Syntheses and crystal structures of a new family of hybrid perovskites: C5H14N2·ABr3·0.5H2O (A = K, Rb, Cs).

The syntheses and crystal structures of three hybrid perovskites, viz. poly[1-methyl-piperizine-1,4-diium [tri-μ-bromido-potassium] hemihydrate], {(C5H14N2)[KBr3]·0.5H2O} n , (I), poly[1-methyl-piperizine-1,4-diium [tri-μ-bromido-rubidium] hemihydrate], {(C5H14N2)[RbBr3]·0.5H2O} n , (II), and poly[1-methyl-piperizine-1,4-diium [tri-μ-bromido-caesium] hemihydrate], {(C5H14N2)[CsBr3]·0.5H2O} n , (III), are described. These isostructural (space group Amm2) phases contain a three-dimensional, corner-sharing network of distorted ABr6 octa-hedra (A = K, Rb, Cs) with the same topology as the classical perovskite structure. The doubly protonated C5H14N2 2+ cations occupy inter-stices bounded by eight octa-hedra and the water mol-ecules lie in square sites bounded by four octa-hedra. N-H⋯Br, N-H⋯(Br,Br), N-H⋯O and O-H⋯Br hydrogen bonds consolidate the structures.

Chemical context

Oxide perovskites of generic formula ABO3, where A and B are metal ions with a combined charge of +6, are probably the most-studied family of inorganic phases on account of their numerous physical properties and structural variety (Tilley, 2016 ▸). The aristotype (highest-possible symmetry) (Megaw, 1973 ▸) for this classic structure type is a three-dimensional network (space group Pm m) of undistorted, vertex-sharing, BO6 octa­hedra encapsulating the A cations in 12-coordinate dodeca­hedral cavities bounded by eight octa­hedra but lower symmetry (‘hettotype’) structures are very common, which can be systematically described in terms of tilting schemes of the octa­hedra (Woodward, 1997 ▸).

‘Hybrid’ RMX 3 perovskites containing both inorganic and organic (mol­ecular) components have been studied intensively in the last few years due to their remarkable photo-voltaic and other optical properties (Xu et al., 2019 ▸; Stylianakis et al., 2019 ▸; Zuo et al., 2019 ▸). The R + or R 2+ organic cation replaces the metallic A cation in an oxide perovskite and the MX 3 (X = halide) octa­hedral network replaces the BO3 component of an oxide perovskite. Many of these studies have focused on lead halides [there are over 1400 papers on CH3NH3PbX 3 (X = Br, I) alone as of July 2019] and tin halides as the inorganic component of the structure (Stoumpos et al., 2016 ▸) but other compositions are possible: several years ago, we described a family of alkali-metal–chloride perovskites templated by C4H12N2 2+ piperizinium (or piperazin-1,4-diium) or C6H14N2 2+ ‘dabconium’ (or 1,4-diazo­niabi­cyclo­[2.2.2]octa­ne) cations (Paton & Harrison, 2010 ▸). Notable features of these structures include the ‘inverse’ charges of the cations (R 2+ > M +) compared to oxide perovskites, the inclusion of water mol­ecules of hydration in the C4H12N2·ACl3·H2O (A = K, Rb, Cs) series and a novel chiral perovskite analogue (space group P3221) for C6H14N2·RbCl3. This family has recently been extended by a number of phases (see Database survey) including C6H14N2·RbBr3 and C7H16N2·RbI3 (C7H16N2 2+ = 1-methyl-1,4-di­aza­bicyclo­[2.2.2]octane-1,4-diium) (Zhang et al., 2017 ▸), C4H12N2·RbBr3 (C4H12N2 2+ = 3-ammonio­pyrrolidinium) (Pan et al., 2017 ▸) and C4H12N2·NaI3 (Chen et al., 2018 ▸), some of which have significant physical properties such as ferroelectricity.

In this paper we describe the syntheses and structures of a new family of isostructural hybrid perovskite hemihydrates of formula C5H14N2·ABr3·0.5H2O (C5H14N2 2+ = 1-methyl piperizinium cation) where A = K (I), Rb (II) and Cs (III).

Structural commentary

Compounds (I), (II) and (III) are isostructural as indicated by their ortho­rhom­bic unit cells, showing the expected trend of volume increase as a result of the increasing ionic radius (Shannon, 1976 ▸) of the alkali-metal cation on going from potassium (r = 1.52) to rubidium (r = 1.66) to caesium (r = 1.81 Å). This description will focus on the structure of (I) and note significant differences for (II) and (III) where applicable.

The asymmetric unit of (I) (Fig. 1 ▸) contains two methyl­ene groups (C1 and C2), an N1H2 + grouping, an N2H+ moiety and the carbon atom (C3) of a methyl group. N1, N2 and C3 lie on a (010) crystallographic mirror plane with y = ½ for the asymmetric atoms. The complete C5H14N2 2+ cation is generated by the mirror to result in a typical (Dennington & Weller, 2018 ▸) chair conformation for this species with N1 and N2 deviating from the C1/C2/C1i/C2i [symmetry code: (i) x, 1 – y, z] plane by −0.623 (7) and 0.708 (6) Å, respectively. The pendant C3 methyl group adopts an equatorial orientation with respect to the ring. A water mol­ecule with the O atom lying on the (½, ½, z) special position with mm2 symmetry (Wyckoff site 2a) is also present.

Figure 1

The asymmetric unit of (I) expanded to show the complete C5H14N2 2+ cation, the complete potassium coordination polyhedra and the water mol­ecule (50% displacement ellipsoids). Symmetry codes: (i) x, 1 − y, z; (ii) 2 − x,  − y,  + z; (iii) x, y − ,  + z; (iv) 2 − x, 1 − y, z; (v) 1 − x, 1 − y, z; (vi) 1 − x,  − y,  + z; (vii) x, y − ,  + z.

The inorganic component of the structure consists of two potassium ions, K1 (site symmetry mm2; Wyckoff site 2b) and K2 (mm2; 2a) and three bromide ions: Br1 [m(100); 4e], Br2 [m(100); 4e] and Br3 [m(010); 4c], which gives an overall inorganic stoichiometry of KBr3. Crystal symmetry constructs Br6 octa­hedra around each potassium ion and the mean K1—Br and K2—Br separations are 3.4770 and 3.3825 Å, respect­ively (Table 1 ▸); equivalent data for (II) (Table 2 ▸) are Rb1—Br = 3.4906 and Rb2—Br = 3.4194 Å; equivalent data for (III) (Table 3 ▸) are Cs1—Br = 3.5432 and Cs2—Br = 3.4780 Å. These data may be compared with the shortest K—Br and Rb—Br separations of 3.299 and 3.425 Å, respectively in the rocksalt-type KBr and RbBr structures and the Cs—Br separation of 3.716 Å in CsBr (eight-coordinate CsCl structure).

Table 1

Selected geometric parameters (Å, °) for (I)

K1—Br1i	3.4184 (13)	K2—Br2	3.4000 (16)
K1—Br1	3.5261 (18)	K2—Br2ii	3.4179 (15)
K1—Br3	3.4865 (10)	K2—Br3	3.3297 (10)
K1iii—Br1—K1	157.98 (5)	K2—Br3—K1	179.19 (5)
K2—Br2—K2iii	177.85 (5)

Symmetry codes: (i) ; (ii) ; (iii) .

Table 2

Selected geometric parameters (Å, °) for (II)

Rb1—Br1i	3.4639 (8)	Rb2—Br2	3.4326 (9)
Rb1—Br1	3.5323 (10)	Rb2—Br2ii	3.4336 (9)
Rb1—Br3	3.4756 (9)	Rb2—Br3	3.3919 (9)
Rb1iii—Br1—Rb1	157.67 (2)	Rb2—Br3—Rb1	178.12 (3)
Rb2—Br2—Rb2iii	176.93 (2)

Symmetry codes: (i) ; (ii) ; (iii) .

Table 3

Selected geometric parameters (Å, °) for (III)

Cs1—Br1i	3.5319 (9)	Cs2—Br2	3.4923 (10)
Cs1—Br1	3.5873 (10)	Cs2—Br2ii	3.4790 (9)
Cs1—Br3	3.5105 (11)	Cs2—Br3	3.4627 (11)
Cs1iii—Br1—Cs1	156.07 (2)	Cs2—Br3—Cs1	175.99 (3)
Cs2iii—Br2—Cs2	174.97 (3)

Symmetry codes: (i) ; (ii) ; (iii) .

The K1 octa­hedron in (I) is considerably distorted with the smallest and largest cis Br—K—Br angles being 66.53 (4) and 110.57 (6)°, respectively and the trans angles spanning the range 157.98 (5)–160.13 (7)°. The K2 octa­hedron is more regular, with cis angles varying from 82.17 (3) to 97.55 (2)°. Two of the trans angles for K2 are close to 180° but the other is much smaller at 158.51 (7)°. The octa­hedral volume for the K1 octa­hedron is 53.2 Å3 and its angular variance (Robinson et al., 1971 ▸) is 125.5°2. The equivalent data for the K2 octa­hedron are 50.7 Å3 and 45.0°2, respectively. The corresponding polyhedra in (II) and (III) are similarly distorted, with respective octa­hedral volumes and angular variances as follows: Rb1 53.7 Å3, 129.7°2; Rb2 52.1 Å3, 56.6°2; Cs1 55.8 Å3, 145.2°2; Cs2 54.2 Å3, 84.7°2.

Bond-valence-sum (BVS) calculations using the ‘extrapolated’ formalism of Brese & O’Keeffe (1991 ▸) give the following values in valence units: K1 0.66, K2 0.86, Rb1 0.88 Rb2 1.07, Cs1 1.21, Cs2 1.44 (expected value = 1.00 in all cases). These data suggest that K1 in (I) is considerably underbonded, which is consistent with the long mean K1—Br separation in (I) compared to the separation in KBr. Conversely, Cs2 in (III) is substanti­ally overbonded and must be a ‘tight fit’ in its octa­hedral site.

Supra­molecular features

The linkage of the KBr6 octa­hedra in (I) in the x, y and z directions through their bromide-ion vertices leads to an infinite network of corner-sharing KBr6 octa­hedra akin to the network of BO6 octa­hedra in the classical ABO3 perovskite structure. Key features of the inorganic network are the K—Br—K bond angles (Table 1 ▸), with Br1 substanti­ally bent from the nominal linear bond [K1—Br1—K1ii = 157.98 (5)°; symmetry code (ii) x,  + y, z − ], but Br2 and Br3 far less so. When the structure of (I) is viewed down [011], alternating (100) layers of K1- and K2-centred octa­hedra are apparent (Fig. 2 ▸). Within these (100) planes, the K1 atoms are linked by the Br1 ions and the K2 atoms are liked by the Br2 ions. Finally, Br3 provides the inter-layer linkages in the [100] direction.

Figure 2

Polyhedral plot of the extended structure of (I) viewed down [011] with the K1Br6 octa­hedra coloured lilac and K2Br6 blue.

The 1-methyl­piperizinium cations occupy the central regions of the cages formed by eight KBr6 octa­hedra, obviously equivalent to the A cation site in a classical perovskite. The water mol­ecules lie at the centres of square sites bounded by four octa­hedra and stack in the [100] direction with alternating occupied and empty sites (see Fig. 3 ▸ and the Database survey section). Hydrogen bonding involving the encapsulated species is an important feature of the structure of (I): the N1H2 + group forms one N—H⋯Br3 link and one N—H⋯O link to the water mol­ecule (Table 4 ▸, Fig. 1 ▸) whereas the methyl­ated N2H+ group forms a rather long (and presumably weak) bifurcated N—H⋯(Br1,Br1) link. As just noted, the water mol­ecule accepts an N—H⋯O hydrogen bond from the organic cation and forms a pair of symmetry-equivalent O—H⋯Br2 hydrogen bonds. It is notable that all the C-bound H atoms in (I) are also potential hydrogen-bond donors to bromide ions based on the H⋯Br separations being significantly less than the van der Waals’ separation of 3.05 Å for these atoms. So far as the bromide ions are concerned, Br1 accepts one classical and three non-classical hydrogen bonds, Br2 accepts one classical and one non-classical and Br3 accepts one classical and two non-classical. The hydrogen-bonding schemes for (II) (Table 5 ▸) and (III) (Table 6 ▸) are essentially the same as that for (I).

Figure 3

Comparison of the structures of (a) MEXMAG (redrawn from Chen et al., 2018 ▸), (b) (I) and (c) GUYMIX (redrawn from Paton and Harrison, 2010 ▸). In MEXMAG, (I) and GUYMIX, the two octa­hedral cages shown are stacked in the [001], [100] and [001] directions, respectively. Note the alternation of water mol­ecules and empty sites in (I) with respect to the [100] direction whereas GUYMIX has a water mol­ecule in every square site in the [001] direction.

Table 4

Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2N⋯O1	0.91	1.89	2.799 (5)	172
N1—H1N⋯Br3	0.91	2.47	3.232 (5)	141
N2—H3N⋯Br1	1.00	2.67	3.438 (4)	133
N2—H3N⋯Br1iv	1.00	2.67	3.438 (4)	133
O1—H1O⋯Br2v	0.87	2.34	3.200 (3)	172
C1—H1A⋯Br2vi	0.99	2.88	3.614 (4)	131
C1—H1B⋯Br1iv	0.99	3.00	3.703 (4)	129
C2—H2B⋯Br1iv	0.99	3.05	3.517 (4)	111
C2—H2B⋯Br3v	0.99	2.82	3.525 (4)	129
C3—H3A⋯Br1vii	0.98	2.96	3.857 (4)	153
C3—H3B⋯Br3viii	0.98	2.75	3.615 (6)	148

Symmetry codes: (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Table 5

Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1	0.91	1.91	2.816 (5)	173
N1—H2N⋯Br3	0.91	2.49	3.243 (4)	140
N2—H3N⋯Br1	1.00	2.68	3.448 (4)	134
N2—H3N⋯Br1iv	1.00	2.68	3.448 (4)	134
O1—H1O⋯Br2v	0.87	2.34	3.212 (3)	173
C1—H1A⋯Br1iv	0.99	3.01	3.717 (4)	129
C1—H1B⋯Br2vi	0.99	2.92	3.652 (4)	131
C2—H2B⋯Br1iv	0.99	3.06	3.531 (4)	111
C2—H2B⋯Br3v	0.99	2.85	3.560 (4)	130
C3—H3A⋯Br1vii	0.99	3.03	3.927 (4)	152
C3—H3B⋯Br3viii	0.99	2.79	3.653 (5)	146

Symmetry codes: (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Table 6

Hydrogen-bond geometry (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2N⋯O1	0.91	1.94	2.845 (7)	173
N1—H1N⋯Br3	0.91	2.51	3.259 (6)	140
N2—H3N⋯Br1	1.00	2.68	3.446 (5)	134
N2—H3N⋯Br1iv	1.00	2.68	3.446 (5)	134
O1—H1O⋯Br2v	0.89	2.36	3.242 (4)	175
C1—H1A⋯Br1iv	0.99	3.07	3.762 (5)	128
C1—H1B⋯Br2vi	0.99	2.99	3.712 (5)	131
C2—H2B⋯Br1iv	0.99	3.08	3.550 (5)	111
C2—H2B⋯Br3v	0.99	2.92	3.643 (4)	131
C3—H3B⋯Br3vii	1.00	2.86	3.726 (7)	145

Symmetry codes: (iv) ; (v) ; (vi) ; (vii) .

Database survey

The title compounds and their significant analogue structures with their space groups and CCDC refcodes (Groom et al., 2016 ▸) are listed in Table 7 ▸. These compounds now represent a significant family of hybrid perovskites featuring several different cations – the protonated forms of piperazine, dabco, 1-methyl­piperazine, 3-amino­pyrrolidine and ‘methyl dabco’ (1-methyl-1,4-di­aza­bicyclo­[2.2.2]octa­ne) – as well as different alkali metal cations and halide anions. The recently reported structure of MEXMAG (Chen et al., 2108) has added sodium to the list of cations that can form these structures. Some structures such as HEJGOV (Zhang et al., 2017 ▸) show notable physical properties such as ferroelectricity, which is of course a classic characteristic of oxide perovskites.

Table 7

Summary of hybrid perovskite structures based on AX 3 alkali-metal–halide octa­hedral networks

Code/refcode	Formula	Space group	Reference
(I)	C5H14N2·KBr3·0.5H2O	Amm2	This work
(II)	C5H14N2·RbBr3·0.5H2O	Amm2	This work
(III)	C5H14N2·CsBr3·0.5H2O	Amm2	This work
GUYMIX	C4H12N2·KCl3·H2O	Pbcm	Paton & Harrison (2010 ▸)
GUYMOD	C4H12N2·RbCl3·H2O	Pbcm	Paton & Harrison (2010 ▸)
GUYMUJ	C4H12N2·CsCl3·H2O	Pbcm	Paton & Harrison (2010 ▸)
MOMLEI	C4H12N2·KBr3·H2O	Pbcm	Harrison (2019a ▸)
MOMSEP	C4H12N2·RbBr3·H2O	Pbcm	Harrison (2019b ▸)
FIZYIZ	C6H14N2·KBr3	P3121	Hongzhang (2019 ▸)
GUYNEU	C6H14N2·RbCl3	P3221	Paton & Harrison (2010 ▸)
HEJGUB	C6H14N2·RbBr3	P3221	Zhang et al. (2017 ▸)
GUYNEU02a	C6H14N2·RbCl3	Pm m	Zhang et al. (2017 ▸)
HEJGUB01a	C6H14N2·RbBr3	Pm m	Zhang et al. (2017 ▸)
GUYNIY	C6H14N2·CsCl3	C2/c	Paton & Harrison (2010 ▸)
HEJGOV	C7H16N2·RbI3	P432	Zhang et al. (2017 ▸)
HEJGOV01	C7H16N2·RbI3	R3	Zhang et al. (2017 ▸)
GEFLOV	C4H12N2·RbBr3	Ia	Pan et al. (2017 ▸)
GEFLOV01a	C4H12N2·RbBr3	Pm m	Pan et al. (2017 ▸)
MEXMAG	C4H12N2·NaI3	C2/c	Chen et al. (2018 ▸)

Redetermined structures not included. Note: (a) high-temperature polymorph.

An inter­esting structural comparison may be made between MEXMAG (an ‘anhydrous’ RAX 3 hybrid perovskite), (I) (an RAX 3·0.5H2O hybrid perovskite hemihydrate) and GUYMIX (an RAX 3·H2O hybrid perovskite hydrate) (Fig. 3 ▸). It may be seen that the pendant methyl groups of the C5H14N2 2+ cations in (I) both point towards an empty square site and their steric bulk presumably prevents water mol­ecules from occupying that site. It is notable that the empty square site in (I) is associated with the reduced K1—Br1—K1 bond angles as noted above. Conversely, in MEXMAG, the iodide ions are perhaps too large to allow a water mol­ecule to fit between them and the piperazinium cation is forced to form long N—H⋯I hydrogen bonds (H⋯I = 3.14 Å) rather than N—H⋯Ow (w = water) links.

Synthesis and crystallization

To prepare (I), 0.3673 g (3.67 mmol) of 1-methyl piperazine and 0.4068 g (3.42 mmol) of KBr were added to 15.0 ml of 1.0 M aqueous HBr solution to result in a clear solution, which was left in a Petri dish to evaporate. After two or three days, colourless blocks of (I) were recovered, rinsed with acetone and dried in air. Compound (II) was prepared in the same way, with 0.4042 g (2.44 mmol) of RbBr replacing the KBr in (I) and (III) was prepared by using 0.4479 g (2.10 mmol) of CsBr in place of the KBr.

ATR–FTIR (cm−1) for (I) (selected): 3215m (NH2 asymmetric stretch), 2940s (NH2 symmetric stretch), 2692s (sp 3 C—H stretch), 1585s (NH2 bend) (assignments from Heacock & Marion, 1956 ▸); for (II) 3217s, 2998s, 2681s, 1548s; for (III) 3221m, 2995s, 2681s, 1548s. The IR spectra of (I), (II) and (III) are available in the supporting information.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 8 ▸. For each structure, the N- and C-bond hydrogen atoms were located geometrically (C—H = 0.98–0.99, N—H = 0.91–1.00Å) and refined as riding atoms. The water H atom was located in a difference map and refined as riding in its as-found relative position. The constraint U iso(H) = 1.2U eq(carrier) or 1.5U eq(methyl C) was applied in all cases.

Table 8

Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	(C5H14N2)[KBr3]·0.5H2O	(C5H14N2)[RbBr3]·0.5H2O	(C5H14N2)[CsBr3]·0.5H2O
M r	390.02	436.39	483.83
Crystal system, space group	Orthorhombic, A m m2	Orthorhombic, A m m2	Orthorhombic, A m m2
Temperature (K)	93	93	93
a, b, c (Å)	13.411 (3), 9.488 (2), 9.790 (2)	13.477 (3), 9.5617 (19), 9.850 (2)	13.610 (3), 9.7201 (19), 9.977 (2)
V (Å3)	1245.7 (5)	1269.3 (5)	1319.9 (5)
Z	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm−1)	10.01	13.31	11.85
Crystal size (mm)	0.10 × 0.08 × 0.08	0.15 × 0.10 × 0.10	0.10 × 0.10 × 0.10
Data collection
Diffractometer	Rigaku Pilatus 200K CCD	Rigaku Pilatus 200K CCD	Rigaku Pilatus 200K CCD
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku, 2017 ▸)	Multi-scan (CrysAlis PRO; Rigaku, 2017 ▸)	Multi-scan (CrysAlis PRO; Rigaku, 2017 ▸)
T min, T max	0.406, 1.000	0.347, 1.000	0.463, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3890, 1235, 1208	6851, 1264, 1244	3718, 1312, 1293
R int	0.033	0.037	0.022
(sin θ/λ)max (Å−1)	0.602	0.602	0.603
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.015, 0.031, 0.90	0.013, 0.028, 1.01	0.013, 0.029, 0.94
No. of reflections	1235	1264	1312
No. of parameters	68	69	68
No. of restraints	1	1	1
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.41, −0.36	0.27, −0.35	0.58, −0.70
Absolute structure	Parsons et al. (2013 ▸)	Parsons et al. (2013 ▸)	Parsons et al. (2013 ▸)
Absolute structure parameter	−0.001 (11)	−0.001 (13)	0.016 (7)

Computer programs: CrysAlis PRO (Rigaku, 2017 ▸), SHELXS7 (Sheldrick, 2008 ▸), SHELXL2014/7 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989019010338/vn2151sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019010338/vn2151Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989019010338/vn2151IIsup3.hkl

Structure factors: contains datablock(s) III. DOI: 10.1107/S2056989019010338/vn2151IIIsup6.hkl

CCDC references: 1941726, 1941725, 1941724

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C5H14N2)[KBr3]·0.5H2O	Dx = 2.080 Mg m−3
Mr = 390.02	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Amm2	Cell parameters from 2257 reflections
a = 13.411 (3) Å	θ = 3.0–27.2°
b = 9.488 (2) Å	µ = 10.01 mm−1
c = 9.790 (2) Å	T = 93 K
V = 1245.7 (5) Å3	Prism, colourless
Z = 4	0.10 × 0.08 × 0.08 mm
F(000) = 748

Rigaku Pilatus 200K CCD diffractometer	1208 reflections with I > 2σ(I)
ω scans	Rint = 0.033
Absorption correction: multi-scan (CrysalisPro; Rigaku, 2017)	θmax = 25.3°, θmin = 3.0°
Tmin = 0.406, Tmax = 1.000	h = −16→16
3890 measured reflections	k = −11→11
1235 independent reflections	l = −11→11

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.015	(Δ/σ)max < 0.001
wR(F2) = 0.031	Δρmax = 0.41 e Å−3
S = 0.90	Δρmin = −0.36 e Å−3
1235 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
68 parameters	Extinction coefficient: 0.00195 (16)
1 restraint	Absolute structure: Parsons et al. (2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.001 (11)
Hydrogen site location: mixed

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.

	x	y	z	Uiso*/Ueq
K1	1.0000	0.5000	0.9058 (2)	0.0145 (4)
K2	0.5000	0.5000	1.0306 (2)	0.0120 (3)
Br1	1.0000	0.70384 (5)	0.60463 (6)	0.01165 (14)
Br2	0.5000	0.74449 (6)	0.77675 (6)	0.01087 (14)
Br3	0.74393 (4)	0.5000	0.96724 (6)	0.01101 (14)
C1	0.7289 (3)	0.3693 (4)	0.6163 (5)	0.0123 (9)
H1A	0.6861	0.2859	0.6321	0.015*
H1B	0.7878	0.3614	0.6767	0.015*
C2	0.7626 (3)	0.3706 (4)	0.4700 (5)	0.0107 (8)
H2A	0.7038	0.3696	0.4089	0.013*
H2B	0.8027	0.2851	0.4510	0.013*
C3	0.8629 (4)	0.5000	0.2985 (6)	0.0145 (12)
H3A	0.9028	0.5851	0.2831	0.022*
H3B	0.8067	0.5000	0.2346	0.022*
N1	0.6720 (3)	0.5000	0.6522 (5)	0.0098 (10)
H1N	0.6586	0.5000	0.7433	0.012*
H2N	0.6128	0.5000	0.6067	0.012*
N2	0.8244 (3)	0.5000	0.4421 (5)	0.0091 (10)
H3N	0.8827	0.5000	0.5059	0.011*
O1	0.5000	0.5000	0.4902 (5)	0.0088 (12)
H1O	0.5000	0.4251	0.4392	0.011*

	U11	U22	U33	U12	U13	U23
K1	0.0132 (9)	0.0147 (8)	0.0156 (10)	0.000	0.000	0.000
K2	0.0105 (8)	0.0138 (8)	0.0117 (9)	0.000	0.000	0.000
Br1	0.0086 (3)	0.0111 (3)	0.0152 (3)	0.000	0.000	−0.0018 (2)
Br2	0.0102 (3)	0.0114 (3)	0.0110 (3)	0.000	0.000	−0.0015 (2)
Br3	0.0119 (3)	0.0102 (3)	0.0110 (3)	0.000	−0.0026 (2)	0.000
C1	0.0105 (17)	0.0092 (18)	0.017 (2)	0.0022 (14)	0.0017 (18)	0.0032 (19)
C2	0.0098 (18)	0.0087 (17)	0.014 (2)	−0.0005 (14)	0.0021 (19)	0.000 (2)
C3	0.017 (3)	0.019 (3)	0.008 (3)	0.000	0.005 (3)	0.000
N1	0.007 (2)	0.014 (2)	0.008 (3)	0.000	0.0026 (19)	0.000
N2	0.009 (2)	0.009 (2)	0.010 (3)	0.000	0.0003 (19)	0.000
O1	0.012 (2)	0.008 (2)	0.007 (3)	0.000	0.000	0.000

K1—Br1i	3.4184 (13)	C1—C2	1.502 (6)
K1—Br1ii	3.4184 (13)	C1—H1A	0.9900
K1—Br1iii	3.5261 (18)	C1—H1B	0.9900
K1—Br1	3.5261 (18)	C2—N2	1.506 (4)
K1—Br3	3.4865 (10)	C2—H2A	0.9900
K1—Br3iii	3.4865 (10)	C2—H2B	0.9900
K2—Br2iv	3.4000 (16)	C3—N2	1.497 (7)
K2—Br2	3.4000 (16)	C3—H3A	0.9800
K2—Br2v	3.4179 (15)	C3—H3B	0.9799
K2—Br2ii	3.4179 (15)	N1—C1vii	1.498 (4)
K2—Br3iv	3.3297 (10)	N1—H1N	0.9100
K2—Br3	3.3297 (10)	N1—H2N	0.9100
Br1—K1vi	3.4183 (13)	N2—C2vii	1.506 (4)
Br2—K2vi	3.4179 (15)	N2—H3N	1.0000
C1—N1	1.498 (4)	O1—H1O	0.8686
Br1i—K1—Br1ii	110.57 (6)	K1vi—Br1—K1	157.98 (5)
Br1i—K1—Br3	84.36 (2)	K2—Br2—K2vi	177.85 (5)
Br1ii—K1—Br3	84.36 (2)	K2—Br3—K1	179.19 (5)
Br1i—K1—Br3iii	84.36 (2)	N1—C1—C2	111.8 (3)
Br1ii—K1—Br3iii	84.36 (2)	N1—C1—H1A	109.3
Br3—K1—Br3iii	160.13 (7)	C2—C1—H1A	109.3
Br1i—K1—Br1iii	157.98 (5)	N1—C1—H1B	109.3
Br1ii—K1—Br1iii	91.449 (19)	C2—C1—H1B	109.3
Br3—K1—Br1iii	98.30 (3)	H1A—C1—H1B	107.9
Br3iii—K1—Br1iii	98.30 (3)	C1—C2—N2	110.2 (3)
Br1i—K1—Br1	91.449 (18)	C1—C2—H2A	109.6
Br1ii—K1—Br1	157.98 (5)	N2—C2—H2A	109.6
Br3—K1—Br1	98.30 (3)	C1—C2—H2B	109.6
Br3iii—K1—Br1	98.30 (3)	N2—C2—H2B	109.6
Br1iii—K1—Br1	66.53 (4)	H2A—C2—H2B	108.1
Br3iv—K2—Br3	158.51 (7)	N2—C3—H3A	109.4
Br3iv—K2—Br2iv	82.17 (3)	N2—C3—H3B	109.5
Br3—K2—Br2iv	82.17 (3)	H3A—C3—H3B	108.7
Br3iv—K2—Br2	82.17 (3)	C1—N1—C1vii	111.7 (4)
Br3—K2—Br2	82.17 (3)	C1—N1—H1N	109.3
Br2iv—K2—Br2	86.05 (5)	C1vii—N1—H1N	109.3
Br3iv—K2—Br2v	97.55 (2)	C1—N1—H2N	109.3
Br3—K2—Br2v	97.55 (2)	C1vii—N1—H2N	109.3
Br2iv—K2—Br2v	177.85 (5)	H1N—N1—H2N	107.9
Br2—K2—Br2v	91.800 (17)	C3—N2—C2vii	111.1 (3)
Br3iv—K2—Br2ii	97.55 (2)	C3—N2—C2	111.1 (3)
Br3—K2—Br2ii	97.55 (2)	C2vii—N2—C2	109.2 (4)
Br2iv—K2—Br2ii	91.800 (17)	C3—N2—H3N	108.4
Br2—K2—Br2ii	177.85 (5)	C2vii—N2—H3N	108.4
Br2v—K2—Br2ii	90.35 (5)	C2—N2—H3N	108.4
N1—C1—C2—N2	56.6 (4)	C1—C2—N2—C3	177.3 (3)
C2—C1—N1—C1vii	−52.9 (5)	C1—C2—N2—C2vii	−59.8 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2N···O1	0.91	1.89	2.799 (5)	172
N1—H1N···Br3	0.91	2.47	3.232 (5)	141
N2—H3N···Br1	1.00	2.67	3.438 (4)	133
N2—H3N···Br1iii	1.00	2.67	3.438 (4)	133
O1—H1O···Br2viii	0.87	2.34	3.200 (3)	172
C1—H1A···Br2iv	0.99	2.88	3.614 (4)	131
C1—H1B···Br1iii	0.99	3.00	3.703 (4)	129
C2—H2B···Br1iii	0.99	3.05	3.517 (4)	111
C2—H2B···Br3viii	0.99	2.82	3.525 (4)	129
C3—H3A···Br1ix	0.98	2.96	3.857 (4)	153
C3—H3B···Br3x	0.98	2.75	3.615 (6)	148

(C5H14N2)[RbBr3]·0.5H2O	Dx = 2.284 Mg m−3
Mr = 436.39	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Amm2	Cell parameters from 2309 reflections
a = 13.477 (3) Å	θ = 3.0–27.4°
b = 9.5617 (19) Å	µ = 13.31 mm−1
c = 9.850 (2) Å	T = 93 K
V = 1269.3 (5) Å3	Prism, colourless
Z = 4	0.15 × 0.10 × 0.10 mm
F(000) = 820

Rigaku Pilatus 200K CCD diffractometer	1244 reflections with I > 2σ(I)
ω scans	Rint = 0.037
Absorption correction: multi-scan (CrysalisPro; Rigaku, 2017)	θmax = 25.3°, θmin = 3.0°
Tmin = 0.347, Tmax = 1.000	h = −16→16
6851 measured reflections	k = −11→11
1264 independent reflections	l = −11→11

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0076P)2] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.013	(Δ/σ)max < 0.001
wR(F2) = 0.028	Δρmax = 0.27 e Å−3
S = 1.01	Δρmin = −0.35 e Å−3
1264 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
69 parameters	Extinction coefficient: 0.00327 (14)
1 restraint	Absolute structure: Parsons et al. (2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.001 (13)
Hydrogen site location: mixed

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.

	x	y	z	Uiso*/Ueq
Rb1	0.0000	0.5000	0.09734 (7)	0.01032 (18)
Rb2	0.5000	0.5000	−0.03670 (8)	0.00968 (16)
Br1	0.0000	0.29829 (5)	0.39777 (6)	0.01090 (14)
Br2	0.5000	0.25694 (6)	0.21977 (6)	0.01073 (13)
Br3	0.25385 (4)	0.5000	0.03510 (6)	0.01017 (13)
C1	0.2708 (3)	0.6293 (4)	0.3838 (4)	0.0124 (8)
H1A	0.2118	0.6366	0.3243	0.015*
H1B	0.3130	0.7123	0.3674	0.015*
C2	0.2378 (3)	0.6284 (4)	0.5303 (5)	0.0117 (8)
H2A	0.2966	0.6293	0.5905	0.014*
H2B	0.1980	0.7131	0.5495	0.014*
C3	0.1383 (4)	0.5000	0.6996 (5)	0.0149 (12)
H3A	0.0985	0.4149	0.7150	0.022*
H3B	0.1945	0.5000	0.7635	0.022*
N1	0.3274 (3)	0.5000	0.3486 (5)	0.0107 (10)
H1N	0.3862	0.5000	0.3941	0.013*
H2N	0.3410	0.5000	0.2581	0.013*
N2	0.1766 (3)	0.5000	0.5584 (4)	0.0087 (9)
H3N	0.1187	0.5000	0.4950	0.010*
O1	0.5000	0.5000	0.5097 (5)	0.0109 (12)
H1O	0.5000	0.5749	0.5607	0.013*

	U11	U22	U33	U12	U13	U23
Rb1	0.0111 (4)	0.0093 (4)	0.0105 (4)	0.000	0.000	0.000
Rb2	0.0114 (4)	0.0091 (3)	0.0086 (3)	0.000	0.000	0.000
Br1	0.0122 (3)	0.0083 (3)	0.0122 (3)	0.000	0.000	0.0006 (2)
Br2	0.0141 (3)	0.0087 (3)	0.0094 (3)	0.000	0.000	0.0001 (2)
Br3	0.0112 (3)	0.0092 (3)	0.0101 (3)	0.000	−0.0012 (2)	0.000
C1	0.013 (2)	0.0077 (19)	0.017 (2)	−0.0003 (15)	−0.0003 (17)	0.0023 (18)
C2	0.013 (2)	0.0054 (18)	0.017 (2)	0.0009 (15)	0.0016 (18)	−0.001 (2)
C3	0.019 (3)	0.021 (3)	0.005 (3)	0.000	0.004 (2)	0.000
N1	0.011 (2)	0.012 (2)	0.009 (2)	0.000	0.0025 (19)	0.000
N2	0.009 (2)	0.010 (2)	0.007 (2)	0.000	−0.0010 (18)	0.000
O1	0.016 (3)	0.006 (2)	0.011 (3)	0.000	0.000	0.000

Rb1—Br1i	3.4639 (8)	C1—C2	1.510 (6)
Rb1—Br1ii	3.4639 (8)	C1—H1A	0.9900
Rb1—Br1iii	3.5323 (10)	C1—H1B	0.9900
Rb1—Br1	3.5323 (10)	C2—N2	1.504 (4)
Rb1—Br3iii	3.4756 (9)	C2—H2A	0.9900
Rb1—Br3	3.4756 (9)	C2—H2B	0.9900
Rb2—Br2iv	3.4326 (9)	C3—N2	1.484 (6)
Rb2—Br2	3.4326 (9)	C3—H3A	0.9868
Rb2—Br2v	3.4336 (9)	C3—H3B	0.9852
Rb2—Br2ii	3.4336 (9)	N1—C1vii	1.494 (4)
Rb2—Br3	3.3919 (9)	N1—H1N	0.9100
Rb2—Br3iv	3.3920 (9)	N1—H2N	0.9100
Br1—Rb1vi	3.4639 (8)	N2—C2vii	1.504 (4)
Br2—Rb2vi	3.4336 (9)	N2—H3N	1.0000
C1—N1	1.494 (4)	O1—H1O	0.8748
Br1i—Rb1—Br1ii	110.85 (3)	Rb1vi—Br1—Rb1	157.67 (2)
Br1i—Rb1—Br3iii	84.255 (10)	Rb2—Br2—Rb2vi	176.93 (2)
Br1ii—Rb1—Br3iii	84.255 (10)	Rb2—Br3—Rb1	178.12 (3)
Br1i—Rb1—Br3	84.255 (10)	N1—C1—C2	111.6 (3)
Br1ii—Rb1—Br3	84.255 (10)	N1—C1—H1A	109.3
Br3iii—Rb1—Br3	159.68 (3)	C2—C1—H1A	109.3
Br1i—Rb1—Br1iii	157.67 (2)	N1—C1—H1B	109.3
Br1ii—Rb1—Br1iii	91.481 (16)	C2—C1—H1B	109.3
Br3iii—Rb1—Br1iii	98.498 (12)	H1A—C1—H1B	108.0
Br3—Rb1—Br1iii	98.498 (12)	N2—C2—C1	110.0 (3)
Br1i—Rb1—Br1	91.481 (15)	N2—C2—H2A	109.7
Br1ii—Rb1—Br1	157.67 (2)	C1—C2—H2A	109.7
Br3iii—Rb1—Br1	98.498 (12)	N2—C2—H2B	109.7
Br3—Rb1—Br1	98.498 (12)	C1—C2—H2B	109.7
Br1iii—Rb1—Br1	66.19 (3)	H2A—C2—H2B	108.2
Br3—Rb2—Br3iv	155.93 (3)	N2—C3—H3A	109.5
Br3—Rb2—Br2iv	81.173 (14)	N2—C3—H3B	109.4
Br3iv—Rb2—Br2iv	81.173 (13)	H3A—C3—H3B	108.6
Br3—Rb2—Br2	81.172 (13)	C1—N1—C1vii	111.7 (4)
Br3iv—Rb2—Br2	81.173 (14)	C1—N1—H1N	109.3
Br2iv—Rb2—Br2	85.22 (3)	C1vii—N1—H1N	109.3
Br3—Rb2—Br2v	98.376 (11)	C1—N1—H2N	109.3
Br3iv—Rb2—Br2v	98.376 (11)	C1vii—N1—H2N	109.3
Br2iv—Rb2—Br2v	176.93 (2)	H1N—N1—H2N	107.9
Br2—Rb2—Br2v	91.702 (16)	C3—N2—C2	111.3 (3)
Br3—Rb2—Br2ii	98.376 (11)	C3—N2—C2vii	111.3 (3)
Br3iv—Rb2—Br2ii	98.376 (11)	C2—N2—C2vii	109.4 (4)
Br2iv—Rb2—Br2ii	91.702 (16)	C3—N2—H3N	108.3
Br2—Rb2—Br2ii	176.93 (2)	C2—N2—H3N	108.3
Br2v—Rb2—Br2ii	91.37 (3)	C2vii—N2—H3N	108.3
N1—C1—C2—N2	−56.8 (4)	C1—C2—N2—C3	−176.8 (3)
C2—C1—N1—C1vii	53.6 (5)	C1—C2—N2—C2vii	59.8 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.91	1.91	2.816 (5)	173
N1—H2N···Br3	0.91	2.49	3.243 (4)	140
N2—H3N···Br1	1.00	2.68	3.448 (4)	134
N2—H3N···Br1iii	1.00	2.68	3.448 (4)	134
O1—H1O···Br2viii	0.87	2.34	3.212 (3)	173
C1—H1A···Br1iii	0.99	3.01	3.717 (4)	129
C1—H1B···Br2iv	0.99	2.92	3.652 (4)	131
C2—H2B···Br1iii	0.99	3.06	3.531 (4)	111
C2—H2B···Br3viii	0.99	2.85	3.560 (4)	130
C3—H3A···Br1ix	0.99	3.03	3.927 (4)	152
C3—H3B···Br3x	0.99	2.79	3.653 (5)	146

(C5H14N2)[CsBr3]·0.5H2O	Dx = 2.435 Mg m−3
Mr = 483.83	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Amm2	Cell parameters from 2407 reflections
a = 13.610 (3) Å	θ = 2.9–27.5°
b = 9.7201 (19) Å	µ = 11.85 mm−1
c = 9.977 (2) Å	T = 93 K
V = 1319.9 (5) Å3	Block, colourless
Z = 4	0.10 × 0.10 × 0.10 mm
F(000) = 892

Rigaku Pilatus 200K CCD diffractometer	1293 reflections with I > 2σ(I)
ω scans	Rint = 0.022
Absorption correction: multi-scan (CrysalisPro; Rigaku, 2017)	θmax = 25.4°, θmin = 2.9°
Tmin = 0.463, Tmax = 1.000	h = −16→15
3718 measured reflections	k = −11→11
1312 independent reflections	l = −11→12

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0012P)2] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.013	(Δ/σ)max < 0.001
wR(F2) = 0.029	Δρmax = 0.57 e Å−3
S = 0.94	Δρmin = −0.70 e Å−3
1312 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
68 parameters	Extinction coefficient: 0.00081 (7)
1 restraint	Absolute structure: Parsons et al. (2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.016 (7)
Hydrogen site location: mixed

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.

	x	y	z	Uiso*/Ueq
Cs1	0.0000	0.5000	0.10292 (5)	0.01104 (16)
Cs2	0.5000	0.5000	−0.04771 (5)	0.01285 (16)
Br1	0.0000	0.30234 (7)	0.40657 (7)	0.01341 (18)
Br2	0.5000	0.26080 (7)	0.21347 (7)	0.01513 (17)
Br3	0.25365 (6)	0.5000	0.03902 (7)	0.01354 (16)
C1	0.2714 (4)	0.6276 (5)	0.3848 (5)	0.0140 (11)
H1A	0.2128	0.6348	0.3263	0.017*
H1B	0.3132	0.7093	0.3686	0.017*
C2	0.2391 (4)	0.6259 (4)	0.5301 (6)	0.0138 (10)
H2A	0.2977	0.6263	0.5890	0.017*
H2B	0.2001	0.7095	0.5497	0.017*
C3	0.1412 (5)	0.5000	0.6985 (7)	0.0189 (16)
H3A	0.1014	0.4149	0.7140	0.028*
H3B	0.1974	0.5000	0.7625	0.028*
N1	0.3276 (4)	0.5000	0.3497 (6)	0.0125 (13)
H1N	0.3408	0.5000	0.2603	0.015*
H2N	0.3859	0.5000	0.3944	0.015*
N2	0.1782 (4)	0.5000	0.5586 (6)	0.0112 (12)
H3N	0.1205	0.5000	0.4965	0.013*
O1	0.5000	0.5000	0.5110 (6)	0.0149 (16)
H1O	0.5000	0.5749	0.5620	0.018*

	U11	U22	U33	U12	U13	U23
Cs1	0.0133 (4)	0.0096 (3)	0.0102 (3)	0.000	0.000	0.000
Cs2	0.0146 (3)	0.0134 (3)	0.0105 (3)	0.000	0.000	0.000
Br1	0.0155 (4)	0.0110 (3)	0.0138 (3)	0.000	0.000	0.0029 (3)
Br2	0.0193 (4)	0.0128 (3)	0.0133 (3)	0.000	0.000	−0.0001 (3)
Br3	0.0143 (3)	0.0140 (3)	0.0123 (4)	0.000	−0.0017 (3)	0.000
C1	0.015 (3)	0.009 (2)	0.018 (3)	0.001 (2)	0.001 (2)	0.003 (2)
C2	0.017 (3)	0.009 (2)	0.016 (2)	0.002 (2)	0.000 (2)	0.001 (3)
C3	0.021 (4)	0.026 (4)	0.009 (3)	0.000	0.003 (4)	0.000
N1	0.010 (3)	0.016 (3)	0.012 (3)	0.000	0.001 (2)	0.000
N2	0.012 (3)	0.012 (3)	0.010 (3)	0.000	0.001 (2)	0.000
O1	0.022 (4)	0.007 (3)	0.016 (4)	0.000	0.000	0.000

Cs1—Br1i	3.5319 (9)	C1—C2	1.515 (7)
Cs1—Br1ii	3.5319 (9)	C1—H1A	0.9900
Cs1—Br1iii	3.5873 (10)	C1—H1B	0.9900
Cs1—Br1	3.5873 (10)	C2—N2	1.505 (6)
Cs1—Br3iii	3.5105 (11)	C2—H2A	0.9900
Cs1—Br3	3.5105 (11)	C2—H2B	0.9900
Cs2—Br2iv	3.4923 (10)	C3—N2	1.484 (9)
Cs2—Br2	3.4923 (10)	C3—H3A	1.0011
Cs2—Br2v	3.4790 (9)	C3—H3B	0.9961
Cs2—Br2ii	3.4790 (9)	N1—C1vii	1.499 (6)
Cs2—Br3	3.4627 (11)	N1—H1N	0.9100
Cs2—Br3iv	3.4627 (11)	N1—H2N	0.9100
Br1—Cs1vi	3.5319 (9)	N2—C2vii	1.505 (6)
Br2—Cs2vi	3.4790 (9)	N2—H3N	1.0000
C1—N1	1.499 (6)	O1—H1O	0.8883
Br3iii—Cs1—Br3	159.07 (3)	Cs1vi—Br1—Cs1	156.07 (2)
Br3iii—Cs1—Br1i	84.218 (9)	Cs2vi—Br2—Cs2	174.97 (3)
Br3—Cs1—Br1i	84.219 (9)	Cs2—Br3—Cs1	175.99 (3)
Br3iii—Cs1—Br1ii	84.218 (9)	N1—C1—C2	111.3 (4)
Br3—Cs1—Br1ii	84.219 (9)	N1—C1—H1A	109.4
Br1i—Cs1—Br1ii	112.63 (3)	C2—C1—H1A	109.4
Br3iii—Cs1—Br1iii	98.823 (12)	N1—C1—H1B	109.4
Br3—Cs1—Br1iii	98.822 (12)	C2—C1—H1B	109.4
Br1i—Cs1—Br1iii	156.07 (2)	H1A—C1—H1B	108.0
Br1ii—Cs1—Br1iii	91.305 (15)	N2—C2—C1	110.4 (4)
Br3iii—Cs1—Br1	98.823 (12)	N2—C2—H2A	109.6
Br3—Cs1—Br1	98.822 (13)	C1—C2—H2A	109.6
Br1i—Cs1—Br1	91.305 (15)	N2—C2—H2B	109.6
Br1ii—Cs1—Br1	156.07 (2)	C1—C2—H2B	109.6
Br1iii—Cs1—Br1	64.76 (3)	H2A—C2—H2B	108.1
Br3—Cs2—Br3iv	151.06 (3)	N2—C3—H3A	109.2
Br3—Cs2—Br2v	99.854 (11)	N2—C3—H3B	110.0
Br3iv—Cs2—Br2v	99.854 (11)	H3A—C3—H3B	108.5
Br3—Cs2—Br2ii	99.854 (11)	C1vii—N1—C1	111.7 (5)
Br3iv—Cs2—Br2ii	99.854 (11)	C1vii—N1—H1N	109.3
Br2v—Cs2—Br2ii	93.55 (3)	C1—N1—H1N	109.3
Br3—Cs2—Br2iv	79.254 (13)	C1vii—N1—H2N	109.3
Br3iv—Cs2—Br2iv	79.255 (13)	C1—N1—H2N	109.3
Br2v—Cs2—Br2iv	174.97 (3)	H1N—N1—H2N	107.9
Br2ii—Cs2—Br2iv	91.485 (16)	C3—N2—C2	111.4 (4)
Br3—Cs2—Br2	79.254 (13)	C3—N2—C2vii	111.4 (4)
Br3iv—Cs2—Br2	79.255 (13)	C2—N2—C2vii	108.8 (5)
Br2v—Cs2—Br2	91.485 (16)	C3—N2—H3N	108.4
Br2ii—Cs2—Br2	174.97 (3)	C2—N2—H3N	108.4
Br2iv—Cs2—Br2	83.48 (3)	C2vii—N2—H3N	108.4
N1—C1—C2—N2	−57.1 (6)	C1—C2—N2—C3	−176.9 (4)
C2—C1—N1—C1vii	53.6 (7)	C1—C2—N2—C2vii	60.0 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2N···O1	0.91	1.94	2.845 (7)	173
N1—H1N···Br3	0.91	2.51	3.259 (6)	140
N2—H3N···Br1	1.00	2.68	3.446 (5)	134
N2—H3N···Br1iii	1.00	2.68	3.446 (5)	134
O1—H1O···Br2viii	0.89	2.36	3.242 (4)	175
C1—H1A···Br1iii	0.99	3.07	3.762 (5)	128
C1—H1B···Br2iv	0.99	2.99	3.712 (5)	131
C2—H2B···Br1iii	0.99	3.08	3.550 (5)	111
C2—H2B···Br3viii	0.99	2.92	3.643 (4)	131
C3—H3B···Br3ix	1.00	2.86	3.726 (7)	145