The crystal structure of (RS)-7-chloro-2-(2,5-di­meth­oxy­phen­yl)-2,3-di­hydro­quinazolin-4(1H)-one: two hydrogen bonds generate an elegant three-dimensional framework structure

Narasimhamurthy, K.H.; Chandra; Sagar, B.K.; Rangappa, K.S.; Yathirajan, H.S.; Glidewell, C.

doi:10.1107/S2056989019007023

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 6| June 2019| Pages 843-847

https://doi.org/10.1107/S2056989019007023

Open

access

The crystal structure of (RS)-7-chloro-2-(2,5-dimethoxyphenyl)-2,3-dihydroquinazolin-4(1H)-one: two hydrogen bonds generate an elegant three-dimensional framework structure

Kereyagalahally H. Narasimhamurthy,^a Chandra,^b Belakavadi K. Sagar,^c Kanchugarakoppal S. Rangappa,^c Hemmige S. Yathirajan ^c ^* and Christopher Glidewell ^d

^aDepartment of Studies in Organic Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, ^bDepartment of Physics, National Institute of Engineering, Mysore-570 008, India, ^cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, and ^dSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
^*Correspondence e-mail: yathirajan@hotmail.com

Edited by M. Zeller, Purdue University, USA (Received 13 May 2019; accepted 14 May 2019; online 21 May 2019)

In the title compound, C₆₁H₁₅ClN₂O₃, the heterocyclic ring adopts an envelope conformation, folded across the N⋯N line, with the 2,5-dimethoxyphenyl unit occupying a quasi-axial site. There are two N—H⋯O hydrogen bonds in the structure: one hydrogen bond links molecules related by a 4₁ screw axis to form a C(6) chain, and the other links inversion-related pairs of molecules to form an R₂²(8) ring. The ring motif links all of the chains into a continuous three-dimensional framework structure. Comparisons are made with the structures of some related compounds.

Keywords: heterocyclic compounds; reduced quinazolinones; crystal structure; molecular conformation; hydrogen bonding; supramolecular assembly.

CCDC reference: 1875494

1. Chemical context

Quinazoline-4-one and its derivatives constitute an important class of fused heterocycles, which are found in more than two hundred naturally occurring alkaloids. In addition, 2,3-dihydroquinazolin-4(1H)-one is a privileged scaffold in drug design (Badolato et al., 2018 ). Despite this, rather few structures have been published for compounds containing this heterocyclic nucleus (see Section 4 below), and with these considerations in mind, we now report the molecular and supramolecular structure of (RS)-7-chloro-2-(2,5-dimethoxyphenyl)-2,3-dihydroquinazolin-4(1H)-one (I) (Fig. 1). The compound was prepared using a recently published (Narasimhamurthy et al., 2014 ) one-step process, which employs a base-promoted cyclization reaction between a (dibromomethyl)arene, here 2-(dibromomethyl)-1,4-dimethoxybenzene, and a 2-aminobenzamide, here 2-amino-4-chlorobenzamide, which after a straightforward purification step gives the product (I) in 79% yield.

Figure 1
The molecular structure of compound (I)

showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

2. Structural commentary

The molecule of compound (I) contains a stereogenic centre at atom C2, and the reference molecule was selected as one having the R configuration at this atom: the centrosymmetric space group confirms that compound (I) has crystallized as a racemic mixture. The heterocyclic ring in compound (I) adopts a conformation close to the envelope form, in which this ring is folded across the line N1⋯N3 (Fig. 1). The ring-puckering parameters, calculated for the atom sequence (N1,C2,N3,C4,C4A,C8A) in the R-enantiomer are Q = 0.258 (2) Å, θ = 121.8 (4)° and φ = 219.3 (6)°. For the ideal envelope form, the puckering angles take the values θ = 54.7° (equivalent to 125.3°) and φ = (60k)°, where k represents an integer (Boeyens, 1978 ). The r.m.s. deviation of the atoms N1, N3, C4, C4A, C8A from their mean plane is only 0.035 Å, with a maximum deviation of 0.0403 (11) Å for atom N3. However, atom C2 is displaced from this plane by 0.355 (3) Å. The 2,5-dimethoxyphenyl substituent occupies the quasi-axial site at atom C2. Within this unit, the two methoxy C atoms are almost coplanar with the aryl ring: the deviations from the mean plane of this ring are 0.020 (5) Å for atom C221 and 0.101 (5) Å for atom C251. Associated with this planarity, the two exocyclic C—C—O angles at atoms C22 and C25 are significantly different, by 11.9° at C22 and by 8.2° at atoms C25, as previously observed in planar or near-planar alkoxyarenes (Seip & Seip, 1973 ; Ferguson et al., 1996 ).

3. Supramolecular features

The structure of compound (I) contains just two N—H⋯O hydrogen bonds (Table 1) but these are sufficient to link all of the molecules into a three-dimensional framework structure, whose formation is readily analysed in terms of the actions of the two individual hydrogen bonds. The hydrogen bond having atom N1 as the donor links molecules related by the 4₁ screw axis along (0.25, 0.5, z) into a C(6) chain (Etter, 1990 ; Etter et al., 1990 ; Bernstein et al., 1995 ) running parallel to the [001] direction (Fig. 2). Four chains of this type pass through each unit cell. The hydrogen bond having atom N3 as the donor links inversion-related pairs of molecules to form a cyclic dimer characterized by an R₂²(8) motif (Fig. 3). This interaction directly links the C(6) chain around the 4₁ screw axis ( $[1\over4]$ , $[1\over2]$ , z) with four similar chains around the screw axes along ( $[3\over4]$ , $[1\over2]$ , z), (− $[1\over4]$ , $[1\over2]$ , z), ( $[1\over4]$ , 0, z) and ( $[1\over4]$ , 1, z) (Fig. 4). Propagation of these hydrogen bonds by the space-group symmetry operations links all of the C(6) chains, so linking all of the molecules into a very elegant three-dimensional structure generated by only two hydrogen bonds.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4ⁱ	0.80 (3)	2.39 (3)	3.161 (3)	162 (2)
N3—H3⋯O4ⁱⁱ	0.83 (3)	2.04 (3)	2.854 (3)	166 (2)
Symmetry codes: (i) $[-y+{\script{3\over 4}}, x+{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Part of the crystal structure of compound (I)

showing the formation of a hydrogen-bonded C(6) chain running parallel to [001]. Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, the H atoms bonded to C atoms have been omitted.

Figure 3
Part of the crystal structure of compound (I)

showing the formation of a cyclic hydrogen-bonded dimer. Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, the unit-cell outline and the H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) are at the symmetry position ( $[{1\over 2}]$ − x, $[{1\over 2}]$ − y, $[{1\over 2}]$ − z).

Figure 4
A projection along [001] of part of the crystal structure of compound (I)

showing the linking of the C(6) chains by the R₂²(8) rings. Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, only the heterocyclic ring, along with its hydrogen-bond acceptors and donors, is shown for each molecule.

4. Database survey

It is of interest briefly to compare the molecular and supramolecular structure of (I) reported here with those of some related structures. In (RS)-2-(2-chlorophenyl)-2,3-dihydroquinazolin-4(1H)-one (Li & Feng, 2009 ), the heterocyclic ring has a screw–boat conformation, as opposed to the envelope form in (I). As in (I), the structure contains two N—H⋯O hydrogen bonds, and these were described in the original report as generating a polymer along b, but without further specification. However, examination of the published atomic coordinates shows clearly that the molecules are linked into a chain of centrosymmetric, edge-fused rings running parallel to the [100] direction, in which R₂²(8) rings centred at (n, 1, 0) alternate with R₄²(12) rings centred at (n + $[1\over2]$ , 1, 0), where n represents an integer in each case (Fig. 5).

Figure 5
Part of the crystal structure of (RS)-2-(2-chlorophenyl)-2,3-dihydroquinazolin-4(1H)-one showing the formation of a hydrogen-bonded chain of edge-fused rings along [100]. The published atomic coordinates (Li & Feng, 2009

) have been used. Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, the H atoms bonded to C atoms have been omitted.

In 5-chloro-3-hydroxy-2,2-dimethyl-2,3-dihydroquinazolin-4(1H)-one (Vembu et al., 2006 ), the heterocyclic ring again adopts the screw–boat conformation, and a combination of N—H⋯O and O—H⋯O hydrogen bonds links the molecules into complex sheets, within which rings of S(5), R₂²(4) and R₂²(10) types can be identified. There is no carbonyl group in (RS)-2-methyl-4-phenyl-3,4-dihydroquinazoline, and here molecules which are related by a 3₁ screw axis are linked by an N-–H⋯N hydrogen bond to form a C(5) chain (Valkonen et al., 2011 ).

Finally, we note the structures of a number of 2,3-dihydroquinazolin-4(1H)-ones in which there is a substituent at atom N3 (Butcher et al., 2007 ; Toze et al., 2018 ; Zaytsev et al., 2018 ). In each of these examples, the molecules are linked by a single N—H⋯O hydrogen bond to form a C(6) chain. However, when the substituent at atom N3 is an arylmethylamino group, the heterocyclic ring adopts a screw–boat conformation (Butcher et al., 2007), but in five examples where this substituent is either a benzyl group or a furanylmethyl unit, the heterocyclic ring adopts an envelope conformation, folded across the N⋯N line (Toze et al., 2018; Zaytsev et al. 2018).

5. Synthesis and crystallization

A sample of compound (I) was prepared using a recently published general procedure (Narasimhamurthy et al., 2014). Potassium tert-butoxide (3.3 mmol) was added to a suspension of 2-(dibromomethyl)-1,4-dimethoxybenzene (3.3 mmol) and 2-amino-4-chlorobenzamide (3.5 mmol) in a pyridine-dimethylformamide mixture (3:1, v/v). The resulting mixture was heated at 313 K for 4 h, with TLC monitoring. When the reaction was judged to be complete, an excess of water was added, followed by extraction with ethyl acetate (2 × 20 ml). The combined organic extract was washed with brine and then dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the crude product was purified by column chromatography using silica gel mesh 60–120, with 30% ethyl acetate in hexane as eluent, to give the product (I) in 79% yield. Crystals suitable for single crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, of a solution in dimethylsulfoxide: m.p. 481–483 K.

6. Refinement

Crystal data, data collection and structure refinement details are given in Table 2. In the setting of space group I4₁/a, No. 88, employed here the origin is located at a centre of inversion. All H atoms were located in difference maps. The H atoms bonded to C atoms were then treated as riding atoms in geometrically idealized position with C—H 0.93 Å (aromatic), 0.96 Å (CH₃) or 0.98 Å (aliphatic C—H), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms bonded to C atoms. For the H atoms bonded to N atoms, the atomic coordinates were refined with U_iso(H) = 1.2U_eq(N), giving the N—H distances shown in Table 1.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₅ClN₂O₃
M_r	318.75
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	296
a, c (Å)	15.314 (7), 25.736 (12)
V (Å³)	6036 (6)
Z	16
Radiation type	Mo Kα
μ (mm⁻¹)	0.27
Crystal size (mm)	0.26 × 0.22 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.913, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	42994, 3149, 1848
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.128, 1.04
No. of reflections	3149
No. of parameters	207
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.27
Computer programs: APEX2 and SAINT (Bruker, 2015), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1875494

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989019007023/zl2756sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019007023/zl2756Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019007023/zl2756Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(RS)-7-Chloro-2-(2,5-dimethoxyphenyl)-2,3-dihydroquinazolin-4(1H)-one top

Crystal data top

C₁₆H₁₅ClN₂O₃	D_x = 1.403 Mg m⁻³
M_r = 318.75	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 3465 reflections
a = 15.314 (7) Å	θ = 1.6–27.6°
c = 25.736 (12) Å	µ = 0.27 mm⁻¹
V = 6036 (6) Å³	T = 296 K
Z = 16	Block, colourless
F(000) = 2656	0.26 × 0.22 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	3149 independent reflections
Radiation source: fine focus sealed tube	1848 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
Detector resolution: 0.3333 pixels mm^-1	θ_max = 26.6°, θ_min = 1.6°
φ and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −19→19
T_min = 0.913, T_max = 0.953	l = −32→26
42994 measured reflections

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.0505P)² + 3.5139P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3149 reflections	Δρ_max = 0.17 e Å⁻³
207 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints

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
N1	0.30909 (14)	0.40264 (14)	0.37953 (7)	0.0531 (6)
H1	0.3275 (17)	0.4092 (16)	0.4083 (10)	0.064*
C2	0.30616 (16)	0.31258 (15)	0.36210 (8)	0.0482 (6)
H2	0.3646	0.2879	0.3670	0.058*
N3	0.28752 (14)	0.31121 (14)	0.30684 (7)	0.0506 (5)
H3	0.2932 (16)	0.2628 (17)	0.2929 (9)	0.061*
C4	0.24435 (15)	0.37295 (16)	0.28060 (8)	0.0467 (6)
O4	0.22338 (12)	0.36121 (11)	0.23471 (6)	0.0603 (5)
C4A	0.22505 (14)	0.45429 (15)	0.30792 (8)	0.0434 (5)
C5	0.17657 (16)	0.51985 (16)	0.28452 (9)	0.0521 (6)
H5	0.1566	0.5118	0.2507	0.062*
C6	0.15743 (16)	0.59599 (17)	0.30984 (9)	0.0569 (7)
H6	0.1250	0.6397	0.2939	0.068*
C7	0.18794 (16)	0.60558 (16)	0.35987 (9)	0.0556 (6)
Cl7	0.16054 (6)	0.70075 (5)	0.39245 (3)	0.0873 (3)
C8	0.23775 (16)	0.54326 (16)	0.38428 (9)	0.0522 (6)
H8	0.2583	0.5527	0.4178	0.063*
C8A	0.25726 (14)	0.46570 (15)	0.35832 (8)	0.0424 (5)
C21	0.24297 (15)	0.25723 (14)	0.39324 (8)	0.0432 (5)
C22	0.26659 (17)	0.23605 (16)	0.44405 (8)	0.0522 (6)
C23	0.2110 (2)	0.18716 (17)	0.47413 (9)	0.0678 (8)
H23	0.2271	0.1735	0.5080	0.081*
C24	0.1321 (2)	0.15794 (18)	0.45543 (10)	0.0682 (8)
H24	0.0951	0.1257	0.4767	0.082*
C25	0.10822 (18)	0.17630 (16)	0.40582 (9)	0.0559 (7)
C26	0.16454 (16)	0.22579 (15)	0.37492 (8)	0.0488 (6)
H26	0.1485	0.2379	0.3408	0.059*
O221	0.34622 (12)	0.26875 (12)	0.45915 (6)	0.0718 (6)
C221	0.3739 (2)	0.2493 (2)	0.51083 (11)	0.0918 (11)
H22A	0.3823	0.1874	0.5143	0.138*
H22B	0.3302	0.2684	0.5350	0.138*
H22C	0.4279	0.2789	0.5179	0.138*
O251	0.03307 (13)	0.14750 (13)	0.38268 (8)	0.0767 (6)
C251	−0.0300 (2)	0.1052 (2)	0.41418 (14)	0.0939 (11)
H25A	−0.0488	0.1442	0.4412	0.141*
H25B	−0.0048	0.0539	0.4294	0.141*
H25C	−0.0793	0.0889	0.3932	0.141*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0655 (14)	0.0565 (13)	0.0373 (10)	−0.0097 (11)	−0.0105 (10)	−0.0042 (10)
C2	0.0520 (14)	0.0582 (15)	0.0343 (12)	0.0045 (12)	−0.0054 (10)	−0.0063 (10)
N3	0.0645 (14)	0.0545 (13)	0.0328 (10)	0.0040 (11)	0.0019 (9)	−0.0061 (9)
C4	0.0508 (14)	0.0574 (15)	0.0321 (11)	−0.0045 (12)	0.0049 (10)	−0.0021 (11)
O4	0.0872 (13)	0.0620 (11)	0.0316 (8)	0.0061 (9)	−0.0056 (8)	−0.0085 (7)
C4A	0.0427 (13)	0.0524 (14)	0.0351 (11)	−0.0070 (11)	0.0026 (10)	−0.0054 (10)
C5	0.0539 (15)	0.0618 (16)	0.0404 (12)	−0.0005 (13)	−0.0050 (11)	−0.0082 (11)
C6	0.0585 (16)	0.0595 (17)	0.0528 (14)	0.0039 (13)	−0.0050 (12)	−0.0054 (12)
C7	0.0568 (16)	0.0551 (16)	0.0548 (14)	−0.0041 (13)	0.0012 (12)	−0.0154 (12)
Cl7	0.1085 (7)	0.0736 (5)	0.0800 (5)	0.0165 (4)	−0.0147 (4)	−0.0338 (4)
C8	0.0580 (16)	0.0593 (16)	0.0395 (12)	−0.0130 (13)	−0.0033 (11)	−0.0104 (11)
C8A	0.0404 (13)	0.0508 (14)	0.0359 (11)	−0.0119 (11)	0.0002 (10)	−0.0033 (10)
C21	0.0560 (15)	0.0410 (13)	0.0326 (11)	0.0068 (11)	−0.0025 (10)	−0.0045 (9)
C22	0.0692 (17)	0.0490 (15)	0.0384 (12)	0.0063 (13)	−0.0121 (12)	−0.0073 (11)
C23	0.109 (2)	0.0588 (17)	0.0354 (13)	0.0081 (17)	−0.0032 (14)	0.0095 (12)
C24	0.088 (2)	0.0621 (18)	0.0540 (16)	−0.0059 (16)	0.0068 (15)	0.0091 (13)
C25	0.0707 (18)	0.0458 (14)	0.0514 (14)	0.0010 (13)	0.0006 (13)	−0.0025 (11)
C26	0.0612 (16)	0.0484 (14)	0.0369 (11)	0.0042 (12)	−0.0039 (11)	0.0006 (10)
O221	0.0866 (14)	0.0768 (13)	0.0521 (11)	0.0029 (11)	−0.0292 (10)	−0.0026 (9)
C221	0.124 (3)	0.091 (2)	0.0607 (17)	0.024 (2)	−0.0496 (18)	−0.0082 (16)
O251	0.0707 (13)	0.0784 (14)	0.0810 (13)	−0.0176 (11)	−0.0024 (11)	0.0074 (11)
C251	0.072 (2)	0.082 (2)	0.128 (3)	−0.0106 (17)	0.012 (2)	0.026 (2)

Geometric parameters (Å, º) top

N1—C8A	1.364 (3)	C21—C26	1.377 (3)
N1—C2	1.451 (3)	C21—C22	1.395 (3)
N1—H1	0.80 (3)	C22—C23	1.373 (4)
C2—N3	1.451 (3)	C22—O221	1.374 (3)
C2—C21	1.516 (3)	C23—C24	1.376 (4)
C2—H2	0.9800	C23—H23	0.9300
N3—C4	1.337 (3)	C24—C25	1.357 (3)
N3—H3	0.83 (2)	C24—H24	0.9300
C4—O4	1.237 (3)	C25—O251	1.369 (3)
C4—C4A	1.461 (3)	C25—C26	1.397 (3)
C4A—C5	1.386 (3)	C26—H26	0.9300
C4A—C8A	1.399 (3)	O221—C221	1.427 (3)
C5—C6	1.368 (3)	C221—H22A	0.9600
C5—H5	0.9300	C221—H22B	0.9600
C6—C7	1.377 (3)	C221—H22C	0.9600
C6—H6	0.9300	O251—C251	1.418 (3)
C7—C8	1.374 (3)	C251—H25A	0.9600
C7—Cl7	1.733 (3)	C251—H25B	0.9600
C8—C8A	1.395 (3)	C251—H25C	0.9600
C8—H8	0.9300

C8A—N1—C2	122.09 (19)	C26—C21—C22	117.8 (2)
C8A—N1—H1	119.2 (19)	C26—C21—C2	124.84 (19)
C2—N1—H1	114.6 (19)	C22—C21—C2	117.4 (2)
N3—C2—N1	108.84 (19)	C23—C22—O221	126.1 (2)
N3—C2—C21	112.62 (19)	C23—C22—C21	119.6 (2)
N1—C2—C21	112.82 (18)	O221—C22—C21	114.2 (2)
N3—C2—H2	107.4	C22—C23—C24	121.7 (2)
N1—C2—H2	107.4	C22—C23—H23	119.2
C21—C2—H2	107.4	C24—C23—H23	119.2
C4—N3—C2	125.6 (2)	C25—C24—C23	119.9 (3)
C4—N3—H3	117.8 (17)	C25—C24—H24	120.1
C2—N3—H3	114.6 (17)	C23—C24—H24	120.1
O4—C4—N3	120.5 (2)	C24—C25—O251	124.7 (2)
O4—C4—C4A	122.1 (2)	C24—C25—C26	118.8 (3)
N3—C4—C4A	117.39 (19)	O251—C25—C26	116.5 (2)
C5—C4A—C8A	120.1 (2)	C21—C26—C25	122.2 (2)
C5—C4A—C4	121.12 (19)	C21—C26—H26	118.9
C8A—C4A—C4	118.8 (2)	C25—C26—H26	118.9
C6—C5—C4A	121.7 (2)	C22—O221—C221	116.8 (2)
C6—C5—H5	119.2	O221—C221—H22A	109.5
C4A—C5—H5	119.2	O221—C221—H22B	109.5
C5—C6—C7	117.6 (2)	H22A—C221—H22B	109.5
C5—C6—H6	121.2	O221—C221—H22C	109.5
C7—C6—H6	121.2	H22A—C221—H22C	109.5
C8—C7—C6	122.8 (2)	H22B—C221—H22C	109.5
C8—C7—Cl7	119.83 (19)	C25—O251—C251	118.1 (2)
C6—C7—Cl7	117.4 (2)	O251—C251—H25A	109.5
C7—C8—C8A	119.4 (2)	O251—C251—H25B	109.5
C7—C8—H8	120.3	H25A—C251—H25B	109.5
C8A—C8—H8	120.3	O251—C251—H25C	109.5
N1—C8A—C8	122.4 (2)	H25A—C251—H25C	109.5
N1—C8A—C4A	119.2 (2)	H25B—C251—H25C	109.5
C8—C8A—C4A	118.4 (2)

C8A—N1—C2—N3	33.6 (3)	C5—C4A—C8A—C8	1.3 (3)
C8A—N1—C2—C21	−92.2 (2)	C4—C4A—C8A—C8	−179.4 (2)
N1—C2—N3—C4	−26.5 (3)	N3—C2—C21—C26	−14.9 (3)
C21—C2—N3—C4	99.4 (3)	N1—C2—C21—C26	108.8 (2)
C2—N3—C4—O4	−171.9 (2)	N3—C2—C21—C22	164.5 (2)
C2—N3—C4—C4A	9.3 (3)	N1—C2—C21—C22	−71.8 (3)
O4—C4—C4A—C5	4.7 (3)	C26—C21—C22—C23	−1.5 (3)
N3—C4—C4A—C5	−176.6 (2)	C2—C21—C22—C23	179.0 (2)
O4—C4—C4A—C8A	−174.6 (2)	C26—C21—C22—O221	179.1 (2)
N3—C4—C4A—C8A	4.1 (3)	C2—C21—C22—O221	−0.4 (3)
C8A—C4A—C5—C6	−1.3 (4)	O221—C22—C23—C24	179.5 (2)
C4—C4A—C5—C6	179.4 (2)	C21—C22—C23—C24	0.2 (4)
C4A—C5—C6—C7	−0.1 (4)	C22—C23—C24—C25	1.0 (4)
C5—C6—C7—C8	1.5 (4)	C23—C24—C25—O251	177.2 (2)
C5—C6—C7—Cl7	−178.02 (19)	C23—C24—C25—C26	−0.8 (4)
C6—C7—C8—C8A	−1.5 (4)	C22—C21—C26—C25	1.8 (3)
Cl7—C7—C8—C8A	178.07 (18)	C2—C21—C26—C25	−178.8 (2)
C2—N1—C8A—C8	158.6 (2)	C24—C25—C26—C21	−0.6 (4)
C2—N1—C8A—C4A	−24.0 (3)	O251—C25—C26—C21	−178.8 (2)
C7—C8—C8A—N1	177.4 (2)	C23—C22—O221—C221	0.6 (4)
C7—C8—C8A—C4A	0.0 (3)	C21—C22—O221—C221	179.9 (2)
C5—C4A—C8A—N1	−176.2 (2)	C24—C25—O251—C251	8.7 (4)
C4—C4A—C8A—N1	3.1 (3)	C26—C25—O251—C251	−173.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.80 (3)	2.39 (3)	3.161 (3)	162 (2)
N3—H3···O4ⁱⁱ	0.83 (3)	2.04 (3)	2.854 (3)	166 (2)

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

Acknowledgements

KHN is grateful to UGC, RFSMS, Government of India for a Research Fellowship. BKS thanks the University of Mysore, for research facilities.

Funding information

KSR and HSY are grateful to UGC, New Delhi, for the award of a BSR Faculty Fellowship for a period of three years.

References

Badolato, M., Aiello, F. & Neamati, N. (2018). RSC Adv. 8, 20894–20921. CrossRef CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Boeyens, J. C. A. (1978). J. Cryst. Mol. Struct. 8, 317–320. CrossRef Web of Science Google Scholar
Bruker (2015). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Butcher, R. J., Jasinski, J. P., Narayana, B., Sunil, K. & Yathirajan, H. S. (2007). Acta Cryst. E63, o4025–o4026. CSD CrossRef IUCr Journals Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Ferguson, G., Glidewell, C. & Patterson, I. L. J. (1996). Acta Cryst. C52, 420–423. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Li, M.-J. & Feng, C.-J. (2009). Acta Cryst. E65, o2145. Web of Science CSD CrossRef IUCr Journals Google Scholar
Narasimhamurthy, K. H., Chandrappa, S., Sharath Kumar, K. S., Harsha, K. B., Ananda, H. & Rangappa, K. S. (2014). RSC Adv. 4, 34479–34486. CrossRef CAS Google Scholar
Seip, H. M. & Seip, R. (1973). Acta Chem. Scand. 27, 4024–4027. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Toze, F. A. A., Zaytsev, V. P., Chervyakova, L. V., Kvyatkovskaya, E. A., Dorovatovskii, P. V. & Khrustalev, V. N. (2018). Acta Cryst. E74, 10–14. CSD CrossRef IUCr Journals Google Scholar
Valkonen, A., Kolehmainen, E., Zakrzewska, A., Skotnicka, A. & Gawinecki, R. (2011). Acta Cryst. E67, o923–o924. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Vembu, N., Spencer, E. C., Lee, J., Kelly, J. G., Nolan, K. B. & Devocelle, M. (2006). Acta Cryst. E62, o5003–o5005. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zaytsev, V. P., Sorokina, E. A., Kvyatkovskaya, E. A., Toze, F. A. A., Mhaldar, S. N., Dorovatovskii, P. V. & Khrustalev, V. N. (2018). Acta Cryst. E74, 1101–1106. CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.