Crystal structure of a new hybrid anti­mony–halide-based compound for possible non-linear optical applications

Ben Rhaiem, T.; Boughzala, H.

doi:10.1107/S2056989015007379

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages 498-501

https://doi.org/10.1107/S2056989015007379

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Crystal structure of a new hybrid antimony–halide-based compound for possible non-linear optical applications

Tarek Ben Rhaiem ^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: tarekbenrhaiem@hotmail.fr

Edited by A. Van der Lee, Université de Montpellier II, France (Received 31 March 2015; accepted 14 April 2015; online 18 April 2015)

The hybrid title compound, catena-poly[[[bis(1,4-diazoniabicyclo[2.2.2]octane) [tetraachloridoantimonate(III)]-μ-chlorido-[tetrachloridoantimonate(III)]-μ-chlorido]] monohydrate], {(C₆H₁₄N₂)₂[Sb₂Cl₁₀]·H₂O}_n, is self-assembled into alternating organic and inorganic layers parallel to the bc plane. The anionic inorganic layer consists of infinite zigzag chains of corner-sharing [SbCl₆]³⁻ octahedra running along the b axis. The organic part is made up of 1,4-diazoniabicyclo[2.2.2]octane dications (dabcoH₂²⁺). The water molecules in the structure connect inorganic and organic layers. Hydrogen-bonding interactions between the ammonium groups, water molecules and Cl atoms ensure the structure cohesion.

Keywords: crystal structure; chloridoantimonate(III); one-dimensional hybrid compound; (dabcoH₂)²⁺ cation.

CCDC reference: 943047

1. Chemical context

Organic–inorganic hybrid structures with the general formula {(R_a)ⁿ⁺M_bX_3b+na} (where R is an organic cation; M is any trivalent metal and X is Cl, Br or/and I) are able to combine desirable characteristics from both types of constituents into a molecular scale composite. These hybrids have been extensively studied for their excitonic and magneto-optical properties. In recent years, a significant number of organic–inorganic hybrid materials based on antimony–halide units have been studied. Six-coordinate antimony halides can arrange themselves in three-, two- or one-dimensional networks through sharing halides in the SbX₆ octahedra, separated by organic cations (Ben Rhaiem et al., 2013 ; Leblanc et al., 2012 ; Piecha et al., 2012 ; Bujack & Angel, 2005 , 2006 ; Bujack & Zaleski, 2004 ). One-dimensional extended chains can be formed by one, two or three bridging halides and combinations thereof. The use of one bridging halide leads to two types of chains; if the two bridging halides connecting the central octahedron to its neighbours are related cis, a zigzag pattern is obtained; if they are trans, the chain is linear.

2. Structural commentary

The asymmetric unit of the new chloridoantimonate(III) compound, (C₆H₁₄N₂)₂[Sb₂Cl₁₀]·H₂O, (I), consists of two symmetry-independant (dabcoH₂)²⁺ dications, a corner sharing bi-octahedron decachloridodiantimonate(III) anion and one crystallization water molecule. The cations are labeled Cat1 (containing atoms N1 and N2) and Cat2 (containing N3 and N4) and the atomic numbering scheme is shown in Fig. 1.

Figure 1
The asymmetric unit of (I)

completed by Cl4ⁱ, showing the atomic numbering scheme. Displacement ellipsoids are shown at 30% probability level. [Symmetry code: (i) x, y − 1, z.]

The structure of the title compound, (I), is self-assembled into an alternating organic and inorganic layered structure. The anionic layer consists of infinite zigzag chains of corner-sharing [SbCl₆]³⁻ octahedra running along the b axis. Thus, (I) can be classified among the one-dimensional hybrid structures. The organic part is made up of (dabcoH₂)²⁺ cations located in the holes around the corner-sharing octahedra. The layers are stacked along the a axis and water molecules connect the organic and inorganic components (Fig. 2).

Figure 2
The organic–inorganic layered structure of (I)

, projected along the c axis, showing the zigzag chains of corner-sharing [SbCl₆]³⁻ octahedra.

The inorganic structural unit part of (I) is build up by two Sb atoms in an octahedral coordination ([Sb1Cl₆]³⁻ and [Sb2Cl₆]³⁻) joined by the Cl2 ion. Both octahedra are severely distorted with Sb—Cl bond lengths lying in the range of 2.5233 (18)–3.073 (2) Å for the bridging ones and 2.4277 (15)–2.8233 (17) Å for the terminal ones. The two bridging halides (Cl2 and Cl4) connecting the central octahedron to its neighbours are related cis, leading to zigzag chain of corner-sharing [SbCl₆]³⁻ octahedra running along the b axis (Fig. 3).

Figure 3
A magnified view of the hydrogen bonding of the inorganic chain in (I)

. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) x, y − 1, z; (ii) x, y + 1, z; (iii) −x + 1, −y + 1, z + $[{1\over 2}]$ ; (iv) −x + 1, −y + 1, z − $[{1\over 2}]$ ; (v) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , z − $[{1\over 2}]$ .]

It is worth noting that at room temperature the DABCO molecule crystallizes in the hexagonal system (P6₃/m) (Nimmo & Lucas, 1976 ). In our case, Cat2 seems to be more distorted than Cat1. In fact, the highest absolute value of the N—C—C—N torsion angle of 7.80 (14)° proves that both (dabcoH₂)²⁺ cations exhibit deviations from ideal D_3h symmetry. The observed lowering symmetry (hexagonal to orthorhombic) is probably due to the distortion of the (dabcoH₂)²⁺ cation and can be related to the complex hydrogen-bond network linking the molecular components (cations, anions and water molecules).

The studied compound crystals are transparent and the structure is noncentrosymmetric (Pna2₁). These are two indispensable conditions making this phase a potential promising candidate for non-linear optical (NLO) behaviour as is the case for the well-known KTiOPO₄ (KTP) and equivalent efficient NLO materials.

3. Supramolecular features

As shown in Fig. 3, every bi-octahedron unit is linked to four (dabcoH₂)²⁺ cations and two water molecules via hydrogen bonds (Table 1): on one side Cat1 via Cl6⋯H1^iv—N1^iv and Cat 2 by Cl8⋯H3^v—N3^v, Cl9⋯H3^v—N3^v [symmetry codes: (iv) −x + 1, −y + 1, −z − $[{1\over 2}]$ ; (v) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , z − $[{1\over 2}]$ ] and the other side Cat1 via Cl1⋯H2ⁱⁱⁱ—N2ⁱⁱⁱ, Cl3⋯H2ⁱⁱⁱ—N2ⁱⁱⁱ and Cat2 by Cl3⋯H4ⁱⁱ—N4ⁱⁱ [symmetry codes: (ii) x, y + 1, z; (iii) −x + 1, −y + 1, z + $[{1\over 2}]$ ]. The water molecules are linked by Cl5⋯H13A—O and Cl9⋯H13B^v—O^v [symmetry code: (v) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , z − $[{1\over 2}]$ ].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl6ⁱ	0.95	2.67	3.391 (6)	134
N2—H2⋯Cl1ⁱⁱ	0.88	2.78	3.378 (4)	126
N2—H2⋯Cl3ⁱⁱ	0.88	2.62	3.281 (6)	133
N2—H2⋯Oⁱⁱ	0.88	2.46	3.040 (7)	124
N3—H3⋯Cl8ⁱⁱⁱ	0.89	2.82	3.418 (7)	126
N3—H3⋯Cl9ⁱⁱⁱ	0.89	2.38	3.132 (9)	143
N4—H4⋯Cl3^iv	0.87	2.66	3.303 (6)	131
N4—H4⋯O^iv	0.87	2.30	3.026 (8)	143
O—H13A⋯Cl5	0.84	2.43	3.185 (7)	151
O—H13B⋯Cl9ⁱⁱⁱ	0.83	2.66	3.210 (5)	126
Symmetry codes: (i) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x, y-1, z.

Using ammonium groups, both cations (Cat1 and Cat2) are linked to the anionic chains by hydrogen bonds via halogenous octahedral vertices. As shown in Fig. 4, Cat1 is linked by N1—H1⋯Cl6ⁱ hydrogen bond and three interactions between N2—H2 group, both vertices Cl1ⁱⁱ—Sb1ⁱⁱ, Cl3ⁱⁱ—Sb1ⁱⁱ and O atom of the water molecule [symmetry codes: (i) −x + 1, −y + 1, z + $[{1\over 2}]$ ; (ii) −x + 1, −y + 1, z − $[{1\over 2}]$ ]. On the other hand, each ammonium group of Cat 2 interacts by two hydrogen bonds. N4—H4 to Cl3ⁱ—Sb1ⁱ and the O atom and N3—H3 group to both Cl8ⁱⁱ—Sb2ⁱⁱ and Cl9ⁱⁱ—Sb2ⁱⁱ vertices (Fig. 5) [symmetry codes: (i) x, y − 1, z; (ii) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ].

Figure 4
The hydrogen-bonding environment of Cat 1 in (I)

. Only H atoms involved in hydrogen bonding have been represented. [Symmetry codes: (i) −x + 1, −y + 1, z + $[{1\over 2}]$ ; (ii) −x + 1, −y + 1, z − $[{1\over 2}]$ .]

Figure 5
The hydrogen-bonding environment of Cat 2 in (I)

. Only H atoms involved in hydrogen bonding have been represented. [Symmetry codes: (i) x, y − 1, z; (ii) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , z + $[{1\over 2}]$ .]

As can be seen in Fig. 6, the water molecule plays an important role in the structure connectivity. It is establishing four hydrogen links joining Cat1 by O⋯H2ⁱⁱ—N2ⁱⁱ, Cat2 through O⋯H4ⁱ—N4ⁱ and two [SbCl₆]³⁻ octahedra via O—H13A⋯Cl5 and O—H13B⋯Cl9ⁱⁱⁱ [symmetry codes: (i) x, y + 1, z; (ii) −x + 1, −y + 1, z + $[{1\over 2}]$ ; (iii) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ].

Figure 6
Water-molecule hydrogen-bonding interactions in (I)

. C—H bonds have been omitted for clarity. [Symmetry codes: (i) x, y + 1, z; (ii) −x + 1, −y + 1, z + $[{1\over 2}]$ ; (iii) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , z + $[{1\over 2}]$ .]

4. Database survey

A search of the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014 ) gave 184 hits for organic–inorganic hybrid materials based on antimony chloride units. For this class of compounds with (dabcoH₂)²⁺ cations, there is only one zero-dimensional compound, (C₆H₁₄N₂)₂[Sb₂Cl₁₀]·2H₂O containing isolated [Sb₂Cl₁₀]⁴⁻ double octahedra, (dabcoH₂)²⁺ cations and water molecules (Ben Rhaiem et al., 2013). Indeed, this compound is a pseudo-polymorph over the title compound. For similar one-dimensional compounds with N,N-dimethylethylenediammonium cations, [(CH₃)₂NH(CH₂)₂NH₃]²⁺, see: Bujack & Angel (2006). For two-dimensional compounds with [{Sb₂Cl₉}_n]³ⁿ⁻ polyanionic layers, see: Bujack & Angel (2005); Bujack & Zaleski (2004).

5. Synthesis and crystallization

A mixture of SbCl₃ (1 mmol) and DABCO (0.5 mmol) was dissolved in a hydrochloric aqueous solution and stirred for several minutes at 353 K. Colourless crystals suitable for X-ray diffraction analysis were obtained by slow evaporation at room temperature after two weeks.

6. Refinement

Data collection and structure refinement details are summarized in Table 2. H atoms were localized from geometrical constraint conditions using adequate AFIX and DFIX SHELXL (Sheldrick, 2008 ) options and parameters were refined with a common isotropic displacement parameter. Water H atoms were found in difference Fourier maps and O—H distances were refined using DFIX and DANG soft restraints. The Flack parameter was refined despite the low Friedel pair coverage because the structure contains a sufficient number of relatively strong anomalous scatterers.

Table 2
Experimental details

Crystal data
Chemical formula	(C₆H₁₄N₂)₂[Sb₂Cl₁₀]·H₂O
M_r	844.40
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	298
a, b, c (Å)	29.122 (3), 8.4029 (10), 11.358 (2)
V (Å³)	2779.4 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.92
Crystal size (mm)	0.13 × 0.06 × 0.02

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968 )
T_min, T_max	0.358, 0.555
No. of measured, independent and observed [I > 2σ(I)] reflections	7000, 3492, 2988
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.070, 1.09
No. of reflections	3492
No. of parameters	273
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.62
Absolute structure	Flack (1983 ), 66 Friedel pairs
Absolute structure parameter	−0.01 (3)
Computer programs: CAD-4 EXPRESS (Duisenberg, 1992 ), XCAD4 (Harms & Wocadlo, 1995 ), SHELXS97 and SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 943047

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015007379/vn2091sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015007379/vn2091Isup2.hkl

checkCIF report

Computing details top

Data collection: CAD-4 EXPRESS (Duisenberg, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

catena-poly[[[bis(1,4-diazoniabicyclo[2.2.2]octane) [tetraachloridoantimonate(III)]-µ-chlorido-[tetrachloridoantimonate(III)]-µ-chlorido]] monohydrate] top

Crystal data top

(C₆H₁₄N₂)₂[Sb₂Cl₁₀]·H₂O	D_x = 2.018 Mg m⁻³
M_r = 844.40	Melting point: 594 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3492 reflections
a = 29.122 (3) Å	θ = 2.4–27.0°
b = 8.4029 (10) Å	µ = 2.92 mm⁻¹
c = 11.358 (2) Å	T = 298 K
V = 2779.4 (7) Å³	Prism, colourless
Z = 4	0.13 × 0.06 × 0.02 mm
F(000) = 1640

Data collection top

Enraf–Nonius CAD-4 diffractometer	2988 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.041
Graphite monochromator	θ_max = 27.0°, θ_min = 2.3°
non–profiled ω/2θ scans	h = −37→1
Absorption correction: ψ scan (North et al., 1968)	k = −10→10
T_min = 0.358, T_max = 0.555	l = −1→14
7000 measured reflections	2 standard reflections every 120 min
3492 independent reflections	intensity decay: −1%

Refinement top

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)] = 0.026	w = 1/[σ²(F_o²) + (0.0316P)² + 2.3277P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.070	(Δ/σ)_max = 0.001
S = 1.09	Δρ_max = 0.72 e Å⁻³
3492 reflections	Δρ_min = −0.62 e Å⁻³
273 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
5 restraints	Extinction coefficient: 0.00168 (12)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 66 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (3)

Special details top

Experimental. Absorption correction: North et al. (1968) Number of psi-scan sets used was 6 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.

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.

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

	x	y	z	U_iso*/U_eq
Sb1	0.593657 (12)	0.74481 (3)	0.49688 (3)	0.02787 (11)
Sb2	0.657146 (11)	0.24077 (3)	0.22050 (3)	0.02842 (11)
Cl1	0.57361 (5)	0.54093 (18)	0.66622 (15)	0.0452 (4)
Cl2	0.61712 (8)	0.5151 (2)	0.3671 (2)	0.0760 (6)
Cl3	0.57606 (5)	0.97355 (17)	0.67100 (15)	0.0437 (3)
Cl4	0.61408 (7)	0.9753 (2)	0.3459 (2)	0.0765 (6)
Cl5	0.67713 (6)	0.75095 (17)	0.56999 (19)	0.0522 (4)
Cl6	0.50864 (7)	0.7328 (2)	0.3883 (2)	0.0619 (5)
Cl7	0.69068 (7)	0.4519 (2)	0.09980 (17)	0.0645 (5)
Cl8	0.68555 (6)	0.0345 (2)	0.08973 (16)	0.0562 (5)
Cl9	0.74068 (5)	0.19561 (18)	0.34215 (18)	0.0430 (3)
Cl10	0.58708 (5)	0.25828 (14)	0.1013 (2)	0.0478 (4)
N1	0.49311 (19)	0.2444 (5)	0.5900 (5)	0.0390 (12)
H1	0.5113 (15)	0.2480 (6)	0.659 (6)	0.047*
N2	0.44602 (17)	0.2354 (5)	0.4084 (5)	0.0378 (11)
H2	0.4294 (4)	0.2318 (5)	0.3440 (16)	0.045*
N3	0.72003 (16)	0.3837 (5)	0.7294 (5)	0.0389 (11)
H3	0.7352 (10)	0.475 (6)	0.7261 (5)	0.047*
N4	0.6767 (2)	0.1317 (6)	0.7367 (7)	0.068 (2)
H4	0.6616 (14)	0.044 (8)	0.7384 (7)	0.082*
C1	0.5235 (2)	0.2498 (6)	0.4859 (7)	0.0455 (16)
H1A	0.5447	0.1609	0.4882	0.055*
H1B	0.5412	0.3475	0.4867	0.055*
C2	0.4952 (2)	0.2417 (8)	0.3748 (8)	0.059 (2)
H2A	0.5010	0.3347	0.3264	0.071*
H2B	0.5033	0.1476	0.3299	0.071*
C3	0.4365 (2)	0.0911 (7)	0.4788 (6)	0.0481 (17)
H3A	0.4434	−0.0030	0.4326	0.058*
H3B	0.4043	0.0880	0.5001	0.058*
C4	0.4656 (2)	0.0921 (7)	0.5887 (6)	0.0479 (15)
H4A	0.4860	0.0010	0.5891	0.057*
H4B	0.4461	0.0865	0.6579	0.057*
C5	0.4622 (2)	0.3851 (8)	0.5871 (6)	0.0510 (16)
H5A	0.4802	0.4821	0.5888	0.061*
H5B	0.4423	0.3844	0.6556	0.061*
C6	0.4333 (2)	0.3800 (6)	0.4754 (6)	0.0467 (17)
H6A	0.4010	0.3773	0.4953	0.056*
H6B	0.4391	0.4742	0.4283	0.056*
C7	0.7097 (3)	0.3302 (8)	0.6095 (6)	0.063 (2)
H7A	0.7381	0.3127	0.5668	0.075*
H7B	0.6924	0.4116	0.5685	0.075*
C8	0.6829 (4)	0.1808 (11)	0.6134 (8)	0.092 (4)
H8A	0.6532	0.1972	0.5767	0.110*
H8B	0.6989	0.0981	0.5702	0.110*
C9	0.6768 (2)	0.4080 (7)	0.7935 (7)	0.0473 (15)
H9A	0.6577	0.4839	0.7516	0.057*
H9B	0.6831	0.4505	0.8712	0.057*
C10	0.6519 (2)	0.2512 (6)	0.8042 (8)	0.0479 (18)
H10A	0.6502	0.2195	0.8862	0.057*
H10B	0.6208	0.2617	0.7744	0.057*
C11	0.7484 (3)	0.2641 (9)	0.7941 (10)	0.081 (3)
H11A	0.7525	0.2964	0.8754	0.097*
H11B	0.7784	0.2535	0.7577	0.097*
C12	0.7221 (3)	0.1056 (10)	0.7878 (11)	0.107 (4)
H12A	0.7391	0.0303	0.7399	0.129*
H12B	0.7190	0.0612	0.8662	0.129*
O	0.65412 (17)	0.8095 (7)	0.8407 (6)	0.0637 (14)
H13A	0.662 (3)	0.760 (8)	0.780 (4)	0.070*
H13B	0.674 (2)	0.788 (9)	0.890 (5)	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb1	0.0343 (2)	0.02365 (18)	0.0257 (2)	−0.00135 (12)	0.00135 (16)	−0.00099 (18)
Sb2	0.03007 (18)	0.02876 (19)	0.0264 (2)	0.00021 (12)	−0.00028 (17)	−0.0021 (2)
Cl1	0.0497 (9)	0.0439 (7)	0.0421 (8)	−0.0053 (6)	−0.0007 (7)	−0.0001 (7)
Cl2	0.0915 (15)	0.0703 (11)	0.0662 (14)	0.0140 (11)	0.0062 (12)	−0.0308 (11)
Cl3	0.0418 (8)	0.0419 (7)	0.0473 (8)	0.0013 (6)	−0.0043 (7)	0.0077 (7)
Cl4	0.0833 (14)	0.0808 (13)	0.0655 (14)	−0.0231 (11)	−0.0066 (13)	0.0276 (12)
Cl5	0.0457 (8)	0.0532 (9)	0.0578 (12)	−0.0055 (7)	0.0018 (8)	0.0039 (8)
Cl6	0.0538 (10)	0.0626 (11)	0.0695 (14)	−0.0031 (8)	0.0168 (10)	0.0005 (10)
Cl7	0.0750 (12)	0.0718 (11)	0.0466 (10)	−0.0361 (9)	−0.0079 (10)	0.0184 (9)
Cl8	0.0638 (11)	0.0643 (9)	0.0406 (9)	0.0285 (8)	−0.0105 (8)	−0.0222 (8)
Cl9	0.0429 (7)	0.0501 (7)	0.0360 (7)	0.0012 (7)	0.0007 (7)	−0.0113 (7)
Cl10	0.0447 (8)	0.0333 (7)	0.0652 (12)	0.0041 (5)	−0.0225 (8)	−0.0034 (7)
N1	0.044 (3)	0.038 (3)	0.035 (3)	0.001 (2)	−0.007 (2)	0.000 (2)
N2	0.039 (3)	0.036 (2)	0.038 (3)	0.0019 (18)	−0.007 (2)	0.003 (2)
N3	0.046 (3)	0.033 (2)	0.038 (3)	−0.0052 (18)	0.004 (3)	−0.003 (2)
N4	0.089 (5)	0.028 (2)	0.088 (5)	−0.010 (3)	0.049 (4)	0.000 (3)
C1	0.034 (3)	0.041 (3)	0.062 (5)	−0.004 (2)	0.004 (3)	0.003 (3)
C2	0.045 (4)	0.089 (6)	0.043 (4)	−0.001 (3)	0.003 (3)	−0.001 (4)
C3	0.057 (4)	0.031 (2)	0.057 (4)	−0.008 (2)	−0.021 (4)	0.009 (3)
C4	0.053 (4)	0.046 (3)	0.044 (4)	−0.011 (3)	−0.002 (3)	0.013 (3)
C5	0.055 (4)	0.051 (3)	0.047 (4)	0.012 (3)	0.000 (3)	−0.009 (3)
C6	0.057 (4)	0.032 (3)	0.051 (4)	0.010 (3)	−0.014 (3)	−0.004 (3)
C7	0.110 (7)	0.051 (3)	0.026 (3)	−0.031 (4)	0.009 (4)	−0.004 (3)
C8	0.133 (9)	0.087 (6)	0.054 (5)	−0.071 (6)	0.028 (6)	−0.035 (5)
C9	0.052 (4)	0.038 (3)	0.052 (4)	0.002 (3)	0.008 (3)	−0.015 (3)
C10	0.047 (4)	0.051 (4)	0.046 (4)	0.004 (3)	0.017 (3)	0.004 (3)
C11	0.056 (5)	0.111 (7)	0.075 (7)	0.033 (5)	−0.011 (5)	−0.004 (5)
C12	0.103 (8)	0.071 (5)	0.148 (10)	0.047 (5)	0.079 (7)	0.060 (6)
O	0.055 (3)	0.067 (3)	0.069 (4)	0.017 (2)	−0.010 (3)	−0.016 (3)

Geometric parameters (Å, º) top

Sb1—Cl2	2.5233 (18)	C1—H1B	0.9700
Sb1—Cl5	2.5695 (18)	C2—H2A	0.9700
Sb1—Cl1	2.6411 (17)	C2—H2B	0.9700
Sb1—Cl4	2.654 (2)	C3—C4	1.507 (9)
Sb1—Cl6	2.768 (2)	C3—H3A	0.9700
Sb1—Cl3	2.8051 (17)	C3—H3B	0.9700
Sb2—Cl8	2.4277 (15)	C4—H4A	0.9700
Sb2—Cl7	2.4457 (17)	C4—H4B	0.9700
Sb2—Cl10	2.4532 (16)	C5—C6	1.521 (9)
Sb2—Cl9	2.8233 (17)	C5—H5A	0.9700
Sb2—Cl2	3.073 (2)	C5—H5B	0.9700
Sb2—Cl4ⁱ	2.9291 (19)	C6—H6A	0.9700
N1—C1	1.477 (9)	C6—H6B	0.9700
N1—C5	1.487 (8)	C7—C8	1.480 (10)
N1—C4	1.510 (7)	C7—H7A	0.9700
N1—H1	0.9496	C7—H7B	0.9700
N2—C3	1.478 (7)	C8—H8A	0.9700
N2—C6	1.481 (7)	C8—H8B	0.9700
N2—C2	1.483 (9)	C9—C10	1.509 (7)
N2—H2	0.8784	C9—H9A	0.9700
N3—C7	1.465 (8)	C9—H9B	0.9700
N3—C9	1.469 (8)	C10—H10A	0.9700
N3—C11	1.494 (9)	C10—H10B	0.9700
N3—H3	0.8858	C11—C12	1.538 (11)
N4—C10	1.456 (8)	C11—H11A	0.9700
N4—C12	1.462 (12)	C11—H11B	0.9700
N4—C8	1.471 (11)	C12—H12A	0.9700
N4—H4	0.8565	C12—H12B	0.9700
C1—C2	1.508 (11)	O—H13A	0.84 (2)
C1—H1A	0.9700	O—H13B	0.82 (2)

Cl2—Sb1—Cl5	87.02 (7)	C1—C2—H2B	110.0
Cl2—Sb1—Cl1	89.38 (7)	H2A—C2—H2B	108.4
Cl5—Sb1—Cl1	89.25 (6)	N2—C3—C4	109.8 (5)
Cl2—Sb1—Cl4	96.90 (9)	N2—C3—H3A	109.7
Cl5—Sb1—Cl4	88.98 (6)	C4—C3—H3A	109.7
Cl1—Sb1—Cl4	173.38 (6)	N2—C3—H3B	109.7
Cl2—Sb1—Cl6	87.36 (7)	C4—C3—H3B	109.7
Cl5—Sb1—Cl6	172.33 (7)	H3A—C3—H3B	108.2
Cl1—Sb1—Cl6	95.92 (6)	C3—C4—N1	108.1 (5)
Cl4—Sb1—Cl6	86.51 (6)	C3—C4—H4A	110.1
Cl2—Sb1—Cl3	170.28 (7)	N1—C4—H4A	110.1
Cl5—Sb1—Cl3	86.05 (5)	C3—C4—H4B	110.1
Cl1—Sb1—Cl3	83.72 (5)	N1—C4—H4B	110.1
Cl4—Sb1—Cl3	89.79 (6)	H4A—C4—H4B	108.4
Cl6—Sb1—Cl3	100.12 (5)	N1—C5—C6	109.3 (5)
Cl8—Sb2—Cl7	92.23 (8)	N1—C5—H5A	109.8
Cl8—Sb2—Cl10	89.35 (6)	C6—C5—H5A	109.8
Cl7—Sb2—Cl10	88.82 (7)	N1—C5—H5B	109.8
Cl8—Sb2—Cl9	84.83 (5)	C6—C5—H5B	109.8
Cl7—Sb2—Cl9	91.59 (6)	H5A—C5—H5B	108.3
Cl10—Sb2—Cl9	174.17 (6)	N2—C6—C5	108.3 (5)
Cl4ⁱ—Sb2—Cl10	87.62 (5)	N2—C6—H6A	110.0
Cl2—Sb2—Cl10	86.49 (6)	C5—C6—H6A	110.0
Cl4ⁱ—Sb2—Cl9	91.63 (5)	N2—C6—H6B	110.0
Cl2—Sb2—Cl9	99.35 (5)	C5—C6—H6B	110.0
Cl8—Sb2—Cl4ⁱ	84.24 (6)	H6A—C6—H6B	108.4
Cl4ⁱ—Sb2—Cl2	98.36 (5)	N3—C7—C8	109.9 (6)
Cl2—Sb2—Cl7	84.89 (6)	N3—C7—H7A	109.7
Cl2—Sb2—Cl8	174.98 (6)	C8—C7—H7A	109.7
Cl4ⁱ—Sb2—Cl7	175.00 (6)	N3—C7—H7B	109.7
C1—N1—C5	108.7 (5)	C8—C7—H7B	109.7
C1—N1—C4	109.6 (5)	H7A—C7—H7B	108.2
C5—N1—C4	110.6 (5)	N4—C8—C7	109.3 (6)
C1—N1—H1	109.3	N4—C8—H8A	109.8
C5—N1—H1	109.3	C7—C8—H8A	109.8
C4—N1—H1	109.3	N4—C8—H8B	109.8
C3—N2—C6	110.4 (5)	C7—C8—H8B	109.8
C3—N2—C2	110.4 (5)	H8A—C8—H8B	108.3
C6—N2—C2	110.1 (5)	N3—C9—C10	109.3 (5)
C3—N2—H2	108.6	N3—C9—H9A	109.8
C6—N2—H2	108.6	C10—C9—H9A	109.8
C2—N2—H2	108.6	N3—C9—H9B	109.8
C7—N3—C9	109.1 (5)	C10—C9—H9B	109.8
C7—N3—C11	111.4 (6)	H9A—C9—H9B	108.3
C9—N3—C11	108.9 (6)	N4—C10—C9	108.7 (5)
C7—N3—H3	109.1	N4—C10—H10A	109.9
C9—N3—H3	109.1	C9—C10—H10A	109.9
C11—N3—H3	109.1	N4—C10—H10B	109.9
C10—N4—C12	110.1 (7)	C9—C10—H10B	109.9
C10—N4—C8	111.6 (7)	H10A—C10—H10B	108.3
C12—N4—C8	108.0 (8)	N3—C11—C12	106.5 (7)
C10—N4—H4	109.0	N3—C11—H11A	110.4
C12—N4—H4	109.0	C12—C11—H11A	110.4
C8—N4—H4	109.0	N3—C11—H11B	110.4
N1—C1—C2	110.0 (5)	C12—C11—H11B	110.4
N1—C1—H1A	109.7	H11A—C11—H11B	108.6
C2—C1—H1A	109.7	N4—C12—C11	109.8 (6)
N1—C1—H1B	109.7	N4—C12—H12A	109.7
C2—C1—H1B	109.7	C11—C12—H12A	109.7
H1A—C1—H1B	108.2	N4—C12—H12B	109.7
N2—C2—C1	108.3 (6)	C11—C12—H12B	109.7
N2—C2—H2A	110.0	H12A—C12—H12B	108.2
C1—C2—H2A	110.0	H13A—O—H13B	105 (4)
N2—C2—H2B	110.0

Symmetry code: (i) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl6ⁱⁱ	0.95	2.67	3.391 (6)	134
N2—H2···Cl1ⁱⁱⁱ	0.88	2.78	3.378 (4)	126
N2—H2···Cl3ⁱⁱⁱ	0.88	2.62	3.281 (6)	133
N2—H2···Oⁱⁱⁱ	0.88	2.46	3.040 (7)	124
N3—H3···Cl8^iv	0.89	2.82	3.418 (7)	126
N3—H3···Cl9^iv	0.89	2.38	3.132 (9)	143
N4—H4···Cl3ⁱ	0.87	2.66	3.303 (6)	131
N4—H4···Oⁱ	0.87	2.30	3.026 (8)	143
O—H13A···Cl5	0.84	2.43	3.185 (7)	151
O—H13B···Cl9^iv	0.83	2.66	3.210 (5)	126

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, z+1/2; (iii) −x+1, −y+1, z−1/2; (iv) −x+3/2, y+1/2, z+1/2.

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