Crystal structures of two dis-symmetric di-Schiff base compounds: 2-({(E)-2-[(E)-2,6-di­chloro­benzyl­idene]hydrazin-1-yl­idene}meth­yl)-6-meth­oxy­phenol and 4-bromo-2-({(E)-2-[(E)-2,6-di­chloro­benzyl­idene]hydrazin-1-yl­idene}meth­yl)phenol

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

doi:10.1107/S2056989020006416

research communications

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ISSN: 2056-9890

Volume 76| Part 6| June 2020| Pages 862-869

https://doi.org/10.1107/S2056989020006416

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Crystal structures of two dis-symmetric di-Schiff base compounds: 2-({(E)-2-[(E)-2,6-dichlorobenzylidene]hydrazin-1-ylidene}methyl)-6-methoxyphenol and 4-bromo-2-({(E)-2-[(E)-2,6-dichlorobenzylidene]hydrazin-1-ylidene}methyl)phenol

Rohit B. Manawar,^a Chandankumar T. Pashavan,^a Manish K. Shah,^a ‡ Mukesh M. Jotani ^b and Edward R. T. Tiekink ^c ^*

^aChemical Research Laboratory, Department of Chemistry Saurashtra University, Rajkot - 360005, Gujarat, India, ^bDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, and ^cResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 12 May 2020; accepted 13 May 2020; online 19 May 2020)

Each of the title dis-symmetric di-Schiff base compounds, C₁₅H₁₂Cl₂N₂O₂ (I) and C₁₄H₉BrCl₂N₂O (II), features a central azo-N—N bond connecting two imine groups, each with an E-configuration. One imine bond in each molecule connects to a 2,6-dichlorobenzene substituent while the other links a 2-hydroxyl-3-methoxy-substituted benzene ring in (I) or a 2-hydroxyl-4-bromo benzene ring in (II). Each molecule features an intramolecular hydroxyl-O—H⋯N(imine) hydrogen bond. The C—N—N—C torsion angles of −151.0 (3)° for (I) and 177.8 (6)° (II) indicates a significant twist in the former. The common feature of the molecular packing is the formation of supramolecular chains. In (I), the linear chains are aligned along the a-axis direction and the molecules are linked by methoxy-C—H⋯O(methoxy) and chlorobenzene-C—Cl⋯π(chlorobenzene) interactions. The chain in (II) is also aligned along the a axis but, has a zigzag topology and is sustained by Br⋯O [3.132 (4) Å] secondary bonding interactions. In each crystal, the chains pack without directional interactions between them. The non-covalent interactions are delineated in the study of the calculated Hirshfeld surfaces. Dispersion forces make the most significant contributions to the identified intermolecular interactions in each of (I) and (II).

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

CCDC references: 2003762; 2003761

1. Chemical context

Schiff base molecules, known for their ease of formation, can be deprotonated to form a prominent class of multidentate ligands for a full range of metal ions leading to a rich coordination chemistry (Vigato & Tamburini, 2004 ; Clarke & Storr, 2014 ). The broad range of biological activities exhibited by Schiff base molecules such as anti-bacterial, anti-viral, anti-fungal, anti-malarial, anti-inflammatory, etc. (Naeimi et al., 2013 ; Mukherjee et al., 2013 ) is a key motivation for studies in this area. Indeed, this is the motivation for the preparation of dis-symmetric di-Schiff base molecules (Liu et al., 2018 ) related to the title compounds and their transition-metal complexes (Manawar et al., 2019a ), complemented by crystallographic studies (Manawar et al., 2019b , 2020 ). In a continuation of these structural studies, the crystal and molecular structures of methoxy- (I) and bromine-substituted (II) analogues of an earlier published dis-symmetric di-Schiff base (Manawar et al., 2019b) are described herein, together with the detailed analysis of the molecular packing by Hirshfeld surface analysis and computation of energy frameworks.

2. Structural commentary

The molecular structures of (I) and (II) are shown in Fig. 1. The common feature of each molecule is the presence of two imine bonds connected by a azo-N—N bond, Table 1. At one end of each molecule is a 2,6-dichlorobenzene substituent. In (I), the molecule is terminated by a 2-hydroxyl-3-methoxy-substituted benzene ring and in (II), the terminal group is a 2-hydroxyl-4-bromo benzene ring. The configuration about each of the imine bonds is E. Each molecule features an intramolecular hydroxyl-O—H⋯N(imine) hydrogen bond with geometric details listed in Tables 2 and 3, respectively. As might be expected and judged from the data in Table 1, there is a close similarity in comparable geometric parameters characterizing molecules (I) and (II) with salient bond lengths being equal within experimental error. The most significant difference in bond angles is seen in the ca 3° wider C9—C8—N2 angle in (II) cf. (I). There is an apparent difference in conformation in the central region of the molecules as seen in the ca 25° difference in the C7—N1—N2—C8 torsion angles indicating a discernible kink in (I). The central C₂N₂ chromophore in (I) exhibits distortions from co-planarity as the r.m.s. deviation of the fitted atoms is 0.1459 Å with maximum deviations to either side of the plane being 0.155 (17) Å for the N2 atom and 0.149 (14) Å for C8. By contrast, the r.m.s. deviation for the central atoms in (II) is 0.0112 Å. Further differences are noted in dihedral angles between the central plane and pendant benzene rings, and between the benzene rings, Table 1, with the maximum difference occurring for the (C7,N1,N2,C8)/(C9–C14) dihedral angles of 23.1 (4) and 1.5 (6)° for (I) and (II), respectively.

Table 1
Selected geometric parameters (Å, °) in (I) and (II)

Parameter	(I)	(II)
N1—N2	1.409 (3)	1.417 (7)
C7—N1	1.283 (3)	1.276 (7)
C8—N2	1.256 (4)	1.234 (7)
N2—N1—C7	112.4 (2)	110.9 (5)
N1—N2—C8	114.2 (2)	114.9 (5)
C1—C7—N1	122.6 (3)	123.1 (6)
C9—C8—N2	121.1 (3)	124.5 (6)
C7—N1—N2—C8	−151.0 (3)	177.8 (6)
C1—C7—N1—N2	−178.8 (2)	−178.9 (5)
C9—C8—N2—N1	179.9 (2)	−179.2 (6)
(C7,N1,N2,C8)/(C1–C6)	20.9 (4)	15.6 (5)
(C7,N1,N2,C8)/(C9–C14)	23.1 (4)	1.5 (6)
(C1–C6)/(C9–C14)	2.41 (17)	15.5 (3)

Table 2
Hydrogen-bond geometry (Å, °) for (I)

Cg1 is the centroid of the (C9–14) ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N1	0.83 (3)	1.91 (3)	2.657 (3)	149 (3)
C15—H15B⋯O2ⁱ	0.96	2.58	3.439 (4)	149
C14—Cl2⋯Cg1ⁱⁱ	1.74 (1)	3.70 (1)	3.765 (3)	79 (1)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ ; (ii) x-1, y, z.

Table 3
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N1	0.83 (6)	1.96 (6)	2.655 (8)	141 (7)

Figure 1
The molecular structures of (a) (I)

and (b) (II)

, showing the atom-labelling schemes and displacement ellipsoids at the 35% probability level.

3. Supramolecular features

The two prominent directional interactions in the molecular packing of (I) are of the type C—H⋯O and C—Cl⋯π, Table 2. Thus, methoxy-C—H⋯O(methoxy) and chlorobenzene-C—Cl⋯π(chlorobenzene) contacts serve to link molecules into supramolecular chain aligned along the a-axis direction, Fig. 2(a). The linear chains thus formed assemble in the crystal without directional contacts between them, Fig. 2(b).

Figure 2
Molecular packing in the crystal of (I)

: (a) supramolecular chain sustained by methoxy-C—H⋯O(methoxy) and chlorobenzene-C—Cl⋯π(chlorobenzene) interactions shown as orange and purple dashed lines, respectively and (b) a view of the unit-cell contents in projection down the a axis with one chain highlighted in space-filling mode.

Supramolecular chains along the a axis are also noted in the packing of (II), Fig. 3(a). In this instance, the contacts between molecules are of the type Br⋯O, i.e. the Br1⋯O1 separation is 3.132 (4) Å for symmetry operation $[{1\over 2}]$ + x, 3 − y, z. With the first such interaction in a crystal being reported in 1954, i.e. in the crystal of Br₂·O(CH₂CH₂)₂O (Hassel & Hvoslef, 1954 ), these well-described secondary bonding interactions (Alcock, 1972 ), are termed halogen-bonding interactions in the current parlance (Tiekink, 2017 ). In (II), the Br⋯O interactions assemble molecules into zigzag chains as these are propagated by glide symmetry. Globally, the supramolecular chains stack along the b axis to form layers and the layers stack along the c axis in an …ABAB… fashion, Fig. 3(b), but there are no directional interactions between the chains.

Figure 3
Molecular packing in the crystal of (II)

: (a) supramolecular, zigzag chain sustained by Br⋯O secondary bonding interactions shown as black dashed lines and (b) a view of the unit-cell contents in projection down the b axis.

4. Hirshfeld surface analysis

The Hirshfeld surfaces for (I) and (II) were calculated employing the Crystal Explorer 17 program (Turner et al., 2017 ) following recently published protocols (Tan et al., 2019 ). The results describe the influence of non-bonded interactions upon the molecular packing in the crystals of (I) and (II), especially in the absence of directional interactions between the chains.

On the Hirshfeld surfaces mapped over d_norm, the presence of the bright-red spots near the methoxy-O2 and H15B atoms for (I) in Fig. 4(a),(b) and those near the Br1 and hydroxyl-O1 atoms in Fig. 5(a) for (II), are indicative of dominant intermolecular C—H⋯O and Br⋯O contacts in their respective crystal structures. The faint-red spots viewed near the imine-N2 and H8 atoms for (I), and near the Cl2 and H7 atoms for (II) in Fig. 4(a),(b) and 5(b), respectively, indicate the influence of short interatomic contacts (Table 4) on their molecular packing. The Hirshfeld surfaces mapped over the calculated electrostatic potential for (I) and (II) showing contributions from different intermolecular interactions are illustrated through blue and red regions corresponding to positive and negative electrostatic potential in Fig. 6. For (I), the presence of a short C—Cl2⋯π(C9–C14) contact, Table 2, is illustrated through a blue bump and a orange concave region in the Hirshfeld surface mapped with the shape-index property in Fig. 4(c).

Table 4
Summary of short interatomic contacts (Å) for (I) and (II)^a

Contact	Distance	Symmetry operation
(I)
H12⋯O1	2.59	−x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z
H8⋯N2	2.58	−1 + x, y, z
H13⋯H15A	2.30	$[{1\over 2}]$ + x, 2 − y, $[{1\over 2}]$ + z
(II)
Br1⋯O1	3.132 (4)	$[{1\over 2}]$ + x, 3 − y, z
Cl2⋯H7	2.69	− $[{1\over 2}]$ + x, 1 − y, z
Notes: (a) The interatomic distances are calculated in Crystal Explorer (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values.

Figure 4
Views of the Hirshfeld surface for (I)

mapped: (a) and (b) over d_norm in the range −0.097 to + 1.103 arbitrary units and (c) with the shape-index property showing intermolecular C—Cl⋯π/π⋯Cl—C contacts.

Figure 5
Views of the Hirshfeld surface for (II)

mapped over d_norm in the range −0.016 to 1.528 arbitrary units.

Figure 6
A view of the Hirshfeld surface mapped over the electrostatic potential (the red and blue regions represent negative and positive electrostatic potentials, respectively): (a) for (I)

in the range −0.071 to +0.038 atomic units and (b) for (II)

in the range −0.063 to +0.040 atomic units.

The overall two-dimensional fingerprint plots for (I), Fig. 7(a), and (II), Fig.7(f), and those delineated into H⋯H, O⋯H/H⋯O, C⋯H/H⋯C and C⋯C contacts for (I) are illustrated in Fig. 7(b)–(e), respectively, and the equivalent plots for (II) are found in Fig. 7(g)–(j). The percentage contributions from the different interatomic contacts to the Hirshfeld surfaces of (I) and (II) are quantitatively summarized in Table 5. For (I), the short interatomic H⋯H contact between the methoxy-H15A and dichlorobenzene-H13 atoms, Table 4, is evident as a pair of almost fused peaks at d_e + d_i ∼2.3 Å in Fig.7(b). In (II), comparable interactions are at interatomic distances farther than the sum of their van der Waals radii. The decrease in the percentage contribution from H⋯H contacts to the Hirshfeld surface of (II) compared to (I), Table 5, can be related, in the main, to the presence of the bromine substituent in the hydroxylbenzene ring, in contrast to the methoxy group in (I), and its participation in a number of surface contacts, most notably Br⋯H/H⋯Br contacts (13.7%).

Table 5
Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) and (II)

Contact		Percentage contribution
	(I)	(II)
H⋯H	31.1	21.1
O⋯H/H⋯O	9.1	4.3
C⋯H/H⋯C	16.4	13.8
Cl⋯H/H⋯Cl	17.3	23.1
N⋯H/H⋯N	8.0	0.4
C⋯Cl/Cl⋯C	6.2	1.0
C⋯C	4.6	7.2
C⋯O/O⋯C	3.7	0.1
C⋯N/N⋯C	0.0	7.1
Cl⋯Cl	3.5	2.7
Cl⋯N/N⋯Cl	0.0	0.6
N⋯O/O⋯N	0.0	0.1
Br⋯H/H⋯Br	–	13.7
Br⋯O/O⋯Br	–	2.6
Br⋯C/C⋯Br	–	1.8
Br⋯Cl/Cl⋯Br	–	0.2
Br⋯Br	–	0.2

Figure 7
(a) A comparison of the full two-dimensional fingerprint plot for (I)

and those delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) C⋯H/H⋯C and (e) C⋯C contacts, (f)–(j) equivalent fingerprint plots for (II)

, (g) N⋯H/H⋯N for (I)

, (h) C⋯Cl/C⋯Cl for (I)

, (i) Cl⋯H/H⋯Cl for (II)

and (j) Br⋯O/O⋯Br for (II)

The presence of C—H⋯O contacts in the crystal of (I) is characterized as the pair of forceps-like tips at d_e + d_i ∼2.5 Å in the fingerprint plot delineated into O⋯H/H⋯O contacts, Fig. 7(c), with the points related to other short interatomic O⋯H contacts merged within. The comparatively small contribution from these contacts in (II), Table 5, show the points to be at distances greater than sum of their van der Waals radii in Fig. 7(h). In the fingerprint plot delineated into C⋯H/H⋯C contacts for both (I) and (II), Fig. 7(d) and (i), the characteristic wings are observed but with different shapes. Their relatively long interatomic distances are consistent with the absence of intermolecular C—H⋯π or short C⋯H contacts in the crystals. The absence of aromatic π–π stacking is also evident from the fingerprint plots delineated into C⋯C contacts, Figs. 7(e) and (j), although significant percentage contributions from these contacts are noted, Table 5. In addition to the above, some specific contacts occur in the crystals of (I) and (II).

The pair of forceps-like tips at d_e + d_i ∼2.5 Å in the fingerprint plot delineated into N⋯H/H⋯N contacts for (I) in Fig. 7(k) indicate the short interatomic N⋯H contact involving the imine-N2 and H12 atoms, Table 4, formed within the supramolecular chain along a axis Fig. 2(a). Also, in the fingerprint plot delineated into C⋯Cl/Cl⋯C contacts for (I), Fig. 7(l), the C—Cl⋯π contacts are highlighted as the pattern of blue points at separations as close as d_e = d_i = 1.85 Å. In the case of (II), in the fingerprint plot delineated into Cl⋯H/H⋯Cl contacts, Fig. 7(m), the short interatomic contact involving the Cl2 and imine-H7 atoms is apparent as the pair of spikes with their tips at d_e + d_i ∼2.7 Å. Finally, the presence of interatomic Br⋯O interactions along the a axis in the crystal is reflected in the pair of thin spikes at d_e + d_i ∼3.2 Å in Fig. 7(n). The comparatively greater percentage contribution from interatomic contacts such as C⋯O/O⋯C and Cl⋯Cl to the surface of (I) and Br⋯H/H⋯Br and C⋯N/N⋯C to that of (II) as well as smaller contributions from other contacts as summarized in Table 5, show negligible effect on the respective molecular packing due to the interatomic separations being equal to or exceeding the respective sums of the van der Waals radii.

5. Energy frameworks

The pairwise interaction energies between the molecules in the crystals of (I) and (II) were calculated by summing up four energy components, these being the electrostatic (E_ele), polarization (E_pol), dispersion (E_dis) and exchange-repulsion (E_rep) terms (Turner et al., 2017). The energies were obtained using the wavefunctions calculated at the B3LYP/6–31 G(d,p) and HF/STO-3 G levels theory for (I) and (II), respectively. The individual energy components as well as the total interaction energy were calculated relative to a reference molecule. The nature and strength of the energies for the key identified intermolecular interactions are summarized in Table 6.

Table 6
Summary of interaction energies (kJ mol⁻¹) calculated for (I) and (II)

Contact	R (Å)	E_ele	E_pol	E_dis	E_rep	E_tot
(I)^a
C15—H15B⋯O2ⁱ	12.93	−12.5	−2.7	−13.1	9.1	−21.1
C14—Cl2 ⋯π(C9–C14)ⁱⁱ +	4.36	−4.7	−3.5	−66.8	36.9	−43.0
N2 ⋯H8ⁱⁱⁱ
H13⋯H15A′^iv	13.64	−0.6	−0.6	−9.7	5.5	−6.1
(II)^b
Br1⋯O1ⁱ	10.21	−4.6	−0.9	−7.2	5.4	−7.5
Cl2⋯H7ⁱⁱ	8.69	−3.9	−0.7	−4.2	0.7	−3.1
Notes: (a) Symmetry operations for (I): (i) −1 + x, y, z; (ii) − $[{1\over 2}]$ + x, $[{5\over 2}]$ − y, − z; (iii) 1 + x, y, z. (b) Symmetry operations for (II): (i) $[{1\over 2}]$ + x, 3 − y, z; (ii) − $[{1\over 2}]$ + x, 1 − y, z.

It is apparent from the interaction energies calculated for (I) that the dispersion component, E_dis, makes the major contribution to the C—Cl⋯π and N⋯H contacts and these are dominant in the molecular packing. By contrast, the C—H⋯O interaction has nearly equal contributions from the electrostatic component, E_ele, and E_dis. The small value of the interaction energy corresponding to the short H⋯H contact arises primarily from E_dis. The intermolecular Br⋯O and Cl⋯H contacts instrumental in the crystal of (II) have small interaction energy values dominated by E_dis.

Fig. 8 represents graphically the magnitudes of intermolecular energies in the form of energy frameworks, which provide a view of the supramolecular architecture of crystals through cylinders joining centroids of molecular pairs by using red, green and blue colour codes for the components E_ele, E_disp and E_tot, respectively. The radius of the cylinder is proportional to the magnitude of the interaction energies which are adjusted to same scale factor of 50 with a cut-off value of 3 kJ mol⁻¹ within 4 × 4 × 4 unit cells. The appearance of the energy frameworks clearly reflect the foregoing discussion, namely the clear dominance of the E_dis terms, especially for (II).

Figure 8
The energy frameworks calculated for (I)

showing the (a) electrostatic potential force, (b) dispersion force and (c) total energy. The energy frameworks were adjusted to the same scale factor of 50 with a cut-off value of 3 kJ mol⁻¹ within 4 × 4 × 4 unit cells. (d)–(f) Equivalent frameworks for (II)

6. Database survey

In a recent contribution describing the structure of the analogue of (I) where the methoxy substituent is absent (Manawar et al., 2019b), i.e. (III), it was noted that crystal structure determinations of molecules with the 2-OH-C₆-C(H)N—NC(H)-C₆ fragment number fewer than ten, and that there is some conformational flexibility in these molecules. This observation is borne out in the present study where there is a disparity of over 25° in the central C7—N1—N2—C8 torsion angle, i.e. −151.0 (3) and 177.8 (6)° for (I) and (II), respectively. These values compare with the equivalent angle of −172.7 (2)° in (III). An overlay diagram for (I)–(III) is shown in Fig. 9: here, the different conformations for (I), cf. (II) and (III), are clearly evident.

Figure 9
Two overlay diagrams of (I)–(III), represented by red, green and blue images, respectively. The molecules have been overlapped so the O1, N1 and C1 atoms are coincident.

7. Synthesis and crystallization

The title compounds were synthesized and characterized as per the procedures reported in the literature (Manawar et al., 2019a). The crystals of (I) and (II) in the form of yellow blocks suitable for the structural study reported here were grown by slow evaporation of their chloroform solutions.

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 7. Carbon-bound H atoms were placed in calculated positions (C—H = 0.93–0.96 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2–1.5U_eq(C). The positions of the O-bound H atoms were refined with O—H = 0.82±0.01 Å, and with U_iso(H) set to 1.5U_eq(O).

Table 7
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₅H₁₂Cl₂N₂O₂	C₁₄H₉BrCl₂N₂O
M_r	323.17	372.04
Crystal system, space group	Orthorhombic, P2₁2₁2₁	Orthorhombic, Pca2₁
Temperature (K)	296	296
a, b, c (Å)	4.3556 (2), 12.8548 (4), 25.9904 (9)	16.4510 (12), 4.4314 (3), 20.0523 (15)
V (Å³)	1455.21 (10)	1461.83 (18)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.45	3.17
Crystal size (mm)	0.30 × 0.25 × 0.25	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.557, 0.746	0.398, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	48935, 3751, 2909	39831, 3569, 2150
R_int	0.070	0.108
(sin θ/λ)_max (Å⁻¹)	0.678	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.099, 1.02	0.038, 0.082, 1.00
No. of reflections	3751	3569
No. of parameters	194	184
No. of restraints	1	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.25	0.30, −0.59
Absolute structure	Flack x determined using 1004 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).	Flack x determined using 829 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013).
Absolute structure parameter	0.12 (3)	0.003 (7)
Computer programs: APEX2 and SAINT (Bruker, 2004), SIR92 (Altomare et al., 1994 ), SHELXL2014/7 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2003762; 2003761

Crystal structure: contains datablock . DOI: https://doi.org/10.1107/S2056989020006416/hb7915sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020006416/hb7915Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989020006416/hb7915IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020006416/hb7915Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989020006416/hb7915IIsup5.cml

checkCIF report

Computing details top

For both structures, 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: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

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

Crystal data top

C₁₅H₁₂Cl₂N₂O₂	D_x = 1.475 Mg m⁻³
M_r = 323.17	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 7669 reflections
a = 4.3556 (2) Å	θ = 2.8–20.9°
b = 12.8548 (4) Å	µ = 0.45 mm⁻¹
c = 25.9904 (9) Å	T = 296 K
V = 1455.21 (10) Å³	Block, yellow
Z = 4	0.30 × 0.25 × 0.25 mm
F(000) = 664

Data collection top

Bruker Kappa APEXII CCD diffractometer	2909 reflections with I > 2σ(I)
Radiation source: X-ray tube	R_int = 0.070
ω and φ scan	θ_max = 28.8°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −5→5
T_min = 0.557, T_max = 0.746	k = −17→17
48935 measured reflections	l = −34→35
3751 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0465P)² + 0.2295P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3751 reflections	Δρ_max = 0.16 e Å⁻³
194 parameters	Δρ_min = −0.25 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1004 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.12 (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	0.5635 (2)	0.58257 (6)	0.17813 (3)	0.0639 (2)
Cl2	−0.1091 (2)	0.85695 (7)	0.29187 (3)	0.0635 (2)
O1	0.0486 (6)	1.03357 (16)	0.07165 (7)	0.0526 (5)
H1O	0.076 (10)	0.990 (2)	0.0947 (10)	0.079*
O2	−0.0282 (6)	1.13830 (16)	−0.01337 (7)	0.0580 (6)
N1	0.2888 (6)	0.86954 (18)	0.11908 (9)	0.0462 (6)
N2	0.3817 (6)	0.80405 (19)	0.15969 (9)	0.0511 (6)
C1	0.3847 (6)	0.9094 (2)	0.03056 (9)	0.0407 (6)
C2	0.1975 (6)	0.9977 (2)	0.02967 (9)	0.0406 (6)
C3	0.1588 (7)	1.0536 (2)	−0.01676 (10)	0.0436 (6)
C4	0.3053 (7)	1.0193 (2)	−0.06085 (10)	0.0529 (8)
H4	0.280990	1.055923	−0.091441	0.063*
C5	0.4876 (8)	0.9312 (3)	−0.05996 (11)	0.0577 (8)
H5	0.581625	0.908278	−0.090022	0.069*
C6	0.5300 (8)	0.8777 (2)	−0.01501 (11)	0.0531 (7)
H6	0.656910	0.819478	−0.014652	0.064*
C7	0.4354 (7)	0.8510 (2)	0.07726 (10)	0.0454 (6)
H7	0.580111	0.797798	0.077020	0.054*
C8	0.1755 (7)	0.7862 (2)	0.19229 (10)	0.0433 (6)
H8	−0.017552	0.815862	0.188063	0.052*
C9	0.2348 (6)	0.7189 (2)	0.23722 (10)	0.0384 (6)
C10	0.4098 (7)	0.6277 (2)	0.23543 (10)	0.0442 (6)
C11	0.4597 (8)	0.5674 (2)	0.27870 (12)	0.0559 (8)
H11	0.578168	0.507359	0.276454	0.067*
C12	0.3337 (8)	0.5965 (3)	0.32511 (12)	0.0597 (8)
H12	0.370349	0.556547	0.354312	0.072*
C13	0.1540 (8)	0.6841 (3)	0.32858 (11)	0.0543 (8)
H13	0.064794	0.702856	0.359734	0.065*
C14	0.1081 (7)	0.7439 (2)	0.28499 (10)	0.0439 (6)
C15	−0.0503 (10)	1.2040 (3)	−0.05738 (12)	0.0743 (11)
H15A	0.146096	1.235029	−0.064168	0.111*
H15B	−0.198696	1.257741	−0.051006	0.111*
H15C	−0.113212	1.163644	−0.086601	0.111*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0822 (6)	0.0538 (4)	0.0555 (4)	0.0136 (4)	0.0063 (4)	−0.0055 (4)
Cl2	0.0727 (5)	0.0550 (4)	0.0628 (5)	0.0050 (4)	0.0086 (4)	−0.0072 (4)
O1	0.0699 (14)	0.0525 (12)	0.0353 (10)	0.0110 (11)	0.0077 (10)	0.0009 (8)
O2	0.0781 (15)	0.0535 (12)	0.0425 (11)	0.0107 (12)	0.0016 (10)	0.0082 (9)
N1	0.0520 (14)	0.0456 (13)	0.0412 (13)	−0.0021 (11)	−0.0001 (11)	0.0106 (10)
N2	0.0489 (13)	0.0557 (14)	0.0486 (13)	0.0001 (12)	−0.0027 (12)	0.0156 (11)
C1	0.0438 (14)	0.0426 (14)	0.0356 (13)	−0.0066 (12)	0.0008 (11)	−0.0029 (11)
C2	0.0476 (15)	0.0438 (14)	0.0303 (12)	−0.0066 (12)	0.0019 (11)	−0.0054 (11)
C3	0.0493 (15)	0.0448 (15)	0.0366 (13)	−0.0063 (13)	−0.0020 (12)	−0.0002 (11)
C4	0.0604 (19)	0.066 (2)	0.0325 (14)	−0.0094 (16)	0.0021 (13)	0.0015 (14)
C5	0.064 (2)	0.0714 (19)	0.0377 (15)	−0.0019 (18)	0.0109 (14)	−0.0091 (14)
C6	0.0553 (17)	0.0555 (17)	0.0484 (16)	−0.0004 (15)	0.0075 (14)	−0.0117 (13)
C7	0.0469 (16)	0.0408 (14)	0.0485 (15)	−0.0024 (13)	−0.0020 (13)	0.0001 (12)
C8	0.0494 (16)	0.0414 (14)	0.0390 (14)	−0.0027 (13)	−0.0062 (12)	0.0021 (11)
C9	0.0406 (13)	0.0377 (13)	0.0370 (13)	−0.0076 (11)	−0.0051 (11)	0.0022 (10)
C10	0.0472 (15)	0.0433 (14)	0.0420 (14)	−0.0030 (13)	−0.0037 (13)	0.0007 (12)
C11	0.0602 (18)	0.0476 (16)	0.0600 (18)	0.0029 (15)	−0.0070 (15)	0.0143 (14)
C12	0.066 (2)	0.065 (2)	0.0481 (17)	−0.0039 (17)	−0.0051 (16)	0.0233 (15)
C13	0.0587 (18)	0.069 (2)	0.0355 (14)	−0.0093 (16)	−0.0006 (13)	0.0059 (14)
C14	0.0456 (15)	0.0442 (14)	0.0419 (14)	−0.0082 (12)	−0.0026 (13)	−0.0016 (12)
C15	0.098 (3)	0.072 (2)	0.0529 (19)	0.014 (2)	−0.001 (2)	0.0195 (17)

Geometric parameters (Å, º) top

Cl1—C10	1.733 (3)	C5—H5	0.9300
Cl2—C14	1.743 (3)	C6—H6	0.9300
O1—C2	1.350 (3)	C7—H7	0.9300
O1—H1O	0.828 (13)	C8—C9	1.476 (4)
O2—C3	1.362 (4)	C8—H8	0.9300
O2—C15	1.425 (3)	C9—C10	1.399 (4)
N1—C7	1.283 (3)	C9—C14	1.396 (4)
N1—N2	1.409 (3)	C10—C11	1.383 (4)
N2—C8	1.256 (4)	C11—C12	1.377 (4)
C1—C2	1.398 (4)	C11—H11	0.9300
C1—C6	1.403 (4)	C12—C13	1.374 (5)
C1—C7	1.444 (4)	C12—H12	0.9300
C2—C3	1.415 (4)	C13—C14	1.384 (4)
C3—C4	1.384 (4)	C13—H13	0.9300
C4—C5	1.383 (4)	C15—H15A	0.9600
C4—H4	0.9300	C15—H15B	0.9600
C5—C6	1.369 (4)	C15—H15C	0.9600

C2—O1—H1O	107 (3)	N2—C8—H8	119.5
C3—O2—C15	117.5 (3)	C9—C8—H8	119.5
C7—N1—N2	112.4 (2)	C10—C9—C14	116.0 (2)
C8—N2—N1	114.2 (2)	C10—C9—C8	124.1 (2)
C2—C1—C6	119.0 (3)	C14—C9—C8	120.0 (3)
C2—C1—C7	121.7 (2)	C11—C10—C9	121.9 (3)
C6—C1—C7	119.3 (3)	C11—C10—Cl1	116.8 (2)
O1—C2—C1	123.0 (2)	C9—C10—Cl1	121.3 (2)
O1—C2—C3	117.3 (3)	C10—C11—C12	119.8 (3)
C1—C2—C3	119.8 (2)	C10—C11—H11	120.1
O2—C3—C4	125.7 (3)	C12—C11—H11	120.1
O2—C3—C2	115.0 (2)	C13—C12—C11	120.5 (3)
C4—C3—C2	119.3 (3)	C13—C12—H12	119.8
C3—C4—C5	120.8 (3)	C11—C12—H12	119.8
C3—C4—H4	119.6	C12—C13—C14	118.9 (3)
C5—C4—H4	119.6	C12—C13—H13	120.5
C6—C5—C4	120.2 (3)	C14—C13—H13	120.5
C6—C5—H5	119.9	C13—C14—C9	122.9 (3)
C4—C5—H5	119.9	C13—C14—Cl2	117.3 (2)
C5—C6—C1	120.9 (3)	C9—C14—Cl2	119.8 (2)
C5—C6—H6	119.5	O2—C15—H15A	109.5
C1—C6—H6	119.5	O2—C15—H15B	109.5
N1—C7—C1	122.6 (3)	H15A—C15—H15B	109.5
N1—C7—H7	118.7	O2—C15—H15C	109.5
C1—C7—H7	118.7	H15A—C15—H15C	109.5
N2—C8—C9	121.1 (3)	H15B—C15—H15C	109.5

C7—N1—N2—C8	−151.0 (3)	C6—C1—C7—N1	−173.4 (3)
C6—C1—C2—O1	179.9 (3)	N1—N2—C8—C9	179.9 (2)
C7—C1—C2—O1	−1.0 (4)	N2—C8—C9—C10	−39.5 (4)
C6—C1—C2—C3	−0.3 (4)	N2—C8—C9—C14	141.8 (3)
C7—C1—C2—C3	178.8 (3)	C14—C9—C10—C11	−1.4 (4)
C15—O2—C3—C4	−7.2 (5)	C8—C9—C10—C11	179.7 (3)
C15—O2—C3—C2	173.5 (3)	C14—C9—C10—Cl1	176.3 (2)
O1—C2—C3—O2	−0.2 (4)	C8—C9—C10—Cl1	−2.5 (4)
C1—C2—C3—O2	180.0 (2)	C9—C10—C11—C12	0.4 (5)
O1—C2—C3—C4	−179.6 (3)	Cl1—C10—C11—C12	−177.4 (2)
C1—C2—C3—C4	0.6 (4)	C10—C11—C12—C13	1.1 (5)
O2—C3—C4—C5	−179.2 (3)	C11—C12—C13—C14	−1.5 (5)
C2—C3—C4—C5	0.1 (4)	C12—C13—C14—C9	0.5 (4)
C3—C4—C5—C6	−1.2 (5)	C12—C13—C14—Cl2	−177.6 (3)
C4—C5—C6—C1	1.5 (5)	C10—C9—C14—C13	1.0 (4)
C2—C1—C6—C5	−0.8 (4)	C8—C9—C14—C13	179.9 (3)
C7—C1—C6—C5	−179.9 (3)	C10—C9—C14—Cl2	179.0 (2)
N2—N1—C7—C1	−178.8 (2)	C8—C9—C14—Cl2	−2.1 (4)
C2—C1—C7—N1	7.5 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the (C9–14) ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.83 (3)	1.91 (3)	2.657 (3)	149 (3)
C15—H15B···O2ⁱ	0.96	2.58	3.439 (4)	149
C14—Cl2···Cg1ⁱⁱ	1.74 (1)	3.70 (1)	3.765 (3)	79 (1)

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

4-Bromo-2-({(E)-2-[(E)-2,6-dichlorobenzylidene]hydrazin-1-ylidene}methyl)phenol (II) top

Crystal data top

C₁₄H₉BrCl₂N₂O	D_x = 1.690 Mg m⁻³
M_r = 372.04	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 4698 reflections
a = 16.4510 (12) Å	θ = 2.5–18.6°
b = 4.4314 (3) Å	µ = 3.17 mm⁻¹
c = 20.0523 (15) Å	T = 296 K
V = 1461.83 (18) Å³	Block, yellow
Z = 4	0.30 × 0.20 × 0.20 mm
F(000) = 736

Data collection top

Bruker Kappa APEXII CCD diffractometer	2150 reflections with I > 2σ(I)
Radiation source: X-ray tube	R_int = 0.108
ω and φ scan	θ_max = 28.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −21→21
T_min = 0.398, T_max = 0.746	k = −5→5
39831 measured reflections	l = −26→26
3569 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.024P)² + 0.3263P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
3569 reflections	Δρ_max = 0.30 e Å⁻³
184 parameters	Δρ_min = −0.59 e Å⁻³
2 restraints	Absolute structure: Flack x determined using 829 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.003 (7)

Special details top

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

	x	y	z	U_iso*/U_eq
Br1	1.17606 (4)	1.58575 (14)	0.09985 (4)	0.0617 (2)
Cl1	0.95249 (10)	0.2117 (4)	0.37299 (9)	0.0682 (5)
Cl2	0.63270 (11)	0.3504 (5)	0.30362 (11)	0.0830 (6)
O1	0.8392 (2)	1.0502 (9)	0.1011 (4)	0.0618 (10)
H1O	0.830 (5)	0.931 (14)	0.132 (3)	0.093*
N1	0.8804 (3)	0.7671 (11)	0.2128 (2)	0.0459 (12)
N2	0.8764 (3)	0.5871 (12)	0.2711 (3)	0.0583 (14)
C1	0.9706 (3)	1.0963 (12)	0.1535 (3)	0.0395 (13)
C2	0.9148 (3)	1.1674 (11)	0.1024 (4)	0.0461 (13)
C3	0.9379 (4)	1.3636 (14)	0.0523 (3)	0.0568 (18)
H3	0.901334	1.412779	0.018641	0.068*
C4	1.0152 (4)	1.4872 (14)	0.0519 (3)	0.0557 (17)
H4	1.029972	1.620146	0.018149	0.067*
C5	1.0700 (3)	1.4155 (11)	0.1008 (5)	0.0454 (12)
C6	1.0480 (4)	1.2229 (13)	0.1514 (3)	0.0450 (15)
H6	1.085312	1.176591	0.184695	0.054*
C7	0.9496 (4)	0.8944 (13)	0.2077 (3)	0.0458 (14)
H7	0.988542	0.855756	0.240209	0.055*
C8	0.8102 (4)	0.4636 (14)	0.2809 (3)	0.0490 (15)
H8	0.769260	0.494996	0.249745	0.059*
C9	0.7918 (4)	0.2707 (15)	0.3384 (3)	0.0441 (15)
C10	0.8495 (4)	0.1490 (13)	0.3823 (3)	0.0471 (15)
C11	0.8267 (4)	−0.0303 (14)	0.4358 (3)	0.0602 (17)
H11	0.866252	−0.109704	0.463911	0.072*
C12	0.7460 (5)	−0.0916 (16)	0.4478 (4)	0.073 (2)
H12	0.731322	−0.211614	0.483867	0.087*
C13	0.6868 (4)	0.0252 (16)	0.4062 (4)	0.066 (2)
H13	0.632125	−0.015359	0.413876	0.079*
C14	0.7104 (4)	0.2044 (17)	0.3525 (3)	0.0525 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0534 (4)	0.0635 (3)	0.0682 (4)	−0.0060 (3)	0.0127 (4)	−0.0003 (5)
Cl1	0.0462 (9)	0.0986 (13)	0.0599 (10)	0.0036 (9)	−0.0082 (8)	0.0084 (10)
Cl2	0.0440 (10)	0.1108 (15)	0.0943 (14)	−0.0090 (11)	−0.0136 (10)	0.0087 (13)
O1	0.048 (2)	0.068 (3)	0.069 (3)	−0.003 (2)	−0.015 (3)	0.010 (3)
N1	0.047 (3)	0.044 (3)	0.047 (3)	0.000 (3)	−0.004 (2)	−0.001 (2)
N2	0.048 (4)	0.067 (4)	0.060 (4)	−0.011 (3)	−0.011 (3)	0.019 (3)
C1	0.043 (3)	0.036 (3)	0.039 (3)	0.003 (3)	0.001 (3)	−0.004 (3)
C2	0.046 (3)	0.044 (3)	0.048 (3)	0.005 (2)	−0.005 (4)	−0.001 (4)
C3	0.063 (5)	0.054 (4)	0.053 (4)	0.009 (3)	−0.013 (3)	0.005 (3)
C4	0.068 (5)	0.049 (4)	0.050 (4)	0.001 (3)	0.004 (4)	0.009 (3)
C5	0.053 (3)	0.038 (3)	0.045 (3)	0.003 (3)	0.006 (4)	−0.003 (4)
C6	0.043 (4)	0.046 (3)	0.046 (4)	0.004 (3)	−0.001 (3)	−0.002 (3)
C7	0.042 (4)	0.049 (3)	0.047 (3)	0.004 (3)	−0.005 (3)	0.002 (3)
C8	0.041 (4)	0.059 (4)	0.047 (4)	0.002 (3)	−0.007 (3)	0.000 (3)
C9	0.044 (4)	0.046 (4)	0.042 (4)	−0.008 (3)	−0.001 (3)	−0.006 (3)
C10	0.048 (4)	0.050 (4)	0.044 (3)	−0.004 (3)	0.001 (3)	−0.008 (3)
C11	0.072 (5)	0.063 (4)	0.046 (4)	−0.004 (4)	−0.005 (4)	−0.002 (3)
C12	0.081 (6)	0.078 (5)	0.058 (4)	−0.021 (5)	0.014 (5)	−0.003 (4)
C13	0.054 (4)	0.080 (5)	0.063 (4)	−0.023 (4)	0.012 (4)	−0.010 (4)
C14	0.046 (4)	0.065 (4)	0.047 (4)	−0.011 (4)	0.005 (3)	−0.007 (3)

Geometric parameters (Å, º) top

Br1—C5	1.901 (5)	C4—H4	0.9300
Cl1—C10	1.727 (6)	C5—C6	1.375 (10)
Cl2—C14	1.736 (8)	C6—H6	0.9300
O1—C2	1.349 (7)	C7—H7	0.9300
O1—H1O	0.827 (14)	C8—C9	1.466 (9)
N1—C7	1.276 (7)	C8—H8	0.9300
N1—N2	1.417 (7)	C9—C10	1.402 (9)
N2—C8	1.234 (7)	C9—C14	1.400 (8)
C1—C6	1.393 (8)	C10—C11	1.388 (9)
C1—C2	1.411 (9)	C11—C12	1.375 (10)
C1—C7	1.448 (8)	C11—H11	0.9300
C2—C3	1.382 (9)	C12—C13	1.384 (11)
C3—C4	1.384 (9)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.392 (10)
C4—C5	1.369 (10)	C13—H13	0.9300

C2—O1—H1O	114 (6)	C1—C7—H7	118.5
C7—N1—N2	110.9 (5)	N2—C8—C9	124.5 (6)
C8—N2—N1	114.9 (5)	N2—C8—H8	117.8
C6—C1—C2	118.8 (5)	C9—C8—H8	117.8
C6—C1—C7	119.3 (5)	C10—C9—C14	116.1 (6)
C2—C1—C7	121.9 (5)	C10—C9—C8	125.3 (6)
O1—C2—C3	118.8 (6)	C14—C9—C8	118.6 (6)
O1—C2—C1	121.9 (6)	C11—C10—C9	121.5 (6)
C3—C2—C1	119.3 (5)	C11—C10—Cl1	116.2 (5)
C2—C3—C4	120.4 (6)	C9—C10—Cl1	122.3 (5)
C2—C3—H3	119.8	C12—C11—C10	120.6 (7)
C4—C3—H3	119.8	C12—C11—H11	119.7
C5—C4—C3	120.6 (6)	C10—C11—H11	119.7
C5—C4—H4	119.7	C11—C12—C13	120.0 (7)
C3—C4—H4	119.7	C11—C12—H12	120.0
C4—C5—C6	119.9 (5)	C13—C12—H12	120.0
C4—C5—Br1	120.4 (6)	C12—C13—C14	118.9 (7)
C6—C5—Br1	119.7 (6)	C12—C13—H13	120.6
C5—C6—C1	120.9 (6)	C14—C13—H13	120.6
C5—C6—H6	119.5	C13—C14—C9	122.9 (6)
C1—C6—H6	119.5	C13—C14—Cl2	116.3 (6)
N1—C7—C1	123.1 (6)	C9—C14—Cl2	120.8 (5)
N1—C7—H7	118.5

C7—N1—N2—C8	177.8 (6)	N1—N2—C8—C9	−179.2 (6)
C6—C1—C2—O1	179.3 (6)	N2—C8—C9—C10	−13.9 (10)
C7—C1—C2—O1	−0.2 (9)	N2—C8—C9—C14	164.6 (7)
C6—C1—C2—C3	−1.0 (8)	C14—C9—C10—C11	1.0 (9)
C7—C1—C2—C3	179.4 (5)	C8—C9—C10—C11	179.5 (6)
O1—C2—C3—C4	−179.7 (6)	C14—C9—C10—Cl1	−179.2 (5)
C1—C2—C3—C4	0.6 (9)	C8—C9—C10—Cl1	−0.6 (9)
C2—C3—C4—C5	0.5 (10)	C9—C10—C11—C12	−0.6 (10)
C3—C4—C5—C6	−1.1 (10)	Cl1—C10—C11—C12	179.5 (5)
C3—C4—C5—Br1	179.9 (5)	C10—C11—C12—C13	0.1 (10)
C4—C5—C6—C1	0.6 (9)	C11—C12—C13—C14	−0.1 (11)
Br1—C5—C6—C1	179.6 (4)	C12—C13—C14—C9	0.5 (11)
C2—C1—C6—C5	0.4 (8)	C12—C13—C14—Cl2	−178.5 (6)
C7—C1—C6—C5	180.0 (5)	C10—C9—C14—C13	−0.9 (10)
N2—N1—C7—C1	−178.9 (5)	C8—C9—C14—C13	−179.6 (6)
C6—C1—C7—N1	−179.3 (6)	C10—C9—C14—Cl2	178.0 (5)
C2—C1—C7—N1	0.3 (9)	C8—C9—C14—Cl2	−0.6 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.83 (6)	1.96 (6)	2.655 (8)	141 (7)

Selected geometric parameters (Å, °) in (I) and (II) top

Parameter	(I)	(II)
N1—N2	1.409 (3)	1.417 (7)
C7—N1	1.283 (3)	1.276 (7)
C8—N2	1.256 (4)	1.234 (7)
N2—N1—C7	112.4 (2)	110.9 (5)
N1—N2—C8	114.2 (2)	114.9 (5)
C1—C7—N1	122.6 (3)	123.1 (6)
C9—C8—N2	121.1 (3)	124.5 (6)
C7—N1—N2—C8	-151.0 (3)	177.8 (6)
C1—C7—N1—N2	-178.8 (2)	-178.9 (5)
C9—C8—N2—N1	179.9 (2)	-179.2 (6)
(C7,N1,N2,C8)/(C1–C6)	20.9 (4)	15.6 (5)
(C7,N1,N2,C8)/(C9–C14)	23.1 (4)	1.5 (6)
(C1–C6)/(C9–C14)	2.41 (17)	15.5 (3)

Summary of short interatomic contacts (Å) for (I) and (II)^a top

Contact	Distance	Symmetry operation
(I)
H12···O1	2.59	-x, 1/2 + y, 1/2 - z
H8···N2	2.58	-1 + x, y, z
H13···H15A	2.30	1/2 + x, 2 - y, 1/2 + z
(II)
Br1···O1	3.132 (4)	1/2 + x, 3 - y, z
Cl2···H7	2.69	-1/2 + x, 1 - y, z

Notes: (a) The interatomic distances are calculated in Crystal Explorer (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) and (II) top

Contact		Percentage contribution
	(I)	(II)
H···H	31.1	21.1
O···H/H···O	9.1	4.3
C···H/H···C	16.4	13.8
Cl···H/H···Cl	17.3	23.1
N···H/H···N	8.0	0.4
C···Cl/Cl···C	6.2	1.0
C···C	4.6	7.2
C···O/O···C	3.7	0.1
C···N/N···C	0.0	7.1
Cl···Cl	3.5	2.7
Cl···N/N···Cl	0.0	0.6
N···O/O···N	0.0	0.1
Br···H/H···Br	–	13.7
Br···O/O···Br	–	2.6
Br···C/C···Br	–	1.8
Br···Cl/Cl···Br	–	0.2
Br···Br	–	0.2

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

Contact	R (Å)	E_ele	E_pol	E_dis	E_rep	E_tot
(I)^a
C15—H15B···O2ⁱ	12.93	-12.5	-2.7	-13.1	9.1	-21.1
C14—Cl2 ···π(C9–C14)ⁱⁱ +	4.36	-4.7	-3.5	-66.8	36.9	-43.0
N2 ···H8ⁱⁱⁱ
H13···H15A'^iv	13.64	-0.6	-0.6	-9.7	5.5	-6.1
(II)^b
Br1···O1ⁱ	10.21	-4.6	-0.9	-7.2	5.4	-7.5
Cl2···H7ⁱⁱ	8.69	-3.9	-0.7	-4.2	0.7	-3.1

Notes: (a) Symmetry operations for (I): (i) -1 + x, y, z; (ii) -1/2 + x, 5/2 - y, - z; (iii) 1 + x, y, z. (b) Symmetry operations for (II): (i) 1/2 + x, 3 - y, z; (ii) -1/2 + x, 1 - y, z.

Footnotes

‡Additional correspondence author, e-mail: drmks2000hotmail.com.

Acknowledgements

The authors thank the Department of Chemistry, Saurashtra University, Rajkot, Gujarat, India, for access to the chemical synthesis laboratory and to the Sophisticated Analytical Instrumentation Centre (SAIC), Tezpur, Assam, India for providing the X-ray intensity data for (I) and (II).

Funding information

Crystallographic research at Sunway University is supported by Sunway University Sdn Bhd (grant No. STR-RCTR-RCCM-001-2019).

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