Crystal structure of (E)-2-[(2-hy­droxy-4-meth­oxy­phen­yl)(phen­yl)methyl­idene]-N-phenyl­hydrazine-1-carboxamide

Annie, C.F.; Sithambaresan, M.; Kurup, M.R.P.

doi:10.1107/S2056989015005757

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ISSN: 2056-9890

Volume 71| Part 4| April 2015| Pages 427-430

doi:10.1107/S2056989015005757

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Crystal structure of (E)-2-[(2-hydroxy-4-methoxyphenyl)(phenyl)methylidene]-N-phenylhydrazine-1-carboxamide

C. F. Annie,^a M. Sithambaresan ^b ^* and M. R. Prathapachandra Kurup ^a

^aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India, and ^bDepartment of Chemistry, Faculty of Science, Eastern University, Chenkalady, Sri Lanka
^*Correspondence e-mail: msithambaresan@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 20 March 2015; accepted 22 March 2015; online 28 March 2015)

The title compound, C₂₁H₁₉N₃O₃, has an E conformation about the azomethine double bond. The central moiety of the hydrazinecarboxamide moiety [–N—N—C(=O)—N–] has an almost coplanar arrangement [maximum deviation for the C atom = 0.010 (2) Å]. This central moiety is flanked by three aromatic rings and its mean plane makes dihedral angles of 24.7 (1), 72.91 (12) and 34.26 (11) Å, respectively, with the phenolic ring, the phenyl ring attached to the same C atom as the phenolic ring, and the phenylhydrazine ring. The adjacent phenolic and phenyl rings are twisted away from each other to reduce steric hindrance and make a dihedral angle of 80.59 (12)°. The phenolic and phenylhydrazine rings are inclined to one another by 28.89 (11)°. The rigidity of the molecule is increased by an intramolecular O—H⋯N hydrogen bond involving the phenolic hydrogen and the azomethine N atom. In the crystal, the carbonyl O atom forms bifurcated hydrogen bonds with the two NH atoms of the hydrazinic group, leading to the formation of chains propagating along [001]. Within the chains there are also C—H⋯O hydrogen bonds present. The chains are linked via C=O⋯π [3.4316 (18) Å] and parallel slipped π–π interactions, involving inversion-related benzene rings [centroid–centroid distance = 3.8850 (14) Å; inter-planar distance = 3.3895 (10) Å; slippage = 1.899 Å], forming sheets lying parallel to (100).

Keywords: crystal structure; hydrazinecarboxamide; supramolecular; hydrogen bonding; C=O⋯π interactions; π–π interactions.

CCDC reference: 1055367

1. Chemical context

Semicarbazones are urea derivatives exhibiting a wide spectrum of biological activities (Beraldo & Gambino, 2004 ). They have been found to be associated with antitumoral (Afrasiabi et al., 2005 ), antimicrobial (Siji et al., 2010 ), antihypertensive, hypolipidemic, antineoplastic, hypnotic and anticonvulsant properties. They can function as excellent ligands to various metal ions (Kala et al., 2007 ; Aiswarya et al., 2013 ; Kurup et al., 2011 ) and can coordinate to metal ions either in the neutral (Siji et al., 2011 ) or in the anionic forms (Reena et al., 2008 ). Single crystals of acetophenone semicarbazones are potential organic non-linear optical (NLO) materials and they have a wide transparency window in the entire visible region, making them ideal candidates for NLO device applications (Vijayan et al., 2001 ). Semicarbazones have been proposed as analytical reagents that can be used in selective and sensitive determination of metal ions (Garg & Jain, 1988 ). The crystal structure of the dimethylformamide solvate of the title compound has been reported (Annie et al., 2012 ).

2. Structural commentary

In the molecule of the title compound (Fig. 1), the conformation about the C7=N1 bond is E, and the central hydrazinecarboxamide moiety [–N1—N2—C14(=O3)—N3–] is almost planar [the maximum deviation is 0.010 (2) Å for atom C14]. This central moiety is flanked by three aromatic rings (C1–C6, C8–C13 and C15–C20) which are inclined to its mean plane by 24.70 (10), 72.91 (12) and 34.26 (11) °, respectively. Rings C1–C6 and C8–C13, attached at the same C atom (C7), are twisted away from each other and make a dihedral angle of 80.59 (12)°. They are inclined to the phenylhydrazine ring (C15–C20) by 28.89 (11) and 52.42 (12)°, respectively. In the crystal structure of the dimethylformamide solvate of the title compound (Annie et al., 2012), the two rings attached at the same C atom (C7) are inclined to one another by 88.47 (10)°, while they are inclined to the phenylhydrazine ring by 14.42 (10)° for the phenolic ring, and by 82.35 (11)° for the phenyl ring. There is an intramolecular O—H⋯N hydrogen bond (Fig. 2) involving the phenolic hydrogen and the azomethine atom N1 (Fig. 2 and Table 1). This hydrogen bond is also present in the structure of the dimethylformamide solvate of the title compound mentioned above.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯N1	0.89 (1)	1.76 (2)	2.563 (2)	149 (3)
N2—H2N⋯O3ⁱ	0.87 (1)	2.13 (1)	2.9301 (19)	152 (2)
N3—H3N⋯O3ⁱ	0.88 (1)	2.09 (1)	2.935 (2)	161 (2)
C12—H12⋯O2ⁱⁱ	0.93	2.44	3.252 (3)	146
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y, z-1.

Figure 1
A view of the molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
A view of the hydrogen-bonding interactions (dashed lines) in the title compound, forming chains propagating along [001] (see Table 1

for details).

3. Supramolecular features

In the crystal, the carbonyl O atom (O3) acts as the acceptor in bifurcated hydrogen bonds with the NH atoms of atoms N2 and N3 of the hydrazinic group, leading to the formation of chains propagating along [001]; Table 1 and Fig. 2. Within the chains there are also C—H⋯O hydrogen bonds present (Table 1 and Fig. 2). The chains are linked via C14=O3⋯π interactions [distance O3⋯Cgⁱ = 3.4316 (18) Å; angle C14=O3⋯Cg = 95.3 (1)°; Cg is the centroid of the C8–C13 ring; symmetry code: (i) x, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ], as shown in Fig. 3. There are also parallel slipped π–π interactions present (Fig. 4), involving inversion-related benzene rings (C15–C20) with a centroid–centroid distance of 3.8850 (14) Å [inter-planar distance = 3.3895 (10) Å; slippage = 1.899 Å]. The result of these interactions leads to the formation of sheets lying parallel to (100), as shown in Fig. 5.

Figure 3
C=O⋯π interaction in the crystal structure of the title compound.

Figure 4
π–π interaction in the crystal structure of the title compound.

Figure 5
A view along the a axis of the formation of the sheets lying parallel to (100) in the crystal structure of the title compound.

4. Synthesis and crystallization

To a warm methanolic solution (25 ml) of N⁴-phenylsemicarbazide (0.302 g, 2 mmol), a methanolic solution (25 ml) of 2-hydroxy-4-methoxybenzophenone (0.4566 g, 2 mmol) was added and the resulting solution was boiled under reflux for 2 h, after adding three drops of conc. HCl. On slow evaporation at room temperature, colourless crystals separated out. They were filtered off and washed with methanol and ether. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of a solution in methanol (yield: 0.1735 g, 76%; m.p.: 498 K). FT–IR (KBr, cm⁻¹) ν_max: 3316 (s, OH), 3249 (m, NH), 3145 (m, NH), 1662 (s, C=O), 1631 (m, C=N), 1059 (m, N–N). ¹H NMR (DMSO-d₆, δ, p.p.m.): 12.94 (s, 1H, OH), 9.10 (s, 1H, NH), 9.03 (s, 1H, NH), 3.90 (s, 3H, OMe), 6.33–7.672 (m, 13H, Ar-H). ESI mass spectrum, m/z: 362.3 (M+1). Analysis calculated for C₂₁H₁₉N₃O₃: C, 69.79, H, 5.30, N, 11.63%. Found: C, 69.68, H, 5.72, N, 11.93%.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The OH and NH H atoms were located in a difference Fourier map and refined with distances restraints of 0.88 (1) Å. The C-bound H atoms were placed in calculated positions and refined as riding atoms: C—H = 0.93–0.96 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₁H₁₉N₃O₃
M_r	361.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	19.965 (2), 9.9788 (9), 9.3366 (7)
β (°)	90.340 (5)
V (Å³)	1860.1 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.28 × 0.24 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.955, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	18641, 4268, 2092
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.143, 1.00
No. of reflections	4240
No. of parameters	257
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.19
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2010 ), and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1055367

Crystal structure: contains datablocks I, Global. DOI: 10.1107/S2056989015005757/su5098sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015005757/su5098Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015005757/su5098Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and publCIF (Westrip, 2010).

(E)-2-[(2-Hydroxy-4-methoxyphenyl)(phenyl)methylidene]-N-phenylhydrazine-1-carboxamide top

Crystal data top

C₂₁H₁₉N₃O₃	F(000) = 760.0
M_r = 361.39	D_x = 1.291 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2338 reflections
a = 19.965 (2) Å	θ = 2.9–22.7°
b = 9.9788 (9) Å	µ = 0.09 mm⁻¹
c = 9.3366 (7) Å	T = 296 K
β = 90.340 (5)°	Block, colourless
V = 1860.1 (3) Å³	0.28 × 0.24 × 0.21 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	4268 independent reflections
Radiation source: fine-focus sealed tube	2092 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ω and φ scan	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −25→25
T_min = 0.955, T_max = 0.961	k = −12→12
18641 measured reflections	l = −10→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0608P)² + 0.0804P] where P = (F_o² + 2F_c²)/3
4240 reflections	(Δ/σ)_max < 0.001
257 parameters	Δρ_max = 0.17 e Å⁻³
3 restraints	Δρ_min = −0.19 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
N1	0.24470 (9)	0.62277 (18)	0.17814 (16)	0.0444 (4)
N2	0.19511 (9)	0.68714 (18)	0.10330 (17)	0.0469 (5)
O3	0.14953 (7)	0.76718 (14)	0.30843 (12)	0.0480 (4)
O2	0.32524 (9)	0.62214 (17)	0.39293 (14)	0.0621 (5)
C14	0.14865 (10)	0.7582 (2)	0.17789 (19)	0.0394 (5)
N3	0.10153 (9)	0.81374 (18)	0.09207 (17)	0.0491 (5)
O1	0.49774 (9)	0.31233 (18)	0.41036 (17)	0.0779 (6)
C7	0.27941 (10)	0.5321 (2)	0.11323 (19)	0.0415 (5)
C2	0.40967 (11)	0.4616 (2)	0.3955 (2)	0.0522 (6)
H2	0.4235	0.4949	0.4838	0.063*
C6	0.33388 (10)	0.4695 (2)	0.19314 (19)	0.0411 (5)
C1	0.35550 (11)	0.5171 (2)	0.32703 (19)	0.0436 (5)
C5	0.36938 (12)	0.3632 (2)	0.1362 (2)	0.0574 (6)
H5	0.3562	0.3293	0.0476	0.069*
C4	0.42306 (13)	0.3056 (2)	0.2043 (2)	0.0632 (7)
H4	0.4452	0.2332	0.1635	0.076*
C15	0.03853 (11)	0.8599 (2)	0.1368 (2)	0.0435 (5)
C3	0.44366 (12)	0.3566 (2)	0.3338 (2)	0.0540 (6)
C8	0.26680 (11)	0.4937 (2)	−0.03890 (19)	0.0434 (5)
C20	−0.01559 (12)	0.8337 (2)	0.0487 (2)	0.0545 (6)
H20	−0.0097	0.7861	−0.0359	0.065*
C13	0.30627 (12)	0.5462 (2)	−0.1443 (2)	0.0596 (6)
H13	0.3413	0.6035	−0.1204	0.072*
C16	0.02980 (13)	0.9330 (2)	0.2607 (2)	0.0580 (6)
H16	0.0663	0.9534	0.3192	0.070*
C9	0.21564 (14)	0.4095 (3)	−0.0764 (2)	0.0700 (8)
H9	0.1883	0.3734	−0.0059	0.084*
C17	−0.03359 (15)	0.9754 (3)	0.2968 (3)	0.0700 (8)
H17	−0.0398	1.0237	0.3809	0.084*
C19	−0.07808 (14)	0.8781 (2)	0.0864 (3)	0.0682 (7)
H19	−0.1144	0.8608	0.0265	0.082*
C11	0.24422 (16)	0.4294 (3)	−0.3212 (3)	0.0796 (9)
H11	0.2372	0.4064	−0.4166	0.096*
C10	0.20429 (16)	0.3776 (3)	−0.2181 (3)	0.0865 (9)
H10	0.1693	0.3205	−0.2429	0.104*
C12	0.29420 (15)	0.5144 (3)	−0.2855 (2)	0.0732 (8)
H12	0.3207	0.5516	−0.3568	0.088*
C21	0.53543 (18)	0.2044 (3)	0.3538 (4)	0.1201 (14)
H21A	0.5074	0.1265	0.3459	0.180*
H21B	0.5726	0.1854	0.4164	0.180*
H21C	0.5518	0.2283	0.2608	0.180*
C18	−0.08757 (14)	0.9475 (3)	0.2108 (3)	0.0732 (8)
H18	−0.1303	0.9754	0.2368	0.088*
H2N	0.1922 (10)	0.6792 (19)	0.0104 (10)	0.050 (6)*
H3N	0.1063 (11)	0.795 (2)	0.0004 (11)	0.058 (7)*
H2O	0.2911 (10)	0.647 (3)	0.337 (3)	0.107 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0438 (11)	0.0557 (11)	0.0336 (9)	0.0068 (9)	−0.0022 (8)	0.0030 (8)
N2	0.0493 (12)	0.0655 (12)	0.0257 (9)	0.0148 (10)	−0.0033 (8)	0.0010 (8)
O3	0.0552 (10)	0.0646 (9)	0.0241 (7)	0.0057 (8)	−0.0020 (6)	−0.0009 (6)
O2	0.0721 (12)	0.0777 (11)	0.0363 (8)	0.0328 (10)	−0.0091 (8)	−0.0112 (8)
C14	0.0411 (13)	0.0493 (12)	0.0277 (10)	0.0010 (10)	−0.0007 (9)	0.0003 (9)
N3	0.0490 (12)	0.0733 (13)	0.0249 (9)	0.0157 (10)	−0.0021 (8)	0.0011 (8)
O1	0.0732 (13)	0.0986 (14)	0.0617 (10)	0.0413 (11)	−0.0122 (9)	−0.0005 (9)
C7	0.0430 (13)	0.0478 (12)	0.0337 (10)	−0.0016 (10)	0.0007 (9)	0.0023 (9)
C2	0.0576 (15)	0.0664 (15)	0.0326 (11)	0.0137 (13)	−0.0040 (10)	0.0012 (10)
C6	0.0449 (13)	0.0450 (12)	0.0335 (10)	0.0024 (10)	0.0007 (9)	0.0005 (9)
C1	0.0487 (14)	0.0509 (12)	0.0314 (10)	0.0094 (11)	0.0062 (9)	0.0031 (9)
C5	0.0663 (17)	0.0582 (14)	0.0476 (12)	0.0123 (13)	−0.0096 (12)	−0.0118 (11)
C4	0.0706 (18)	0.0619 (16)	0.0571 (14)	0.0247 (14)	−0.0020 (13)	−0.0077 (12)
C15	0.0489 (14)	0.0469 (12)	0.0347 (10)	0.0093 (11)	0.0040 (10)	0.0075 (9)
C3	0.0530 (15)	0.0617 (14)	0.0473 (13)	0.0181 (12)	−0.0004 (11)	0.0072 (11)
C8	0.0457 (13)	0.0489 (12)	0.0355 (11)	0.0019 (11)	−0.0007 (10)	−0.0007 (9)
C20	0.0558 (16)	0.0542 (14)	0.0534 (13)	0.0072 (12)	−0.0064 (12)	−0.0015 (10)
C13	0.0611 (17)	0.0745 (16)	0.0432 (12)	−0.0076 (14)	0.0038 (11)	−0.0028 (11)
C16	0.0703 (18)	0.0616 (15)	0.0421 (12)	0.0153 (13)	−0.0028 (11)	−0.0033 (11)
C9	0.078 (2)	0.0788 (18)	0.0527 (14)	−0.0260 (16)	−0.0001 (13)	−0.0057 (13)
C17	0.079 (2)	0.0709 (17)	0.0598 (15)	0.0280 (16)	0.0135 (15)	−0.0021 (13)
C19	0.0517 (17)	0.0654 (16)	0.0873 (19)	0.0040 (14)	−0.0091 (14)	0.0015 (15)
C11	0.094 (2)	0.103 (2)	0.0423 (14)	0.0101 (19)	−0.0110 (15)	−0.0219 (14)
C10	0.095 (2)	0.099 (2)	0.0659 (18)	−0.0282 (19)	−0.0122 (17)	−0.0209 (16)
C12	0.083 (2)	0.098 (2)	0.0383 (13)	0.0036 (18)	0.0053 (13)	0.0006 (13)
C21	0.116 (3)	0.138 (3)	0.106 (3)	0.086 (3)	−0.024 (2)	−0.019 (2)
C18	0.0589 (18)	0.0712 (18)	0.090 (2)	0.0184 (15)	0.0185 (16)	0.0137 (16)

Geometric parameters (Å, º) top

N1—C7	1.293 (2)	C15—C16	1.379 (3)
N1—N2	1.369 (2)	C8—C9	1.367 (3)
N2—C14	1.362 (3)	C8—C13	1.368 (3)
N2—H2N	0.873 (9)	C20—C19	1.372 (3)
O3—C14	1.222 (2)	C20—H20	0.9300
O2—C1	1.359 (2)	C13—C12	1.376 (3)
O2—H2O	0.890 (10)	C13—H13	0.9300
C14—N3	1.351 (2)	C16—C17	1.378 (3)
N3—C15	1.405 (3)	C16—H16	0.9300
N3—H3N	0.881 (9)	C9—C10	1.377 (3)
O1—C3	1.364 (3)	C9—H9	0.9300
O1—C21	1.417 (3)	C17—C18	1.369 (3)
C7—C6	1.456 (3)	C17—H17	0.9300
C7—C8	1.491 (3)	C19—C18	1.367 (3)
C2—C1	1.370 (3)	C19—H19	0.9300
C2—C3	1.376 (3)	C11—C12	1.350 (4)
C2—H2	0.9300	C11—C10	1.357 (4)
C6—C5	1.384 (3)	C11—H11	0.9300
C6—C1	1.403 (3)	C10—H10	0.9300
C5—C4	1.369 (3)	C12—H12	0.9300
C5—H5	0.9300	C21—H21A	0.9600
C4—C3	1.373 (3)	C21—H21B	0.9600
C4—H4	0.9300	C21—H21C	0.9600
C15—C20	1.379 (3)	C18—H18	0.9300

C7—N1—N2	118.52 (16)	C13—C8—C7	119.48 (19)
C14—N2—N1	118.42 (15)	C19—C20—C15	119.8 (2)
C14—N2—H2N	120.9 (13)	C19—C20—H20	120.1
N1—N2—H2N	120.6 (13)	C15—C20—H20	120.1
C1—O2—H2O	106.6 (19)	C8—C13—C12	120.1 (2)
O3—C14—N3	124.56 (19)	C8—C13—H13	119.9
O3—C14—N2	122.83 (18)	C12—C13—H13	119.9
N3—C14—N2	112.59 (16)	C17—C16—C15	119.2 (2)
C14—N3—C15	125.39 (17)	C17—C16—H16	120.4
C14—N3—H3N	114.4 (14)	C15—C16—H16	120.4
C15—N3—H3N	117.3 (14)	C8—C9—C10	120.4 (2)
C3—O1—C21	118.1 (2)	C8—C9—H9	119.8
N1—C7—C6	117.45 (17)	C10—C9—H9	119.8
N1—C7—C8	122.56 (18)	C18—C17—C16	121.0 (2)
C6—C7—C8	119.97 (18)	C18—C17—H17	119.5
C1—C2—C3	120.2 (2)	C16—C17—H17	119.5
C1—C2—H2	119.9	C18—C19—C20	120.8 (2)
C3—C2—H2	119.9	C18—C19—H19	119.6
C5—C6—C1	116.52 (19)	C20—C19—H19	119.6
C5—C6—C7	120.98 (18)	C12—C11—C10	120.0 (2)
C1—C6—C7	122.42 (18)	C12—C11—H11	120.0
O2—C1—C2	116.90 (18)	C10—C11—H11	120.0
O2—C1—C6	121.97 (18)	C11—C10—C9	120.0 (3)
C2—C1—C6	121.10 (19)	C11—C10—H10	120.0
C4—C5—C6	123.0 (2)	C9—C10—H10	120.0
C4—C5—H5	118.5	C11—C12—C13	120.5 (3)
C6—C5—H5	118.5	C11—C12—H12	119.8
C5—C4—C3	118.9 (2)	C13—C12—H12	119.8
C5—C4—H4	120.5	O1—C21—H21A	109.5
C3—C4—H4	120.5	O1—C21—H21B	109.5
C20—C15—C16	119.9 (2)	H21A—C21—H21B	109.5
C20—C15—N3	117.38 (19)	O1—C21—H21C	109.5
C16—C15—N3	122.7 (2)	H21A—C21—H21C	109.5
O1—C3—C4	125.0 (2)	H21B—C21—H21C	109.5
O1—C3—C2	114.7 (2)	C19—C18—C17	119.3 (3)
C4—C3—C2	120.3 (2)	C19—C18—H18	120.4
C9—C8—C13	118.92 (19)	C17—C18—H18	120.4
C9—C8—C7	121.58 (19)

C7—N1—N2—C14	164.67 (18)	C5—C4—C3—O1	−177.4 (2)
N1—N2—C14—O3	0.2 (3)	C5—C4—C3—C2	1.7 (4)
N1—N2—C14—N3	−178.30 (17)	C1—C2—C3—O1	178.3 (2)
O3—C14—N3—C15	−17.1 (3)	C1—C2—C3—C4	−0.8 (4)
N2—C14—N3—C15	161.40 (19)	N1—C7—C8—C9	−79.3 (3)
N2—N1—C7—C6	177.23 (17)	C6—C7—C8—C9	102.6 (3)
N2—N1—C7—C8	−0.9 (3)	N1—C7—C8—C13	99.2 (3)
N1—C7—C6—C5	174.0 (2)	C6—C7—C8—C13	−78.9 (3)
C8—C7—C6—C5	−7.8 (3)	C16—C15—C20—C19	−1.4 (3)
N1—C7—C6—C1	−9.4 (3)	N3—C15—C20—C19	−179.1 (2)
C8—C7—C6—C1	168.75 (19)	C9—C8—C13—C12	0.2 (4)
C3—C2—C1—O2	−178.7 (2)	C7—C8—C13—C12	−178.4 (2)
C3—C2—C1—C6	−0.5 (3)	C20—C15—C16—C17	2.0 (3)
C5—C6—C1—O2	179.1 (2)	N3—C15—C16—C17	179.6 (2)
C7—C6—C1—O2	2.4 (3)	C13—C8—C9—C10	0.3 (4)
C5—C6—C1—C2	1.0 (3)	C7—C8—C9—C10	178.8 (2)
C7—C6—C1—C2	−175.72 (19)	C15—C16—C17—C18	−0.8 (4)
C1—C6—C5—C4	−0.1 (4)	C15—C20—C19—C18	−0.4 (4)
C7—C6—C5—C4	176.6 (2)	C12—C11—C10—C9	−1.4 (5)
C6—C5—C4—C3	−1.2 (4)	C8—C9—C10—C11	0.3 (4)
C14—N3—C15—C20	−139.5 (2)	C10—C11—C12—C13	1.8 (4)
C14—N3—C15—C16	42.9 (3)	C8—C13—C12—C11	−1.2 (4)
C21—O1—C3—C4	−0.9 (4)	C20—C19—C18—C17	1.6 (4)
C21—O1—C3—C2	−179.9 (2)	C16—C17—C18—C19	−0.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···N1	0.89 (1)	1.76 (2)	2.563 (2)	149 (3)
N2—H2N···O3ⁱ	0.87 (1)	2.13 (1)	2.9301 (19)	152 (2)
N3—H3N···O3ⁱ	0.88 (1)	2.09 (1)	2.935 (2)	161 (2)
C12—H12···O2ⁱⁱ	0.93	2.44	3.252 (3)	146

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

Acknowledgements

CFA is thankful to the University Grants Commission, Bangalore, India, for the award of a Teacher Fellowship under the faculty improvement programme. MRPK is grateful to UGC, New Delhi, India, for a UGC–BSR one-time grant to the Faculty. We also thank the Sophisticated Analytical Instruments Facility, Cochin University of S & T, Kochi-22, India, for the diffraction measurements.

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