Crystal structure of the new hybrid material bis­(1,4-diazo­niabi­cyclo­[2.2.2]octa­ne) di-μ-chlorido-bis­[tetra­chlorido­bis­muthate(III)] dihydrate

Chouri, M.; Boughzala, H.

doi:10.1107/S2056989015019933

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Volume 71| Part 11| November 2015| Pages 1384-1387

https://doi.org/10.1107/S2056989015019933

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Crystal structure of the new hybrid material bis(1,4-diazoniabicyclo[2.2.2]octane) di-μ-chlorido-bis[tetrachloridobismuthate(III)] dihydrate

Marwen Chouri ^a and Habib Boughzala ^a ^*

^aLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092 Manar II Tunis, Tunisia
^*Correspondence e-mail: habib.boughzala@ipein.rnu.tn

Edited by A. Van der Lee, Université de Montpellier II, France (Received 14 October 2015; accepted 21 October 2015; online 28 October 2015)

The title compound bis(1,4-diazoniabicyclo[2.2.2]octane) di-μ-chlorido-bis[tetrachloridobismuthate(III)] dihydrate, (C₆H₁₄N₂)₂[Bi₂Cl₁₀]·2H₂O, was obtained by slow evaporation at room temperature of a hydrochloric aqueous solution (pH = 1) containing bismuth(III) nitrate and 1,4-diazabicyclo[2.2.2]octane (DABCO) in a 1:2 molar ratio. The structure displays a two-dimensional arrangement parallel to (100) of isolated [Bi₂Cl₁₀]⁴⁻ bioctahedra (site symmetry -1) separated by layers of organic 1,4-diazoniabicyclo[2.2.2]octane dications [(DABCOH₂)²⁺] and water molecules. O—H⋯Cl, N—H⋯O and N—H⋯Cl hydrogen bonds lead to additional cohesion of the structure.

Keywords: crystal structure; hybrid material; DABCO.

CCDC reference: 971956

1. Chemical context

In recent years, many new organic–inorganic hybrid compounds have been synthesized because of their interesting physical behaviour and applications in optoelectronics (Jakubas & Sobczyk, 1990 ). The main interesting optical activity observed in this kind of compounds is generally the result of the presence of an active ns² lone pair (Chaabouni et al., 1998 ) in the inorganic parts. It can also be the result of an important structural distortion in the organic cations (Ishihara et al., 1990 ; Lacroix et al., 1994 ). The combination of the particular properties of the organic and inorganic moieties can induce interesting new properties. In particular for the halogenated bismuth or antimony anionic networks (Ahmed et al., 2001 ; Jakubas et al., 2005 ), the anionic arrangement leads to four kinds of dimensionalities: quantum dots (zero-dimensional, 0D) observed in hybrids such as (C₆H₁₄N₂)₂[Sb₂Cl₁₀]·2H₂O (Ben Rhaiem et al., 2013 ), quantum wires (one-dimensional, 1D) as is the case in the structure of (C₂H₇N₄O)₂ [BiCl₅] (Ferjani et al., 2012 ), quantum wells (two-dimensional, 2D) and a bulk (three-dimensional, 3D) topology. The organic cations are usually filling the empty space left by the inorganic network. Here we report the structure of a new hybrid bismuthate compounds having a 0D dimensionality with respect to its inorganic part.

2. Structural commentary

The structural unit (Fig. 1) of the compound is built up by an isolated dimeric decachloridobismuthate(III) [Bi₂Cl₁₀]⁴⁻ anion, two organic 1,4-diazoniabicyclo[2.2.2]octane dications [(DABCOH₂)²⁺] and two water molecules. These components are linked by strong hydrogen bonds. The inorganic moiety is an edge-sharing dioctahedron located site with symmetry $[\overline 1]$ . The two (DABCOH₂)²⁺ dications (Fig. 4) in the structural unit are related to the dimeric [Bi₂Cl₁₀]⁴⁻ units by means of N2—H2⋯Cl2 and N2—H2⋯Cl1 interactions.

Figure 1
Plot of the molecular entities of (C₆H₁₄N₂)₂[Bi₂Cl₁₀]. 2H₂O, showing the atom numbering scheme. Atomic displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radius. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x + 2, y + 0.5, −z + 0.5; (iii) x − 1, −y + 0.5, z + 0.5.]

Figure 4
Hydrogen-bonding environment of the cationic organic part of the title compound.

The bond lengths and angles of the dication are within normal ranges and are comparable to those observed in similar structures. Table 1 summarizes the most important distances in these molecules. The C—N bond lengths vary from 1.479 (11) to 1.508 (12) Å. The C—C bond lengths vary from 1.500 (13) to 1.535 (13) Å. The angles in this molecule are between 109.8 (7) and 110.7 (8)° for C—N—C and between 108.1 (8) and 109.2 (8)° for N—C—C.

Table 1
Selected geometric parameters (Å)

Bi—Cl5	2.588 (2)	N1—C5	1.504 (9)
Bi—Cl3	2.601 (2)	N2—C4	1.489 (10)
Bi—Cl2	2.6611 (19)	N2—C2	1.492 (9)
Bi—Cl4	2.704 (2)	N2—C6	1.494 (10)
Bi—Cl1	2.8610 (19)	C1—C2	1.517 (11)
Bi—Cl1ⁱ	2.884 (2)	C6—C5	1.531 (11)
N1—C1	1.485 (9)	C3—C4	1.493 (11)
N1—C3	1.503 (9)
Symmetry code: (i) -x+1, -y+1, -z+1.

As listed in Table 1, the bond lengths of bismuth to terminal chlorides [2.587 (5)–2.704 (5) Å] are shorter than the bridging ones [2.863 (4) and 2.884 (4) Å]. The Cl—Bi—Cl angles vary from 84.46 (12) to 95.4 (2)° for the cis and 173.25 (15) to 176.64 (15)° for the trans arrangement. Using Shannon's method (Shannon, 1976 ), the distortion index of 1.87 (9) × 10⁻³ reveals only a small distortion in the BiCl₆ octahedron. The bismuth 6s² electron pair has stereochemical activity and the hydrogen-bond orientation can be related to the bismuth polyhedra distortion. The final Fourier difference map reveals four large peaks at approximately 1 Å from the bismuth atom that can be attributed to the delocalization of the 6s² electron pair as is the case in most other bismuth-based structures.

The (C₆H₁₄N₂)₂[Bi₂Cl₁₀]·2H₂O structure is very close to that of (C₆H₁₄N₂)₂[Sb₂Cl₁₀]·2H₂O (Ben Rhaiem et al., 2013). The cell parameters of both structures can be compared after making a necessary transformation (cba) in the Pnnm antimony unit cell to be comparable to the bismuth one (Table 2). Apart from the higher symmetry of the antimony structure, an important distortion is noted in the SbCl₆ octahedra confirmed by the Shannon's distortion index (Shannon,1976) [6.20 (9) × 10⁻³], more than three times larger than the one for the title bismuth compound [1.87 (9) × 10⁻³] . It is worth noting that the water molecule plays a more efficient role in the bismuth based compound. In (C₆H₁₄N₂)₂[Sb₂Cl₁₀]·2H₂O, the H₂O molecules are only linked to (DABCOH₂)²⁺ and in the (C₆H₁₄N₂)₂[Bi₂Cl₁₀]·2H₂O structure they are directly hydrogen bonded to both the organic and inorganic parts (Fig. 3). The atomic radius of bismuth is larger than that for antimony, and thus an increase of the cell volume is expected. In fact, the main increase is observed for the c axis [13.99 (2) Å] because the metallic coordination polyhedra are aligned along this axis. On the other hand, a roughly equivalent decrease of the b parameter is observed causing the unit-cell volume of the two compounds approximately to be the same. A general comparison of the two structures reveals that they have a similar 3D pattern, built up by isolated bioctahedra, (DABCOH₂)²⁺ cations and water molecules leaving empty the same voids. On the other hand, the water molecule immediate environment is more regular in the Sb structure (Fig. 3b) and the (DABCOH₂)²⁺ cation is more distorted in the Bi structure (Fig. 3a) explaining the lowering of the symmetry in the title compound.

Table 2
Comparison of the cell parameters of the structures of [Bi₂Cl₁₀](C₆H₁₄N₂)₂·2H₂O and [Sb₂Cl₁₀](C₆H₁₄N₂)₂·2H₂O.

	[Bi₂Cl₁₀](C₆H₁₄N₂)₂·2H₂O	[Sb₂Cl₁₀](C₆H₁₄N₂)₂·2H₂O	Parameter variation (%) [(X_Bi—X_Sb)/(X_Sb)]·100
Crystal system	monoclinic	orthorhombic	-
Space group	P2₁/c	Pnnm → Pnmn (cba)	-
a (Å)	7.875 (3)	9.162 (1) => 7.566 (2)	4.08 (2)
b (Å)	18.379 (5)	20.689 (7) => 20.689 (7)	−11.16 (3)
c (Å)	10.444 (4)	7.566 (2) => 9.162 (1)	13.99 (2)
β (Å)	105.95 (3)	90.00	-
V (Å³)	1453.4 (9)	1446.8 (7)	0.45 (7)

Figure 3
Water-molecule hydrogen-bonding interaction between organic and inorganic parts: (a) in the title compound [symmetry codes: (i) x + 1, −y + 0.5, z − 0.5; (ii) x, −y + 0.5, z + 0.5]; (b) in the structure of (C₆H₁₄N₂)₂[Sb₂Cl₁₀]·2H₂O

3. Supramolecular features

As shown in Fig. 2, every anionic unit is linked to four water molecules and two organic cations. The water molecules (Fig. 3) are strongly hydrogen bonded to the inorganic part by means of O—HW1⋯Cl5ⁱⁱ [symmetry code: (ii) x, −y + 0.5, z + 0.5] and O—HW2⋯Cl5 interactions. The DABCO cations are hydrogen bonded to water molecules, leading to chains composed of organic moieties, inorganic clusters and H₂O molecules running along the b direction (Fig. 1). The water molecules stabilize the structure by playing a bridge role between organic and inorganic parts. Furthermore, they ensure the link in the other directions leading to a hydrogen-bond-based three-dimensional network. The structure can be seen (Fig. 5) as an alternation of organic and inorganic layers parallel to (100) which are linked by a strong hydrogen-bond pattern (Table 3).

Table 3
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
Ow—Hw2⋯Cl5	0.91	2.63	3.458 (8)	163
N1—H1⋯Owⁱⁱ	0.91	1.87	2.739 (10)	159
Ow—Hw1⋯Cl5ⁱⁱⁱ	0.91	2.80	3.475 (9)	138
N2—H2⋯Cl1	0.91	2.73	3.352 (6)	127
N2—H2⋯Cl2	0.91	2.65	3.325 (7)	132
Symmetry codes: (ii) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Hydrogen-bonding environment of the anionic part of the structure. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x + 1, −y + 1, −z + 1.5; (iii) x, −y + 0.5, z − 0.5.]

Figure 5
Projection of the crystal structure of the bismuthate hybrid compound along the c axis, showing the alternation of organic and inorganic layers.

4. Synthesis and crystallization

(C₆H₁₄N₂)₂[Bi₂Cl₁₀]·2H₂O crystals were obtained at ambient conditions by dissolving Bi(NO₃)₃·5H₂O and DABCO (C₆H₁₂N₂) in water in a 1:2 molar ratio. The pH of the solution was adjusted to 1 with HCl. The mixture was stirred and kept for several days. Colourless crystals were obtained after a few weeks.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The isotropic displacement parameter of the hydrogen atoms for the water molecule were fixed to be restrained to be approximately 1.5 times those of the parent atom and the water molecule geometries were regularised using distance restraints

Table 4
Experimental details

Crystal data
Chemical formula	(C₆H₁₄N₂)₂[Bi₂Cl₁₀]·2H₂O
M_r	1036.88
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.875 (3), 18.379 (5), 10.444 (4)
β (°)	105.95 (3)
V (Å³)	1453.4 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	13.03
Crystal size (mm)	0.5 × 0.3 × 0.2

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968 )
T_min, T_max	0.013, 0.074
No. of measured, independent and observed [I > 2σ(I)] reflections	3159, 3159, 2681
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.102, 1.06
No. of reflections	3159
No. of parameters	142
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	3.48, −2.57
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994 ), XCAD4 (Harms & Wocadlo, 1995 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 971956

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019933/vn2102sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019933/vn2102Isup2.hkl

checkCIF report

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(1,4-diazoniabicyclo[2.2.2]octane) di-µ-chlorido-bis[tetrachloridobismuthate(III)] dihydrate top

Crystal data top

(C₆H₁₄N₂)₂[Bi₂Cl₁₀]·2H₂O	F(000) = 968
M_r = 1036.88	D_x = 2.369 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.875 (3) Å	Cell parameters from 3158 reflections
b = 18.379 (5) Å	θ = 2.2–2.7°
c = 10.444 (4) Å	µ = 13.03 mm⁻¹
β = 105.95 (3)°	T = 293 K
V = 1453.4 (9) Å³	Prism, colourless
Z = 2	0.5 × 0.3 × 0.2 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	2681 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.0°, θ_min = 2.2°
ω/2θ scans	h = −10→1
Absorption correction: ψ scan North et al. (1968). Number of ψ scan sets used was 5 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.	k = −1→23
T_min = 0.013, T_max = 0.074	l = −12→13
3159 measured reflections	2 standard reflections every 120 min
3159 independent reflections	intensity decay: 10%

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0625P)² + 4.4831P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3159 reflections	Δρ_max = 3.48 e Å⁻³
142 parameters	Δρ_min = −2.57 e Å⁻³

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Bi	0.42097 (3)	0.42073 (2)	0.34670 (2)	0.02518 (11)
Cl1	0.2576 (2)	0.50934 (10)	0.50438 (18)	0.0329 (4)
Cl2	0.4635 (3)	0.32483 (10)	0.54389 (18)	0.0361 (4)
Cl3	0.1117 (3)	0.36755 (11)	0.2279 (2)	0.0441 (5)
Cl4	0.3821 (3)	0.52442 (12)	0.1571 (2)	0.0438 (5)
Cl5	0.5941 (4)	0.33648 (14)	0.2288 (3)	0.0635 (7)
OW	0.7852 (9)	0.2151 (4)	0.4798 (8)	0.0609 (18)
HW1	0.701 (11)	0.194 (6)	0.501 (12)	0.070*
HW2	0.732 (14)	0.251 (4)	0.434 (10)	0.070*
N1	0.0157 (8)	0.3538 (3)	0.8660 (6)	0.0291 (12)
H1	−0.0668	0.3405	0.9173	0.035*
N2	0.2250 (8)	0.3886 (3)	0.7369 (6)	0.0319 (13)
H2	0.3082	0.4026	0.6866	0.038*
C1	0.1780 (10)	0.3089 (4)	0.9111 (8)	0.0340 (16)
H1A	0.1513	0.2584	0.8867	0.041*
H1B	0.2238	0.3117	1.0072	0.041*
C6	0.0703 (11)	0.3511 (5)	0.6456 (7)	0.0403 (19)
H6A	0.1062	0.3045	0.6179	0.048*
H6B	0.0224	0.3805	0.5668	0.048*
C3	0.0613 (10)	0.4331 (4)	0.8868 (8)	0.0344 (16)
H3A	−0.0457	0.4618	0.8708	0.041*
H3B	0.1310	0.4413	0.9778	0.041*
C4	0.1641 (11)	0.4551 (4)	0.7924 (8)	0.0385 (17)
H4A	0.0904	0.4841	0.7209	0.046*
H4B	0.2650	0.4843	0.8386	0.046*
C5	−0.0695 (11)	0.3398 (5)	0.7206 (7)	0.0386 (17)
H5A	−0.1673	0.3731	0.6874	0.046*
H5B	−0.1147	0.2905	0.7078	0.046*
C2	0.3144 (11)	0.3374 (4)	0.8454 (8)	0.0385 (17)
H2A	0.4078	0.3625	0.9105	0.046*
H2B	0.3663	0.2973	0.8090	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Bi	0.02361 (17)	0.02675 (16)	0.02414 (16)	−0.00230 (9)	0.00482 (11)	−0.00228 (8)
Cl1	0.0253 (8)	0.0374 (9)	0.0354 (9)	0.0006 (7)	0.0073 (7)	0.0026 (7)
Cl2	0.0343 (9)	0.0360 (9)	0.0374 (9)	0.0016 (7)	0.0087 (7)	0.0066 (7)
Cl3	0.0352 (10)	0.0522 (11)	0.0396 (10)	−0.0140 (9)	0.0011 (8)	0.0003 (8)
Cl4	0.0282 (9)	0.0570 (12)	0.0434 (10)	−0.0072 (8)	0.0052 (8)	0.0165 (9)
Cl5	0.0703 (16)	0.0640 (15)	0.0643 (15)	0.0110 (12)	0.0319 (13)	−0.0197 (12)
OW	0.045 (4)	0.073 (5)	0.067 (5)	0.017 (3)	0.019 (3)	−0.016 (4)
N1	0.024 (3)	0.037 (3)	0.030 (3)	−0.001 (2)	0.013 (2)	−0.002 (2)
N2	0.027 (3)	0.035 (3)	0.037 (3)	0.003 (2)	0.016 (3)	0.005 (3)
C1	0.032 (4)	0.034 (4)	0.036 (4)	0.010 (3)	0.009 (3)	0.011 (3)
C6	0.044 (5)	0.054 (5)	0.021 (3)	0.002 (4)	0.005 (3)	−0.003 (3)
C3	0.032 (4)	0.030 (3)	0.043 (4)	0.002 (3)	0.012 (3)	−0.007 (3)
C4	0.038 (4)	0.030 (4)	0.050 (5)	−0.003 (3)	0.017 (4)	0.001 (3)
C5	0.033 (4)	0.050 (4)	0.028 (4)	−0.005 (3)	−0.001 (3)	−0.005 (3)
C2	0.034 (4)	0.041 (4)	0.040 (4)	0.012 (3)	0.010 (3)	0.014 (3)

Geometric parameters (Å, º) top

Bi—Cl5	2.588 (2)	N2—H2	0.9800
Bi—Cl3	2.601 (2)	C1—C2	1.517 (11)
Bi—Cl2	2.6611 (19)	C1—H1A	0.9700
Bi—Cl4	2.704 (2)	C1—H1B	0.9700
Bi—Cl1	2.8610 (19)	C6—C5	1.531 (11)
Bi—Cl1ⁱ	2.884 (2)	C6—H6A	0.9700
Cl1—Biⁱ	2.884 (2)	C6—H6B	0.9700
OW—HW1	0.850 (10)	C3—C4	1.493 (11)
OW—HW2	0.850 (10)	C3—H3A	0.9700
N1—C1	1.485 (9)	C3—H3B	0.9700
N1—C3	1.503 (9)	C4—H4A	0.9700
N1—C5	1.504 (9)	C4—H4B	0.9700
N1—H1	0.9800	C5—H5A	0.9700
N2—C4	1.489 (10)	C5—H5B	0.9700
N2—C2	1.492 (9)	C2—H2A	0.9700
N2—C6	1.494 (10)	C2—H2B	0.9700

Cl5—Bi—Cl3	95.45 (9)	C2—C1—H1B	110.0
Cl5—Bi—Cl2	90.07 (8)	H1A—C1—H1B	108.4
Cl3—Bi—Cl2	91.28 (7)	N2—C6—C5	108.1 (6)
Cl5—Bi—Cl4	92.39 (9)	N2—C6—H6A	110.1
Cl3—Bi—Cl4	90.73 (7)	C5—C6—H6A	110.1
Cl2—Bi—Cl4	176.66 (6)	N2—C6—H6B	110.1
Cl5—Bi—Cl1	173.58 (7)	C5—C6—H6B	110.1
Cl3—Bi—Cl1	88.74 (7)	H6A—C6—H6B	108.4
Cl2—Bi—Cl1	84.97 (6)	C4—C3—N1	108.6 (6)
Cl4—Bi—Cl1	92.41 (7)	C4—C3—H3A	110.0
Cl5—Bi—Cl1ⁱ	91.38 (8)	N1—C3—H3A	110.0
Cl3—Bi—Cl1ⁱ	173.16 (6)	C4—C3—H3B	110.0
Cl2—Bi—Cl1ⁱ	88.44 (6)	N1—C3—H3B	110.0
Cl4—Bi—Cl1ⁱ	89.25 (6)	H3A—C3—H3B	108.4
Cl1—Bi—Cl1ⁱ	84.43 (6)	N2—C4—C3	109.0 (6)
Bi—Cl1—Biⁱ	95.57 (6)	N2—C4—H4A	109.9
HW1—OW—HW2	102 (10)	C3—C4—H4A	109.9
C1—N1—C3	110.0 (6)	N2—C4—H4B	109.9
C1—N1—C5	109.4 (6)	C3—C4—H4B	109.9
C3—N1—C5	109.5 (6)	H4A—C4—H4B	108.3
C1—N1—H1	109.3	N1—C5—C6	108.0 (6)
C3—N1—H1	109.3	N1—C5—H5A	110.1
C5—N1—H1	109.3	C6—C5—H5A	110.1
C4—N2—C2	110.9 (6)	N1—C5—H5B	110.1
C4—N2—C6	109.5 (6)	C6—C5—H5B	110.1
C2—N2—C6	109.1 (6)	H5A—C5—H5B	108.4
C4—N2—H2	109.1	N2—C2—C1	108.5 (6)
C2—N2—H2	109.1	N2—C2—H2A	110.0
C6—N2—H2	109.1	C1—C2—H2A	110.0
N1—C1—C2	108.6 (5)	N2—C2—H2B	110.0
N1—C1—H1A	110.0	C1—C2—H2B	110.0
C2—C1—H1A	110.0	H2A—C2—H2B	108.4
N1—C1—H1B	110.0

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
Ow—Hw2···Cl5	0.91	2.63	3.458 (8)	163
N1—H1···Owⁱⁱ	0.91	1.87	2.739 (10)	159
Ow—Hw1···Cl5ⁱⁱⁱ	0.91	2.80	3.475 (9)	138
N2—H2···Cl1	0.91	2.73	3.352 (6)	127
N2—H2···Cl2	0.91	2.65	3.325 (7)	132

Symmetry codes: (ii) x−1, −y+1/2, z+1/2; (iii) x, −y+1/2, z+1/2.

Comparison of the cell parameters of the structures of [Bi₂Cl₁₀](C₆H₁₄N₂)₂.2H₂O and [Sb₂Cl₁₀](C₆H₁₄N₂)₂.2H₂O. top

Structural unit	[Bi₂Cl₁₀](C₆H₁₄N₂)₂.2H₂O	[Sb₂Cl₁₀](C₆H₁₄N₂)₂.2H₂O	Parameter variation (%) [(X_Bi-X_Sb)/(X_Sb)].100
Crystal system	monoclinic	orthorhombic	-
Space group	P 2₁/c	Pnnm => Pnmn (cba)	-
a (Å)	7.875 (3)	9.162 (1) => 7.566 (2)	4.08 (2)
b (Å)	18.379 (5)	20.689 (7) => 20.689 (7)	-11.16 (3)
c (Å)	10.444 (4)	7.566 (2) => 9.162 (1)	13.99 (2)
β (Å)	105.95 (3)	90.00	-
V (Å³)	1453.4 (9)	1446.8 (7)	0.45 (7)

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