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

Sebhaoui, J.; El Bakri, Y.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314616016965

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161696

https://doi.org/10.1107/S2414314616016965

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

Jihad Sebhaoui,^a ^* Youness El Bakri,^a El Mokhtar Essassi ^a and Joel T. Mague ^b

^aHeterocyclic Organic Chemistry Laboratory URAC 21, Faculty of Sciences, Mohammed V University in Rabat, Av Ibn Battouta, BP 1014 Rabat, Morocco, and ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: sebhaoui.jihad@gmail.com

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 12 October 2016; accepted 23 October 2016; online 1 November 2016)

In the title compound, C₂₄H₃₆N₂O₂, the orientation of the 2-oxopropylidene substituent is determined by the formation of an intramolecular N—H⋯O hydrogen bond. The benzodiazepine seven-membered ring adopts a slightly twisted boat conformation. The molecules pack in a bilayer fashion with the dodecyl chains intercalated to form the inner portion, and the benzodiazepine moieties on the outer surfaces.

Keywords: crystal structure; benzodiazepine; hydrogen bonding; bilayer.

CCDC reference: 1511185

Structure description

1,5-Benzodiazepine derivatives are an important class of heterocyclic compounds with versatile biological actions. They are used as anticonvulsivants, myorelaxants (Rudolph et al., 1999 ), anxiolytics, hypnotics and sedatives (Zellou et al., 1999 ). The commercial applications of these compounds as dyes for acrylic fibres and in photography have also been reported (Mauget-Fa et al., 2001 ; Bishop et al., 2007 ). Two published works indicate that 2,3,4,5-tetrahydro-1H-1,5-benzodiazepine derivatives carrying carboxamide substituents are potentially important as therapeutic and prophylactic agents for diabetes, diabetic nephropathy, or glomerulosclerosis (Finch et al., 1996 ; Ohtake et al., 2007 ).

In the title molecule, the seven-membered ring adopts a slightly twisted boat conformation. An analysis of the conformation (Cremer & Pople, 1975 ) yielded the puckering parameters q₂ = 0.893 (2), q₃ = 0.255 (2) Å, φ₂ = 18.2 (1) and φ₃ = 130.0°. The overall puckering amplitude is 0.916 (2) Å. The dodecyl chain is oriented approximately over the bicyclic portion (Fig. 1), while the orientation of the 2-oxopropylidene substituent is determined by the intramolecular hydrogen bond N1—H1⋯O2 (Table 1 and Fig. 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.88 (2)	1.94 (2)	2.637 (2)	136 (2)
C5—H5⋯O1ⁱ	0.98 (2)	2.54 (2)	3.500 (2)	165.6 (17)
C2—H2⋯O2ⁱⁱ	0.97 (2)	2.48 (3)	3.276 (2)	139.4 (19)
Symmetry codes: (i) x, y-1, z; (ii) x-1, y+1, z.

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

In the crystal, the dodecyl chains intercalate to form the hydrophobic portion of a bilayer, with the more polar bicyclic portions forming the outer faces (Fig. 2). Weak C5—H5⋯O1ⁱ and C2—H2⋯O2ⁱⁱ [symmetry codes: (i) x, y − 1, z; (ii) x − 1, y + 1, z] hydrogen bonds help in establishing the surfaces of the bilayer (Table 1 and Fig. 3).

Figure 2
Packing viewed along the b axis showing the intercalation of the alkyl chains.

Figure 3
Detail of the intermolecular C—H⋯O hydrogen bonding [symmetry codes: (i) x, y − 1, z; (ii) x − 1, y + 1, z].

Synthesis and crystallization

A mixture of (4Z)-2-oxopropylidene-1,5-benzodiazepin-2-one (0.01 mol), K₂CO₃ (0.02 mol), dodecane bromide (0.02 mol) and tetra-n-butylammonium bromide (0.001 mol) in dimethylformamide (60 ml) was stirred at room temperature for 48 h. The solution was filtered by suction filtration. The solvent was removed under reduced pressure. The residue was chromatographed on a silica-gel column using a mixture of hexane and ethyl acetate (80:20 v/v) as eluent, to afford the title compound as colourless crystals.

Refinement

Crystal and refinement details are presented in Table 2. All H atoms were found in difference maps and refined with free coordinates and U_iso parameters.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₃₆N₂O₂
M_r	384.55
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	8.2589 (9), 8.3715 (9), 18.097 (2)
α, β, γ (°)	87.327 (6), 82.242 (6), 63.248 (7)
V (Å³)	1106.9 (2)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	0.57
Crystal size (mm)	0.16 × 0.11 × 0.06

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan SADABS (Bruker, 2016 )
T_min, T_max	0.84, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	8388, 4075, 3242
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.138, 1.07
No. of reflections	4075
No. of parameters	397
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.27
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Bruker, 2016).

Structural data

CCDC reference: 1511185

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616016965/bh4017sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016965/bh4017Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616016965/bh4017Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314616016965/bh4017Isup4.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: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Bruker, 2016).

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

Crystal data top

C₂₄H₃₆N₂O₂	Z = 2
M_r = 384.55	F(000) = 420
Triclinic, P1	D_x = 1.154 Mg m⁻³
a = 8.2589 (9) Å	Cu Kα radiation, λ = 1.54178 Å
b = 8.3715 (9) Å	Cell parameters from 5933 reflections
c = 18.097 (2) Å	θ = 2.5–71.6°
α = 87.327 (6)°	µ = 0.57 mm⁻¹
β = 82.242 (6)°	T = 150 K
γ = 63.248 (7)°	Block, colourless
V = 1106.9 (2) Å³	0.16 × 0.11 × 0.06 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	4075 independent reflections
Radiation source: INCOATEC IµS micro-focus source	3242 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.037
Detector resolution: 10.4167 pixels mm^-1	θ_max = 71.6°, θ_min = 4.9°
ω scans	h = −10→10
Absorption correction: multi-scan SADABS (Bruker, 2016)	k = −10→10
T_min = 0.84, T_max = 0.96	l = −20→22
8388 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)] = 0.050	Hydrogen site location: difference Fourier map
wR(F²) = 0.138	All H-atom parameters refined
S = 1.07	w = 1/[σ²(F_o²) + (0.0635P)² + 0.2871P] where P = (F_o² + 2F_c²)/3
4075 reflections	(Δ/σ)_max = 0.001
397 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

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

	x	y	z	U_iso*/U_eq
O1	0.49804 (17)	0.95715 (16)	0.11351 (8)	0.0363 (3)
O2	0.85523 (18)	0.18662 (16)	0.11278 (8)	0.0419 (3)
N1	0.5318 (2)	0.46760 (19)	0.12365 (8)	0.0279 (3)
H1	0.600 (3)	0.356 (3)	0.1351 (13)	0.052 (7)*
N2	0.30375 (19)	0.84404 (17)	0.16331 (8)	0.0260 (3)
C1	0.2303 (2)	0.7192 (2)	0.16034 (9)	0.0265 (4)
C2	0.0418 (2)	0.7796 (2)	0.17719 (10)	0.0328 (4)
H2	−0.037 (3)	0.906 (3)	0.1849 (14)	0.055 (7)*
C3	−0.0324 (3)	0.6602 (3)	0.18364 (11)	0.0378 (4)
H3	−0.166 (3)	0.700 (3)	0.1962 (11)	0.032 (5)*
C4	0.0812 (3)	0.4774 (3)	0.17338 (10)	0.0350 (4)
H4	0.025 (3)	0.395 (3)	0.1791 (12)	0.044 (6)*
C5	0.2664 (3)	0.4168 (2)	0.15358 (10)	0.0310 (4)
H5	0.352 (3)	0.291 (3)	0.1420 (12)	0.039 (5)*
C6	0.3426 (2)	0.5368 (2)	0.14575 (9)	0.0261 (3)
C7	0.6123 (2)	0.5373 (2)	0.06987 (9)	0.0255 (3)
H7	0.844 (3)	0.493 (3)	0.0001 (11)	0.032 (5)*
C8	0.4925 (2)	0.7223 (2)	0.04494 (9)	0.0260 (4)
H8A	0.380 (3)	0.723 (3)	0.0262 (11)	0.037 (5)*
H8B	0.556 (3)	0.759 (3)	0.0042 (11)	0.033 (5)*
C9	0.4323 (2)	0.8528 (2)	0.10986 (9)	0.0259 (4)
C10	0.7909 (2)	0.4437 (2)	0.04016 (10)	0.0277 (4)
C11	0.9060 (2)	0.2644 (2)	0.06113 (10)	0.0315 (4)
C12	1.0942 (3)	0.1678 (3)	0.01860 (13)	0.0393 (5)
H12A	1.181 (4)	0.172 (3)	0.0470 (14)	0.059 (7)*
H12B	1.116 (3)	0.228 (3)	−0.0302 (15)	0.058 (7)*
H12C	1.119 (4)	0.050 (4)	0.0081 (18)	0.087 (10)*
C13	0.2425 (3)	0.9605 (2)	0.23012 (10)	0.0315 (4)
H13A	0.103 (3)	1.037 (3)	0.2358 (12)	0.046 (6)*
H13B	0.305 (3)	1.039 (3)	0.2213 (11)	0.038 (5)*
C14	0.2929 (2)	0.8527 (2)	0.30084 (10)	0.0319 (4)
H14A	0.228 (3)	0.780 (3)	0.3095 (12)	0.041 (6)*
H14B	0.251 (3)	0.935 (3)	0.3452 (13)	0.051 (6)*
C15	0.4971 (2)	0.7328 (2)	0.30015 (10)	0.0317 (4)
H15A	0.544 (3)	0.640 (3)	0.2587 (12)	0.037 (5)*
H15B	0.563 (3)	0.812 (3)	0.2879 (12)	0.040 (5)*
C16	0.5431 (3)	0.6367 (3)	0.37373 (10)	0.0336 (4)
H16A	0.472 (3)	0.571 (3)	0.3864 (12)	0.043 (6)*
H16B	0.498 (3)	0.731 (3)	0.4173 (14)	0.052 (6)*
C17	0.7447 (3)	0.5139 (2)	0.37574 (10)	0.0340 (4)
H17A	0.791 (3)	0.417 (3)	0.3350 (14)	0.052 (6)*
H17B	0.816 (3)	0.585 (3)	0.3631 (12)	0.042 (6)*
C18	0.7845 (3)	0.4253 (3)	0.45129 (10)	0.0346 (4)
H18A	0.707 (3)	0.359 (3)	0.4649 (13)	0.051 (6)*
H18B	0.737 (3)	0.520 (3)	0.4902 (13)	0.047 (6)*
C19	0.9837 (3)	0.3002 (2)	0.45673 (10)	0.0343 (4)
H19A	1.029 (3)	0.202 (3)	0.4173 (13)	0.044 (6)*
H19B	1.058 (3)	0.369 (3)	0.4447 (13)	0.048 (6)*
C20	1.0145 (3)	0.2144 (2)	0.53318 (10)	0.0343 (4)
H20A	0.939 (3)	0.147 (3)	0.5437 (13)	0.049 (6)*
H20B	0.967 (3)	0.312 (3)	0.5731 (13)	0.043 (6)*
C21	1.2120 (3)	0.0869 (2)	0.54133 (10)	0.0338 (4)
H21A	1.259 (3)	−0.011 (3)	0.5017 (13)	0.046 (6)*
H21B	1.287 (3)	0.154 (3)	0.5297 (12)	0.042 (6)*
C22	1.2391 (3)	0.0029 (3)	0.61809 (11)	0.0357 (4)
H22A	1.159 (3)	−0.059 (3)	0.6320 (13)	0.052 (6)*
H22B	1.193 (3)	0.099 (3)	0.6567 (13)	0.048 (6)*
C23	1.4358 (3)	−0.1263 (3)	0.62625 (12)	0.0401 (4)
H23A	1.516 (4)	−0.063 (3)	0.6143 (14)	0.058 (7)*
H23B	1.479 (3)	−0.219 (3)	0.5888 (14)	0.050 (6)*
C24	1.4624 (4)	−0.2082 (3)	0.70285 (14)	0.0550 (6)
H24A	1.600 (4)	−0.300 (4)	0.7042 (16)	0.077 (9)*
H24B	1.426 (4)	−0.117 (4)	0.7445 (16)	0.066 (8)*
H24C	1.388 (4)	−0.273 (4)	0.7164 (17)	0.082 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0366 (7)	0.0284 (6)	0.0495 (8)	−0.0200 (6)	−0.0030 (6)	−0.0033 (5)
O2	0.0400 (8)	0.0286 (7)	0.0529 (9)	−0.0124 (6)	−0.0063 (6)	0.0098 (6)
N1	0.0302 (7)	0.0216 (7)	0.0320 (8)	−0.0118 (6)	−0.0044 (6)	0.0038 (6)
N2	0.0288 (7)	0.0220 (7)	0.0276 (7)	−0.0117 (6)	−0.0037 (5)	−0.0004 (5)
C1	0.0315 (9)	0.0260 (8)	0.0250 (8)	−0.0153 (7)	−0.0049 (6)	0.0019 (6)
C2	0.0326 (9)	0.0310 (9)	0.0352 (10)	−0.0151 (8)	−0.0032 (7)	0.0033 (7)
C3	0.0322 (10)	0.0435 (11)	0.0416 (10)	−0.0213 (9)	−0.0029 (8)	0.0045 (8)
C4	0.0432 (10)	0.0398 (10)	0.0326 (9)	−0.0280 (9)	−0.0059 (7)	0.0045 (8)
C5	0.0424 (10)	0.0290 (9)	0.0271 (9)	−0.0206 (8)	−0.0062 (7)	0.0028 (7)
C6	0.0309 (8)	0.0257 (8)	0.0246 (8)	−0.0147 (7)	−0.0067 (6)	0.0040 (6)
C7	0.0310 (8)	0.0235 (8)	0.0260 (8)	−0.0148 (7)	−0.0068 (6)	0.0000 (6)
C8	0.0271 (8)	0.0230 (8)	0.0276 (8)	−0.0110 (7)	−0.0048 (6)	0.0044 (6)
C9	0.0254 (8)	0.0198 (8)	0.0317 (9)	−0.0087 (7)	−0.0070 (6)	0.0036 (6)
C10	0.0281 (8)	0.0248 (8)	0.0318 (9)	−0.0128 (7)	−0.0064 (7)	0.0021 (7)
C11	0.0310 (9)	0.0257 (8)	0.0397 (10)	−0.0128 (7)	−0.0110 (7)	−0.0001 (7)
C12	0.0296 (10)	0.0303 (10)	0.0570 (13)	−0.0116 (8)	−0.0071 (9)	−0.0034 (9)
C13	0.0363 (10)	0.0244 (8)	0.0317 (9)	−0.0118 (8)	−0.0023 (7)	−0.0039 (7)
C14	0.0331 (9)	0.0338 (9)	0.0296 (9)	−0.0158 (8)	−0.0014 (7)	−0.0037 (7)
C15	0.0336 (9)	0.0332 (9)	0.0285 (9)	−0.0155 (8)	−0.0025 (7)	−0.0013 (7)
C16	0.0355 (10)	0.0354 (9)	0.0305 (9)	−0.0163 (8)	−0.0045 (7)	0.0012 (8)
C17	0.0378 (10)	0.0344 (9)	0.0305 (9)	−0.0166 (9)	−0.0059 (7)	0.0017 (8)
C18	0.0379 (10)	0.0340 (10)	0.0315 (10)	−0.0156 (8)	−0.0056 (7)	0.0013 (8)
C19	0.0396 (10)	0.0347 (10)	0.0303 (9)	−0.0181 (9)	−0.0053 (7)	0.0016 (8)
C20	0.0390 (10)	0.0340 (10)	0.0320 (10)	−0.0179 (9)	−0.0057 (7)	0.0022 (8)
C21	0.0381 (10)	0.0330 (9)	0.0314 (9)	−0.0166 (8)	−0.0067 (7)	0.0037 (8)
C22	0.0431 (11)	0.0350 (10)	0.0327 (10)	−0.0204 (9)	−0.0062 (8)	0.0025 (8)
C23	0.0464 (11)	0.0379 (10)	0.0394 (11)	−0.0200 (9)	−0.0139 (9)	0.0040 (9)
C24	0.0745 (17)	0.0507 (13)	0.0491 (14)	−0.0320 (13)	−0.0288 (12)	0.0158 (11)

Geometric parameters (Å, º) top

O1—C9	1.2263 (19)	C14—H14A	0.97 (2)
O2—C11	1.247 (2)	C14—H14B	1.00 (2)
N1—C7	1.360 (2)	C15—C16	1.525 (3)
N1—C6	1.405 (2)	C15—H15A	1.01 (2)
N1—H1	0.88 (2)	C15—H15B	1.03 (2)
N2—C9	1.362 (2)	C16—C17	1.517 (3)
N2—C1	1.4309 (19)	C16—H16A	0.97 (2)
N2—C13	1.473 (2)	C16—H16B	1.05 (2)
C1—C2	1.396 (2)	C17—C18	1.528 (3)
C1—C6	1.400 (2)	C17—H17A	1.02 (2)
C2—C3	1.382 (2)	C17—H17B	1.01 (2)
C2—H2	0.97 (2)	C18—C19	1.515 (3)
C3—C4	1.394 (3)	C18—H18A	1.03 (3)
C3—H3	1.00 (2)	C18—H18B	0.99 (2)
C4—C5	1.376 (3)	C19—C20	1.527 (3)
C4—H4	0.98 (2)	C19—H19A	1.01 (2)
C5—C6	1.399 (2)	C19—H19B	1.01 (2)
C5—H5	0.98 (2)	C20—C21	1.518 (3)
C7—C10	1.365 (2)	C20—H20A	1.01 (2)
C7—C8	1.502 (2)	C20—H20B	1.02 (2)
C8—C9	1.515 (2)	C21—C22	1.525 (3)
C8—H8A	1.03 (2)	C21—H21A	1.01 (2)
C8—H8B	0.96 (2)	C21—H21B	1.01 (2)
C10—C11	1.436 (2)	C22—C23	1.516 (3)
C10—H7	0.97 (2)	C22—H22A	1.01 (2)
C11—C12	1.506 (3)	C22—H22B	0.99 (2)
C12—H12A	0.95 (3)	C23—C24	1.516 (3)
C12—H12B	1.03 (3)	C23—H23A	1.02 (3)
C12—H12C	0.94 (3)	C23—H23B	0.96 (2)
C13—C14	1.525 (3)	C24—H24A	1.05 (3)
C13—H13A	1.03 (2)	C24—H24B	1.02 (3)
C13—H13B	1.00 (2)	C24—H24C	0.99 (3)
C14—C15	1.524 (3)

C7—N1—C6	125.16 (15)	C14—C15—C16	112.49 (15)
C7—N1—H1	115.3 (16)	C14—C15—H15A	110.6 (12)
C6—N1—H1	117.0 (16)	C16—C15—H15A	108.4 (12)
C9—N2—C1	123.31 (14)	C14—C15—H15B	107.5 (12)
C9—N2—C13	119.43 (13)	C16—C15—H15B	111.2 (12)
C1—N2—C13	117.17 (13)	H15A—C15—H15B	106.5 (16)
C2—C1—C6	119.07 (15)	C17—C16—C15	114.65 (15)
C2—C1—N2	118.86 (15)	C17—C16—H16A	110.3 (13)
C6—C1—N2	121.94 (15)	C15—C16—H16A	110.0 (14)
C3—C2—C1	120.67 (17)	C17—C16—H16B	108.4 (13)
C3—C2—H2	119.9 (15)	C15—C16—H16B	109.6 (13)
C1—C2—H2	119.4 (15)	H16A—C16—H16B	103.3 (18)
C2—C3—C4	120.01 (17)	C16—C17—C18	112.69 (15)
C2—C3—H3	122.0 (11)	C16—C17—H17A	109.8 (14)
C4—C3—H3	117.9 (11)	C18—C17—H17A	109.3 (14)
C5—C4—C3	119.89 (16)	C16—C17—H17B	108.9 (13)
C5—C4—H4	121.9 (13)	C18—C17—H17B	110.0 (13)
C3—C4—H4	118.2 (13)	H17A—C17—H17B	105.9 (18)
C4—C5—C6	120.54 (17)	C19—C18—C17	115.22 (15)
C4—C5—H5	123.4 (12)	C19—C18—H18A	109.9 (13)
C6—C5—H5	116.0 (12)	C17—C18—H18A	109.4 (13)
C5—C6—C1	119.64 (16)	C19—C18—H18B	110.1 (14)
C5—C6—N1	117.97 (15)	C17—C18—H18B	108.6 (14)
C1—C6—N1	122.39 (14)	H18A—C18—H18B	103.0 (18)
N1—C7—C10	121.79 (15)	C18—C19—C20	112.74 (15)
N1—C7—C8	116.00 (14)	C18—C19—H19A	108.9 (13)
C10—C7—C8	122.22 (15)	C20—C19—H19A	109.0 (13)
C7—C8—C9	109.41 (14)	C18—C19—H19B	108.8 (13)
C7—C8—H8A	109.1 (11)	C20—C19—H19B	110.5 (13)
C9—C8—H8A	109.9 (11)	H19A—C19—H19B	106.7 (18)
C7—C8—H8B	111.1 (12)	C21—C20—C19	114.78 (16)
C9—C8—H8B	109.7 (12)	C21—C20—H20A	108.5 (13)
H8A—C8—H8B	107.6 (17)	C19—C20—H20A	108.7 (13)
O1—C9—N2	123.08 (15)	C21—C20—H20B	108.9 (13)
O1—C9—C8	121.36 (15)	C19—C20—H20B	109.2 (12)
N2—C9—C8	115.55 (13)	H20A—C20—H20B	106.5 (17)
C7—C10—C11	123.18 (16)	C20—C21—C22	113.78 (16)
C7—C10—H7	120.6 (12)	C20—C21—H21A	108.8 (13)
C11—C10—H7	116.0 (12)	C22—C21—H21A	109.5 (13)
O2—C11—C10	122.41 (16)	C20—C21—H21B	108.3 (12)
O2—C11—C12	119.32 (17)	C22—C21—H21B	110.3 (12)
C10—C11—C12	118.27 (17)	H21A—C21—H21B	105.8 (17)
C11—C12—H12A	109.1 (15)	C23—C22—C21	113.99 (16)
C11—C12—H12B	114.8 (14)	C23—C22—H22A	109.3 (14)
H12A—C12—H12B	102 (2)	C21—C22—H22A	111.5 (14)
C11—C12—H12C	109.9 (19)	C23—C22—H22B	109.1 (14)
H12A—C12—H12C	112 (2)	C21—C22—H22B	109.3 (13)
H12B—C12—H12C	109 (2)	H22A—C22—H22B	103.0 (18)
N2—C13—C14	111.77 (14)	C24—C23—C22	113.8 (2)
N2—C13—H13A	110.2 (12)	C24—C23—H23A	109.4 (15)
C14—C13—H13A	108.4 (13)	C22—C23—H23A	109.5 (14)
N2—C13—H13B	105.3 (12)	C24—C23—H23B	109.9 (14)
C14—C13—H13B	110.9 (12)	C22—C23—H23B	108.4 (15)
H13A—C13—H13B	110.3 (17)	H23A—C23—H23B	105.5 (19)
C15—C14—C13	114.11 (15)	C23—C24—H24A	110.0 (16)
C15—C14—H14A	108.9 (13)	C23—C24—H24B	113.5 (15)
C13—C14—H14A	110.0 (13)	H24A—C24—H24B	108 (2)
C15—C14—H14B	107.8 (14)	C23—C24—H24C	112.0 (18)
C13—C14—H14B	110.0 (14)	H24A—C24—H24C	108 (2)
H14A—C14—H14B	105.6 (18)	H24B—C24—H24C	106 (2)

C9—N2—C1—C2	−135.43 (17)	C13—N2—C9—O1	−1.8 (3)
C13—N2—C1—C2	48.1 (2)	C1—N2—C9—C8	1.0 (2)
C9—N2—C1—C6	48.7 (2)	C13—N2—C9—C8	177.42 (14)
C13—N2—C1—C6	−127.77 (17)	C7—C8—C9—O1	105.68 (18)
C6—C1—C2—C3	3.7 (3)	C7—C8—C9—N2	−73.53 (18)
N2—C1—C2—C3	−172.29 (16)	N1—C7—C10—C11	1.9 (3)
C1—C2—C3—C4	0.1 (3)	C8—C7—C10—C11	−177.63 (15)
C2—C3—C4—C5	−2.9 (3)	C7—C10—C11—O2	−6.3 (3)
C3—C4—C5—C6	1.9 (3)	C7—C10—C11—C12	173.45 (16)
C4—C5—C6—C1	1.9 (3)	C9—N2—C13—C14	−115.69 (17)
C4—C5—C6—N1	−178.46 (16)	C1—N2—C13—C14	61.0 (2)
C2—C1—C6—C5	−4.6 (2)	N2—C13—C14—C15	58.3 (2)
N2—C1—C6—C5	171.20 (15)	C13—C14—C15—C16	176.23 (14)
C2—C1—C6—N1	175.74 (16)	C14—C15—C16—C17	179.39 (15)
N2—C1—C6—N1	−8.4 (2)	C15—C16—C17—C18	178.22 (15)
C7—N1—C6—C5	133.69 (17)	C16—C17—C18—C19	179.72 (16)
C7—N1—C6—C1	−46.7 (2)	C17—C18—C19—C20	−179.42 (15)
C6—N1—C7—C10	−165.76 (15)	C18—C19—C20—C21	179.65 (15)
C6—N1—C7—C8	13.8 (2)	C19—C20—C21—C22	−179.93 (15)
N1—C7—C8—C9	63.24 (18)	C20—C21—C22—C23	179.33 (16)
C10—C7—C8—C9	−117.19 (17)	C21—C22—C23—C24	179.49 (17)
C1—N2—C9—O1	−178.22 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.88 (2)	1.94 (2)	2.637 (2)	136 (2)
C5—H5···O1ⁱ	0.98 (2)	2.54 (2)	3.500 (2)	165.6 (17)
C2—H2···O2ⁱⁱ	0.97 (2)	2.48 (3)	3.276 (2)	139.4 (19)

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

Acknowledgements

The support of NSF–MRI Grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

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