A monoclinic modification of (4Z)-1-benzyl-4-(2-oxo­propyl­idene)-2,3,4,5-tetra­hydro-1H-1,5-benzodiazepin-2-one

Samba, M.; Minnih, M.S.; El Bakri, Y.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314618003267

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 2| February 2018| x180326

https://doi.org/10.1107/S2414314618003267

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A monoclinic modification of (4Z)-1-benzyl-4-(2-oxopropylidene)-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-one

Mohamed Samba,^a,^b ^* Mohamed Said Minnih,^b Youness El Bakri,^a El Mokhtar Essassi ^a and Joel T. Mague ^c

^aLaboratoire de Chimie Organique Hétérocyclique, Centre de Recherche des Sciences des médicaments, URAC 21, Pôle de Compétence Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, ^bUnité de Chimie Moleculaire et Environnement, Faculté des Sciences et, Techniques, Université de Sciences, de Technologie et de Médecine, Nouakchott, Mauritania, and ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: sam.mmohamed18@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 23 January 2018; accepted 25 February 2018; online 28 February 2018)

In the title molecule, C₁₉H₁₈N₂O₂, the orientation of the oxopropylidene substituent is largely determined by an intramolecular N—H⋯O hydrogen bond. In the crystal, C—H⋯O hydrogen bonds form zigzag chains, which are elaborated into sheets lying parallel to (101) by complementary C—H⋯π interactions. Comparisons to the structure of the triclinic modification are made.

Keywords: crystal structure; benzodiazepine; hydrogen bond; π-stacking.

CCDC reference: 1825637

Structure description

Benzodiazepine derivatives are widely used as anticonvulsants, antidepressives, sedatives and analgesics (Schultz et al., 1982 ; Olkkola et al., 2008 ). In addition, they are used as medicinal agents in the treatment of central nervous system (CNS) disturbances (Stefancich et al., 1992 ). They also exhibit antitumor and antineoplastic activities (Werner et al., 1990 ). As part of our ongoing studies in this area (Sebhaoui et al., 2016 , 2017 ) we now describe the synthesis and crystal structure of a monoclinic modification of the title compound to complement the known triclinic polymorph (Samba et al., 2016 ).

The dihedral angle between the mean planes of the C1–C6 and C11–C16 rings is 79.02 (5)°. A puckering analysis of the seven-membered ring gave the parameters Q(2) = 0.866 (1) Å, Q(3) = 0.230 (1) Å, φ(2) = 210.27 (7)° and φ(3) = 311.2 (2)°. The orientation of the oxopropylidene substituent is largely determined by the intramolecular N2—H2A⋯O2 hydrogen bond (Table 1 and Fig. 1). In the crystal, C5—H5⋯O1ⁱ and C10—H10A⋯O1ⁱ hydrogen bonds form zigzag chains aligned with the a/2 + c/2 diagonal of the ac face (Table 1 and Fig. 2). The chains have the benzyl substituents all protruding from the same side and are joined into sheets lying parallel to (10 $[\overline{1}]$ ) by complementary C2—H2⋯π(Cg2)ⁱⁱⁱ interactions (Table 1 and Figs. 2 and 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C11–C16 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2	0.927 (16)	1.921 (15)	2.6613 (11)	135.4 (12)
C5—H5⋯O1ⁱ	0.943 (15)	2.350 (15)	3.2823 (12)	170.0 (13)
C10—H10A⋯O1ⁱ	1.005 (14)	2.571 (14)	3.5518 (12)	165.2 (11)
C2—H2⋯Cg2ⁱⁱ	0.973 (14)	2.81 (2)	3.625 (1)	142 (1)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1.

Figure 1
The title molecule with the labelling scheme and 50% probability ellipsoids. The intramolecular N—H⋯O hydrogen bond is shown as a dashed line.

Figure 2
Details of the intermolecular C—H⋯O hydrogen bonding (black dashed lines) and the C—H⋯π(ring) interactions (green dashed lines). [Symmetry codes: (i) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ii) −x + 1, −y + 1, −z + 1; (iii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

Figure 3
Packing viewed along the a-axis direction with intermolecular interactions depicted as in Fig. 2

While the various conformational parameters of the title compound are quite similar to those of the two independent molecules in the triclinic modification (Samba et al., 2016; CSD refcode AWUXUN) [e.g. Q(2) = 0.872 (1) Å, Q(3) = 0.208 (1) Å, φ(2) = 206.93 (3)° and φ(3) = 303.3 (4)° for molecule 1, while for molecule 2, the corresponding values are 0.814 (1) Å, 0.199 (1) Å, 207.66 (9)° and 313.3 (4)°, respectively), the crystal packing is distinctly different. In the triclinic form, complementary C—H⋯O hydrogen bonds between centrosymmetrically related pairs of molecule 2 form weak dimers with each member of the pair making a weak C—H⋯O hydrogen bond to a molecule 1. These entities then pack in rows extending parallel to the c-axis direction.

Synthesis and crystallization

(4Z)-4-(2-Oxopropylidene)-1,5-benzodiazepin-2-one (0.01 mol) and potassium carbonate K₂CO₃ (0.02 mol) were dissolved in DMF, then benzylbromide (0.02 mol) and tetrabutylammonium bromide as a phase-transfer catalyst (0.001 mol) were added. The reaction mixture was stirred at room temperature for 48 h. The residue obtained, after evaporation of solvent, was chromatographed on a silica gel column using a hexane/ethyl acetate 9:1 mixture as eluent. The solid obtained was crystallized from dichloromethane solution to afford as colourless blocks. The triclinic modification was crystallized from ethanol solution (Samba et al., 2016).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₈N₂O₂
M_r	306.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	8.9229 (5), 18.8922 (10), 9.7147 (5)
β (°)	104.879 (1)
V (Å³)	1582.73 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.43 × 0.34 × 0.33

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.90, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	30264, 4290, 3840
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.120, 1.03
No. of reflections	4290
No. of parameters	269
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.28
Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ), SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1825637

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618003267/hb4207sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618003267/hb4207Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618003267/hb4207Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314618003267/hb4207Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(4Z)-1-Benzyl-4-(2-oxopropylidene)-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-one top

Crystal data top

C₁₉H₁₈N₂O₂	F(000) = 648
M_r = 306.35	D_x = 1.286 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.9229 (5) Å	Cell parameters from 9497 reflections
b = 18.8922 (10) Å	θ = 2.8–29.2°
c = 9.7147 (5) Å	µ = 0.08 mm⁻¹
β = 104.879 (1)°	T = 100 K
V = 1582.73 (15) Å³	Block, colourless
Z = 4	0.43 × 0.34 × 0.33 mm

Data collection top

Bruker SMART APEX CCD diffractometer	4290 independent reflections
Radiation source: fine-focus sealed tube	3840 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 8.3333 pixels mm^-1	θ_max = 29.2°, θ_min = 2.2°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −25→25
T_min = 0.90, T_max = 0.97	l = −13→13
30264 measured reflections

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)] = 0.043	Hydrogen site location: mixed
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0723P)² + 0.4643P] where P = (F_o² + 2F_c²)/3
4290 reflections	(Δ/σ)_max = 0.001
269 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Special details top

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = –30.00 and 210.00°. The scan time was 15 sec/frame.

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. Independent refinement of the hydrogens attached to C19 led to an unsatisfacory geometry so they were placed in calculated positions and included as riding contributions.

Independent refinement of the H atoms attached to C19 led to an unsatisfacory geometry so they were placed in calculated positions and included as riding contributions.

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

	x	y	z	U_iso*/U_eq
O1	0.32106 (9)	0.28428 (4)	0.06813 (8)	0.02234 (17)
O2	0.18336 (10)	0.57963 (4)	0.09910 (9)	0.02928 (19)
N1	0.47383 (10)	0.33296 (4)	0.27077 (8)	0.01491 (17)
N2	0.40185 (10)	0.48362 (4)	0.20128 (9)	0.01720 (17)
H2A	0.3522 (18)	0.5254 (8)	0.2131 (15)	0.029 (4)*
C1	0.53064 (11)	0.46141 (5)	0.30978 (9)	0.01433 (18)
C2	0.62092 (12)	0.51468 (5)	0.39148 (10)	0.01812 (19)
H2	0.5929 (16)	0.5639 (8)	0.3687 (15)	0.024 (3)*
C3	0.74494 (12)	0.49803 (5)	0.50523 (11)	0.0212 (2)
H3	0.8050 (17)	0.5351 (8)	0.5616 (15)	0.028 (4)*
C4	0.78186 (12)	0.42744 (6)	0.53783 (11)	0.0220 (2)
H4	0.8681 (18)	0.4154 (8)	0.6179 (16)	0.031 (4)*
C5	0.69518 (12)	0.37418 (5)	0.45648 (11)	0.0189 (2)
H5	0.7218 (17)	0.3265 (8)	0.4788 (16)	0.027 (3)*
C6	0.56769 (10)	0.38998 (5)	0.34242 (9)	0.01408 (18)
C7	0.40872 (11)	0.33147 (5)	0.12711 (10)	0.01607 (19)
C8	0.44886 (12)	0.39302 (5)	0.04263 (10)	0.0187 (2)
H8A	0.5607 (16)	0.4023 (7)	0.0738 (15)	0.025 (3)*
H8B	0.4211 (16)	0.3796 (7)	−0.0595 (15)	0.023 (3)*
C9	0.36035 (11)	0.45702 (5)	0.06729 (10)	0.0178 (2)
C10	0.45330 (12)	0.27023 (5)	0.35546 (10)	0.01635 (19)
H10A	0.5572 (16)	0.2486 (8)	0.4007 (14)	0.021 (3)*
H10B	0.3908 (17)	0.2358 (8)	0.2861 (15)	0.025 (3)*
C11	0.37144 (11)	0.28643 (5)	0.46926 (10)	0.01497 (18)
C12	0.44441 (14)	0.27264 (5)	0.61138 (11)	0.0233 (2)
H12	0.5538 (18)	0.2535 (8)	0.6382 (16)	0.034 (4)*
C13	0.36628 (18)	0.28330 (6)	0.71659 (12)	0.0318 (3)
H13	0.417 (2)	0.2742 (10)	0.8183 (19)	0.048 (5)*
C14	0.21624 (17)	0.30856 (6)	0.68034 (14)	0.0338 (3)
H14	0.163 (2)	0.3172 (10)	0.752 (2)	0.058 (6)*
C15	0.14262 (14)	0.32281 (7)	0.53895 (15)	0.0318 (3)
H15	0.041 (2)	0.3410 (10)	0.513 (2)	0.053 (5)*
C16	0.22028 (12)	0.31183 (6)	0.43331 (12)	0.0224 (2)
H16	0.1684 (18)	0.3224 (8)	0.3322 (17)	0.033 (4)*
C17	0.24371 (13)	0.48605 (6)	−0.03786 (11)	0.0229 (2)
H17	0.2218 (18)	0.4641 (8)	−0.1292 (17)	0.031 (4)*
C18	0.15993 (13)	0.54845 (6)	−0.01710 (12)	0.0257 (2)
C19	0.04049 (15)	0.57702 (7)	−0.14480 (14)	0.0367 (3)
H19A	−0.021533	0.613573	−0.113690	0.055*
H19B	−0.027467	0.538449	−0.191022	0.055*
H19C	0.093060	0.597542	−0.212431	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0274 (4)	0.0206 (3)	0.0178 (4)	−0.0092 (3)	0.0035 (3)	−0.0039 (3)
O2	0.0279 (4)	0.0269 (4)	0.0280 (4)	0.0030 (3)	−0.0019 (3)	0.0056 (3)
N1	0.0192 (4)	0.0135 (3)	0.0120 (4)	−0.0021 (3)	0.0041 (3)	−0.0009 (3)
N2	0.0186 (4)	0.0168 (4)	0.0135 (4)	0.0007 (3)	−0.0009 (3)	0.0003 (3)
C1	0.0148 (4)	0.0155 (4)	0.0119 (4)	0.0002 (3)	0.0019 (3)	−0.0002 (3)
C2	0.0204 (4)	0.0155 (4)	0.0169 (4)	−0.0010 (3)	0.0018 (4)	−0.0021 (3)
C3	0.0202 (5)	0.0211 (5)	0.0190 (5)	−0.0016 (4)	−0.0011 (4)	−0.0056 (4)
C4	0.0185 (4)	0.0242 (5)	0.0191 (5)	0.0042 (4)	−0.0026 (4)	−0.0027 (4)
C5	0.0193 (4)	0.0172 (4)	0.0185 (4)	0.0040 (3)	0.0017 (4)	−0.0006 (3)
C6	0.0154 (4)	0.0142 (4)	0.0126 (4)	−0.0005 (3)	0.0036 (3)	−0.0019 (3)
C7	0.0184 (4)	0.0170 (4)	0.0136 (4)	−0.0026 (3)	0.0056 (3)	−0.0022 (3)
C8	0.0250 (5)	0.0197 (4)	0.0122 (4)	−0.0071 (4)	0.0061 (3)	−0.0011 (3)
C9	0.0203 (4)	0.0187 (4)	0.0133 (4)	−0.0072 (3)	0.0026 (3)	0.0021 (3)
C10	0.0228 (5)	0.0120 (4)	0.0153 (4)	0.0012 (3)	0.0069 (3)	0.0004 (3)
C11	0.0195 (4)	0.0114 (4)	0.0147 (4)	−0.0012 (3)	0.0058 (3)	−0.0001 (3)
C12	0.0347 (6)	0.0191 (4)	0.0160 (5)	0.0062 (4)	0.0063 (4)	0.0025 (3)
C13	0.0605 (8)	0.0210 (5)	0.0184 (5)	0.0015 (5)	0.0183 (5)	0.0023 (4)
C14	0.0510 (7)	0.0248 (5)	0.0378 (7)	−0.0117 (5)	0.0338 (6)	−0.0077 (5)
C15	0.0218 (5)	0.0322 (6)	0.0462 (7)	−0.0062 (4)	0.0172 (5)	−0.0133 (5)
C16	0.0184 (5)	0.0241 (5)	0.0237 (5)	−0.0015 (4)	0.0035 (4)	−0.0055 (4)
C17	0.0247 (5)	0.0254 (5)	0.0150 (5)	−0.0083 (4)	−0.0016 (4)	0.0052 (4)
C18	0.0217 (5)	0.0256 (5)	0.0245 (5)	−0.0069 (4)	−0.0038 (4)	0.0113 (4)
C19	0.0321 (6)	0.0351 (6)	0.0327 (6)	−0.0030 (5)	−0.0102 (5)	0.0163 (5)

Geometric parameters (Å, º) top

O1—C7	1.2267 (12)	C9—C17	1.3716 (14)
O2—C18	1.2425 (15)	C10—C11	1.5047 (13)
N1—C7	1.3674 (12)	C10—H10A	1.005 (14)
N1—C6	1.4309 (11)	C10—H10B	0.997 (14)
N1—C10	1.4806 (12)	C11—C16	1.3891 (14)
N2—C9	1.3552 (12)	C11—C12	1.3915 (14)
N2—C1	1.4091 (12)	C12—C13	1.3918 (16)
N2—H2A	0.927 (16)	C12—H12	1.010 (16)
C1—C2	1.4012 (13)	C13—C14	1.379 (2)
C1—C6	1.4061 (12)	C13—H13	0.990 (18)
C2—C3	1.3844 (14)	C14—C15	1.388 (2)
C2—H2	0.973 (14)	C14—H14	0.95 (2)
C3—C4	1.3907 (14)	C15—C16	1.3934 (16)
C3—H3	0.963 (15)	C15—H15	0.941 (19)
C4—C5	1.3861 (14)	C16—H16	0.993 (16)
C4—H4	0.971 (15)	C17—C18	1.4376 (17)
C5—C6	1.4013 (13)	C17—H17	0.954 (16)
C5—H5	0.943 (15)	C18—C19	1.5123 (15)
C7—C8	1.5182 (13)	C19—H19A	0.9800
C8—C9	1.4968 (14)	C19—H19B	0.9800
C8—H8A	0.981 (14)	C19—H19C	0.9800
C8—H8B	0.992 (14)

C7—N1—C6	123.66 (8)	N1—C10—C11	113.46 (7)
C7—N1—C10	118.03 (8)	N1—C10—H10A	109.7 (8)
C6—N1—C10	118.22 (7)	C11—C10—H10A	109.2 (8)
C9—N2—C1	125.27 (9)	N1—C10—H10B	105.9 (8)
C9—N2—H2A	114.4 (9)	C11—C10—H10B	109.7 (8)
C1—N2—H2A	119.0 (9)	H10A—C10—H10B	108.8 (11)
C2—C1—C6	119.60 (8)	C16—C11—C12	119.40 (9)
C2—C1—N2	116.73 (8)	C16—C11—C10	120.58 (9)
C6—C1—N2	123.63 (8)	C12—C11—C10	119.94 (9)
C3—C2—C1	120.96 (9)	C11—C12—C13	120.43 (11)
C3—C2—H2	120.3 (8)	C11—C12—H12	119.8 (9)
C1—C2—H2	118.7 (8)	C13—C12—H12	119.7 (8)
C2—C3—C4	119.59 (9)	C14—C13—C12	119.94 (11)
C2—C3—H3	120.2 (9)	C14—C13—H13	118.5 (11)
C4—C3—H3	120.2 (9)	C12—C13—H13	121.5 (11)
C5—C4—C3	120.10 (9)	C13—C14—C15	120.09 (11)
C5—C4—H4	119.8 (9)	C13—C14—H14	120.5 (12)
C3—C4—H4	120.1 (9)	C15—C14—H14	119.4 (12)
C4—C5—C6	121.13 (9)	C14—C15—C16	120.09 (11)
C4—C5—H5	119.5 (9)	C14—C15—H15	120.8 (12)
C6—C5—H5	119.4 (9)	C16—C15—H15	119.1 (12)
C5—C6—C1	118.62 (8)	C11—C16—C15	120.04 (11)
C5—C6—N1	118.63 (8)	C11—C16—H16	119.6 (9)
C1—C6—N1	122.59 (8)	C15—C16—H16	120.3 (9)
O1—C7—N1	122.99 (9)	C9—C17—C18	123.08 (10)
O1—C7—C8	120.99 (9)	C9—C17—H17	117.0 (9)
N1—C7—C8	116.02 (8)	C18—C17—H17	119.8 (9)
C9—C8—C7	108.95 (8)	O2—C18—C17	122.95 (10)
C9—C8—H8A	110.0 (8)	O2—C18—C19	119.66 (11)
C7—C8—H8A	109.4 (8)	C17—C18—C19	117.38 (11)
C9—C8—H8B	111.1 (8)	C18—C19—H19A	109.5
C7—C8—H8B	108.2 (8)	C18—C19—H19B	109.5
H8A—C8—H8B	109.1 (12)	H19A—C19—H19B	109.5
N2—C9—C17	122.35 (10)	C18—C19—H19C	109.5
N2—C9—C8	115.34 (8)	H19A—C19—H19C	109.5
C17—C9—C8	122.31 (9)	H19B—C19—H19C	109.5

C9—N2—C1—C2	136.19 (10)	N1—C7—C8—C9	−75.07 (11)
C9—N2—C1—C6	−46.44 (14)	C1—N2—C9—C17	−172.77 (9)
C6—C1—C2—C3	−0.89 (15)	C1—N2—C9—C8	8.21 (13)
N2—C1—C2—C3	176.59 (9)	C7—C8—C9—N2	67.29 (11)
C1—C2—C3—C4	0.87 (16)	C7—C8—C9—C17	−111.73 (10)
C2—C3—C4—C5	0.22 (16)	C7—N1—C10—C11	−120.24 (9)
C3—C4—C5—C6	−1.29 (16)	C6—N1—C10—C11	63.16 (11)
C4—C5—C6—C1	1.25 (15)	N1—C10—C11—C16	62.23 (12)
C4—C5—C6—N1	−174.18 (9)	N1—C10—C11—C12	−121.00 (10)
C2—C1—C6—C5	−0.16 (14)	C16—C11—C12—C13	0.79 (15)
N2—C1—C6—C5	−177.46 (9)	C10—C11—C12—C13	−176.02 (9)
C2—C1—C6—N1	175.07 (8)	C11—C12—C13—C14	−0.83 (17)
N2—C1—C6—N1	−2.22 (14)	C12—C13—C14—C15	0.53 (18)
C7—N1—C6—C5	−142.94 (10)	C13—C14—C15—C16	−0.19 (18)
C10—N1—C6—C5	33.45 (12)	C12—C11—C16—C15	−0.45 (15)
C7—N1—C6—C1	41.82 (13)	C10—C11—C16—C15	176.34 (9)
C10—N1—C6—C1	−141.79 (9)	C14—C15—C16—C11	0.15 (17)
C6—N1—C7—O1	−175.57 (9)	N2—C9—C17—C18	2.56 (16)
C10—N1—C7—O1	8.03 (14)	C8—C9—C17—C18	−178.49 (9)
C6—N1—C7—C8	3.42 (13)	C9—C17—C18—O2	−2.38 (17)
C10—N1—C7—C8	−172.98 (8)	C9—C17—C18—C19	176.56 (10)
O1—C7—C8—C9	103.94 (10)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C11–C16 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2	0.927 (16)	1.921 (15)	2.6613 (11)	135.4 (12)
C5—H5···O1ⁱ	0.943 (15)	2.350 (15)	3.2823 (12)	170.0 (13)
C10—H10A···O1ⁱ	1.005 (14)	2.571 (14)	3.5518 (12)	165.2 (11)
C2—H2···Cg2ⁱⁱ	0.973 (14)	2.81 (2)	3.625 (1)	142 (1)

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

Acknowledgements

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.

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