research communications
Syntheses and structures of piperazin-1-ium ABr2 (A = Cs or Rb): hybrid solids containing `curtain wall' layers of face- and edge-sharing ABr6 trigonal prisms
aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, and bDepartment of Chemistry, University of St Andrews, St Andrews KY16 9ST, Scotland
*Correspondence e-mail: w.harrison@abdn.ac.uk
The isostructural title compounds, poly[piperazin-1-ium [di-μ-bromido-caesium]], {(C4H11N2)[CsBr2]}n, and poly[piperazin-1-ium [di-μ-bromido-rubidium]], {(C4H11N2)[RbBr2]}n, contain singly-protonated piperazin-1-ium cations and unusual ABr6 (A = Cs or Rb) trigonal prisms. The prisms are linked into a distinctive `curtain wall' arrangement propagating in the (010) plane by face and edge sharing. In each case, a network of N—H⋯N, N—H⋯Br and N—H⋯(Br,Br) hydrogen bonds consolidates the structure.
Keywords: crystal structure; hybrid solid; caesium; rubidium; trigonal prism.
1. Chemical context
Oxide perovskites of generic formula ABO3, where A and B are metal ions, have been studied for decades because of their physical properties and structural variety (Tilley, 2016). The (highest-possible symmetry) for this familiar structure type is a cubic network (space group Pmm) of vertex-sharing, regular, BO6 octahedra encapsulating the A cations in 12-coordinate cavities bounded by eight octahedra, but lower symmetry structures are very common (Woodward, 1997). More recently, `hybrid' RMX3 perovskites containing organic cations and MX3 (M = Pb, Sn…; X = halide ion) octahedral networks have attracted intense interest because of their remarkable photophysical properties (Xu et al., 2019; Stylianakis et al., 2019; Zuo et al., 2019). A number of different organic cations occur in these hybrid structures, one of which is the doubly protonated C4H12N22+ piperizinium (or piperazin-1,4-diium) ion as found in the C4H12N2·ACl3·H2O (A = K, Rb, Cs) family (Paton & Harrison, 2010) and C4H12N2·NaI3 (Chen et al., 2018).
As an extension of these studies, we now describe the title hybrid compounds, containing the singly protonated C4H11N2+ piperazin-1-ium cation, which have a generic formula of RMX2 and totally different crystal structures to RMX3 hybrid perovskites.
2. Structural commentary
Compounds (I) and (II) are isostructural and crystallize in the orthorhombic Pbcm. The smaller unit-cell volume (by 5.3%) of (II) presumably reflects the smaller ionic radius (Shannon, 1976) of the Rb+ cation (r = 1.66 Å) compared to Cs+ (r = 1.81 Å). This structure description will focus on (I) and note significant differences for (II) where applicable.
The consists of two methylene groups, an NH group and an NH2+ group; both nitrogen atoms and their attached H atoms lie on a (001) crystallographic mirror plan (at z = 1/4 for the asymmetric atoms). The structure is completed by a caesium atom [site symmetry m(001), Wyckoff site 4d] and two bromine atoms: Br1 [m(001); 4d] and Br2 (2[100]; 4c). The structure of (I) is shown in (Fig. 1).
of (I)The complete C4H11N2+ cation is generated by reflection to result in a typical (Brüning et al., 2009) chair conformation for the ring: N1 and N2 deviate from the mean plane of C1/C2/C1i/C2i [symmetry code: (i) x, y, − z] by 0.656 (5) and −0.682 (4) Å, respectively. The H atom of the neutral N2—H3N group has an equatorial orientation with respect to the ring.
The caesium is completed by crystal symmetry, resulting in a distinctive CsBr6 trigonal prism (Fig. 1): the prism has longitudinal (001) mirror symmetry, with the Br1 atoms and the metal atom lying on the mirror. The mean Cs—Br bond length based on four distinct Cs—Br bonds (Table 1) is 3.573 Å [mean Rb—Br bond length for (II) = 3.461 Å; Table 2]. These data may be compared with the shortest Cs—Br separation of 3.716 Å in CsBr (8-coordinate caesium chloride structure) and the shortest Rb—Br separation of 3.427 Å in RbBr (6-coordinate rocksalt structure).
in (I)
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In (I), the prism ends (Br1/Br2/Br2i and Br1iii/Br2ii/Br2iii; see Fig. 1 for symmetry codes) are parallel by symmetry and separated by 4.5787 (8) Å, i.e., the a unit-cell parameter, hence there is no twisting of the end faces and the Br⋯Br⋯Br angles vary from 56.65 (1)–61.68 (1)° [the equivalent prism-end separation for (II) is 4.4675 (13) Å]. The caesium cation in (I) is not quite equidistant from the prism-ends mentioned in the previous sentence, being displaced from them by 2.3177 (6) and 2.2605 (5) Å, respectively. The equivalent data for the Rb atom in (II) are 2.2581 (9) and 2.2091 (9) Å, respectively. The bond-valence sum (BVS) for Cs1 (in valence units) using the formalism of Brese & O'Keeffe (1991) in (I) is 1.12 and the equivalent value for Rb1 in (II) is 0.95 (expected value in both cases = 1.00). This indicates that the bond valences of these cations are satisfied without notable underbonding or overbonding in these unusual coordination environments.
It may be finally noted that the bromide ions have very different coordination environments: Br1 bridges to two metal atoms [Cs1—Br1—Cs1iv = 78.17 (2) in (I); Rb1—Br1—Rb1iv = 79.21 (3)° in (II); symmetry code: (iv) x + 1, y, z] whereas Br2 has an unusual distorted square planar BrCs4 arrangement: the cis Cs—Br2—Cs bond angles in (I) vary between 80.367 (13) and 100.865 (16)°; the five atoms are exactly co-planar by symmetry.
3. Supramolecular features
The extended structure of (I) is consolidated by hydrogen bonds (Fig. 2, Table 3. The N1—H1N⋯N2 bond from the protonated NH2+ group to the unprotonated N atom in an adjacent molecule links the organic cations into [100] chains with adjacent cations related by translation symmetry and the N1—H2N⋯Br1 bond connects the organic cation to the inorganic network. The neutral N2—H3N moiety forms a bifurcated N—H⋯(Br2,Br2) hydrogen bond; the H⋯Br contacts are long at 3.07 (3) Å but given their apparent role in bridging the (010) CsBr2 layers we judge them to be structurally significant. The hydrogen-bonding scheme for (II) (Table 4) is almost identical to that in (I).
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The CsBr6 prisms in (I) are linked into a striking (010) `curtain wall' arrangement (Fig. 3) by face sharing in the [100] direction and edge sharing (via a pair of Br2 atoms) in the [001] direction; the Cs⋯Cs separation through the prism-ends is 4.5787 (8) Å (by the symmetry operations x + 1, y, z and x − 1, y, z) and the separation between metal ions in adjacent columns is 5.42014 (12) Å (symmetry operations x, − y, −z and x, − y, + z). The equivalent data for the Rb atoms in (II) are 4.4675 (13) and 5.2338 (14) Å, respectively. When viewed down [100], the prisms adopt a `saw-tooth' arrangement with respect to the [010] direction, with alternating columns of prisms pointing `up' and `down' (Fig. 4).
4. Database survey
So far as we are aware, the RABr2 topology of the title compounds is a novel one. A search of the Cambridge Structural Database (CSD, version 5.40, last update 19 May 2019; Groom et al., 2016) for the mono-protonated C4H11N2+ cation returned 55 crystal structures but none of them bear a close resemblance to the title compound. As noted in the chemical context section, the doubly protonated C4H12N22+ species occurs in several hybrid RMX3 perovskites including C4H12N2·ACl3·H2O with A = K (CSD refcode GUYMIX), Rb (GUYMOD) and Cs (GUYMUJ) (Paton & Harrison, 2010) and C4H12N2·NaI3 (MEXMAG; Chen et al., 2018).
5. Synthesis and crystallization
Compound (I) was prepared by adding 0.213 g (1.0 mmol) of CsBr and 0.086 g (1.0 mmol) of piperazine to 11.0 ml (1.1 mmol) of a 0.1 M HBr solution in a Petri dish to result in a clear solution. Colourless rods of (I) formed after a few days as the water evaporated. Colourless rods of (II) were prepared in the same way, with 0.165 g (1.0 mmol) of RbBr replacing the CsBr. The quantity of acid appears to be critical to the syntheses of (I) and (II): smaller amounts lead to recrystallized CsBr and RbBr and larger amounts lead to different structures containing doubly protonated C4H12N22+ cations.
6. Refinement
Crystal data, data collection and structure . The N-bonded H atoms were located in difference-Fourier maps: for (I), their positions were freely refined, for (II) they were refined as riding atoms in their as-found relative positions. The C-bound H atoms were placed geometrically (C—H = 0.99 Å) and refined as riding atoms for both structures. The constraint Uiso(H) = 1.2Ueq(carrier) was applied in all cases. The displacement ellipsoids for the C and N atoms in (II) refined to somewhat elongated shapes suggestive of positional disorder of the C4H11N2+ cations but attempts to model this did not lead to a significant improvement in fit.
details are summarized in Table 5
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Supporting information
https://doi.org/10.1107/S2056989019010375/su5506sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019010375/su5506Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019010375/su5506IIsup3.hkl
For both structures, data collection: CrystalClear (Rigaku, 2013); cell
CrystalClear (Rigaku, 2013); data reduction: CrystalClear (Rigaku, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and ATOMS (Shape Software, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).(C4H11N2)[CsBr2] | Dx = 2.573 Mg m−3 |
Mr = 379.88 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbcm | Cell parameters from 3076 reflections |
a = 4.5787 (8) Å | θ = 2.8–27.5° |
b = 23.325 (5) Å | µ = 11.86 mm−1 |
c = 9.1828 (17) Å | T = 93 K |
V = 980.7 (3) Å3 | Rod, colourless |
Z = 4 | 0.20 × 0.05 × 0.05 mm |
F(000) = 696 |
Rigaku Pilatus 200K CCD diffractometer | 917 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.056 |
ω scans | θmax = 25.4°, θmin = 3.5° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2013) | h = −5→5 |
Tmin = 0.639, Tmax = 1.000 | k = −28→28 |
11592 measured reflections | l = −11→11 |
959 independent reflections |
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)] = 0.021 | w = 1/[σ2(Fo2) + (0.0387P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.055 | (Δ/σ)max = 0.001 |
S = 1.10 | Δρmax = 1.34 e Å−3 |
959 reflections | Δρmin = −0.96 e Å−3 |
55 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0010 (2) |
Primary atom site location: structure-invariant direct methods |
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 | 0.02411 (5) | 0.31176 (2) | 0.250000 | 0.01125 (13) | |
Br1 | 0.52127 (7) | 0.43259 (2) | 0.250000 | 0.01635 (15) | |
Br2 | 0.53501 (7) | 0.250000 | 0.000000 | 0.01654 (16) | |
C1 | −0.0049 (5) | 0.56445 (11) | 0.3834 (4) | 0.0205 (7) | |
H1A | 0.120469 | 0.560779 | 0.470727 | 0.025* | |
H1B | −0.158445 | 0.534633 | 0.388670 | 0.025* | |
C2 | −0.1448 (6) | 0.62308 (9) | 0.3811 (2) | 0.0209 (5) | |
H2A | −0.267978 | 0.628079 | 0.468749 | 0.025* | |
H2B | 0.008673 | 0.652975 | 0.382326 | 0.025* | |
N1 | 0.1740 (7) | 0.55578 (12) | 0.250000 | 0.0217 (7) | |
H1N | 0.336 (9) | 0.5788 (16) | 0.250000 | 0.026* | |
H2N | 0.251 (8) | 0.5231 (17) | 0.250000 | 0.026* | |
N2 | −0.3243 (7) | 0.62943 (11) | 0.250000 | 0.0186 (6) | |
H3N | −0.427 (7) | 0.6650 (19) | 0.250000 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cs1 | 0.01245 (18) | 0.00867 (18) | 0.01263 (18) | −0.00053 (6) | 0.000 | 0.000 |
Br1 | 0.0165 (2) | 0.0071 (2) | 0.0255 (3) | 0.00065 (10) | 0.000 | 0.000 |
Br2 | 0.0141 (2) | 0.0171 (2) | 0.0185 (2) | 0.000 | 0.000 | −0.00791 (13) |
C1 | 0.0259 (16) | 0.0170 (17) | 0.0187 (19) | −0.0048 (8) | −0.0058 (9) | 0.0063 (10) |
C2 | 0.0238 (15) | 0.0173 (11) | 0.0216 (12) | −0.0030 (10) | 0.0029 (12) | −0.0062 (9) |
N1 | 0.0218 (19) | 0.0067 (14) | 0.0367 (16) | 0.0036 (12) | 0.000 | 0.000 |
N2 | 0.0182 (16) | 0.0104 (14) | 0.0272 (14) | 0.0037 (11) | 0.000 | 0.000 |
Cs1—Br2i | 3.5157 (5) | C1—H1A | 0.9900 |
Cs1—Br2ii | 3.5157 (4) | C1—H1B | 0.9900 |
Cs1—Br2iii | 3.5801 (5) | C2—N2 | 1.465 (3) |
Cs1—Br2 | 3.5801 (5) | C2—H2A | 0.9900 |
Cs1—Br1 | 3.6228 (6) | C2—H2B | 0.9900 |
Cs1—Br1i | 3.6392 (7) | N1—H1N | 0.92 (4) |
C1—N1 | 1.488 (4) | N1—H2N | 0.84 (4) |
C1—C2 | 1.510 (3) | N2—H3N | 0.95 (4) |
Br2i—Cs1—Br2ii | 81.534 (14) | N1—C1—C2 | 110.2 (2) |
Br2i—Cs1—Br2iii | 132.072 (12) | N1—C1—H1A | 109.6 |
Br2ii—Cs1—Br2iii | 80.366 (13) | C2—C1—H1A | 109.6 |
Br2i—Cs1—Br2 | 80.366 (12) | N1—C1—H1B | 109.6 |
Br2ii—Cs1—Br2 | 132.072 (12) | C2—C1—H1B | 109.6 |
Br2iii—Cs1—Br2 | 79.768 (14) | H1A—C1—H1B | 108.1 |
Br2i—Cs1—Br1 | 135.970 (7) | N2—C2—C1 | 110.0 (2) |
Br2ii—Cs1—Br1 | 135.970 (7) | N2—C2—H2A | 109.7 |
Br2iii—Cs1—Br1 | 84.402 (12) | C1—C2—H2A | 109.7 |
Br2—Cs1—Br1 | 84.401 (13) | N2—C2—H2B | 109.7 |
Br2i—Cs1—Br1i | 85.085 (12) | C1—C2—H2B | 109.7 |
Br2ii—Cs1—Br1i | 85.085 (13) | H2A—C2—H2B | 108.2 |
Br2iii—Cs1—Br1i | 136.466 (7) | C1—N1—C1iii | 110.9 (3) |
Br2—Cs1—Br1i | 136.466 (7) | C1—N1—H1N | 111.5 (11) |
Br1—Cs1—Br1i | 78.173 (18) | C1iii—N1—H1N | 111.5 (11) |
Cs1—Br1—Cs1iv | 78.173 (17) | C1—N1—H2N | 110.7 (13) |
Cs1iv—Br2—Cs1v | 100.865 (16) | C1iii—N1—H2N | 110.7 (13) |
Cs1iv—Br2—Cs1vi | 178.768 (8) | H1N—N1—H2N | 101 (3) |
Cs1v—Br2—Cs1vi | 80.367 (13) | C2iii—N2—C2 | 110.5 (3) |
Cs1iv—Br2—Cs1 | 80.366 (13) | C2iii—N2—H3N | 111.4 (10) |
Cs1v—Br2—Cs1 | 178.768 (8) | C2—N2—H3N | 111.4 (10) |
Cs1vi—Br2—Cs1 | 98.402 (15) | ||
N1—C1—C2—N2 | 57.7 (3) | C1—C2—N2—C2iii | −60.2 (3) |
C2—C1—N1—C1iii | −55.9 (3) |
Symmetry codes: (i) x−1, y, z; (ii) x−1, y, −z+1/2; (iii) x, y, −z+1/2; (iv) x+1, y, z; (v) x+1, −y+1/2, −z; (vi) x, −y+1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2iv | 0.92 (4) | 1.95 (4) | 2.868 (4) | 179 (3) |
N1—H2N···Br1 | 0.84 (4) | 2.45 (4) | 3.284 (3) | 174 (4) |
N2—H3N···Br2vii | 0.95 (4) | 3.07 (3) | 3.756 (2) | 130 (1) |
N2—H3N···Br2viii | 0.95 (4) | 3.07 (3) | 3.756 (2) | 130 (1) |
Symmetry codes: (iv) x+1, y, z; (vii) −x, −y+1, z+1/2; (viii) −x, −y+1, −z. |
(C4H11N2)[RbBr2] | Dx = 2.378 Mg m−3 |
Mr = 332.44 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbcm | Cell parameters from 1939 reflections |
a = 4.4675 (13) Å | θ = 2.9–27.5° |
b = 23.036 (7) Å | µ = 13.87 mm−1 |
c = 9.021 (3) Å | T = 93 K |
V = 928.4 (5) Å3 | Rod, colourless |
Z = 4 | 0.20 × 0.05 × 0.05 mm |
F(000) = 624 |
Rigaku Pilatus 200K CCD diffractometer | 771 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.086 |
ω scans | θmax = 25.3°, θmin = 2.9° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2013) | h = −5→5 |
Tmin = 0.597, Tmax = 1.000 | k = −27→25 |
11351 measured reflections | l = −10→10 |
908 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.023 | H-atom parameters constrained |
wR(F2) = 0.057 | w = 1/[σ2(Fo2) + (0.036P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
908 reflections | Δρmax = 0.74 e Å−3 |
48 parameters | Δρmin = −0.47 e Å−3 |
0 restraints |
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 | 0.02991 (9) | 0.30763 (2) | 0.250000 | 0.01411 (14) | |
Br1 | 0.52893 (9) | 0.42482 (2) | 0.250000 | 0.01792 (15) | |
Br2 | 0.53856 (10) | 0.250000 | 0.000000 | 0.02184 (16) | |
C1 | 0.0103 (9) | 0.56211 (19) | 0.3859 (5) | 0.0433 (13) | |
H1A | −0.150237 | 0.532584 | 0.391919 | 0.052* | |
H1B | 0.138441 | 0.558250 | 0.474894 | 0.052* | |
C2 | −0.1233 (9) | 0.62095 (17) | 0.3812 (4) | 0.0371 (10) | |
H2A | −0.247265 | 0.627233 | 0.470786 | 0.045* | |
H2B | 0.037661 | 0.650481 | 0.380468 | 0.045* | |
N1 | 0.1926 (10) | 0.55235 (19) | 0.250000 | 0.0490 (17) | |
H1N | 0.264148 | 0.515363 | 0.250000 | 0.059* | |
H2N | 0.351831 | 0.577000 | 0.250001 | 0.059* | |
N2 | −0.3067 (9) | 0.62729 (18) | 0.250000 | 0.0358 (12) | |
H3N | −0.409568 | 0.662828 | 0.250000 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rb1 | 0.0154 (2) | 0.0163 (3) | 0.0106 (2) | −0.00032 (16) | 0.000 | 0.000 |
Br1 | 0.0178 (3) | 0.0145 (3) | 0.0215 (3) | 0.00069 (17) | 0.000 | 0.000 |
Br2 | 0.0161 (3) | 0.0330 (3) | 0.0165 (3) | 0.000 | 0.000 | −0.01151 (19) |
C1 | 0.050 (3) | 0.045 (3) | 0.035 (2) | −0.027 (2) | −0.031 (2) | 0.024 (2) |
C2 | 0.047 (2) | 0.038 (2) | 0.027 (2) | −0.024 (2) | 0.020 (2) | −0.0183 (18) |
N1 | 0.018 (2) | 0.010 (2) | 0.118 (6) | 0.0018 (18) | 0.000 | 0.000 |
N2 | 0.020 (2) | 0.018 (2) | 0.070 (4) | 0.0028 (18) | 0.000 | 0.000 |
Rb1—Br2i | 3.4157 (8) | C1—H1A | 0.9900 |
Rb1—Br2ii | 3.4157 (8) | C1—H1B | 0.9900 |
Rb1—Br2 | 3.4659 (8) | C2—N2 | 1.447 (5) |
Rb1—Br2iii | 3.4659 (8) | C2—H2A | 0.9900 |
Rb1—Br1 | 3.5013 (9) | C2—H2B | 0.9900 |
Rb1—Br1i | 3.5068 (9) | N1—H1N | 0.9100 |
C1—C2 | 1.482 (6) | N1—H2N | 0.9100 |
C1—N1 | 1.489 (5) | N2—H3N | 0.9389 |
Br2i—Rb1—Br2ii | 82.64 (3) | C2—C1—N1 | 109.6 (3) |
Br2i—Rb1—Br2 | 80.96 (2) | C2—C1—H1A | 109.8 |
Br2ii—Rb1—Br2 | 134.60 (2) | N1—C1—H1A | 109.8 |
Br2i—Rb1—Br2iii | 134.60 (2) | C2—C1—H1B | 109.8 |
Br2ii—Rb1—Br2iii | 80.96 (2) | N1—C1—H1B | 109.8 |
Br2—Rb1—Br2iii | 81.19 (3) | H1A—C1—H1B | 108.2 |
Br2i—Rb1—Br1 | 135.144 (12) | N2—C2—C1 | 110.1 (3) |
Br2ii—Rb1—Br1 | 135.143 (12) | N2—C2—H2A | 109.6 |
Br2—Rb1—Br1 | 82.98 (2) | C1—C2—H2A | 109.6 |
Br2iii—Rb1—Br1 | 82.984 (19) | N2—C2—H2B | 109.6 |
Br2i—Rb1—Br1i | 83.63 (2) | C1—C2—H2B | 109.6 |
Br2ii—Rb1—Br1i | 83.63 (2) | H2A—C2—H2B | 108.2 |
Br2—Rb1—Br1i | 135.505 (12) | C1—N1—C1iii | 110.8 (4) |
Br2iii—Rb1—Br1i | 135.505 (13) | C1—N1—H1N | 109.5 |
Br1—Rb1—Br1i | 79.21 (3) | C1iii—N1—H1N | 109.5 |
Rb1—Br1—Rb1iv | 79.21 (3) | C1—N1—H2N | 109.5 |
Rb1iv—Br2—Rb1v | 100.02 (3) | C1iii—N1—H2N | 109.5 |
Rb1iv—Br2—Rb1vi | 179.021 (14) | H1N—N1—H2N | 108.1 |
Rb1v—Br2—Rb1vi | 80.96 (2) | C2—N2—C2iii | 109.8 (4) |
Rb1iv—Br2—Rb1 | 80.96 (2) | C2—N2—H3N | 111.4 |
Rb1v—Br2—Rb1 | 179.021 (14) | C2iii—N2—H3N | 111.4 |
Rb1vi—Br2—Rb1 | 98.06 (3) | ||
N1—C1—C2—N2 | 58.4 (4) | C1—C2—N2—C2iii | −62.1 (5) |
C2—C1—N1—C1iii | −55.3 (5) |
Symmetry codes: (i) x−1, y, z; (ii) x−1, y, −z+1/2; (iii) x, y, −z+1/2; (iv) x+1, y, z; (v) x+1, −y+1/2, −z; (vi) x, −y+1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2N···N2iv | 0.91 | 1.92 | 2.825 (6) | 179 |
N1—H1N···Br1 | 0.91 | 2.40 | 3.300 (4) | 171 |
N2—H3N···Br2vii | 0.94 | 3.07 | 3.762 (3) | 131 |
N2—H3N···Br2viii | 0.94 | 3.07 | 3.762 (3) | 131 |
Symmetry codes: (iv) x+1, y, z; (vii) −x, −y+1, z+1/2; (viii) −x, −y+1, −z. |
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