015 (8)
C21	0.0392 (9)	0.0485 (11)	0.0453 (11)	0.0029 (8)	0.0019 (8)	−0.0030 (8)
C22	0.0567 (12)	0.0504 (12)	0.0560 (13)	0.0011 (10)	0.0016 (10)	−0.0038 (10)
C23	0.0587 (12)	0.0423 (11)	0.0675 (14)	0.0023 (9)	0.0125 (11)	0.0006 (9)
C24	0.0846 (16)	0.0482 (12)	0.0834 (18)	−0.0020 (11)	0.0259 (13)	−0.0074 (11)
C25	0.100 (2)	0.0599 (17)	0.151 (3)	0.0070 (16)	0.044 (2)	−0.0247 (19)
C26	0.080 (2)	0.0546 (18)	0.225 (5)	0.0196 (16)	0.026 (3)	−0.001 (2)
C27	0.0746 (18)	0.0697 (19)	0.155 (3)	0.0167 (14)	−0.014 (2)	0.015 (2)
C28	0.0703 (15)	0.0615 (15)	0.0896 (19)	0.0109 (12)	−0.0023 (13)	0.0016 (14)
N1	0.0413 (8)	0.0669 (11)	0.0565 (11)	−0.0005 (8)	0.0024 (8)	−0.0014 (8)
N2	0.0518 (9)	0.0649 (11)	0.0561 (11)	−0.0053 (8)	0.0063 (8)	0.0000 (9)
N3	0.0450 (9)	0.0476 (9)	0.0621 (11)	0.0068 (7)	−0.0001 (7)	−0.0033 (8)
N4	0.0521 (9)	0.0492 (10)	0.0669 (12)	0.0105 (7)	−0.0030 (8)	−0.0061 (8)
Cl1	0.0823 (5)	0.0966 (5)	0.1213 (7)	−0.0196 (3)	0.0373 (4)	0.0068 (4)
Cl2	0.1651 (8)	0.0968 (5)	0.0677 (5)	−0.0074 (5)	0.0083 (5)	−0.0249 (4)

Geometric parameters (Å, º) top

C1—C2	1.383 (3)	C15—C16	1.384 (3)
C1—C6	1.384 (3)	C15—H11	0.88 (2)
C1—H1	0.97 (2)	C16—C17	1.363 (4)
C2—C3	1.357 (4)	C16—H12	0.96 (3)
C2—H2	0.97 (3)	C17—C18	1.359 (4)
C3—C4	1.375 (4)	C17—H13	1.00 (3)
C3—H3	0.91 (3)	C18—C19	1.374 (3)
C4—C5	1.381 (4)	C18—H14	0.96 (3)
C4—H4	0.92 (3)	C19—C20	1.379 (3)
C5—C6	1.388 (3)	C19—H15	0.92 (2)
C5—H5	0.90 (2)	C20—C21	1.475 (2)
C6—C7	1.467 (3)	C21—N3	1.274 (2)
C7—N1	1.286 (2)	C22—N4	1.256 (2)
C7—C21	1.513 (2)	C22—C23	1.456 (3)
C8—N2	1.261 (3)	C22—H16	0.91 (2)
C8—C9	1.460 (3)	C23—C24	1.388 (3)
C8—H6	1.00 (2)	C23—C28	1.394 (3)
C9—C14	1.389 (3)	C24—C25	1.383 (4)
C9—C10	1.394 (3)	C24—Cl2	1.731 (3)
C10—C11	1.400 (4)	C25—C26	1.354 (5)
C10—Cl1	1.736 (2)	C25—H17	0.96 (3)
C11—C12	1.366 (4)	C26—C27	1.378 (5)
C11—H7	0.99 (3)	C26—H18	0.93 (4)
C12—C13	1.364 (4)	C27—C28	1.376 (4)
C12—H8	0.99 (3)	C27—H19	0.90 (3)
C13—C14	1.375 (3)	C28—H20	1.00 (2)
C13—H9	1.08 (3)	N1—N2	1.404 (2)
C14—H10	1.00 (3)	N3—N4	1.409 (2)
C15—C20	1.373 (3)

C2—C1—C6	120.6 (2)	C16—C15—H11	118.8 (15)
C2—C1—H1	120.4 (13)	C17—C16—C15	119.9 (3)
C6—C1—H1	119.0 (13)	C17—C16—H12	123.3 (16)
C3—C2—C1	120.8 (3)	C15—C16—H12	116.8 (17)
C3—C2—H2	121.7 (19)	C18—C17—C16	120.5 (2)
C1—C2—H2	117.5 (19)	C18—C17—H13	119.2 (16)
C2—C3—C4	119.7 (3)	C16—C17—H13	120.3 (16)
C2—C3—H3	125.3 (17)	C17—C18—C19	119.5 (3)
C4—C3—H3	115.0 (17)	C17—C18—H14	121.9 (18)
C3—C4—C5	120.2 (3)	C19—C18—H14	118.4 (18)
C3—C4—H4	121.4 (18)	C18—C19—C20	121.2 (2)
C5—C4—H4	118.4 (18)	C18—C19—H15	120.3 (14)
C4—C5—C6	120.7 (3)	C20—C19—H15	118.5 (14)
C4—C5—H5	121.8 (15)	C15—C20—C19	118.31 (19)
C6—C5—H5	117.4 (15)	C15—C20—C21	121.66 (18)
C1—C6—C5	118.1 (2)	C19—C20—C21	120.03 (18)
C1—C6—C7	121.70 (18)	N3—C21—C20	117.93 (15)
C5—C6—C7	120.2 (2)	N3—C21—C7	123.89 (15)
N1—C7—C6	118.62 (17)	C20—C21—C7	118.18 (15)
N1—C7—C21	122.19 (17)	N4—C22—C23	122.5 (2)
C6—C7—C21	119.07 (16)	N4—C22—H16	121.3 (13)
N2—C8—C9	121.0 (2)	C23—C22—H16	116.2 (13)
N2—C8—H6	119.1 (14)	C24—C23—C28	118.0 (2)
C9—C8—H6	119.9 (14)	C24—C23—C22	121.1 (2)
C14—C9—C10	117.4 (2)	C28—C23—C22	120.9 (2)
C14—C9—C8	120.23 (19)	C25—C24—C23	121.4 (3)
C10—C9—C8	122.3 (2)	C25—C24—Cl2	118.3 (2)
C9—C10—C11	120.6 (2)	C23—C24—Cl2	120.28 (18)
C9—C10—Cl1	120.11 (19)	C26—C25—C24	119.0 (3)
C11—C10—Cl1	119.3 (2)	C26—C25—H17	125.8 (18)
C12—C11—C10	119.3 (3)	C24—C25—H17	115.2 (18)
C12—C11—H7	125.3 (18)	C25—C26—C27	121.4 (3)
C10—C11—H7	115.2 (19)	C25—C26—H18	119 (2)
C13—C12—C11	121.5 (3)	C27—C26—H18	120 (2)
C13—C12—H8	115.1 (19)	C28—C27—C26	119.7 (4)
C11—C12—H8	123.4 (19)	C28—C27—H19	119 (2)
C12—C13—C14	119.1 (3)	C26—C27—H19	121.4 (19)
C12—C13—H9	120.0 (14)	C27—C28—C23	120.4 (3)
C14—C13—H9	120.9 (14)	C27—C28—H20	124.2 (14)
C13—C14—C9	122.1 (3)	C23—C28—H20	115.3 (13)
C13—C14—H10	121.2 (13)	C7—N1—N2	112.85 (16)
C9—C14—H10	116.7 (13)	C8—N2—N1	112.18 (17)
C20—C15—C16	120.5 (2)	C21—N3—N4	114.60 (15)
C20—C15—H11	120.7 (15)	C22—N4—N3	111.50 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H8···Cl2ⁱ	0.99 (3)	2.79 (3)	3.640 (4)	145 (2)
C5—H5···N1	0.90 (2)	2.48 (2)	2.802 (3)	101.5 (17)
C8—H6···Cl1	1.00 (2)	2.67 (2)	3.056 (2)	102.9 (15)
C19—H15···N3	0.92 (2)	2.47 (2)	2.778 (3)	99.9 (16)
C22—H16···Cl2	0.91 (2)	2.65 (2)	3.023 (2)	105.6 (16)

Symmetry code: (i) −x+1/2, y−1/2, −z+5/2.

(BDHMCB) 1-(3-Chlorobenzylidene)-2-{2-[2-(2-chlorobenzylidene)hydrazin-1-ylidene]-1,2-diphenylethylidene}hydrazine top

Crystal data top

C₂₈H₂₀Cl₂N₄	F(000) = 1000
M_r = 483.38	D_x = 1.301 Mg m⁻³
Orthorhombic, Pnna	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2bc	Cell parameters from 380 reflections
a = 11.619 (4) Å	θ = 2.5–26.0°
b = 23.173 (8) Å	µ = 0.29 mm⁻¹
c = 9.165 (3) Å	T = 298 K
V = 2467.6 (15) Å³	Block, yellow
Z = 4	0.38 × 0.32 × 0.25 mm

Data collection top

Bruker SMART CCD area detector diffractometer	2835 independent reflections
Radiation source: fine-focus sealed tube	1277 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
phi and ω scans	θ_max = 27.6°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→14
T_min = 0.898, T_max = 0.932	k = −29→29
13835 measured reflections	l = −11→11

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)] = 0.049	Hydrogen site location: difference Fourier map
wR(F²) = 0.151	All H-atom parameters refined
S = 0.98	w = 1/[σ²(F_o²) + (0.0694P)² + 0.0138P] where P = (F_o² + 2F_c²)/3
2835 reflections	(Δ/σ)_max = 0.001
194 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.6399 (2)	0.88360 (10)	0.5185 (3)	0.0882 (7)
C2	0.6557 (3)	0.83900 (11)	0.6152 (3)	0.1012 (9)
C3	0.7494 (3)	0.83695 (11)	0.7039 (4)	0.0960 (8)
C4	0.8303 (2)	0.87958 (10)	0.6940 (3)	0.0930 (7)
C5	0.81619 (19)	0.92379 (9)	0.5972 (3)	0.0798 (7)
C6	0.72127 (16)	0.92730 (7)	0.5087 (2)	0.0667 (6)
C7	0.70496 (16)	0.97683 (8)	0.4118 (2)	0.0671 (5)
C8	0.5128 (2)	1.03802 (12)	0.1865 (3)	0.0901 (7)
C9	0.4866 (2)	1.08818 (14)	0.0995 (3)	0.0954 (8)
C10	0.5512 (3)	1.13736 (14)	0.1112 (3)	0.1024 (8)
C11	0.5269 (3)	1.18549 (16)	0.0282 (4)	0.1400 (13)
C12	0.4386 (5)	1.1843 (3)	−0.0685 (6)	0.177 (3)
C13	0.3718 (5)	1.1357 (4)	−0.0809 (5)	0.174 (2)
C14	0.3945 (3)	1.0876 (2)	0.0006 (4)	0.1273 (12)
N1	0.61133 (14)	0.98128 (7)	0.3382 (2)	0.0797 (5)
N2	0.60586 (14)	1.03291 (7)	0.2578 (2)	0.0833 (6)
Cl1	0.60920 (10)	1.24635 (4)	0.04030 (15)	0.2034 (7)
H1	0.581 (2)	0.8856 (9)	0.449 (2)	0.098 (8)*
H2	0.600 (2)	0.8119 (10)	0.619 (3)	0.116 (9)*
H3	0.7602 (17)	0.8073 (10)	0.774 (2)	0.094 (7)*
H4	0.896 (2)	0.8770 (10)	0.758 (2)	0.107 (8)*
H5	0.8736 (16)	0.9520 (8)	0.590 (2)	0.079 (6)*
H6	0.4641 (19)	1.0070 (10)	0.190 (2)	0.098 (8)*
H7	0.6109 (19)	1.1424 (9)	0.187 (2)	0.091 (7)*
H8	0.414 (4)	1.2125 (18)	−0.145 (5)	0.217 (16)*
H9	0.313 (3)	1.1369 (13)	−0.153 (4)	0.170 (13)*
H10	0.357 (2)	1.0502 (13)	0.008 (3)	0.123 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0783 (16)	0.0754 (16)	0.111 (2)	−0.0185 (12)	−0.0027 (15)	−0.0001 (14)
C2	0.101 (2)	0.0711 (16)	0.132 (2)	−0.0261 (15)	0.0133 (18)	0.0009 (16)
C3	0.114 (2)	0.0660 (15)	0.108 (2)	0.0040 (15)	0.0182 (17)	0.0098 (15)
C4	0.0870 (17)	0.0835 (17)	0.108 (2)	0.0022 (14)	−0.0081 (16)	0.0108 (15)
C5	0.0677 (13)	0.0662 (13)	0.1053 (18)	−0.0094 (11)	−0.0017 (13)	0.0058 (13)
C6	0.0559 (11)	0.0585 (12)	0.0859 (15)	−0.0072 (9)	0.0050 (11)	−0.0086 (10)
C7	0.0529 (11)	0.0633 (12)	0.0852 (15)	−0.0055 (8)	0.0018 (11)	−0.0057 (10)
C8	0.0620 (14)	0.104 (2)	0.104 (2)	−0.0012 (14)	−0.0035 (13)	−0.0037 (16)
C9	0.0630 (14)	0.130 (2)	0.0933 (18)	0.0251 (15)	0.0000 (13)	0.0050 (16)
C10	0.0757 (17)	0.121 (2)	0.111 (2)	0.0317 (16)	0.0156 (16)	0.0249 (18)
C11	0.116 (3)	0.165 (3)	0.139 (3)	0.076 (2)	0.052 (2)	0.051 (2)
C12	0.163 (5)	0.232 (6)	0.137 (4)	0.122 (4)	0.059 (4)	0.066 (4)
C13	0.124 (4)	0.296 (7)	0.101 (3)	0.121 (4)	−0.006 (3)	0.027 (4)
C14	0.081 (2)	0.189 (4)	0.112 (3)	0.048 (2)	−0.0007 (19)	−0.008 (2)
N1	0.0632 (11)	0.0739 (11)	0.1021 (14)	−0.0084 (8)	−0.0074 (10)	0.0002 (10)
N2	0.0634 (11)	0.0833 (13)	0.1030 (15)	−0.0015 (9)	−0.0123 (10)	0.0032 (10)
Cl1	0.1921 (10)	0.1272 (8)	0.2911 (15)	0.0564 (7)	0.1174 (10)	0.0850 (8)

Geometric parameters (Å, º) top

C1—C2	1.374 (4)	C8—C9	1.442 (4)
C1—C6	1.388 (3)	C8—H6	0.91 (2)
C1—H1	0.94 (2)	C9—C10	1.369 (4)
C2—C3	1.359 (4)	C9—C14	1.403 (4)
C2—H2	0.90 (2)	C10—C11	1.380 (4)
C3—C4	1.367 (3)	C10—H7	0.99 (2)
C3—H3	0.95 (2)	C11—C12	1.356 (7)
C4—C5	1.365 (3)	C11—Cl1	1.708 (4)
C4—H4	0.96 (2)	C12—C13	1.372 (7)
C5—C6	1.371 (3)	C12—H8	1.00 (4)
C5—H5	0.936 (19)	C13—C14	1.366 (7)
C6—C7	1.464 (3)	C13—H9	0.96 (3)
C7—N1	1.284 (2)	C14—H10	0.97 (3)
C7—C7ⁱ	1.500 (3)	N1—N2	1.407 (2)
C8—N2	1.269 (3)

C2—C1—C6	120.0 (3)	N2—C8—H6	115.9 (15)
C2—C1—H1	125.0 (14)	C9—C8—H6	121.3 (15)
C6—C1—H1	114.7 (14)	C10—C9—C14	118.5 (3)
C3—C2—C1	121.3 (3)	C10—C9—C8	120.8 (2)
C3—C2—H2	122.1 (16)	C14—C9—C8	120.7 (3)
C1—C2—H2	116.6 (16)	C9—C10—C11	121.2 (3)
C2—C3—C4	119.1 (3)	C9—C10—H7	122.5 (13)
C2—C3—H3	122.5 (13)	C11—C10—H7	115.9 (13)
C4—C3—H3	118.5 (13)	C12—C11—C10	119.9 (5)
C5—C4—C3	120.2 (3)	C12—C11—Cl1	118.9 (4)
C5—C4—H4	122.6 (15)	C10—C11—Cl1	121.1 (3)
C3—C4—H4	117.2 (15)	C11—C12—C13	119.9 (5)
C4—C5—C6	121.7 (2)	C11—C12—H8	132 (3)
C4—C5—H5	119.0 (12)	C13—C12—H8	108 (3)
C6—C5—H5	119.3 (12)	C14—C13—C12	121.0 (5)
C5—C6—C1	117.8 (2)	C14—C13—H9	123 (2)
C5—C6—C7	120.63 (17)	C12—C13—H9	116 (2)
C1—C6—C7	121.6 (2)	C13—C14—C9	119.5 (5)
N1—C7—C6	119.43 (16)	C13—C14—H10	132.6 (18)
N1—C7—C7ⁱ	122.27 (18)	C9—C14—H10	107.9 (18)
C6—C7—C7ⁱ	118.11 (16)	C7—N1—N2	112.43 (16)
N2—C8—C9	122.6 (2)	C8—N2—N1	112.78 (19)

Symmetry code: (i) −x+3/2, −y+2, z.

(BDHPCB) 1-(4-Chlorobenzylidene)-2-{2-[2-(2-chlorobenzylidene)hydrazin-1-ylidene]-1,2-diphenylethylidene}hydrazine top

Crystal data top

C₂₈H₂₀Cl₂N₄	Z = 2
M_r = 483.38	F(000) = 500
Triclinic, P1	D_x = 1.293 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.661 (5) Å	Cell parameters from 380 reflections
b = 11.492 (6) Å	θ = 2.5–26.0°
c = 13.018 (7) Å	µ = 0.29 mm⁻¹
α = 111.040 (7)°	T = 298 K
β = 109.532 (7)°	Block, yellow
γ = 93.954 (7)°	0.38 × 0.26 × 0.18 mm
V = 1241.7 (11) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	4757 independent reflections
Radiation source: fine-focus sealed tube	2699 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
phi and ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→11
T_min = 0.914, T_max = 0.954	k = −14→14
6793 measured reflections	l = −15→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.058	All H-atom parameters refined
wR(F²) = 0.158	w = 1/[σ²(F_o²) + (0.0918P)²] where P = (F_o² + 2F_c²)/3
S = 0.91	(Δ/σ)_max < 0.001
4757 reflections	Δρ_max = 0.30 e Å⁻³
388 parameters	Δρ_min = −0.44 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.033 (4)

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.3977 (3)	0.5324 (3)	0.2655 (3)	0.0692 (8)
C2	0.4360 (4)	0.5111 (3)	0.1689 (3)	0.0900 (10)
C3	0.4965 (5)	0.6119 (4)	0.1527 (3)	0.0978 (11)
C4	0.5180 (4)	0.7344 (3)	0.2321 (3)	0.0856 (10)
C5	0.4801 (3)	0.7565 (3)	0.3290 (3)	0.0631 (7)
C6	0.4206 (2)	0.6563 (2)	0.3487 (2)	0.0488 (6)
C7	0.3868 (2)	0.6822 (2)	0.4556 (2)	0.0456 (5)
C8	0.2211 (3)	0.5467 (3)	0.5866 (3)	0.0590 (6)
C9	0.1943 (3)	0.5707 (2)	0.6951 (2)	0.0559 (6)
C10	0.2739 (3)	0.6789 (3)	0.7981 (3)	0.0621 (7)
C11	0.2449 (3)	0.7056 (3)	0.8989 (3)	0.0698 (8)
C12	0.1313 (3)	0.6229 (3)	0.8966 (3)	0.0707 (8)
C13	0.0518 (4)	0.5145 (3)	0.7972 (3)	0.0718 (8)
C14	0.0830 (3)	0.4876 (3)	0.6963 (3)	0.0671 (7)
C15	0.6769 (3)	0.7390 (3)	0.6461 (2)	0.0584 (7)
C16	0.8145 (3)	0.7579 (3)	0.7349 (3)	0.0703 (8)
C17	0.8721 (3)	0.8713 (3)	0.8311 (3)	0.0743 (8)
C18	0.7947 (4)	0.9675 (3)	0.8383 (3)	0.0824 (9)
C19	0.6583 (3)	0.9498 (3)	0.7502 (2)	0.0695 (8)
C20	0.5964 (2)	0.8344 (2)	0.65252 (19)	0.0446 (5)
C21	0.4506 (2)	0.8128 (2)	0.55597 (19)	0.0444 (5)
C22	0.1910 (3)	0.9688 (3)	0.4592 (2)	0.0555 (6)
C23	0.0526 (3)	0.9583 (2)	0.3630 (2)	0.0565 (6)
C24	−0.0154 (3)	1.0615 (3)	0.3738 (3)	0.0680 (8)
C25	−0.1458 (4)	1.0557 (4)	0.2843 (3)	0.0778 (9)
C26	−0.2066 (3)	0.9459 (4)	0.1840 (3)	0.0771 (9)
C27	−0.1423 (3)	0.8417 (4)	0.1700 (3)	0.0853 (9)
C28	−0.0126 (3)	0.8486 (3)	0.2605 (3)	0.0734 (8)
N1	0.3121 (2)	0.59119 (18)	0.46430 (17)	0.0548 (5)
N2	0.2974 (2)	0.63244 (19)	0.57530 (18)	0.0589 (5)
N3	0.3862 (2)	0.90753 (18)	0.55885 (17)	0.0521 (5)
N4	0.2515 (2)	0.87315 (19)	0.45753 (18)	0.0564 (5)
Cl1	0.08981 (13)	0.66030 (9)	1.02296 (9)	0.1160 (4)
Cl2	−0.36990 (9)	0.93629 (11)	0.06886 (10)	0.1202 (4)
H1	0.354 (3)	0.465 (3)	0.280 (3)	0.092 (10)*
H2	0.422 (3)	0.424 (3)	0.121 (3)	0.082 (9)*
H3	0.528 (4)	0.596 (4)	0.089 (4)	0.134 (13)*
H4	0.566 (3)	0.810 (3)	0.231 (3)	0.098 (10)*
H5	0.496 (3)	0.839 (3)	0.388 (3)	0.074 (8)*
H6	0.177 (3)	0.467 (2)	0.522 (2)	0.056 (7)*
H7	0.354 (3)	0.735 (2)	0.801 (2)	0.068 (7)*
H8	0.298 (3)	0.778 (3)	0.974 (3)	0.074 (8)*
H9	−0.034 (3)	0.457 (3)	0.790 (3)	0.093 (9)*
H10	0.029 (3)	0.413 (3)	0.629 (2)	0.070 (8)*
H11	0.640 (2)	0.659 (2)	0.583 (2)	0.056 (7)*
H12	0.866 (3)	0.690 (3)	0.732 (2)	0.084 (9)*
H13	0.965 (3)	0.882 (3)	0.888 (3)	0.082 (9)*
H14	0.830 (3)	1.050 (3)	0.906 (3)	0.090 (9)*
H15	0.604 (3)	1.015 (3)	0.756 (2)	0.088 (9)*
H16	0.238 (3)	1.050 (2)	0.528 (2)	0.058 (7)*
H17	0.031 (3)	1.139 (3)	0.443 (2)	0.070 (8)*
H18	−0.184 (3)	1.134 (3)	0.295 (3)	0.087 (9)*
H19	−0.185 (4)	0.761 (3)	0.102 (3)	0.101 (11)*
H20	0.027 (3)	0.783 (3)	0.250 (3)	0.080 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.089 (2)	0.0533 (17)	0.0569 (17)	0.0143 (14)	0.0273 (15)	0.0142 (14)
C2	0.134 (3)	0.062 (2)	0.063 (2)	0.026 (2)	0.046 (2)	0.0068 (17)
C3	0.141 (3)	0.094 (3)	0.074 (2)	0.031 (2)	0.067 (2)	0.027 (2)
C4	0.119 (3)	0.072 (2)	0.075 (2)	0.0142 (19)	0.055 (2)	0.0256 (18)
C5	0.0763 (18)	0.0564 (17)	0.0563 (17)	0.0118 (14)	0.0311 (14)	0.0180 (14)
C6	0.0467 (13)	0.0489 (14)	0.0431 (13)	0.0126 (10)	0.0101 (10)	0.0166 (11)
C7	0.0404 (12)	0.0458 (13)	0.0432 (13)	0.0114 (10)	0.0090 (10)	0.0163 (11)
C8	0.0561 (15)	0.0528 (16)	0.0597 (17)	0.0056 (12)	0.0159 (13)	0.0209 (14)
C9	0.0559 (15)	0.0539 (15)	0.0607 (16)	0.0132 (12)	0.0199 (12)	0.0284 (13)
C10	0.0585 (16)	0.0643 (17)	0.0680 (19)	0.0074 (14)	0.0222 (14)	0.0349 (15)
C11	0.0784 (19)	0.0629 (18)	0.066 (2)	0.0116 (15)	0.0271 (16)	0.0259 (16)
C12	0.0841 (19)	0.0664 (19)	0.084 (2)	0.0249 (15)	0.0444 (17)	0.0419 (17)
C13	0.078 (2)	0.0632 (19)	0.090 (2)	0.0133 (16)	0.0417 (18)	0.0410 (18)
C14	0.0681 (18)	0.0548 (17)	0.077 (2)	0.0055 (14)	0.0265 (16)	0.0283 (16)
C15	0.0575 (15)	0.0477 (15)	0.0548 (16)	0.0124 (12)	0.0080 (12)	0.0166 (13)
C16	0.0593 (16)	0.0659 (18)	0.075 (2)	0.0227 (15)	0.0084 (15)	0.0310 (16)
C17	0.0604 (18)	0.082 (2)	0.0608 (19)	0.0111 (16)	−0.0025 (15)	0.0315 (17)
C18	0.086 (2)	0.068 (2)	0.0517 (18)	0.0124 (17)	−0.0041 (15)	0.0082 (16)
C19	0.0747 (18)	0.0571 (16)	0.0527 (17)	0.0233 (14)	0.0080 (14)	0.0096 (13)
C20	0.0454 (12)	0.0438 (13)	0.0415 (13)	0.0078 (10)	0.0130 (10)	0.0177 (11)
C21	0.0439 (12)	0.0467 (13)	0.0431 (13)	0.0130 (10)	0.0165 (10)	0.0186 (11)
C22	0.0551 (15)	0.0557 (16)	0.0539 (16)	0.0190 (13)	0.0183 (12)	0.0216 (14)
C23	0.0514 (14)	0.0690 (17)	0.0611 (17)	0.0246 (13)	0.0234 (12)	0.0358 (15)
C24	0.0714 (18)	0.0689 (19)	0.073 (2)	0.0309 (16)	0.0272 (16)	0.0368 (17)
C25	0.074 (2)	0.089 (2)	0.096 (3)	0.0395 (18)	0.0331 (18)	0.060 (2)
C26	0.0473 (15)	0.115 (3)	0.093 (2)	0.0262 (17)	0.0220 (15)	0.071 (2)
C27	0.0668 (19)	0.091 (2)	0.076 (2)	0.0125 (18)	0.0062 (17)	0.030 (2)
C28	0.0675 (18)	0.073 (2)	0.068 (2)	0.0283 (16)	0.0146 (15)	0.0237 (17)
N1	0.0557 (12)	0.0519 (12)	0.0493 (12)	0.0060 (9)	0.0175 (10)	0.0161 (10)
N2	0.0607 (13)	0.0587 (13)	0.0552 (13)	0.0051 (10)	0.0222 (10)	0.0222 (11)
N3	0.0510 (11)	0.0515 (12)	0.0478 (12)	0.0179 (9)	0.0129 (9)	0.0179 (9)
N4	0.0517 (12)	0.0581 (13)	0.0512 (12)	0.0218 (10)	0.0117 (10)	0.0189 (10)
Cl1	0.1693 (10)	0.0998 (7)	0.1126 (8)	0.0236 (6)	0.0946 (8)	0.0437 (6)
Cl2	0.0670 (5)	0.1721 (10)	0.1308 (9)	0.0229 (6)	0.0031 (5)	0.1043 (8)

Geometric parameters (Å, º) top

C1—C2	1.372 (4)	C15—C20	1.382 (3)
C1—C6	1.392 (3)	C15—H11	0.93 (2)
C1—H1	0.97 (3)	C16—C17	1.356 (4)
C2—C3	1.375 (5)	C16—H12	0.95 (3)
C2—H2	0.94 (3)	C17—C18	1.370 (4)
C3—C4	1.365 (5)	C17—H13	0.92 (3)
C3—H3	0.94 (4)	C18—C19	1.371 (4)
C4—C5	1.373 (4)	C18—H14	0.97 (3)
C4—H4	0.97 (3)	C19—C20	1.380 (3)
C5—C6	1.392 (3)	C19—H15	0.94 (3)
C5—H5	0.94 (3)	C20—C21	1.473 (3)
C6—C7	1.467 (3)	C21—N3	1.286 (3)
C7—N1	1.290 (3)	C22—N4	1.276 (3)
C7—C21	1.505 (3)	C22—C23	1.457 (3)
C8—N2	1.269 (3)	C22—H16	0.97 (3)
C8—C9	1.454 (4)	C23—C28	1.374 (4)
C8—H6	0.94 (3)	C23—C24	1.381 (4)
C9—C10	1.384 (4)	C24—C25	1.378 (4)
C9—C14	1.397 (4)	C24—H17	0.96 (3)
C10—C11	1.365 (4)	C25—C26	1.358 (5)
C10—H7	0.95 (3)	C25—H18	0.98 (3)
C11—C12	1.387 (4)	C26—C27	1.369 (5)
C11—H8	0.96 (3)	C26—Cl2	1.739 (3)
C12—C13	1.364 (4)	C27—C28	1.377 (4)
C12—Cl1	1.734 (3)	C27—H19	0.97 (3)
C13—C14	1.377 (4)	C28—H20	0.85 (3)
C13—H9	0.98 (3)	N1—N2	1.409 (3)
C14—H10	0.93 (3)	N3—N4	1.413 (3)
C15—C16	1.380 (4)

C2—C1—C6	120.3 (3)	C20—C15—H11	122.2 (14)
C2—C1—H1	123.2 (18)	C17—C16—C15	120.0 (3)
C6—C1—H1	116.5 (18)	C17—C16—H12	119.5 (18)
C1—C2—C3	120.4 (3)	C15—C16—H12	120.4 (18)
C1—C2—H2	113.9 (17)	C16—C17—C18	119.7 (3)
C3—C2—H2	125.6 (17)	C16—C17—H13	118.4 (18)
C4—C3—C2	120.4 (3)	C18—C17—H13	121.9 (18)
C4—C3—H3	120 (2)	C17—C18—C19	120.7 (3)
C2—C3—H3	120 (2)	C17—C18—H14	122.9 (17)
C3—C4—C5	119.6 (3)	C19—C18—H14	116.3 (17)
C3—C4—H4	126.1 (18)	C18—C19—C20	120.5 (3)
C5—C4—H4	114.2 (18)	C18—C19—H15	120.8 (18)
C4—C5—C6	121.3 (3)	C20—C19—H15	118.7 (18)
C4—C5—H5	122.8 (16)	C19—C20—C15	118.0 (2)
C6—C5—H5	115.8 (16)	C19—C20—C21	121.7 (2)
C1—C6—C5	118.0 (2)	C15—C20—C21	120.3 (2)
C1—C6—C7	121.7 (2)	N3—C21—C20	118.5 (2)
C5—C6—C7	120.3 (2)	N3—C21—C7	122.9 (2)
N1—C7—C6	119.5 (2)	C20—C21—C7	118.55 (18)
N1—C7—C21	121.9 (2)	N4—C22—C23	121.8 (3)
C6—C7—C21	118.4 (2)	N4—C22—H16	118.8 (13)
N2—C8—C9	121.7 (3)	C23—C22—H16	119.5 (13)
N2—C8—H6	119.6 (15)	C28—C23—C24	118.5 (3)
C9—C8—H6	118.6 (15)	C28—C23—C22	122.0 (2)
C10—C9—C14	118.4 (3)	C24—C23—C22	119.5 (3)
C10—C9—C8	120.9 (2)	C25—C24—C23	121.2 (3)
C14—C9—C8	120.6 (3)	C25—C24—H17	119.6 (15)
C11—C10—C9	121.5 (3)	C23—C24—H17	119.1 (16)
C11—C10—H7	118.4 (16)	C26—C25—C24	118.6 (3)
C9—C10—H7	120.1 (16)	C26—C25—H18	123.8 (17)
C10—C11—C12	118.8 (3)	C24—C25—H18	117.3 (18)
C10—C11—H8	125.3 (16)	C25—C26—C27	121.8 (3)
C12—C11—H8	115.9 (16)	C25—C26—Cl2	119.7 (2)
C13—C12—C11	121.3 (3)	C27—C26—Cl2	118.5 (3)
C13—C12—Cl1	120.0 (2)	C26—C27—C28	118.9 (3)
C11—C12—Cl1	118.7 (3)	C26—C27—H19	124.0 (19)
C12—C13—C14	119.5 (3)	C28—C27—H19	116.9 (19)
C12—C13—H9	123.6 (18)	C23—C28—C27	120.9 (3)
C14—C13—H9	116.6 (18)	C23—C28—H20	121 (2)
C13—C14—C9	120.4 (3)	C27—C28—H20	118 (2)
C13—C14—H10	119.4 (16)	C7—N1—N2	111.31 (19)
C9—C14—H10	120.2 (16)	C8—N2—N1	113.5 (2)
C16—C15—C20	121.1 (3)	C21—N3—N4	111.75 (19)
C16—C15—H11	116.6 (14)	C22—N4—N3	111.3 (2)

Calculated reaction enthalpy changes (ΔH) (kJ mol^-1) top

Schiff base	ΔH_gas	ΔH_cpcm
BDHMOCB	-2.588743	-8.217815
BDHOCB	-6.597881501	-12.513133
BDHMMCB	-0.855913	-6.4561045
BDHMCB	-5.159107501	-10.6569045
BDHMPCB	-0.2179165	-5.854865
BDHPCB	-4.7285255	-10.0267845

Calculated reaction Gibbs free energy changes (ΔG) (kJ mol^-1) top

Schiff base	ΔG_gas	ΔG_cpcm
BDHMOCB	5.6527015	0.0918925
BDHOCB	3.549676	-4.1509155
BDHMMCB	6.810547	0.5172235
BDHMCB	4.4607245	0.168032
BDHMPCB	7.82399	2.118778499
BDHPCB	3.62319	-1.714451501

Energy gaps between HOMO and LUMO (ΔE) (kJ mol^-1). top

Schiff base	ΔE_gas	ΔE_cpcm
BDHMOCB	327.2685251	340.6848281
BDHOCB	377.8619024	375.1576378
BDHMMCB	322.1750559	343.6516426
BDHMCB	368.6989088	380.749952
BDHMPCB	322.9889608	338.6369384
BDHPCB	375.7352478	376.7329376

Selected π–π interaction geometry for BDHOCB. top

d is the centroid–centroid distance (Å), α is the dihedral angle (α/°), β is the slippage angle between the centroid–centroid distance and the normal to plane I (°), γ is the slippage angle between the centroid–centroid distance and the normal to plane J (°), e is the perpendicular distance of centroid I to plane J (Å) and f is the perpendicular distance of centroid J to plane I (Å).

π–π interactions (I→J)	d	α	β	γ	e	f
Cg1→Cg2ⁱ	4.754 (2)	66.28	10.69	75.49	1.191	4.671
Cg1→Cg4ⁱⁱ	4.108 (2)	20.78	22.72	16.21	3.945	3.789
Cg2→Cg3ⁱⁱⁱ	4.851 (2)	72.63	9.82	65.95	1.977	4.780
Cg2→Cg3^iv	5.467 (2)	85.33	32.92	53.32	3.265	4.589
Cg2→Cg4^v	5.222 (2)	77.27	20.83	68.43	1.919	4.880
Cg2→Cg4^vi	5.560 (3)	29.58	50.81	63.42	2.488	3.514
Cg3→Cg1^vi	5.673 (3)	86.14	25.42	72.85	1.673	5.124
Cg3→Cg3ⁱⁱⁱ	5.595 (3)	0.02	53.86	53.86	3.299	3.299
Cg3→Cg4ⁱⁱ	4.834 (3)	56.21	13.58	64.57	2.076	4.699
Cg4→Cg4^v	4.595 (3)	0.00	37.35	37.35	3.653	3.652

Cg1 is the centroid of the C1–C6 ring, Cg2 is the centroid of the C9–C14 ring, Cg3 is the centroid of the C15–C20 ring and Cg4 is the centroid of the C23–C28 ring. Symmetry codes: (i) x-1/2, -y+1/2, z-1/2; (ii) -x+3/2, y+1/2, -z+1/2; (iii) -x+2, -y+1, -z+1; (iv) x-1/2, -y+1/2, z+1/2; (v) -x+1, -y, -z+1; (vi) x+1/2, -y+1/2, z+1/2.

Selected C—H···π interaction geometry for BDHOCB. top

H···Cg is the distance between a H atom and the centroid of the benzene ring (Å), H-Perp is the perpendicular distance of a H atom to the benzene plane (Å), γ is the slippage angle between the C—H distance and the normal to the benzene plane (°), C—H···Cg is the angle of C—H with the centroid (°) and C···Cg is the C–centroid distance (Å).

C—H···π interactions	H···Cg	H-Perp	γ	C—H···Cg	C···Cg
C13—H9···Cg1ⁱ	2.77 (3)	2.688	14.33	129.6 (18)	3.559 (3)
C17—H13···Cg2ⁱⁱ	3.11 (3)	2.807	25.35	123.8 (18)	3.756 (3)
C26—H18···Cg2ⁱⁱⁱ	3.20 (3)	2.777	29.63	144 (3)	3.984 (4)
C27—H19···Cg3^iv	3.02 (3)	2.975	10.01	130 (3)	3.668 (5)

Cg1 is the centroid of the C1–C6 ring, Cg2 is the centroid of the C9–C14 ring and Cg3 is the centroid of the C15–C20 ring. Symmetry codes: (i) x+1/2, -y+1/2, z+1/2; (ii) -x+2, -y+1,-z+1; (iii) -x+1, -y, -z+1; (iv) -x+3/2, y-1/2, -z+1/2.

Selected π–π interaction geometry for BDHMCB. top

π–π interactions (I→J)	d	α	β	γ	e	f
Cg1→Cg2ⁱ	4.180 (2)	12.79	37.25	26.49	3.741	3.327
Cg2→Cg1ⁱⁱ	5.158 (3)	88.54	15.30	82.33	0.688	4.975
Cg2→Cg2ⁱⁱⁱ	5.816 (3)	88.77	54.70	49.80	3.754	3.361

Cg1 is the centroid of the C1–C6 ring and Cg2 is the centroid of the C9–C14 ring. Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1/2, -y, z+1; (iii) x-1/2, y, -z+2.

Selected C—H···π interaction geometry for BDHMCB. top

C—H···π interactions	H···Cg	H-Perp	γ	C—H···Cg	C···Cg
C4—H4···Cg2ⁱ	2.90 (2)	2.802	14.60	162.5 (17)	3.826 (3)

Cg2 is the centroid of the C9—C14 ring. Symmetry code: (i) -x+1/2, -y, z-1.

Selected π–π interaction geometry for BDHPCB. top

π–π interactions (I→J)	d	α	β	γ	e	f
Cg1→Cg2ⁱ	5.459 (3)	28.10	44.56	51.41	3.405	3.890
Cg1→Cg2ⁱⁱ	4.736 (3)	28.10	39.65	29.26	4.132	3.646
Cg2→Cg3ⁱⁱⁱ	5.244 (3)	83.00	14.35	83.85	0.562	5.081
Cg2→Cg4^iv	5.645 (4)	87.63	34.55	61.16	2.723	4.649
Cg2→Cg4^v	5.995 (4)	87.63	50.21	59.96	3.001	3.836
Cg3→Cg1ⁱⁱ	5.828 (4)	83.79	42.57	85.50	0.457	4.292
Cg3→Cg4^vi	3.966 (3)	5.48	26.81	22.14	3.674	3.540
Cg4→Cg1ⁱⁱⁱ	5.437 (4)	78.37	27.42	63.67	2.412	4.827
Cg4→Cg4^iv	5.258 (3)	0.00	53.25	53.25	3.146	3.146

Cg1 is the centroid of the C1–C6 ring, Cg2 is the centroid of the C9–C14 ring, Cg3 is the centroid of the C15–C20 ring and Cg4 is the centroid of the C23–C28 ring.

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

Selected C—H···π interaction geometry for BDHPCB. top

C—H···π interactions	H···Cg	H-Perp	γ	C—H···Cg	C···Cg
C16—H12···Cg2ⁱ	3.09 (3)	2.920	19.19	150 (2)	3.943 (4)

Cg2 is the centroid of the C9–C14 ring. Symmetry code: (i) z-1, y, z.

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Experimental and theoretical studies of the products of addition–elimination reactions between benzil dihydrazone and three isomeric chloro­benz­aldehydes

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Experimental and theoretical studies of the products of addition–elimination reactions between benzil dihydrazone and three isomeric chlorobenzaldehydes