research papers
Metal-free enantiomorphic perovskite [dabcoH2]2+[H3O]+Br−3 and its one-dimensional polar polymorph
aNational Centre for Nuclear Research, Andrzeja Sołtana 7, Otwock, Świerk 05-400, Poland, bInstitute of Physics; Department of Structure Analysis, Academy of Sciences of the Czech Republic, Cukrovarnicka 10, Prague 6 16253, Czech Republic, and cFaculty of Chemistry, Adam Mickiewicz University in Poznań, Umultowska 89 b, Poznań 61-614, Poland
*Correspondence e-mail: armand.budzianowski@ncbj.gov.pl, katran@amu.edu.pl
The structure and stoichiometry of a new metal-free and ammonium-free compound [dabcoH2]2+H3O+Br−3 (where [dabcoH2]2+ = 1,4-diazabicyclo[2.2.2]octane dication) correspond to the general formula ABX3 characteristic of perovskites. In enantiomorphic trigonal polymorph α of [dabcoH2]2+H3O+Br−3, the corner-sharing [H3O]Br6 octahedra combine into a 3D framework embedding [dabcoH2]2+ dications in pseudo-cubic cages. In the more dense polymorph β, the face-sharing [H3O]Br6 octahedra form 1D polyanionic columns separated by [dabcoH2]2+ dications. These different topologies correlate with different crystal fields around the cations and their different disorder types: orientational disorders of [dabcoH2]2+ dications and H3O+ cations in polymorph α and positional disorder of [H3O]+ cations in polymorph β. The orientational disorder increases the lengths of OH⋯Br hydrogen bonds in polymorph α, but NH⋯Br distances of ordered dabcoH2 dications are longer in polymorph β. The presence of polar [H3O]+ cations in [dabcoH2]2+H3O+Br−3 polymorphs offers additional polarizability of the centres compared with analogous metal-free [dabcoH2]2+[NH4]+Br−3 perovskite.
Keywords: metal-free perovskite; polymorphism; disorder; ionic crystals.
1. Introduction
Perovskites constitute a wide group of crystalline materials with the characteristic formula ABX3 and structures built from corner-sharing BX6 octahedra and A cations in the cubic voids. The importance of perovskites is connected with their properties such as ferroelectric and relaxor properties (Strukov & Levanyuk, 1998), and numerous applications, for example as digital memories (Scott, 2000), sensors or photovoltaics (Szafrański & Katrusiak, 2017, 2016). The mineral CaTiO3, discovered in 1839 by Gustav Rose in the Ural mountains was named perovskite, after mineralogist Lev Alekseyevich von Perovski. Later, the name perovskite was used to describe a wider group of minerals with analogous structures and the general formula ABO3, then extended to ABX3, where X was a halide anion. Finally, organic–inorganic hybrid perovskites were designed, with large complex unit cells, and which still correspond to the networks built of corner-sharing octahedra or the octahedra corners connected through organic linkers, sometimes of considerable size (Boström & Goodwin, 2021). Also, 2D and 1D perovskite analogues differentiated in the composition (e.g. ABO4, CsPb2Br5), ionicity and topologies (e.g. corner/edge/face-sharing octahedra) are also often described as perovskite analogues. Properties and applications of perovskite materials are often connected with their phase transitions and symmetry changes at phase transitions, involving ionic displacements or tilts of the BX6 octahedra (Glazer, 1972; Howard & Carpenter, 2010; Carpenter & Howard, 2009). They can induce spontaneous polarization and ferroelectricity of crystals, such as for example in BaTiO3 and PbTiO3 (Megaw, 1946, 1952; Shirane et al., 1950; Shirane & Takeda, 1952; Shirane & Pepinsky, 1953; Nelmes & Kuhs, 1985). In some structures, the symmetry and properties are connected with the disorder of the ions. In recent years, metal-free perovskites are sought for their applications in sensors, detectors, light-emitting diodes (LEDs), photovoltaics and, generally, optoelectronics (Song et al., 2020; 2021a; 2021b). The main advantages of organic and hybrid organic–inorganic substitutes of ceramic perovskites are their reduced toxicity, owing to the absence of heavy metals, lower cost of production and processing (formation of thin layers, also in the flexible form) and their easier environment-friendly disposal and recycling. Owing to weaker cohesion forces, bio-friendly metal-free perovskites can exhibit increased sensitivity to external stimuli (Cui et al., 2021).
Recently, metal-free perovskites involving piperazine, dabco and ammonium cations (NH4+) were discovered (Bremner et al., 2002), and later their analogues [dabcoH]2+[NH4]+Br−3 and [MdabcoH]2+[NH4]+Br−3 (Mdabco stands for N-methylated dabco, i.e. 1,4-diazabicyclo[2.2.2]octane, C6H12N2) were thoroughly investigated (Ye et al., 2018; Morita et al., 2020). These are considered environment-friendly and cheap alternatives to mineral perovskites (Li & Ji, 2018; Gao et al., 2021). At present, we report another metal-free perovskite compound [dabcoH2]2+[H3O]+Br−3 obtained in the form of two polymorphs, α and β. Polymorph α has the structure of the analogous metal-free 3D perovskite [dabcoH2]2+[NH4]+Br−3, where the [H3O]Br6 octahedra share vertices (Ye et al., 2018). In the structure of polymorph β, [H3O]Br6 octahedra share faces in 1D columns (Bremner et al., 2002; Ye et al., 2018). Both polymorphs α and β of [dabcoH2]2+[H3O]+Br−3 are disordered, but in a different manner. It is characteristic that disorder effects are essential for the properties of many types of crystals, including perovskites and dabco monosalts, where the disorder is connected to the ferroelectric and relaxor properties (Szafrański & Katrusiak, 2004). Our present study is primarily aimed at identifying the structural features of the [dabcoH2]2+H3O+Br−3 polymorphs.
2. Experimental
Single crystals of [dabcoH2]2+[H3O]+Br−3, where [dabcoH2]2+ of the formula [C6H14N2]2+ stands for diprotonated 1,4-diazabicyclo[2.2.2]octane, were found as a small fraction of crystallizations aimed at growing relaxor ferroelectric dabcoH+ bromide (dabcoHBr) from the aqueous solution of dabco and HBr in a 1:1 equimolar ratio (Budzianowski & Katrusiak, 2006; Szafrański & Katrusiak, 2004). The X-ray diffraction studies of selected single crystals revealed the presence of a tri-component salt [dabcoH2]2+ hydronium tribromide, [dabcoH2]2+[H3O]+Br−3 (polymorph α). Later, this compound (polymorph β) was obtained close to 100% yield by cooling and slowly evaporating the aqueous solution of dabco with the hydrobromic acid at a 1:3 molar ratio (the initial crystallization of the equimolar dabco:HBr aqueous solution revealed polymorph α only). The single-crystal X-ray diffraction data (Table 1) were measured with a KUMA KM4-CCD diffractometer with a graphite-monochromated fine-focus Mo Kα tube and an Oxford Diffraction XCalibur R diffractometer with a fine-focus X-ray source from a Cu Kα tube and Ruby CCD detector; using the latest version of CrysAlis and CrysAlis PRO software (Rigaku OD, 2003, 2019a). The of polymorph α-[dabcoH2]2+[H3O]+Br−3 was partly solved by in ShelxS-97 (Sheldrick, 2008) and then JANA (Petříček et al., 2014) produced the model. Because of the disorder in the structure, we attempted structural refinements in the lower-symmetry space groups with ShelxL (Sheldrick, 2015; Barbour, 2020; Hübschle et al., 2011) and JANA (Petříček et al., 2014). Finally, we established that polymorph α-[dabcoH2]2+[H3O]+Br−3 crystallizes in the enantiomorphic trigonal P3221 (no indication of racemic was detected); the of its structure revealed disorder of the dabcoH2 dications in two orientations with nearly equal site-occupation factors of 0.53:0.47(2) (Table 1). Similar procedures were applied for solving and refining polymorph β-[dabcoH2]2+[H3O]+Br−3 in the trigonal P3c1, where positional disorder was found for two of three symmetry-independent H3O+ cations; they are disordered at different rates, each in two sites located on a threefold axis (Table 1). The structure of polymorph β approximates the structure with a 3× smaller and the symmetry of the P62c (cf. Table S1, Model 4 of the supporting information). The drawings of crystal structures were prepared with the programs Mercury (Macrae et al., 2020), POV-Ray (Barbour, 2020; Cason, 2004) and Vesta (Momma & Izumi, 2011). Selected structures were presented as autostereograms to facilitate their 3D perception (Katrusiak, 2001).
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The final crystal and structural data and experimental details for both polymorphs are summarized in https://www.ccdc.cam.ac.uk/structures/.
format in the Cambridge Crystallographic Database Centre as supplementary publications 2132130 and 2132131. They can be obtained free of charge from the Cambridge Structural Database at3. Discussion
The structure of polymorph α-[dabcoH2]2+[H3O]+Br−3, where the corner-sharing [H3O]Br6 octahedra are connected in a 3D framework occluding dabcoH2 dications (Fig. 1) clearly corresponds to the classical perovskite structures of the formula ABBr3 (Glazer, 1972; Megaw, 1946). Moreover, the symmetry of the polymorph α-[dabcoH2]2+[H3O]+Br−3 can be connected to the tilts of the [H3O]Br6 octahedra, consistent with Glazer's code a-a-a- for mineral perovskites. However, due to the non-spherical symmetry of H3O+ and [dabcoH2]2+ cations, the unit-cell volume is increased and the crystal symmetry of α-[dabcoH2]2+[H3O]+Br−3 is lowered to one of the enantiomeric space groups P3221 or P3121. The trigonal (Z = 6) of α-[dabcoH2]2+[H3O]+Br−3 comprises six prototypic perovskite pseudo-rhombohedral sub-units (Z′ = 1). An average prototypic pseudo-rhombohedral unit (pR) can be represented in terms of the trigonal (Tr) unit vectors according to the matrix (cf. Figs. 1 and 2):
where the vector indices refer to lattices Tr and pR. This transformation yields the idealized prototypic rhombohedral apR = 6.753 Å and αpR = 90.40°, close to the average of the true dimensions of the pseudo-rhombohedral cell: apR = 6.720, bpR = 6.784, cpR = 6.755 Å, αpR = 90.12°, βpR = 90.67° and αpR = 90.42° (cf. Figs. 1 and 2). The reverse transformation, from the prototypic rhombohedral sub-unit pR to the trigonal Tr, is
of the dimensionsIn ABX3 perovskite structures the interactions between cations (B) and anions (X) forming the 3D polyanionic framework [BX3]n are mainly electrostatic, like those between the framework and cations A contained in the cages. The shortest contacts in the structure of α-[dabcoH2]2+[H3O]+Br−3 confirm that the H3O+ cations are OH⋯Br− bonded into the 3D framework (Table 2). The shortest distances C—H⋯Br− are listed in Table 3. Also, the [dabcoH2]2+ cations are NH⋯Br− bonded to the linker anions, and these hydrogen bonds are somewhat shorter than those assigned to the framework. Such short contacts between the central cation and the atoms that form the cages are often present in perovskite structures and are considered a significant contribution to the stability and stiffness of the crystals (Ciupa-Litwa et al., 2020; Collings et al., 2016; Scatena et al., 2021; Adjogri & Meyer, 2020; Hou et al., 2020).
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All hydrogen donors in the structure of α-[dabcoH2]2+[H3O]+Br−3 are disordered. The hydronium H3O+ cations are orientationally disordered in two positions around the oxygen atom. The three hydrogen atoms are located in six half-occupied sites, consistent with the H3O+ dimensions (Lundren & Olovsson, 1976), as shown in Figs. 1, 2 and S1–S8 (Table S2). Each of the six half-occupied hydrogen sites is involved in one OH⋯Br− hydrogen bond [Figs. S3(a) and S3(b)]. Dication [dabcoH2]2+ is disordered in two orientations. The dication is involved in two OH⋯Br− hydrogen bonds. Each of these hydrogen bonds is split between two half-occupied hydrogen sites (Fig. 2). There are also short distances (∼2.8 to ∼3 Å) between Br ions and methylene hydrogen atoms. All hydrogen bonds listed in Table 2 can be classified as weak interactions, which are consistent with the considerable disorder of this structure. Like for the mineral perovskites, the symmetry of the crystal field around the cations plays a crucial role in their disorder.
In addition to the trigonal polymorph α-[dabcoH2]2+[H3O]+Br−3, we found another concomitant trigonal polymorph β-[dabcoH2]2+[H3O]+Br−3 (Table 1, Fig. 3). In its structure, the octahedra of hydronium cations and bromine anions ([H3O]Br6) are face-to-face arranged into columns and the [dabcoH2]2+ dications are located between these columns. However, in contrast to polymorph α, in polymorph β-[dabcoH2]2+[H3O]+Br−3 the [dabcoH2]2+ dications are ordered in general positions, while out of three independent hydronium cations [H3O]+ two are disordered. Each of these two [H3O]+ cations is disordered between a pair of sites along the same column along z, as illustrated in Fig. 4. The distance between the pairs of partially occupied oxygen sites (Table 1) is approximately equal to 1/4 of the unit-cell parameter c, i.e. about 2 Å. It is intriguing that the oxygen sites disordered along the threefold axes lie off the centre of the [H3O]+Br6 octahedra, while the centres of the octahedra are at the midpoints between the oxygen sites; the disordered [H3O]+ cation is also located off its octahedron centre (Fig. 4). These off-centre sites of the oxygen atoms result in O⋯Br distances (Table 3) significantly shorter compared with those in α-[dabcoH2]2+[H3O]+Br−3 (Table 2). The off-centre positional disorder of hydronium cations in β-[dabcoH2]2+[H3O]+Br−3 suggests that the OH⋯Br hydrogen bonds favour shorter distances than those between the bromine anion and the octahedron centre. The longer O⋯Br distances in α-[dabcoH2]2+[H3O]+Br−3 can be attributed to the orientational dynamic disorder of the H3O+ cation; its hydrogen atoms share the tetrahedrally located sites with the lone-electron pair: the tetrahedral sites do not match the octahedral locations of the bromine anions around, while the lone-electron pair does not contribute to the attraction of the hydrogen bonds, but it can be associated with some repulsion. On the other hand, the [dabcoH2]2+ dications in β-[dabcoH2]2+[H3O]+Br−3 are stabilized in the ordered position by their trigonal environment and form NH⋯Br− contacts that are significantly longer than those of disordered [dabcoH2]2+ dications in the pseudo-cubic crystal environment of α-[dabcoH2]2+[H3O]+Br−3 (Tables 2 and 3).
The crystallographic information about polymorphs explains the origin of different disorder types in their structure. The [dabcoH2]2+ dications can assume either the D3 twisted left or right propeller conformation, or the averaged D3h symmetry (Olejniczak et al., 2013). However, in polymorph α the dications are located in the pseudo-cubic cages, approximating the Oh symmetry. Consequently, the crystal environment of polymorph α does not stabilize one specific orientation of the cation. On the other hand, the trigonal symmetry of polymorph β results in the trigonal surrounding of the dications, matching their symmetry well. Indeed, the shape of pseudo-D3h-symmetric dications is consistent with the trigonal crystal environment. In polymorph α, the hydronium cations are located at the vertices of the pseudo-cubic cages, which does not favour any of their displacements. In polymorph β, the [H3O]+ cations are located in the channel-like surrounding of the threefold axes, which does not appear to strongly favour any site along z and results in the disorder of the cations. Interestingly, the structure of polymorph β approximates the higher symmetry of P62c, with the 3× smaller (Figs. S9–S16, Tables S1 and S2). This high symmetry is broken by small tilts of the dications and displacements of the Br anions, as well as by the differences between the hydronium cations, ordered and disordered to different extents (Table 1), as shown in the structure projections in Fig. 4.
4. Conclusions
Polymorphs of [dabcoH2]2+[H3O]+Br−3 illustrate the universality of perovskite structures and their characteristic features. The general formula ABX3 of perovskites, initially associated with minerals and ionic crystals, can clearly be extended to various hybrid organic–inorganic compounds, where organic central A cations interact with (in)organic X linkers, binding the B metal centres in the systems with much weaker cohesion forces, such as hydrogen bonds and electrostatic interactions between molecular ions. Even the metal-free compounds still display the characteristic structural properties of perovskites, controlled by the tilts of BX6 octahedra and disorder of the cations: the size and orientation of the molecular ions are additional factors responsible for the crystal symmetry and macroscopic properties of the hybrid and metal-free perovskites. The structures of both polymorphs of [dabcoH2]2+[H3O]+Br−3 are disordered under normal conditions, which is an indication of possible temperature and pressure-induced phase transitions of properties. Both orientational and positional disorder are present and they interplay with the crystal field around the cations and their hydrogen bond capabilities. Polymorph α-[dabcoH2]2+[H3O]+Br−3, like its close analogue [dabcoH2]2+[NH4]+Br−3, is one of very few enantiomorphic and polar perovskites reported so far. With the exception of C4H14N2RbCl3 (Paton & Harrison, 2010), the previously reported enantiomorphic perovskites employed chiral cations, for example in (R)-, (S)-3-(fluoropyrrolidinium)MnBr3 and in (R)-, (S)-N,N-dimethyl-3-fluoropyrrolidinium CdCl3 (Gao et al., 2020; Peng et al., 2021), where the enantiomorphic form of the crystal was permanently connected with the chiral cation used for the synthesis. To our knowledge, the polymorphs [dabcoH2]2+[NH4]+Br−3 and α-[dabcoH2]2+[H3O]+Br−3 are the first metal-free enantiomorphic and polar 3D perovskite structures where no permanent chiral cations are present and therefore this structure can be switched between two enantiomorphs. The structure of polymorph β-[dabcoH2]2+[H3O]+Br−3 is polar, which can also potentially result in ferroelectric properties. Thus, in both polymorphs, the substitution of the non-polar [NH4]+ cation with the polar [H3O]+ cation can result in increased polarizability of the system and advantageous switchable properties desired for practical applications in optoelectronic devices.
5. Related literature
The following references are cited in the supporting information: Rigaku OD (2019b, 2020, 2021); Clark & Reid (1995); Laetsch & Downs (2006).
Supporting information
https://doi.org/10.1107/S2052252522006406/ct5016sup1.cif
contains datablocks dhbr1af_41001, dabco1_h168b6_abs2. DOI:Supporting figures and tables. DOI: https://doi.org/10.1107/S2052252522006406/ct5016sup2.pdf
Data collection: CrysAlis Version 1.171.13 beta (release 14.11.2003 CrysAlis171 VC++) for dhbr1af_41001; CrysAlis PRO 1.171.39.25a (Rigaku OD, 2015) for dabco1_h168b6_abs2. For both structures, cell
CrysAlis PRO 1.171.40.57a (Rigaku OD, 2019); data reduction: CrysAlis PRO 1.171.40.57a (Rigaku OD, 2019). Program(s) used to solve structure: SHELXS2013/1 (Sheldrick, 1990) JANA2006 for dhbr1af_41001; SHELXL2018/1 (Sheldrick, 2018) for dabco1_h168b6_abs2. Program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2016) JANA2006 for dhbr1af_41001; SHELXL2016/6 (Sheldrick, 2016) for dabco1_h168b6_abs2. Molecular graphics: X-SEED (Barbour, 2001) ShelXle (Hubschle et al., 2011) VESTA ( Momma & Izumi, 2011) for dhbr1af_41001; X-SEED (Barbour, 2020) ShelXle (Hubschle et al., 2011) Persistence of Vision Pty. Ltd. (2004). for dabco1_h168b6_abs2.C6H14N2·3(Br)·H3O | Dx = 2.011 Mg m−3 |
Mr = 372.94 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P3221 | Cell parameters from 3200 reflections |
a = 9.5838 (3) Å | θ = 3.0–25.3° |
c = 23.2270 (8) Å | µ = 9.79 mm−1 |
V = 1847.56 (13) Å3 | T = 296 K |
Z = 6 | Block, clear colourless |
F(000) = 1080 | 0.10 × 0.10 × 0.10 mm |
Xcalibur, Sapphire2, large Be window diffractometer | 3159 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 2323 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 8.1929 pixels mm-1 | θmax = 29.3°, θmin = 2.5° |
Absorption correction: analytical CrysAlisPro 1.171.40.57a (Rigaku Oxford Diffraction, 2019) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. | h = −13→12 |
Tmin = 0.956, Tmax = 0.985 | k = −9→12 |
14765 measured reflections | l = −31→30 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F > 3σ(F)] = 0.042 | w = 1/[σ2(Fo2) + (0.020P)2 + 0.7694P] where P = (Fo2 + 2Fc2)/3 |
wR(F) = 0.074 | (Δ/σ)max = 0.001 |
S = 1.08 | Δρmax = 0.55 e Å−3 |
3159 reflections | Δρmin = −0.61 e Å−3 |
201 parameters | Absolute structure: Flack x determined using 737 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
84 restraints | Absolute structure parameter: 0.005 (15) |
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 | Occ. (<1) | |
Br1A | 0.14646 (8) | 0.47635 (9) | 0.41669 (3) | 0.04436 (19) | |
Br2A | 0.03007 (9) | 0.20114 (9) | 0.09569 (3) | 0.0434 (2) | |
Br3A | 0.64491 (9) | 0.53260 (9) | 0.40619 (3) | 0.0431 (2) | |
O2W | 1.000000 | 0.6615 (7) | 0.333333 | 0.069 (3) | |
H21W | 0.961 (10) | 0.573 (4) | 0.318 (3) | 0.083* | 0.5 |
H22W | 0.953 (5) | 0.704 (5) | 0.319 (2) | 0.083* | 0.5 |
H23W | 1.092 (3) | 0.715 (8) | 0.321 (3) | 0.083* | 0.5 |
O1W | 0.3328 (7) | 0.3328 (7) | 0.500000 | 0.072 (3) | |
H11W | 0.398 (6) | 0.404 (4) | 0.5211 (18) | 0.086* | 0.5 |
H12W | 0.313 (5) | 0.376 (5) | 0.4734 (17) | 0.086* | 0.5 |
H13W | 0.250 (3) | 0.280 (7) | 0.5184 (19) | 0.086* | 0.5 |
N1A | 0.2147 (19) | 0.292 (2) | 0.2188 (7) | 0.047 (4) | 0.54 (2) |
H1A | 0.120326 | 0.249251 | 0.193511 | 0.056* | 0.54 (2) |
N2A | 0.4474 (19) | 0.4055 (19) | 0.2864 (7) | 0.041 (4) | 0.54 (2) |
H2A | 0.540795 | 0.449120 | 0.312218 | 0.050* | 0.54 (2) |
C1A | 0.1656 (19) | 0.213 (2) | 0.2777 (11) | 0.060 (7) | 0.54 (2) |
H11A | 0.097958 | 0.247409 | 0.296999 | 0.072* | 0.54 (2) |
H12A | 0.104691 | 0.096914 | 0.273575 | 0.072* | 0.54 (2) |
C2A | 0.315 (3) | 0.262 (3) | 0.3126 (7) | 0.056 (5) | 0.54 (2) |
H21A | 0.298666 | 0.284010 | 0.351993 | 0.067* | 0.54 (2) |
H22A | 0.339590 | 0.174943 | 0.313010 | 0.067* | 0.54 (2) |
C3A | 0.339 (3) | 0.258 (3) | 0.1933 (7) | 0.069 (7) | 0.54 (2) |
H31A | 0.359083 | 0.290642 | 0.153211 | 0.083* | 0.54 (2) |
H32A | 0.305404 | 0.144716 | 0.196076 | 0.083* | 0.54 (2) |
C4A | 0.4919 (19) | 0.361 (2) | 0.2301 (11) | 0.053 (6) | 0.54 (2) |
H41A | 0.546263 | 0.300017 | 0.237262 | 0.063* | 0.54 (2) |
H42A | 0.565359 | 0.457734 | 0.209188 | 0.063* | 0.54 (2) |
C5A | 0.289 (3) | 0.475 (2) | 0.2254 (12) | 0.065 (9) | 0.54 (2) |
H51A | 0.347941 | 0.529602 | 0.190892 | 0.077* | 0.54 (2) |
H51B | 0.204493 | 0.501672 | 0.231345 | 0.077* | 0.54 (2) |
C6A | 0.401 (4) | 0.529 (3) | 0.2769 (13) | 0.045 (7) | 0.54 (2) |
H61A | 0.496260 | 0.632526 | 0.269325 | 0.054* | 0.54 (2) |
H62A | 0.347565 | 0.538912 | 0.310694 | 0.054* | 0.54 (2) |
N1B | 0.290 (2) | 0.3273 (18) | 0.2004 (6) | 0.036 (4) | 0.46 (2) |
H1B | 0.248456 | 0.304912 | 0.160888 | 0.043* | 0.46 (2) |
N2B | 0.386 (2) | 0.383 (2) | 0.3020 (7) | 0.032 (4) | 0.46 (2) |
H2B | 0.425369 | 0.405904 | 0.341768 | 0.039* | 0.46 (2) |
C1B | 0.177 (2) | 0.188 (2) | 0.2390 (10) | 0.046 (6) | 0.46 (2) |
H11B | 0.184309 | 0.093376 | 0.230003 | 0.056* | 0.46 (2) |
H12B | 0.066254 | 0.162580 | 0.232698 | 0.056* | 0.46 (2) |
C2B | 0.224 (3) | 0.237 (3) | 0.3014 (9) | 0.044 (6) | 0.46 (2) |
H21B | 0.146575 | 0.259385 | 0.319827 | 0.053* | 0.46 (2) |
H22B | 0.226435 | 0.150516 | 0.322256 | 0.053* | 0.46 (2) |
C3B | 0.450 (3) | 0.341 (3) | 0.2019 (8) | 0.048 (6) | 0.46 (2) |
H31B | 0.527807 | 0.438403 | 0.182104 | 0.058* | 0.46 (2) |
H32B | 0.446256 | 0.249201 | 0.183365 | 0.058* | 0.46 (2) |
C4B | 0.496 (2) | 0.349 (3) | 0.2669 (9) | 0.041 (5) | 0.46 (2) |
H41B | 0.485626 | 0.246908 | 0.278565 | 0.049* | 0.46 (2) |
H42B | 0.606662 | 0.432909 | 0.272761 | 0.049* | 0.46 (2) |
C5B | 0.287 (2) | 0.477 (2) | 0.2227 (10) | 0.026 (5) | 0.46 (2) |
H1 | 0.338318 | 0.564642 | 0.195196 | 0.031* | 0.46 (2) |
H52B | 0.177153 | 0.453127 | 0.228704 | 0.031* | 0.46 (2) |
C6B | 0.379 (4) | 0.523 (3) | 0.2789 (11) | 0.031 (6) | 0.46 (2) |
H61B | 0.487004 | 0.611957 | 0.272742 | 0.037* | 0.46 (2) |
H62B | 0.325371 | 0.557011 | 0.306348 | 0.037* | 0.46 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1A | 0.0381 (4) | 0.0417 (4) | 0.0497 (4) | 0.0173 (4) | −0.0012 (3) | 0.0058 (3) |
Br2A | 0.0477 (5) | 0.0446 (4) | 0.0371 (4) | 0.0225 (4) | −0.0084 (3) | −0.0032 (3) |
Br3A | 0.0438 (5) | 0.0476 (4) | 0.0374 (4) | 0.0224 (4) | −0.0079 (4) | −0.0047 (3) |
O2W | 0.064 (6) | 0.061 (4) | 0.083 (7) | 0.032 (3) | −0.002 (5) | −0.001 (2) |
O1W | 0.072 (5) | 0.072 (5) | 0.072 (6) | 0.037 (5) | −0.007 (2) | 0.007 (2) |
N1A | 0.032 (8) | 0.065 (11) | 0.050 (9) | 0.029 (9) | −0.023 (7) | −0.014 (9) |
N2A | 0.036 (9) | 0.043 (8) | 0.044 (10) | 0.019 (7) | −0.014 (7) | −0.006 (7) |
C1A | 0.031 (9) | 0.037 (10) | 0.091 (18) | 0.001 (8) | 0.021 (10) | 0.021 (14) |
C2A | 0.079 (16) | 0.044 (10) | 0.042 (9) | 0.028 (12) | −0.003 (8) | 0.010 (8) |
C3A | 0.088 (18) | 0.112 (19) | 0.048 (10) | 0.080 (16) | −0.017 (9) | −0.033 (9) |
C4A | 0.031 (8) | 0.042 (11) | 0.089 (17) | 0.021 (8) | 0.022 (10) | −0.004 (14) |
C5A | 0.08 (2) | 0.054 (13) | 0.08 (2) | 0.053 (15) | −0.005 (14) | 0.019 (12) |
C6A | 0.036 (12) | 0.023 (10) | 0.072 (17) | 0.011 (9) | 0.017 (9) | −0.001 (9) |
N1B | 0.037 (9) | 0.032 (8) | 0.023 (7) | 0.006 (8) | −0.008 (6) | 0.002 (6) |
N2B | 0.037 (10) | 0.044 (11) | 0.026 (8) | 0.028 (10) | −0.008 (7) | −0.009 (7) |
C1B | 0.035 (9) | 0.031 (9) | 0.055 (14) | 0.003 (8) | −0.014 (9) | 0.019 (9) |
C2B | 0.051 (15) | 0.038 (12) | 0.039 (11) | 0.019 (13) | 0.020 (11) | 0.018 (10) |
C3B | 0.052 (13) | 0.064 (16) | 0.034 (10) | 0.033 (13) | 0.012 (10) | −0.012 (12) |
C4B | 0.040 (10) | 0.047 (11) | 0.044 (12) | 0.029 (9) | −0.012 (8) | −0.021 (11) |
C5B | 0.009 (11) | 0.030 (10) | 0.025 (13) | −0.001 (9) | 0.000 (8) | 0.007 (9) |
C6B | 0.034 (14) | 0.034 (12) | 0.028 (13) | 0.020 (11) | −0.012 (10) | −0.004 (9) |
O2W—H21W | 0.8201 (14) | C4A—H42A | 0.9700 |
O2W—H22W | 0.8201 (14) | C5A—C6A | 1.519 (17) |
O2W—H23W | 0.8201 (15) | C5A—H51A | 0.9700 |
O2W—H21Wi | 0.8201 (14) | C5A—H51B | 0.9700 |
O2W—H22Wi | 0.8201 (14) | C6A—H61A | 0.9700 |
O2W—H23Wi | 0.8201 (14) | C6A—H62A | 0.9700 |
O1W—H11W | 0.8201 (14) | N1B—C3B | 1.47 (2) |
O1W—H12W | 0.8201 (14) | N1B—C1B | 1.519 (18) |
O1W—H13W | 0.8201 (15) | N1B—C5B | 1.537 (17) |
O1W—H11Wii | 0.8201 (14) | N1B—H1B | 0.9800 |
O1W—H12Wii | 0.8201 (14) | N2B—C6B | 1.477 (17) |
O1W—H13Wii | 0.8201 (14) | N2B—C2B | 1.48 (2) |
N1A—C3A | 1.507 (19) | N2B—C4B | 1.494 (19) |
N1A—C1A | 1.519 (19) | N2B—H2B | 0.9800 |
N1A—C5A | 1.537 (17) | C1B—C2B | 1.52 (2) |
N1A—H1A | 0.9800 | C1B—H11B | 0.9700 |
N2A—C2A | 1.461 (19) | C1B—H12B | 0.9700 |
N2A—C6A | 1.470 (16) | C2B—H21B | 0.9700 |
N2A—C4A | 1.504 (19) | C2B—H22B | 0.9700 |
N2A—H2A | 0.9800 | C3B—C4B | 1.56 (2) |
C1A—C2A | 1.502 (19) | C3B—H31B | 0.9700 |
C1A—H11A | 0.9700 | C3B—H32B | 0.9700 |
C1A—H12A | 0.9700 | C4B—H41B | 0.9700 |
C2A—H21A | 0.9700 | C4B—H42B | 0.9700 |
C2A—H22A | 0.9700 | C5B—C6B | 1.511 (16) |
C3A—C4A | 1.55 (2) | C5B—H1 | 0.9700 |
C3A—H31A | 0.9700 | C5B—H52B | 0.9700 |
C3A—H32A | 0.9700 | C6B—H61B | 0.9700 |
C4A—H41A | 0.9700 | C6B—H62B | 0.9700 |
H21W—O2W—H22W | 105 (4) | N2A—C4A—H42A | 109.6 |
H21W—O2W—H23W | 107 (4) | C3A—C4A—H42A | 109.6 |
H22W—O2W—H23W | 104 (4) | H41A—C4A—H42A | 108.1 |
H21W—O2W—H21Wi | 72 (10) | C6A—C5A—N1A | 108.0 (13) |
H22W—O2W—H21Wi | 175 (8) | C6A—C5A—H51A | 110.1 |
H23W—O2W—H21Wi | 81 (9) | N1A—C5A—H51A | 110.1 |
H21W—O2W—H22Wi | 175 (8) | C6A—C5A—H51B | 110.1 |
H22W—O2W—H22Wi | 78 (7) | N1A—C5A—H51B | 110.1 |
H23W—O2W—H22Wi | 68 (8) | H51A—C5A—H51B | 108.4 |
H21Wi—O2W—H22Wi | 105 (4) | N2A—C6A—C5A | 107.1 (13) |
H21W—O2W—H23Wi | 81 (9) | N2A—C6A—H61A | 110.3 |
H22W—O2W—H23Wi | 68 (8) | C5A—C6A—H61A | 110.3 |
H23W—O2W—H23Wi | 170 (10) | N2A—C6A—H62A | 110.3 |
H21Wi—O2W—H23Wi | 107 (4) | C5A—C6A—H62A | 110.3 |
H22Wi—O2W—H23Wi | 104 (4) | H61A—C6A—H62A | 108.6 |
H11W—O1W—H12W | 108 (2) | C3B—N1B—C1B | 108.6 (14) |
H11W—O1W—H13W | 108 (2) | C3B—N1B—C5B | 114.1 (15) |
H12W—O1W—H13W | 108 (2) | C1B—N1B—C5B | 106.6 (14) |
H11W—O1W—H11Wii | 74 (8) | C3B—N1B—H1B | 109.2 |
H12W—O1W—H11Wii | 58 (6) | C1B—N1B—H1B | 109.2 |
H13W—O1W—H11Wii | 165 (7) | C5B—N1B—H1B | 109.2 |
H11W—O1W—H12Wii | 58 (6) | C6B—N2B—C2B | 110.7 (18) |
H12W—O1W—H12Wii | 164 (6) | C6B—N2B—C4B | 111.0 (18) |
H13W—O1W—H12Wii | 85 (5) | C2B—N2B—C4B | 107.9 (14) |
H11Wii—O1W—H12Wii | 108 (2) | C6B—N2B—H2B | 109.1 |
H11W—O1W—H13Wii | 165 (7) | C2B—N2B—H2B | 109.1 |
H12W—O1W—H13Wii | 85 (5) | C4B—N2B—H2B | 109.1 |
H13W—O1W—H13Wii | 75 (9) | N1B—C1B—C2B | 108.6 (14) |
H11Wii—O1W—H13Wii | 108 (2) | N1B—C1B—H11B | 110.0 |
H12Wii—O1W—H13Wii | 108 (2) | C2B—C1B—H11B | 110.0 |
C3A—N1A—C1A | 109.2 (13) | N1B—C1B—H12B | 110.0 |
C3A—N1A—C5A | 108.7 (17) | C2B—C1B—H12B | 110.0 |
C1A—N1A—C5A | 109.2 (15) | H11B—C1B—H12B | 108.4 |
C3A—N1A—H1A | 109.9 | N2B—C2B—C1B | 108.1 (13) |
C1A—N1A—H1A | 109.9 | N2B—C2B—H21B | 110.1 |
C5A—N1A—H1A | 109.9 | C1B—C2B—H21B | 110.1 |
C2A—N2A—C6A | 110.7 (18) | N2B—C2B—H22B | 110.1 |
C2A—N2A—C4A | 109.2 (13) | C1B—C2B—H22B | 110.1 |
C6A—N2A—C4A | 109.9 (16) | H21B—C2B—H22B | 108.4 |
C2A—N2A—H2A | 109.0 | N1B—C3B—C4B | 106.6 (13) |
C6A—N2A—H2A | 109.0 | N1B—C3B—H31B | 110.4 |
C4A—N2A—H2A | 109.0 | C4B—C3B—H31B | 110.4 |
C2A—C1A—N1A | 108.8 (12) | N1B—C3B—H32B | 110.4 |
C2A—C1A—H11A | 109.9 | C4B—C3B—H32B | 110.4 |
N1A—C1A—H11A | 109.9 | H31B—C3B—H32B | 108.6 |
C2A—C1A—H12A | 109.9 | N2B—C4B—C3B | 108.8 (15) |
N1A—C1A—H12A | 109.9 | N2B—C4B—H41B | 109.9 |
H11A—C1A—H12A | 108.3 | C3B—C4B—H41B | 109.9 |
N2A—C2A—C1A | 108.1 (14) | N2B—C4B—H42B | 109.9 |
N2A—C2A—H21A | 110.1 | C3B—C4B—H42B | 109.9 |
C1A—C2A—H21A | 110.1 | H41B—C4B—H42B | 108.3 |
N2A—C2A—H22A | 110.1 | C6B—C5B—N1B | 106.5 (13) |
C1A—C2A—H22A | 110.1 | C6B—C5B—H1 | 110.4 |
H21A—C2A—H22A | 108.4 | N1B—C5B—H1 | 110.4 |
N1A—C3A—C4A | 104.3 (12) | C6B—C5B—H52B | 110.4 |
N1A—C3A—H31A | 110.9 | N1B—C5B—H52B | 110.4 |
C4A—C3A—H31A | 110.9 | H1—C5B—H52B | 108.6 |
N1A—C3A—H32A | 110.9 | N2B—C6B—C5B | 109.5 (14) |
C4A—C3A—H32A | 110.9 | N2B—C6B—H61B | 109.8 |
H31A—C3A—H32A | 108.9 | C5B—C6B—H61B | 109.8 |
N2A—C4A—C3A | 110.4 (12) | N2B—C6B—H62B | 109.8 |
N2A—C4A—H41A | 109.6 | C5B—C6B—H62B | 109.8 |
C3A—C4A—H41A | 109.6 | H61B—C6B—H62B | 108.2 |
C3A—N1A—C1A—C2A | 51 (2) | C3B—N1B—C1B—C2B | 71 (2) |
C5A—N1A—C1A—C2A | −68 (2) | C5B—N1B—C1B—C2B | −52 (2) |
C6A—N2A—C2A—C1A | 51 (2) | C6B—N2B—C2B—C1B | 69 (2) |
C4A—N2A—C2A—C1A | −71 (2) | C4B—N2B—C2B—C1B | −53 (2) |
N1A—C1A—C2A—N2A | 19 (3) | N1B—C1B—C2B—N2B | −14 (3) |
C1A—N1A—C3A—C4A | −71 (2) | C1B—N1B—C3B—C4B | −52 (2) |
C5A—N1A—C3A—C4A | 48 (2) | C5B—N1B—C3B—C4B | 67 (2) |
C2A—N2A—C4A—C3A | 49 (2) | C6B—N2B—C4B—C3B | −50 (2) |
C6A—N2A—C4A—C3A | −73 (2) | C2B—N2B—C4B—C3B | 71 (2) |
N1A—C3A—C4A—N2A | 19 (2) | N1B—C3B—C4B—N2B | −15 (3) |
C3A—N1A—C5A—C6A | −76 (3) | C3B—N1B—C5B—C6B | −48 (2) |
C1A—N1A—C5A—C6A | 43 (3) | C1B—N1B—C5B—C6B | 72 (2) |
C2A—N2A—C6A—C5A | −75 (3) | C2B—N2B—C6B—C5B | −49 (3) |
C4A—N2A—C6A—C5A | 46 (3) | C4B—N2B—C6B—C5B | 71 (3) |
N1A—C5A—C6A—N2A | 22 (3) | N1B—C5B—C6B—N2B | −20 (3) |
Symmetry codes: (i) −x+2, −x+y+1, −z+2/3; (ii) y, x, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H21W···Br1Aiii | 0.82 (1) | 2.56 (2) | 3.370 (5) | 168 (6) |
O2W—H22W···Br2Aiv | 0.82 (1) | 2.62 (2) | 3.394 (4) | 158 (6) |
O2W—H23W···Br3Ai | 0.82 (1) | 2.63 (2) | 3.4303 (12) | 167 (6) |
O1W—H11W···Br3Aii | 0.82 (1) | 2.62 (2) | 3.411 (5) | 162 (6) |
O1W—H12W···Br1A | 0.82 (1) | 2.59 (2) | 3.3591 (9) | 156 (5) |
O1W—H13W···Br2Av | 0.82 (1) | 2.64 (2) | 3.439 (5) | 166 (6) |
N1Aa—H1Aa···Br2A | 0.98 | 2.39 | 3.244 (13) | 145 |
N2Aa—H2Aa···Br3A | 0.98 | 2.37 | 3.240 (14) | 148 |
C1Aa—H11Aa···Br1Av | 0.97 | 3.03 | 3.74 (2) | 131 |
C1Aa—H12Aa···Br2Avi | 0.97 | 2.88 | 3.77 (2) | 154 |
C2Aa—H22Aa···Br3Aiii | 0.97 | 3.08 | 3.98 (2) | 154 |
C3Aa—H31Aa···Br3Avii | 0.97 | 3.04 | 3.606 (15) | 118 |
C3Aa—H32Aa···Br3Aiii | 0.97 | 3.12 | 3.95 (2) | 145 |
C4Aa—H41Aa···Br1Aiii | 0.97 | 2.83 | 3.652 (18) | 143 |
C4Aa—H42Aa···Br2Aiv | 0.97 | 3.04 | 3.812 (18) | 137 |
C5Aa—H51Aa···Br1Aviii | 0.97 | 2.94 | 3.90 (3) | 176 |
C5Aa—H51Ba···Br1Av | 0.97 | 2.95 | 3.72 (3) | 138 |
C6Aa—H61Aa···Br2Aiv | 0.97 | 2.86 | 3.70 (3) | 146 |
C6Aa—H62Aa···Br1A | 0.97 | 3.00 | 3.94 (3) | 165 |
N1Bb—H1Bb···Br2A | 0.98 | 2.36 | 3.249 (15) | 150 |
N2Bb—H2Bb···Br3A | 0.98 | 2.36 | 3.243 (16) | 149 |
C1Bb—H12Bb···Br2Avi | 0.97 | 3.07 | 3.549 (16) | 112 |
C2Bb—H21Bb···Br1A | 0.97 | 3.06 | 3.83 (2) | 137 |
C2Bb—H22Bb···Br2Aix | 0.97 | 2.92 | 3.78 (2) | 149 |
C3Bb—H32Bb···Br3Avii | 0.97 | 2.94 | 3.770 (19) | 145 |
C4Bb—H41Bb···Br3Aiii | 0.97 | 3.05 | 3.93 (2) | 151 |
C4Bb—H42Bb···Br1Aiii | 0.97 | 3.03 | 3.544 (18) | 114 |
C5Bb—H1b···Br1Aviii | 0.97 | 3.02 | 3.85 (2) | 145 |
C5Bb—H52Bb···Br1Av | 0.97 | 2.76 | 3.71 (2) | 170 |
C6Bb—H61Bb···Br2Aiv | 0.97 | 2.96 | 3.89 (4) | 162 |
C6Bb—H62Bb···Br1A | 0.97 | 2.96 | 3.79 (4) | 145 |
Symmetry codes: (i) −x+2, −x+y+1, −z+2/3; (ii) y, x, −z+1; (iii) −x+1, −x+y, −z+2/3; (iv) x−y+1, −y+1, −z+1/3; (v) −x, −x+y, −z+2/3; (vi) x−y, −y, −z+1/3; (vii) −y+1, x−y, z−1/3; (viii) −y+1, x−y+1, z−1/3; (ix) −x+y, −x, z+1/3. |
C6H14N2·3Br·H3O· | Dx = 2.093 Mg m−3 |
Mr = 372.94 | Cu Kα radiation, λ = 1.54184 Å |
Trigonal, P3c1 | Cell parameters from 15432 reflections |
a = 16.0425 (1) Å | θ = 5.5–71.2° |
c = 7.9666 (7) Å | µ = 12.37 mm−1 |
V = 1775.61 (16) Å3 | T = 299 K |
Z = 6 | Plate, clear colourless |
F(000) = 1080 | 0.48 × 0.28 × 0.14 mm |
Xcalibur, Ruby diffractometer | 2269 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source | 2033 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 10.4922 pixels mm-1 | θmax = 71.2°, θmin = 3.2° |
Absorption correction: analytical CrysAlisPro 1.171.40.57a (Rigaku Oxford Diffraction, 2019) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. | h = −19→19 |
Tmin = 0.060, Tmax = 0.334 | k = −19→19 |
37462 measured reflections | l = −9→9 |
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0539P)2 + 0.2214P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.029 | (Δ/σ)max = 0.001 |
wR(F2) = 0.081 | Δρmax = 0.44 e Å−3 |
S = 1.05 | Δρmin = −0.47 e Å−3 |
2269 reflections | Extinction correction: SHELXL-2016/6 (Sheldrick 2016), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
131 parameters | Extinction coefficient: 0.00143 (13) |
13 restraints | Absolute structure: Flack x determined using 934 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (2) |
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 | Occ. (<1) | |
O1W | 0.333333 | 0.666667 | 0.6967 (16) | 0.066 (3) | 0.834 (14) |
H1W | 0.381 (5) | 0.664 (9) | 0.727 (9) | 0.079* | 0.834 (14) |
O2W | 1.000000 | 1.000000 | 0.942 (3) | 0.086 (7) | 0.51 (2) |
H2W | 0.946 (5) | 0.985 (16) | 0.906 (12) | 0.103* | 0.51 (2) |
O1WA | 0.333333 | 0.666667 | 0.910 (8) | 0.066 (3) | 0.166 (14) |
H1WA | 0.380 (19) | 0.66 (3) | 0.879 (17) | 0.079* | 0.166 (14) |
O2WA | 1.000000 | 1.000000 | 0.687 (2) | 0.060 (5) | 0.49 (2) |
H2WA | 0.951 (7) | 0.951 (7) | 0.719 (12) | 0.072* | 0.49 (2) |
Br1 | 0.52723 (5) | 0.68784 (4) | 0.8224 (5) | 0.0517 (5) | |
Br2 | 0.82726 (5) | 0.80611 (5) | 0.8231 (5) | 0.0522 (5) | |
Br3 | 0.64555 (4) | 0.50584 (4) | 0.85219 (2) | 0.0452 (3) | |
O3W | 0.666667 | 0.333333 | 0.9623 (16) | 0.078 (3) | |
H3W | 0.644 (7) | 0.366 (6) | 0.917 (8) | 0.094* | |
N1 | 0.6640 (3) | 0.6712 (3) | 0.4887 (8) | 0.0378 (11) | |
H1 | 0.661536 | 0.674732 | 0.611311 | 0.045* | |
N2 | 0.6690 (3) | 0.6620 (3) | 0.1785 (8) | 0.0385 (11) | |
H2 | 0.671266 | 0.658507 | 0.055929 | 0.046* | |
C1 | 0.7133 (5) | 0.7713 (4) | 0.4200 (9) | 0.0480 (13) | |
H1A | 0.778349 | 0.807337 | 0.463699 | 0.058* | |
H1B | 0.678756 | 0.803958 | 0.452757 | 0.058* | |
C2 | 0.5636 (5) | 0.6166 (5) | 0.4237 (10) | 0.0527 (14) | |
H2A | 0.528646 | 0.649129 | 0.454940 | 0.063* | |
H2B | 0.530725 | 0.552524 | 0.472008 | 0.063* | |
C3 | 0.7188 (5) | 0.6220 (5) | 0.4445 (7) | 0.0432 (11) | |
H3A | 0.687836 | 0.558006 | 0.493104 | 0.052* | |
H3B | 0.783715 | 0.658036 | 0.488639 | 0.052* | |
C4 | 0.7155 (5) | 0.7647 (4) | 0.2288 (9) | 0.0489 (13) | |
H4A | 0.681498 | 0.794306 | 0.178587 | 0.059* | |
H4B | 0.781525 | 0.798806 | 0.189398 | 0.059* | |
C5 | 0.5668 (4) | 0.6100 (5) | 0.2326 (9) | 0.0471 (12) | |
H5A | 0.536379 | 0.543127 | 0.198198 | 0.057* | |
H5B | 0.532336 | 0.638739 | 0.181034 | 0.057* | |
C6 | 0.7217 (5) | 0.6154 (5) | 0.2529 (7) | 0.0435 (12) | |
H6A | 0.787920 | 0.647992 | 0.214220 | 0.052* | |
H6B | 0.691385 | 0.548487 | 0.218507 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1W | 0.043 (4) | 0.043 (4) | 0.111 (9) | 0.0214 (19) | 0.000 | 0.000 |
O2W | 0.066 (9) | 0.066 (9) | 0.12 (2) | 0.033 (4) | 0.000 | 0.000 |
O1WA | 0.043 (4) | 0.043 (4) | 0.111 (9) | 0.0214 (19) | 0.000 | 0.000 |
O2WA | 0.054 (7) | 0.054 (7) | 0.071 (11) | 0.027 (3) | 0.000 | 0.000 |
Br1 | 0.0500 (4) | 0.0368 (4) | 0.0632 (11) | 0.0179 (2) | 0.0049 (3) | −0.0009 (2) |
Br2 | 0.0507 (4) | 0.0500 (4) | 0.0650 (11) | 0.0320 (3) | −0.0031 (3) | −0.0045 (3) |
Br3 | 0.0369 (4) | 0.0508 (4) | 0.0440 (7) | 0.0190 (2) | 0.0000 (2) | −0.0049 (2) |
O3W | 0.053 (4) | 0.053 (4) | 0.129 (10) | 0.0264 (18) | 0.000 | 0.000 |
N1 | 0.045 (2) | 0.038 (2) | 0.033 (3) | 0.0228 (18) | 0.0001 (13) | −0.0007 (14) |
N2 | 0.046 (2) | 0.045 (2) | 0.032 (2) | 0.0276 (19) | 0.0003 (13) | 0.0017 (15) |
C1 | 0.053 (3) | 0.031 (2) | 0.056 (4) | 0.018 (2) | −0.014 (3) | −0.011 (2) |
C2 | 0.034 (3) | 0.055 (3) | 0.060 (4) | 0.016 (2) | 0.016 (2) | 0.002 (3) |
C3 | 0.057 (3) | 0.050 (3) | 0.037 (3) | 0.038 (3) | −0.002 (2) | 0.003 (2) |
C4 | 0.057 (3) | 0.036 (3) | 0.048 (3) | 0.019 (2) | 0.016 (2) | 0.017 (2) |
C5 | 0.035 (2) | 0.053 (3) | 0.052 (3) | 0.021 (2) | −0.015 (2) | −0.009 (2) |
C6 | 0.051 (3) | 0.055 (3) | 0.039 (3) | 0.037 (3) | −0.003 (2) | −0.011 (2) |
O1W—H1W | 0.82 (2) | N2—C5 | 1.484 (7) |
O1W—H1Wi | 0.82 (2) | N2—C4 | 1.485 (7) |
O1W—H1Wii | 0.83 (2) | N2—C6 | 1.503 (7) |
O2W—H2W | 0.83 (2) | N2—H2 | 0.9800 |
O2W—H2Wiii | 0.83 (2) | C1—C4 | 1.529 (8) |
O2W—H2Wiv | 0.83 (2) | C1—H1A | 0.9700 |
O1WA—H1WA | 0.83 (2) | C1—H1B | 0.9700 |
O1WA—H1WAi | 0.83 (2) | C2—C5 | 1.529 (8) |
O1WA—H1WAii | 0.83 (2) | C2—H2A | 0.9700 |
O2WA—H2WA | 0.83 (2) | C2—H2B | 0.9700 |
O2WA—H2WAiii | 0.83 (2) | C3—C6 | 1.532 (7) |
O2WA—H2WAiv | 0.83 (2) | C3—H3A | 0.9700 |
O3W—H3W | 0.84 (3) | C3—H3B | 0.9700 |
O3W—H3Wv | 0.84 (3) | C4—H4A | 0.9700 |
O3W—H3Wvi | 0.84 (3) | C4—H4B | 0.9700 |
N1—C3 | 1.488 (7) | C5—H5A | 0.9700 |
N1—C2 | 1.489 (8) | C5—H5B | 0.9700 |
N1—C1 | 1.494 (7) | C6—H6A | 0.9700 |
N1—H1 | 0.9800 | C6—H6B | 0.9700 |
H1W—O1W—H1Wi | 112 (5) | N1—C2—C5 | 108.9 (5) |
H1W—O1W—H1Wii | 112 (5) | N1—C2—H2A | 109.9 |
H1Wi—O1W—H1Wii | 112 (5) | C5—C2—H2A | 109.9 |
H2W—O2W—H2Wiii | 109 (7) | N1—C2—H2B | 109.9 |
H2W—O2W—H2Wiv | 109 (7) | C5—C2—H2B | 109.9 |
H2Wiii—O2W—H2Wiv | 109 (7) | H2A—C2—H2B | 108.3 |
H1WA—O1WA—H1WAi | 111 (9) | N1—C3—C6 | 108.7 (5) |
H2WA—O2WA—H2WAiv | 111 (7) | N1—C3—H3A | 110.0 |
H2WAiii—O2WA—H2WAiv | 111 (7) | C6—C3—H3A | 110.0 |
H3W—O3W—H3Wv | 103 (5) | N1—C3—H3B | 110.0 |
H3W—O3W—H3Wvi | 103 (5) | C6—C3—H3B | 110.0 |
H3Wv—O3W—H3Wvi | 103 (5) | H3A—C3—H3B | 108.3 |
C3—N1—C2 | 111.0 (4) | N2—C4—C1 | 109.2 (5) |
C3—N1—C1 | 110.3 (4) | N2—C4—H4A | 109.8 |
C2—N1—C1 | 109.9 (4) | C1—C4—H4A | 109.8 |
C3—N1—H1 | 108.5 | N2—C4—H4B | 109.8 |
C2—N1—H1 | 108.5 | C1—C4—H4B | 109.8 |
C1—N1—H1 | 108.5 | H4A—C4—H4B | 108.3 |
C5—N2—C4 | 110.2 (4) | N2—C5—C2 | 108.4 (5) |
C5—N2—C6 | 110.2 (4) | N2—C5—H5A | 110.0 |
C4—N2—C6 | 110.6 (4) | C2—C5—H5A | 110.0 |
C5—N2—H2 | 108.6 | N2—C5—H5B | 110.0 |
C4—N2—H2 | 108.6 | C2—C5—H5B | 110.0 |
C6—N2—H2 | 108.6 | H5A—C5—H5B | 108.4 |
N1—C1—C4 | 108.0 (5) | N2—C6—C3 | 108.3 (5) |
N1—C1—H1A | 110.1 | N2—C6—H6A | 110.0 |
C4—C1—H1A | 110.1 | C3—C6—H6A | 110.0 |
N1—C1—H1B | 110.1 | N2—C6—H6B | 110.0 |
C4—C1—H1B | 110.1 | C3—C6—H6B | 110.0 |
H1A—C1—H1B | 108.4 | H6A—C6—H6B | 108.4 |
Symmetry codes: (i) −x+y, −x+1, z; (ii) −y+1, x−y+1, z; (iii) −x+y+1, −x+2, z; (iv) −y+2, x−y+1, z; (v) −y+1, x−y, z; (vi) −x+y+1, −x+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···Br1 | 0.82 (2) | 2.31 (3) | 3.121 (4) | 169 (12) |
O2W—H2W···Br2 | 0.83 (2) | 2.6 (2) | 3.102 (8) | 119 (18) |
O1WA—H1WA···Br1 | 0.83 (2) | 2.23 (11) | 3.037 (15) | 165 (40) |
O2WA—H2WA···Br2 | 0.83 (2) | 2.33 (4) | 3.148 (6) | 171 (17) |
O3W—H3W···Br3 | 0.84 (3) | 2.30 (5) | 3.079 (4) | 154 (9) |
N1—H1···Br1 | 0.98 | 2.82 | 3.541 (6) | 131 |
N1—H1···Br2 | 0.98 | 2.96 | 3.602 (7) | 124 |
N1—H1···Br3 | 0.98 | 3.22 | 3.837 (5) | 122 |
N2—H2···Br1vii | 0.98 | 3.18 | 3.787 (6) | 122 |
N2—H2···Br2vii | 0.98 | 3.06 | 3.734 (7) | 127 |
N2—H2···Br3vii | 0.98 | 2.79 | 3.497 (5) | 130 |
C1—H1A···Br2 | 0.97 | 2.97 | 3.598 (6) | 123 |
C1—H1B···Br1viii | 0.97 | 2.95 | 3.738 (7) | 139 |
C2—H2A···Br1 | 0.97 | 3.00 | 3.521 (7) | 115 |
C2—H2B···Br3ix | 0.97 | 3.08 | 3.817 (7) | 134 |
C3—H3A···Br3 | 0.97 | 2.96 | 3.635 (6) | 128 |
C3—H3B···Br2x | 0.97 | 3.12 | 3.840 (7) | 132 |
C4—H4A···Br1viii | 0.97 | 3.12 | 3.838 (7) | 132 |
C4—H4B···Br2vii | 0.97 | 3.00 | 3.593 (6) | 121 |
C5—H5A···Br3ix | 0.97 | 3.01 | 3.781 (7) | 137 |
C5—H5B···Br1vii | 0.97 | 2.98 | 3.665 (6) | 129 |
C6—H6A···Br2x | 0.97 | 2.97 | 3.751 (6) | 139 |
C6—H6B···Br3vii | 0.97 | 3.00 | 3.553 (6) | 117 |
Symmetry codes: (vii) x, y, z−1; (viii) x, x−y+1, z−1/2; (ix) −y+1, −x+1, z−1/2; (x) −x+y+1, y, z−1/2. |
Funding information
This research was supported by the statutory funds of our institutions.
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