Benzyltripropylammonium bromide: a structure in polar space group P4₂bc

Crystals of the title compound, C₁₆H₂₈N⁺·Br⁻, were grown from solution in a mixture of acetone and propan-2-ol by slow evaporation. The structure was solved in the polar space group P4₂bc with five moieties in the asymmetric unit, namely two benzyl­tri­propyl­ammonium cations in general positions, and two Br⁻ anions in special Wyckoff positions (4a2.. and 4b2..) and one in a general position. The structure consists of two kinds of molecular columns parallel to c, built of cations connected through C—H...π hydrogen bonds and stabilized by weak C—H...Br interactions.

S1. Comment

Quaternary alkyl ammonium cations are the subject of wide interest because they are able to change the nature of the surface of clay minerals, such as montmorillonite or bentonite, from hydrophilic to hydrophobic. The surface of the resultant organoclays can adsorb organic pollutants which have low solubility in water (Lee et al., 1989; Lo et al., 1997; Polubesova et al., 1997). Recently, the cation of the title compound was investigated for its sorption properties on montmorillonite (Lorenc, 2001) and was found to have a significantly lower ability than benzyltrimethylammonium used as a reference cation.

The crystal structure analysis of selected quaternary alkyl ammonium salts was undertaken to find the relationship between the length and conformation of the alkyl chains and the packing properties of the ammonium cations. The other important question we wished to address was how a possible mutual arrangement of the cations could influence their sorption behaviour, either on a montmorillonite or on a bentonite. Here, the tetragonal polar structure of crystals of benzyltripropylammonium bromide, (I), is reported. \sch

The asymmetric part of the unit cell of (I) contains five distinct moieties: two symmetrically independent benzyltripropyloammonium (BTPA) cations, A and B, and three Br⁻ anions. The bond lengths and angles of these symmetry-independent molecules are quite similar (Table 1) and the normal probability plot analysis (Abrahams & Keve, 1971; International Tables for X-ray Crystallography, 1974, Vol. IV, pp. 293–309) shows that the differences are of a statistical rather than systematic nature. The correlation coefficients between experimental and theoretical distributions are 0.9962 for bond lengths and 0.9903 for bond angles.

The conformation of the BTPA cations in the crystalline state is shown in Fig. 1. Each cation has a synclinal (gauche) conformation of two propyl chains against the benzyl moiety, defined by the C4(benzyl)-N1—C1—C11 and C4(benzyl)-N1—C2—C21 torsion angles for cation A, and C8(benzyl)-N2—C5—C51 and C8(benzyl)-N2—C6—C61 for cation B, with an anti-periplanar conformation for the third propyl substituent in each case (Table 1). All propyl chains have a zigzag-like conformation, with NX—CX—CX1—CX2 torsion angles close to −180°.

The packing in the structure of (I) is given in Fig. 2. The ammonium cations form a framework enclosing two types of molecular columns running along the [001] direction, one at Wyckoff positions 0,0,z (4 a 2..) and the second at 0,1/2,z (4 b 2..). The column at 0,0,z (of 4₂ symmetry) is built up of translationally repeated kerbs, each containing four BTPA cations of type A, arranged into two dimers rotated relative to each other by 90°. The cations included in these dimers are interconnected by C—H···π interactions (Fig. 3a). Such a kerb is stabilized by Coulombic interactions with the Br1⁻ counterion (Fig. 3c). The second molecular column at 0,1/2,z is also of twofold symmetry but results from crossing two c glide planes. Here, the dimers are formed of type B cations symmetrically independent of the first type but stabilized according to a similar scheme (i.e. C—H···π interactions and Coulombic interactions with the Br2⁻ cation; Fig. 3 b,d). Both columns are joined together into a tetragonal structure via interactions with the Br3⁻ anions in the general position. The geometry of the short C—H···Br contacts and weak C—H..π hydrogen bonds is given in Table 2.

In conclusion, the three propyl-chain substituents of (I), with their specific conformations relative to the benzyl moiety, could sterically hinder the hypothetical direct interaction of N⁺ cations with the negatively charged surface of montmorillonite particles when adsorbed at the surface of grains or intercalated between silicate particles. Such steric hindrance could be the reason for the much worse sorption properties of BTPA cations on montmorillonite clay than those of the benzyltrimethylammonium cations used as reference (Lorenc, 2001). Additonally, the tendency of BTPA to form molecular columns, through hydrophobic interactions between the cations, hampers their intercalation between montmorillonite particles.

Table 2. Geometry of short C—H···Br contacts and weak C—H···π hydrogen bonds (Å, °). Cg1 is the centroid of the C41/C46 benzene ring and Cg2 the centroid of the C81/C86 ring.

S2. Experimental

The title salt was obtained using the procedure described by Lorenc (2001) and was recrystallized from solution in a mixture of acetone and propan-2-ol (Ratio?).

S3. Refinement

The space group P4₂bc was assigned from the systematic absences observed in the diffraction pattern: hkl - no systematic absences, 0kl k = 2n+1 (h0l h = 2n+1), hhl l = 2n+1, 00 l l = 2n+1, and h00 h = 2n+1 (0k0 k = 2n+1). Among 352 space group extinctions only a few reflections could be considered as observed (7 reflections of type 0kl and 3 reflections of type hhl), with intensities in the range 4–7σ(I). The systematic absences are identical for space groups P4₂bc and P4₂/mbc. Nevertheless, all tests [mean ABS(E²-1) of SHELXS97 (Sheldrick, 1997), as well as ABS(E) distribution and the N(z) test of Nonius maXus] clearly indicated that the intensity distribution is acentric. Examination of the structure with PLATON (Spek, 2003) detected no obvious extra crystallographic symmetry. The absolute structure was established by the anomalous dispersion effect of the Br atoms in diffraction measurements on the crystal (3569 Bijvoet pairs) and is described by a Flack parameter of −0.006 (8) (Flack, 1983; Flack & Bernardinelli, 1999, 2000). More than half of the total number of H-atom positions were observed in the Fourier difference map. Nevertheless, in the refinement procedure all H atoms were included from geometrical constraints in a riding model (C—H 0.93–0.97 Å) and were refined with isotropic displacement factors, with U_iso(H) = 1.2U_eq(C). Please check that added text is OK.

Computing details

Data collection: COLLECT (Nonius, 1997); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The asymmetric part of the unit cell of (I), showing the conformation of the two independent BTPA cations containing (a) atom N1 and (b) atom N2, and the atom-numbering schemes. H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Projection of the structure of (I) on to the ab plane. A cross-section of two types of channels at 00z and 01/2z can be distinguished.
	Fig. 3. C—H···π interactions of type III (Malone et al., 1997) in the dimers formed by (a) cation A (θ = 78.4° and d = 0.62 Å) and (b) cation B (θ = 84.8° and d = 0.28 Å), viewed along [001]. Two types of kerbs at (c) 00z (4a2..) and (d) 01/2z (4 b 2..) are shown along [100].

Benzyltripropylammonium bromide

Crystal data

C16H28BrN	Dx = 1.240 Mg m^−3
Mr = 314.31	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42bc	Cell parameters from 7799 reflections
a = 22.4411 (4) Å	θ = 1.0–27.5°
c = 13.3749 (2) Å	µ = 2.43 mm^−1
V = 6735.6 (2) Å^3	T = 293 K
Z = 16	Prism, colourless
F(000) = 2656	0.25 × 0.20 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer	7591 independent reflections
Radiation source: fine-focus sealed tube	5740 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	Rint = 0.031
ϕ and ω scans to fill Ewald sphere	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (HKL DENZO and SCALEPACK; Otwinowski & Minor, 1997)	h = −29→29
Tmin = 0.582, Tmax = 0.642	k = −20→20
14346 measured reflections	l = −17→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.076	Calculated w = 1/[σ^2(Fo^2) + (0.0221P)^2 + 1.9763P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
7591 reflections	Δρmax = 0.25 e Å^−3
325 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.006 (8)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	1.0000	0.0000	1.14210 (3)	0.05987 (13)
Br2	0.5000	0.0000	0.6520	0.05580 (12)
Br3	0.761147 (13)	−0.187038 (13)	1.00905 (5)	0.05642 (9)
N1	1.12528 (10)	−0.06281 (10)	1.39785 (19)	0.0438 (5)
C1	1.07834 (14)	−0.10733 (14)	1.4324 (3)	0.0527 (8)
H11	1.0974	−0.1458	1.4405	0.063*
H12	1.0640	−0.0950	1.4976	0.063*
C11	1.02495 (15)	−0.11501 (17)	1.3637 (3)	0.0662 (9)
H111	1.0064	−0.0767	1.3515	0.079*
H112	1.0377	−0.1314	1.3001	0.079*
C12	0.98094 (17)	−0.15665 (18)	1.4130 (4)	0.0888 (14)
H121	0.9470	−0.1619	1.3701	0.107*
H122	0.9682	−0.1400	1.4756	0.107*
H123	0.9996	−0.1945	1.4246	0.107*
C2	1.17915 (14)	−0.06774 (15)	1.4663 (2)	0.0483 (8)
H21	1.1979	−0.1061	1.4549	0.058*
H22	1.2076	−0.0372	1.4473	0.058*
C21	1.16685 (18)	−0.06171 (19)	1.5764 (3)	0.0634 (10)
H211	1.1409	−0.0937	1.5984	0.076*
H212	1.1470	−0.0241	1.5896	0.076*
C22	1.2253 (2)	−0.0643 (2)	1.6330 (3)	0.0945 (14)
H221	1.2177	−0.0607	1.7034	0.113*
H222	1.2505	−0.0322	1.6116	0.113*
H223	1.2446	−0.1016	1.6198	0.113*
C3	1.14531 (14)	−0.07467 (13)	1.2911 (2)	0.0496 (7)
H31	1.1776	−0.0476	1.2753	0.060*
H32	1.1125	−0.0654	1.2465	0.060*
C31	1.1660 (2)	−0.13793 (17)	1.2694 (3)	0.0722 (11)
H311	1.1941	−0.1505	1.3203	0.087*
H312	1.1322	−0.1648	1.2713	0.087*
C32	1.1950 (2)	−0.14114 (19)	1.1688 (3)	0.0837 (12)
H321	1.2078	−0.1813	1.1562	0.100*
H322	1.2289	−0.1150	1.1673	0.100*
H323	1.1670	−0.1292	1.1184	0.100*
C4	1.09752 (12)	−0.00034 (13)	1.4018 (2)	0.0467 (6)
H41	1.0646	0.0011	1.3548	0.056*
H42	1.0811	0.0058	1.4681	0.056*
C41	1.13932 (13)	0.05047 (12)	1.3787 (2)	0.0439 (7)
C42	1.14464 (14)	0.07202 (14)	1.2815 (2)	0.0516 (8)
H421	1.1236	0.0538	1.2300	0.062*
C43	1.18101 (17)	0.12035 (16)	1.2606 (3)	0.0670 (10)
H431	1.1846	0.1340	1.1953	0.080*
C44	1.21179 (17)	0.14816 (15)	1.3360 (3)	0.0668 (10)
H441	1.2367	0.1801	1.3215	0.080*
C45	1.20582 (18)	0.12877 (16)	1.4326 (3)	0.0721 (10)
H451	1.2260	0.1481	1.4839	0.086*
C46	1.16983 (17)	0.08044 (15)	1.4536 (3)	0.0628 (9)
H461	1.1660	0.0677	1.5195	0.075*
N2	0.62845 (10)	−0.04681 (10)	0.90576 (17)	0.0390 (5)
C5	0.59141 (13)	−0.09908 (13)	0.9408 (2)	0.0443 (7)
H51	0.5765	−0.0902	1.0072	0.053*
H52	0.6172	−0.1336	0.9464	0.053*
C51	0.53898 (14)	−0.11549 (14)	0.8748 (2)	0.0560 (8)
H511	0.5127	−0.0815	0.8676	0.067*
H512	0.5531	−0.1267	0.8089	0.067*
C52	0.50548 (16)	−0.16680 (15)	0.9212 (3)	0.0695 (10)
H521	0.4722	−0.1772	0.8795	0.083*
H522	0.4913	−0.1554	0.9861	0.083*
H523	0.5316	−0.2005	0.9274	0.083*
C6	0.68219 (13)	−0.04064 (15)	0.97385 (19)	0.0449 (7)
H61	0.7087	−0.0739	0.9611	0.054*
H62	0.7033	−0.0046	0.9555	0.054*
C61	0.66964 (16)	−0.03840 (16)	1.0846 (2)	0.0549 (8)
H611	0.6595	−0.0779	1.1087	0.066*
H612	0.6362	−0.0122	1.0975	0.066*
C62	0.72470 (18)	−0.0156 (2)	1.1387 (3)	0.0851 (13)
H621	0.7170	−0.0140	1.2093	0.102*
H622	0.7344	0.0236	1.1149	0.102*
H623	0.7575	−0.0420	1.1262	0.102*
C7	0.65076 (13)	−0.05582 (13)	0.7990 (2)	0.0433 (6)
H71	0.6172	−0.0512	0.7539	0.052*
H72	0.6790	−0.0243	0.7838	0.052*
C71	0.68038 (17)	−0.11522 (16)	0.7768 (2)	0.0603 (9)
H711	0.7111	−0.1232	0.8260	0.072*
H712	0.6511	−0.1470	0.7801	0.072*
C72	0.70748 (17)	−0.11280 (17)	0.6737 (2)	0.0674 (10)
H721	0.7266	−0.1501	0.6592	0.081*
H722	0.7363	−0.0813	0.6709	0.081*
H723	0.6767	−0.1055	0.6252	0.081*
C8	0.58974 (12)	0.00949 (11)	0.9083 (2)	0.0429 (6)
H81	0.5588	0.0056	0.8582	0.052*
H82	0.5704	0.0117	0.9731	0.052*
C81	0.62231 (12)	0.06690 (12)	0.8905 (2)	0.0458 (7)
C82	0.62927 (16)	0.08891 (14)	0.7944 (3)	0.0579 (8)
H821	0.6137	0.0679	0.7404	0.070*
C83	0.6593 (2)	0.14216 (17)	0.7782 (4)	0.0829 (14)
H831	0.6641	0.1566	0.7135	0.099*
C84	0.68177 (19)	0.17332 (18)	0.8575 (4)	0.0871 (13)
H841	0.7029	0.2083	0.8463	0.105*
C85	0.6734 (2)	0.15356 (17)	0.9525 (4)	0.0884 (14)
H851	0.6877	0.1758	1.0061	0.106*
C86	0.64384 (17)	0.10061 (15)	0.9701 (3)	0.0687 (10)
H861	0.6383	0.0874	1.0353	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0755 (3)	0.0572 (3)	0.0469 (3)	−0.0120 (3)	0.000	0.000
Br2	0.0761 (3)	0.0487 (3)	0.0426 (3)	0.0045 (2)	0.000	0.000
Br3	0.05087 (16)	0.05375 (17)	0.06462 (16)	−0.00048 (13)	0.0020 (2)	−0.0071 (2)
N1	0.0414 (13)	0.0394 (13)	0.0505 (13)	0.0076 (10)	0.0072 (11)	0.0106 (11)
C1	0.0461 (18)	0.0436 (17)	0.0685 (19)	0.0008 (14)	0.0075 (15)	0.0161 (15)
C11	0.051 (2)	0.060 (2)	0.087 (2)	−0.0070 (17)	−0.0059 (18)	0.0207 (19)
C12	0.060 (2)	0.070 (3)	0.136 (4)	−0.0137 (19)	−0.012 (2)	0.035 (3)
C2	0.0384 (17)	0.0470 (19)	0.0594 (17)	0.0070 (14)	−0.0007 (13)	0.0087 (14)
C21	0.062 (2)	0.071 (3)	0.0572 (19)	0.009 (2)	0.0028 (17)	0.0169 (18)
C22	0.077 (3)	0.136 (4)	0.070 (2)	−0.007 (3)	−0.019 (2)	0.005 (3)
C3	0.0518 (19)	0.0469 (18)	0.0502 (16)	0.0047 (15)	0.0066 (14)	0.0031 (14)
C31	0.090 (3)	0.053 (2)	0.074 (2)	0.013 (2)	0.016 (2)	0.0028 (17)
C32	0.101 (3)	0.070 (3)	0.080 (3)	−0.001 (2)	0.024 (2)	−0.017 (2)
C4	0.0436 (15)	0.0428 (15)	0.0537 (15)	0.0081 (14)	0.0069 (14)	0.0048 (14)
C41	0.0421 (16)	0.0371 (16)	0.0526 (17)	0.0087 (12)	0.0019 (13)	0.0040 (13)
C42	0.056 (2)	0.0481 (19)	0.0510 (16)	0.0002 (16)	−0.0027 (15)	0.0084 (14)
C43	0.070 (3)	0.055 (2)	0.076 (2)	0.005 (2)	0.0073 (18)	0.0167 (17)
C44	0.056 (2)	0.0414 (19)	0.103 (3)	−0.0002 (16)	−0.001 (2)	0.0074 (19)
C45	0.076 (3)	0.050 (2)	0.091 (3)	−0.0030 (19)	−0.022 (2)	−0.0029 (19)
C46	0.084 (3)	0.051 (2)	0.0529 (18)	0.0077 (18)	−0.0094 (17)	0.0012 (16)
N2	0.0382 (13)	0.0399 (13)	0.0390 (11)	0.0022 (10)	0.0022 (10)	0.0020 (10)
C5	0.0438 (17)	0.0425 (16)	0.0466 (14)	−0.0030 (13)	0.0006 (12)	0.0070 (12)
C51	0.0515 (19)	0.0473 (18)	0.069 (2)	−0.0083 (15)	−0.0063 (16)	0.0055 (16)
C52	0.056 (2)	0.060 (2)	0.092 (3)	−0.0136 (18)	−0.0074 (19)	0.0167 (19)
C6	0.0380 (16)	0.0458 (17)	0.0509 (17)	0.0015 (14)	−0.0017 (12)	0.0014 (13)
C61	0.055 (2)	0.061 (2)	0.0490 (17)	−0.0035 (17)	−0.0061 (15)	0.0019 (16)
C62	0.072 (3)	0.123 (4)	0.060 (2)	−0.019 (2)	−0.017 (2)	−0.005 (2)
C7	0.0454 (17)	0.0438 (17)	0.0405 (14)	0.0027 (13)	0.0055 (12)	0.0030 (12)
C71	0.070 (2)	0.056 (2)	0.0552 (17)	0.0167 (17)	0.0041 (16)	−0.0007 (15)
C72	0.066 (2)	0.076 (3)	0.0594 (19)	0.0124 (19)	0.0063 (17)	−0.0143 (17)
C8	0.0400 (15)	0.0388 (16)	0.0501 (15)	0.0070 (12)	0.0047 (13)	0.0014 (12)
C81	0.0387 (16)	0.0390 (15)	0.0597 (18)	0.0042 (12)	0.0029 (14)	−0.0039 (14)
C82	0.068 (2)	0.0410 (18)	0.065 (2)	0.0017 (16)	0.0114 (17)	0.0038 (15)
C83	0.095 (3)	0.046 (2)	0.108 (3)	0.005 (2)	0.033 (3)	0.013 (2)
C84	0.063 (3)	0.042 (2)	0.156 (4)	−0.0071 (18)	0.006 (3)	0.006 (3)
C85	0.092 (3)	0.049 (2)	0.124 (4)	−0.002 (2)	−0.043 (3)	−0.007 (2)
C86	0.083 (3)	0.047 (2)	0.076 (2)	0.0017 (19)	−0.0170 (18)	−0.0097 (16)

Geometric parameters (Å, º)

N1—C1	1.523 (4)	N2—C5	1.512 (3)
N1—C2	1.521 (4)	N2—C6	1.518 (3)
N1—C3	1.521 (4)	N2—C7	1.527 (3)
N1—C4	1.535 (4)	N2—C8	1.534 (3)
C1—C11	1.519 (5)	C5—C51	1.517 (4)
C1—H11	0.9700	C5—H51	0.9700
C1—H12	0.9700	C5—H52	0.9700
C11—C12	1.511 (5)	C51—C52	1.508 (4)
C11—H111	0.9700	C51—H511	0.9700
C11—H112	0.9700	C51—H512	0.9700
C12—H121	0.9600	C52—H521	0.9600
C12—H122	0.9600	C52—H522	0.9600
C12—H123	0.9600	C52—H523	0.9600
C2—C21	1.504 (4)	C6—C61	1.509 (4)
C2—H21	0.9700	C6—H61	0.9700
C2—H22	0.9700	C6—H62	0.9700
C21—C22	1.515 (5)	C61—C62	1.521 (5)
C21—H211	0.9700	C61—H611	0.9700
C21—H212	0.9700	C61—H612	0.9700
C22—H221	0.9600	C62—H621	0.9600
C22—H222	0.9600	C62—H622	0.9600
C22—H223	0.9600	C62—H623	0.9600
C3—C31	1.522 (5)	C7—C71	1.519 (4)
C3—H31	0.9700	C7—H71	0.9700
C3—H32	0.9700	C7—H72	0.9700
C31—C32	1.496 (5)	C71—C72	1.509 (4)
C31—H311	0.9700	C71—H711	0.9700
C31—H312	0.9700	C71—H712	0.9700
C32—H321	0.9600	C72—H721	0.9600
C32—H322	0.9600	C72—H722	0.9600
C32—H323	0.9600	C72—H723	0.9600
C4—C41	1.509 (4)	C8—C81	1.500 (4)
C4—H41	0.9700	C8—H81	0.9700
C4—H42	0.9700	C8—H82	0.9700
C41—C46	1.388 (4)	C81—C82	1.386 (4)
C41—C42	1.393 (4)	C81—C86	1.392 (4)
C42—C43	1.386 (5)	C82—C83	1.389 (5)
C42—H421	0.9300	C82—H821	0.9300
C43—C44	1.372 (5)	C83—C84	1.367 (6)
C43—H431	0.9300	C83—H831	0.9300
C44—C45	1.370 (5)	C84—C85	1.359 (6)
C44—H441	0.9300	C84—H841	0.9300
C45—C46	1.381 (5)	C85—C86	1.381 (5)
C45—H451	0.9300	C85—H851	0.9300
C46—H461	0.9300	C86—H861	0.9300
C1—N1—C2	108.6 (2)	C5—N2—C6	108.8 (2)
C1—N1—C3	112.0 (2)	C5—N2—C7	111.6 (2)
C2—N1—C3	108.5 (2)	C6—N2—C7	108.2 (2)
C1—N1—C4	107.9 (2)	C5—N2—C8	108.7 (2)
C2—N1—C4	111.6 (2)	C6—N2—C8	111.2 (2)
C3—N1—C4	108.2 (2)	C7—N2—C8	108.4 (2)
N1—C1—C11	115.9 (2)	N2—C5—C51	115.7 (2)
C11—C1—H11	108.3	N2—C5—H51	108.3
N1—C1—H11	108.3	C51—C5—H51	108.3
C11—C1—H12	108.3	N2—C5—H52	108.3
N1—C1—H12	108.3	C51—C5—H52	108.3
H11—C1—H12	107.4	H51—C5—H52	107.4
C12—C11—C1	108.8 (3)	C52—C51—C5	109.4 (3)
C12—C11—H111	109.9	C52—C51—H511	109.8
C1—C11—H111	109.9	C5—C51—H511	109.8
C12—C11—H112	109.9	C52—C51—H512	109.8
C1—C11—H112	109.9	C5—C51—H512	109.8
H111—C11—H112	108.3	H511—C51—H512	108.2
C11—C12—H121	109.5	C51—C52—H521	109.5
C11—C12—H122	109.5	C51—C52—H522	109.5
H121—C12—H122	109.5	H521—C52—H522	109.5
C11—C12—H123	109.5	C51—C52—H523	109.5
H121—C12—H123	109.5	H521—C52—H523	109.5
H122—C12—H123	109.5	H522—C52—H523	109.5
C21—C2—N1	115.9 (3)	C61—C6—N2	116.4 (3)
C21—C2—H21	108.3	C61—C6—H61	108.2
N1—C2—H21	108.3	N2—C6—H61	108.2
C21—C2—H22	108.3	C61—C6—H62	108.2
N1—C2—H22	108.3	N2—C6—H62	108.2
H21—C2—H22	107.4	H61—C6—H62	107.4
C2—C21—C22	109.0 (3)	C6—C61—C62	109.1 (3)
C2—C21—H211	109.9	C6—C61—H611	109.9
C22—C21—H211	109.9	C62—C61—H611	109.9
C2—C21—H212	109.9	C6—C61—H612	109.9
C22—C21—H212	109.9	C62—C61—H612	109.9
H211—C21—H212	108.3	H611—C61—H612	108.3
C21—C22—H221	109.5	C61—C62—H621	109.5
C21—C22—H222	109.5	C61—C62—H622	109.5
H221—C22—H222	109.5	H621—C62—H622	109.5
C21—C22—H223	109.5	C61—C62—H623	109.5
H221—C22—H223	109.5	H621—C62—H623	109.5
H222—C22—H223	109.5	H622—C62—H623	109.5
C31—C3—N1	115.7 (2)	C71—C7—N2	116.2 (2)
N1—C3—H31	108.4	C71—C7—H71	108.2
C31—C3—H31	108.4	N2—C7—H71	108.2
N1—C3—H32	108.4	C71—C7—H72	108.2
C31—C3—H32	108.4	N2—C7—H72	108.2
H31—C3—H32	107.4	H71—C7—H72	107.4
C32—C31—C3	110.5 (3)	C72—C71—C7	108.9 (3)
C32—C31—H311	109.6	C72—C71—H711	109.9
C3—C31—H311	109.6	C7—C71—H711	109.9
C32—C31—H312	109.6	C72—C71—H712	109.9
C3—C31—H312	109.6	C7—C71—H712	109.9
H311—C31—H312	108.1	H711—C71—H712	108.3
C31—C32—H321	109.5	C71—C72—H721	109.5
C31—C32—H322	109.5	C71—C72—H722	109.5
H321—C32—H322	109.5	H721—C72—H722	109.5
C31—C32—H323	109.5	C71—C72—H723	109.5
H321—C32—H323	109.5	H721—C72—H723	109.5
H322—C32—H323	109.5	H722—C72—H723	109.5
C41—C4—N1	115.5 (2)	C81—C8—N2	115.3 (2)
C41—C4—H41	108.4	C81—C8—H81	108.4
N1—C4—H41	108.4	N2—C8—H81	108.4
C41—C4—H42	108.4	C81—C8—H82	108.4
N1—C4—H42	108.4	N2—C8—H82	108.4
H41—C4—H42	107.5	H81—C8—H82	107.5
C42—C41—C46	117.6 (3)	C82—C81—C86	118.5 (3)
C46—C41—C4	121.7 (3)	C82—C81—C8	120.6 (3)
C42—C41—C4	120.5 (3)	C86—C81—C8	120.9 (3)
C43—C42—C41	120.7 (3)	C81—C82—C83	120.4 (4)
C43—C42—H421	119.7	C81—C82—H821	119.8
C41—C42—H421	119.7	C83—C82—H821	119.8
C44—C43—C42	120.3 (3)	C84—C83—C82	119.9 (4)
C44—C43—H431	119.8	C84—C83—H831	120.1
C42—C43—H431	119.8	C82—C83—H831	120.1
C45—C44—C43	119.9 (3)	C85—C84—C83	120.5 (4)
C45—C44—H441	120.0	C85—C84—H841	119.7
C43—C44—H441	120.0	C83—C84—H841	119.7
C44—C45—C46	119.9 (3)	C84—C85—C86	120.4 (4)
C44—C45—H451	120.0	C84—C85—H851	119.8
C46—C45—H451	120.0	C86—C85—H851	119.8
C45—C46—C41	121.4 (3)	C85—C86—C81	120.3 (4)
C45—C46—H461	119.3	C85—C86—H861	119.9
C41—C46—H461	119.3	C81—C86—H861	119.9
C2—N1—C1—C11	−171.5 (3)	C6—N2—C5—C51	−174.2 (2)
C3—N1—C1—C11	−51.7 (4)	C7—N2—C5—C51	−54.9 (3)
C4—N1—C1—C11	67.3 (4)	C8—N2—C5—C51	64.6 (3)
N1—C1—C11—C12	−175.5 (3)	N2—C5—C51—C52	−178.2 (3)
C1—N1—C2—C21	−53.7 (4)	C5—N2—C6—C61	−51.9 (4)
C3—N1—C2—C21	−175.7 (3)	C7—N2—C6—C61	−173.2 (3)
C4—N1—C2—C21	65.1 (4)	C8—N2—C6—C61	67.8 (3)
N1—C2—C21—C22	−176.9 (3)	N2—C6—C61—C62	−164.7 (3)
C1—N1—C3—C31	−52.9 (4)	C5—N2—C7—C71	−49.4 (3)
C2—N1—C3—C31	67.0 (4)	C6—N2—C7—C71	70.2 (3)
C4—N1—C3—C31	−171.7 (3)	C8—N2—C7—C71	−169.1 (3)
N1—C3—C31—C32	−169.4 (3)	N2—C7—C71—C72	−171.7 (3)
C3—N1—C4—C41	−63.8 (3)	C5—N2—C8—C81	171.2 (2)
C2—N1—C4—C41	55.5 (3)	C6—N2—C8—C81	51.5 (3)
C1—N1—C4—C41	174.8 (3)	C7—N2—C8—C81	−67.4 (3)
N1—C4—C41—C46	−93.1 (4)	N2—C8—C81—C82	89.4 (3)
N1—C4—C41—C42	92.3 (3)	N2—C8—C81—C86	−93.6 (3)
C46—C41—C42—C43	2.4 (5)	C86—C81—C82—C83	2.7 (5)
C4—C41—C42—C43	177.2 (3)	C8—C81—C82—C83	179.8 (3)
C41—C42—C43—C44	−0.8 (5)	C81—C82—C83—C84	−0.5 (6)
C42—C43—C44—C45	−1.1 (6)	C82—C83—C84—C85	−2.0 (7)
C43—C44—C45—C46	1.4 (6)	C83—C84—C85—C86	2.2 (7)
C44—C45—C46—C41	0.2 (6)	C84—C85—C86—C81	0.1 (6)
C42—C41—C46—C45	−2.1 (5)	C82—C81—C86—C85	−2.5 (5)
C4—C41—C46—C45	−176.8 (3)	C8—C81—C86—C85	−179.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H12···Br1^i	0.97	3.22	4.094 (3)	151
C4—H42···Br1^i	0.97	2.96	3.888 (3)	161
C4—H41···Br1	0.97	3.19	4.106 (3)	157
C8—H81···Br2	0.97	3.06	3.982 (3)	159
C8—H82···Br2^ii	0.97	2.88	3.837 (3)	169
C61—H612···Br2^ii	0.97	3.15	4.006 (4)	148
C7—H71···Br2	0.97	3.18	4.108 (3)	161
C82—H821···Br2	0.93	3.20	4.003 (4)	146
C6—H61···Br3	0.97	2.87	3.762 (3)	153
C71—H711···Br3	0.97	3.05	3.941 (3)	153
C1—H11···Br3^i	0.97	3.04	3.964 (3)	160
C43—H431···Br3^iii	0.93	3.02	3.905 (4)	160
C2—H21···Br3^i	0.97	3.08	3.886 (3)	142
C31—H311···Br3^i	0.97	3.21	3.953 (4)	134
C45—H451···Br3^iv	0.93	3.22	3.956 (4)	138
C12—H121···Cg1^iii	0.96	3.07	3.791 (15)	133
C52—H521···Cg2^v	0.96	3.06	3.735 (15)	128

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