The crystal structures and Hirshfeld surface analysis of N′,N′′′-((1E,1′E)-{[methyl­enebis(­oxy)]bis­(6-bromo-3,1-phenyl­ene)}bis­(methan­ylyl­idene))bis­(isonicotinohydrazide) dihydrate and N′,N′′′-((1E,1′E)-{[butane-1,4-diylbis(­oxy)]bis­(2,1-phenyl­ene)}bis­(methan­ylyl­idene))bis­(isonicotino­hydrazide) [+ solvent]

Syed Abuthahir, S.; NizamMohideen, M.; Viswanathan, V.; Abiraman, T.; Balasubramanian, S.

doi:10.1107/S2056989019005048

research communications

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ISSN: 2056-9890

Volume 75| Part 5| May 2019| Pages 655-661

https://doi.org/10.1107/S2056989019005048

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The crystal structures and Hirshfeld surface analysis of N′,N′′′-((1E,1′E)-{[methylenebis(oxy)]bis(6-bromo-3,1-phenylene)}bis(methanylylidene))bis(isonicotinohydrazide) dihydrate and N′,N′′′-((1E,1′E)-{[butane-1,4-diylbis(oxy)]bis(2,1-phenylene)}bis(methanylylidene))bis(isonicotinohydrazide) [+ solvent]

S. Syed Abuthahir,^a M. NizamMohideen,^a ^* V. Viswanathan,^b Tamilselvan Abiraman ^c and Sengottuvelan Balasubramanian ^c

^aPG & Research Department of Physics, The New College (Autonomous), Chennai 600 014, Tamil Nadu, India, ^bDepartment of Biophysics, All India Institute of Medical Sciences, New Delhi 110 029, India, and ^cDepartment of Inorganic Chemistry, University of Madras, Chennai 600 025, India
^*Correspondence e-mail: mnizam.new@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 5 April 2019; accepted 12 April 2019; online 18 April 2019)

The title compounds, C₂₇H₂₀Br₂N₆O₄·2H₂O, (I), and C₃₀H₂₈N₆O₄·[+ solvent], (II), both crystallize with one half-molecule in the asymmetric unit. The whole molecule of (I) is generated by twofold rotation symmetry, with the twofold rotation axis bisecting the C atom of the –O—CH₂—O– bridge. This results in a folded or U-shaped conformation of the molecule. The whole molecule of (II) is generated by inversion symmetry, with the central CH₂—CH₂ bond of the –O—(CH₂)₄—O– bridge being located about a center of inversion. This results in a step-like conformation of the molecule. The central C(=O)N—N=C regions of the isonicotinohydrazide moieties in both compounds are planar and the configuration about the imine C=N bonds is E. In compound (I), the benzene and pyridine rings are inclined to each other by 37.60 (6)°. The two symmetry-related pyridine rings are inclined to each other by 74.24 (6)°, and the two symmetry-related benzene rings by 7.69 (6)°. In compound (II), the benzene and pyridine rings are inclined to each other by 25.56 (11)°. The symmetry-related pyridine rings are parallel, as are the two symmetry-related benzene rings. In the crystal of (I), a pair of water molecules link the organic molecules via O_water—H⋯O and O_water—H⋯N hydrogen bonds, forming chains along [001], and enclosing an R₄²(8) and two R₁²(5) ring motifs. The chains are linked by N—H⋯N_pyridine hydrogen bonds, forming a supramolecular framework. There are also a number of C—H⋯O hydrogen bonds, and C—H⋯π and offset π–π interactions [interplanar distance = 3.294 (1) Å] present reinforcing the framework. In the crystal of (II), molecules are linked by N—H⋯N_pyridine hydrogen bonds, forming a supramolecular framework. Here too there are also a number of C—H⋯O hydrogen bonds present, and a C—H⋯π interaction, reinforcing the framework. For compound (II), a region of disordered electron density was corrected for using the SQUEEZE [Spek (2015 ). Acta Cryst. C71, 9–18] routine in PLATON. Their formula mass and unit-cell characteristics were not taken into account during refinement.

Keywords: crystal structure; isonicotinoyl; hydrazide; pyridine; amide; hydrogen bonding; Hirshfeld surface analysis; supramolecular framework.

CCDC references: 1907912; 1907913

1. Chemical context

Hydrazide-hydrazone compounds are found to be associated with a wide spectrum of biological and medicinal applications. such as antimicrobial, anticonvulsant, analgesic, anti-inflammatory (Kaplancikli et al., 2012 ), anti-platelet, antibacterial, antifungal, anti-tubercular and anti-tumor properties (Babahan et al., 2013 ; Bedia et al., 2006 ). Schiff bases of the general type p-R′-C₆H₄—CH—N—C₆H₄—R"-p are well-known reagents that find practical application in various areas, e.g. photography and medicinal and pharmaceutical chemistry (Sethuram et al., 2013 ). Hydrazide Schiff base ligands arise owing to the presence of electron-donating nitrogen and oxygen atoms, allowing these to act as multidentate ligands, and their transition-metal complexes have been used in the treatment of tuberculosis, in colorimetric or fluorimetric analytic determinations, as well as in applications involving catalytic processes (Torje et al., 2012 ) and, in some cases, function as supramolecular building blocks in their molecular assemblies (Wei et al., 2015 ). Hydrazone derivatives containing an azomethine (–CONHN=CH–) group act as cytotoxic agents with the capability to prevent cell series in cancerous cells through different mechanisms (Patil et al., 2011 ). Pyridine heterocycles and their derivatives are present in many large molecules having photo-chemical, electrochemical and catalytic applications (Thirunavukkarsu et al., 2017 ; Venda et al., 2017 ; Jauhar et al., 2016 ; Babu et al., 2014a ,b , 2015 ; Rajkumar et al., 2014 , 2015 ; Huq et al., 2010 ). As a part of our research study, we report herein the synthesis and the crystal structures of the title compounds, (I) and (II), which contain several donor functions of a different nature: hydrazide and pyridine.

2. Structural commentary

The molecular structures of the title compounds (I) and (II) are illustrated in Figs. 1 and 2, respectively. Selected bond lengths and angles are given in Tables 1 and 2 for compounds (I) and (II), respectively. The conformations of the two molecules differ considerably. Compound (I) has a folded or U-shaped conformation, while compound (II) has an open step-like conformation. In compound (I), the benzene (C8–C13) and pyridine (N1/C1–C5) rings are inclined to each other by 37.60 (6)°. The two symmetry-related pyridine rings are inclined to each other by 74.24 (6)°, and the two symmetry-related benzene rings by 7.69 (6)°. In compound (II), the benzene and pyridine rings are inclined to each other by 25.56 (11)°. The symmetry-related pyridine rings are parallel, as are the two symmetry-related benzene rings. In both compounds, the hydrazone molecule adopts an E configuration with respect to the hydrazone bridge N3=C7, with torsion angle N2—N3—C7—C8 = 176.82 (11) ° in (I) and 179.5 (2)° in (II). On the other hand, torsion angles N3—N2—C6—C1 [−179.8 (1) ° for (I) and 171.5 (2)° for (II)] and C6—N2—N3—C7 [−173.8 (1) ° for (I) and 179.1 (2)° for (II)], are consistent with an all-trans relationship in the central chain.

Table 1
Selected geometric parameters (Å, °) for (I)

O1—C6	1.2300 (16)	N3—C7	1.2820 (16)
N2—C6	1.3512 (16)	C1—C6	1.4976 (17)
N2—N3	1.3857 (15)	C7—C8	1.4677 (17)

C6—N2—N3	117.46 (11)	O1—C6—C1	120.81 (11)
C7—N3—N2	114.86 (11)	N2—C6—C1	115.38 (11)
O1—C6—N2	123.81 (12)

C6—N2—N3—C7	−173.82 (11)	N3—N2—C6—C1	−179.82 (10)
N3—N2—C6—O1	0.24 (19)	N2—N3—C7—C8	176.82 (11)

Table 2
Selected geometric parameters (Å, °) for (II)

O1—C6	1.223 (2)	N3—C7	1.278 (2)
N2—C6	1.355 (2)	C1—C6	1.501 (3)
N2—N3	1.388 (2)	C7—C8	1.463 (3)

C6—N2—N3	118.93 (15)	O1—C6—C1	120.65 (16)
C7—N3—N2	115.07 (15)	N2—C6—C1	115.29 (15)
O1—C6—N2	124.00 (17)

C6—N2—N3—C7	179.08 (17)	N3—N2—C6—C1	171.51 (15)
N3—N2—C6—O1	−5.6 (3)	N2—N3—C7—C8	179.54 (15)

Figure 1
View of the molecular structure of compound (I)

, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by a twofold rotation axis [symmetry code (i): −x + 1, y, −z + $[{3\over 2}]$ ]. For clarity, the two water molecules of crystallization have been omitted.

Figure 2
View of the molecular structure of compound (II)

, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by inversion symmetry [symmetry code (i): −x, −y + 1, −z].

The bond lengths and angles in the carbohydrazide group of the title compounds can be compared with the values reported for related structures (Prabhu et al., 2011 ; Bikas et al., 2010 ). The N3—N2—C6—O1 torsion angle of 0.2 (2) and −5.6 (3)° for (I) and (II), respectively, indicates the cis configuration of the O1 atom with respect to the hydrazine nitrogen atom N3. The C6—N2 and C7=N3 bond lengths differ by 0.068 (2) Å in (I) and by 0.077 (2) Å in (II), hence these two bonds are properly assigned as single and double bonds, respectively. Bond lengths in the amide unit of aroyl hydrazones are in the ranges 1.218–1.292 Å for C=O bonds and 1.313–1.365 Å for C—N bonds in the keto tautomeric form, and 1.284—1.314 Å for C=O bonds and 1.291–1.331 Å for C—N bonds in the enol tautomeric form (Hosseini-Monfared et al., 2013 ). Hence, compounds (I) and (II) are in the keto tautomeric form, which can be verified from the C=O and C—NH bond lengths of the amide unit: O1=C6 [1.230 (2) Å for (I) and 1.223 (2) Å for (II)] and N2—C6 [1.351 (2) Å for (I) and 1.355 (2) Å for (II)]. The bond distances C7=N3 [1.282 (2) Å for (I) and 1.278 (2) Å for (II)] and C6=O1 [1.229 (2) Å for (I) and 1.220 (2) Å for (II)], are very close to the recognized double C=N and C=O bond lengths (Prasanna et al., 2013 ; Wang et al., 2010 ), confirming that the carbohydrazide exists as an amido tautomer in the solid state. In the two compounds, the three bond angles around atom C6 (see Tables 1 and 2) differ from 120°, probably in order to decrease the repulsion between the lone pairs present on atoms N2 and O1.

3. Supramolecular features

In the crystal of (I), a pair of water molecules link the organic molecules via O_water—H⋯O and O_water—H⋯N hydrogen bonds, forming chains along [001] and enclosing an R₄²(8) and two R₁²(5) ring motifs (Table 3 and Fig. 3). The chains are linked by N—H⋯N_pyridine hydrogen bonds, forming a supramolecular framework. There are also a number of C—H⋯O hydrogen bonds, and C—H⋯π and offset π–π interactions [interplanar distance = 3.294 (1) Å] present, reinforcing the framework (Table 3). The offset π-π- interactions involve inversion-related C8–C13 benzene rings, centroid Cg2. The intercentroid distance Cg2⋯Cg2(−x + 1, −y + 1, −z + 1) is 3.766 (1) Å, α = 0.00 (6)°, β = 29°, interplanar distance = 3.294 (1) Å, offset of 1.824 Å.

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

Cg1 is the centroid of N1/C1–C5 pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—HN2⋯N1ⁱ	0.85 (2)	2.179 (19)	3.0261 (16)	174 (2)
O1W—H1W⋯O1	0.86 (2)	2.06 (2)	2.8756 (15)	158 (2)
O1W—H1W⋯N3	0.86 (2)	2.61 (2)	3.2476 (16)	131.3 (19)
O1W—H2W⋯O1ⁱⁱ	0.83 (3)	2.19 (3)	3.0244 (16)	174 (2)
C3—H3⋯O1Wⁱⁱⁱ	0.93	2.56	3.4450 (17)	159
C4—H4⋯Br1^iv	0.93	2.94	3.8554 (13)	169
C10—H10⋯O1^v	0.93	2.56	3.4123 (17)	152
C13—H13⋯O1W	0.93	2.59	3.5148 (18)	171
C14—H14A⋯Cg1^v	0.97	2.74	3.594 (1)	144
C14—H14B⋯Cg1^vi	0.97	2.74	3.594 (1)	144
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y+2, -z+1; (iii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) x, y-1, z; (vi) $[-x+1, y-1, -z+{\script{3\over 2}}]$ .

Figure 3
The crystal packing of compound (I)

, viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 3

for details). For clarity, the C-bound H atoms have been omitted.

In the crystal of (II), molecules are linked by N—H⋯N_pyridine hydrogen bonds, forming a supramolecular framework (Table 4 and Fig. 4). Here too there are also a number of C—H⋯O hydrogen bonds present, and a C—H⋯π interaction (Table 4), reinforcing the framework, but no π–π interactions are observed.

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

Cg2 is the centroid of the C8–C13 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯N1ⁱ	0.91 (2)	2.04 (2)	2.907 (2)	159 (2)
C3—H3⋯O1ⁱⁱ	0.93	2.60	3.449 (3)	153
C3—H3⋯N3ⁱⁱ	0.93	2.55	3.223 (3)	129
C7—H7⋯N1ⁱ	0.93	2.63	3.372 (3)	137
C12—H12⋯O1ⁱⁱⁱ	0.93	2.43	3.331 (2)	163
C15—H15A⋯Cg2^iv	0.97	2.91	3.748 (2)	145
Symmetry codes: (i) $[y-{\script{1\over 3}}, -x+y+{\script{1\over 3}}, -z+{\script{1\over 3}}]$ ; (ii) $[x-y+{\script{2\over 3}}, x+{\script{1\over 3}}, -z+{\script{4\over 3}}]$ ; (iii) $[-y+{\script{1\over 3}}, x-y+{\script{2\over 3}}, z-{\script{1\over 3}}]$ ; (iv) x, y, z-1.

Figure 4
The crystal packing of compound (II)

, viewed along the c axis. The hydrogen bonds are shown as dashed lines (see Table 4

for details). For clarity, the C-bound H atoms have been omitted. The cylindrical cavities are shown in yellow and brown (Mercury; Macrae et al., 2008

For compound (II) a region of disordered electron density with a potential solvent-accessible void of volume 1220 Å³ with an electron count of 357 per unit cell was corrected for using the SQUEEZE routine in PLATON (Spek, 2015). The voids in the crystal structure of (II) are illustrated in Fig. 4.

4. Hirshfeld surface analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ), and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ), were calculated to analyse the intermolecular contacts in the crystals. The various calculations were performed with CrystalExplorer17 (Turner et al., 2017 ). The use of such calculations to analyse intermolecular contacts in crystals has been reported on recently by Tiekink and collaborators (Tan et al., 2019 ).

The Hirshfeld surfaces of compounds (I) and (II) mapped over d_norm are given in Figs. 5 and 6, respectively. For (I) the intermolecular contacts are illustrated in Fig. 7, and for (II) in Fig. 8. They are colour-mapped with the normalized contact distance, d_norm, from red (distances shorter than the sum of the van der Waals radii) through white to blue (distances longer than the sum of the van der Waals radii). The d_norm surface was mapped over a fixed colour scale of −0.512 (red) to 1.285 (blue) for compound (I) and −0.490 (red) to 4.945 (blue) for compound (II), where the red spots indicate the intermolecular contacts involved in hydrogen bonding (remembering that the disordered solvent in the channels of (II) have been SQUEEZED out).

Figure 5
The Hirshfeld surfaces of compound (I)

, mapped over d_norm; fixed colour scale of −0.512 (red) to 1.285 (blue) arbitrary units.

Figure 6
The Hirshfeld surfaces of compound (II)

, mapped over d_norm; fixed colour scale of −0.490 (red) to 4.945 (blue) arbitrary units.

Figure 7
A view of the Hirshfeld surface mapped over d_norm of compound (I)

, showing the various intermolecular contacts in the crystal.

Figure 8
A view of the Hirshfeld surface mapped over d_norm of compound (II)

, showing the various intermolecular contacts in the crystal.

The fingerprint plots are given in Figs. 9 and 10, for compounds (I) and (II), respectively. For compound (I), the principal intermolecular contacts are H⋯H at 28.9% (Fig. 9b), O⋯H/H⋯O at 13.8% (Fig. 9c), N⋯H/H⋯N at 11.3% (Fig. 9d), Br⋯H/H⋯Br at 14.3% (Fig. 9e) and C⋯H/H⋯C contacts at 13.6% (Fig. 9f). C⋯C contacts account for 8.4%, while C⋯Br are 3.0%, C⋯N are 3.0%, and finally C⋯O contacts amount to 1.4%.

Figure 9
The full two-dimensional fingerprint plot for compound (I)

, and fingerprint plots delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) N⋯H/H⋯N, (e) Br⋯H/H⋯Br and (f) C⋯H/H⋯C contacts.

Figure 10
The full two-dimensional fingerprint plot for compound (II)

, and fingerprint plots delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) N⋯H/H⋯N, (e) C⋯H/H⋯C contacts.

For compound (II), the fingerprint plots reveal that the principal intermolecular contacts are H⋯H at 35.0% (Fig. 10b), O⋯H/H⋯O at 13.3% (Fig. 10c), N⋯H/H⋯N at 16.2% (Fig. 10d), and C⋯H/H⋯C at 33.6% (Fig. 10e). The remaining contacts are extremely weak, ca 1% each.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40, February 2019; Groom et al., 2016 ) for compounds with an O atom in position 3 of the benzylidene ring, i.e. (3-OR-benzylidene)isonicotinohydrazide (R = C) skeleton gave 51 hits (supporting information file S1). The majority of these compounds were with an OMe or an OEt substituent.

A search for compounds with an O atom in position 2 of the benzylidene ring, i.e. (2-OR-benzylidene)isonicotinohydrazide (R = C) skeleton gave 23 hits (supporting information file S2). Again, the majority of these compounds have an OMe or an OEt substituent. However, here the most interesting and relevant compound concerns the ligand N′,N′′-[ethane-1,2-diylbis(oxy-2,1-phenylenemethylylidene)]bis(pyridine-4-carbohydrazide), in which a 1,2-dioxyethane bridge links two N′-benzylideneisonicotinohydrazide units. The crystal structures of two polymorphs have been described: a monoclinic P2₁ polymorph that crystallizes as a methanol disolvate (BAXLAQ; Mahmoudi et al., 2017 ) and a triclinic P $[\overline{1}]$ polymorph (FIXJIG; Tai et al., 2004 ). The conformation of both compounds is U-shaped, similar to that of compound (I). The molecular structures of compounds (I), BAXLAQ and FIXJIG are compared in Fig. 11. The principal difference in the conformation of the three molecules is reflected in the dihedral angle involving the benzene rings, which are inclined to each other by 7.69 (6)° in (I), by 25.0 (2)° in BAXLAQ and by 55.27 (7)° in FIXJIG.

Figure 11
The molecular structures of compounds (I)

, BAXLAQ (Mahmoudi et al., 2017

) and FIXJIG (Tai et al., 2004

An interesting HgI₂ complex of this ligand, bis(μ-{N′,N′′-[ethane-1,2-diylbis(oxy-2,1-phenylenemethylylidene)] bis(pyridine-4-carbohydrazide)})tetrakis(iodo)dimercury methanol disolvate (BAXKUJ; Mahmoudi et al., 2017), has a metallamacrocyclic architecture.

6. Synthesis and crystallization

Compound I: To 2-hydroxybenzaldehyde (5 mmol), in a 250 ml round-bottom (RB) flask was added DMF (30 ml) and potassium carbonate (12.5 mmol). The mixture was stirred at room temperature and then 1,1-diiodobutane (2.5 mmol) was added dropwise and the reaction mixture was stirred for 12 h. It was then partitioned between water and ethyl acetate. The ethyl acetate layer was collected and concentrated under reduced pressure. To 1,4-bis(2-carboxyaldehydephenoxy)butane (2 mmol) and isonicotinic acid hydrazide (4 mmol) in a 250 ml RB flask was added 100 ml of methanol and two drops of glacial acetic acid. The reaction mixture was stirred at room temperature and within 5 min a white-coloured product had formed. The reaction was continued for a further 30 min. The title compound was isolated by filtration and washed with methanol, then chloroform and followed by acetone. The final product was recrystallized using DMSO and yielded colourless block-like crystals of compound (I).

Compound I: To 5-bromo-2-hydroxybenzaldehyde (5 mmol), in a 250 ml RB flask, was added 50 ml of DMF and potassium carbonate (12.5 mmol). The mixture was stirred at room temperature and then 1,1-diiodomethane (2.5 mmol) was added dropwise. Then, the reaction mixture was stirred for 12 h. The product obtained was extracted in ethyl acetate medium. Methanol (100 ml) and two drops of glacial acetic acid were added to a mixture of 6,6′-[methylenebis(oxy)] bis(3-bromobenzaldehyde) (2 mmol) and isoniazid (4 mmol) in a 250 ml RB flask. The reaction mixture was stirred at room temperature and within 5 min a white-coloured product had formed and the reaction was continued for a further 30 min. The solid obtained was washed with methanol, then chloroform and followed by acetone. The final product was recrystallized using DMSO and yielded colourless block-like crystals of compound (II).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. The NH H atoms for both compounds, and the water molecule H atoms for compound (I), were located in difference-Fourier maps and refined freely. For both compounds the C-bound H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms: C—H = 0.93-0.97 Å with U_iso(H) = 1.2U_eq(C).

Table 5
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₂₇H₂₀Br₂N₆O₄·2H₂O	C₃₀H₂₈N₆O₄[+solvent]
M_r	688.34	536.58
Crystal system, space group	Monoclinic, C2/c	Trigonal, R $[\overline{3}]$ :H
Temperature (K)	293	293
a, b, c (Å)	15.1206 (2), 10.1497 (2), 18.0253 (3)	34.3186 (2), 34.3186 (2), 6.7855 (3)
α, β, γ (°)	90, 100.7960 (4), 90	90, 90, 120
V (Å³)	2717.37 (8)	6921.0 (3)
Z	4	9
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	3.04	0.08
Crystal size (mm)	0.38 × 0.28 × 0.21	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.499, 0.746	0.630, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	29418, 3387, 3202	22262, 3805, 2619
R_int	0.033	0.076
(sin θ/λ)_max (Å⁻¹)	0.668	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.054, 1.05	0.057, 0.142, 1.05
No. of reflections	3387	3805
No. of parameters	199	185
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)	0.49, −0.32	0.47, −0.34
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS2018 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ), publCIF (Westrip, 2010 ) and PLATON (Spek, 2009 ).

For compound (II), a region of disordered electron density with a potential solvent accessible void of volume 1220 Å³ with an electron count of 357 per unit cell was corrected for using the SQUEEZE routine in PLATON (Spek, 2015). Their formula mass and unit-cell characteristics were not taken into account during refinement.

Supporting information

CCDC references: 1907912; 1907913

Crystal structure: contains datablocks global, I, II. DOI: https://doi.org/10.1107/S2056989019005048/su5495sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019005048/su5495Isup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019005048/su5495Isup4.cml

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019005048/su5495IIsup5.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019005048/su5495IIsup5.cml

CSD search S1. DOI: https://doi.org/10.1107/S2056989019005048/su5495sup6.pdf

CSD Search S2. DOI: https://doi.org/10.1107/S2056989019005048/su5495sup7.pdf

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS2018 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

N',N'''-((1E,1'E)-{[Methylenebis(oxy)]bis(6-bromo-3,1-phenylene)}bis(methanylylidene))bis(isonicotinohydrazide) dihydrate (I) top

Crystal data top

C₂₇H₂₀Br₂N₆O₄·2H₂O	F(000) = 1384
M_r = 688.34	D_x = 1.683 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.1206 (2) Å	Cell parameters from 3387 reflections
b = 10.1497 (2) Å	θ = 1.8–26.9°
c = 18.0253 (3) Å	µ = 3.04 mm⁻¹
β = 100.7960 (4)°	T = 293 K
V = 2717.37 (8) Å³	Block, colourless
Z = 4	0.38 × 0.28 × 0.21 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	3202 reflections with I > 2σ(I)
ω and φ scans	R_int = 0.033
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 28.4°, θ_min = 2.8°
T_min = 0.499, T_max = 0.746	h = −20→20
29418 measured reflections	k = −13→13
3387 independent reflections	l = −24→24

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0247P)² + 3.4271P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.002
3387 reflections	Δρ_max = 0.49 e Å⁻³
199 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Extinction correction: (SHELXL2018; Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00152 (17)

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	0.70412 (2)	0.52186 (2)	0.47663 (2)	0.01933 (6)
O1	0.45281 (7)	1.00457 (9)	0.61053 (6)	0.0176 (2)
O2	0.45956 (6)	0.35751 (9)	0.68829 (5)	0.01363 (18)
N1	0.22417 (8)	1.19161 (11)	0.75048 (7)	0.0152 (2)
N2	0.41385 (7)	0.82530 (10)	0.67331 (6)	0.0115 (2)
HN2	0.3760 (12)	0.7919 (18)	0.6974 (10)	0.019 (4)*
N3	0.47208 (7)	0.74664 (10)	0.64190 (6)	0.0120 (2)
C1	0.34534 (8)	1.03494 (11)	0.68973 (7)	0.0105 (2)
C2	0.30431 (9)	1.14287 (12)	0.65037 (7)	0.0125 (2)
H2	0.317244	1.165550	0.603561	0.015*
C3	0.24360 (9)	1.21635 (13)	0.68217 (7)	0.0144 (2)
H3	0.214768	1.286668	0.654615	0.017*
C4	0.26812 (9)	1.09117 (13)	0.78941 (8)	0.0160 (3)
H4	0.257654	1.074883	0.837801	0.019*
C5	0.32847 (9)	1.00994 (12)	0.76160 (8)	0.0135 (2)
H5	0.356824	0.940616	0.790387	0.016*
C6	0.40899 (9)	0.95414 (12)	0.65410 (7)	0.0111 (2)
C7	0.46797 (8)	0.62336 (12)	0.65637 (7)	0.0105 (2)
H7	0.430077	0.593995	0.688011	0.013*
C8	0.52265 (8)	0.52824 (12)	0.62335 (7)	0.0101 (2)
C9	0.51576 (8)	0.39410 (12)	0.63961 (7)	0.0114 (2)
C10	0.55993 (9)	0.29921 (13)	0.60449 (8)	0.0154 (3)
H10	0.552015	0.210250	0.613749	0.018*
C11	0.61571 (9)	0.33760 (14)	0.55570 (8)	0.0164 (3)
H11	0.646693	0.275109	0.532790	0.020*
C12	0.62469 (9)	0.47104 (13)	0.54149 (7)	0.0136 (2)
C13	0.57828 (8)	0.56652 (13)	0.57324 (7)	0.0118 (2)
H13	0.583938	0.654965	0.561477	0.014*
C14	0.500000	0.27859 (17)	0.750000	0.0157 (4)
H14A	0.454724	0.222442	0.765344	0.019*	0.5
H14B	0.545278	0.222447	0.734654	0.019*	0.5
O1W	0.60456 (7)	0.90764 (12)	0.55169 (7)	0.0256 (2)
H1W	0.5551 (16)	0.914 (2)	0.5685 (12)	0.037 (6)*
H2W	0.5926 (16)	0.934 (2)	0.5072 (14)	0.041 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01383 (9)	0.03079 (10)	0.01546 (8)	−0.00484 (5)	0.00808 (5)	−0.00590 (5)
O1	0.0203 (5)	0.0125 (4)	0.0235 (5)	0.0021 (4)	0.0133 (4)	0.0048 (4)
O2	0.0142 (4)	0.0126 (4)	0.0148 (4)	0.0007 (3)	0.0046 (3)	0.0048 (3)
N1	0.0150 (5)	0.0127 (5)	0.0192 (6)	−0.0003 (4)	0.0067 (4)	−0.0031 (4)
N2	0.0114 (5)	0.0095 (5)	0.0158 (5)	0.0010 (4)	0.0080 (4)	0.0013 (4)
N3	0.0116 (5)	0.0108 (5)	0.0147 (5)	0.0021 (4)	0.0052 (4)	−0.0003 (4)
C1	0.0095 (6)	0.0082 (5)	0.0143 (6)	−0.0016 (4)	0.0035 (4)	−0.0019 (4)
C2	0.0138 (6)	0.0123 (5)	0.0115 (5)	0.0001 (4)	0.0024 (4)	−0.0008 (4)
C3	0.0144 (6)	0.0122 (5)	0.0163 (6)	0.0023 (5)	0.0020 (5)	−0.0008 (5)
C4	0.0204 (7)	0.0135 (6)	0.0167 (6)	−0.0017 (5)	0.0099 (5)	−0.0003 (5)
C5	0.0164 (6)	0.0097 (5)	0.0154 (6)	−0.0013 (4)	0.0055 (5)	0.0015 (4)
C6	0.0104 (6)	0.0106 (5)	0.0125 (6)	0.0000 (4)	0.0027 (4)	0.0000 (4)
C7	0.0091 (5)	0.0116 (5)	0.0108 (5)	0.0003 (4)	0.0023 (4)	0.0008 (4)
C8	0.0080 (6)	0.0104 (5)	0.0112 (6)	0.0006 (4)	0.0003 (4)	0.0000 (4)
C9	0.0098 (6)	0.0117 (5)	0.0124 (5)	0.0006 (4)	0.0012 (4)	0.0012 (4)
C10	0.0176 (6)	0.0112 (6)	0.0169 (6)	0.0028 (5)	0.0020 (5)	−0.0006 (5)
C11	0.0144 (6)	0.0178 (6)	0.0170 (6)	0.0044 (5)	0.0030 (5)	−0.0044 (5)
C12	0.0087 (6)	0.0211 (6)	0.0118 (6)	−0.0007 (5)	0.0036 (5)	−0.0018 (5)
C13	0.0095 (6)	0.0128 (5)	0.0128 (6)	−0.0004 (4)	0.0014 (4)	0.0000 (4)
C14	0.0271 (10)	0.0076 (7)	0.0118 (8)	0.000	0.0019 (7)	0.000
O1W	0.0151 (5)	0.0396 (7)	0.0241 (6)	0.0057 (5)	0.0085 (4)	0.0119 (5)

Geometric parameters (Å, º) top

Br1—C12	1.8978 (13)	C4—H4	0.9300
O1—C6	1.2300 (16)	C5—H5	0.9300
O2—C9	1.3818 (16)	C7—C8	1.4677 (17)
O2—C14	1.4134 (13)	C7—H7	0.9300
N1—C4	1.3412 (18)	C8—C13	1.3997 (18)
N1—C3	1.3421 (18)	C8—C9	1.4007 (17)
N2—C6	1.3512 (16)	C9—C10	1.3904 (18)
N2—N3	1.3857 (15)	C10—C11	1.384 (2)
N2—HN2	0.851 (18)	C10—H10	0.9300
N3—C7	1.2820 (16)	C11—C12	1.3897 (19)
C1—C2	1.3869 (17)	C11—H11	0.9300
C1—C5	1.3898 (18)	C12—C13	1.3818 (18)
C1—C6	1.4976 (17)	C13—H13	0.9300
C2—C3	1.3873 (18)	C14—H14A	0.9700
C2—H2	0.9300	C14—H14B	0.9700
C3—H3	0.9300	O1W—H1W	0.86 (2)
C4—C5	1.3910 (19)	O1W—H2W	0.83 (3)

C9—O2—C14	115.16 (8)	C8—C7—H7	119.8
C4—N1—C3	116.75 (11)	C13—C8—C9	118.83 (12)
C6—N2—N3	117.46 (11)	C13—C8—C7	122.10 (11)
C6—N2—HN2	120.5 (12)	C9—C8—C7	119.00 (11)
N3—N2—HN2	121.2 (12)	O2—C9—C10	120.53 (11)
C7—N3—N2	114.86 (11)	O2—C9—C8	118.22 (11)
C2—C1—C5	118.58 (12)	C10—C9—C8	121.14 (12)
C2—C1—C6	118.36 (11)	C11—C10—C9	119.76 (12)
C5—C1—C6	123.00 (11)	C11—C10—H10	120.1
C1—C2—C3	118.72 (12)	C9—C10—H10	120.1
C1—C2—H2	120.6	C10—C11—C12	118.94 (12)
C3—C2—H2	120.6	C10—C11—H11	120.5
N1—C3—C2	123.64 (12)	C12—C11—H11	120.5
N1—C3—H3	118.2	C13—C12—C11	122.17 (12)
C2—C3—H3	118.2	C13—C12—Br1	119.57 (10)
N1—C4—C5	123.79 (13)	C11—C12—Br1	118.26 (10)
N1—C4—H4	118.1	C12—C13—C8	119.06 (12)
C5—C4—H4	118.1	C12—C13—H13	120.5
C1—C5—C4	118.37 (12)	C8—C13—H13	120.5
C1—C5—H5	120.8	O2ⁱ—C14—O2	110.96 (14)
C4—C5—H5	120.8	O2ⁱ—C14—H14A	109.4
O1—C6—N2	123.81 (12)	O2—C14—H14A	109.4
O1—C6—C1	120.81 (11)	O2ⁱ—C14—H14B	109.4
N2—C6—C1	115.38 (11)	O2—C14—H14B	109.4
N3—C7—C8	120.47 (11)	H14A—C14—H14B	108.0
N3—C7—H7	119.8	H1W—O1W—H2W	106 (2)

C6—N2—N3—C7	−173.82 (11)	N3—C7—C8—C9	−179.26 (12)
C5—C1—C2—C3	−4.17 (18)	C14—O2—C9—C10	57.04 (16)
C6—C1—C2—C3	178.46 (11)	C14—O2—C9—C8	−126.67 (12)
C4—N1—C3—C2	1.2 (2)	C13—C8—C9—O2	−179.05 (11)
C1—C2—C3—N1	2.3 (2)	C7—C8—C9—O2	−2.05 (17)
C3—N1—C4—C5	−2.8 (2)	C13—C8—C9—C10	−2.79 (18)
C2—C1—C5—C4	2.71 (19)	C7—C8—C9—C10	174.21 (12)
C6—C1—C5—C4	179.95 (12)	O2—C9—C10—C11	179.78 (11)
N1—C4—C5—C1	0.9 (2)	C8—C9—C10—C11	3.60 (19)
N3—N2—C6—O1	0.24 (19)	C9—C10—C11—C12	−1.5 (2)
N3—N2—C6—C1	−179.82 (10)	C10—C11—C12—C13	−1.4 (2)
C2—C1—C6—O1	29.80 (18)	C10—C11—C12—Br1	178.26 (10)
C5—C1—C6—O1	−147.44 (13)	C11—C12—C13—C8	2.17 (19)
C2—C1—C6—N2	−150.15 (12)	Br1—C12—C13—C8	−177.48 (9)
C5—C1—C6—N2	32.61 (18)	C9—C8—C13—C12	−0.08 (18)
N2—N3—C7—C8	176.82 (11)	C7—C8—C13—C12	−176.98 (11)
N3—C7—C8—C13	−2.37 (19)	C9—O2—C14—O2ⁱ	87.86 (9)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of N1/C1–C5 pyridine ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN2···N1ⁱⁱ	0.85 (2)	2.179 (19)	3.0261 (16)	174 (2)
O1W—H1W···O1	0.86 (2)	2.06 (2)	2.8756 (15)	158 (2)
O1W—H1W···N3	0.86 (2)	2.61 (2)	3.2476 (16)	131.3 (19)
O1W—H2W···O1ⁱⁱⁱ	0.83 (3)	2.19 (3)	3.0244 (16)	174 (2)
C3—H3···O1W^iv	0.93	2.56	3.4450 (17)	159
C4—H4···Br1^v	0.93	2.94	3.8554 (13)	169
C10—H10···O1^vi	0.93	2.56	3.4123 (17)	152
C13—H13···O1W	0.93	2.59	3.5148 (18)	171
C14—H14A···Cg1^vi	0.97	2.74	3.594 (1)	144
C14—H14B···Cg1^vii	0.97	2.74	3.594 (1)	144

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

N',N'''-((1E,1'E)-{[Butane-1,4-diylbis(oxy)]\ bis(2,1-phenylene)}bis(methanylylidene))bis(isonicotinohydrazide) (II) top

Crystal data top

C₃₀H₂₈N₆O₄[+solvent]	D_x = 1.159 Mg m⁻³
M_r = 536.58	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3:H	Cell parameters from 3792 reflections
a = 34.3186 (2) Å	θ = 1.8–26.9°
c = 6.7855 (3) Å	µ = 0.08 mm⁻¹
V = 6921.0 (3) Å³	T = 293 K
Z = 9	Block, colourless
F(000) = 2538	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2619 reflections with I > 2σ(I)
ω and φ scans	R_int = 0.076
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 28.3°, θ_min = 2.1°
T_min = 0.630, T_max = 0.746	h = −45→36
22262 measured reflections	k = −29→45
3805 independent reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: mixed
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0533P)² + 11.1328P] where P = (F_o² + 2F_c²)/3
3805 reflections	(Δ/σ)_max < 0.001
185 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.34 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
O1	0.20009 (4)	0.45231 (5)	0.72823 (18)	0.0262 (3)
O2	0.02621 (4)	0.46026 (4)	0.34035 (18)	0.0214 (3)
N1	0.31092 (6)	0.49292 (7)	0.1812 (2)	0.0346 (4)
N2	0.16142 (5)	0.46016 (5)	0.4732 (2)	0.0218 (3)
H2N	0.1653 (8)	0.4749 (8)	0.358 (3)	0.033 (6)*
N3	0.12211 (5)	0.44325 (5)	0.5828 (2)	0.0210 (3)
C1	0.23686 (6)	0.47415 (6)	0.4186 (3)	0.0223 (4)
C2	0.27559 (8)	0.47786 (10)	0.4947 (3)	0.0471 (7)
H2	0.277753	0.474161	0.629269	0.056*
C3	0.31139 (8)	0.48705 (10)	0.3729 (3)	0.0480 (7)
H3	0.337126	0.489203	0.428924	0.058*
C4	0.27280 (9)	0.48779 (11)	0.1061 (3)	0.0538 (8)
H4	0.271346	0.490922	−0.029363	0.065*
C5	0.23528 (8)	0.47810 (10)	0.2170 (3)	0.0457 (7)
H5	0.209289	0.474298	0.156458	0.055*
C6	0.19813 (6)	0.46179 (6)	0.5561 (3)	0.0201 (4)
C7	0.08925 (6)	0.44343 (6)	0.4950 (3)	0.0207 (4)
H7	0.093119	0.454627	0.367374	0.025*
C8	0.04564 (6)	0.42628 (6)	0.5923 (3)	0.0197 (4)
C9	0.03514 (7)	0.40109 (6)	0.7662 (3)	0.0240 (4)
H9	0.056366	0.395193	0.822447	0.029*
C10	−0.00624 (7)	0.38487 (7)	0.8553 (3)	0.0243 (4)
H10	−0.012915	0.368208	0.970983	0.029*
C11	−0.03787 (6)	0.39371 (6)	0.7700 (3)	0.0216 (4)
H11	−0.065758	0.382899	0.830143	0.026*
C12	−0.02860 (6)	0.41838 (6)	0.5968 (3)	0.0188 (4)
H12	−0.050141	0.423846	0.540846	0.023*
C13	0.01323 (6)	0.43478 (6)	0.5082 (2)	0.0177 (4)
C14	−0.00685 (6)	0.46611 (6)	0.2364 (2)	0.0178 (4)
H14A	−0.018719	0.480568	0.320625	0.021*
H14B	−0.031546	0.437179	0.195219	0.021*
C15	0.01615 (6)	0.49521 (6)	0.0585 (3)	0.0186 (4)
H15A	0.027315	0.480095	−0.025658	0.022*
H15B	0.041679	0.523411	0.101427	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0225 (7)	0.0348 (8)	0.0211 (6)	0.0142 (6)	−0.0014 (5)	0.0027 (6)
O2	0.0183 (6)	0.0283 (7)	0.0212 (6)	0.0143 (6)	−0.0004 (5)	0.0057 (5)
N1	0.0244 (9)	0.0535 (12)	0.0251 (9)	0.0188 (9)	0.0017 (7)	−0.0010 (8)
N2	0.0211 (8)	0.0262 (9)	0.0211 (8)	0.0142 (7)	0.0002 (6)	0.0028 (7)
N3	0.0177 (8)	0.0254 (8)	0.0232 (8)	0.0132 (7)	0.0008 (6)	0.0005 (6)
C1	0.0206 (9)	0.0237 (9)	0.0228 (9)	0.0113 (8)	−0.0012 (7)	−0.0003 (7)
C2	0.0322 (12)	0.094 (2)	0.0212 (10)	0.0365 (14)	0.0023 (9)	0.0105 (12)
C3	0.0279 (12)	0.092 (2)	0.0276 (11)	0.0325 (13)	−0.0028 (9)	0.0021 (12)
C4	0.0447 (15)	0.110 (2)	0.0207 (10)	0.0492 (17)	0.0037 (10)	0.0085 (13)
C5	0.0340 (13)	0.087 (2)	0.0291 (11)	0.0399 (14)	−0.0010 (10)	0.0054 (12)
C6	0.0206 (9)	0.0199 (9)	0.0205 (9)	0.0108 (8)	−0.0020 (7)	−0.0010 (7)
C7	0.0232 (9)	0.0244 (10)	0.0186 (8)	0.0149 (8)	−0.0006 (7)	0.0017 (7)
C8	0.0202 (9)	0.0204 (9)	0.0206 (8)	0.0118 (8)	−0.0023 (7)	−0.0034 (7)
C9	0.0255 (10)	0.0283 (10)	0.0233 (9)	0.0174 (9)	−0.0037 (8)	0.0000 (8)
C10	0.0298 (10)	0.0259 (10)	0.0203 (9)	0.0162 (9)	0.0024 (8)	0.0045 (8)
C11	0.0204 (9)	0.0228 (9)	0.0223 (9)	0.0113 (8)	0.0009 (7)	−0.0027 (7)
C12	0.0178 (9)	0.0194 (9)	0.0206 (8)	0.0103 (7)	−0.0043 (7)	−0.0043 (7)
C13	0.0204 (9)	0.0169 (8)	0.0172 (8)	0.0103 (7)	−0.0024 (7)	−0.0027 (7)
C14	0.0157 (8)	0.0215 (9)	0.0193 (8)	0.0116 (7)	−0.0022 (7)	−0.0004 (7)
C15	0.0173 (9)	0.0198 (9)	0.0199 (8)	0.0102 (8)	−0.0011 (7)	−0.0003 (7)

Geometric parameters (Å, º) top

O1—C6	1.223 (2)	C7—C8	1.463 (3)
O2—C13	1.368 (2)	C7—H7	0.9300
O2—C14	1.433 (2)	C8—C9	1.399 (3)
N1—C3	1.318 (3)	C8—C13	1.405 (2)
N1—C4	1.331 (3)	C9—C10	1.379 (3)
N2—C6	1.355 (2)	C9—H9	0.9300
N2—N3	1.388 (2)	C10—C11	1.391 (3)
N2—H2N	0.91 (2)	C10—H10	0.9300
N3—C7	1.278 (2)	C11—C12	1.389 (3)
C1—C2	1.371 (3)	C11—H11	0.9300
C1—C5	1.379 (3)	C12—C13	1.390 (2)
C1—C6	1.501 (3)	C12—H12	0.9300
C2—C3	1.380 (3)	C14—C15	1.513 (2)
C2—H2	0.9300	C14—H14A	0.9700
C3—H3	0.9300	C14—H14B	0.9700
C4—C5	1.381 (3)	C15—C15ⁱ	1.527 (3)
C4—H4	0.9300	C15—H15A	0.9700
C5—H5	0.9300	C15—H15B	0.9700

C13—O2—C14	118.16 (13)	C13—C8—C7	119.36 (16)
C3—N1—C4	116.33 (19)	C10—C9—C8	120.95 (17)
C6—N2—N3	118.93 (15)	C10—C9—H9	119.5
C6—N2—H2N	117.6 (15)	C8—C9—H9	119.5
N3—N2—H2N	122.5 (15)	C9—C10—C11	119.22 (17)
C7—N3—N2	115.07 (15)	C9—C10—H10	120.4
C2—C1—C5	116.64 (18)	C11—C10—H10	120.4
C2—C1—C6	118.21 (17)	C12—C11—C10	121.25 (17)
C5—C1—C6	124.87 (17)	C12—C11—H11	119.4
C1—C2—C3	120.44 (19)	C10—C11—H11	119.4
C1—C2—H2	119.8	C11—C12—C13	119.25 (17)
C3—C2—H2	119.8	C11—C12—H12	120.4
N1—C3—C2	123.3 (2)	C13—C12—H12	120.4
N1—C3—H3	118.4	O2—C13—C12	124.04 (16)
C2—C3—H3	118.4	O2—C13—C8	115.63 (15)
N1—C4—C5	124.1 (2)	C12—C13—C8	120.32 (16)
N1—C4—H4	118.0	O2—C14—C15	107.28 (13)
C5—C4—H4	118.0	O2—C14—H14A	110.3
C1—C5—C4	119.1 (2)	C15—C14—H14A	110.3
C1—C5—H5	120.4	O2—C14—H14B	110.3
C4—C5—H5	120.4	C15—C14—H14B	110.3
O1—C6—N2	124.00 (17)	H14A—C14—H14B	108.5
O1—C6—C1	120.65 (16)	C14—C15—C15ⁱ	111.20 (18)
N2—C6—C1	115.29 (15)	C14—C15—H15A	109.4
N3—C7—C8	121.04 (16)	C15ⁱ—C15—H15A	109.4
N3—C7—H7	119.5	C14—C15—H15B	109.4
C8—C7—H7	119.5	C15ⁱ—C15—H15B	109.4
C9—C8—C13	119.01 (17)	H15A—C15—H15B	108.0
C9—C8—C7	121.63 (16)

C6—N2—N3—C7	179.08 (17)	N3—C7—C8—C13	167.81 (17)
C5—C1—C2—C3	2.7 (4)	C13—C8—C9—C10	−0.3 (3)
C6—C1—C2—C3	176.9 (2)	C7—C8—C9—C10	−179.49 (17)
C4—N1—C3—C2	−2.6 (4)	C8—C9—C10—C11	0.2 (3)
C1—C2—C3—N1	0.3 (5)	C9—C10—C11—C12	0.2 (3)
C3—N1—C4—C5	1.8 (4)	C10—C11—C12—C13	−0.5 (3)
C2—C1—C5—C4	−3.4 (4)	C14—O2—C13—C12	−7.6 (2)
C6—C1—C5—C4	−177.2 (2)	C14—O2—C13—C8	173.57 (15)
N1—C4—C5—C1	1.2 (5)	C11—C12—C13—O2	−178.45 (16)
N3—N2—C6—O1	−5.6 (3)	C11—C12—C13—C8	0.4 (3)
N3—N2—C6—C1	171.51 (15)	C9—C8—C13—O2	178.94 (16)
C2—C1—C6—O1	−4.9 (3)	C7—C8—C13—O2	−1.8 (2)
C5—C1—C6—O1	168.8 (2)	C9—C8—C13—C12	0.0 (3)
C2—C1—C6—N2	177.9 (2)	C7—C8—C13—C12	179.25 (16)
C5—C1—C6—N2	−8.4 (3)	C13—O2—C14—C15	−179.86 (14)
N2—N3—C7—C8	179.54 (15)	O2—C14—C15—C15ⁱ	−178.00 (17)
N3—C7—C8—C9	−13.0 (3)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C8–C13 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N1ⁱⁱ	0.91 (2)	2.04 (2)	2.907 (2)	159 (2)
C3—H3···O1ⁱⁱⁱ	0.93	2.60	3.449 (3)	153
C3—H3···N3ⁱⁱⁱ	0.93	2.55	3.223 (3)	129
C7—H7···N1ⁱⁱ	0.93	2.63	3.372 (3)	137
C12—H12···O1^iv	0.93	2.43	3.331 (2)	163
C15—H15A···Cg2^v	0.97	2.91	3.748 (2)	145

Symmetry codes: (ii) y−1/3, −x+y+1/3, −z+1/3; (iii) x−y+2/3, x+1/3, −z+4/3; (iv) −y+1/3, x−y+2/3, z−1/3; (v) x, y, z−1.

Acknowledgements

The authors are grateful to the SAIF, IIT, Madras, India, for the data collection.

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