Crystal structures and Hirshfeld surface analyses of methyl (2Z)-(4-bromo­phen­yl)[2-(4-methyl­phen­yl)hydrazinyl­idene]acetate, methyl (2Z)-(4-bromophen­yl)[2-(3,5-di­methyl­phen­yl)hydrazinyl­idene]acetate, methyl (2Z)-[2-(4-meth­oxy­phen­yl)hydrazinyl­idene](3-nitro­phen­yl)acetate, methyl (2E)-(4-chlorophen­yl)(2-phenyl­hydrazinyl­idene)acetate and methyl (2Z)-[2-(4-bromo­phen­yl)hydrazinylidene](4-chloro­phen­yl)acetate

Shikhaliyev, N.Q.; Babazade, A.A.; Atakishiyeva, G.T.; Shikhaliyeva, I.M.; Maharramov, A.M.; Khrustalev, V.N.; Atioğlu, Z.; Akkurt, M.; Bhattarai, A.

doi:10.1107/S2056989025002051

research communications

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ISSN: 2056-9890

Volume 81| Part 4| April 2025| Pages 314-323

https://doi.org/10.1107/S2056989025002051

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Crystal structures and Hirshfeld surface analyses of methyl (2Z)-(4-bromophenyl)[2-(4-methylphenyl)hydrazinylidene]acetate, methyl (2Z)-(4-bromophenyl)[2-(3,5-dimethylphenyl)hydrazinylidene]acetate, methyl (2Z)-[2-(4-methoxyphenyl)hydrazinylidene](3-nitrophenyl)acetate, methyl (2E)-(4-chlorophenyl)(2-phenylhydrazinylidene)acetate and methyl (2Z)-[2-(4-bromophenyl)hydrazinylidene](4-chlorophenyl)acetate

Namiq Q. Shikhaliyev,^a Aliyar A. Babazade,^b Gulnar T. Atakishiyeva,^b Irada M. Shikhaliyeva,^b Abel M. Maharramov,^b Victor N. Khrustalev,^c,^d Zeliha Atioğlu,^e Mehmet Akkurt ^f and Ajaya Bhattarai ^g ^*

^aDepartment of Chemical Engineering, Baku Engineering University, Khirdalan City, 120 AZ0101 Hasan Aliyev Street, Baku, Azerbaijan, ^bOrganic Chemistry Department, Baku State University, Z. Khalilov str. 23, AZ 1148 Baku, Azerbaijan, ^cPeoples' Friendship University of Russia (RUDN University), Miklukho-Maklay St. 6, Moscow, 117198, Russian Federation, ^dN. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prosp. 47, Moscow, 119991, Russian Federation, ^eDepartment of Aircraft Electrics and Electronics, School of Applied Sciences, Cappadocia University, Mustafapaşa, 50420 Ürgüp, Nevşehir, Türkiye, ^fDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, and ^gDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np

Edited by M. Weil, Vienna University of Technology, Austria (Received 7 January 2025; accepted 4 March 2025; online 14 March 2025)

Molecules of the title compounds, methyl (Z)-2-(4-bromophenyl)-2-[2-(4-methylphenyl)hydrazin-1-ylidene]acetate, C₁₆H₁₅BrN₂O₂, (1), methyl (Z)-2-(4-bromophenyl)-2-[2-(3,5-dimethylphenyl)hydrazin-1-ylidene]acetate, C₁₇H₁₇BrN₂O₂, (2), methyl (Z)-2-[2-(4-methoxyphenyl)hydrazin-1-ylidene]-2-(3-nitrophenyl)acetate, C₁₆H₁₅N₃O₅, (3), and methyl (Z)-2-[2-(4-bromophenyl)hydrazin-1-ylidene]-2-(4-chlorophenyl)acetate, C₁₅H₁₂BrClN₂O₂, (5), adopt a Z configuration with respect to the central C=N bond, while methyl (E)-2-(4-chlorophenyl)-2-(2-phenylhydrazin-1-ylidene)acetate, C₁₅H₁₃ClN₂O₂, (4), adopts an E configuration. The atoms of the phenyl ring of the bromophenyl group of (1) are disordered over two sets of sites with equal occupancies. In the crystal structure of (1), molecules connected by C—H⋯N hydrogen bonds are further linked by C—H⋯π interactions, forming ribbons parallel to [010]. In (2), pairs of molecules are linked by C—H⋯π interactions parallel to [100]. In (3), C—H⋯O hydrogen bonds form ribbons parallel to [010], while in (4), the molecules are bonded together by C—H⋯N, C—H⋯Cl, C—H⋯O and C—H⋯π interactions parallel to [010]. In (5), C—H⋯Br, C—H⋯O and C—H⋯Cl interactions lead to the formation of layers parallel to (002). C—H⋯π interactions also occur between these planes. Hirshfeld surface analyses were performed to investigate and quantify the intermolecular interactions between the molecules of all compounds.

Keywords: crystal structure; esters; hydrogen bonds; C—H⋯π interactions; configuration..

CCDC references: 2428835; 2428834; 2428833; 2428832; 2428831

1. Chemical context

Catalytic olefination of hydrazones is a versatile method for the construction of halogenated alkenes starting from hydrazones (Adonin et al., 2019 ; Bertani et al., 2010 ; Metrangolo & Resnati, 2008 ; Askerova et al., 2024 , Sergeev et al., 2020a ,b ). In the case of the reaction with N-substituted hydrazones the reaction leads to formation of dichlorodiazadienes (Nenajdenko et al., 2017 ). By using carbon tetrabromide for olefination it is possible to prepare dibromosubstituted diazadienes as well (Nenajdenko et al., 2023 ). Recently, these type of building blocks attracted attention for preparation of numerous classes of nitrogen-containing heterocycles with interesting properties (Vitaku et al., 2014 ; Das et al., 2019 ; Sergeev et al., 2020c ; Tsyrenova et al., 2023 ; Safronov et al., 2023 ; Tsyrenova et al., 2020a ,b ). It is particularly important to note that the solvolysis reaction of dichlorodiazadienes simultaneously yields Z and E isomers of arylhydrazones of α-keto esters (Shikhaliyev et al., 2021a ).

In this context, the methanolysis reaction of some dichlorodiazadienes was carried out and the synthesis of arylhydrazo derivatives (1)–(5) of the corresponding α-keto esters was achieved (Fig. 1).

Figure 1
Schematic representation of the synthesis of compounds (1)–(5).

2. Structural commentary

C₁₆H₁₅BrN₂O₂ (1) (Fig. 2) crystallizes in the monoclinic C2/c space group with Z = 8. The atoms of the phenyl ring of the bromophenyl group of (1) are disordered over two sets of sites with equal occupancies. C₁₇H₁₇BrN₂O₂ (2) (Fig. 3) crystallizes with two molecules A and B in the asymmetric unit in the triclinic P $[\overline{1}]$ space group with Z = 4. An overlay fit of molecule B on molecule A of (2) is shown in Fig. 4; the weighted r.m.s. fit of the 22 non-H atoms is 0.268 Å with the major differences in the phenyl groups (C4A–C9A/C4B–C9B and C10A–C15A/C10B–C15B) of molecules A and B. C₁₆H₁₅N₃O₅ (3) (Fig. 5) crystallizes in the monoclinic C2/c space group with Z = 8, C₁₅H₁₃ClN₂O₂ (4) (Fig. 6) crystallizes in the orthorhombic Pbca space group with Z = 8, and C₁₅H₁₂BrClN₂O₂ (5) (Fig. 7) crystallizes in the orthorhombic Pca2₁ space group with Z = 4.

Figure 2
The molecular structure of (1), showing the atom labelling and displacement ellipsoids drawn at the 50% probability level. The phenyl ring atoms of the bromophenyl group of (1) are disordered over two sets of sites with equal occupancies. N2—H2⋯O1 and C9—H9⋯O2 intramolecular hydrogen bonds are shown by dashed lines.

Figure 3
The two molecules, A and B, in the asymmetric unit of (2), showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Figure 4
A least-squares overlay of the two independent molecules A (black) and B (red) of (2).

Figure 5
The molecular structure of (3), showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Figure 6
The molecular structure of (4), showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Figure 7
The molecular structure of (5), showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Molecules (1), (2), (3) and (5) adopt a Z configuration with respect to the central C=N bond, while (4) adopts an E configuration. This also affects intra- and intermolecular hydrogen-bonding and, consequently, the packing arrangement (see next section for details). The molecular shapes of compounds (1), (2) and (5) are stabilized by intramolecular N—H⋯O and C—H⋯O hydrogen bonds (Tables 1, 2 , 5), forming S(6) ring motifs (Bernstein et al., 1995 ), while the stability of molecule (3) is provided only by intramolecular N—H⋯O interactions (Table 3) with the same kind of hydrogen-bonding pattern. In the molecule of (4) intramolecular hydrogen bonds do not occur. In the five molecules, the angles between the phenyl rings connected by the —NH—N=C— bridge are different. The corresponding angle is 44.40 (18)° for (1) for one of the two orientations in the disordered parts and 52.74 (19)° for the other orientation, while the dihedral angle between the disordered phenyl rings in (1) is 83.1 (2)°. In (2), the angle is 32.31 (18)° for molecule A and 45.62 (18)° for molecule B. In (3) it is 51.09 (7)°, in (4) 83.69 (6)° and in (5) 49.9 (3)°. Other bond lengths and angles within the five molecules are in normal ranges and consistent with those of the related compounds described in the Database survey (Section 4).

Table 1
Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.95 (4)	1.93 (4)	2.668 (3)	133 (4)
C9—H9⋯O2	0.95	2.49	2.862 (6)	103
C9A—H9A⋯N1ⁱ	0.95	2.55	3.488 (6)	169
C5A—H5A⋯Cg2ⁱⁱ	0.95	2.85	3.611 (6)	138
C8—H8⋯Cg5ⁱⁱⁱ	0.95	2.81	3.677 (6)	152
C8A—H8A⋯Cg2ⁱ	0.95	2.86	3.607 (6)	136
C16—H16B⋯Cg7ⁱⁱ	0.98	2.74	3.544 (3)	139
Symmetry codes: (i) ; (ii) ; (iii) $[-x+1, y, -z+{\script{1\over 2}}]$ .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2A⋯O1A	1.00 (5)	1.82 (5)	2.631 (4)	136 (4)
N2B—H2B⋯O1B	0.81 (5)	2.03 (5)	2.645 (4)	133 (5)
C9A—H9A⋯O2A	0.95	2.47	2.827 (4)	102
C9B—H9B⋯O2B	0.95	2.58	2.898 (4)	100
C5A—H5A⋯Cg3ⁱ	0.95	2.88	3.637 (4)	137
Symmetry code: (i) .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.86 (2)	1.98 (2)	2.657 (2)	134 (2)
C7—H7⋯O4ⁱ	0.95	2.44	3.245 (2)	142
C12—H12⋯O1ⁱⁱ	0.95	2.52	3.401 (2)	154
Symmetry codes: (i) $[x, -y+2, z+{\script{1\over 2}}]$ ; (ii) .

Table 4
Hydrogen-bond geometry (Å, °) for 4

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯N1ⁱ	0.98	2.55	3.5099 (15)	168
C3—H3C⋯Cl1ⁱⁱ	0.98	2.82	3.6422 (12)	142
C6—H6⋯O1ⁱⁱⁱ	0.95	2.40	3.3113 (15)	161
C15—H15⋯O1^iv	0.95	2.40	3.2759 (14)	153
C14—H14⋯Cg1^v	0	2.80	3.4792 (12)	129
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 5
Hydrogen-bond geometry (Å, °) for 5

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.93 (5)	2.00 (6)	2.666 (4)	127 (4)
C9—H9⋯O2	0.95	2.58	2.953 (6)	103
C11—H11⋯Br1ⁱ	0.95	2.75	3.689 (4)	172
C12—H12⋯O1ⁱⁱ	0.95	2.54	3.479 (4)	168
C14—H14⋯Cl1ⁱⁱⁱ	0.95	2.70	3.616 (4)	161
C8—H8⋯Cg1^iv	0.95	2.70	3.591 (6)	157
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y, z]$ ; (ii) $[x-{\script{1\over 2}}, -y, z]$ ; (iii) $[x-{\script{1\over 2}}, -y+1, z]$ ; (iv) $[-x+2, -y+1, z-{\script{1\over 2}}]$ .

3. Supramolecular features and Hirshfeld surface analysis

In the crystal of (1), non-classical C9A—H9A⋯N1 hydrogen bonds connect adjacent molecules parallel to [010] to form C(5) chains (Table 1; Fig. 8). In addition, molecules are connected by C—H⋯π interactions to form ribbons along the propagation direction (Fig. 9). Significant intermolecular hydrogen bonding is not observed in (2). The molecules are aligned in ribbons parallel to [100] in the (010) plane (Fig. 10) whereby pairs of molecules are formed by C5—H5⋯Cg3 interactions (Table 2; Fig. 11). The crystal structure is consolidated through van der Waals interactions. In the crystal of (3), C7—H7⋯O4 and C12—H12⋯O1 interactions form ribbons along [010] (Table 3; Figs. 12 and 13) , but C—H⋯π interactions are not observed. The crystal structure is consolidated through van der Waals interactions between the ribbons. In the crystal structure of (4), C3—H3B⋯N1, C3—H3C⋯Cl1, C6⋯H6⋯O1 and C15—H15⋯O1 intermolecular interactions connect the molecules under formation of layers parallel to the (001) plane (Table 4; Figs. 14, 15). At the same time, C14—H14⋯Cg1 interactions link the molecules together in the (001) plane along [100] (Fig. 16). The crystal structure is consolidated by van der Waals interactions between the layers. In the crystal structure of (5), C11—H11⋯Br1, C12—H12⋯O1 and C14—H14⋯Cl1 intermolecular hydrogen bonds form layers parallel to (002) (Table 5; Figs. 17, 18). C8—H8⋯Cg1 interactions also take place between these planes and consolidate the crystal structure (Fig. 19).

Figure 8
View of the intra- and intermolecular hydrogen bonds of (1) along the b axis.

Figure 9
View of the C—H⋯π interactions of (1) in the unit cell along the b axis.

Figure 10
A general view of the molecular packing of (2) in the unit cell.

Figure 11
A view of the C—H⋯π interactions of (2) along the c axis.

Figure 12
A view of the packing of (3) along the a axis.

Figure 13
A view of the packing of (3) along the c axis.

Figure 14
A view of the hydrogen bonds present in (4) in a view along the b axis.

Figure 15
A view of the hydrogen bonds present in (4) in a view along the c axis.

Figure 16
A view of the C—H⋯π contacts of (4) along the a axis.

Figure 17
A view of the hydrogen bonds present in (5) in a view along the a axis.

Figure 18
A view of the hydrogen bonds present in (5) in a view along the c axis.

Figure 19
A view of the C—H⋯π contacts of (5) in a view along the a axis.

To quantify the intermolecular interactions between the molecules in (1)–(5) in their respective crystal structures, Hirshfeld surfaces (Fig. 20) and their corresponding two-dimensional fingerprint plots (Fig. 21) were calculated with CrystalExplorer (Spackman et al., 2021 ). The dominant interactions in all compounds are H⋯H [(1): 59.9%, (2A): 41.8%, (2B): 46.4, (3): 38.9%, (4): 39.0% and (5): 26.3%] and C⋯H/H⋯C [(1): 13.3%, (2A): 26.8%, (2B): 21.0, (3): 16.0%, (4): 21.4% and (5): 25.1%]. In (3) and (4), O⋯H/H⋯O interactions are also important interactions [(3): 28.5% and (4): 12.7%]. Br⋯H/H⋯Br in Br-containing compounds (1), (2) and (5) [(1): 12.5%, (2A): 15.7%, (2B): 15.6% and (5): 15.8%] and Cl⋯H/H⋯Cl interactions in Cl-containing compound (5) [(5): 14.5%] also contribute to the stability of the crystal structures. The full percentage contributions of interatomic contacts calculated for each compound are given in Table 6. The presence of different functional groups in the compounds leads to some differences in the remaining weak interactions.

Table 6
Percentage contributions of interatomic contacts to the Hirshfeld surface for compounds 1, 2, 3, 4 and 5

Contact	1	2A	3B	3	4	5
H⋯H	59.9	41.8	46.4	38.9	39.0	26.3
C⋯H/H⋯C	13.3	26.8	21.0	16.0	21.4	25.1
Br⋯H/H⋯Br	12.5	15.7	15.6	—	—	15.8
O⋯H/H⋯O	6.2	6.9	8.5	28.5	12.7	5.6
N⋯H/H⋯N	2.0	3.2	3.2	2.4	5.7	1.9
N⋯C/C⋯N	2.2	1.7	1.7	3.4	2.0	1.0
C⋯C	1.4	1.1	1.1	3.6	1.2	2.3
O⋯C/C⋯O	1.1	1.4	1.4	3.9	1.4	3.9
O⋯N/N⋯O	0.9	0.7	0.7	1.9	—	—
O⋯O	—	0.1	—	0.9	0.2	—
N⋯N	—	—	—	0.4	—	1.5
Br⋯O/O⋯Br	0.5	—	—	—	—	—
Br⋯C/C⋯Br	0.1	0.5	0.2	—	—	0.6
Br⋯Br	—	—	—	—	—	0.1
Cl⋯H/H⋯Cl	—	—	—	—	—	14.5
Cl⋯O/O⋯Cl	—	—	—	—	—	1.3

Figure 20
Front (a) and back (b) views of the three-dimensional Hirshfeld surface of the molecules (1), (2), (3), (4) and (5), with some C—H⋯O, C—H⋯Br, C—H⋯Cl and O—H⋯O hydrogen bonds shown as dashed lines.

Figure 21
The full two-dimensional fingerprint plots for (1), (2), (3), (4) and (5), showing (a) H⋯H, (b) C⋯H/H⋯C, (c) Cl⋯H/H⋯Cl or Br⋯H/H⋯Br and (d) O⋯H/H⋯O interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ) for structures with the (1E)-1-benzylidene-2-phenylhydrazine moiety revealed that the three most similar compounds are KOGYEN (Akhramez et al., 2019 ), UREKIM (Jasinski et al., 2011 ) and SOJQAL (Sultan et al., 2014 ).

KOGYEN crystallizes in the monoclinic Cc space group with Z = 4, UREKIM in the triclinic P $[\overline{1}]$ space group with Z = 2, and SOJQAL in the orthorhombic P2₁2₁2₁ space group with Z = 4.

In KOGYEN, molecules are linked by a C—H⋯π-phenyl interaction, forming zigzag chains propagating along [100]. The N—H group does not participate in hydrogen bonding but is directed towards the phenyl ring of an adjacent molecule, so linking the chains via weak N—H⋯π interactions into the three-periodic structure. In UREKIM, crystal packing is stabilized by N—H⋯O hydrogen bonds, weak C—H⋯O and C—H⋯F intermolecular interactions and centroid-to-centroid π-ring stacking interactions. In SOJQAL, molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds into zigzag chains propagating along [100].

5. Synthesis and crystallization

Compounds (1), (2) (3), (4) and (5) were synthesized according to a literature protocol (Shikhaliyev et al., 2021b ). For the procedure, 10 mg of the corresponding dichlorodiazadiene and 30 ml of methanol were mixed and stirred for 2 h. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and dichloromethane (1/1 v/v), and corresponding ethers were obtained as polycrystalline yellow solids.

Methyl (2Z)-(4-bromophenyl)[2-(4-methylphenyl)hydrazinylidene]acetate (1): yield 75%; m.p. 370 K. ¹H NMR (300 MHz, chloroform-d, ppm) δ 12.48 (s, 1H, –NH), 7.53 (d, J = 2.8 Hz, 4H, Ar), 7.19 (t, J = 7.0 Hz, 4H, Ar), 3.89 (s, 3H, –OCH₃), 2.34 (s, 3H, --CH₃). ¹³C NMR (75 MHz, CDCl₃, ppm) δ 140.8, 140.6, 135.4, 132.5, 131.0, 130.1, 129.9, 121.5, 114.3, 114.1, 51.7, 20.8

Methyl (2Z)-(4-bromo-phenyl)[2-(3,5-dimethylphenyl)hydrazinylidene]acetate (2): yield 37%; m.p. 383 K. ¹H NMR (300 MHz, chloroform-d, ppm) δ 12.44 (s, 1H, –NH), 7.54 (s, 4H, Ar), 6.93 (s, 2H, Ar), 6.71 (s, 1H, Ar), 3.89 (s, 3H, –OCH₃) , 2.34 (s, 6H, –CH₃,). ¹³C NMR (75 MHz, chloroform-d, ppm) δ 163.8, 142.8, 139.2, 135.4, 131.0, 130.2, 126.0, 124.8, 121.6, 112.2, 51.8, 21.4.

Methyl (2Z)-[2-(4-methoxyphenyl)hydrazinylidene](3-nitrophenyl)acetate (3): yield 63%; m.p. 375.18 K. ¹H NMR (300 MHz, chloroform-d, ppm) δ 12.67 (s, 1H, –NH), 8.55 (s, 1H, Ar), 8.14 (dd, J = 8.2, 1.3 Hz, 1H, Ar), 8.01 (d, J = 7.9 Hz, 1H, Ar), 7.53 (t, J = 8.0 Hz, 1H, Ar), 7.27 (d, J = 2.1 Hz, 1H, Ar), 7.25 (d, J = 2.0 Hz, 1H, Ar), 6.96–6.89 (m, 2H, Ar), 3.92 (s, 3H, –OCH₃), 3.82 (s, 3H, –OCH₃). ¹³C NMR (75 MHz, CDCl₃, ppm) δ 163.7, 156.2, 148.0, 138.2, 136.3, 134.1, 128.6, 123.6, 123.2, 121.7, 115.8, 114.8, 55.6, 51.9.

Methyl (2E)-(4-chloro-phenyl)(2-phenylhydrazinylidene)acetate (4): yield 63%; m.p. 375 K. ¹H NMR (300 MHz, chloroform-d, ppm) δ 8.07 (s, 1H, –NH), 7.55 (d, J = 8.4 Hz, 2H, Ar), 7.30 (dd, J = 7.8, 5.4 Hz, 4H, Ar), 7.16 (d, J = 7.7 Hz, 2H, Ar), 7.01 (t, J = 7.3 Hz, 1H, Ar), 3.88 (s, 3H, –OCH₃). ¹³C NMR (75 MHz, CDCl₃) δ 163.8, 142.9, 134.8, 133.5, 129.8, 129.4, 128.0, 126.4, 122.8, 114.3, 77.5, 77.0, 76.7, 76.6, 51.8.

Methyl (2Z)-[2-(4-bromophenyl)-hydrazinylidene](4-chlorophenyl)acetate (5): yield 42%; m.p. 382 K. ¹H NMR (300 MHz, chloroform-d, ppm) δ 12.43 (s, 1H, –NH), 7.58 (d, J = 8.3 Hz, 2H, Ar), 7.44 (d, J = 8.4 Hz, 2H, Ar), 7.37 (d, J = 8.2 Hz, 2H, Ar), 7.16 (d, J = 8.4 Hz, 2H, Ar), 3.90 (s, 3H, –OCH₃). ¹³C NMR (75 MHz, CDCl₃) δ 132.34, 132.29, 129.91, 129.88, 128.20, 128.15, 117.52, 115.92, 63.76, 52.02, 29.72.

Compounds (1), (2) (3), (4) and (5) were dissolved in dichloromethane and then left at room temperature for slow evaporation; red single crystals of all compounds suitable for X-ray diffraction analysis started to form after ca 2 d.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 7. The Moscow synchrotron radiation source was used to collect the data for crystals (2) and (5), while the data for crystals (1), (3) and (4) were collected using Cu Kα radiation on a laboratory diffractometer. In all five compounds, C-bound H atoms were positioned geometrically and treated as riding atoms, with C—H = 0.95 and 0.98 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C-methyl). The NH group hydrogen atoms were found by difference-Fourier maps for all five crystals and were refined freely for (1), (4) and (5), while those in (2) and (3) were refined with U_iso(H) = 1.2U_eq(N) of the attached nitrogen atom. In (1), the phenyl ring atoms of the bromophenyl group are disordered over two sets of sites with equal occupancies. In (2) owing to poor agreement between observed and calculated intensities, 23 reflections were omitted from the final cycles of refinement.

Table 7
Experimental details

	1	2	3	4	5
Crystal data
Chemical formula	C₁₆H₁₅BrN₂O₂	C₁₇H₁₇BrN₂O₂	C₁₆H₁₅N₃O₅	C₁₅H₁₃ClN₂O₂	C₁₅H₁₂BrClN₂O₂
M_r	347.20	361.23	329.31	288.72	367.62
Crystal system, space group	Monoclinic, C2/c	Triclinic, P $[\overline{1}]$	Monoclinic, C2/c	Orthorhombic, Pbca	Orthorhombic, Pca2₁
Temperature (K)	100	100	100	100	100
a, b, c (Å)	34.6329 (5), 4.84061 (6), 19.1365 (3)	9.8859 (9), 12.3021 (11), 13.9790 (12)	18.8022 (5), 21.9649 (6), 7.43092 (15)	15.86326 (8), 8.79608 (3), 19.24680 (8)	14.0199 (16), 16.5940 (19), 6.4471 (9)
α, β, γ (°)	90, 109.8598 (16), 90	83.480 (9), 73.266 (7), 81.695 (8)	90, 96.156 (2), 90	90, 90, 90	90, 90, 90
V (Å³)	3017.33 (8)	1606.4 (3)	3051.19 (13)	2685.59 (2)	1499.9 (3)
Z	8	4	8	8	4
Radiation type	Cu Kα	Synchrotron, λ = 0.75270 Å	Cu Kα	Cu Kα	Synchrotron, λ = 0.75270 Å
μ (mm⁻¹)	3.77	2.97	0.91	2.55	3.35
Crystal size (mm)	0.20 × 0.05 × 0.03	0.12 × 0.09 × 0.07	0.29 × 0.10 × 0.09	0.12 × 0.11 × 0.06	0.18 × 0.15 × 0.13

Data collection
Diffractometer	Rigaku XtaLAB Synergy-S, HyPix-6000HE area-detector	Rayonix SX165 CCD	Rigaku XtaLAB Synergy-S, HyPix-6000HE area-detector	Rigaku XtaLAB Synergy-S, HyPix-6000HE area-detector	Rayonix SX165 CCD
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ).	Multi-scan (SCALA; Evans, 2006 )	Gaussian (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ).	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ).	Multi-scan (SCALA; Evans, 2006)
T_min, T_max	0.745, 1.000	0.666, 0.789	0.322, 1.000	0.676, 1.000	0.514, 0.633
No. of measured, independent and observed [I > 2σ(I)] reflections	30865, 3282, 3031	21921, 8417, 6338	21181, 3303, 2634	51407, 2935, 2871	12123, 3908, 3677
R_int	0.047	0.036	0.072	0.030	0.039
(sin θ/λ)_max (Å⁻¹)	0.639	0.686	0.639	0.639	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.12	0.064, 0.190, 1.07	0.046, 0.126, 1.07	0.030, 0.082, 1.08	0.040, 0.110, 1.09
No. of reflections	3282	8417	3303	2935	3908
No. of parameters	232	410	223	186	196
No. of restraints	0	0	0	0	1
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	H atoms treated by a mixture of independent and constrained refinement	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)	1.17, −1.20	1.89, −0.94	0.27, −0.25	0.29, −0.28	1.27, −0.67
Absolute structure	–	–	–	–	Refined as an inversion twin
Absolute structure parameter	–	–	–	–	0.167 (15)
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), Marccd (Doyle, 2011 ), iMosflm (Battye et al., 2011 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC references: 2428835; 2428834; 2428833; 2428832; 2428831

Crystal structure: contains datablocks 1, 2, 3, 4, 5, global. DOI: https://doi.org/10.1107/S2056989025002051/wm5749sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989025002051/wm57491sup7.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025002051/wm57491sup7.cml

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989025002051/wm57492sup8.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025002051/wm57492sup8.cml

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S2056989025002051/wm57493sup9.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025002051/wm57493sup9.cml

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S2056989025002051/wm57494sup10.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025002051/wm57494sup10.cml

Structure factors: contains datablock 5. DOI: https://doi.org/10.1107/S2056989025002051/wm57495sup11.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025002051/wm57495sup11.cml

checkCIF report

Computing details top

Methyl (Z)-2-(4-bromophenyl)-2-[2-(4-methylphenyl)hydrazin-1-ylidene]acetate (1) top

Crystal data top

C₁₆H₁₅BrN₂O₂	F(000) = 1408
M_r = 347.20	D_x = 1.529 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 34.6329 (5) Å	Cell parameters from 15931 reflections
b = 4.84061 (6) Å	θ = 2.7–79.1°
c = 19.1365 (3) Å	µ = 3.77 mm⁻¹
β = 109.8598 (16)°	T = 100 K
V = 3017.33 (8) Å³	Needle, yellow
Z = 8	0.20 × 0.05 × 0.03 mm

Data collection top

Rigaku XtaLAB Synergy-S, HyPix-6000HE area-detector diffractometer	3031 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.047
φ and ω scans	θ_max = 80.0°, θ_min = 2.7°
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2021).	h = −44→44
T_min = 0.745, T_max = 1.000	k = −6→5
30865 measured reflections	l = −24→24
3282 independent reflections

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: mixed
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0672P)² + 8.4257P] where P = (F_o² + 2F_c²)/3
3282 reflections	(Δ/σ)_max = 0.003
232 parameters	Δρ_max = 1.17 e Å⁻³
0 restraints	Δρ_min = −1.20 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	Occ. (<1)
Br1	0.57358 (2)	0.73045 (7)	0.43385 (2)	0.03156 (14)
O1	0.32249 (6)	0.6995 (4)	0.20483 (12)	0.0287 (4)
O2	0.38021 (6)	0.9149 (4)	0.20583 (10)	0.0237 (4)
N1	0.37298 (7)	0.3715 (5)	0.32724 (12)	0.0242 (4)
N2	0.33381 (7)	0.3087 (5)	0.30821 (13)	0.0250 (5)
H2	0.3151 (12)	0.417 (8)	0.270 (2)	0.035 (10)*
C1	0.38646 (8)	0.5648 (5)	0.29398 (14)	0.0218 (5)
C2	0.35954 (9)	0.7297 (5)	0.23131 (16)	0.0229 (5)
C3	0.35571 (9)	1.0778 (6)	0.14355 (15)	0.0288 (6)
H3A	0.3424	0.9561	0.1013	0.043*
H3B	0.3734	1.2099	0.1298	0.043*
H3C	0.3347	1.1783	0.1572	0.043*
C4	0.43162 (8)	0.6094 (5)	0.32521 (14)	0.0215 (5)
C5	0.45024 (15)	0.6230 (11)	0.4017 (3)	0.0218 (9)	0.5
H5	0.4338	0.6105	0.4325	0.026*	0.5
C6	0.49249 (16)	0.6545 (11)	0.4344 (3)	0.0249 (10)	0.5
H6	0.5050	0.6596	0.4869	0.030*	0.5
C5A	0.45868 (17)	0.3824 (11)	0.3370 (3)	0.0261 (10)	0.5
H5A	0.4480	0.2021	0.3234	0.031*	0.5
C6A	0.50112 (17)	0.4202 (12)	0.3687 (3)	0.0268 (10)	0.5
H6A	0.5193	0.2676	0.3758	0.032*	0.5
C7	0.51588 (8)	0.6783 (6)	0.38907 (14)	0.0231 (5)
C8	0.49822 (16)	0.6675 (12)	0.3116 (3)	0.0234 (10)	0.5
H8	0.5148	0.6812	0.2811	0.028*	0.5
C9	0.45600 (16)	0.6364 (11)	0.2801 (3)	0.0219 (9)	0.5
H9	0.4435	0.6334	0.2276	0.026*	0.5
C8A	0.49031 (19)	0.9093 (12)	0.3792 (3)	0.0315 (12)	0.5
H8A	0.5014	1.0883	0.3937	0.038*	0.5
C9A	0.44817 (18)	0.8689 (11)	0.3474 (3)	0.0293 (11)	0.5
H9A	0.4303	1.0230	0.3408	0.035*	0.5
C10	0.32137 (8)	0.1052 (5)	0.34874 (14)	0.0244 (5)
C11	0.27995 (9)	0.0484 (6)	0.33053 (14)	0.0270 (5)
H11	0.2603	0.1459	0.2913	0.032*
C12	0.26724 (8)	−0.1513 (6)	0.36979 (15)	0.0251 (5)
H12	0.2387	−0.1896	0.3563	0.030*
C13	0.29469 (9)	−0.2977 (5)	0.42819 (15)	0.0226 (5)
C14	0.33647 (9)	−0.2381 (5)	0.44565 (16)	0.0266 (6)
H14	0.3561	−0.3352	0.4850	0.032*
C15	0.34988 (8)	−0.0385 (6)	0.40626 (15)	0.0263 (5)
H15	0.3784	−0.0012	0.4188	0.032*
C16	0.28049 (10)	−0.5098 (6)	0.47178 (16)	0.0308 (6)
H16A	0.2842	−0.4373	0.5214	0.046*
H16B	0.2967	−0.6791	0.4762	0.046*
H16C	0.2514	−0.5510	0.4460	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01941 (19)	0.0424 (2)	0.02934 (19)	−0.00077 (10)	0.00364 (13)	0.00388 (11)
O1	0.0183 (9)	0.0295 (9)	0.0366 (10)	−0.0017 (7)	0.0069 (8)	0.0004 (8)
O2	0.0202 (8)	0.0263 (9)	0.0254 (8)	−0.0009 (7)	0.0087 (7)	0.0027 (7)
N1	0.0229 (10)	0.0259 (11)	0.0256 (10)	−0.0046 (9)	0.0107 (8)	−0.0049 (8)
N2	0.0222 (11)	0.0291 (11)	0.0234 (10)	−0.0026 (9)	0.0074 (9)	0.0006 (9)
C1	0.0226 (12)	0.0208 (11)	0.0234 (11)	−0.0012 (9)	0.0097 (9)	−0.0023 (9)
C2	0.0220 (13)	0.0221 (12)	0.0273 (12)	−0.0019 (9)	0.0118 (11)	−0.0031 (9)
C3	0.0290 (13)	0.0307 (13)	0.0267 (12)	0.0038 (11)	0.0092 (11)	0.0044 (11)
C4	0.0210 (12)	0.0204 (11)	0.0227 (11)	0.0005 (9)	0.0068 (9)	0.0004 (9)
C5	0.020 (2)	0.025 (2)	0.021 (2)	−0.0017 (19)	0.0077 (18)	0.0001 (18)
C6	0.023 (2)	0.026 (2)	0.022 (2)	−0.001 (2)	0.0038 (19)	0.0021 (19)
C5A	0.027 (3)	0.021 (2)	0.032 (3)	−0.002 (2)	0.011 (2)	0.000 (2)
C6A	0.028 (3)	0.026 (2)	0.031 (3)	0.003 (2)	0.015 (2)	0.006 (2)
C7	0.0188 (11)	0.0264 (12)	0.0230 (12)	−0.0007 (10)	0.0056 (9)	0.0029 (10)
C8	0.019 (2)	0.029 (2)	0.023 (2)	0.002 (2)	0.0072 (19)	0.002 (2)
C9	0.021 (2)	0.026 (2)	0.019 (2)	0.0015 (19)	0.0082 (18)	−0.0001 (18)
C8A	0.029 (3)	0.023 (2)	0.037 (3)	0.001 (2)	0.005 (2)	−0.002 (2)
C9A	0.027 (3)	0.018 (2)	0.037 (3)	0.003 (2)	0.004 (2)	−0.003 (2)
C10	0.0289 (13)	0.0249 (12)	0.0217 (11)	−0.0033 (10)	0.0115 (10)	−0.0046 (9)
C11	0.0275 (13)	0.0306 (13)	0.0218 (11)	−0.0013 (11)	0.0071 (10)	0.0009 (10)
C12	0.0200 (12)	0.0304 (13)	0.0243 (11)	−0.0030 (10)	0.0068 (10)	−0.0016 (10)
C13	0.0271 (13)	0.0198 (11)	0.0234 (12)	−0.0007 (10)	0.0117 (10)	−0.0013 (9)
C14	0.0239 (14)	0.0279 (13)	0.0269 (13)	0.0050 (10)	0.0071 (11)	−0.0028 (10)
C15	0.0202 (12)	0.0294 (13)	0.0313 (13)	−0.0036 (10)	0.0114 (10)	−0.0088 (10)
C16	0.0401 (16)	0.0237 (12)	0.0357 (14)	−0.0013 (11)	0.0222 (13)	0.0022 (11)

Geometric parameters (Å, º) top

Br1—C7	1.905 (3)	C6A—H6A	0.9500
O1—C2	1.218 (4)	C7—C8A	1.399 (6)
O2—C2	1.338 (3)	C7—C8	1.400 (6)
O2—C3	1.441 (3)	C8—C9	1.387 (7)
N1—C1	1.304 (3)	C8—H8	0.9500
N1—N2	1.315 (3)	C9—H9	0.9500
N2—C10	1.409 (4)	C8A—C9A	1.391 (8)
N2—H2	0.96 (4)	C8A—H8A	0.9500
C1—C2	1.478 (4)	C9A—H9A	0.9500
C1—C4	1.488 (4)	C10—C11	1.384 (4)
C3—H3A	0.9800	C10—C15	1.390 (4)
C3—H3B	0.9800	C11—C12	1.385 (4)
C3—H3C	0.9800	C11—H11	0.9500
C4—C9A	1.386 (6)	C12—C13	1.390 (4)
C4—C5	1.387 (5)	C12—H12	0.9500
C4—C9	1.403 (5)	C13—C14	1.400 (4)
C4—C5A	1.412 (6)	C13—C16	1.507 (4)
C5—C6	1.390 (7)	C14—C15	1.398 (4)
C5—H5	0.9500	C14—H14	0.9500
C6—C7	1.378 (6)	C15—H15	0.9500
C6—H6	0.9500	C16—H16A	0.9800
C5A—C6A	1.398 (8)	C16—H16B	0.9800
C5A—H5A	0.9500	C16—H16C	0.9800
C6A—C7	1.356 (6)

C2—O2—C3	115.5 (2)	C8A—C7—Br1	118.3 (3)
C1—N1—N2	122.5 (2)	C8—C7—Br1	119.7 (3)
N1—N2—C10	119.3 (2)	C9—C8—C7	118.7 (4)
N1—N2—H2	117 (2)	C9—C8—H8	120.6
C10—N2—H2	124 (2)	C7—C8—H8	120.6
N1—C1—C2	123.5 (2)	C8—C9—C4	120.6 (4)
N1—C1—C4	114.2 (2)	C8—C9—H9	119.7
C2—C1—C4	122.3 (2)	C4—C9—H9	119.7
O1—C2—O2	123.2 (3)	C9A—C8A—C7	118.0 (5)
O1—C2—C1	123.9 (2)	C9A—C8A—H8A	121.0
O2—C2—C1	112.9 (2)	C7—C8A—H8A	121.0
O2—C3—H3A	109.5	C4—C9A—C8A	121.6 (5)
O2—C3—H3B	109.5	C4—C9A—H9A	119.2
H3A—C3—H3B	109.5	C8A—C9A—H9A	119.2
O2—C3—H3C	109.5	C11—C10—C15	119.8 (2)
H3A—C3—H3C	109.5	C11—C10—N2	119.0 (2)
H3B—C3—H3C	109.5	C15—C10—N2	121.2 (2)
C5—C4—C9	118.9 (3)	C10—C11—C12	119.7 (3)
C9A—C4—C5A	118.2 (4)	C10—C11—H11	120.1
C9A—C4—C1	121.6 (3)	C12—C11—H11	120.1
C5—C4—C1	118.6 (3)	C11—C12—C13	122.4 (2)
C9—C4—C1	122.4 (3)	C11—C12—H12	118.8
C5A—C4—C1	120.1 (3)	C13—C12—H12	118.8
C4—C5—C6	121.4 (4)	C12—C13—C14	117.1 (2)
C4—C5—H5	119.3	C12—C13—C16	122.0 (3)
C6—C5—H5	119.3	C14—C13—C16	120.9 (3)
C7—C6—C5	118.7 (4)	C15—C14—C13	121.3 (3)
C7—C6—H6	120.7	C15—C14—H14	119.4
C5—C6—H6	120.7	C13—C14—H14	119.4
C6A—C5A—C4	120.7 (5)	C10—C15—C14	119.7 (2)
C6A—C5A—H5A	119.6	C10—C15—H15	120.1
C4—C5A—H5A	119.6	C14—C15—H15	120.1
C7—C6A—C5A	118.9 (5)	C13—C16—H16A	109.5
C7—C6A—H6A	120.6	C13—C16—H16B	109.5
C5A—C6A—H6A	120.6	H16A—C16—H16B	109.5
C6A—C7—C8A	122.6 (4)	C13—C16—H16C	109.5
C6—C7—C8	121.7 (4)	H16A—C16—H16C	109.5
C6A—C7—Br1	119.1 (3)	H16B—C16—H16C	109.5
C6—C7—Br1	118.6 (3)

C1—N1—N2—C10	−177.4 (2)	C5—C6—C7—C8	−0.9 (7)
N2—N1—C1—C2	−0.9 (4)	C5—C6—C7—Br1	178.5 (4)
N2—N1—C1—C4	178.3 (2)	C6A—C7—C8—C9	68.3 (5)
C3—O2—C2—O1	−0.6 (4)	C6—C7—C8—C9	1.0 (7)
C3—O2—C2—C1	178.6 (2)	C8A—C7—C8—C9	−60.4 (5)
N1—C1—C2—O1	−0.4 (4)	Br1—C7—C8—C9	−178.4 (4)
C4—C1—C2—O1	−179.5 (3)	C7—C8—C9—C4	−1.6 (8)
N1—C1—C2—O2	−179.7 (2)	C9A—C4—C9—C8	61.1 (5)
C4—C1—C2—O2	1.2 (3)	C5—C4—C9—C8	2.0 (7)
N1—C1—C4—C9A	−126.8 (4)	C5A—C4—C9—C8	−63.7 (5)
C2—C1—C4—C9A	52.4 (4)	C1—C4—C9—C8	−177.6 (4)
N1—C1—C4—C5	−45.3 (4)	C6A—C7—C8A—C9A	0.3 (8)
C2—C1—C4—C5	133.9 (3)	C6—C7—C8A—C9A	−66.2 (6)
N1—C1—C4—C9	134.2 (3)	C8—C7—C8A—C9A	61.5 (6)
C2—C1—C4—C9	−46.6 (4)	Br1—C7—C8A—C9A	−179.1 (4)
N1—C1—C4—C5A	49.4 (4)	C5—C4—C9A—C8A	66.2 (6)
C2—C1—C4—C5A	−131.4 (4)	C9—C4—C9A—C8A	−60.2 (6)
C9A—C4—C5—C6	−67.0 (5)	C5A—C4—C9A—C8A	1.3 (8)
C9—C4—C5—C6	−1.9 (7)	C1—C4—C9A—C8A	177.6 (5)
C5A—C4—C5—C6	58.9 (5)	C7—C8A—C9A—C4	−0.7 (9)
C1—C4—C5—C6	177.7 (4)	N1—N2—C10—C11	177.2 (2)
C4—C5—C6—C7	1.3 (8)	N1—N2—C10—C15	−2.8 (4)
C9A—C4—C5A—C6A	−1.5 (7)	C15—C10—C11—C12	0.0 (4)
C5—C4—C5A—C6A	−60.5 (5)	N2—C10—C11—C12	179.9 (2)
C9—C4—C5A—C6A	65.3 (5)	C10—C11—C12—C13	0.7 (4)
C1—C4—C5A—C6A	−177.8 (4)	C11—C12—C13—C14	−0.9 (4)
C4—C5A—C6A—C7	1.1 (7)	C11—C12—C13—C16	178.5 (3)
C5A—C6A—C7—C6	60.5 (5)	C12—C13—C14—C15	0.4 (4)
C5A—C6A—C7—C8A	−0.5 (7)	C16—C13—C14—C15	−179.0 (2)
C5A—C6A—C7—C8	−67.0 (5)	C11—C10—C15—C14	−0.4 (4)
C5A—C6A—C7—Br1	178.9 (4)	N2—C10—C15—C14	179.6 (2)
C5—C6—C7—C6A	−62.6 (5)	C13—C14—C15—C10	0.2 (4)
C5—C6—C7—C8A	66.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.95 (4)	1.93 (4)	2.668 (3)	133 (4)
C9—H9···O2	0.95	2.49	2.862 (6)	103
C9A—H9A···N1ⁱ	0.95	2.55	3.488 (6)	169
C5A—H5A···Cg2ⁱⁱ	0.95	2.85	3.611 (6)	138
C8—H8···Cg5ⁱⁱⁱ	0.95	2.81	3.677 (6)	152
C8A—H8A···Cg2ⁱ	0.95	2.86	3.607 (6)	136
C16—H16B···Cg7ⁱⁱ	0.98	2.74	3.544 (3)	139

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

Methyl (Z)-2-(4-bromophenyl)-2-[2-(3,5-dimethylphenyl)hydrazin-1-ylidene]acetate (2) top

Crystal data top

C₁₇H₁₇BrN₂O₂	Z = 4
M_r = 361.23	F(000) = 736
Triclinic, P1	D_x = 1.494 Mg m⁻³
a = 9.8859 (9) Å	Synchrotron radiation, λ = 0.75270 Å
b = 12.3021 (11) Å	Cell parameters from 1000 reflections
c = 13.9790 (12) Å	θ = 1.8–30.0°
α = 83.480 (9)°	µ = 2.97 mm⁻¹
β = 73.266 (7)°	T = 100 K
γ = 81.695 (8)°	Prism, yellow
V = 1606.4 (3) Å³	0.12 × 0.09 × 0.07 mm

Data collection top

Rayonix SX165 CCD diffractometer	6338 reflections with I > 2σ(I)
/f scan	R_int = 0.036
Absorption correction: multi-scan (Scala; Evans, 2006)	θ_max = 31.1°, θ_min = 1.8°
T_min = 0.666, T_max = 0.789	h = −13→13
21921 measured reflections	k = −16→16
8417 independent reflections	l = −18→19

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.064	w = 1/[σ²(F_o²) + (0.1079P)² + 1.6265P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.190	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 1.89 e Å⁻³
8417 reflections	Δρ_min = −0.94 e Å⁻³
410 parameters	Extinction correction: SHELXL-2019/2 (Sheldrick, 2015a), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.044 (3)

Special details top

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

	x	y	z	U_iso*/U_eq
C1A	0.4335 (3)	0.3106 (3)	0.6750 (3)	0.0279 (6)
C2A	0.4825 (3)	0.4119 (3)	0.6932 (3)	0.0294 (7)
C3A	0.6205 (4)	0.5560 (3)	0.6248 (3)	0.0423 (9)
H3AA	0.677439	0.585644	0.560006	0.063*
H3AB	0.677900	0.543397	0.672504	0.063*
H3AC	0.536763	0.608779	0.650156	0.063*
C4A	0.5061 (3)	0.2504 (3)	0.5848 (2)	0.0261 (6)
C5A	0.4260 (3)	0.1991 (3)	0.5392 (3)	0.0316 (7)
H5A	0.325686	0.203652	0.566444	0.038*
C6A	0.4906 (4)	0.1420 (3)	0.4553 (3)	0.0319 (7)
H6A	0.435177	0.106993	0.425294	0.038*
C7A	0.6361 (4)	0.1361 (3)	0.4152 (3)	0.0301 (7)
C8A	0.7196 (3)	0.1832 (3)	0.4598 (3)	0.0318 (7)
H8A	0.819991	0.177166	0.432725	0.038*
C9A	0.6534 (3)	0.2393 (3)	0.5451 (3)	0.0309 (7)
H9A	0.709808	0.270754	0.576918	0.037*
C10A	0.1256 (4)	0.2743 (3)	0.8804 (3)	0.0316 (7)
C11A	0.0567 (4)	0.3239 (3)	0.9683 (3)	0.0369 (8)
H11A	0.092046	0.385259	0.984307	0.044*
C12A	−0.0639 (4)	0.2842 (3)	1.0332 (3)	0.0375 (8)
C13A	−0.1141 (4)	0.1949 (3)	1.0083 (3)	0.0327 (7)
H13A	−0.197025	0.168028	1.052340	0.039*
C14A	−0.0465 (4)	0.1436 (3)	0.9208 (3)	0.0307 (7)
C15A	0.0755 (4)	0.1845 (3)	0.8550 (3)	0.0314 (7)
H15A	0.122838	0.151241	0.794216	0.038*
C16A	−0.1391 (5)	0.3384 (4)	1.1287 (3)	0.0500 (11)
H16C	−0.236055	0.368284	1.127359	0.075*
H16D	−0.087377	0.398205	1.134887	0.075*
H16E	−0.142998	0.283830	1.185948	0.075*
C17A	−0.1000 (4)	0.0467 (3)	0.8954 (3)	0.0363 (8)
H17C	−0.070369	−0.019532	0.933805	0.054*
H17D	−0.060773	0.037247	0.823594	0.054*
H17E	−0.204056	0.058564	0.912015	0.054*
Br1A	0.72473 (4)	0.06195 (3)	0.29756 (3)	0.03885 (15)
N1A	0.3195 (3)	0.2721 (2)	0.7342 (2)	0.0305 (6)
N2A	0.2473 (3)	0.3176 (3)	0.8175 (2)	0.0318 (6)
O1A	0.4383 (3)	0.4574 (2)	0.7710 (2)	0.0333 (5)
O2A	0.5755 (3)	0.4536 (2)	0.6125 (2)	0.0331 (5)
H2A	0.294 (5)	0.376 (4)	0.835 (4)	0.040*
C1B	0.9468 (3)	0.3394 (3)	0.6648 (2)	0.0260 (6)
C2B	1.0061 (3)	0.4347 (3)	0.6847 (2)	0.0262 (6)
C3B	1.1954 (4)	0.5434 (3)	0.6364 (3)	0.0322 (7)
H3BA	1.285785	0.549359	0.584772	0.048*
H3BB	1.212847	0.530187	0.702487	0.048*
H3BC	1.131891	0.612029	0.633975	0.048*
C4B	1.0166 (3)	0.2763 (3)	0.5762 (2)	0.0258 (6)
C5B	1.0352 (3)	0.1616 (3)	0.5884 (3)	0.0282 (6)
H5B	1.003525	0.125356	0.653181	0.034*
C6B	1.0992 (3)	0.1001 (3)	0.5070 (3)	0.0303 (7)
H6B	1.114012	0.022028	0.516203	0.036*
C7B	1.1416 (3)	0.1523 (3)	0.4120 (3)	0.0283 (6)
C8B	1.1236 (3)	0.2656 (3)	0.3969 (3)	0.0300 (7)
H8B	1.152827	0.301006	0.331502	0.036*
C9B	1.0619 (3)	0.3266 (3)	0.4793 (3)	0.0283 (6)
H9B	1.049927	0.404698	0.469699	0.034*
C10B	0.6466 (3)	0.2975 (3)	0.8746 (3)	0.0275 (6)
C11B	0.5797 (4)	0.3428 (3)	0.9656 (3)	0.0298 (7)
H11B	0.613998	0.404242	0.982436	0.036*
C12B	0.4637 (4)	0.2990 (3)	1.0317 (3)	0.0328 (7)
C13B	0.4136 (4)	0.2099 (3)	1.0046 (3)	0.0316 (7)
H13B	0.333141	0.180104	1.049162	0.038*
C14B	0.4789 (3)	0.1636 (3)	0.9135 (3)	0.0295 (7)
C15B	0.5967 (3)	0.2091 (3)	0.8484 (2)	0.0277 (6)
H15B	0.642570	0.178951	0.785965	0.033*
C16B	0.3916 (5)	0.3463 (4)	1.1314 (3)	0.0427 (9)
H16F	0.291085	0.370073	1.135972	0.064*
H16G	0.437852	0.409619	1.137109	0.064*
H16H	0.399070	0.289955	1.185660	0.064*
C17B	0.4269 (4)	0.0673 (3)	0.8860 (3)	0.0342 (7)
H17F	0.451926	0.067228	0.812845	0.051*
H17G	0.323359	0.071899	0.913332	0.051*
H17H	0.471205	−0.000818	0.913587	0.051*
Br1B	1.22812 (4)	0.06754 (3)	0.30080 (3)	0.03961 (16)
N1B	0.8342 (3)	0.3006 (2)	0.7260 (2)	0.0275 (5)
N2B	0.7636 (3)	0.3450 (2)	0.8103 (2)	0.0278 (6)
O1B	0.9482 (3)	0.4914 (2)	0.7546 (2)	0.0334 (5)
O2B	1.1299 (2)	0.45294 (19)	0.61850 (18)	0.0279 (5)
H2B	0.793 (5)	0.396 (4)	0.827 (4)	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.0274 (14)	0.0292 (15)	0.0269 (16)	−0.0017 (11)	−0.0068 (12)	−0.0047 (12)
C2A	0.0272 (14)	0.0316 (16)	0.0290 (17)	−0.0008 (12)	−0.0074 (12)	−0.0056 (13)
C3A	0.050 (2)	0.0344 (19)	0.039 (2)	−0.0136 (16)	0.0002 (17)	−0.0116 (16)
C4A	0.0258 (14)	0.0258 (14)	0.0259 (16)	−0.0016 (11)	−0.0065 (11)	−0.0022 (12)
C5A	0.0266 (14)	0.0354 (17)	0.0334 (18)	−0.0009 (12)	−0.0097 (13)	−0.0055 (14)
C6A	0.0316 (16)	0.0342 (17)	0.0315 (18)	−0.0042 (12)	−0.0092 (13)	−0.0074 (14)
C7A	0.0365 (16)	0.0252 (15)	0.0263 (16)	0.0007 (12)	−0.0060 (13)	−0.0045 (12)
C8A	0.0264 (14)	0.0255 (15)	0.041 (2)	−0.0021 (11)	−0.0049 (13)	−0.0054 (13)
C9A	0.0304 (15)	0.0268 (15)	0.0366 (19)	−0.0048 (12)	−0.0088 (13)	−0.0063 (13)
C10A	0.0292 (15)	0.0319 (16)	0.0299 (17)	0.0010 (12)	−0.0047 (13)	−0.0017 (13)
C11A	0.0404 (18)	0.0351 (18)	0.0331 (19)	−0.0020 (14)	−0.0065 (15)	−0.0062 (15)
C12A	0.0423 (19)	0.0365 (18)	0.0295 (18)	−0.0017 (14)	−0.0037 (14)	−0.0054 (14)
C13A	0.0298 (15)	0.0377 (18)	0.0260 (17)	0.0002 (13)	−0.0030 (12)	−0.0015 (13)
C14A	0.0307 (15)	0.0310 (16)	0.0293 (17)	0.0008 (12)	−0.0089 (13)	−0.0011 (13)
C15A	0.0318 (16)	0.0364 (17)	0.0237 (16)	0.0039 (13)	−0.0071 (12)	−0.0048 (13)
C16A	0.053 (2)	0.052 (2)	0.036 (2)	−0.0084 (19)	0.0076 (18)	−0.0136 (19)
C17A	0.0341 (17)	0.0366 (18)	0.036 (2)	−0.0039 (14)	−0.0060 (14)	−0.0038 (15)
Br1A	0.0446 (2)	0.0352 (2)	0.0327 (2)	0.00094 (15)	−0.00333 (16)	−0.01194 (15)
N1A	0.0312 (13)	0.0321 (14)	0.0267 (14)	0.0011 (11)	−0.0079 (11)	−0.0022 (11)
N2A	0.0325 (14)	0.0310 (14)	0.0303 (15)	−0.0042 (11)	−0.0048 (11)	−0.0056 (12)
O1A	0.0336 (12)	0.0338 (13)	0.0314 (13)	−0.0013 (9)	−0.0064 (10)	−0.0086 (10)
O2A	0.0379 (13)	0.0268 (11)	0.0324 (13)	−0.0061 (9)	−0.0033 (10)	−0.0070 (10)
C1B	0.0259 (13)	0.0263 (14)	0.0249 (15)	−0.0037 (11)	−0.0046 (11)	−0.0029 (12)
C2B	0.0262 (14)	0.0286 (15)	0.0222 (15)	−0.0003 (11)	−0.0052 (11)	−0.0026 (12)
C3B	0.0317 (16)	0.0310 (16)	0.0339 (18)	−0.0067 (12)	−0.0069 (13)	−0.0045 (13)
C4B	0.0236 (13)	0.0267 (15)	0.0253 (15)	−0.0017 (11)	−0.0031 (11)	−0.0058 (12)
C5B	0.0285 (14)	0.0270 (15)	0.0284 (16)	−0.0043 (11)	−0.0061 (12)	−0.0021 (12)
C6B	0.0322 (15)	0.0244 (14)	0.0344 (18)	−0.0050 (11)	−0.0078 (13)	−0.0052 (13)
C7B	0.0277 (14)	0.0316 (16)	0.0254 (16)	−0.0034 (12)	−0.0034 (12)	−0.0111 (13)
C8B	0.0315 (15)	0.0322 (16)	0.0257 (16)	−0.0062 (12)	−0.0050 (12)	−0.0041 (13)
C9B	0.0278 (14)	0.0275 (15)	0.0262 (16)	0.0000 (11)	−0.0033 (12)	−0.0029 (12)
C10B	0.0256 (14)	0.0303 (15)	0.0238 (16)	0.0015 (11)	−0.0039 (11)	−0.0038 (12)
C11B	0.0322 (15)	0.0296 (16)	0.0252 (16)	−0.0035 (12)	−0.0032 (12)	−0.0052 (12)
C12B	0.0326 (16)	0.0347 (17)	0.0253 (17)	−0.0005 (13)	0.0003 (13)	−0.0045 (13)
C13B	0.0296 (15)	0.0328 (17)	0.0268 (17)	−0.0023 (12)	−0.0002 (12)	−0.0008 (13)
C14B	0.0274 (14)	0.0282 (15)	0.0317 (17)	−0.0011 (11)	−0.0080 (12)	−0.0004 (13)
C15B	0.0279 (14)	0.0296 (15)	0.0218 (15)	0.0013 (11)	−0.0027 (11)	−0.0032 (12)
C16B	0.046 (2)	0.047 (2)	0.0292 (19)	−0.0101 (17)	0.0057 (15)	−0.0131 (16)
C17B	0.0324 (16)	0.0307 (17)	0.039 (2)	−0.0043 (13)	−0.0076 (14)	−0.0062 (14)
Br1B	0.0464 (2)	0.0367 (2)	0.0340 (2)	−0.00589 (15)	−0.00226 (16)	−0.01727 (16)
N1B	0.0269 (12)	0.0299 (13)	0.0246 (14)	−0.0008 (10)	−0.0057 (10)	−0.0046 (11)
N2B	0.0276 (13)	0.0308 (14)	0.0228 (14)	−0.0024 (10)	−0.0020 (10)	−0.0079 (11)
O1B	0.0344 (12)	0.0319 (12)	0.0314 (13)	−0.0052 (9)	−0.0025 (10)	−0.0084 (10)
O2B	0.0272 (11)	0.0292 (11)	0.0266 (12)	−0.0049 (8)	−0.0042 (9)	−0.0052 (9)

Geometric parameters (Å, º) top

C1A—N1A	1.307 (4)	C1B—N1B	1.308 (4)
C1A—C2A	1.473 (5)	C1B—C2B	1.471 (4)
C1A—C4A	1.480 (5)	C1B—C4B	1.478 (4)
C2A—O1A	1.217 (4)	C2B—O1B	1.219 (4)
C2A—O2A	1.337 (4)	C2B—O2B	1.336 (4)
C3A—O2A	1.439 (4)	C3B—O2B	1.444 (4)
C3A—H3AA	0.9800	C3B—H3BA	0.9800
C3A—H3AB	0.9800	C3B—H3BB	0.9800
C3A—H3AC	0.9800	C3B—H3BC	0.9800
C4A—C9A	1.394 (4)	C4B—C5B	1.394 (4)
C4A—C5A	1.399 (4)	C4B—C9B	1.400 (5)
C5A—C6A	1.380 (5)	C5B—C6B	1.382 (5)
C5A—H5A	0.9500	C5B—H5B	0.9500
C6A—C7A	1.380 (5)	C6B—C7B	1.383 (5)
C6A—H6A	0.9500	C6B—H6B	0.9500
C7A—C8A	1.387 (5)	C7B—C8B	1.379 (5)
C7A—Br1A	1.893 (3)	C7B—Br1B	1.893 (3)
C8A—C9A	1.390 (5)	C8B—C9B	1.386 (4)
C8A—H8A	0.9500	C8B—H8B	0.9500
C9A—H9A	0.9500	C9B—H9B	0.9500
C10A—C11A	1.384 (5)	C10B—C15B	1.382 (5)
C10A—C15A	1.393 (5)	C10B—C11B	1.391 (5)
C10A—N2A	1.405 (4)	C10B—N2B	1.402 (4)
C11A—C12A	1.388 (5)	C11B—C12B	1.384 (5)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—C13A	1.385 (5)	C12B—C13B	1.396 (5)
C12A—C16A	1.505 (5)	C12B—C16B	1.510 (5)
C13A—C14A	1.387 (5)	C13B—C14B	1.396 (5)
C13A—H13A	0.9500	C13B—H13B	0.9500
C14A—C15A	1.409 (5)	C14B—C15B	1.399 (5)
C14A—C17A	1.487 (5)	C14B—C17B	1.487 (5)
C15A—H15A	0.9500	C15B—H15B	0.9500
C16A—H16C	0.9800	C16B—H16F	0.9800
C16A—H16D	0.9800	C16B—H16G	0.9800
C16A—H16E	0.9800	C16B—H16H	0.9800
C17A—H17C	0.9800	C17B—H17F	0.9800
C17A—H17D	0.9800	C17B—H17G	0.9800
C17A—H17E	0.9800	C17B—H17H	0.9800
N1A—N2A	1.316 (4)	N1B—N2B	1.317 (4)
N2A—H2A	0.99 (5)	N2B—H2B	0.81 (5)

N1A—C1A—C2A	122.2 (3)	N1B—C1B—C2B	123.0 (3)
N1A—C1A—C4A	116.2 (3)	N1B—C1B—C4B	115.2 (3)
C2A—C1A—C4A	121.6 (3)	C2B—C1B—C4B	121.7 (3)
O1A—C2A—O2A	122.7 (3)	O1B—C2B—O2B	123.4 (3)
O1A—C2A—C1A	124.4 (3)	O1B—C2B—C1B	123.4 (3)
O2A—C2A—C1A	112.9 (3)	O2B—C2B—C1B	113.2 (3)
O2A—C3A—H3AA	109.5	O2B—C3B—H3BA	109.5
O2A—C3A—H3AB	109.5	O2B—C3B—H3BB	109.5
H3AA—C3A—H3AB	109.5	H3BA—C3B—H3BB	109.5
O2A—C3A—H3AC	109.5	O2B—C3B—H3BC	109.5
H3AA—C3A—H3AC	109.5	H3BA—C3B—H3BC	109.5
H3AB—C3A—H3AC	109.5	H3BB—C3B—H3BC	109.5
C9A—C4A—C5A	118.2 (3)	C5B—C4B—C9B	118.0 (3)
C9A—C4A—C1A	122.2 (3)	C5B—C4B—C1B	119.1 (3)
C5A—C4A—C1A	119.6 (3)	C9B—C4B—C1B	122.8 (3)
C6A—C5A—C4A	120.9 (3)	C6B—C5B—C4B	120.6 (3)
C6A—C5A—H5A	119.5	C6B—C5B—H5B	119.7
C4A—C5A—H5A	119.5	C4B—C5B—H5B	119.7
C5A—C6A—C7A	119.6 (3)	C5B—C6B—C7B	119.9 (3)
C5A—C6A—H6A	120.2	C5B—C6B—H6B	120.0
C7A—C6A—H6A	120.2	C7B—C6B—H6B	120.0
C6A—C7A—C8A	121.1 (3)	C8B—C7B—C6B	121.1 (3)
C6A—C7A—Br1A	119.8 (3)	C8B—C7B—Br1B	119.1 (3)
C8A—C7A—Br1A	119.0 (3)	C6B—C7B—Br1B	119.7 (3)
C7A—C8A—C9A	118.7 (3)	C7B—C8B—C9B	118.4 (3)
C7A—C8A—H8A	120.7	C7B—C8B—H8B	120.8
C9A—C8A—H8A	120.7	C9B—C8B—H8B	120.8
C8A—C9A—C4A	121.3 (3)	C8B—C9B—C4B	121.8 (3)
C8A—C9A—H9A	119.3	C8B—C9B—H9B	119.1
C4A—C9A—H9A	119.3	C4B—C9B—H9B	119.1
C11A—C10A—C15A	121.0 (3)	C15B—C10B—C11B	120.4 (3)
C11A—C10A—N2A	117.9 (3)	C15B—C10B—N2B	121.4 (3)
C15A—C10A—N2A	121.1 (3)	C11B—C10B—N2B	118.2 (3)
C10A—C11A—C12A	120.2 (4)	C12B—C11B—C10B	120.5 (3)
C10A—C11A—H11A	119.9	C12B—C11B—H11B	119.7
C12A—C11A—H11A	119.9	C10B—C11B—H11B	119.7
C13A—C12A—C11A	119.0 (3)	C11B—C12B—C13B	118.7 (3)
C13A—C12A—C16A	120.7 (4)	C11B—C12B—C16B	121.0 (3)
C11A—C12A—C16A	120.3 (4)	C13B—C12B—C16B	120.2 (3)
C12A—C13A—C14A	121.8 (3)	C14B—C13B—C12B	121.6 (3)
C12A—C13A—H13A	119.1	C14B—C13B—H13B	119.2
C14A—C13A—H13A	119.1	C12B—C13B—H13B	119.2
C13A—C14A—C15A	119.0 (3)	C13B—C14B—C15B	118.4 (3)
C13A—C14A—C17A	121.4 (3)	C13B—C14B—C17B	121.3 (3)
C15A—C14A—C17A	119.6 (3)	C15B—C14B—C17B	120.3 (3)
C10A—C15A—C14A	119.0 (3)	C10B—C15B—C14B	120.4 (3)
C10A—C15A—H15A	120.5	C10B—C15B—H15B	119.8
C14A—C15A—H15A	120.5	C14B—C15B—H15B	119.8
C12A—C16A—H16C	109.5	C12B—C16B—H16F	109.5
C12A—C16A—H16D	109.5	C12B—C16B—H16G	109.5
H16C—C16A—H16D	109.5	H16F—C16B—H16G	109.5
C12A—C16A—H16E	109.5	C12B—C16B—H16H	109.5
H16C—C16A—H16E	109.5	H16F—C16B—H16H	109.5
H16D—C16A—H16E	109.5	H16G—C16B—H16H	109.5
C14A—C17A—H17C	109.5	C14B—C17B—H17F	109.5
C14A—C17A—H17D	109.5	C14B—C17B—H17G	109.5
H17C—C17A—H17D	109.5	H17F—C17B—H17G	109.5
C14A—C17A—H17E	109.5	C14B—C17B—H17H	109.5
H17C—C17A—H17E	109.5	H17F—C17B—H17H	109.5
H17D—C17A—H17E	109.5	H17G—C17B—H17H	109.5
C1A—N1A—N2A	121.7 (3)	C1B—N1B—N2B	122.5 (3)
N1A—N2A—C10A	120.6 (3)	N1B—N2B—C10B	119.9 (3)
N1A—N2A—H2A	114 (3)	N1B—N2B—H2B	120 (3)
C10A—N2A—H2A	125 (3)	C10B—N2B—H2B	120 (3)
C2A—O2A—C3A	115.0 (3)	C2B—O2B—C3B	115.6 (3)

N1A—C1A—C2A—O1A	13.0 (5)	N1B—C1B—C2B—O1B	−7.1 (5)
C4A—C1A—C2A—O1A	−170.9 (3)	C4B—C1B—C2B—O1B	176.8 (3)
N1A—C1A—C2A—O2A	−163.1 (3)	N1B—C1B—C2B—O2B	172.9 (3)
C4A—C1A—C2A—O2A	13.0 (4)	C4B—C1B—C2B—O2B	−3.2 (4)
N1A—C1A—C4A—C9A	−145.6 (3)	N1B—C1B—C4B—C5B	−43.2 (4)
C2A—C1A—C4A—C9A	38.1 (5)	C2B—C1B—C4B—C5B	133.2 (3)
N1A—C1A—C4A—C5A	32.0 (5)	N1B—C1B—C4B—C9B	134.9 (3)
C2A—C1A—C4A—C5A	−144.4 (3)	C2B—C1B—C4B—C9B	−48.7 (5)
C9A—C4A—C5A—C6A	−2.1 (5)	C9B—C4B—C5B—C6B	1.3 (5)
C1A—C4A—C5A—C6A	−179.7 (3)	C1B—C4B—C5B—C6B	179.5 (3)
C4A—C5A—C6A—C7A	−0.5 (5)	C4B—C5B—C6B—C7B	−1.9 (5)
C5A—C6A—C7A—C8A	2.4 (5)	C5B—C6B—C7B—C8B	1.2 (5)
C5A—C6A—C7A—Br1A	−178.0 (3)	C5B—C6B—C7B—Br1B	−179.6 (2)
C6A—C7A—C8A—C9A	−1.6 (5)	C6B—C7B—C8B—C9B	0.1 (5)
Br1A—C7A—C8A—C9A	178.8 (3)	Br1B—C7B—C8B—C9B	−179.1 (2)
C7A—C8A—C9A—C4A	−1.1 (5)	C7B—C8B—C9B—C4B	−0.6 (5)
C5A—C4A—C9A—C8A	2.9 (5)	C5B—C4B—C9B—C8B	−0.1 (5)
C1A—C4A—C9A—C8A	−179.6 (3)	C1B—C4B—C9B—C8B	−178.2 (3)
C15A—C10A—C11A—C12A	0.3 (6)	C15B—C10B—C11B—C12B	0.9 (5)
N2A—C10A—C11A—C12A	−179.9 (3)	N2B—C10B—C11B—C12B	180.0 (3)
C10A—C11A—C12A—C13A	−0.2 (6)	C10B—C11B—C12B—C13B	−1.1 (5)
C10A—C11A—C12A—C16A	−179.8 (4)	C10B—C11B—C12B—C16B	179.1 (4)
C11A—C12A—C13A—C14A	0.5 (6)	C11B—C12B—C13B—C14B	0.9 (5)
C16A—C12A—C13A—C14A	−179.9 (4)	C16B—C12B—C13B—C14B	−179.3 (4)
C12A—C13A—C14A—C15A	−0.8 (5)	C12B—C13B—C14B—C15B	−0.4 (5)
C12A—C13A—C14A—C17A	179.1 (4)	C12B—C13B—C14B—C17B	178.7 (3)
C11A—C10A—C15A—C14A	−0.5 (5)	C11B—C10B—C15B—C14B	−0.4 (5)
N2A—C10A—C15A—C14A	179.6 (3)	N2B—C10B—C15B—C14B	−179.5 (3)
C13A—C14A—C15A—C10A	0.8 (5)	C13B—C14B—C15B—C10B	0.2 (5)
C17A—C14A—C15A—C10A	−179.1 (3)	C17B—C14B—C15B—C10B	−178.9 (3)
C2A—C1A—N1A—N2A	−4.7 (5)	C2B—C1B—N1B—N2B	0.9 (5)
C4A—C1A—N1A—N2A	179.0 (3)	C4B—C1B—N1B—N2B	177.2 (3)
C1A—N1A—N2A—C10A	−179.6 (3)	C1B—N1B—N2B—C10B	−177.8 (3)
C11A—C10A—N2A—N1A	178.1 (3)	C15B—C10B—N2B—N1B	−4.6 (5)
C15A—C10A—N2A—N1A	−2.0 (5)	C11B—C10B—N2B—N1B	176.3 (3)
O1A—C2A—O2A—C3A	0.4 (5)	O1B—C2B—O2B—C3B	2.0 (5)
C1A—C2A—O2A—C3A	176.7 (3)	C1B—C2B—O2B—C3B	−178.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2A···O1A	1.00 (5)	1.82 (5)	2.631 (4)	136 (4)
N2B—H2B···O1B	0.81 (5)	2.03 (5)	2.645 (4)	133 (5)
C9A—H9A···O2A	0.95	2.47	2.827 (4)	102
C9B—H9B···O2B	0.95	2.58	2.898 (4)	100
C5A—H5A···Cg3ⁱ	0.95	2.88	3.637 (4)	137

Symmetry code: (i) x−1, y, z.

Methyl (Z)-2-[2-(4-methoxyphenyl)hydrazin-1-ylidene]-2-(3-nitrophenyl)acetate (3) top

Crystal data top

C₁₆H₁₅N₃O₅	F(000) = 1376
M_r = 329.31	D_x = 1.434 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 18.8022 (5) Å	Cell parameters from 4042 reflections
b = 21.9649 (6) Å	θ = 4.0–78.2°
c = 7.43092 (15) Å	µ = 0.91 mm⁻¹
β = 96.156 (2)°	T = 100 K
V = 3051.19 (13) Å³	Prismatic needle, yellow
Z = 8	0.29 × 0.10 × 0.09 mm

Data collection top

Rigaku XtaLAB Synergy-S, HyPix-6000HE area-detector diffractometer	2634 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.072
φ and ω scans	θ_max = 80.0°, θ_min = 3.1°
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2021).	h = −23→23
T_min = 0.322, T_max = 1.000	k = −28→27
21181 measured reflections	l = −6→9
3303 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)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0486P)² + 2.64P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
3303 reflections	Δρ_max = 0.27 e Å⁻³
223 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: difference Fourier map	Extinction coefficient: 0.00022 (2)

Special details top

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

	x	y	z	U_iso*/U_eq
O1	0.61696 (7)	0.61943 (6)	0.38295 (16)	0.0270 (3)
O2	0.68370 (6)	0.70446 (6)	0.37126 (17)	0.0268 (3)
O3	0.63758 (7)	0.86543 (6)	−0.02805 (16)	0.0303 (3)
O4	0.59273 (7)	0.95144 (6)	0.04857 (17)	0.0288 (3)
O5	0.24312 (6)	0.55365 (6)	0.76639 (16)	0.0246 (3)
N1	0.50639 (8)	0.69827 (7)	0.50010 (18)	0.0221 (3)
N2	0.49323 (8)	0.63946 (7)	0.5152 (2)	0.0243 (3)
H2	0.5246 (12)	0.6133 (11)	0.488 (3)	0.029*
N3	0.60948 (8)	0.89818 (7)	0.07922 (18)	0.0230 (3)
C1	0.56661 (9)	0.71660 (8)	0.4425 (2)	0.0210 (3)
C2	0.62303 (9)	0.67454 (8)	0.3949 (2)	0.0220 (4)
C3	0.74375 (10)	0.66734 (9)	0.3324 (3)	0.0317 (4)
H3A	0.7313	0.6450	0.2192	0.048*
H3B	0.7554	0.6384	0.4314	0.048*
H3C	0.7852	0.6935	0.3203	0.048*
C4	0.57519 (8)	0.78340 (8)	0.4289 (2)	0.0197 (3)
C5	0.59311 (8)	0.80907 (8)	0.2672 (2)	0.0202 (3)
H5	0.6038	0.7840	0.1695	0.024*
C6	0.59483 (9)	0.87167 (8)	0.2535 (2)	0.0200 (3)
C7	0.58109 (9)	0.91057 (8)	0.3922 (2)	0.0225 (3)
H7	0.5819	0.9535	0.3770	0.027*
C8	0.56615 (9)	0.88470 (9)	0.5545 (2)	0.0237 (4)
H8	0.5582	0.9100	0.6539	0.028*
C9	0.56288 (9)	0.82174 (8)	0.5716 (2)	0.0222 (4)
H9	0.5520	0.8046	0.6828	0.027*
C10	0.42944 (9)	0.61927 (8)	0.5796 (2)	0.0228 (4)
C11	0.42116 (9)	0.55701 (8)	0.6003 (2)	0.0240 (4)
H11	0.4579	0.5302	0.5712	0.029*
C12	0.35965 (9)	0.53308 (8)	0.6634 (2)	0.0233 (4)
H12	0.3545	0.4904	0.6778	0.028*
C13	0.30601 (9)	0.57256 (8)	0.7047 (2)	0.0216 (4)
C14	0.31391 (9)	0.63514 (8)	0.6835 (2)	0.0233 (4)
H14	0.2770	0.6619	0.7117	0.028*
C15	0.37540 (9)	0.65865 (8)	0.6213 (2)	0.0239 (4)
H15	0.3806	0.7014	0.6073	0.029*
C16	0.23032 (9)	0.48938 (8)	0.7635 (2)	0.0254 (4)
H16A	0.2302	0.4742	0.6395	0.038*
H16B	0.1839	0.4811	0.8069	0.038*
H16C	0.2681	0.4689	0.8423	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0297 (7)	0.0239 (7)	0.0277 (6)	−0.0003 (5)	0.0043 (5)	−0.0002 (5)
O2	0.0191 (6)	0.0262 (7)	0.0357 (7)	0.0005 (5)	0.0057 (5)	0.0010 (5)
O3	0.0396 (7)	0.0329 (7)	0.0196 (6)	−0.0022 (6)	0.0088 (5)	−0.0013 (5)
O4	0.0310 (7)	0.0246 (7)	0.0305 (6)	−0.0009 (6)	0.0024 (5)	0.0085 (5)
O5	0.0221 (6)	0.0250 (6)	0.0278 (6)	−0.0020 (5)	0.0071 (5)	0.0003 (5)
N1	0.0231 (7)	0.0240 (7)	0.0189 (6)	−0.0025 (6)	0.0002 (5)	0.0034 (6)
N2	0.0242 (7)	0.0233 (8)	0.0256 (7)	−0.0026 (6)	0.0041 (6)	0.0028 (6)
N3	0.0229 (7)	0.0258 (8)	0.0201 (7)	−0.0039 (6)	0.0015 (5)	0.0028 (6)
C1	0.0212 (7)	0.0249 (9)	0.0165 (7)	−0.0010 (7)	0.0005 (6)	0.0026 (6)
C2	0.0226 (8)	0.0255 (9)	0.0176 (7)	−0.0024 (7)	0.0013 (6)	0.0015 (6)
C3	0.0231 (9)	0.0322 (10)	0.0405 (10)	0.0045 (8)	0.0059 (8)	−0.0002 (8)
C4	0.0169 (7)	0.0236 (9)	0.0182 (7)	−0.0012 (6)	−0.0005 (6)	0.0021 (6)
C5	0.0189 (7)	0.0256 (9)	0.0160 (7)	−0.0002 (7)	0.0018 (6)	−0.0014 (6)
C6	0.0184 (7)	0.0245 (9)	0.0168 (7)	−0.0023 (6)	0.0012 (6)	0.0023 (6)
C7	0.0208 (7)	0.0213 (8)	0.0252 (8)	−0.0010 (7)	0.0020 (6)	−0.0022 (7)
C8	0.0214 (8)	0.0299 (9)	0.0199 (8)	0.0008 (7)	0.0035 (6)	−0.0034 (7)
C9	0.0189 (7)	0.0303 (9)	0.0178 (7)	−0.0004 (7)	0.0032 (6)	0.0024 (7)
C10	0.0238 (8)	0.0267 (9)	0.0178 (7)	−0.0045 (7)	0.0005 (6)	0.0011 (7)
C11	0.0226 (8)	0.0241 (9)	0.0256 (8)	0.0004 (7)	0.0046 (6)	0.0000 (7)
C12	0.0247 (8)	0.0217 (9)	0.0235 (8)	−0.0019 (7)	0.0029 (6)	0.0005 (7)
C13	0.0219 (8)	0.0261 (9)	0.0168 (7)	−0.0038 (7)	0.0018 (6)	0.0005 (6)
C14	0.0240 (8)	0.0253 (9)	0.0206 (8)	0.0007 (7)	0.0019 (6)	−0.0015 (7)
C15	0.0267 (8)	0.0229 (9)	0.0216 (8)	−0.0016 (7)	0.0006 (6)	0.0014 (7)
C16	0.0255 (8)	0.0262 (9)	0.0248 (8)	−0.0041 (7)	0.0040 (7)	0.0034 (7)

Geometric parameters (Å, º) top

O1—C2	1.218 (2)	C5—H5	0.9500
O2—C2	1.344 (2)	C6—C7	1.385 (2)
O2—C3	1.447 (2)	C7—C8	1.388 (2)
O3—N3	1.2339 (19)	C7—H7	0.9500
O4—N3	1.227 (2)	C8—C9	1.391 (3)
O5—C13	1.3774 (19)	C8—H8	0.9500
O5—C16	1.432 (2)	C9—H9	0.9500
N1—C1	1.316 (2)	C10—C11	1.387 (2)
N1—N2	1.322 (2)	C10—C15	1.394 (3)
N2—C10	1.410 (2)	C11—C12	1.396 (2)
N2—H2	0.86 (2)	C11—H11	0.9500
N3—C6	1.472 (2)	C12—C13	1.389 (2)
C1—C2	1.478 (2)	C12—H12	0.9500
C1—C4	1.481 (2)	C13—C14	1.393 (2)
C3—H3A	0.9800	C14—C15	1.390 (2)
C3—H3B	0.9800	C14—H14	0.9500
C3—H3C	0.9800	C15—H15	0.9500
C4—C9	1.393 (2)	C16—H16A	0.9800
C4—C5	1.401 (2)	C16—H16B	0.9800
C5—C6	1.379 (2)	C16—H16C	0.9800

C2—O2—C3	116.24 (15)	C8—C7—H7	121.1
C13—O5—C16	116.19 (13)	C7—C8—C9	120.11 (15)
C1—N1—N2	120.14 (15)	C7—C8—H8	119.9
N1—N2—C10	120.66 (15)	C9—C8—H8	119.9
N1—N2—H2	119.4 (15)	C8—C9—C4	121.25 (15)
C10—N2—H2	119.9 (15)	C8—C9—H9	119.4
O4—N3—O3	123.74 (14)	C4—C9—H9	119.4
O4—N3—C6	118.16 (14)	C11—C10—C15	119.60 (16)
O3—N3—C6	118.10 (14)	C11—C10—N2	117.23 (16)
N1—C1—C2	123.46 (16)	C15—C10—N2	123.17 (17)
N1—C1—C4	115.42 (15)	C10—C11—C12	121.02 (16)
C2—C1—C4	121.12 (14)	C10—C11—H11	119.5
O1—C2—O2	123.38 (16)	C12—C11—H11	119.5
O1—C2—C1	125.07 (15)	C13—C12—C11	119.10 (16)
O2—C2—C1	111.52 (15)	C13—C12—H12	120.5
O2—C3—H3A	109.5	C11—C12—H12	120.5
O2—C3—H3B	109.5	O5—C13—C12	123.69 (16)
H3A—C3—H3B	109.5	O5—C13—C14	116.16 (15)
O2—C3—H3C	109.5	C12—C13—C14	120.14 (15)
H3A—C3—H3C	109.5	C15—C14—C13	120.44 (16)
H3B—C3—H3C	109.5	C15—C14—H14	119.8
C9—C4—C5	118.99 (16)	C13—C14—H14	119.8
C9—C4—C1	121.26 (14)	C14—C15—C10	119.70 (17)
C5—C4—C1	119.69 (15)	C14—C15—H15	120.1
C6—C5—C4	118.33 (15)	C10—C15—H15	120.1
C6—C5—H5	120.8	O5—C16—H16A	109.5
C4—C5—H5	120.8	O5—C16—H16B	109.5
C5—C6—C7	123.51 (15)	H16A—C16—H16B	109.5
C5—C6—N3	117.87 (14)	O5—C16—H16C	109.5
C7—C6—N3	118.58 (15)	H16A—C16—H16C	109.5
C6—C7—C8	117.73 (16)	H16B—C16—H16C	109.5
C6—C7—H7	121.1

C1—N1—N2—C10	178.96 (15)	C5—C6—C7—C8	1.2 (3)
N2—N1—C1—C2	−1.1 (2)	N3—C6—C7—C8	178.90 (14)
N2—N1—C1—C4	179.31 (14)	C6—C7—C8—C9	−2.2 (2)
C3—O2—C2—O1	−0.9 (2)	C7—C8—C9—C4	0.8 (2)
C3—O2—C2—C1	177.22 (14)	C5—C4—C9—C8	1.8 (2)
N1—C1—C2—O1	9.1 (3)	C1—C4—C9—C8	−175.54 (15)
C4—C1—C2—O1	−171.35 (15)	N1—N2—C10—C11	−176.81 (14)
N1—C1—C2—O2	−169.00 (15)	N1—N2—C10—C15	3.5 (2)
C4—C1—C2—O2	10.5 (2)	C15—C10—C11—C12	−0.4 (3)
N1—C1—C4—C9	49.2 (2)	N2—C10—C11—C12	179.97 (15)
C2—C1—C4—C9	−130.37 (17)	C10—C11—C12—C13	0.3 (3)
N1—C1—C4—C5	−128.10 (16)	C16—O5—C13—C12	−8.3 (2)
C2—C1—C4—C5	52.3 (2)	C16—O5—C13—C14	171.31 (14)
C9—C4—C5—C6	−2.7 (2)	C11—C12—C13—O5	179.49 (15)
C1—C4—C5—C6	174.63 (14)	C11—C12—C13—C14	−0.1 (2)
C4—C5—C6—C7	1.3 (2)	O5—C13—C14—C15	−179.76 (14)
C4—C5—C6—N3	−176.41 (14)	C12—C13—C14—C15	−0.1 (2)
O4—N3—C6—C5	160.87 (15)	C13—C14—C15—C10	0.1 (2)
O3—N3—C6—C5	−18.7 (2)	C11—C10—C15—C14	0.1 (2)
O4—N3—C6—C7	−16.9 (2)	N2—C10—C15—C14	179.77 (15)
O3—N3—C6—C7	163.47 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86 (2)	1.98 (2)	2.657 (2)	134 (2)
C7—H7···O4ⁱ	0.95	2.44	3.245 (2)	142
C12—H12···O1ⁱⁱ	0.95	2.52	3.401 (2)	154

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

Methyl (E)-2-(4-chlorophenyl)-2-(2-phenylhydrazin-1-ylidene)acetate (4) top

Crystal data top

C₁₅H₁₃ClN₂O₂	D_x = 1.428 Mg m⁻³
M_r = 288.72	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 35974 reflections
a = 15.86326 (8) Å	θ = 4.6–79.5°
b = 8.79608 (3) Å	µ = 2.55 mm⁻¹
c = 19.24680 (8) Å	T = 100 K
V = 2685.59 (2) Å³	Prism, yellow
Z = 8	0.12 × 0.11 × 0.06 mm
F(000) = 1200

Data collection top

Rigaku XtaLAB Synergy-S, HyPix-6000HE area-detector diffractometer	2871 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.030
φ and ω scans	θ_max = 80.1°, θ_min = 4.6°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021).	h = −20→20
T_min = 0.676, T_max = 1.000	k = −11→10
51407 measured reflections	l = −24→24
2935 independent reflections

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: mixed
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0407P)² + 1.4066P] where P = (F_o² + 2F_c²)/3
2935 reflections	(Δ/σ)_max = 0.001
186 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.28 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
Cl1	0.62856 (2)	0.69084 (3)	0.30196 (2)	0.02208 (10)
O1	0.55614 (6)	−0.13395 (10)	0.46392 (4)	0.02205 (19)
O2	0.52650 (5)	0.03451 (9)	0.37933 (4)	0.01828 (18)
N1	0.68620 (6)	0.05063 (11)	0.50371 (5)	0.0165 (2)
N2	0.74780 (6)	0.14132 (11)	0.52647 (5)	0.0176 (2)
H2	0.7585 (10)	0.227 (2)	0.5070 (9)	0.025 (4)*
C1	0.63703 (7)	0.09638 (13)	0.45406 (6)	0.0161 (2)
C2	0.57050 (7)	−0.01517 (13)	0.43440 (6)	0.0168 (2)
C3	0.45741 (7)	−0.06150 (15)	0.35765 (6)	0.0213 (2)
H3A	0.4278	−0.0137	0.3187	0.032*
H3B	0.4182	−0.0753	0.3965	0.032*
H3C	0.4794	−0.1607	0.3431	0.032*
C4	0.64041 (7)	0.24740 (13)	0.41905 (6)	0.0157 (2)
C5	0.61040 (8)	0.37765 (14)	0.45216 (6)	0.0188 (2)
H5	0.5916	0.3719	0.4989	0.023*
C6	0.60782 (8)	0.51597 (14)	0.41715 (6)	0.0194 (2)
H6	0.5869	0.6046	0.4394	0.023*
C7	0.63640 (7)	0.52207 (13)	0.34913 (6)	0.0176 (2)
C8	0.66907 (8)	0.39514 (14)	0.31583 (6)	0.0197 (2)
H8	0.6903	0.4024	0.2698	0.024*
C9	0.67013 (7)	0.25752 (13)	0.35102 (6)	0.0188 (2)
H9	0.6913	0.1693	0.3285	0.023*
C10	0.79852 (7)	0.09200 (13)	0.58191 (6)	0.0155 (2)
C11	0.77436 (7)	−0.03165 (13)	0.62277 (6)	0.0167 (2)
H11	0.7228	−0.0829	0.6137	0.020*
C12	0.82608 (8)	−0.07924 (13)	0.67669 (6)	0.0196 (2)
H12	0.8101	−0.1646	0.7039	0.023*
C13	0.90101 (8)	−0.00373 (14)	0.69152 (6)	0.0203 (2)
H13	0.9360	−0.0367	0.7286	0.024*
C14	0.92395 (7)	0.12079 (13)	0.65114 (6)	0.0187 (2)
H14	0.9746	0.1740	0.6613	0.022*
C15	0.87377 (7)	0.16839 (13)	0.59610 (6)	0.0169 (2)
H15	0.8905	0.2523	0.5683	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02274 (16)	0.01621 (15)	0.02730 (17)	0.00088 (10)	−0.00065 (10)	0.00687 (10)
O1	0.0299 (5)	0.0155 (4)	0.0207 (4)	−0.0003 (3)	−0.0038 (3)	0.0027 (3)
O2	0.0199 (4)	0.0184 (4)	0.0165 (4)	−0.0008 (3)	−0.0041 (3)	0.0022 (3)
N1	0.0190 (5)	0.0163 (4)	0.0143 (4)	0.0019 (4)	−0.0007 (3)	−0.0008 (4)
N2	0.0214 (5)	0.0146 (4)	0.0168 (4)	−0.0008 (4)	−0.0033 (4)	0.0031 (4)
C1	0.0200 (5)	0.0146 (5)	0.0138 (5)	0.0031 (4)	−0.0002 (4)	−0.0006 (4)
C2	0.0209 (5)	0.0151 (5)	0.0143 (5)	0.0043 (4)	−0.0002 (4)	−0.0010 (4)
C3	0.0182 (5)	0.0247 (6)	0.0211 (5)	−0.0022 (5)	−0.0020 (4)	−0.0009 (5)
C4	0.0165 (5)	0.0148 (5)	0.0159 (5)	0.0010 (4)	−0.0042 (4)	0.0007 (4)
C5	0.0241 (6)	0.0176 (6)	0.0146 (5)	0.0012 (5)	−0.0016 (4)	−0.0013 (4)
C6	0.0226 (6)	0.0152 (5)	0.0204 (6)	0.0022 (4)	−0.0028 (4)	−0.0021 (4)
C7	0.0162 (5)	0.0149 (5)	0.0216 (6)	−0.0013 (4)	−0.0039 (4)	0.0035 (4)
C8	0.0206 (6)	0.0200 (6)	0.0184 (5)	0.0016 (4)	0.0017 (4)	0.0025 (4)
C9	0.0209 (5)	0.0168 (5)	0.0187 (5)	0.0028 (4)	0.0008 (4)	−0.0005 (4)
C10	0.0181 (5)	0.0151 (5)	0.0134 (5)	0.0040 (4)	0.0002 (4)	−0.0010 (4)
C11	0.0183 (5)	0.0147 (5)	0.0172 (5)	−0.0009 (4)	−0.0005 (4)	−0.0003 (4)
C12	0.0256 (6)	0.0167 (5)	0.0164 (5)	0.0004 (4)	−0.0005 (4)	0.0030 (4)
C13	0.0220 (6)	0.0218 (6)	0.0173 (5)	0.0042 (5)	−0.0037 (4)	0.0005 (4)
C14	0.0170 (5)	0.0194 (5)	0.0197 (5)	0.0006 (4)	−0.0001 (4)	−0.0036 (4)
C15	0.0183 (5)	0.0149 (5)	0.0176 (5)	0.0006 (4)	0.0031 (4)	−0.0005 (4)

Geometric parameters (Å, º) top

Cl1—C7	1.7446 (12)	C6—C7	1.3864 (17)
O1—C2	1.2109 (14)	C6—H6	0.9500
O2—C2	1.3423 (14)	C7—C8	1.3878 (17)
O2—C3	1.4451 (14)	C8—C9	1.3872 (16)
N1—C1	1.2975 (15)	C8—H8	0.9500
N1—N2	1.3354 (14)	C9—H9	0.9500
N2—C10	1.4050 (14)	C10—C11	1.3959 (16)
N2—H2	0.861 (18)	C10—C15	1.3967 (16)
C1—C2	1.4899 (16)	C11—C12	1.3876 (16)
C1—C4	1.4905 (16)	C11—H11	0.9500
C3—H3A	0.9800	C12—C13	1.3911 (18)
C3—H3B	0.9800	C12—H12	0.9500
C3—H3C	0.9800	C13—C14	1.3914 (17)
C4—C9	1.3945 (16)	C13—H13	0.9500
C4—C5	1.3948 (16)	C14—C15	1.3897 (17)
C5—C6	1.3914 (17)	C14—H14	0.9500
C5—H5	0.9500	C15—H15	0.9500

C2—O2—C3	115.60 (9)	C6—C7—Cl1	120.07 (9)
C1—N1—N2	119.75 (10)	C8—C7—Cl1	118.09 (9)
N1—N2—C10	118.94 (9)	C9—C8—C7	118.75 (11)
N1—N2—H2	121.8 (11)	C9—C8—H8	120.6
C10—N2—H2	119.2 (11)	C7—C8—H8	120.6
N1—C1—C2	114.11 (10)	C8—C9—C4	120.66 (11)
N1—C1—C4	126.00 (11)	C8—C9—H9	119.7
C2—C1—C4	119.84 (10)	C4—C9—H9	119.7
O1—C2—O2	123.61 (11)	C11—C10—C15	119.96 (10)
O1—C2—C1	125.62 (11)	C11—C10—N2	120.74 (10)
O2—C2—C1	110.76 (10)	C15—C10—N2	119.30 (10)
O2—C3—H3A	109.5	C12—C11—C10	119.61 (11)
O2—C3—H3B	109.5	C12—C11—H11	120.2
H3A—C3—H3B	109.5	C10—C11—H11	120.2
O2—C3—H3C	109.5	C11—C12—C13	120.97 (11)
H3A—C3—H3C	109.5	C11—C12—H12	119.5
H3B—C3—H3C	109.5	C13—C12—H12	119.5
C9—C4—C5	119.48 (11)	C12—C13—C14	119.00 (11)
C9—C4—C1	119.57 (10)	C12—C13—H13	120.5
C5—C4—C1	120.88 (10)	C14—C13—H13	120.5
C6—C5—C4	120.46 (11)	C15—C14—C13	120.87 (11)
C6—C5—H5	119.8	C15—C14—H14	119.6
C4—C5—H5	119.8	C13—C14—H14	119.6
C7—C6—C5	118.79 (11)	C14—C15—C10	119.58 (11)
C7—C6—H6	120.6	C14—C15—H15	120.2
C5—C6—H6	120.6	C10—C15—H15	120.2
C6—C7—C8	121.81 (11)

C1—N1—N2—C10	177.79 (10)	C5—C6—C7—Cl1	176.33 (9)
N2—N1—C1—C2	−179.28 (9)	C6—C7—C8—C9	2.39 (18)
N2—N1—C1—C4	−1.64 (17)	Cl1—C7—C8—C9	−175.45 (9)
C3—O2—C2—O1	1.85 (16)	C7—C8—C9—C4	−1.20 (18)
C3—O2—C2—C1	−177.15 (9)	C5—C4—C9—C8	−0.84 (17)
N1—C1—C2—O1	5.92 (17)	C1—C4—C9—C8	176.03 (11)
C4—C1—C2—O1	−171.89 (11)	N1—N2—C10—C11	−14.31 (16)
N1—C1—C2—O2	−175.10 (9)	N1—N2—C10—C15	165.87 (10)
C4—C1—C2—O2	7.09 (14)	C15—C10—C11—C12	−0.95 (17)
N1—C1—C4—C9	108.05 (14)	N2—C10—C11—C12	179.23 (10)
C2—C1—C4—C9	−74.43 (14)	C10—C11—C12—C13	1.22 (18)
N1—C1—C4—C5	−75.13 (16)	C11—C12—C13—C14	−0.27 (18)
C2—C1—C4—C5	102.39 (13)	C12—C13—C14—C15	−0.95 (18)
C9—C4—C5—C6	1.78 (18)	C13—C14—C15—C10	1.21 (17)
C1—C4—C5—C6	−175.04 (11)	C11—C10—C15—C14	−0.25 (17)
C4—C5—C6—C7	−0.65 (18)	N2—C10—C15—C14	179.58 (10)
C5—C6—C7—C8	−1.47 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···N1ⁱ	0.98	2.55	3.5099 (15)	168
C3—H3C···Cl1ⁱⁱ	0.98	2.82	3.6422 (12)	142
C6—H6···O1ⁱⁱⁱ	0.95	2.40	3.3113 (15)	161
C15—H15···O1^iv	0.95	2.40	3.2759 (14)	153
C14—H14···Cg1^v	0	2.80	3.4792 (12)	129

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

Methyl (Z)-2-[2-(4-bromophenyl)hydrazin-1-ylidene]-2-(4-chlorophenyl)acetate (5) top

Crystal data top

C₁₅H₁₂BrClN₂O₂	D_x = 1.628 Mg m⁻³
M_r = 367.62	Synchrotron radiation, λ = 0.75270 Å
Orthorhombic, Pca2₁	Cell parameters from 1000 reflections
a = 14.0199 (16) Å	θ = 2.0–30.0°
b = 16.5940 (19) Å	µ = 3.35 mm⁻¹
c = 6.4471 (9) Å	T = 100 K
V = 1499.9 (3) Å³	Prism, yellow
Z = 4	0.18 × 0.15 × 0.13 mm
F(000) = 736

Data collection top

Rayonix SX165 CCD diffractometer	3677 reflections with I > 2σ(I)
/f scan	R_int = 0.039
Absorption correction: multi-scan (Scala; Evans, 2006)	θ_max = 30.9°, θ_min = 2.0°
T_min = 0.514, T_max = 0.633	h = −19→18
12123 measured reflections	k = −18→22
3908 independent reflections	l = −8→8

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.040	w = 1/[σ²(F_o²) + (0.0506P)² + 2.3974P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.110	(Δ/σ)_max = 0.001
S = 1.09	Δρ_max = 1.27 e Å⁻³
3908 reflections	Δρ_min = −0.67 e Å⁻³
196 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.014 (1)
Primary atom site location: difference Fourier map	Absolute structure: Refined as an inversion twin.
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.167 (15)

Special details top

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
Br1	0.35303 (3)	0.07176 (3)	0.51060 (10)	0.03049 (18)
Cl1	0.86147 (9)	0.63637 (7)	0.4619 (3)	0.0430 (5)
O1	0.95706 (19)	0.14905 (16)	0.5120 (8)	0.0231 (5)
O2	1.04385 (18)	0.26332 (17)	0.5082 (9)	0.0251 (6)
N1	0.7900 (2)	0.24954 (19)	0.5158 (9)	0.0196 (6)
N2	0.7689 (2)	0.17193 (19)	0.5187 (9)	0.0203 (6)
H2	0.816 (4)	0.133 (3)	0.534 (11)	0.028 (14)*
C1	0.8774 (3)	0.2762 (2)	0.5109 (10)	0.0192 (7)
C2	0.9619 (3)	0.2222 (2)	0.5112 (11)	0.0204 (6)
C3	1.1298 (3)	0.2153 (3)	0.5058 (17)	0.0320 (9)
H3A	1.1856	0.2509	0.5035	0.048*
H3B	1.1302	0.1810	0.3821	0.048*
H3C	1.1320	0.1815	0.6303	0.048*
C4	0.8846 (3)	0.3657 (2)	0.5107 (10)	0.0193 (6)
C5	0.8273 (4)	0.4089 (3)	0.6459 (8)	0.0273 (9)
H5	0.7915	0.3809	0.7482	0.033*
C6	0.8212 (4)	0.4922 (3)	0.6349 (9)	0.0306 (10)
H6	0.7813	0.5212	0.7278	0.037*
C7	0.8734 (3)	0.5318 (3)	0.4883 (12)	0.0283 (11)
C8	0.9341 (4)	0.4911 (3)	0.3510 (8)	0.0296 (10)
H8	0.9705	0.5197	0.2508	0.035*
C9	0.9397 (4)	0.4077 (3)	0.3655 (8)	0.0271 (9)
H9	0.9813	0.3788	0.2760	0.033*
C10	0.6727 (3)	0.1497 (2)	0.5157 (11)	0.0197 (6)
C11	0.6488 (3)	0.0683 (2)	0.5221 (18)	0.0257 (9)
H11	0.6978	0.0289	0.5285	0.031*
C12	0.5535 (3)	0.0441 (2)	0.5193 (12)	0.0260 (8)
H12	0.5370	−0.0115	0.5219	0.031*
C13	0.4838 (2)	0.1026 (2)	0.5125 (12)	0.0220 (7)
C14	0.5058 (3)	0.1841 (2)	0.5129 (11)	0.0214 (7)
H14	0.4562	0.2231	0.5133	0.026*
C15	0.6005 (3)	0.2082 (2)	0.5128 (11)	0.0198 (7)
H15	0.6164	0.2639	0.5109	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0175 (2)	0.0280 (2)	0.0460 (3)	−0.00531 (13)	−0.0003 (3)	−0.0011 (3)
Cl1	0.0338 (6)	0.0200 (5)	0.0750 (14)	−0.0015 (4)	−0.0054 (6)	0.0041 (6)
O1	0.0214 (12)	0.0224 (12)	0.0255 (13)	0.0014 (10)	−0.0026 (19)	−0.0035 (19)
O2	0.0157 (11)	0.0254 (13)	0.0343 (14)	−0.0009 (10)	−0.001 (2)	−0.001 (2)
N1	0.0205 (14)	0.0213 (14)	0.0168 (13)	−0.0035 (11)	0.002 (2)	−0.0016 (18)
N2	0.0156 (13)	0.0185 (13)	0.0268 (15)	0.0000 (10)	0.000 (2)	0.000 (2)
C1	0.0175 (15)	0.0205 (15)	0.0195 (15)	−0.0019 (12)	−0.010 (3)	−0.003 (2)
C2	0.0183 (15)	0.0248 (16)	0.0183 (15)	−0.0013 (12)	0.000 (3)	−0.001 (2)
C3	0.0186 (17)	0.033 (2)	0.044 (2)	0.0030 (15)	−0.009 (4)	−0.003 (3)
C4	0.0165 (14)	0.0210 (15)	0.0205 (15)	−0.0029 (12)	0.001 (2)	0.001 (3)
C5	0.023 (2)	0.027 (2)	0.031 (2)	−0.0007 (19)	0.0050 (18)	−0.0013 (18)
C6	0.023 (2)	0.027 (2)	0.042 (3)	−0.0032 (18)	0.006 (2)	0.000 (2)
C7	0.0209 (17)	0.0198 (17)	0.044 (3)	−0.0005 (14)	−0.002 (3)	0.007 (2)
C8	0.024 (2)	0.034 (3)	0.030 (2)	−0.0049 (19)	0.0017 (19)	0.0018 (19)
C9	0.023 (2)	0.034 (2)	0.025 (2)	−0.0040 (19)	0.0067 (18)	0.0016 (19)
C10	0.0166 (15)	0.0205 (15)	0.0218 (16)	−0.0020 (12)	−0.004 (2)	−0.002 (2)
C11	0.0201 (18)	0.0171 (16)	0.040 (3)	0.0017 (13)	0.001 (3)	0.000 (2)
C12	0.0218 (17)	0.0168 (15)	0.040 (2)	−0.0019 (13)	−0.004 (3)	0.003 (3)
C13	0.0150 (14)	0.0218 (16)	0.0292 (17)	−0.0024 (12)	0.000 (3)	0.000 (2)
C14	0.0198 (15)	0.0183 (15)	0.0262 (16)	0.0013 (12)	0.000 (3)	0.000 (2)
C15	0.0209 (16)	0.0185 (15)	0.0202 (15)	−0.0010 (12)	−0.001 (3)	−0.002 (2)

Geometric parameters (Å, º) top

Br1—C13	1.904 (3)	C5—H5	0.9500
Cl1—C7	1.752 (4)	C6—C7	1.365 (8)
O1—C2	1.217 (4)	C6—H6	0.9500
O2—C2	1.335 (4)	C7—C8	1.401 (8)
O2—C3	1.445 (5)	C8—C9	1.390 (7)
N1—C1	1.303 (5)	C8—H8	0.9500
N1—N2	1.322 (4)	C9—H9	0.9500
N2—C10	1.397 (5)	C10—C11	1.392 (5)
N2—H2	0.93 (6)	C10—C15	1.403 (5)
C1—C2	1.485 (5)	C11—C12	1.396 (5)
C1—C4	1.489 (5)	C11—H11	0.9500
C3—H3A	0.9800	C12—C13	1.379 (5)
C3—H3B	0.9800	C12—H12	0.9500
C3—H3C	0.9800	C13—C14	1.385 (5)
C4—C5	1.385 (7)	C14—C15	1.388 (5)
C4—C9	1.399 (7)	C14—H14	0.9500
C5—C6	1.387 (7)	C15—H15	0.9500

C2—O2—C3	115.9 (3)	C6—C7—Cl1	119.5 (4)
C1—N1—N2	122.8 (3)	C8—C7—Cl1	118.3 (5)
N1—N2—C10	118.2 (3)	C9—C8—C7	118.1 (5)
N1—N2—H2	121 (3)	C9—C8—H8	120.9
C10—N2—H2	121 (3)	C7—C8—H8	120.9
N1—C1—C2	123.1 (3)	C8—C9—C4	120.6 (5)
N1—C1—C4	113.7 (3)	C8—C9—H9	119.7
C2—C1—C4	123.2 (3)	C4—C9—H9	119.7
O1—C2—O2	123.9 (3)	C11—C10—N2	119.2 (3)
O1—C2—C1	123.8 (3)	C11—C10—C15	119.8 (3)
O2—C2—C1	112.2 (3)	N2—C10—C15	120.9 (3)
O2—C3—H3A	109.5	C10—C11—C12	120.7 (3)
O2—C3—H3B	109.5	C10—C11—H11	119.7
H3A—C3—H3B	109.5	C12—C11—H11	119.7
O2—C3—H3C	109.5	C13—C12—C11	118.4 (3)
H3A—C3—H3C	109.5	C13—C12—H12	120.8
H3B—C3—H3C	109.5	C11—C12—H12	120.8
C5—C4—C9	119.0 (4)	C12—C13—C14	122.0 (3)
C5—C4—C1	118.5 (5)	C12—C13—Br1	119.5 (3)
C9—C4—C1	122.3 (5)	C14—C13—Br1	118.4 (3)
C4—C5—C6	121.3 (5)	C13—C14—C15	119.6 (3)
C4—C5—H5	119.4	C13—C14—H14	120.2
C6—C5—H5	119.4	C15—C14—H14	120.2
C7—C6—C5	118.8 (5)	C14—C15—C10	119.4 (3)
C7—C6—H6	120.6	C14—C15—H15	120.3
C5—C6—H6	120.6	C10—C15—H15	120.3
C6—C7—C8	122.1 (4)

C1—N1—N2—C10	−177.5 (6)	C6—C7—C8—C9	0.7 (9)
N2—N1—C1—C2	−0.9 (11)	Cl1—C7—C8—C9	−176.8 (4)
N2—N1—C1—C4	−179.3 (6)	C7—C8—C9—C4	1.2 (8)
C3—O2—C2—O1	0.0 (11)	C5—C4—C9—C8	−2.7 (8)
C3—O2—C2—C1	−179.3 (7)	C1—C4—C9—C8	170.7 (5)
N1—C1—C2—O1	1.5 (11)	N1—N2—C10—C11	−179.0 (8)
C4—C1—C2—O1	179.8 (7)	N1—N2—C10—C15	−1.0 (10)
N1—C1—C2—O2	−179.2 (6)	N2—C10—C11—C12	180.0 (8)
C4—C1—C2—O2	−0.9 (9)	C15—C10—C11—C12	2.0 (14)
N1—C1—C4—C5	44.2 (8)	C10—C11—C12—C13	−0.8 (14)
C2—C1—C4—C5	−134.2 (6)	C11—C12—C13—C14	−1.4 (13)
N1—C1—C4—C9	−129.2 (6)	C11—C12—C13—Br1	−179.5 (7)
C2—C1—C4—C9	52.3 (9)	C12—C13—C14—C15	2.3 (13)
C9—C4—C5—C6	2.3 (8)	Br1—C13—C14—C15	−179.5 (5)
C1—C4—C5—C6	−171.4 (5)	C13—C14—C15—C10	−1.0 (11)
C4—C5—C6—C7	−0.4 (8)	C11—C10—C15—C14	−1.1 (11)
C5—C6—C7—C8	−1.1 (9)	N2—C10—C15—C14	−179.0 (7)
C5—C6—C7—Cl1	176.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.93 (5)	2.00 (6)	2.666 (4)	127 (4)
C9—H9···O2	0.95	2.58	2.953 (6)	103
C11—H11···Br1ⁱ	0.95	2.75	3.689 (4)	172
C12—H12···O1ⁱⁱ	0.95	2.54	3.479 (4)	168
C14—H14···Cl1ⁱⁱⁱ	0.95	2.70	3.616 (4)	161
C8—H8···Cg1^iv	0.95	2.70	3.591 (6)	157

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

Percentage contributions of interatomic contacts to the Hirshfeld surface for compounds 1, 2, 3, 4 and 5 top

Contact	1	2A	3B	3	4	5
H···H	59.9	41.8	46.4	38.9	39.0	26.3
C···H/H···C	13.3	26.8	21.0	16.0	21.4	25.1
Br···H/H···Br	12.5	15.7	15.6	—	—	15.8
O···H/H···O	6.2	6.9	8.5	28.5	12.7	5.6
N···H/H···N	2.0	3.2	3.2	2.4	5.7	1.9
N···C/C···N	2.2	1.7	1.7	3.4	2.0	1.0
C···C	1.4	1.1	1.1	3.6	1.2	2.3
O···C/C···O	1.1	1.4	1.4	3.9	1.4	3.9
O···N/N···O	0.9	0.7	0.7	1.9	—	—
O···O	—	0.1	—	0.9	0.2	—
N···N	—	—	—	0.4	—	1.5
Br···O/O···Br	0.5	—	—	—	—	—
Br···C/C···Br	0.1	0.5	0.2	—	—	0.6
Br···Br	—	—	—	—	—	0.1
Cl···H/H···Cl	—	—	—	—	—	14.5
Cl···O/O···Cl	—	—	—	—	—	1.3

Acknowledgements

The author's contributions are as follows. Conceptualization, NQS, MA and AB; synthesis, AAB and GTA; X-ray analysis, ZA, VNK and MA; writing (review and editing of the manuscript) ZA, MA and AB; funding acquisition, NQS, IMS, AMM; supervision, NQS, MA and AB.

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