Pentane-1,5-diaminium dibromide

The crystal structure of the title salt, C₅H₁₆N₂²⁺·2Br^-, with Z = 12 and more unusually Z' = 3, forms part of a small group of crystal structures in the Cambridge Structural Database that are ammonium bromide salts. One of the diaminium cation chains in the asymmetric unit exhibits positional disorder, which was modelled using a suitable disorder model. This compound also exhibits organic-inorganic layering in its packing arrangement that is typical of this class of compound. An extensive complex three-dimensional hydrogen-bonding network is also identified. The hydrogen bonds evident in this crystal structure were identified as being most likely strong charge-assisted hydrogen bonds.

S1. Comment

The crystal structure of pentane-1,5-diaminium dibromide, (I), was determined as part of an ongoing study of the structural characteristics and noncovalent interactions of organic–inorganic hybrid salts. A search of the Cambridge Structural Database (CSD, Version 5.33, August 2012 update; Allen, 2002) revealed that this compound had not been determined previously, so it is presented here.

The asymmetric unit of (I) contains three diammonium cations and six bromide anions with Z = 12 and Z' = 3. Since structures with Z' > 1 are not a common occurrence, a search was carried out to determine the number of structures in the CSD with Z' = 3, limited to organic crystal structures and also only those structures that contain C, H, N and Br. This search resulted in 11 hits, only five of which are ammonium bromide salts, namely dimethyldi-n-propylammonium bromide (CSD refcode CANYOG; Busi et al., 2005), 1-isopropyl-3-methylimidazol-3-ium bromide (JIRCAP01; Kawahata et al., 2009), 1-decyl-1-methylpyrrolidinium bromide (YUHFUD; Getsis & Mudring, 2009), 1-dodecyl-1-methylpyrrolidinium bromide (YUHGAK; Getsis & Mudring, 2009) and propane-1,3-bis(N-methylpyrrolidinium) dibromide (FELCOP; Anderson et al., 2005). Interestingly, the title salt, (I), is only the second diammonium dibromide salt with similar crystallographic properties, i.e. Z' = 3.

One of the diammonium cations of (I) was found to be disordered and a suitable model was used to resolve the disorder. This diammonium chain is disordered over two positions, with occupancies of 0.5485 (3) and 0.4515 (3) [0.552 (10) and 0.449 (8) in CIF tables - please clarify]. The disordered atoms were refined anisotropically with interatomic distance restraints and displacement-parameter constraints. Fig. 1 shows the molecular structure of (I) and also only depicts one of the disorder models [Major or minor occupancy?] of the one disordered cation chain. As a result of this disorder, the diammonium cation chain deviates substantially from planarity, as is evident in the torsion angles along the chain (Table 1 lists selected torsion angles for both disordered chain models).

The other two, ordered, diammonium cation chains also deviate slightly from planarity and have a bowed zigzag configuration. This is particularly noticeable in the centre of the cation chains, where the C1A—C2A—C3A—C4A torsion angle is 166.3 (3)° and the C2B—C3B—C4B—C5B torsion angle is 169.4 (3)° (see Table 1).

These n-alkyldiammonium dihalide salts usually exhibit an organic–inorganic layering effect, where the organic diammonium cation chain layers are sandwiched between inorganic anion layers (consisting of counteranions, in this case bromide anions). This phenomenon has been demonstrated in our previous work (van Blerk & Kruger, 2007a,b, 2009; Arderne & Kruger, 2011; Arderne, 2011) and in work done by our colleagues (Lemmerer & Billing, 2006; Rademeyer, 2006). Salt (I) clearly shows this layering effect (Fig. 2), which is evident primarily because of the intricate and complex three-dimensional hydrogen-bonding network that is present in this crystal structure, consisting entirely of N—H···Br hydrogen bonds. This means that the distance between the organic and inorganic layers will be approximately equal to the N···Br distance (on average, this distance is around 3.3 Å). One of the interlayer distances (i.e. the distance between the two inorganic layers) is 4.597 Å (Mercury; Macrae et al., 2008) (Fig. 3). The N—H···Br hydrogen bonds are postulated to be relatively strong charge-assisted hydrogen bonds because of their directionality (many of them are close to 180°) and their relatively short H···A distances.

This organic–inorganic layering effect is also evident in two of the crystal structures found in the CSD search, namely YUHFUD and YUHGAK. The layering effect was not evident in CANYOG, JIRCAP01 and FELCOP. In the case of YUHFUD and YUHGAK, the layering effect is evident not as a result of hydrogen bonding, but primarily as a result of hydrocarbon chain stacking, since YUHFUD and YUHGAK have ten-carbon and 12-carbon hydrocarbon chains, respectively. This chain stacking is common in hydrocarbon-type materials and is a result of weak van der Waals interactions between the layers (Dorset, 2005).

Related literature

For related literature, see: Allen (2002); Anderson et al. (2005); Arderne (2011); Arderne & Kruger (2011); Blerk & Kruger (2007a, 2009); Busi et al. (2005); Dorset (2005); Getsis & Mudring (2009); Kawahata et al. (2009); Lemmerer & Billing (2006); Macrae et al. (2008); Rademeyer (2006).

S2. Experimental

The title compound was prepared by adding butane-1,5-diamine (0.050 g, 0.489 mmol) to 47% hydrobromic acid (2 ml, 37 mmol) in a sample vial. The mixture was then refluxed at 363 K for 2 h. The solution was cooled slowly at a rate of 2 K h^-1 to room temperature. Colourless crystals of butane-1,5-diammonium dibromide, (I), were collected.

S3. Refinement

One of the cations in (I) is completely disordered over two positions. The occupation factor of the major orientation of this cation refined to 0.552 (10). The N—C distances in the disordered cation were restrained to be similar with a restraint s.u. value of 0.01 Å, while rigid bond and similarity restraints were applied to the anisotropic displacement parameters of neighbouring disordered atoms within and between the two orientations. Atom N2CB was also restrained to be pseudo-isotropic. All H atoms were placed in idealized positions and refined using a riding model, with N—H = 0.91 Å and C—H = 0.99 Å and with U_iso(H) = 1.2U_eq(parent atom).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL97 (Sheldrick 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Only one of the disordered pentane-1,5-diammonium cation chains is shown [Major or minor occupancy?]. Selected hydrogen bonds are indicated by dashed lines.
	Fig. 2. A packing diagram for (I), viewed down the b axis, clearly showing the organic–inorganic layering effect. [Where is the origin (O) ?]
	Fig. 3. A packing diagram for (I), viewed down the b axis, showing the inorganic interlayer distance (highlighted with a dotted line). [Where is the origin (O) ?]

Pentane-1,5-diaminium dibromide

Crystal data

C5H16N2^2+·2Br^−	F(000) = 1560
Mr = 264.02	Dx = 1.788 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 4.5971 (3) Å	Cell parameters from 8965 reflections
b = 15.4607 (11) Å	θ = 3.9–28.0°
c = 41.389 (3) Å	µ = 8.20 mm^−1
β = 90.310 (5)°	T = 150 K
V = 2941.7 (4) Å^3	Flat plate, colourless
Z = 12	0.26 × 0.15 × 0.08 mm

Data collection

Oxford Xcalibur2 diffractometer	6280 independent reflections
Radiation source: fine-focus sealed tube	4223 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 8.4190 pixels mm^-1	θmax = 27.0°, θmin = 4.0°
ϕ and ω scans	h = −4→5
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −18→19
Tmin = 0.225, Tmax = 0.546	l = −47→52
17961 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.049	H-atom parameters constrained
S = 0.89	w = 1/[σ^2(Fo^2) + (0.0187P)^2], where P = (Fo^2 + 2Fc^2)/3
6280 reflections	(Δ/σ)max = 0.003
316 parameters	Δρmax = 0.72 e Å^−3
298 restraints	Δρmin = −0.61 e Å^−3

Special details

Experimental. Absorption correction: CrysAlis RED, (Oxford Diffraction, 2006), Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (Blessing, 1995).

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

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.

The crystal structure was refined in OLEX2 (Dolomanov et. al., 2009) as follows:

1. Fixed Uiso At 1.2 times of: {H1AA,H1AB,H1AC} of N1A, {H4CC,H4CD} of C4CA, {H5CA,H5CB} of C5CA, {H3CC, H3CD} of C3CA, {H3BA,H3BB} of C3B, {H2AA,H2AB,H2AC} of N2A, {H1AD,H1AE} of C1A, {H2AD,H2AE} of C2A, {H1BA,H1BB,H1BC} of N1B, {H5AA,H5AB} of C5A, {H2BA, H2BB,H2BC} of N2B, {H2BD,H2BE} of C2B, {H3AA,H3AB} of C3A, {H1BD,H1BE} of C1B, {H4AA,H4AB} of C4A, {H5CC,H5CD} of C5CB, {H4CA,H4CB} of C4CB, {H3CA,H3CB} of C3CB, {H1CF,H1CG,H1CH} of N1CA, {H2CD,H2CE} of C2CB, {H1CI,H1CJ} of C1CA, {H2CI,H2CJ} of C2CA, {H2CF,H2CG,H2CH} of N2CA, {H1CA,H1CB,H1CC} of N1CB, {H2CA,H2CB,H2CC} of N2CB, {H1CD,H1CE} of C1CB, {H4BA,H4BB} of C4B, {H5BA, H5BB} of C5B

2. Restrained distances N1CA-C1CA, N1CB-C1CB, N2CB-C5CA, N2CA-C5CB with sigma of 0.01

3. Rigid bond restraints N2CB, N2CA, C5CB, C5CA, C4CB, C4CA, C2CB, C3CB, C2CA, C3CA, C1CB, C1CA, N1CB, N1CA with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01

4. Uiso/Uaniso restraints and constraints N2CB, N2CA, C5CB, C5CA, C4CB, C4CA, C3CB, C3CA, C2CB, C2CA, C1CB, C1CA, N1CB N1CA: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 Uanis(N1CB) Ueq, Uanis(C1CB) Ueq, Uanis(C2CB) Ueq, Uanis(C3CB) Ueq, Uanis(C4CB) Ueq, Uanis(C5CB) Ueq, Uanis(N1CA) Ueq, Uanis(N2CA) Ueq, Uanis(C1CA) Ueq, Uanis(C2CA) Ueq, Uanis(C3CA) Ueq, Uanis(C4CA) Ueq, Uanis(C5CA) Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01 Uanis(N2CB) Ueq: with sigma of 0.0025 and sigma for terminal atoms of 0.005

5. Others 1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1- Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1- Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1- Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=1-Sof(H1CA)=Sof(N1CA)=Sof(H1CF)= Sof(H1CG)=Sof(H1CH)=Sof(N2CA)=Sof(H2CF)=Sof(H2CG)=Sof(H2CH)=Sof(C1CA)= Sof(H1CI)=Sof(H1CJ)=Sof(C2CA)=Sof(H2CI)=Sof(H2CJ)=Sof(C3CA)=Sof(H3CC)= Sof(H3CD)=Sof(C4CA)=Sof(H4CC)=Sof(H4CD)=Sof(C5CA)=Sof(H5CA)=Sof(H5CB)

6.a Secondary CH2 refined with riding coordinates: C1A(H1AD,H1AE), C2A(H2AD,H2AE), C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA, H5AB), C1B(H1BD,H1BE), C2B(H2BD,H2BE), C3B(H3BA,H3BB), C4B(H4BA,H4BB), C5B(H5BA,H5BB), C1CB(H1CD,H1CE), C2CB(H2CD,H2CE), C3CB(H3CA,H3CB), C4CB(H4CA, H4CB), C5CB(H5CC,H5CD), C1CA(H1CI,H1CJ), C2CA(H2CI,H2CJ), C3CA(H3CC,H3CD), C4CA(H4CC,H4CD), C5CA(H5CA,H5CB)

6.b Idealised Me refined as rotating group: N1A(H1AA,H1AB,H1AC), N2A(H2AA,H2AB,H2AC), N1B(H1BA,H1BB,H1BC), N2B(H2BA,H2BB, H2BC), N1CB(H1CA,H1CB,H1CC), N2CB(H2CA,H2CB,H2CC), N1CA(H1CF,H1CG,H1CH), N2CA(H2CF,H2CG,H2CH)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	1.47772 (7)	0.75787 (2)	0.71013 (2)	0.02154 (9)
Br2	0.59461 (7)	0.12633 (3)	0.64898 (2)	0.02762 (10)
Br3	1.33274 (7)	0.02700 (2)	0.73833 (2)	0.01994 (9)
Br4	1.37893 (7)	0.92942 (2)	0.45899 (2)	0.02096 (9)
Br5	0.51019 (7)	0.64105 (3)	0.61085 (2)	0.02760 (10)
Br6	0.49897 (8)	0.68026 (3)	0.50448 (2)	0.03657 (12)
N1A	0.9825 (5)	0.64060 (18)	0.67175 (7)	0.0237 (7)
H1AA	0.9066	0.6354	0.6515	0.028*
H1AB	1.1168	0.6839	0.6720	0.028*
H1AC	0.8377	0.6531	0.6859	0.028*
N2A	0.8478 (5)	0.17742 (18)	0.72262 (6)	0.0194 (7)
H2AA	0.7345	0.1600	0.7057	0.023*
H2AB	0.7327	0.1963	0.7390	0.023*
H2AC	0.9580	0.1322	0.7296	0.023*
C1A	1.1242 (6)	0.5577 (2)	0.68127 (8)	0.0197 (8)
H1AD	1.2047	0.5636	0.7034	0.024*
H1AE	1.2884	0.5462	0.6665	0.024*
C2A	0.9181 (6)	0.4814 (2)	0.68041 (8)	0.0181 (8)
H2AD	0.8495	0.4715	0.6580	0.022*
H2AE	0.7466	0.4936	0.6940	0.022*
C3A	1.0739 (7)	0.4013 (2)	0.69283 (8)	0.0203 (8)
H3AA	1.2155	0.3820	0.6764	0.024*
H3AB	1.1842	0.4166	0.7126	0.024*
C4A	0.8703 (6)	0.3270 (2)	0.70043 (8)	0.0195 (8)
H4AA	0.7574	0.3116	0.6808	0.023*
H4AB	0.7315	0.3451	0.7173	0.023*
C5A	1.0406 (6)	0.2487 (2)	0.71204 (8)	0.0195 (8)
H5AA	1.1664	0.2278	0.6943	0.023*
H5AB	1.1681	0.2660	0.7303	0.023*
N1B	0.8432 (5)	0.93923 (18)	0.69062 (6)	0.0201 (7)
H1BA	0.7166	0.9827	0.6858	0.024*
H1BB	0.9589	0.9555	0.7075	0.024*
H1BC	0.7420	0.8909	0.6961	0.024*
N2B	0.8828 (5)	0.86320 (19)	0.51298 (6)	0.0250 (7)
H2BA	1.0029	0.8692	0.4957	0.030*
H2BB	0.7509	0.9071	0.5130	0.030*
H2BC	0.7877	0.8117	0.5116	0.030*
C1B	1.0274 (6)	0.9206 (2)	0.66181 (7)	0.0180 (8)
H1BD	1.1725	0.8758	0.6675	0.022*
H1BE	1.1343	0.9737	0.6557	0.022*
C2B	0.8487 (6)	0.8899 (2)	0.63327 (7)	0.0174 (8)
H2BD	0.6929	0.9324	0.6286	0.021*
H2BE	0.7557	0.8340	0.6386	0.021*
C3B	1.0385 (6)	0.8789 (2)	0.60342 (7)	0.0199 (8)
H3BA	1.1520	0.9326	0.6000	0.024*
H3BB	1.1780	0.8312	0.6073	0.024*
C4B	0.8654 (6)	0.8597 (2)	0.57326 (7)	0.0180 (8)
H4BA	0.7024	0.9012	0.5714	0.022*
H4BB	0.7821	0.8008	0.5748	0.022*
C5B	1.0560 (6)	0.8658 (2)	0.54313 (7)	0.0198 (8)
H5BA	1.1682	0.9205	0.5439	0.024*
H5BB	1.1965	0.8173	0.5431	0.024*
N1CB	0.111 (6)	0.1629 (12)	0.5880 (7)	0.021 (4)	0.448 (10)
H1CA	0.2378	0.1488	0.5720	0.025*	0.448 (10)
H1CB	−0.0398	0.1249	0.5879	0.025*	0.448 (10)
H1CC	0.2046	0.1605	0.6074	0.025*	0.448 (10)
N2CB	0.013 (5)	0.5938 (10)	0.5573 (6)	0.022 (5)	0.449 (8)
H2CA	0.0573	0.6288	0.5403	0.026*	0.448 (10)
H2CB	0.1778	0.5809	0.5685	0.026*	0.448 (10)
H2CC	−0.1148	0.6214	0.5705	0.026*	0.448 (10)
C1CB	−0.001 (3)	0.2523 (11)	0.5826 (5)	0.025 (3)	0.448 (10)
H1CD	−0.1828	0.2600	0.5950	0.030*	0.448 (10)
H1CE	−0.0493	0.2594	0.5594	0.030*	0.448 (10)
C2CB	0.212 (3)	0.3211 (10)	0.5923 (4)	0.024 (3)	0.448 (10)
H2CD	0.3920	0.3150	0.5796	0.029*	0.448 (10)
H2CE	0.2624	0.3143	0.6155	0.029*	0.448 (10)
C3CB	0.076 (3)	0.4131 (13)	0.5865 (5)	0.033 (4)	0.448 (10)
H3CA	−0.1240	0.4141	0.5953	0.039*	0.448 (10)
H3CB	0.1921	0.4566	0.5984	0.039*	0.448 (10)
C4CB	0.065 (2)	0.4380 (7)	0.5513 (3)	0.027 (2)	0.448 (10)
H4CA	0.2641	0.4514	0.5439	0.032*	0.448 (10)
H4CB	−0.0072	0.3881	0.5386	0.032*	0.448 (10)
C5CB	−0.008 (3)	0.5031 (8)	0.5428 (3)	0.020 (3)	0.449 (8)
H5CC	0.1798	0.4879	0.5327	0.024*	0.448 (10)
H5CD	−0.1577	0.5006	0.5256	0.024*	0.448 (10)
N1CA	0.087 (4)	0.1535 (10)	0.5948 (6)	0.024 (4)	0.552 (10)
H1CF	0.0550	0.1120	0.5796	0.029*	0.552 (10)
H1CG	−0.0627	0.1541	0.6091	0.029*	0.552 (10)
H1CH	0.2562	0.1418	0.6056	0.029*	0.552 (10)
N2CA	0.014 (5)	0.5954 (9)	0.5533 (5)	0.036 (5)	0.552 (10)
H2CF	0.1525	0.6228	0.5414	0.043*	0.552 (10)
H2CG	0.0647	0.5976	0.5746	0.043*	0.552 (10)
H2CH	−0.1602	0.6220	0.5504	0.043*	0.552 (10)
C1CA	0.110 (2)	0.2399 (9)	0.5788 (4)	0.024 (3)	0.552 (10)
H1CI	−0.0614	0.2485	0.5645	0.029*	0.552 (10)
H1CJ	0.2858	0.2411	0.5651	0.029*	0.552 (10)
C2CA	0.125 (3)	0.3125 (8)	0.6027 (3)	0.028 (3)	0.552 (10)
H2CI	0.2840	0.3007	0.6184	0.034*	0.552 (10)
H2CJ	−0.0595	0.3150	0.6149	0.034*	0.552 (10)
C3CA	0.179 (2)	0.4006 (9)	0.5866 (4)	0.020 (3)	0.552 (10)
H3CC	0.2246	0.4441	0.6034	0.024*	0.552 (10)
H3CD	0.3502	0.3961	0.5722	0.024*	0.552 (10)
C4CA	−0.079 (2)	0.4303 (5)	0.5673 (2)	0.034 (2)	0.552 (10)
H4CC	−0.2302	0.4513	0.5823	0.040*	0.552 (10)
H4CD	−0.1604	0.3803	0.5554	0.040*	0.552 (10)
C5CA	−0.122 (2)	0.5124 (6)	0.5450 (2)	0.030 (2)	0.552 (10)
H5CA	−0.3122	0.5036	0.5555	0.036*	0.552 (10)
H5CB	−0.1561	0.5176	0.5214	0.036*	0.552 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.02310 (18)	0.0219 (2)	0.0196 (2)	−0.00424 (16)	−0.00119 (15)	0.00108 (17)
Br2	0.0354 (2)	0.0298 (3)	0.0177 (2)	−0.00330 (18)	−0.00635 (16)	0.00320 (18)
Br3	0.01884 (17)	0.0231 (2)	0.0179 (2)	−0.00097 (16)	−0.00081 (14)	0.00046 (17)
Br4	0.01968 (18)	0.0250 (2)	0.0182 (2)	−0.00122 (16)	−0.00010 (14)	0.00041 (17)
Br5	0.02360 (19)	0.0393 (3)	0.0200 (2)	−0.00110 (18)	0.00088 (15)	0.00088 (18)
Br6	0.0310 (2)	0.0537 (3)	0.0250 (2)	−0.0188 (2)	−0.00533 (17)	0.0109 (2)
N1A	0.0173 (15)	0.021 (2)	0.0327 (19)	−0.0016 (14)	−0.0035 (13)	−0.0032 (15)
N2A	0.0184 (15)	0.0182 (19)	0.0216 (17)	0.0022 (13)	−0.0008 (12)	0.0007 (14)
C1A	0.0173 (18)	0.018 (2)	0.023 (2)	0.0041 (16)	−0.0005 (15)	0.0023 (17)
C2A	0.0179 (17)	0.019 (2)	0.017 (2)	0.0010 (16)	0.0019 (14)	0.0002 (16)
C3A	0.0191 (18)	0.018 (2)	0.024 (2)	0.0018 (16)	0.0003 (15)	0.0023 (17)
C4A	0.0169 (18)	0.020 (2)	0.022 (2)	−0.0002 (16)	−0.0030 (15)	−0.0002 (17)
C5A	0.0189 (18)	0.022 (2)	0.018 (2)	−0.0033 (17)	−0.0011 (15)	0.0012 (17)
N1B	0.0222 (15)	0.0202 (19)	0.0180 (17)	−0.0070 (13)	−0.0013 (12)	−0.0020 (14)
N2B	0.0219 (15)	0.041 (2)	0.0118 (16)	−0.0069 (15)	0.0018 (12)	0.0034 (15)
C1B	0.0159 (17)	0.022 (2)	0.0159 (19)	0.0012 (16)	0.0023 (14)	0.0008 (17)
C2B	0.0196 (18)	0.021 (2)	0.0121 (19)	0.0011 (16)	−0.0024 (14)	0.0011 (16)
C3B	0.0169 (18)	0.028 (2)	0.015 (2)	0.0017 (16)	−0.0006 (15)	−0.0020 (17)
C4B	0.0170 (17)	0.024 (2)	0.0129 (19)	−0.0009 (16)	−0.0019 (14)	0.0004 (16)
C5B	0.0152 (17)	0.025 (2)	0.019 (2)	0.0015 (16)	−0.0044 (15)	−0.0040 (17)
N1CB	0.018 (6)	0.029 (7)	0.016 (8)	−0.009 (6)	0.005 (5)	−0.014 (7)
N2CB	0.014 (5)	0.030 (4)	0.018 (5)	−0.006 (4)	0.010 (4)	−0.003 (3)
C1CB	0.019 (8)	0.031 (6)	0.025 (7)	−0.003 (6)	−0.001 (6)	0.005 (5)
C2CB	0.015 (6)	0.025 (6)	0.032 (8)	−0.002 (5)	0.002 (5)	−0.006 (6)
C3CB	0.028 (9)	0.031 (6)	0.039 (6)	0.000 (7)	−0.003 (8)	−0.006 (5)
C4CB	0.026 (5)	0.032 (6)	0.021 (5)	−0.003 (4)	0.006 (4)	−0.007 (4)
C5CB	0.019 (4)	0.026 (4)	0.018 (4)	0.004 (4)	−0.003 (4)	−0.001 (3)
N1CA	0.013 (6)	0.022 (5)	0.037 (11)	0.001 (4)	−0.006 (5)	0.004 (5)
N2CA	0.021 (5)	0.062 (8)	0.026 (8)	−0.012 (3)	0.012 (4)	−0.010 (4)
C1CA	0.021 (6)	0.028 (6)	0.025 (5)	−0.006 (6)	0.001 (5)	0.005 (4)
C2CA	0.025 (6)	0.028 (5)	0.032 (7)	0.000 (5)	0.000 (4)	0.004 (4)
C3CA	0.020 (6)	0.020 (6)	0.019 (4)	−0.002 (5)	−0.007 (5)	0.002 (4)
C4CA	0.031 (5)	0.039 (5)	0.031 (5)	0.010 (4)	−0.008 (4)	0.003 (4)
C5CA	0.031 (5)	0.037 (6)	0.023 (5)	−0.012 (4)	0.009 (4)	−0.004 (4)

Geometric parameters (Å, º)

N1A—H1AA	0.9100	N1CB—H1CA	0.9100
N1A—H1AB	0.9100	N1CB—H1CB	0.9100
N1A—H1AC	0.9100	N1CB—H1CC	0.9100
N1A—C1A	1.490 (4)	N1CB—C1CB	1.492 (8)
N2A—H2AA	0.9100	N2CB—H2CA	0.9100
N2A—H2AB	0.9100	N2CB—H2CB	0.9100
N2A—H2AC	0.9100	N2CB—H2CC	0.9100
N2A—C5A	1.482 (4)	N2CB—C5CA	1.490 (8)
C1A—H1AD	0.9900	C1CB—H1CD	0.9900
C1A—H1AE	0.9900	C1CB—H1CE	0.9900
C1A—C2A	1.514 (4)	C1CB—C2CB	1.50 (2)
C2A—H2AD	0.9900	C2CB—H2CD	0.9900
C2A—H2AE	0.9900	C2CB—H2CE	0.9900
C2A—C3A	1.519 (4)	C2CB—C3CB	1.57 (2)
C3A—H3AA	0.9900	C3CB—H3CA	0.9900
C3A—H3AB	0.9900	C3CB—H3CB	0.9900
C3A—C4A	1.515 (4)	C3CB—C4CB	1.51 (2)
C4A—H4AA	0.9900	C4CB—H4CA	0.9900
C4A—H4AB	0.9900	C4CB—H4CB	0.9900
C4A—C5A	1.518 (4)	C4CB—C5CA	1.457 (13)
C5A—H5AA	0.9900	C5CB—H5CC	0.9900
C5A—H5AB	0.9900	C5CB—H5CD	0.9900
N1B—H1BA	0.9100	C5CB—N2CA	1.494 (8)
N1B—H1BB	0.9100	C5CB—C4CA	1.550 (14)
N1B—H1BC	0.9100	N1CA—H1CF	0.9100
N1B—C1B	1.494 (4)	N1CA—H1CG	0.9100
N2B—H2BA	0.9100	N1CA—H1CH	0.9100
N2B—H2BB	0.9100	N1CA—C1CA	1.496 (8)
N2B—H2BC	0.9100	N2CA—H2CF	0.9100
N2B—C5B	1.477 (4)	N2CA—H2CG	0.9100
C1B—H1BD	0.9900	N2CA—H2CH	0.9100
C1B—H1BE	0.9900	C1CA—H1CI	0.9900
C1B—C2B	1.512 (4)	C1CA—H1CJ	0.9900
C2B—H2BD	0.9900	C1CA—C2CA	1.50 (2)
C2B—H2BE	0.9900	C2CA—H2CI	0.9900
C2B—C3B	1.526 (4)	C2CA—H2CJ	0.9900
C3B—H3BA	0.9900	C2CA—C3CA	1.538 (18)
C3B—H3BB	0.9900	C3CA—H3CC	0.9900
C3B—C4B	1.506 (4)	C3CA—H3CD	0.9900
C4B—H4BA	0.9900	C3CA—C4CA	1.500 (12)
C4B—H4BB	0.9900	C4CA—H4CC	0.9900
C4B—C5B	1.531 (4)	C4CA—H4CD	0.9900
C5B—H5BA	0.9900	C5CA—H5CA	0.9900
C5B—H5BB	0.9900	C5CA—H5CB	0.9900
H1AA—N1A—H1AB	109.5	H1CA—N1CB—H1CB	109.5
H1AA—N1A—H1AC	109.5	H1CA—N1CB—H1CC	109.5
H1AB—N1A—H1AC	109.5	H1CB—N1CB—H1CC	109.5
C1A—N1A—H1AA	109.5	C1CB—N1CB—H1CA	109.5
C1A—N1A—H1AB	109.5	C1CB—N1CB—H1CB	109.5
C1A—N1A—H1AC	109.5	C1CB—N1CB—H1CC	109.5
H2AA—N2A—H2AB	109.5	H2CA—N2CB—H2CB	109.5
H2AA—N2A—H2AC	109.5	H2CA—N2CB—H2CC	109.5
H2AB—N2A—H2AC	109.5	H2CB—N2CB—H2CC	109.5
C5A—N2A—H2AA	109.5	C5CA—N2CB—H2CA	109.5
C5A—N2A—H2AB	109.5	C5CA—N2CB—H2CB	109.5
C5A—N2A—H2AC	109.5	C5CA—N2CB—H2CC	109.5
N1A—C1A—H1AD	109.0	N1CB—C1CB—H1CD	109.0
N1A—C1A—H1AE	109.0	N1CB—C1CB—H1CE	109.0
N1A—C1A—C2A	113.1 (2)	N1CB—C1CB—C2CB	113.0 (16)
H1AD—C1A—H1AE	107.8	H1CD—C1CB—H1CE	107.8
C2A—C1A—H1AD	109.0	C2CB—C1CB—H1CD	109.0
C2A—C1A—H1AE	109.0	C2CB—C1CB—H1CE	109.0
C1A—C2A—H2AD	109.8	C1CB—C2CB—H2CD	109.6
C1A—C2A—H2AE	109.8	C1CB—C2CB—H2CE	109.6
C1A—C2A—C3A	109.5 (2)	C1CB—C2CB—C3CB	110.1 (13)
H2AD—C2A—H2AE	108.2	H2CD—C2CB—H2CE	108.2
C3A—C2A—H2AD	109.8	C3CB—C2CB—H2CD	109.6
C3A—C2A—H2AE	109.8	C3CB—C2CB—H2CE	109.6
C2A—C3A—H3AA	108.9	C2CB—C3CB—H3CA	109.0
C2A—C3A—H3AB	108.9	C2CB—C3CB—H3CB	109.0
H3AA—C3A—H3AB	107.7	H3CA—C3CB—H3CB	107.8
C4A—C3A—C2A	113.4 (3)	C4CB—C3CB—C2CB	113.1 (15)
C4A—C3A—H3AA	108.9	C4CB—C3CB—H3CA	109.0
C4A—C3A—H3AB	108.9	C4CB—C3CB—H3CB	109.0
C3A—C4A—H4AA	109.5	C3CB—C4CB—H4CA	108.9
C3A—C4A—H4AB	109.5	C3CB—C4CB—H4CB	108.9
C3A—C4A—C5A	110.6 (3)	H4CA—C4CB—H4CB	107.8
H4AA—C4A—H4AB	108.1	C5CA—C4CB—C3CB	113.2 (11)
C5A—C4A—H4AA	109.5	C5CA—C4CB—H4CA	108.9
C5A—C4A—H4AB	109.5	C5CA—C4CB—H4CB	108.9
N2A—C5A—C4A	112.2 (2)	H5CC—C5CB—H5CD	106.8
N2A—C5A—H5AA	109.2	N2CA—C5CB—H5CC	107.0
N2A—C5A—H5AB	109.2	N2CA—C5CB—H5CD	107.0
C4A—C5A—H5AA	109.2	N2CA—C5CB—C4CA	121.2 (12)
C4A—C5A—H5AB	109.2	C4CA—C5CB—H5CC	107.0
H5AA—C5A—H5AB	107.9	C4CA—C5CB—H5CD	107.0
H1BA—N1B—H1BB	109.5	H1CF—N1CA—H1CG	109.5
H1BA—N1B—H1BC	109.5	H1CF—N1CA—H1CH	109.5
H1BB—N1B—H1BC	109.5	H1CG—N1CA—H1CH	109.5
C1B—N1B—H1BA	109.5	C1CA—N1CA—H1CF	109.5
C1B—N1B—H1BB	109.5	C1CA—N1CA—H1CG	109.5
C1B—N1B—H1BC	109.5	C1CA—N1CA—H1CH	109.5
H2BA—N2B—H2BB	109.5	C5CB—N2CA—H2CF	109.5
H2BA—N2B—H2BC	109.5	C5CB—N2CA—H2CG	109.5
H2BB—N2B—H2BC	109.5	C5CB—N2CA—H2CH	109.5
C5B—N2B—H2BA	109.5	H2CF—N2CA—H2CG	109.5
C5B—N2B—H2BB	109.5	H2CF—N2CA—H2CH	109.5
C5B—N2B—H2BC	109.5	H2CG—N2CA—H2CH	109.5
N1B—C1B—H1BD	109.2	N1CA—C1CA—H1CI	109.2
N1B—C1B—H1BE	109.2	N1CA—C1CA—H1CJ	109.2
N1B—C1B—C2B	112.1 (2)	N1CA—C1CA—C2CA	112.2 (14)
H1BD—C1B—H1BE	107.9	H1CI—C1CA—H1CJ	107.9
C2B—C1B—H1BD	109.2	C2CA—C1CA—H1CI	109.2
C2B—C1B—H1BE	109.2	C2CA—C1CA—H1CJ	109.2
C1B—C2B—H2BD	109.5	C1CA—C2CA—H2CI	109.1
C1B—C2B—H2BE	109.5	C1CA—C2CA—H2CJ	109.1
C1B—C2B—C3B	110.9 (2)	C1CA—C2CA—C3CA	112.5 (11)
H2BD—C2B—H2BE	108.0	H2CI—C2CA—H2CJ	107.8
C3B—C2B—H2BD	109.5	C3CA—C2CA—H2CI	109.1
C3B—C2B—H2BE	109.5	C3CA—C2CA—H2CJ	109.1
C2B—C3B—H3BA	109.0	C2CA—C3CA—H3CC	109.2
C2B—C3B—H3BB	109.0	C2CA—C3CA—H3CD	109.2
H3BA—C3B—H3BB	107.8	H3CC—C3CA—H3CD	107.9
C4B—C3B—C2B	113.0 (2)	C4CA—C3CA—C2CA	111.9 (11)
C4B—C3B—H3BA	109.0	C4CA—C3CA—H3CC	109.2
C4B—C3B—H3BB	109.0	C4CA—C3CA—H3CD	109.2
C3B—C4B—H4BA	109.4	C5CB—C4CA—H4CC	108.8
C3B—C4B—H4BB	109.4	C5CB—C4CA—H4CD	108.8
C3B—C4B—C5B	111.1 (2)	C3CA—C4CA—C5CB	113.6 (9)
H4BA—C4B—H4BB	108.0	C3CA—C4CA—H4CC	108.8
C5B—C4B—H4BA	109.4	C3CA—C4CA—H4CD	108.8
C5B—C4B—H4BB	109.4	H4CC—C4CA—H4CD	107.7
N2B—C5B—C4B	112.2 (2)	N2CB—C5CA—H5CA	109.4
N2B—C5B—H5BA	109.2	N2CB—C5CA—H5CB	109.4
N2B—C5B—H5BB	109.2	C4CB—C5CA—N2CB	111.2 (12)
C4B—C5B—H5BA	109.2	C4CB—C5CA—H5CA	109.4
C4B—C5B—H5BB	109.2	C4CB—C5CA—H5CB	109.4
H5BA—C5B—H5BB	107.9	H5CA—C5CA—H5CB	108.0
N1A—C1A—C2A—C3A	−175.8 (3)	N1CB—C1CB—C2CB—C3CB	−178.9 (15)
C1A—C2A—C3A—C4A	166.3 (3)	C1CB—C2CB—C3CB—C4CB	−74.4 (19)
C2A—C3A—C4A—C5A	178.9 (3)	C2CB—C3CB—C4CB—C5CA	165.9 (11)
C3A—C4A—C5A—N2A	174.7 (3)	C3CB—C4CB—C5CA—N2CB	71.7 (18)
N1B—C1B—C2B—C3B	175.1 (3)	N1CA—C1CA—C2CA—C3CA	174.2 (11)
C1B—C2B—C3B—C4B	−172.5 (3)	N2CA—C5CB—C4CA—C3CA	−81.0 (15)
C2B—C3B—C4B—C5B	169.4 (3)	C1CA—C2CA—C3CA—C4CA	69.5 (16)
C3B—C4B—C5B—N2B	−169.5 (3)	C2CA—C3CA—C4CA—C5CB	−163.0 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···Br5	0.91	2.47	3.318 (3)	154
N1A—H1AB···Br1	0.91	2.55	3.310 (3)	141
N1A—H1AC···Br1^i	0.91	2.53	3.352 (3)	151
N2A—H2AA···Br2	0.91	2.49	3.351 (3)	159
N2A—H2AB···Br1^ii	0.91	2.51	3.403 (3)	167
N2A—H2AC···Br3	0.91	2.39	3.284 (3)	166
N1B—H1BA···Br2^iii	0.91	2.75	3.553 (3)	148
N1B—H1BB···Br3^iii	0.91	2.41	3.280 (2)	161
N1B—H1BC···Br1^i	0.91	2.46	3.369 (3)	179
N2B—H2BA···Br4	0.91	2.49	3.361 (3)	161
N2B—H2BB···Br4^iv	0.91	2.84	3.618 (3)	144
N2B—H2BC···Br6	0.91	2.44	3.351 (3)	175
N1CB—H1CA···Br4^v	0.91	2.50	3.37 (2)	161
N1CB—H1CB···Br2^i	0.91	3.04	3.52 (2)	115
N1CB—H1CB···Br4^vi	0.91	2.62	3.29 (3)	131
N1CB—H1CC···Br2	0.91	2.53	3.40 (3)	160
N2CB—H2CA···Br6	0.91	2.64	3.41 (3)	142
N2CB—H2CB···Br5	0.91	2.50	3.26 (2)	142
N2CB—H2CC···Br5^i	0.91	2.43	3.29 (3)	159
N1CA—H1CF···Br4^vi	0.91	2.63	3.34 (2)	136
N1CA—H1CG···Br2^i	0.91	2.33	3.22 (2)	167
N1CA—H1CH···Br2	0.91	2.38	3.25 (2)	160
N2CA—H2CF···Br6	0.91	2.39	3.29 (2)	172
N2CA—H2CG···Br5	0.91	2.62	3.361 (18)	139
N2CA—H2CH···Br5^i	0.91	2.95	3.41 (2)	113
N2CA—H2CH···Br6^i	0.91	2.62	3.37 (2)	141

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