Crystal structure of (±)-[trans-cyclo­hexane-1,2-diylbis(aza­nedi­yl)]di­phospho­nium dibromide dichloro­methane disolvate

Rodríguez Álvarez, A.; Tlahuext, H.; Grévy, J.-M.

doi:10.1107/S2056989016004576

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Volume 72| Part 4| April 2016| Pages 559-562

https://doi.org/10.1107/S2056989016004576

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Crystal structure of (±)-[trans-cyclohexane-1,2-diylbis(azanediyl)]diphosphonium dibromide dichloromethane disolvate

Aurora Rodríguez Álvarez,^a Hugo Tlahuext ^a and Jean-Michel Grévy ^a ^*

^aCentro de Investigaciónes Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad No. 1001, Col. Chamilpa, CP 62209, Cuernavaca Mor., Mexico
^*Correspondence e-mail: jeanmichelg@gmail.com

Edited by H. Ishida, Okayama University, Japan (Received 20 January 2016; accepted 16 March 2016; online 31 March 2016)

The cation of the title solvated salt, C₄₂H₄₂N₂P₂²⁺·2Br⁻·2CH₂Cl₂, lies on a crystallographic twofold rotation axis. The 1,2-diaminocyclohexane fragment has a chair conformation with two N atoms in a transoid conformation [N—C—C—N = 163.4 (2)°]. In the crystal, the cations are linked to the anions by N—H⋯Br and C—H⋯Br hydrogen bonds, forming a chain structure along the c axis. The dichloromethane molecule takes part in the hydrogen-bond network through C—H⋯π and C—H⋯Br interactions.

Keywords: crystal structure; trans-diaminocyclohexane; diphosphonium ligands; C—H⋯Br and C—H⋯π interactions.

CCDC reference: 1469040

1. Chemical context

Quaternary phosphonium salts are very attractive compounds possessing widespread applications in synthetic organic chemistry and have played various important roles as stoichiometric reagents, phase-transfer reagents, reactive intermediates, ionic liquids, building blocks for supramolecular assemblies and catalysts (Werner, 2009 ). In particular, P,P,P-triaryl-P-aminophosphonium salts bearing a primary amino group are isolable intermediates in the Horner & Oediger (1959 ) synthesis of iminophosphoranes. The title phosphonium compound was used to synthesize new chiral iminophosphorane complexes in view of its catalytic application for organic transformations including olefin-CO copolymerization (Tardif et al., 1998 ) and enantioselective copper-catalysed cyclopropanation (Reetz & Bohres, 1998 ), but its crystal structure had not been determined.

2. Structural commentary

The cation is situated on a crystallographic twofold rotation axis (Fig. 1). The 1,2-diaminocyclohexane fragment has a chair conformation with N atoms in a transoid conformation [N1—C19—C19ⁱ—N1ⁱ = 163.4 (2)°; symmetry code: (i) −x + 1, y, −z + $[{3\over 2}]$ ]. The phosphorus atom has a tetrahedral geometry; the C—P—C angles are in the range 108.61 (12)–108.89 (12)° and the N—P—C angles in the range 109.47 (12)–111.00 (12)°. The N—P distance is 1.623 (2) Å.

Figure 1
The molecular structure of the title compound, showing the atom-labelling scheme. Atoms with the suffix A are at the symmetry position (−x + 1, y, −z + $[{3\over 2}]$ ).

3. Supramolecular features

The Br anion is an acceptor of four hydrogen bonds, three of which are donated by phenyl and amine groups of the trans-1,2-diamino(N,N′-ditriphenylphosphonio)cyclohexane molecule and the last is donated by the solvent dichloromethane molecule (Table 1). In the hydrogen-bond pattern, the graph-set motif R₄²(22) involving atoms (–C19—N1—H1⋯Br1⋯H5—C5—C6—C1—P1—N1—C19–)₂ can be distinguished (Fig. 2). The R₄²(22) pattern generates a supramolecular chain running along the c axis. The dichloromethane molecule is also linked to the chain via C—H⋯π and C—H⋯Br interactions (Fig. 3 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br1	0.86 (3)	2.43 (3)	3.285 (2)	172 (3)
C6—H6⋯Br1ⁱ	0.93	2.80	3.670 (3)	157
C15—H15⋯Br1ⁱⁱ	0.93	2.84	3.718 (3)	158
C22—H22A⋯Br1ⁱⁱ	0.97	2.80	3.562 (3)	136
C22—H22B⋯Cgⁱⁱ	0.97	2.54	3.479	163
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Figure 2
A cation dimer of the title compound formed by N—H⋯Br and C—H⋯Br hydrogen bonds (dashed lines) with a centrosymmetric R₄²(22) motif.

Figure 3
A view of the supramolecular chain, generated by the N—H⋯Br and C—H⋯Br interactions, running along the c axis. The solvent dichloromethane molecule also makes C—H⋯π and C—H⋯Br interactions to the chain. The N—H⋯Br and C—H⋯Br hydrogen bonds are indicated by dashed lines. Hydrogen atoms not involved in the hydrogen bonds are omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (Version 5.37; Groom & Allen, 2014 ) revealed the existence of 33 deposited phosphonium structures of general formula [R₃PNHR′]⁺, where R and R′ are either aryl or alkyl groups. Amongst those, only two structures are polycationic: MELCIQ (Alajarín et al., 2006 ) is tricationic with a tricyclic structure and trifluoroacetate counter-ions, and WERROB (Demange et al., 2006 ) is dicationic and contains bromide counter-ions. All the remaining structures are monocationic and only four of them contain a bromide counter-ion: ECUJOC (Boubekeur et al., 2006 ), NEPZUF (Martínez de León et al., 2013 ), ZOFYAU and ZOFYEY (Imrie et al., 1995 ). For all the reported compounds, the P—N bond distances assume a partial double-bond character with values falling within the narrow range of 1.60–1.66 Å, regardless of the counter-ion and substituents on both N and P. The N—P distance of the title compound [1.623 (2) Å] agrees with these values. In addition, the P—N—C angle in the present compound [126.9 (2)°] indicates a planar sp² geometry for the N atom, and falls within the range of 120–133° reported for all related phosphonium structures.

5. Synthesis and crystallization

Under an N₂ atmosphere, a solution of 3.07 g of Br₂ in 5 ml of CH₂Cl₂ was added dropwise under stirring at 273 K, to a solution of Ph₃P (5.04 g, 19.24 mmol) in 100 ml of the same solvent. After four h of stirring at room temperature and the formation of white precipitate, a mixture of half an equivalent of (±)-trans-1,2-diaminocyclohexane (1.09 g, 9.62 mmol) and one equivalent of triethylamine (2.68 ml, 19.24 mmol) in 10 ml of CH₂Cl₂ was added dropwise under stirring at 273 K. The suspension was left under continuous stirring for 12 h at room temperature. Then the reactant was extracted twice with 25 ml of distilled water, and the organic phase was dried over MgSO₄. All volatiles were eliminated under vacuum, and the resulting light-yellow solid was stirred with Et₂O overnight. After filtration, 6.0 g of the title compound was obtained as a white powder (yield 93%, m.p. 563 K). Single crystals suitable for X-ray diffraction were grown by slow evaporation of a dichloromethane solution at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The N-bound H atom was located in a difference Fourier map and its coordinates were refined with a distance restraint of N—H = 0.86 (1) Å with U_iso(H) = 1.2U_eq(N). Other H atoms were positioned geometrically (C—H = 0.93 or 0.97 Å) and constrained using the riding-model approximation with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₄₂H₄₂N₂P₂²⁺·2Br⁻·2CH₂Cl₂
M_r	966.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	17.1911 (2), 14.9027 (2), 18.4492 (2)
β (°)	114.2547 (15)
V (Å³)	4309.34 (10)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	5.63
Crystal size (mm)	0.17 × 0.12 × 0.09

Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with an EosS2 detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.145, 0.602
No. of measured, independent and observed [I > 2σ(I)] reflections	16763, 4256, 4203
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.098, 1.04
No. of reflections	4256
No. of parameters	248
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.54, −1.50
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1469040

Crystal structure: contains datablocks Global, I. DOI: https://doi.org/10.1107/S2056989016004576/is5441sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016004576/is5441Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(±)-[trans-Cyclohexane-1,2-diylbis(azanediyl)]diphosphonium dibromide dichloromethane disolvate top

Crystal data top

C₄₂H₄₂N₂P₂²⁺·2Br⁻·2CH₂Cl₂	F(000) = 1968
M_r = 966.39	D_x = 1.490 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 17.1911 (2) Å	Cell parameters from 13228 reflections
b = 14.9027 (2) Å	θ = 2.6–72.5°
c = 18.4492 (2) Å	µ = 5.63 mm⁻¹
β = 114.2547 (15)°	T = 100 K
V = 4309.34 (10) Å³	Plate, colourless
Z = 4	0.17 × 0.12 × 0.09 mm

Data collection top

Agilent SuperNova Dual Source diffractometer with an EosS2 detector	4256 independent reflections
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source	4203 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.021
Detector resolution: 8.0769 pixels mm^-1	θ_max = 72.7°, θ_min = 4.1°
ω scans	h = −20→21
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −18→18
T_min = 0.145, T_max = 0.602	l = −22→22
16763 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.041P)² + 29.4173P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.098	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 1.54 e Å⁻³
4256 reflections	Δρ_min = −1.50 e Å⁻³
248 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.00026 (3)

Special details top

Experimental. MS (FAB⁺) 716 m/z (M-Br)⁺ 12%; ³¹P NMR (CDCl₃, 80 MHz, 20°C) 37.05 p.p.m; ¹H NMR (400 MHz, CDCl₃, 20°C): δ = 0.909-0.859 (m, 2H, CH₂), 1.349-1.493 (m, 2H, CH₂) 1.525-1.493(m, 2H, CH₂), 1.928-1.902(m, 2H, CH₂), 3.626-3.615 (m, 2H, CH-N), 7.918-7.864 (m, 12H, o-C₆H₅), 7.677-7.635 (m, 12H, m-C₆H₅), 7.553-7.505(m, 6H, p-C₆H₅), δ 8.59 (s, 2H, NH); ¹³C NMR (100 MHz, CDCl₃, 20°C): 24.34 (s, 2C, CH₂), 36.10 (s, 2C, CH₂), 57.949 (dd, ²J_CP = 2.9 Hz, ³J_CP = 10.3 Hz, 2C, CH-N), 121.372 (d, ¹J_CP=102.5 Hz, 6 Cipso, C₆H₅), 129.599 (d, ³J_CP = 13.2 Hz, 12 Cmeta, C₆H₅), 134.307 (d, ⁴J_CP = 2.9 Hz, 6 Cpara, C₆H₅,), 134.505 (d, ²J_CP = 7.9 Hz, 12 Corto, C₆H₅).

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
Br1	0.64866 (2)	0.38834 (2)	0.63298 (2)	0.02162 (12)
P1	0.67384 (4)	0.61073 (4)	0.77021 (4)	0.00659 (15)
Cl1	0.80208 (4)	0.46666 (4)	1.00873 (4)	0.01662 (16)
Cl2	0.88621 (4)	0.41641 (5)	1.17643 (4)	0.02132 (17)
N1	0.61012 (14)	0.52543 (15)	0.75374 (13)	0.0112 (4)
H1	0.619 (2)	0.4854 (17)	0.7247 (17)	0.013*
C1	0.78312 (15)	0.57703 (17)	0.82238 (14)	0.0077 (5)
C2	0.80581 (16)	0.48708 (17)	0.82314 (15)	0.0107 (5)
H2	0.7643	0.4441	0.7977	0.013*
C3	0.89130 (17)	0.46215 (19)	0.86238 (16)	0.0146 (5)
H3	0.9068	0.4022	0.8639	0.017*
C4	0.95309 (17)	0.5265 (2)	0.89913 (16)	0.0151 (5)
H4	1.0100	0.5096	0.9248	0.018*
C5	0.93061 (17)	0.61616 (19)	0.89792 (16)	0.0143 (5)
H5	0.9726	0.6590	0.9224	0.017*
C6	0.84553 (16)	0.64224 (18)	0.86028 (15)	0.0105 (5)
H6	0.8303	0.7021	0.8602	0.013*
C7	0.66066 (16)	0.66197 (17)	0.67754 (15)	0.0097 (5)
C8	0.58964 (17)	0.6405 (2)	0.60814 (16)	0.0154 (5)
H8	0.5494	0.5999	0.6100	0.018*
C9	0.57900 (18)	0.6797 (2)	0.53601 (16)	0.0190 (6)
H9	0.5317	0.6655	0.4898	0.023*
C10	0.63935 (19)	0.7401 (2)	0.53352 (16)	0.0178 (6)
H10	0.6326	0.7659	0.4854	0.021*
C11	0.71012 (18)	0.76242 (19)	0.60279 (17)	0.0158 (6)
H11	0.7501	0.8031	0.6007	0.019*
C12	0.72098 (17)	0.72393 (18)	0.67497 (16)	0.0123 (5)
H12	0.7679	0.7391	0.7212	0.015*
C13	0.64931 (15)	0.69184 (17)	0.82921 (15)	0.0084 (5)
C14	0.66580 (16)	0.67095 (18)	0.90835 (15)	0.0115 (5)
H14	0.6924	0.6172	0.9305	0.014*
C15	0.64235 (18)	0.73048 (19)	0.95346 (16)	0.0143 (5)
H15	0.6519	0.7162	1.0055	0.017*
C16	0.60443 (17)	0.81180 (18)	0.92062 (16)	0.0148 (5)
H16	0.5890	0.8519	0.9510	0.018*
C17	0.58951 (18)	0.83340 (19)	0.84306 (17)	0.0163 (6)
H17	0.5647	0.8882	0.8218	0.020*
C18	0.61150 (17)	0.77332 (18)	0.79696 (16)	0.0134 (5)
H18	0.6009	0.7876	0.7447	0.016*
C19	0.54401 (15)	0.51184 (17)	0.78478 (14)	0.0089 (5)
H19	0.5465	0.5627	0.8194	0.011*
C20	0.55975 (19)	0.4261 (2)	0.83400 (18)	0.0231 (7)
H20A	0.6181	0.4261	0.8739	0.028*
H20B	0.5222	0.4253	0.8614	0.028*
C21	0.5447 (2)	0.3415 (2)	0.7836 (3)	0.0352 (9)
H21A	0.5515	0.2891	0.8168	0.042*
H21B	0.5868	0.3382	0.7612	0.042*
C22	0.79291 (18)	0.4616 (2)	1.10118 (17)	0.0178 (6)
H22A	0.7831	0.5215	1.1164	0.021*
H22B	0.7443	0.4247	1.0955	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02498 (19)	0.01596 (17)	0.0295 (2)	−0.00524 (11)	0.01685 (14)	−0.00967 (12)
P1	0.0049 (3)	0.0080 (3)	0.0064 (3)	−0.0004 (2)	0.0019 (2)	−0.0009 (2)
Cl1	0.0175 (3)	0.0173 (3)	0.0136 (3)	0.0011 (2)	0.0049 (2)	0.0002 (2)
Cl2	0.0207 (3)	0.0256 (4)	0.0166 (3)	0.0007 (3)	0.0065 (3)	0.0065 (3)
N1	0.0089 (10)	0.0127 (11)	0.0148 (11)	−0.0054 (8)	0.0075 (9)	−0.0065 (9)
C1	0.0056 (11)	0.0111 (12)	0.0059 (11)	0.0000 (9)	0.0018 (9)	0.0011 (9)
C2	0.0104 (12)	0.0108 (12)	0.0103 (12)	−0.0009 (10)	0.0038 (10)	−0.0004 (9)
C3	0.0146 (13)	0.0147 (13)	0.0142 (13)	0.0049 (10)	0.0058 (11)	0.0021 (10)
C4	0.0094 (12)	0.0252 (15)	0.0102 (12)	0.0029 (11)	0.0036 (10)	0.0026 (11)
C5	0.0087 (12)	0.0212 (14)	0.0106 (12)	−0.0057 (10)	0.0014 (10)	−0.0026 (10)
C6	0.0111 (12)	0.0101 (12)	0.0095 (11)	−0.0016 (10)	0.0033 (10)	−0.0013 (9)
C7	0.0111 (12)	0.0117 (12)	0.0071 (11)	0.0043 (10)	0.0046 (10)	0.0010 (9)
C8	0.0086 (12)	0.0236 (14)	0.0127 (13)	−0.0004 (11)	0.0032 (10)	0.0002 (11)
C9	0.0149 (13)	0.0284 (16)	0.0094 (12)	0.0038 (12)	0.0006 (11)	0.0017 (11)
C10	0.0229 (15)	0.0201 (14)	0.0100 (12)	0.0072 (11)	0.0064 (11)	0.0052 (11)
C11	0.0198 (14)	0.0129 (13)	0.0160 (13)	0.0015 (11)	0.0087 (11)	0.0031 (10)
C12	0.0132 (12)	0.0114 (12)	0.0111 (12)	0.0011 (10)	0.0037 (10)	0.0007 (10)
C13	0.0063 (11)	0.0092 (11)	0.0103 (11)	−0.0017 (9)	0.0038 (9)	−0.0027 (9)
C14	0.0122 (12)	0.0108 (12)	0.0096 (12)	−0.0003 (10)	0.0024 (10)	0.0000 (10)
C15	0.0173 (13)	0.0165 (13)	0.0089 (12)	−0.0029 (11)	0.0051 (10)	−0.0027 (10)
C16	0.0161 (13)	0.0132 (13)	0.0162 (13)	−0.0019 (10)	0.0078 (11)	−0.0073 (10)
C17	0.0193 (14)	0.0101 (12)	0.0200 (14)	0.0037 (10)	0.0084 (11)	0.0001 (11)
C18	0.0152 (13)	0.0138 (13)	0.0119 (12)	0.0028 (10)	0.0062 (10)	0.0028 (10)
C19	0.0068 (12)	0.0125 (12)	0.0085 (11)	−0.0028 (9)	0.0042 (10)	−0.0022 (9)
C20	0.0123 (13)	0.0358 (18)	0.0209 (14)	0.0096 (12)	0.0067 (11)	0.0199 (13)
C21	0.043 (2)	0.0136 (15)	0.070 (3)	0.0149 (14)	0.043 (2)	0.0217 (16)
C22	0.0172 (14)	0.0196 (14)	0.0205 (14)	0.0039 (11)	0.0118 (12)	0.0039 (11)

Geometric parameters (Å, º) top

P1—C13	1.789 (3)	C11—C10	1.395 (4)
P1—N1	1.623 (2)	C12—H12	0.9300
P1—C7	1.800 (3)	C12—C11	1.390 (4)
P1—C1	1.795 (2)	C12—C7	1.404 (4)
Cl1—C22	1.778 (3)	C13—C14	1.403 (4)
Cl2—C22	1.767 (3)	C13—C18	1.390 (4)
N1—H1	0.856 (10)	C14—H14	0.9300
N1—C19	1.482 (3)	C14—C15	1.385 (4)
C2—H2	0.9300	C15—H15	0.9300
C2—C1	1.395 (4)	C16—H16	0.9300
C3—H3	0.9300	C16—C17	1.384 (4)
C3—C2	1.396 (4)	C16—C15	1.392 (4)
C4—H4	0.9300	C17—H17	0.9300
C4—C3	1.385 (4)	C18—H18	0.9300
C5—H5	0.9300	C18—C17	1.390 (4)
C5—C4	1.388 (4)	C19—C19ⁱ	1.530 (5)
C5—C6	1.392 (4)	C19—H19	0.9800
C6—H6	0.9300	C19—C20	1.526 (4)
C6—C1	1.403 (3)	C20—H20A	0.9700
C8—H8	0.9300	C20—H20B	0.9700
C8—C7	1.396 (4)	C21—C21ⁱ	1.527 (8)
C8—C9	1.395 (4)	C21—H21A	0.9700
C9—H9	0.9300	C21—H21B	0.9700
C10—H10	0.9300	C21—C20	1.524 (5)
C10—C9	1.389 (4)	C22—H22A	0.9700
C11—H11	0.9300	C22—H22B	0.9700

C13—P1—C7	108.80 (12)	C7—C12—H12	120.2
C13—P1—C1	108.61 (12)	C14—C13—P1	119.1 (2)
N1—P1—C13	109.47 (12)	C18—C13—P1	121.0 (2)
N1—P1—C7	110.03 (12)	C18—C13—C14	119.9 (2)
N1—P1—C1	111.00 (12)	C13—C14—H14	120.0
C1—P1—C7	108.89 (12)	C15—C14—C13	119.9 (2)
P1—N1—H1	113 (2)	C15—C14—H14	120.0
C19—N1—P1	126.91 (18)	C14—C15—C16	119.7 (2)
C19—N1—H1	121 (2)	C14—C15—H15	120.1
C6—C1—P1	119.42 (19)	C16—C15—H15	120.1
C2—C1—P1	120.07 (19)	C17—C16—H16	119.8
C2—C1—C6	120.5 (2)	C17—C16—C15	120.5 (2)
C3—C2—H2	120.3	C15—C16—H16	119.8
C1—C2—C3	119.5 (2)	C16—C17—C18	120.1 (3)
C1—C2—H2	120.3	C16—C17—H17	120.0
C4—C3—H3	119.9	C18—C17—H17	120.0
C4—C3—C2	120.1 (3)	C13—C18—H18	120.1
C2—C3—H3	119.9	C17—C18—C13	119.8 (2)
C5—C4—H4	119.8	C17—C18—H18	120.1
C3—C4—C5	120.4 (2)	N1—C19—C19ⁱ	109.1 (2)
C3—C4—H4	119.8	N1—C19—H19	108.1
C6—C5—H5	119.8	N1—C19—C20	111.6 (2)
C4—C5—H5	119.8	C19ⁱ—C19—H19	108.1
C4—C5—C6	120.3 (2)	C20—C19—C19ⁱ	111.81 (18)
C5—C6—H6	120.4	C20—C19—H19	108.1
C5—C6—C1	119.1 (2)	C19—C20—H20A	109.1
C1—C6—H6	120.4	C19—C20—H20B	109.1
C12—C7—P1	120.3 (2)	C21—C20—C19	112.6 (3)
C8—C7—P1	119.7 (2)	C21—C20—H20A	109.1
C8—C7—C12	120.0 (2)	C21—C20—H20B	109.1
C7—C8—H8	120.0	H20A—C20—H20B	107.8
C9—C8—H8	120.0	C21ⁱ—C21—H21A	109.5
C9—C8—C7	120.1 (3)	C21ⁱ—C21—H21B	109.5
C8—C9—H9	120.1	H21A—C21—H21B	108.0
C10—C9—C8	119.8 (3)	C20—C21—C21ⁱ	110.9 (2)
C10—C9—H9	120.1	C20—C21—H21A	109.5
C11—C10—H10	119.8	C20—C21—H21B	109.5
C9—C10—C11	120.4 (3)	Cl1—C22—H22A	109.4
C9—C10—H10	119.8	Cl1—C22—H22B	109.4
C12—C11—H11	119.9	Cl2—C22—Cl1	111.12 (15)
C12—C11—C10	120.2 (3)	Cl2—C22—H22A	109.4
C10—C11—H11	119.9	Cl2—C22—H22B	109.4
C11—C12—H12	120.2	H22A—C22—H22B	108.0
C11—C12—C7	119.6 (2)

P1—C13—C14—C15	−176.0 (2)	C7—P1—C13—C18	10.7 (2)
P1—C13—C18—C17	177.0 (2)	C7—P1—N1—C19	−122.4 (2)
P1—N1—C19—C19ⁱ	115.00 (18)	C7—P1—C1—C6	75.4 (2)
P1—N1—C19—C20	−121.0 (2)	C7—P1—C1—C2	−102.7 (2)
N1—P1—C13—C14	68.0 (2)	C7—C12—C11—C10	0.5 (4)
N1—P1—C13—C18	−109.6 (2)	C7—C8—C9—C10	0.1 (4)
N1—P1—C7—C12	−166.0 (2)	C9—C8—C7—P1	−179.9 (2)
N1—P1—C7—C8	14.6 (3)	C9—C8—C7—C12	0.7 (4)
N1—P1—C1—C6	−163.30 (19)	C11—C12—C7—P1	179.6 (2)
N1—P1—C1—C2	18.5 (2)	C11—C12—C7—C8	−1.0 (4)
N1—C19—C20—C21	−69.6 (3)	C11—C10—C9—C8	−0.6 (4)
C1—P1—C13—C14	−53.3 (2)	C12—C11—C10—C9	0.3 (4)
C1—P1—C13—C18	129.0 (2)	C13—P1—N1—C19	−2.9 (3)
C1—P1—N1—C19	117.0 (2)	C13—P1—C7—C12	74.1 (2)
C1—P1—C7—C12	−44.1 (2)	C13—P1—C7—C8	−105.4 (2)
C1—P1—C7—C8	136.4 (2)	C13—P1—C1—C6	−42.9 (2)
C3—C2—C1—P1	178.5 (2)	C13—P1—C1—C2	138.9 (2)
C3—C2—C1—C6	0.4 (4)	C13—C14—C15—C16	−1.6 (4)
C4—C5—C6—C1	−1.2 (4)	C13—C18—C17—C16	−0.6 (4)
C4—C3—C2—C1	−1.0 (4)	C14—C13—C18—C17	−0.6 (4)
C5—C6—C1—P1	−177.4 (2)	C15—C16—C17—C18	0.7 (4)
C5—C6—C1—C2	0.7 (4)	C17—C16—C15—C14	0.4 (4)
C5—C4—C3—C2	0.6 (4)	C18—C13—C14—C15	1.7 (4)
C6—C5—C4—C3	0.5 (4)	C19ⁱ—C19—C20—C21	52.9 (3)
C7—P1—C13—C14	−171.7 (2)	C21ⁱ—C21—C20—C19	−55.1 (4)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.86 (3)	2.43 (3)	3.285 (2)	172 (3)
C6—H6···Br1ⁱⁱ	0.93	2.80	3.670 (3)	157
C15—H15···Br1ⁱⁱⁱ	0.93	2.84	3.718 (3)	158
C22—H22A···Br1ⁱⁱⁱ	0.97	2.80	3.562 (3)	136
C22—H22B···Cgⁱⁱⁱ	0.97	2.54	3.479	163

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

Acknowledgements

This work was supported by CONACyT (project CB2009–134528). ARA is grateful for a scholarship (No. 292979) provided by this project.

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