research communications
Synthesis, 6H6N3)2[BiCl5]·2H2O
and Hirshfeld surface analysis of a polymeric bismuthate(III) halide complex, (CaLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and bDepartment of Chemical and Pharmaceutical Sciences, Centre for Structural, Diffractometry, University of Ferrara, Via L. Borsari 46, I-44121 Ferrara, Italy
*Correspondence e-mail: ch.boukoum@gmail.com
The synthesis and the catena-poly[bis(1,2,3-benzotriazolium) [[tetrachloridobismuth(III)]-μ-chlorido] dihydrate], {(C6H6N3)2[BiCl5]·2H2O}n are reported. The structure comprises polyanionic zigzag chains of formula [(BiCl5)2−]n running along the c-axis direction. The 1,2,3-benzotriazolium cations are linked between these polymer chains, via the water molecules, giving rise to left- and right-handed helical chains. Hirshfeld surface analysis and fingerprint plots were used to decode the intermolecular interactions in the crystal network and determine the contribution of the component units for the construction of the three-dimensional architecture.
of a new halide-bridged polymer, namelyCCDC reference: 1580458
1. Chemical context
Bismuth–halide complexes are of contemporary interest because of their structural diversity and numerous promising physical properties such as dielectric, ferroelectric, ferroelastic, non-linear optical and thermochromism (Bator et al., 1997; Bednarska-Bolek et al., 2000; Sobczyk et al., 1997; Bator et al., 1998). Generally, in these compounds, the BiX6 octahedra may join to form discrete (i.e. mononuclear) or extended (i.e. polynuclear) inorganic networks of corner-, edge-, or face-sharing octahedra, leading to an extensive family of bismuth halogenoanions (Jakubas, 1986; Jakubas et al., 1988, 1995). A variety of organic cations, ring shaped or linear, have a strong impact on the arrangements of BiX6 octahedra and the formation of hydrogen bonds (Dammak et al., 2015; Elfaleh & Kamoun, 2014). This class of compounds has also attracted much attention in the field of crystal engineering over the last decade on account of their capability for the creation of extended architectures via intermolecular non-covalent binding interactions. (i.e. hydrogen bonding, ionic and π–π stacking interactions; Belter & Fronczek, 2013; Thirunavukkarasu et al., 2013; Aloui et al., 2015).
As part of our studies in this area, we chose benzotriazole, which is an aromatic heterocyclic base with three protonatable nitrogen atoms, as the organic cation.
2. Structural commentary
The single-crystal X-ray 6H6N3]2[BiCl5]·2H2O, (I), crystallizes in the non-centrosymmetric Cmc21 and the comprises one Bi3+ cation, four chlorine atoms, one water molecule and one benzotriazolium cation (Fig. 1). The bismuth atom is six-coordinated by four distinct chlorine atoms (Cl1, Cl2, Cl3, Cl4). The Bi—Cl bond lengths (Table 1) vary from 2.545 (3) to 2.674 (4) Å (ΔBi—Cl = 0.129 Å) and 2.757 (4) to 2.856 (4) Å (ΔBi—Cl = 0.099 Å) for non-bridging and bridging Cl atoms, respectively, which are comparable with values found in {(C2H7N4O)2[BiCl5]n (Ferjani et al., 2012) and [NH3(CH2)6NH3]BiCl5 (Ouasri et al., 2013). The Cl—Bi—Cl bond angles in (I) range from 85.93 (17) to 91.88 (13)° (ΔCl—Bi—Cl =5.95°) and are less distorted than those observed in [NH3(CH2)6NH3]BiCl5 and [H2mdap][BiCl5] (Ouasri et al., 2013; Wang et al., 2017).
shows that the title compound [C
|
In the extended structure of (I), adjacent BiCl6 octahedra are connected through Cl4 and Cl4iii so as to form [(BiCl5)2−]n polyanionic zigzag chains propagating along the c-axis direction, with the shortest intrachain Bi⋯Bi distance of 5.508 (1) Å and a Cl4—Bi—Cl4ii angle of 89.61 (3)° (Fig. 2) The overall negative charges of the resulting polymers are counter-balanced by the protonated 1,2,3-benzotriazolium cations (Fig. 2b). As usual, this aromatic amine is protonated at the N3 atom and the C—C, N—N and C—N bond lengths vary from 1.358 (18) to 1.402 (15), 1.293 (15) to 1.308 (15) Å and 1.364 (16) to 1.370 (15) Å, respectively, which agree well with those observed in bis(1,2,3-benzotriazolium) sulfate dihydrate (Randolph et al., 2013) and benzotriazolium picrate (Zeng et al., 2011).
3. Supramolecular features
The heterocyclic cations alternately bridge the water molecules (O1W) via N—H⋯O hydrogen bonds, forming (benzo-OW)n helical chains in a right- and left–handed sequence extending along the c-axis direction (Table 2, Fig. 2). The phenyl rings of adjacent chains are alternately stacked in a parallel-displaced face-to-face arrangement (Fig. 3), with centroid–centroid distances of 3.8675 (1) Å and an inter-planar spacing of 1.13 Å. The anionic and cationic chains are further assembled into a three-dimensional supramolecular framework through N—H⋯O, O—H⋯Cl and C—H⋯Cl hydrogen bonds (Table 2, Fig. 3).
4. Hirshfeld surface analysis
The Hirshfeld surface (Wolff et al., 2012) mapped with a dnorm function for the for the title compounds clearly shows the red spots derived from H⋯O and H⋯Cl/Cl⋯H contacts (Fig. 4). The two-dimensional fingerprint plot shows that the H⋯Cl/Cl⋯H contacts associated with O—H⋯Cl hydrogen bonding appear to be the major contributor in the crystal packing (55.8%): these contacts are represented as regions in the top left (de > di, Cl⋯H) and bottom right (de < di, H⋯Cl) of the related plots in Fig. 5. Interactions of the type H⋯H appear in the middle of the scattered points in the fingerprint maps; they comprise 10.9% of the entire surface. The decomposition of the fingerprint plot shows that N⋯H/H⋯N, C⋯H/H⋯C, O⋯H/H⋯O and N⋯Cl/Cl⋯N contacts have percentage contributions of 7.8%, 6.5%, 4.5% and 4.3% respectively, of the total Hirshfeld surface. The C⋯C contacts associated with π–π interactions amount to 3.4% of the surface: their presence is indicated by the appearance of red and blue triangles on the shape-indexed surfaces in Fig. 6. The Cl⋯Bi/Bi⋯Cl (3%) interactions are represented as points in the top area. The Cl⋯Cl, C⋯Cl/Cl⋯C, C⋯N, and N⋯N interactions are in the middle of the fingerprint plots, and comprise a very small contribution of 1.3%, 1.2%, 0.9% and 0.4%, respectively.
The intermolecular interactions were further evaluated by using the enrichment ratio (ER; Jelsch et al., 2014). The largest contribution to the Hirshfeld surface is from H⋯Cl/Cl⋯H contacts associated with O—H⋯Cl hydrogen bonds and their ER value is 1.73. The H⋯H contacts are the second largest contributor, but they display an enrichment ratio significantly below unity (ERHH = 0.47). The formation of extensive π–π interactions is reflected in the relatively high ERCC of 3.94.
5. Synthesis and crystallization
The title compound was prepared by dropwise addition of an ethanolic solution of 1H-benzotriazole (0.061 g, 0.5 mmol) to 1 mmol of a bismuth nitrate solution [Bi(NO3)3·5H2O], dissolved in 0.05 mL of a concentrated HCl aqueous solution. The resulting aqueous solution was stirred for 30 min. and kept at room temperature for crystallization. After two week of slow evaporation, colourless single crystals of (I) (yield = 75%) were formed in the solution. Analysis observed (calculated) for [C6H6N3]2[BiCl5]·2H2O (%): C 21.6 (21.0), H 2.66 (2.41), N 34.6 (33.8).
6. Refinement
Crystal data, data collection and structure . The N-bound and C-bound hydrogen atoms were positioned geometrically and treated as riding: N—H = 0.86 Å and C—H = 0.93 Å with Uiso(H) = 1.2Ueq(N,C). The O—H and H⋯H separations in the water molecule were restrained using a DFIX model to be 0.90 and 1.46 Å, respectively, and refined with Uiso(H) = 1.5Ueq(O).
details are summarized in Table 3Supporting information
CCDC reference: 1580458
https://doi.org/10.1107/S2056989017015134/hb7714sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017015134/hb7714Isup2.hkl
Data collection: Kappa CCD server software (Nonius, 1997); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and WinGX (Farrugia, 2012).(C6H6N3)2[BiCl5]·2H2O | F(000) = 1256 |
Mr = 662.54 | Dx = 2.116 Mg m−3 |
Orthorhombic, Cmc21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2c -2 | Cell parameters from 8027 reflections |
a = 19.4627 (4) Å | θ = 4.4–7.3° |
b = 13.8181 (4) Å | µ = 9.14 mm−1 |
c = 7.7343 (2) Å | T = 293 K |
V = 2080.04 (9) Å3 | Rod, colourless |
Z = 4 | 0.55 × 0.34 × 0.23 mm |
Nonius KappaCCD diffractometer | 1670 independent reflections |
Radiation source: fine-focus sealed tube | 1643 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
f scans and w scans | θmax = 24.4°, θmin = 4.4° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −22→22 |
Tmin = 0.011, Tmax = 0.053 | k = −16→16 |
6050 measured reflections | l = −8→8 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0704P)2 + 2.8002P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.096 | (Δ/σ)max = 0.038 |
S = 1.11 | Δρmax = 1.68 e Å−3 |
1670 reflections | Δρmin = −0.76 e Å−3 |
131 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
4 restraints | Extinction coefficient: 0.0028 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 731 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.036 (14) |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Bi1 | 0.5000 | 0.35812 (2) | 0.08277 (6) | 0.0310 (2) | |
Cl1 | 0.36329 (14) | 0.3716 (2) | 0.0695 (12) | 0.0685 (10) | |
Cl2 | 0.5000 | 0.2105 (2) | −0.1139 (6) | 0.0458 (7) | |
Cl3 | 0.5000 | 0.2501 (3) | 0.3697 (5) | 0.0500 (8) | |
Cl4 | 0.5000 | 0.5302 (3) | 0.2874 (5) | 0.0652 (10) | |
O1W | 0.6246 (4) | 0.3531 (5) | 0.585 (3) | 0.0570 (18) | |
C1 | 0.6621 (5) | 0.0963 (7) | 0.7492 (14) | 0.042 (2) | |
C2 | 0.6058 (5) | 0.0522 (8) | 0.6684 (15) | 0.049 (2) | |
H2C | 0.5704 | 0.0873 | 0.6175 | 0.058* | |
C3 | 0.6071 (6) | −0.0470 (8) | 0.6707 (16) | 0.054 (3) | |
H3 | 0.5705 | −0.0804 | 0.6215 | 0.065* | |
C4 | 0.6607 (6) | −0.1001 (8) | 0.7433 (16) | 0.056 (2) | |
H4 | 0.6590 | −0.1673 | 0.7390 | 0.067* | |
C5 | 0.7154 (7) | −0.0568 (8) | 0.8201 (15) | 0.047 (3) | |
H5 | 0.7511 | −0.0926 | 0.8684 | 0.057* | |
C6 | 0.7153 (6) | 0.0439 (9) | 0.8229 (14) | 0.040 (2) | |
N3 | 0.7585 (5) | 0.1125 (8) | 0.8909 (15) | 0.050 (2) | |
H3A | 0.7954 | 0.0992 | 0.9469 | 0.060* | |
N1 | 0.6790 (5) | 0.1908 (7) | 0.7770 (15) | 0.058 (2) | |
H1 | 0.6545 | 0.2390 | 0.7434 | 0.070* | |
N2 | 0.7371 (5) | 0.1995 (8) | 0.8609 (16) | 0.061 (3) | |
H11 | 0.600 (5) | 0.400 (8) | 0.638 (18) | 0.091* | |
H22 | 0.595 (5) | 0.320 (10) | 0.520 (18) | 0.091* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.0321 (3) | 0.0286 (3) | 0.0323 (3) | 0.000 | 0.000 | −0.0007 (2) |
Cl1 | 0.0362 (11) | 0.0924 (19) | 0.077 (3) | 0.0003 (11) | 0.008 (2) | −0.013 (2) |
Cl2 | 0.0575 (19) | 0.0308 (16) | 0.0490 (17) | 0.000 | 0.000 | −0.0089 (14) |
Cl3 | 0.0605 (19) | 0.0469 (19) | 0.0427 (16) | 0.000 | 0.000 | 0.0107 (16) |
Cl4 | 0.088 (3) | 0.053 (2) | 0.054 (2) | 0.000 | 0.000 | −0.0215 (16) |
O1W | 0.042 (3) | 0.060 (5) | 0.069 (5) | 0.002 (2) | 0.002 (10) | −0.010 (5) |
C1 | 0.041 (5) | 0.033 (5) | 0.051 (5) | 0.001 (4) | 0.009 (4) | −0.002 (4) |
C2 | 0.047 (5) | 0.050 (6) | 0.049 (5) | 0.008 (4) | 0.001 (4) | −0.002 (4) |
C3 | 0.048 (5) | 0.056 (7) | 0.059 (6) | −0.008 (5) | −0.001 (5) | −0.011 (5) |
C4 | 0.064 (6) | 0.042 (6) | 0.062 (6) | −0.004 (5) | 0.016 (5) | −0.005 (5) |
C5 | 0.053 (7) | 0.042 (6) | 0.047 (6) | 0.011 (5) | 0.002 (5) | 0.001 (5) |
C6 | 0.032 (5) | 0.046 (5) | 0.040 (5) | 0.004 (4) | 0.002 (4) | −0.007 (5) |
N3 | 0.044 (5) | 0.053 (6) | 0.053 (6) | −0.002 (5) | 0.005 (4) | −0.006 (4) |
N1 | 0.052 (5) | 0.037 (5) | 0.085 (7) | −0.001 (4) | 0.011 (5) | −0.005 (5) |
N2 | 0.053 (6) | 0.050 (6) | 0.080 (7) | −0.016 (5) | 0.010 (5) | −0.018 (5) |
Bi1—Cl1 | 2.669 (3) | C2—H2C | 0.9300 |
Bi1—Cl1i | 2.669 (3) | C3—C4 | 1.394 (17) |
Bi1—Cl2 | 2.545 (3) | C3—H3 | 0.9300 |
Bi1—Cl3 | 2.674 (4) | C4—C5 | 1.358 (18) |
Bi1—Cl4ii | 2.757 (4) | C4—H4 | 0.9300 |
Bi1—Cl4 | 2.856 (4) | C5—C6 | 1.392 (13) |
Cl4—Bi1iii | 2.757 (4) | C5—H5 | 0.9300 |
O1W—H11 | 0.90 (2) | C6—N3 | 1.370 (15) |
O1W—H22 | 0.90 (2) | N3—N2 | 1.293 (15) |
C1—N1 | 1.364 (16) | N3—H3A | 0.8600 |
C1—C6 | 1.387 (16) | N1—N2 | 1.308 (15) |
C1—C2 | 1.402 (15) | N1—H1 | 0.8600 |
C2—C3 | 1.371 (16) | ||
Cl2—Bi1—Cl1 | 91.88 (13) | C3—C2—H2C | 122.8 |
Cl2—Bi1—Cl1i | 91.88 (13) | C1—C2—H2C | 122.8 |
Cl1—Bi1—Cl1i | 170.9 (2) | C2—C3—C4 | 123.0 (10) |
Cl2—Bi1—Cl3 | 92.80 (16) | C2—C3—H3 | 118.5 |
Cl1—Bi1—Cl3 | 94.06 (17) | C4—C3—H3 | 118.5 |
Cl1i—Bi1—Cl3 | 94.06 (17) | C5—C4—C3 | 122.1 (10) |
Cl2—Bi1—Cl4ii | 87.32 (14) | C5—C4—H4 | 118.9 |
Cl1—Bi1—Cl4ii | 85.93 (17) | C3—C4—H4 | 118.9 |
Cl1i—Bi1—Cl4ii | 85.93 (17) | C4—C5—C6 | 116.5 (12) |
Cl3—Bi1—Cl4ii | 179.88 (13) | C4—C5—H5 | 121.8 |
Cl2—Bi1—Cl4 | 176.93 (13) | C6—C5—H5 | 121.8 |
Cl1—Bi1—Cl4 | 87.90 (13) | N3—C6—C1 | 104.7 (10) |
Cl1i—Bi1—Cl4 | 87.90 (13) | N3—C6—C5 | 134.1 (13) |
Cl3—Bi1—Cl4 | 90.27 (13) | C1—C6—C5 | 121.1 (13) |
Cl4ii—Bi1—Cl4 | 89.61 (3) | N2—N3—C6 | 112.1 (10) |
Bi1iii—Cl4—Bi1 | 157.68 (19) | N2—N3—H3A | 123.9 |
H11—O1W—H22 | 106 (3) | C6—N3—H3A | 123.9 |
N1—C1—C6 | 104.8 (10) | N2—N1—C1 | 112.0 (10) |
N1—C1—C2 | 132.5 (10) | N2—N1—H1 | 124.0 |
C6—C1—C2 | 122.7 (10) | C1—N1—H1 | 124.0 |
C3—C2—C1 | 114.5 (10) | N3—N2—N1 | 106.4 (9) |
Symmetry codes: (i) −x+1, y, z; (ii) −x+1, −y+1, z−1/2; (iii) −x+1, −y+1, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.86 | 2.08 | 2.891 (17) | 157 |
N3—H3A···O1Wiv | 0.86 | 2.00 (2) | 2.767 (18) | 148 |
O1W—H11···Cl4iii | 0.89 (11) | 2.47 (11) | 3.306 (13) | 157 (9) |
O1W—H22···Cl3 | 0.90 (12) | 2.38 (12) | 3.268 (14) | 169 (11) |
C5—H5···Cl1v | 0.93 | 2.73 | 3.603 (14) | 157 |
Symmetry codes: (iii) −x+1, −y+1, z+1/2; (iv) −x+3/2, −y+1/2, z+1/2; (v) x+1/2, y−1/2, z+1. |
Acknowledgements
This work was supported by the Tunisian Ministry of High Education Scientific Research.
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