(1S,2R,8R)-11-Amino-2,2-di­chloro-3,7,7,10-tetra­methyl­tri­cyclo­[6.4.0.01,3]dodec-10-en-9-one

Ait Elhad, M.; Benharref, A.; El Ammari, L.; Saadi, M.; Oukhrib, A.; Berraho, M.

doi:10.1107/S2414314617002553

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170255

https://doi.org/10.1107/S2414314617002553

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access

(1S,2R,8R)-11-Amino-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.0^1,3]dodec-10-en-9-one

Mustapha Ait Elhad,^a ^* Ahmed Benharref,^a Lahcen El Ammari,^b Mohamed Saadi,^b Abdelouahd Oukhrib ^a and Moha Berraho ^a

^aLaboratoire de Chimie des Substances Naturelles, `Unité Associé au CNRST (URAC16)', Faculté des Sciences Semlalia, BP 2390 Bd My Abdellah, Université Cadi Ayyad, 40000 Marrakech, Morocco, and ^bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014 Rabat, Morocco
^*Correspondence e-mail: aitelhad2017@gmail.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 11 February 2017; accepted 14 February 2017; online 24 February 2017)

The title compound, C₁₆H₂₃Cl₂NO, crystallizes in the monoclinic space group P2₁ with two independent molecules (A and B) in the asymmetric unit. They have essentially the same conformation. Each molecule is built up from fused six- and seven-membered rings and an additional three-membered ring. The six-membered ring has an envelope conformation, with the C atom belonging to the three-membered ring forming the flap, while the seven-membered ring displays a boat conformation. In the crystal, molecules are linked into chains propagating along the a-axis direction by N—H⋯O hydrogen bonds.

Keywords: crystal structure; β-himachalene; Atlas cedar.

CCDC reference: 1532588

Structure description

As part of our studies of the essential oil of the Atlas cedar (Cedrus atlantica) made up mainly (50%) of β-himachalene (Benharref et al., 2013 ; El Haib et al., 2011 ), the reactivity of this sesquiterpene and its derivatives has been studied extensively by our team in order to prepare new products having biological properties (El Jamili et al., 2002 ; Zaki et al., 2014 ; Benharref et al., 2015 , 2016 ). Indeed, these compounds have been tested, using the food-poisoning technique, for their potential antifungal activity against the phytopathogen Botrytis cinerea (Daoubi et al., 2004 ).

The asymmetric unit (Fig. 1) includes two crystallographically independent molecules (A and B). A least-squares overlay of the two molecules (Spek, 2009 ) is shown in Fig. 2 and reveals that there is almost no difference between them. In both molecules, the six-membered rings has an envelope conformation as indicated by the total puckering amplitude Q_T = 0.438 (3) Å and spherical polar angle θ2 = 121.6 (4)° with φ2 = −164.2 (5)°, whereas the seven-membered ring displays a boat conformation with Q_T = 1.133 (3) Å, θ2 = 88.37 (17)°; φ2 =-49.66 (16)° and φ3 = −86.92 (5).

Figure 1
The molecular structure of the title compound, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.

Figure 2
The AutoMolFit (PLATON; Spek, 2009

) of molecule B (red) on molecule A (black).

In the crystal, molecules are linked via N—H⋯O hydrogen bonds (Table 1), forming chains along [100] as shown in Fig. 3. Owing to the presence of Cl atoms, the absolute configuration could be determined, by refining the Flack parameter as C1(S), C3(R), C8(R) and C17(S), C19(R), C24(R), respectively.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.86	2.00	2.816 (3)	159
N2—H2B⋯O2ⁱ	0.86	2.06	2.873 (3)	159
Symmetry code: (i) x-1, y, z.

Figure 3
Crystal structure projection along the b axis of the title compound, showing molecules linked by N—H⋯O hydrogen bonds, forming chains along [100].

Synthesis and crystallization

To a solution of (1S,3R,8R)-2,2-dichloro-3,7,7,10-tetramethyltricyclo [6. 4.0.0¹,³]dodec-9-en-11-one (1 g, 3.32 mmol) (Benharref et al., 2010 ) in 20 ml of trifuoroacetic acid at 10°C was added with stirring (500 mg, 7, 8 mmol) of NaN₃. After being stirred at room temperature for 24 h, the mixture was neutralized with Na₂CO₃ and extracted with diethyl ether solution. The combined organic phases were dried on sodium sulfate and concentrated at reduced pressure to give the crude product, which was chromatographed on a silica gel column(cyclohexane–ether, 20–80 by volume) to give 630 mg (2 mmol) of the title product, which was recrystallized from diethyl ether.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₂₃Cl₂NO
M_r	316.25
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	6.9962 (13), 18.654 (4), 12.426 (3)
β (°)	91.273 (5)
V (Å³)	1621.4 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.40
Crystal size (mm)	0.24 × 0.2 × 0.15

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.629, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	58110, 8375, 6511
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.094, 1.02
No. of reflections	8375
No. of parameters	369
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.18
Absolute structure	Flack x determined using 2672 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.010 (18)
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1532588

Crystal structure: contains datablocks I, block. DOI: https://doi.org/10.1107/S2414314617002553/bt4041sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002553/bt4041Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617002553/bt4041Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

(1S,2R,8R)-11-Amino-2,2-dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.0^1,3]dodec-10-en-9-one top

Crystal data top

C₁₆H₂₃Cl₂NO	F(000) = 672
M_r = 316.25	D_x = 1.296 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.9962 (13) Å	Cell parameters from 6632 reflections
b = 18.654 (4) Å	θ = 1.6–26.4°
c = 12.426 (3) Å	µ = 0.40 mm⁻¹
β = 91.273 (5)°	T = 296 K
V = 1621.4 (5) Å³	Prismatic, colourless
Z = 4	0.24 × 0.2 × 0.15 mm

Data collection top

Bruker X8 APEX diffractometer	6511 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.053
φ and ω scans	θ_max = 28.7°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→8
T_min = 0.629, T_max = 0.747	k = −25→25
58110 measured reflections	l = −16→16
8375 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0442P)² + 0.1774P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.094	(Δ/σ)_max = 0.001
S = 1.02	Δρ_max = 0.26 e Å⁻³
8375 reflections	Δρ_min = −0.18 e Å⁻³
369 parameters	Absolute structure: Flack x determined using 2672 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.010 (18)

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
C1	0.3670 (4)	0.62609 (15)	0.5109 (2)	0.0342 (6)
C2	0.3868 (5)	0.69648 (17)	0.5700 (2)	0.0469 (7)
C3	0.3294 (5)	0.63016 (17)	0.6324 (2)	0.0452 (7)
C4	0.4790 (6)	0.59418 (18)	0.7054 (2)	0.0540 (8)
H4A	0.4594	0.6086	0.7793	0.065*
H4B	0.6054	0.6099	0.6852	0.065*
C5	0.4675 (6)	0.51212 (19)	0.6972 (3)	0.0610 (10)
H5A	0.5883	0.4923	0.7228	0.073*
H5B	0.3694	0.4955	0.7452	0.073*
C6	0.4241 (5)	0.48237 (17)	0.5853 (2)	0.0497 (8)
H6A	0.2932	0.4951	0.5664	0.060*
H6B	0.4292	0.4305	0.5902	0.060*
C7	0.5494 (4)	0.50495 (15)	0.4912 (2)	0.0419 (7)
C8	0.5481 (4)	0.58915 (14)	0.4760 (2)	0.0336 (6)
H8	0.6508	0.6076	0.5232	0.040*
C9	0.5984 (4)	0.61206 (16)	0.3623 (2)	0.0375 (6)
C10	0.4512 (4)	0.63564 (15)	0.2889 (2)	0.0345 (6)
C11	0.2637 (4)	0.63392 (14)	0.3179 (2)	0.0321 (5)
C12	0.2033 (4)	0.61729 (17)	0.4302 (2)	0.0374 (6)
H12A	0.1563	0.5684	0.4330	0.045*
H12B	0.0996	0.6490	0.4493	0.045*
C13	0.1274 (6)	0.6244 (2)	0.6731 (3)	0.0649 (10)
H13A	0.1181	0.6502	0.7396	0.097*
H13B	0.0963	0.5749	0.6846	0.097*
H13C	0.0397	0.6445	0.6208	0.097*
C14	0.7561 (6)	0.4808 (2)	0.5124 (4)	0.0719 (11)
H14A	0.7604	0.4294	0.5177	0.108*
H14B	0.8032	0.5014	0.5786	0.108*
H14C	0.8343	0.4962	0.4543	0.108*
C15	0.4721 (6)	0.46588 (19)	0.3904 (3)	0.0609 (9)
H15A	0.5429	0.4807	0.3290	0.091*
H15B	0.3395	0.4775	0.3791	0.091*
H15C	0.4857	0.4151	0.4002	0.091*
C16	0.5071 (5)	0.65700 (18)	0.1765 (2)	0.0463 (7)
H16A	0.4695	0.6200	0.1267	0.069*
H16B	0.6431	0.6636	0.1746	0.069*
H16C	0.4442	0.7010	0.1569	0.069*
C17	−0.0333 (4)	0.41311 (14)	−0.0173 (2)	0.0318 (6)
C18	−0.0172 (4)	0.49436 (15)	−0.0174 (2)	0.0393 (6)
C19	−0.0796 (4)	0.45709 (16)	0.0835 (2)	0.0415 (7)
C20	0.0609 (6)	0.45095 (18)	0.1779 (2)	0.0522 (8)
H20A	0.0326	0.4878	0.2303	0.063*
H20B	0.1892	0.4593	0.1528	0.063*
C21	0.0535 (7)	0.3772 (2)	0.2327 (3)	0.0652 (10)
H21A	0.1744	0.3691	0.2705	0.078*
H21B	−0.0455	0.3783	0.2861	0.078*
C22	0.0149 (6)	0.31356 (18)	0.1570 (3)	0.0562 (9)
H22A	−0.1151	0.3182	0.1292	0.067*
H22B	0.0194	0.2703	0.2004	0.067*
C23	0.1448 (5)	0.30144 (16)	0.0602 (2)	0.0447 (7)
C24	0.1500 (4)	0.36961 (14)	−0.0151 (2)	0.0324 (6)
H24	0.2501	0.4011	0.0148	0.039*
C25	0.2082 (4)	0.35152 (15)	−0.1298 (2)	0.0348 (6)
C26	0.0656 (4)	0.34250 (15)	−0.2124 (2)	0.0342 (6)
C27	−0.1239 (4)	0.35081 (14)	−0.1896 (2)	0.0306 (5)
C28	−0.1911 (4)	0.37905 (15)	−0.0838 (2)	0.0337 (6)
H28A	−0.2459	0.3400	−0.0433	0.040*
H28B	−0.2910	0.4142	−0.0971	0.040*
C29	−0.2869 (5)	0.4639 (2)	0.1167 (3)	0.0613 (9)
H29A	−0.3029	0.5074	0.1567	0.092*
H29B	−0.3201	0.4237	0.1608	0.092*
H29C	−0.3686	0.4648	0.0536	0.092*
C30	0.3499 (6)	0.2850 (3)	0.0979 (4)	0.0789 (13)
H30A	0.3518	0.2413	0.1386	0.118*
H30B	0.3970	0.3236	0.1423	0.118*
H30C	0.4296	0.2799	0.0365	0.118*
C31	0.0658 (6)	0.23478 (18)	−0.0001 (3)	0.0628 (10)
H31A	0.0671	0.1944	0.0478	0.094*
H31B	0.1441	0.2247	−0.0607	0.094*
H31C	−0.0629	0.2440	−0.0247	0.094*
C32	0.1267 (5)	0.31821 (19)	−0.3219 (2)	0.0491 (8)
H32A	0.0893	0.2692	−0.3330	0.074*
H32B	0.2631	0.3222	−0.3266	0.074*
H32C	0.0668	0.3478	−0.3762	0.074*
N1	0.1202 (4)	0.64687 (15)	0.24803 (19)	0.0442 (6)
H1A	0.1440	0.6567	0.1821	0.053*
H1B	0.0039	0.6453	0.2690	0.053*
N2	−0.2662 (3)	0.33465 (14)	−0.25976 (19)	0.0419 (6)
H2A	−0.2403	0.3182	−0.3224	0.050*
H2B	−0.3832	0.3407	−0.2420	0.050*
O1	0.7681 (3)	0.60721 (15)	0.3360 (2)	0.0583 (6)
O2	0.3815 (3)	0.34305 (14)	−0.14593 (19)	0.0532 (6)
Cl1	0.20775 (13)	0.53695 (4)	−0.02330 (7)	0.0559 (2)
Cl2	−0.18423 (14)	0.54562 (5)	−0.09233 (7)	0.0629 (2)
Cl3	0.61389 (17)	0.73707 (5)	0.58908 (8)	0.0714 (3)
Cl4	0.21570 (18)	0.76477 (5)	0.54750 (8)	0.0734 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0363 (15)	0.0378 (14)	0.0286 (12)	−0.0006 (11)	0.0015 (10)	0.0034 (10)
C2	0.064 (2)	0.0387 (16)	0.0383 (16)	0.0063 (14)	−0.0031 (14)	0.0014 (12)
C3	0.063 (2)	0.0415 (16)	0.0313 (14)	0.0066 (14)	0.0002 (13)	−0.0024 (12)
C4	0.081 (2)	0.0484 (18)	0.0322 (15)	0.0021 (17)	−0.0087 (15)	0.0000 (13)
C5	0.095 (3)	0.0488 (19)	0.0386 (17)	0.0041 (18)	−0.0074 (17)	0.0117 (14)
C6	0.066 (2)	0.0350 (15)	0.0483 (17)	−0.0053 (14)	0.0016 (15)	0.0064 (13)
C7	0.0438 (18)	0.0338 (14)	0.0480 (17)	−0.0002 (12)	−0.0011 (13)	0.0021 (12)
C8	0.0306 (15)	0.0324 (13)	0.0375 (14)	−0.0032 (11)	−0.0042 (11)	0.0023 (11)
C9	0.0280 (15)	0.0396 (15)	0.0450 (15)	−0.0056 (12)	0.0046 (12)	0.0011 (12)
C10	0.0317 (15)	0.0381 (14)	0.0339 (13)	−0.0042 (11)	0.0042 (11)	0.0034 (11)
C11	0.0319 (15)	0.0307 (13)	0.0337 (13)	−0.0025 (10)	0.0006 (11)	0.0022 (10)
C12	0.0305 (14)	0.0486 (16)	0.0334 (13)	0.0018 (12)	0.0043 (11)	0.0030 (11)
C13	0.082 (3)	0.072 (2)	0.0418 (18)	0.012 (2)	0.0242 (17)	0.0027 (17)
C14	0.055 (2)	0.050 (2)	0.111 (3)	0.0146 (17)	0.002 (2)	0.015 (2)
C15	0.086 (3)	0.0411 (18)	0.0554 (19)	−0.0044 (18)	0.0070 (18)	−0.0075 (15)
C16	0.0466 (19)	0.0526 (18)	0.0400 (16)	−0.0035 (14)	0.0112 (13)	0.0070 (13)
C17	0.0338 (15)	0.0302 (13)	0.0314 (13)	−0.0025 (11)	0.0028 (11)	−0.0043 (10)
C18	0.0471 (17)	0.0319 (14)	0.0385 (15)	−0.0022 (12)	−0.0060 (12)	−0.0032 (11)
C19	0.0534 (19)	0.0340 (14)	0.0374 (14)	−0.0024 (13)	0.0043 (12)	−0.0089 (12)
C20	0.079 (2)	0.0444 (17)	0.0331 (14)	−0.0099 (16)	−0.0053 (14)	−0.0059 (13)
C21	0.105 (3)	0.055 (2)	0.0358 (17)	−0.013 (2)	−0.0030 (18)	0.0026 (15)
C22	0.084 (3)	0.0430 (18)	0.0419 (17)	−0.0079 (17)	0.0071 (17)	0.0063 (13)
C23	0.0509 (19)	0.0364 (15)	0.0468 (17)	−0.0008 (13)	0.0002 (14)	0.0063 (13)
C24	0.0300 (14)	0.0326 (13)	0.0346 (13)	−0.0033 (11)	−0.0029 (11)	−0.0023 (10)
C25	0.0276 (15)	0.0336 (13)	0.0432 (15)	−0.0025 (11)	0.0049 (11)	−0.0008 (11)
C26	0.0316 (15)	0.0363 (14)	0.0351 (13)	−0.0040 (11)	0.0053 (11)	−0.0061 (11)
C27	0.0307 (14)	0.0290 (12)	0.0323 (12)	−0.0040 (10)	0.0011 (10)	−0.0028 (10)
C28	0.0252 (13)	0.0375 (14)	0.0386 (14)	−0.0015 (11)	0.0040 (11)	−0.0087 (11)
C29	0.067 (2)	0.059 (2)	0.059 (2)	0.0056 (19)	0.0206 (17)	−0.0196 (18)
C30	0.071 (3)	0.081 (3)	0.084 (3)	0.017 (2)	−0.016 (2)	0.030 (2)
C31	0.091 (3)	0.0307 (15)	0.067 (2)	0.0023 (17)	0.012 (2)	−0.0013 (15)
C32	0.0436 (18)	0.060 (2)	0.0441 (17)	−0.0082 (15)	0.0144 (14)	−0.0128 (15)
N1	0.0338 (14)	0.0620 (17)	0.0367 (13)	−0.0003 (12)	−0.0009 (10)	0.0118 (12)
N2	0.0331 (13)	0.0545 (15)	0.0379 (12)	−0.0010 (11)	−0.0001 (10)	−0.0134 (11)
O1	0.0245 (11)	0.0809 (18)	0.0700 (15)	−0.0016 (11)	0.0104 (10)	0.0140 (13)
O2	0.0244 (11)	0.0735 (16)	0.0620 (14)	0.0005 (10)	0.0066 (9)	−0.0087 (12)
Cl1	0.0660 (5)	0.0450 (4)	0.0565 (4)	−0.0231 (4)	−0.0068 (4)	0.0036 (4)
Cl2	0.0772 (6)	0.0421 (4)	0.0684 (5)	0.0142 (4)	−0.0204 (4)	−0.0017 (4)
Cl3	0.0953 (8)	0.0444 (4)	0.0734 (6)	−0.0183 (5)	−0.0224 (5)	−0.0053 (4)
Cl4	0.1074 (8)	0.0535 (5)	0.0593 (5)	0.0355 (5)	0.0064 (5)	0.0030 (4)

Geometric parameters (Å, º) top

C1—C2	1.509 (4)	C17—C18	1.520 (4)
C1—C8	1.514 (4)	C17—C19	1.538 (4)
C1—C12	1.515 (4)	C18—C19	1.506 (4)
C1—C3	1.540 (4)	C18—Cl2	1.760 (3)
C2—C3	1.519 (4)	C18—Cl1	1.766 (3)
C2—Cl4	1.766 (3)	C19—C20	1.518 (4)
C2—Cl3	1.771 (4)	C19—C29	1.522 (5)
C3—C13	1.515 (5)	C20—C21	1.536 (5)
C3—C4	1.525 (4)	C20—H20A	0.9700
C4—C5	1.536 (5)	C20—H20B	0.9700
C4—H4A	0.9700	C21—C22	1.534 (5)
C4—H4B	0.9700	C21—H21A	0.9700
C5—C6	1.521 (4)	C21—H21B	0.9700
C5—H5A	0.9700	C22—C23	1.541 (5)
C5—H5B	0.9700	C22—H22A	0.9700
C6—C7	1.536 (4)	C22—H22B	0.9700
C6—H6A	0.9700	C23—C30	1.530 (5)
C6—H6B	0.9700	C23—C31	1.547 (5)
C7—C14	1.533 (5)	C23—C24	1.580 (4)
C7—C15	1.537 (5)	C24—C25	1.529 (4)
C7—C8	1.582 (4)	C24—H24	0.9800
C8—C9	1.524 (4)	C25—O2	1.243 (3)
C8—H8	0.9800	C25—C26	1.425 (4)
C9—O1	1.241 (3)	C26—C27	1.371 (4)
C9—C10	1.430 (4)	C26—C32	1.506 (4)
C10—C11	1.369 (4)	C27—N2	1.343 (3)
C10—C16	1.512 (4)	C27—C28	1.501 (3)
C11—N1	1.335 (3)	C28—H28A	0.9700
C11—C12	1.499 (4)	C28—H28B	0.9700
C12—H12A	0.9700	C29—H29A	0.9600
C12—H12B	0.9700	C29—H29B	0.9600
C13—H13A	0.9600	C29—H29C	0.9600
C13—H13B	0.9600	C30—H30A	0.9600
C13—H13C	0.9600	C30—H30B	0.9600
C14—H14A	0.9600	C30—H30C	0.9600
C14—H14B	0.9600	C31—H31A	0.9600
C14—H14C	0.9600	C31—H31B	0.9600
C15—H15A	0.9600	C31—H31C	0.9600
C15—H15B	0.9600	C32—H32A	0.9600
C15—H15C	0.9600	C32—H32B	0.9600
C16—H16A	0.9600	C32—H32C	0.9600
C16—H16B	0.9600	N1—H1A	0.8600
C16—H16C	0.9600	N1—H1B	0.8600
C17—C28	1.505 (4)	N2—H2A	0.8600
C17—C24	1.517 (4)	N2—H2B	0.8600

C2—C1—C8	117.9 (2)	C28—C17—C19	120.5 (2)
C2—C1—C12	118.4 (3)	C24—C17—C19	117.7 (2)
C8—C1—C12	112.7 (2)	C18—C17—C19	59.03 (18)
C2—C1—C3	59.76 (19)	C19—C18—C17	61.08 (18)
C8—C1—C3	117.8 (2)	C19—C18—Cl2	119.3 (2)
C12—C1—C3	120.8 (2)	C17—C18—Cl2	119.6 (2)
C1—C2—C3	61.13 (19)	C19—C18—Cl1	121.2 (2)
C1—C2—Cl4	119.8 (2)	C17—C18—Cl1	121.0 (2)
C3—C2—Cl4	118.8 (2)	Cl2—C18—Cl1	108.38 (16)
C1—C2—Cl3	120.6 (2)	C18—C19—C20	118.9 (3)
C3—C2—Cl3	121.7 (2)	C18—C19—C29	118.9 (3)
Cl4—C2—Cl3	108.40 (18)	C20—C19—C29	113.6 (3)
C13—C3—C2	119.1 (3)	C18—C19—C17	59.90 (17)
C13—C3—C4	113.8 (3)	C20—C19—C17	116.4 (3)
C2—C3—C4	118.4 (3)	C29—C19—C17	119.0 (3)
C13—C3—C1	120.3 (3)	C19—C20—C21	112.5 (3)
C2—C3—C1	59.10 (19)	C19—C20—H20A	109.1
C4—C3—C1	115.5 (3)	C21—C20—H20A	109.1
C3—C4—C5	111.4 (3)	C19—C20—H20B	109.1
C3—C4—H4A	109.3	C21—C20—H20B	109.1
C5—C4—H4A	109.3	H20A—C20—H20B	107.8
C3—C4—H4B	109.3	C22—C21—C20	115.4 (3)
C5—C4—H4B	109.3	C22—C21—H21A	108.4
H4A—C4—H4B	108.0	C20—C21—H21A	108.4
C6—C5—C4	115.7 (3)	C22—C21—H21B	108.4
C6—C5—H5A	108.4	C20—C21—H21B	108.4
C4—C5—H5A	108.4	H21A—C21—H21B	107.5
C6—C5—H5B	108.4	C21—C22—C23	119.5 (3)
C4—C5—H5B	108.4	C21—C22—H22A	107.4
H5A—C5—H5B	107.4	C23—C22—H22A	107.4
C5—C6—C7	119.3 (3)	C21—C22—H22B	107.4
C5—C6—H6A	107.5	C23—C22—H22B	107.4
C7—C6—H6A	107.5	H22A—C22—H22B	107.0
C5—C6—H6B	107.5	C30—C23—C22	110.8 (3)
C7—C6—H6B	107.5	C30—C23—C31	108.1 (3)
H6A—C6—H6B	107.0	C22—C23—C31	106.6 (3)
C14—C7—C6	109.9 (3)	C30—C23—C24	108.0 (3)
C14—C7—C15	108.3 (3)	C22—C23—C24	111.5 (3)
C6—C7—C15	107.1 (3)	C31—C23—C24	111.9 (3)
C14—C7—C8	108.4 (3)	C17—C24—C25	110.1 (2)
C6—C7—C8	111.2 (2)	C17—C24—C23	114.2 (2)
C15—C7—C8	111.9 (3)	C25—C24—C23	112.6 (2)
C1—C8—C9	110.5 (2)	C17—C24—H24	106.4
C1—C8—C7	114.8 (2)	C25—C24—H24	106.4
C9—C8—C7	112.9 (2)	C23—C24—H24	106.4
C1—C8—H8	106.0	O2—C25—C26	122.6 (2)
C9—C8—H8	106.0	O2—C25—C24	117.3 (2)
C7—C8—H8	106.0	C26—C25—C24	120.0 (2)
O1—C9—C10	122.3 (3)	C27—C26—C25	120.2 (2)
O1—C9—C8	117.7 (3)	C27—C26—C32	121.1 (2)
C10—C9—C8	120.0 (2)	C25—C26—C32	118.5 (2)
C11—C10—C9	120.4 (2)	N2—C27—C26	123.2 (2)
C11—C10—C16	121.2 (3)	N2—C27—C28	113.9 (2)
C9—C10—C16	118.2 (2)	C26—C27—C28	122.9 (2)
N1—C11—C10	122.4 (2)	C27—C28—C17	112.9 (2)
N1—C11—C12	114.8 (2)	C27—C28—H28A	109.0
C10—C11—C12	122.8 (2)	C17—C28—H28A	109.0
C11—C12—C1	111.7 (2)	C27—C28—H28B	109.0
C11—C12—H12A	109.3	C17—C28—H28B	109.0
C1—C12—H12A	109.3	H28A—C28—H28B	107.8
C11—C12—H12B	109.3	C19—C29—H29A	109.5
C1—C12—H12B	109.3	C19—C29—H29B	109.5
H12A—C12—H12B	107.9	H29A—C29—H29B	109.5
C3—C13—H13A	109.5	C19—C29—H29C	109.5
C3—C13—H13B	109.5	H29A—C29—H29C	109.5
H13A—C13—H13B	109.5	H29B—C29—H29C	109.5
C3—C13—H13C	109.5	C23—C30—H30A	109.5
H13A—C13—H13C	109.5	C23—C30—H30B	109.5
H13B—C13—H13C	109.5	H30A—C30—H30B	109.5
C7—C14—H14A	109.5	C23—C30—H30C	109.5
C7—C14—H14B	109.5	H30A—C30—H30C	109.5
H14A—C14—H14B	109.5	H30B—C30—H30C	109.5
C7—C14—H14C	109.5	C23—C31—H31A	109.5
H14A—C14—H14C	109.5	C23—C31—H31B	109.5
H14B—C14—H14C	109.5	H31A—C31—H31B	109.5
C7—C15—H15A	109.5	C23—C31—H31C	109.5
C7—C15—H15B	109.5	H31A—C31—H31C	109.5
H15A—C15—H15B	109.5	H31B—C31—H31C	109.5
C7—C15—H15C	109.5	C26—C32—H32A	109.5
H15A—C15—H15C	109.5	C26—C32—H32B	109.5
H15B—C15—H15C	109.5	H32A—C32—H32B	109.5
C10—C16—H16A	109.5	C26—C32—H32C	109.5
C10—C16—H16B	109.5	H32A—C32—H32C	109.5
H16A—C16—H16B	109.5	H32B—C32—H32C	109.5
C10—C16—H16C	109.5	C11—N1—H1A	120.0
H16A—C16—H16C	109.5	C11—N1—H1B	120.0
H16B—C16—H16C	109.5	H1A—N1—H1B	120.0
C28—C17—C24	113.2 (2)	C27—N2—H2A	120.0
C28—C17—C18	118.3 (2)	C27—N2—H2B	120.0
C24—C17—C18	118.1 (2)	H2A—N2—H2B	120.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.86	2.00	2.816 (3)	159
N2—H2B···O2ⁱ	0.86	2.06	2.873 (3)	159

Symmetry code: (i) x−1, y, z.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

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