Crystal structures of isotypic poly[bis­(benz­imid­azolium) [tetra-μ-iodido-stannate(II)]] and poly[bis­(5,6-di­fluoro­benzimidazolium) [tetra-μ-iodido-stannate(II)]]

Zimmermann, I.; Keene, T.D.; Hauser, J.; Decurtins, S.; Liu, S.-X.

doi:10.1107/S1600536814019151

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ISSN: 2056-9890

Volume 70| Part 10| October 2014| Pages 178-182

doi:10.1107/S1600536814019151

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Crystal structures of isotypic poly[bis(benzimidazolium) [tetra-μ-iodido-stannate(II)]] and poly[bis(5,6-difluorobenzimidazolium) [tetra-μ-iodido-stannate(II)]]

Iwan Zimmermann,^a Tony D. Keene,^a Jürg Hauser,^a Silvio Decurtins ^a and Shi-Xia Liu ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland
^*Correspondence e-mail: liu@dcb.unibe.ch

Edited by M. Weil, Vienna University of Technology, Austria (Received 25 July 2014; accepted 25 August 2014; online 10 September 2014)

The isostructural title compounds, {(C₇H₇N₂)₂[SnI₄]}_n, (1), and {(C₇H₅F₂N₂)₂[SnI₄]}_n, (2), show a layered perovskite-type structure composed of anionic {[SnI₄]²⁻}_n sheets parallel to (100), which are decorated on both sides with templating benzimidazolium or 5,6-difluorobenzimidazolium cations, respectively. These planar organic heterocycles mainly form N—H⋯I hydrogen bonds to the terminal I atoms of the corner-sharing [SnI₆] octahedra (point group symmetry 2) from the inorganic layer, but not to the bridging ones. This is in contrast to most of the reported structures of related compounds where ammonium cations are involved. Here hydrogen bonding to both types of iodine atoms and thereby a distortion of the inorganic layers to various extents is observed. For (1) and (2), all Sn—I—Sn angles are linear and no out-of-plane distortions of the inorganic layers occur, a fact of relevance in view of the material properties. The arrangement of the aromatic cations is mainly determined through the direction of the N—H⋯I hydrogen bonds. The coherence between organic bilayers along [100] is mainly achieved through van der Waals interactions.

Keywords: crystal structure; benzimidazolium; tin(II) iodide layers; perovskite layer.

CCDC references: 1021082; 1021083

1. Chemical context

For most reported layered perovskites, these organic molecules are terminated with one or two protonated primary amine groups. Thereby, the ammonium head(s) form N—H⋯X hydrogen bonds to any of the bridging and terminal halogen atoms in the inorganic layers (Mitzi et al., 2002 ; Mercier et al., 2004 ; Sourisseau et al., 2007 ; Pradeesh et al., 2013 ). In the actual case, however, as a novel aspect, the bicyclic aromatic benzimidazole unit is introduced as an organic part. There are numerous general examples of benzimidazole acting as a neutral ligand (Keene et al., 2010 ) and similarly in its protonated form (Mouchaham et al., 2010 ). In this context, the present study explicitly demonstrates that benzimidazolium cations and corresponding derivatives can stabilize the layered perovskite structure as well, while fitting perfectly into the `footprint' provided by the inorganic framework. This observation bears importance since the extent of the in- and out-of-plane angular distortions, twisting and buckling of the anionic sheets, is largely determined by the relative charge density, steric requirements and hydrogen-bonding pattern of the organic cations (Knutson & Martin, 2005 ; Takahashi et al., 2007 ). These distortions correlate with the band gaps of the perovskite-type semiconductors. It is interesting to note that perovskite-based solar cells have recently been catapulted to the cutting edge of thin-film photovoltaic research (Hao et al., 2014 ; Marchioro et al., 2014 ). Consequently, the chemical variability which comes with the imidazolium cation, especially the range of possible substitutions on its molecular skeleton, gives an additional structural diversity to this class of compounds. As a case in point, consider the difluoro-substituted compound (2) which renders not only modified van der Waals interactions for the organic bilayers, but also tailors the `chemistry' of the crystal surfaces.

2. Structural commentary

Compounds (1) and (2) are isostructural. Their asymmetric units, Figs. 1 and 2, consist of an Sn²⁺ cation situated on a twofold rotation axis (Wyckoff position 4e), three iodine atoms [one in a general position, one on an inversion centre (4a) and one on a twofold rotation axis (4e)] and a benzimidazolium or 5,6-difluorobenzimidazolium cation, respectively. The main building blocks of the structure are corner-sharing [SnI₆] octahedra, which form planar sheets with formula {[SnI₄]²⁻}_n which extend parallel to (100). The negative charge of these layers is compensated by the organic cations, which are on both sides of the layer, attached by strong hydrogen-bonding and Coulombic interactions (Figs. 3 and 4). This structural motif can be regarded as an A–B–A layer system, where A represents the aromatic cation and B the tin iodide layer. The coherence between organic bilayers along [100] is mainly achieved through van der Waals interactions. The Sn—I bond lengths for (1) range from 3.0626 (3) Å to 3.1607 (3) Å [(2): 3.0491 (5) Å to 3.1596 (3) Å], with no distinct pattern for bridging compared to terminal iodine atoms (Tables 1 and 2). These values are in agreement with those reported previously for related tin iodide perovskite structures, as for example [(C₄H₉NH₃)₂[SnI₄]], where the bond lengths range from 3.133 Å to 3.16 Å (Mitzi, 1996 ). The I—Sn—I angles of the [SnI₆] octahedra in the title structures deviate slightly from the ideal octahedral geometry. With 83.886 (4)° for (1) [(2): 84.077 (6)°], the I2—Sn1—I3 angle has the largest difference. On the other hand, all Sn—I—Sn angles are linear, which leads to the formation of an almost rectangular grid (Fig. 5). There is no out-of-plane distortion of the inorganic sheet. The arrangement of the aromatic cations is mainly determined through the direction of N—H⋯I hydrogen bonds to the apical iodine atoms (Tables 3 and 4; Figs. 3 and 4). There is no N—H⋯I_bridging contact smaller than the sum of the respective van der Waals radii (H: 1.2, I: 1.98 Å; Bondi, 1964 ). This is in contrast to primary ammonium cations, which form hydrogen bonds to both apical and bridging iodine atoms. The shortest H⋯I_bridging distance is C3—H3⋯I2 with 3.12 Å for (1) [(2): 3.19 Å] close to the sum of van der Waals radii. Adjacent cations within an organic layer show a plane-to-plane distance of 3.786 Å for (1) [(2): 3.730 Å] (Fig. 6). The shortest contact distances between the organic bilayers for both compounds are close to the sums of the van der Waals radii [C8⋯H6ⁱ 2.801 Å in (1) and F8⋯H9ⁱⁱ 2.557 Å in (2); (i): $[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (ii): $[{1\over 2}]$ − x, $[{1\over 2}]$ − y, −z]. The larger size of the fluorine atom in comparison to the hydrogen atom is reflected in a larger A–B–A layer spacing of 14.407 Å for (2) compared to 13.950 Å for (1).

Table 1
Selected geometric parameters (Å, °) for (1)

Sn1—I1	3.1571 (2)	Sn1—I3	3.1607 (3)
Sn1—I2	3.1242 (1)	Sn1—I3ⁱ	3.0626 (3)

I1—Sn1—I2	89.357 (3)	I2—Sn1—I3	83.886 (4)
I1—Sn1—I2ⁱⁱ	90.984 (3)	I1—Sn1—I3ⁱ	88.396 (4)
I1—Sn1—I1ⁱⁱ	176.793 (9)	I2—Sn1—I3ⁱ	96.114 (4)
I2—Sn1—I2ⁱⁱ	167.773 (7)	I3—Sn1—I3ⁱ	180.0
I1—Sn1—I3	91.604 (4)
Symmetry codes: (i) x, y+1, z; (ii) $[-x, y, -z+{\script{1\over 2}}]$ .

Table 2
Selected geometric parameters (Å, °) for (2)

Sn1—I1	3.1596 (3)	Sn1—I3	3.1310 (5)
Sn1—I2	3.1129 (1)	Sn1—I3ⁱ	3.0491 (5)

I1—Sn1—I2	89.374 (6)	I2—Sn1—I3	84.077 (6)
I1—Sn1—I2ⁱⁱ	90.984 (6)	I1—Sn1—I3ⁱ	88.269 (7)
I1—Sn1—I1ⁱⁱ	176.539 (14)	I2—Sn1—I3ⁱ	95.923 (6)
I2—Sn1—I2ⁱⁱ	168.154 (12)	I3—Sn1—I3ⁱ	180.0
I1—Sn1—I3	91.731 (7)
Symmetry codes: (i) x, y+1, z; (ii) $[-x, y, -z+{\script{1\over 2}}]$ .

Table 3
Hydrogen-bond geometry (Å, °) for (1)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯I1ⁱⁱⁱ	0.81 (3)	2.85 (3)	3.615 (2)	158 (3)
N4—H4⋯I1ⁱ	0.85 (3)	2.86 (3)	3.630 (2)	151 (2)
Symmetry codes: (i) x, y+1, z; (iii) $[x, -y, z-{\script{1\over 2}}]$ .

Table 4
Hydrogen-bond geometry (Å, °) for (2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯I1ⁱⁱⁱ	0.95 (6)	2.79 (6)	3.610 (4)	145 (4)
N4—H4⋯I1ⁱ	0.75 (5)	2.88 (6)	3.587 (4)	157 (6)
Symmetry codes: (i) x, y+1, z; (iii) $[x, -y, z-{\script{1\over 2}}]$ .

Figure 1
The main building units of (1), showing atom labeling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) x, y + 1, z; (ii) −x, y, −z + $[{1\over 2}]$ .]

Figure 2
The main building units of (2), showing atom labeling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) x, y + 1, z; (ii) −x, y, −z + $[{1\over 2}]$ .]

Figure 3
The crystal packing of compound (1) viewed along [010]. N—H⋯I hydrogen bonds are shown as dashed lines.

Figure 4
The crystal packing of compound (2) viewed along [010]. N—H⋯I hydrogen bonds are shown as dashed lines.

Figure 5
View along the a* axis of a tin iodide layer of (2). For clarity, the atoms are represented as spheres with uniform sizes selected for each atom type.

Figure 6
View along the a* axis of a double layer of tin iodide and the organic cations of (2). For clarity, the [SnI₆] octahedra are shown as polyhedra, the atoms of the organic cations are represented as spheres with uniform sizes selected for each atom type.

3. Database survey

In the Cambridge Structural Database (Version 5.35, last update November 2013; Allen, 2002 ) no structures of compounds containing a (benz)imidazolium cation for layered perovskites are listed, making the two examples presented herein the only ones reported so far.

4. Synthesis and crystallization

Compound (1) was synthesized and crystallized by a solvothermal method using a mixture of tin(II) iodide and benzimidazole in a 1:2 molar ratio. In a 50 ml round-bottom flask, 4 ml concentrated HI (57 wt. %, stabilized with hypophosphorous acid) was mixed with 2 mmol (0.236 g) benzimidazole. After stirring for one minute, this solution was added to a sample flask containing 1 mmol (0.372 g) tin(II) iodide. The reaction flask was put in a 23 ml Teflon container. The reaction was conducted at 363 K for ten h after which the autoclave was slowly cooled (1 K/h) to room temperature. Thin, black plate-like crystals were obtained. The synthetic procedure for (2) was identical to that for (1), only using 0.5 mmol (0.77 g) 5,6-difluorobenzimidazole and 0.25 mmol (0.093 g) tin(II) iodide as starting materials. Thin, black plate-like crystals were obtained.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. The N-H hydrogen atoms were located in difference Fourier maps and were freely refined. The C-bound hydrogen atoms were included in calculated positions and treated as riding atoms with C—H = 0.95 Å. The isotropic displacement parameters of all H atoms were constrained to 1.2U_eq of their parent atoms. The crystal of compound (2) was a non-merohedral twin. The two twin components were related by a twofold rotation about the c* axis. The data from both twin components were integrated to give 8236 and 7625 non-overlapped reflections for twin components 1 and 2, respectively, plus 13836 overlapping reflections from both twin components. Symmetry-equivalent reflections were merged. The major twin fraction, component 1, refined to 0.6870 (12).

Table 5
Experimental details

	(1)	(2)
Crystal data
Chemical formula	(C₇H₇N₂)₂[SnI₄]	(C₇H₅F₂N₂)₂[SnI₄]
M_r	864.58	936.55
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c
Temperature (K)	123	123
a, b, c (Å)	29.6316 (5), 6.22328 (10), 12.4258 (2)	31.3825 (6), 6.18011 (12), 12.38507 (13)
β (°)	109.6798 (8)	109.3241 (7)
V (Å³)	2157.55 (6)	2266.72 (7)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	6.91	6.61
Crystal size (mm)	0.15 × 0.10 × 0.05	0.33 × 0.33 × 0.01

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001 )	Multi-scan (TWINABS; Bruker, 2001)
T_min, T_max	0.570, 0.747	0.322, 0.522
No. of measured, independent and observed [I > 2σ(I)] reflections	24695, 3713, 3222	29697, 5792, 5179
R_int	0.033	?
(sin θ/λ)_max (Å⁻¹)	0.772	0.768

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.045, 1.06	0.035, 0.124, 1.07
No. of reflections	3713	5792
No. of parameters	113	132
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.70, −1.15	1.95, −1.74
Computer programs: APEX2 and SAINT-Plus (Bruker, 2001), SIR97 (Altomare et al., 1999 ), SHELXL2014 (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ), VESTA (Momma & Izumi, 2011 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1021082; 1021083

Crystal structure: contains datablocks 1, 2. DOI: 10.1107/S1600536814019151/wm5043sup1.cif

Structure factors: contains datablock 1. DOI: 10.1107/S1600536814019151/wm50431sup2.hkl

Structure factors: contains datablock 2. DOI: 10.1107/S1600536814019151/wm50432sup3.hkl

checkCIF report

Chemical context top

The title compounds, (1) and (2), belong to an extensive family of materials exhibiting a perovskite-type structure, which can vary with respect to the dimensionality of its extended inorganic framework, ranging from two-dimensional, [MX₄]_n²ⁿ^-, to three-dimensional, [MX₃]_nⁿ^- (Mitzi, 1999, 2001, 2004; Mitzi et al., 2001; Zhengtao et al., 2003a,b). The former case is exemplified by anionic [MX₄]_n²ⁿ^- sheets (M = divalent metal ion; X = halogen) of corner-sharing MX₆ octahedra, which are separated by bilayers of organic cations. For most reported layered perovskites, these organic molecules are terminated with one or two protonated primary amine groups. Thereby, the ammonium head(s) form N—H···X hydrogen bonds to any of the bridging and terminal halogen atoms in the inorganic layers (Mitzi et al., 2002; Mercier et al., 2004; Sourisseau et al., 2007; Pradeesh et al., 2013). In the actual case, however, as a novel aspect, the bicyclic aromatic benzimidazole unit is introduced as an organic part. There are numerous general examples of benzimidazole acting as a neutral ligand (Keene et al., 2010) and similarly in its protonated form (Mouchaham et al., 2010). In this context, the present study explicitly demonstrates that benzimidazolium cations and corresponding derivatives can stabilize the layered perovskite structure as well, while fitting perfectly into the `footprint' provided by the inorganic framework. This observation bears importance since the extent of the in- and out-of-plane angular distortions, twisting and buckling of the anionic sheets, is largely determined by the relative charge density, steric requirements and hydrogen-bonding pattern of the organic cations (Knutson & Martin, 2005; Takahashi et al., 2007). These distortions correlate with the band gaps of the perovskite-type semiconductors. It is interesting to note that perovskite-based solar cells have recently been catapulted to the cutting edge of thin-film photovoltaic research (Hao et al., 2014; Marchioro et al., 2014). Consequently, the chemical variability which comes with the imidazolium cation, especially the range of possible substitutions on its molecular skeleton, gives an additional structural diversity to this class of compounds. As a case in point, consider the difluoro-substituted compound (2) which renders not only modified van der Waals interactions for the organic bilayers, but also tailors the `chemistry' of the crystal surfaces.

Structural commentary top

Compounds (1) and (2) are isostructural. Their asymmetric units, Figs. 1 and 2, consist of an Sn²⁺ cation situated on a twofold rotation axis (Wyckoff position 4e), three iodine atoms [one in a general position, one on an inversion centre (4a) and one on a twofold rotation axis (4e)] and a benzimidazolium or 5,6-difluorobenzimidazolium cation, respectively. The main building blocks of the structure are corner-sharing [SnI₆] octahedra, which form planar sheets with formula {[SnI₄]^2-}_n which extend parallel to (100). The negative charge of these layers is compensated by the organic cations, which are on both sides of the layer, attached by strong hydrogen-bonding and Coulombic interactions (Figs. 3 and 4). This structural motif can be regarded as an A–B–A layer system, where A represents the aromatic cation and B the tin iodide layer. The coherence between organic bilayers along [100] is mainly achieved through van der Waals interactions. The Sn—I bond lengths for (1) range from 3.0626 (3) Å to 3.1607 (3) Å [(2): 3.0491 (5) Å to 3.1596 (3) Å], with no distinct pattern for bridging compared to terminal iodine atoms (Tables 1 and 2). These values are in agreement with those reported previously for related tin iodide perovskite structures, as for example [(C₄H₉NH₃)₂[SnI₄]], where the bond lengths range from 3.133 Å to 3.16 Å (Mitzi, 1996). The I—Sn—I angles of the [SnI₆] octahedra in the title structures deviate slightly from the ideal octahedral geometry. With 83.886 (4)° for (1) [(2): 84.077 (6)°], the I2—Sn1—I3 angle has the largest difference. On the other hand, all Sn—I—Sn angles are linear, which leads to the formation of an almost rectangular grid (Fig. 5). There is no out-of-plane distortion of the inorganic sheet. The arrangement of the aromatic cations is mainly determined through the direction of N—H···I hydrogen bonds to the apical iodine atoms (Tables 3 and 4; Figs. 3 and 4). There is no N—H···I_bridging contact smaller than the sum of the respective van der Waals radii (H: 1.2, I: 1.98 Å; Bondi, 1964). This is in contrast to primary ammonium cations, which form hydrogen bonds to both apical and bridging iodine atoms. The shortest H···I_bridging distance is C3—H3···I2 with 3.12Å for (1) [(2): 3.19Å] close to the sum of van der Waals radii (H: 1.2, I: 1.98 Å; Bondi, 1964). Adjacent cations within an organic layer show a plane-to-plane distance of 3.786 Å for (1) [(2): 3.730 Å] (Fig. 6). The shortest contact distances between the organic bilayers for both compounds are close to the sums of the van der Waals radii [C8···H6ⁱ 2.801 Å in (1) and F8···H9ⁱⁱ 2.557 Å in (2); (i): 1/2-x, -1/2+y, 1/2-z; (ii): 1/2-x, 1/2-y, -z]. The larger size of the fluorine atom in comparison to the hydrogen atom is reflected in a larger A–B–A layer spacing of 14.407 Å for (2) compared to 13.950 Å for (1).

Database survey top

In the Cambridge Structural Database (Version 5.35, last update November 2013; Allen, 2002) no structures of compounds containing a (benz)imidazolium cation for layered perovskites are listed, making the two examples presented herein the only ones reported so far.

Synthesis and crystallization top

Compound (1) was synthesized and crystallized by a solvothermal method using a mixture of tin(II) iodide and benzimidazole in a 1:2 molar ratio. In a 50 ml round-bottom flask, 4 ml concentrated HI (57 wt. %, stabilized with hypophosphorous acid) was mixed with 2 mmol (0.236 g) benzimidazole. After stirring for one minute, this solution was added to a sample flask containing 1 mmol (0.372 g) tin(II) iodide. The reaction flask was put in a 23 ml Teflon container. The reaction was conducted at 363 K for ten hours after which the autoclave was slowly cooled (1 K/h) to room temperature. Thin, black plate-like crystals were obtained. The synthetic procedure for (2) was identical to that for (1), only using 0.5 mmol (0.77 g) 5,6-difluorobenzimidazole and 0.25 mmol (0.093 g) tin(II) iodide as starting materials. Thin, black plate-like crystals were obtained.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 5. The N—H hydrogen atoms were located in difference Fourier maps and were freely refined. The C-bound hydrogen atoms were included in calculated positions and treated as riding atoms with C—H = 0.95 Å. The isotropic displacement parameters of all H atoms were constrained to 1.2U_eq of their parent atoms. The crystal of compound (2) was a non-merohedral twin. The two twin components were related by a twofold rotation about the c* axis. The data from both twin components were integrated to give 8236 and 7625 non-overlapped reflections for twin components 1 and 2, respectively, plus 13836 overlapping reflections from both twin components. Symmetry-equivalent reflections were merged. The major twin fraction, component 1, refined to 0.6870 (12).

Related literature top

For related literature, see: Allen (2002); Bondi (1964); Hao et al. (2014); Keene et al. (2010); Knutson & Martin (2005); Marchioro et al. (2014); Mercier et al. (2004); Mitzi (1996, 1999, 2001, 2004); Mitzi et al. (2002); Mitzi, Dimitrakopoulos & Kosbar (2001); Mouchaham et al. (2010); Pradeesh et al. (2013); Sourisseau et al. (2007); Takahashi et al. (2007); Zhengtao et al. (2003a, 2003b).

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008) and VESTA (Momma & Izumi, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The main building units of (1), showing atom labeling and thermal ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) x, y+1, z; (ii) -x, y, -z+1/2.]
	Fig. 2. The main building units of (2), showing atom labeling and thermal ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) x, y+1, z; (ii) -x, y, -z+1/2.]
	Fig. 3. The crystal packing of compound (1) viewed along [010]. N—H···I hydrogen bonds are shown as dashed lines.
	Fig. 4. The crystal packing of compound (2) viewed along [010]. N—H···I hydrogen bonds are shown as dashed lines.
	Fig. 5. View along the a* axis of a tin iodide layer of (2). For clarity, the atoms are represented as spheres with uniform sizes selected for each atom type.
	Fig. 6. View along the a* axis of a double layer of tin iodide and the organic cations of (2). For clarity, the [SnI₆] octahedra are shown as polyhedra, the atoms of the organic cations are represented as spheres with uniform sizes selected for each atom type.

(1) Poly[bis(benzimidazolium) [tetra-µ-iodido-stannate(II)]] top

Crystal data top

(C₇H₇N₂)₂[SnI₄]	F(000) = 1552
M_r = 864.58	D_x = 2.662 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 29.6316 (5) Å	Cell parameters from 9894 reflections
b = 6.22328 (10) Å	θ = 2.9–33.1°
c = 12.4258 (2) Å	µ = 6.91 mm⁻¹
β = 109.6798 (8)°	T = 123 K
V = 2157.55 (6) Å³	Plate, black
Z = 4	0.15 × 0.10 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	3713 independent reflections
Radiation source: fine-focus sealed tube	3222 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 33.3°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −44→45
T_min = 0.570, T_max = 0.747	k = −8→9
24695 measured reflections	l = −18→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.045	w = 1/[σ²(F_o²) + (0.0195P)² + 1.2708P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3713 reflections	Δρ_max = 0.70 e Å⁻³
113 parameters	Δρ_min = −1.15 e Å⁻³

Crystal data top

(C₇H₇N₂)₂[SnI₄]	V = 2157.55 (6) Å³
M_r = 864.58	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 29.6316 (5) Å	µ = 6.91 mm⁻¹
b = 6.22328 (10) Å	T = 123 K
c = 12.4258 (2) Å	0.15 × 0.10 × 0.05 mm
β = 109.6798 (8)°

Data collection top

Bruker APEXII CCD diffractometer	3713 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3222 reflections with I > 2σ(I)
T_min = 0.570, T_max = 0.747	R_int = 0.033
24695 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.045	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.70 e Å⁻³
3713 reflections	Δρ_min = −1.15 e Å⁻³
113 parameters

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
Sn1	0.0000	0.05346 (3)	0.2500	0.01164 (5)
I1	0.11310 (2)	0.06766 (2)	0.33720 (2)	0.01725 (5)
I2	0.0000	0.0000	0.0000	0.01759 (5)
I3	0.0000	−0.45442 (3)	0.2500	0.01775 (5)
C1	0.15716 (9)	0.4629 (4)	0.0612 (2)	0.0185 (5)
N2	0.11246 (8)	0.3669 (4)	0.02976 (18)	0.0233 (4)
H2	0.1040 (10)	0.271 (5)	−0.017 (2)	0.028*
C3	0.08537 (9)	0.4715 (4)	0.0783 (2)	0.0244 (5)
H3	0.0530	0.4374	0.0692	0.029*
N4	0.11030 (7)	0.6311 (4)	0.14131 (18)	0.0218 (4)
H4	0.0991 (10)	0.726 (5)	0.175 (2)	0.026*
C5	0.15559 (8)	0.6333 (4)	0.1327 (2)	0.0192 (5)
C6	0.19471 (9)	0.7684 (4)	0.1792 (2)	0.0259 (5)
H6	0.1937	0.8850	0.2278	0.031*
C7	0.23491 (9)	0.7241 (5)	0.1511 (2)	0.0290 (6)
H7	0.2626	0.8114	0.1821	0.035*
C8	0.23624 (10)	0.5553 (4)	0.0788 (2)	0.0270 (6)
H8	0.2646	0.5321	0.0610	0.032*
C9	0.19775 (9)	0.4211 (4)	0.0323 (2)	0.0247 (5)
H9	0.1988	0.3059	−0.0169	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01576 (10)	0.00942 (10)	0.01029 (10)	0.000	0.00511 (8)	0.000
I1	0.01570 (8)	0.01759 (8)	0.01778 (8)	−0.00079 (5)	0.00476 (6)	−0.00078 (5)
I2	0.02292 (11)	0.01962 (11)	0.01103 (10)	−0.00274 (9)	0.00676 (8)	−0.00021 (8)
I3	0.02441 (11)	0.00891 (10)	0.02168 (11)	0.000	0.01005 (9)	0.000
C1	0.0188 (11)	0.0171 (12)	0.0178 (11)	0.0025 (9)	0.0035 (9)	0.0000 (9)
N2	0.0235 (11)	0.0231 (11)	0.0228 (11)	−0.0026 (9)	0.0073 (9)	−0.0078 (9)
C3	0.0188 (12)	0.0264 (14)	0.0282 (14)	−0.0015 (10)	0.0084 (10)	−0.0034 (11)
N4	0.0212 (10)	0.0219 (11)	0.0235 (11)	0.0002 (9)	0.0092 (9)	−0.0062 (9)
C5	0.0199 (11)	0.0186 (11)	0.0187 (11)	0.0027 (10)	0.0059 (9)	0.0005 (9)
C6	0.0240 (13)	0.0264 (13)	0.0248 (13)	−0.0027 (11)	0.0049 (10)	−0.0057 (11)
C7	0.0184 (12)	0.0337 (15)	0.0290 (14)	−0.0031 (11)	0.0002 (10)	−0.0004 (12)
C8	0.0201 (12)	0.0331 (15)	0.0298 (14)	0.0061 (11)	0.0111 (11)	0.0055 (11)
C9	0.0246 (13)	0.0262 (13)	0.0244 (13)	0.0067 (11)	0.0096 (11)	0.0006 (10)

Geometric parameters (Å, º) top

Sn1—I1	3.1571 (2)	N4—C5	1.382 (3)
Sn1—I2	3.1242 (1)	N4—H4	0.85 (3)
Sn1—I3	3.1607 (3)	C5—C6	1.390 (3)
Sn1—I3ⁱ	3.0626 (3)	C6—C7	1.377 (4)
C1—N2	1.384 (3)	C6—H6	0.9500
C1—C9	1.390 (3)	C7—C8	1.392 (4)
C1—C5	1.394 (3)	C7—H7	0.9500
N2—C3	1.326 (3)	C8—C9	1.374 (4)
N2—H2	0.81 (3)	C8—H8	0.9500
C3—N4	1.325 (3)	C9—H9	0.9500
C3—H3	0.9500

I1—Sn1—I2	89.357 (3)	C1—N2—H2	124 (2)
I1—Sn1—I2ⁱⁱ	90.984 (3)	N4—C3—N2	109.6 (2)
I1—Sn1—I1ⁱⁱ	176.793 (9)	N4—C3—H3	125.2
I2—Sn1—I2ⁱⁱ	167.773 (7)	N2—C3—H3	125.2
I1—Sn1—I3	91.604 (4)	C3—N4—C5	108.9 (2)
I2—Sn1—I3	83.886 (4)	C3—N4—H4	125.2 (19)
I1—Sn1—I3ⁱ	88.396 (4)	C5—N4—H4	125.5 (19)
I2—Sn1—I3ⁱ	96.114 (4)	N4—C5—C6	132.0 (2)
I3—Sn1—I3ⁱ	180.0	N4—C5—C1	106.5 (2)
I3ⁱ—Sn1—I2ⁱⁱ	96.113 (4)	C6—C5—C1	121.5 (2)
I3ⁱ—Sn1—I1ⁱⁱ	88.396 (4)	C7—C6—C5	116.4 (2)
I2—Sn1—I1ⁱⁱ	90.984 (3)	C7—C6—H6	121.8
I2ⁱⁱ—Sn1—I1ⁱⁱ	89.357 (3)	C5—C6—H6	121.8
I2ⁱⁱ—Sn1—I3	83.887 (4)	C6—C7—C8	122.0 (3)
I1ⁱⁱ—Sn1—I3	91.604 (4)	C6—C7—H7	119.0
Sn1ⁱⁱⁱ—I2—Sn1	180.0	C8—C7—H7	119.0
Sn1^iv—I3—Sn1	180.0	C9—C8—C7	122.0 (2)
N2—C1—C9	132.5 (2)	C9—C8—H8	119.0
N2—C1—C5	105.9 (2)	C7—C8—H8	119.0
C9—C1—C5	121.6 (2)	C8—C9—C1	116.5 (2)
C3—N2—C1	109.2 (2)	C8—C9—H9	121.8
C3—N2—H2	127 (2)	C1—C9—H9	121.8

C9—C1—N2—C3	−178.0 (3)	C9—C1—C5—C6	−0.5 (4)
C5—C1—N2—C3	0.2 (3)	N4—C5—C6—C7	−179.3 (3)
C1—N2—C3—N4	−0.7 (3)	C1—C5—C6—C7	−0.2 (4)
N2—C3—N4—C5	0.8 (3)	C5—C6—C7—C8	0.9 (4)
C3—N4—C5—C6	178.5 (3)	C6—C7—C8—C9	−0.9 (4)
C3—N4—C5—C1	−0.7 (3)	C7—C8—C9—C1	0.1 (4)
N2—C1—C5—N4	0.3 (3)	N2—C1—C9—C8	178.6 (3)
C9—C1—C5—N4	178.7 (2)	C5—C1—C9—C8	0.6 (4)
N2—C1—C5—C6	−179.0 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···I1^v	0.81 (3)	2.85 (3)	3.615 (2)	158 (3)
N4—H4···I1ⁱ	0.85 (3)	2.86 (3)	3.630 (2)	151 (2)

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

(2) Poly[bis(5,6-difluorobenzimidazolium) [tetra-µ-iodido-stannate(II)]] top

Crystal data top

(C₇H₅F₂N₂)₂[SnI₄]	F(000) = 1680
M_r = 936.55	D_x = 2.744 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 31.3825 (6) Å	Cell parameters from 9949 reflections
b = 6.18011 (12) Å	θ = 5.5–65.4°
c = 12.38507 (13) Å	µ = 6.61 mm⁻¹
β = 109.3241 (7)°	T = 123 K
V = 2266.72 (7) Å³	Plate, black
Z = 4	0.33 × 0.33 × 0.01 mm

Data collection top

Bruker APEXII CCD diffractometer	5792 independent reflections
Radiation source: fine-focus sealed tube	5179 reflections with I > 2σ(I)
Graphite monochromator	θ_max = 33.1°, θ_min = 2.8°
rotation method scans	h = −47→43
Absorption correction: multi-scan (TWINABS; Bruker, 2001)	k = 0→9
T_min = 0.322, T_max = 0.522	l = 0→18
29697 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0948P)²] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
5792 reflections	Δρ_max = 1.95 e Å⁻³
132 parameters	Δρ_min = −1.74 e Å⁻³

Crystal data top

(C₇H₅F₂N₂)₂[SnI₄]	V = 2266.72 (7) Å³
M_r = 936.55	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 31.3825 (6) Å	µ = 6.61 mm⁻¹
b = 6.18011 (12) Å	T = 123 K
c = 12.38507 (13) Å	0.33 × 0.33 × 0.01 mm
β = 109.3241 (7)°

Data collection top

Bruker APEXII CCD diffractometer	29697 measured reflections
Absorption correction: multi-scan (TWINABS; Bruker, 2001)	5792 independent reflections
T_min = 0.322, T_max = 0.522	5179 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 1.95 e Å⁻³
5792 reflections	Δρ_min = −1.74 e Å⁻³
132 parameters

Special details top

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq
Sn1	0.0000	0.05198 (5)	0.2500	0.01458 (10)
I1	0.10663 (2)	0.06742 (4)	0.33581 (3)	0.02019 (10)
I2	0.0000	0.0000	0.0000	0.02079 (11)
I3	0.0000	−0.45465 (5)	0.2500	0.02092 (11)
C1	0.14859 (19)	0.4618 (7)	0.0571 (4)	0.0227 (9)
N2	0.10624 (15)	0.3704 (7)	0.0285 (3)	0.0249 (8)
H2	0.092 (2)	0.260 (10)	−0.025 (5)	0.030*
C3	0.08158 (18)	0.4824 (8)	0.0780 (5)	0.0271 (10)
H3	0.0511	0.4521	0.0709	0.033*
N4	0.10586 (15)	0.6417 (7)	0.1383 (3)	0.0251 (8)
H4	0.099 (2)	0.714 (9)	0.178 (5)	0.030*
C5	0.14871 (16)	0.6384 (8)	0.1291 (4)	0.0232 (9)
C6	0.18595 (18)	0.7714 (8)	0.1732 (4)	0.0283 (10)
H6	0.1860	0.8918	0.2210	0.034*
C7	0.22244 (18)	0.7166 (9)	0.1429 (5)	0.0319 (11)
F7	0.26085 (11)	0.8325 (7)	0.1827 (3)	0.0460 (9)
C8	0.22240 (19)	0.5394 (9)	0.0718 (5)	0.0307 (12)
F8	0.26118 (12)	0.5015 (6)	0.0508 (4)	0.0447 (8)
C9	0.18591 (19)	0.4095 (9)	0.0276 (4)	0.0279 (10)
H9	0.1861	0.2901	−0.0205	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0230 (2)	0.00982 (18)	0.01224 (19)	0.000	0.00759 (19)	0.000
I1	0.02280 (16)	0.01818 (15)	0.01977 (16)	−0.00088 (9)	0.00728 (14)	−0.00114 (10)
I2	0.0304 (2)	0.02089 (19)	0.01304 (19)	−0.00124 (18)	0.00977 (19)	−0.00007 (13)
I3	0.0319 (2)	0.00964 (17)	0.0243 (2)	0.000	0.0134 (2)	0.000
C1	0.029 (3)	0.022 (2)	0.019 (2)	0.0032 (17)	0.0095 (19)	−0.0028 (15)
N2	0.027 (2)	0.022 (2)	0.0249 (19)	−0.0011 (17)	0.0085 (17)	−0.0036 (16)
C3	0.030 (3)	0.029 (2)	0.024 (2)	−0.002 (2)	0.012 (2)	−0.0046 (19)
N4	0.030 (2)	0.023 (2)	0.025 (2)	0.0035 (17)	0.0123 (18)	−0.0023 (16)
C5	0.027 (2)	0.026 (2)	0.0158 (18)	0.0022 (18)	0.0064 (17)	−0.0023 (17)
C6	0.035 (3)	0.026 (2)	0.025 (2)	−0.003 (2)	0.010 (2)	−0.0064 (18)
C7	0.027 (2)	0.034 (3)	0.030 (2)	−0.006 (2)	0.004 (2)	−0.003 (2)
F7	0.0326 (18)	0.055 (2)	0.048 (2)	−0.0165 (17)	0.0106 (16)	−0.0163 (19)
C8	0.024 (3)	0.042 (3)	0.027 (3)	0.005 (2)	0.011 (2)	−0.002 (2)
F8	0.0299 (18)	0.057 (2)	0.050 (2)	0.0018 (16)	0.0168 (19)	−0.0133 (19)
C9	0.034 (3)	0.026 (2)	0.025 (2)	0.001 (2)	0.011 (2)	−0.0035 (18)

Geometric parameters (Å, º) top

Sn1—I1	3.1596 (3)	C3—H3	0.9500
Sn1—I2	3.1129 (1)	N4—C5	1.387 (6)
Sn1—I3	3.1310 (5)	N4—H4	0.75 (5)
Sn1—I3ⁱ	3.0491 (5)	C5—C6	1.385 (7)
Sn1—I1ⁱⁱ	3.1596 (3)	C6—C7	1.361 (7)
C1—C9	1.376 (7)	C6—H6	0.9500
C1—N2	1.378 (7)	C7—F7	1.348 (6)
C1—C5	1.408 (6)	C7—C8	1.404 (7)
N2—C3	1.330 (7)	C8—F8	1.347 (6)
N2—H2	0.95 (6)	C8—C9	1.357 (8)
C3—N4	1.316 (7)	C9—H9	0.9500

I1—Sn1—I2	89.374 (6)	C1—N2—H2	131 (3)
I1—Sn1—I2ⁱⁱ	90.984 (6)	N4—C3—N2	109.6 (5)
I1—Sn1—I1ⁱⁱ	176.539 (14)	N4—C3—H3	125.2
I2—Sn1—I2ⁱⁱ	168.154 (12)	N2—C3—H3	125.2
I1—Sn1—I3	91.731 (7)	C3—N4—C5	109.7 (4)
I2—Sn1—I3	84.077 (6)	C3—N4—H4	125 (5)
I1—Sn1—I3ⁱ	88.269 (7)	C5—N4—H4	124 (5)
I2—Sn1—I3ⁱ	95.923 (6)	C6—C5—N4	132.3 (4)
I3—Sn1—I3ⁱ	180.0	C6—C5—C1	122.3 (5)
I3ⁱ—Sn1—I2ⁱⁱ	95.923 (6)	N4—C5—C1	105.3 (4)
I2ⁱⁱ—Sn1—I3	84.077 (6)	C7—C6—C5	114.9 (4)
I3ⁱ—Sn1—I1ⁱⁱ	88.270 (7)	C7—C6—H6	122.6
I2—Sn1—I1ⁱⁱ	90.984 (6)	C5—C6—H6	122.6
I2ⁱⁱ—Sn1—I1ⁱⁱ	89.374 (6)	F7—C7—C6	119.9 (5)
I3—Sn1—I1ⁱⁱ	91.730 (7)	F7—C7—C8	117.4 (5)
Sn1ⁱⁱⁱ—I2—Sn1	180.0	C6—C7—C8	122.7 (5)
Sn1^iv—I3—Sn1	180.0	F8—C8—C9	121.0 (5)
C9—C1—N2	131.9 (4)	F8—C8—C7	116.3 (5)
C9—C1—C5	121.7 (5)	C9—C8—C7	122.7 (5)
N2—C1—C5	106.3 (4)	C8—C9—C1	115.6 (5)
C3—N2—C1	109.1 (4)	C8—C9—H9	122.2
C3—N2—H2	119 (3)	C1—C9—H9	122.2

C9—C1—N2—C3	−179.2 (6)	C1—C5—C6—C7	−0.8 (7)
C5—C1—N2—C3	0.5 (6)	C5—C6—C7—F7	−178.7 (5)
C1—N2—C3—N4	−0.5 (6)	C5—C6—C7—C8	0.3 (8)
N2—C3—N4—C5	0.2 (6)	F7—C7—C8—F8	0.4 (8)
C3—N4—C5—C6	178.4 (5)	C6—C7—C8—F8	−178.7 (5)
C3—N4—C5—C1	0.1 (6)	F7—C7—C8—C9	179.2 (5)
C9—C1—C5—C6	0.9 (8)	C6—C7—C8—C9	0.2 (9)
N2—C1—C5—C6	−178.9 (4)	F8—C8—C9—C1	178.7 (5)
C9—C1—C5—N4	179.4 (5)	C7—C8—C9—C1	−0.2 (8)
N2—C1—C5—N4	−0.4 (5)	N2—C1—C9—C8	179.4 (5)
N4—C5—C6—C7	−178.9 (5)	C5—C1—C9—C8	−0.4 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···I1^v	0.95 (6)	2.79 (6)	3.610 (4)	145 (4)
N4—H4···I1ⁱ	0.75 (5)	2.88 (6)	3.587 (4)	157 (6)

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

Selected geometric parameters (Å, º) for (1) top

Sn1—I1	3.1571 (2)	Sn1—I3	3.1607 (3)
Sn1—I2	3.1242 (1)	Sn1—I3ⁱ	3.0626 (3)

I1—Sn1—I2	89.357 (3)	I2—Sn1—I3	83.886 (4)
I1—Sn1—I2ⁱⁱ	90.984 (3)	I1—Sn1—I3ⁱ	88.396 (4)
I1—Sn1—I1ⁱⁱ	176.793 (9)	I2—Sn1—I3ⁱ	96.114 (4)
I2—Sn1—I2ⁱⁱ	167.773 (7)	I3—Sn1—I3ⁱ	180.0
I1—Sn1—I3	91.604 (4)

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

Selected geometric parameters (Å, º) for (2) top

Sn1—I1	3.1596 (3)	Sn1—I3	3.1310 (5)
Sn1—I2	3.1129 (1)	Sn1—I3ⁱ	3.0491 (5)

I1—Sn1—I2	89.374 (6)	I2—Sn1—I3	84.077 (6)
I1—Sn1—I2ⁱⁱ	90.984 (6)	I1—Sn1—I3ⁱ	88.269 (7)
I1—Sn1—I1ⁱⁱ	176.539 (14)	I2—Sn1—I3ⁱ	95.923 (6)
I2—Sn1—I2ⁱⁱ	168.154 (12)	I3—Sn1—I3ⁱ	180.0
I1—Sn1—I3	91.731 (7)

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

Hydrogen-bond geometry (Å, º) for (1) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···I1ⁱⁱⁱ	0.81 (3)	2.85 (3)	3.615 (2)	158 (3)
N4—H4···I1ⁱ	0.85 (3)	2.86 (3)	3.630 (2)	151 (2)

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

Hydrogen-bond geometry (Å, º) for (2) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···I1ⁱⁱⁱ	0.95 (6)	2.79 (6)	3.610 (4)	145 (4)
N4—H4···I1ⁱ	0.75 (5)	2.88 (6)	3.587 (4)	157 (6)

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

Experimental details

	(1)	(2)
Crystal data
Chemical formula	(C₇H₇N₂)₂[SnI₄]	(C₇H₅F₂N₂)₂[SnI₄]
M_r	864.58	936.55
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c
Temperature (K)	123	123
a, b, c (Å)	29.6316 (5), 6.22328 (10), 12.4258 (2)	31.3825 (6), 6.18011 (12), 12.38507 (13)
β (°)	109.6798 (8)	109.3241 (7)
V (Å³)	2157.55 (6)	2266.72 (7)
Z	4	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	6.91	6.61
Crystal size (mm)	0.15 × 0.10 × 0.05	0.33 × 0.33 × 0.01

Data collection
Diffractometer	Bruker APEXII CCD diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)	Multi-scan (TWINABS; Bruker, 2001)
T_min, T_max	0.570, 0.747	0.322, 0.522
No. of measured, independent and observed [I > 2σ(I)] reflections	24695, 3713, 3222	29697, 5792, 5179
R_int	0.033	?
(sin θ/λ)_max (Å⁻¹)	0.772	0.768

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.045, 1.06	0.035, 0.124, 1.07
No. of reflections	3713	5792
No. of parameters	113	132
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.70, −1.15	1.95, −1.74

Computer programs: APEX2 (Bruker, 2001), SAINT-Plus (Bruker, 2001), SIR97 (Altomare et al., 1999), SHELXL2014 (Sheldrick, 2008), Mercury (Macrae et al., 2008) and VESTA (Momma & Izumi, 2011), publCIF (Westrip, 2010).

Acknowledgements

This work was supported by the Swiss National Science Foundation (grant No. 200021–147143).

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Volume 70| Part 10| October 2014| Pages 178-182

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of isotypic poly[bis­­(benz­imid­azolium) [tetra-μ-iodido-stannate(II)]] and poly[bis­­(5,6-di­fluoro­benzimidazolium) [tetra-μ-iodido-stannate(II)]]

1. Chemical context

2. Structural commentary

3. Database survey

4. Synthesis and crystallization

5. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structures of isotypic poly[bis(benzimidazolium) [tetra-μ-iodido-stannate(II)]] and poly[bis(5,6-difluorobenzimidazolium) [tetra-μ-iodido-stannate(II)]]