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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages 178-182

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

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.

1. Chemical context

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[Mitzi, D. B. (1999). Progress in Inorganic Chemistry, Vol. 48, edited by K. D. Karlin. New York: Wiley & Sons Inc.], 2001[Mitzi, D. B. (2001). J. Chem. Soc. Dalton Trans. pp. 1-12.], 2004[Mitzi, D. B. (2004). J. Mater. Chem. 14, 2355-2365.]; Mitzi et al., 2001[Mitzi, D. B., Dimitrakopoulos, C. D. & Kosbar, L. L. (2001). Chem. Mater. 13, 3728-3740.]; Zhengtao et al., 2003a[Zhengtao, X., Mitzi, D. B. & Medeiros, D. R. (2003a). Inorg. Chem. 42, 1400-1402.],b[Zhengtao, X., Mitzi, D. B., Dimitrakopoulos, C. D. & Maxcy, K. R. (2003b). Inorg. Chem. 42, 2031-2039.]). 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.

[Scheme 1]

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[Mitzi, D. B., Medeiros, D. R. & Malenfant, R. L. (2002). Inorg. Chem. 41, 2134-2145.]; Mercier et al., 2004[Mercier, N., Poiroux, S., Riou, A. & Batail, P. (2004). Inorg. Chem. 43, 8361-8366.]; Sourisseau et al., 2007[Sourisseau, S., Louvain, N., Bi, W., Mercier, N., Rondeau, D., Boucher, F., Buzaré, J.-Y. & Legein, C. (2007). Chem. Mater. 19, 600-607.]; Pradeesh et al., 2013[Pradeesh, K., Rao, K. N. & Prakash, G. V. (2013). J. Appl. Phys. 113, 083523-9.]). 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[Keene, T. D., Zimmermann, I., Neels, A., Sereda, O., Hauser, J., Bonin, M., Hursthouse, M. B., Price, D. J. & Decurtins, S. (2010). Dalton Trans. 39, 4937-4950.]) and similarly in its protonated form (Mouchaham et al., 2010[Mouchaham, G., Roques, N., Imaz, I., Duhayon, C. & Sutter, J.-P. (2010). Cryst. Growth Des. 10, 4906-4919.]). 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[Knutson, J. L. & Martin, J. D. (2005). Inorg. Chem. 44, 4699-4705.]; Takahashi et al., 2007[Takahashi, Y., Obara, R., Nakagawa, K., Nakano, M., Tokita, J. & Inabe, T. (2007). Chem. Mater. 19, 6312-6316.]). 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[Hao, F., Stoumpos, C. C., Chang, R. P. H. & Kanatzidis, M. G. (2014). J. Am. Chem. Soc. 136, 8094-8099.]; Marchioro et al., 2014[Marchioro, A., Teuscher, J., Friedrich, D., Kunst, M., van de Krol, R., Moehl, T., Grätzel, M. & Moser, J.-E. (2014). Nature Photonics, 8, 250-255.]). 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[link] and 2[link], 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[link] and 4[link]). 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[link] and 2[link]). 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[Mitzi, D. B. (1996). Chem. Mater. 8, pp. 791-800.]). 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[link]). 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[link] and 4[link]; Figs. 3[link] and 4[link]). There is no N—H⋯Ibridging contact smaller than the sum of the respective van der Waals radii (H: 1.2, I: 1.98 Å; Bondi, 1964[Bondi, A. (1964). J. Phys. Chem. 68, 441-451.]). This is in contrast to primary ammonium cations, which form hydrogen bonds to both apical and bridging iodine atoms. The shortest H⋯Ibridging 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[link]). 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)[link]

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)[link]

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)[link]

D—H⋯A D—H H⋯A DA 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)[link]

D—H⋯A D—H H⋯A DA 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]
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]
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]
Figure 3
The crystal packing of compound (1) viewed along [010]. N—H⋯I hydrogen bonds are shown as dashed lines.
[Figure 4]
Figure 4
The crystal packing of compound (2) viewed along [010]. N—H⋯I hydrogen bonds are shown as dashed lines.
[Figure 5]
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]
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[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) 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[link]. 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 1.2Ueq 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]
Mr 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)
V3) 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[Bruker (2001). APEX2, SAINT-Plus, SADABS and TWINABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Multi-scan (TWINABS; Bruker, 2001[Bruker (2001). APEX2, SAINT-Plus, SADABS and TWINABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.570, 0.747 0.322, 0.522
No. of measured, independent and observed [I > 2σ(I)] reflections 24695, 3713, 3222 29697, 5792, 5179
Rint 0.033 ?
(sin θ/λ)max−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
Δρmax, Δρmin (e Å−3) 0.70, −1.15 1.95, −1.74
Computer programs: APEX2 and SAINT-Plus (Bruker, 2001[Bruker (2001). APEX2, SAINT-Plus, SADABS and TWINABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SIR97 (Altomare et al., 1999[Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119.]), SHELXL2014 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]), VESTA (Momma & Izumi, 2011[Momma, K. & Izumi, F. (2011). J. Appl. Cryst. 44, 1272-1276.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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···Ibridging 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···Ibridging 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 1.2Ueq 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
[Figure 1] 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.]
[Figure 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.]
[Figure 3] Fig. 3. The crystal packing of compound (1) viewed along [010]. N—H···I hydrogen bonds are shown as dashed lines.
[Figure 4] Fig. 4. The crystal packing of compound (2) viewed along [010]. N—H···I hydrogen bonds are shown as dashed lines.
[Figure 5] 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.
[Figure 6] 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
Mr = 864.58Dx = 2.662 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 29.6316 (5) ÅCell parameters from 9894 reflections
b = 6.22328 (10) Åθ = 2.9–33.1°
c = 12.4258 (2) ŵ = 6.91 mm1
β = 109.6798 (8)°T = 123 K
V = 2157.55 (6) Å3Plate, black
Z = 40.15 × 0.10 × 0.05 mm
Data collection top
Bruker APEXII CCD
diffractometer
3713 independent reflections
Radiation source: fine-focus sealed tube3222 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ω scansθmax = 33.3°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 4445
Tmin = 0.570, Tmax = 0.747k = 89
24695 measured reflectionsl = 1818
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.045 w = 1/[σ2(Fo2) + (0.0195P)2 + 1.2708P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
3713 reflectionsΔρmax = 0.70 e Å3
113 parametersΔρmin = 1.15 e Å3
Crystal data top
(C7H7N2)2[SnI4]V = 2157.55 (6) Å3
Mr = 864.58Z = 4
Monoclinic, C2/cMo Kα radiation
a = 29.6316 (5) ŵ = 6.91 mm1
b = 6.22328 (10) ÅT = 123 K
c = 12.4258 (2) Å0.15 × 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)
Tmin = 0.570, Tmax = 0.747Rint = 0.033
24695 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.045H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.70 e Å3
3713 reflectionsΔρmin = 1.15 e Å3
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
xyzUiso*/Ueq
Sn10.00000.05346 (3)0.25000.01164 (5)
I10.11310 (2)0.06766 (2)0.33720 (2)0.01725 (5)
I20.00000.00000.00000.01759 (5)
I30.00000.45442 (3)0.25000.01775 (5)
C10.15716 (9)0.4629 (4)0.0612 (2)0.0185 (5)
N20.11246 (8)0.3669 (4)0.02976 (18)0.0233 (4)
H20.1040 (10)0.271 (5)0.017 (2)0.028*
C30.08537 (9)0.4715 (4)0.0783 (2)0.0244 (5)
H30.05300.43740.06920.029*
N40.11030 (7)0.6311 (4)0.14131 (18)0.0218 (4)
H40.0991 (10)0.726 (5)0.175 (2)0.026*
C50.15559 (8)0.6333 (4)0.1327 (2)0.0192 (5)
C60.19471 (9)0.7684 (4)0.1792 (2)0.0259 (5)
H60.19370.88500.22780.031*
C70.23491 (9)0.7241 (5)0.1511 (2)0.0290 (6)
H70.26260.81140.18210.035*
C80.23624 (10)0.5553 (4)0.0788 (2)0.0270 (6)
H80.26460.53210.06100.032*
C90.19775 (9)0.4211 (4)0.0323 (2)0.0247 (5)
H90.19880.30590.01690.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.01576 (10)0.00942 (10)0.01029 (10)0.0000.00511 (8)0.000
I10.01570 (8)0.01759 (8)0.01778 (8)0.00079 (5)0.00476 (6)0.00078 (5)
I20.02292 (11)0.01962 (11)0.01103 (10)0.00274 (9)0.00676 (8)0.00021 (8)
I30.02441 (11)0.00891 (10)0.02168 (11)0.0000.01005 (9)0.000
C10.0188 (11)0.0171 (12)0.0178 (11)0.0025 (9)0.0035 (9)0.0000 (9)
N20.0235 (11)0.0231 (11)0.0228 (11)0.0026 (9)0.0073 (9)0.0078 (9)
C30.0188 (12)0.0264 (14)0.0282 (14)0.0015 (10)0.0084 (10)0.0034 (11)
N40.0212 (10)0.0219 (11)0.0235 (11)0.0002 (9)0.0092 (9)0.0062 (9)
C50.0199 (11)0.0186 (11)0.0187 (11)0.0027 (10)0.0059 (9)0.0005 (9)
C60.0240 (13)0.0264 (13)0.0248 (13)0.0027 (11)0.0049 (10)0.0057 (11)
C70.0184 (12)0.0337 (15)0.0290 (14)0.0031 (11)0.0002 (10)0.0004 (12)
C80.0201 (12)0.0331 (15)0.0298 (14)0.0061 (11)0.0111 (11)0.0055 (11)
C90.0246 (13)0.0262 (13)0.0244 (13)0.0067 (11)0.0096 (11)0.0006 (10)
Geometric parameters (Å, º) top
Sn1—I13.1571 (2)N4—C51.382 (3)
Sn1—I23.1242 (1)N4—H40.85 (3)
Sn1—I33.1607 (3)C5—C61.390 (3)
Sn1—I3i3.0626 (3)C6—C71.377 (4)
C1—N21.384 (3)C6—H60.9500
C1—C91.390 (3)C7—C81.392 (4)
C1—C51.394 (3)C7—H70.9500
N2—C31.326 (3)C8—C91.374 (4)
N2—H20.81 (3)C8—H80.9500
C3—N41.325 (3)C9—H90.9500
C3—H30.9500
I1—Sn1—I289.357 (3)C1—N2—H2124 (2)
I1—Sn1—I2ii90.984 (3)N4—C3—N2109.6 (2)
I1—Sn1—I1ii176.793 (9)N4—C3—H3125.2
I2—Sn1—I2ii167.773 (7)N2—C3—H3125.2
I1—Sn1—I391.604 (4)C3—N4—C5108.9 (2)
I2—Sn1—I383.886 (4)C3—N4—H4125.2 (19)
I1—Sn1—I3i88.396 (4)C5—N4—H4125.5 (19)
I2—Sn1—I3i96.114 (4)N4—C5—C6132.0 (2)
I3—Sn1—I3i180.0N4—C5—C1106.5 (2)
I3i—Sn1—I2ii96.113 (4)C6—C5—C1121.5 (2)
I3i—Sn1—I1ii88.396 (4)C7—C6—C5116.4 (2)
I2—Sn1—I1ii90.984 (3)C7—C6—H6121.8
I2ii—Sn1—I1ii89.357 (3)C5—C6—H6121.8
I2ii—Sn1—I383.887 (4)C6—C7—C8122.0 (3)
I1ii—Sn1—I391.604 (4)C6—C7—H7119.0
Sn1iii—I2—Sn1180.0C8—C7—H7119.0
Sn1iv—I3—Sn1180.0C9—C8—C7122.0 (2)
N2—C1—C9132.5 (2)C9—C8—H8119.0
N2—C1—C5105.9 (2)C7—C8—H8119.0
C9—C1—C5121.6 (2)C8—C9—C1116.5 (2)
C3—N2—C1109.2 (2)C8—C9—H9121.8
C3—N2—H2127 (2)C1—C9—H9121.8
C9—C1—N2—C3178.0 (3)C9—C1—C5—C60.5 (4)
C5—C1—N2—C30.2 (3)N4—C5—C6—C7179.3 (3)
C1—N2—C3—N40.7 (3)C1—C5—C6—C70.2 (4)
N2—C3—N4—C50.8 (3)C5—C6—C7—C80.9 (4)
C3—N4—C5—C6178.5 (3)C6—C7—C8—C90.9 (4)
C3—N4—C5—C10.7 (3)C7—C8—C9—C10.1 (4)
N2—C1—C5—N40.3 (3)N2—C1—C9—C8178.6 (3)
C9—C1—C5—N4178.7 (2)C5—C1—C9—C80.6 (4)
N2—C1—C5—C6179.0 (2)
Symmetry codes: (i) x, y+1, z; (ii) x, y, z+1/2; (iii) x, y, z; (iv) x, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···I1v0.81 (3)2.85 (3)3.615 (2)158 (3)
N4—H4···I1i0.85 (3)2.86 (3)3.630 (2)151 (2)
Symmetry codes: (i) x, y+1, z; (v) x, y, z1/2.
(2) Poly[bis(5,6-difluorobenzimidazolium) [tetra-µ-iodido-stannate(II)]] top
Crystal data top
(C7H5F2N2)2[SnI4]F(000) = 1680
Mr = 936.55Dx = 2.744 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 31.3825 (6) ÅCell parameters from 9949 reflections
b = 6.18011 (12) Åθ = 5.5–65.4°
c = 12.38507 (13) ŵ = 6.61 mm1
β = 109.3241 (7)°T = 123 K
V = 2266.72 (7) Å3Plate, black
Z = 40.33 × 0.33 × 0.01 mm
Data collection top
Bruker APEXII CCD
diffractometer
5792 independent reflections
Radiation source: fine-focus sealed tube5179 reflections with I > 2σ(I)
Graphite monochromatorθmax = 33.1°, θmin = 2.8°
rotation method scansh = 4743
Absorption correction: multi-scan
(TWINABS; Bruker, 2001)
k = 09
Tmin = 0.322, Tmax = 0.522l = 018
29697 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.124 w = 1/[σ2(Fo2) + (0.0948P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
5792 reflectionsΔρmax = 1.95 e Å3
132 parametersΔρmin = 1.74 e Å3
Crystal data top
(C7H5F2N2)2[SnI4]V = 2266.72 (7) Å3
Mr = 936.55Z = 4
Monoclinic, C2/cMo Kα radiation
a = 31.3825 (6) ŵ = 6.61 mm1
b = 6.18011 (12) ÅT = 123 K
c = 12.38507 (13) Å0.33 × 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
Tmin = 0.322, Tmax = 0.5225179 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.124H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 1.95 e Å3
5792 reflectionsΔρmin = 1.74 e Å3
132 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.

Refinement. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn10.00000.05198 (5)0.25000.01458 (10)
I10.10663 (2)0.06742 (4)0.33581 (3)0.02019 (10)
I20.00000.00000.00000.02079 (11)
I30.00000.45465 (5)0.25000.02092 (11)
C10.14859 (19)0.4618 (7)0.0571 (4)0.0227 (9)
N20.10624 (15)0.3704 (7)0.0285 (3)0.0249 (8)
H20.092 (2)0.260 (10)0.025 (5)0.030*
C30.08158 (18)0.4824 (8)0.0780 (5)0.0271 (10)
H30.05110.45210.07090.033*
N40.10586 (15)0.6417 (7)0.1383 (3)0.0251 (8)
H40.099 (2)0.714 (9)0.178 (5)0.030*
C50.14871 (16)0.6384 (8)0.1291 (4)0.0232 (9)
C60.18595 (18)0.7714 (8)0.1732 (4)0.0283 (10)
H60.18600.89180.22100.034*
C70.22244 (18)0.7166 (9)0.1429 (5)0.0319 (11)
F70.26085 (11)0.8325 (7)0.1827 (3)0.0460 (9)
C80.22240 (19)0.5394 (9)0.0718 (5)0.0307 (12)
F80.26118 (12)0.5015 (6)0.0508 (4)0.0447 (8)
C90.18591 (19)0.4095 (9)0.0276 (4)0.0279 (10)
H90.18610.29010.02050.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0230 (2)0.00982 (18)0.01224 (19)0.0000.00759 (19)0.000
I10.02280 (16)0.01818 (15)0.01977 (16)0.00088 (9)0.00728 (14)0.00114 (10)
I20.0304 (2)0.02089 (19)0.01304 (19)0.00124 (18)0.00977 (19)0.00007 (13)
I30.0319 (2)0.00964 (17)0.0243 (2)0.0000.0134 (2)0.000
C10.029 (3)0.022 (2)0.019 (2)0.0032 (17)0.0095 (19)0.0028 (15)
N20.027 (2)0.022 (2)0.0249 (19)0.0011 (17)0.0085 (17)0.0036 (16)
C30.030 (3)0.029 (2)0.024 (2)0.002 (2)0.012 (2)0.0046 (19)
N40.030 (2)0.023 (2)0.025 (2)0.0035 (17)0.0123 (18)0.0023 (16)
C50.027 (2)0.026 (2)0.0158 (18)0.0022 (18)0.0064 (17)0.0023 (17)
C60.035 (3)0.026 (2)0.025 (2)0.003 (2)0.010 (2)0.0064 (18)
C70.027 (2)0.034 (3)0.030 (2)0.006 (2)0.004 (2)0.003 (2)
F70.0326 (18)0.055 (2)0.048 (2)0.0165 (17)0.0106 (16)0.0163 (19)
C80.024 (3)0.042 (3)0.027 (3)0.005 (2)0.011 (2)0.002 (2)
F80.0299 (18)0.057 (2)0.050 (2)0.0018 (16)0.0168 (19)0.0133 (19)
C90.034 (3)0.026 (2)0.025 (2)0.001 (2)0.011 (2)0.0035 (18)
Geometric parameters (Å, º) top
Sn1—I13.1596 (3)C3—H30.9500
Sn1—I23.1129 (1)N4—C51.387 (6)
Sn1—I33.1310 (5)N4—H40.75 (5)
Sn1—I3i3.0491 (5)C5—C61.385 (7)
Sn1—I1ii3.1596 (3)C6—C71.361 (7)
C1—C91.376 (7)C6—H60.9500
C1—N21.378 (7)C7—F71.348 (6)
C1—C51.408 (6)C7—C81.404 (7)
N2—C31.330 (7)C8—F81.347 (6)
N2—H20.95 (6)C8—C91.357 (8)
C3—N41.316 (7)C9—H90.9500
I1—Sn1—I289.374 (6)C1—N2—H2131 (3)
I1—Sn1—I2ii90.984 (6)N4—C3—N2109.6 (5)
I1—Sn1—I1ii176.539 (14)N4—C3—H3125.2
I2—Sn1—I2ii168.154 (12)N2—C3—H3125.2
I1—Sn1—I391.731 (7)C3—N4—C5109.7 (4)
I2—Sn1—I384.077 (6)C3—N4—H4125 (5)
I1—Sn1—I3i88.269 (7)C5—N4—H4124 (5)
I2—Sn1—I3i95.923 (6)C6—C5—N4132.3 (4)
I3—Sn1—I3i180.0C6—C5—C1122.3 (5)
I3i—Sn1—I2ii95.923 (6)N4—C5—C1105.3 (4)
I2ii—Sn1—I384.077 (6)C7—C6—C5114.9 (4)
I3i—Sn1—I1ii88.270 (7)C7—C6—H6122.6
I2—Sn1—I1ii90.984 (6)C5—C6—H6122.6
I2ii—Sn1—I1ii89.374 (6)F7—C7—C6119.9 (5)
I3—Sn1—I1ii91.730 (7)F7—C7—C8117.4 (5)
Sn1iii—I2—Sn1180.0C6—C7—C8122.7 (5)
Sn1iv—I3—Sn1180.0F8—C8—C9121.0 (5)
C9—C1—N2131.9 (4)F8—C8—C7116.3 (5)
C9—C1—C5121.7 (5)C9—C8—C7122.7 (5)
N2—C1—C5106.3 (4)C8—C9—C1115.6 (5)
C3—N2—C1109.1 (4)C8—C9—H9122.2
C3—N2—H2119 (3)C1—C9—H9122.2
C9—C1—N2—C3179.2 (6)C1—C5—C6—C70.8 (7)
C5—C1—N2—C30.5 (6)C5—C6—C7—F7178.7 (5)
C1—N2—C3—N40.5 (6)C5—C6—C7—C80.3 (8)
N2—C3—N4—C50.2 (6)F7—C7—C8—F80.4 (8)
C3—N4—C5—C6178.4 (5)C6—C7—C8—F8178.7 (5)
C3—N4—C5—C10.1 (6)F7—C7—C8—C9179.2 (5)
C9—C1—C5—C60.9 (8)C6—C7—C8—C90.2 (9)
N2—C1—C5—C6178.9 (4)F8—C8—C9—C1178.7 (5)
C9—C1—C5—N4179.4 (5)C7—C8—C9—C10.2 (8)
N2—C1—C5—N40.4 (5)N2—C1—C9—C8179.4 (5)
N4—C5—C6—C7178.9 (5)C5—C1—C9—C80.4 (8)
Symmetry codes: (i) x, y+1, z; (ii) x, y, z+1/2; (iii) x, y, z; (iv) x, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···I1v0.95 (6)2.79 (6)3.610 (4)145 (4)
N4—H4···I1i0.75 (5)2.88 (6)3.587 (4)157 (6)
Symmetry codes: (i) x, y+1, z; (v) x, y, z1/2.
Selected geometric parameters (Å, º) for (1) top
Sn1—I13.1571 (2)Sn1—I33.1607 (3)
Sn1—I23.1242 (1)Sn1—I3i3.0626 (3)
I1—Sn1—I289.357 (3)I2—Sn1—I383.886 (4)
I1—Sn1—I2ii90.984 (3)I1—Sn1—I3i88.396 (4)
I1—Sn1—I1ii176.793 (9)I2—Sn1—I3i96.114 (4)
I2—Sn1—I2ii167.773 (7)I3—Sn1—I3i180.0
I1—Sn1—I391.604 (4)
Symmetry codes: (i) x, y+1, z; (ii) x, y, z+1/2.
Selected geometric parameters (Å, º) for (2) top
Sn1—I13.1596 (3)Sn1—I33.1310 (5)
Sn1—I23.1129 (1)Sn1—I3i3.0491 (5)
I1—Sn1—I289.374 (6)I2—Sn1—I384.077 (6)
I1—Sn1—I2ii90.984 (6)I1—Sn1—I3i88.269 (7)
I1—Sn1—I1ii176.539 (14)I2—Sn1—I3i95.923 (6)
I2—Sn1—I2ii168.154 (12)I3—Sn1—I3i180.0
I1—Sn1—I391.731 (7)
Symmetry codes: (i) x, y+1, z; (ii) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (1) top
D—H···AD—HH···AD···AD—H···A
N2—H2···I1iii0.81 (3)2.85 (3)3.615 (2)158 (3)
N4—H4···I1i0.85 (3)2.86 (3)3.630 (2)151 (2)
Symmetry codes: (i) x, y+1, z; (iii) x, y, z1/2.
Hydrogen-bond geometry (Å, º) for (2) top
D—H···AD—HH···AD···AD—H···A
N2—H2···I1iii0.95 (6)2.79 (6)3.610 (4)145 (4)
N4—H4···I1i0.75 (5)2.88 (6)3.587 (4)157 (6)
Symmetry codes: (i) x, y+1, z; (iii) x, y, z1/2.

Experimental details

(1)(2)
Crystal data
Chemical formula(C7H7N2)2[SnI4](C7H5F2N2)2[SnI4]
Mr864.58936.55
Crystal system, space groupMonoclinic, C2/cMonoclinic, C2/c
Temperature (K)123123
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)
V3)2157.55 (6)2266.72 (7)
Z44
Radiation typeMo KαMo Kα
µ (mm1)6.916.61
Crystal size (mm)0.15 × 0.10 × 0.050.33 × 0.33 × 0.01
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Bruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Multi-scan
(TWINABS; Bruker, 2001)
Tmin, Tmax0.570, 0.7470.322, 0.522
No. of measured, independent and
observed [I > 2σ(I)] reflections
24695, 3713, 3222 29697, 5792, 5179
Rint0.033?
(sin θ/λ)max1)0.7720.768
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.045, 1.06 0.035, 0.124, 1.07
No. of reflections37135792
No. of parameters113132
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.70, 1.151.95, 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).

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationAltomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBondi, A. (1964). J. Phys. Chem. 68, 441–451.  CrossRef CAS Web of Science Google Scholar
First citationBruker (2001). APEX2, SAINT-Plus, SADABS and TWINABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHao, F., Stoumpos, C. C., Chang, R. P. H. & Kanatzidis, M. G. (2014). J. Am. Chem. Soc. 136, 8094–8099.  Web of Science CrossRef CAS PubMed Google Scholar
First citationKeene, T. D., Zimmermann, I., Neels, A., Sereda, O., Hauser, J., Bonin, M., Hursthouse, M. B., Price, D. J. & Decurtins, S. (2010). Dalton Trans. 39, 4937–4950.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationKnutson, J. L. & Martin, J. D. (2005). Inorg. Chem. 44, 4699–4705.  Web of Science CrossRef PubMed CAS Google Scholar
First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationMarchioro, A., Teuscher, J., Friedrich, D., Kunst, M., van de Krol, R., Moehl, T., Grätzel, M. & Moser, J.-E. (2014). Nature Photonics, 8, 250–255.  Web of Science CrossRef CAS Google Scholar
First citationMercier, N., Poiroux, S., Riou, A. & Batail, P. (2004). Inorg. Chem. 43, 8361–8366.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationMitzi, D. B. (1996). Chem. Mater. 8, pp. 791–800.  CSD CrossRef CAS Web of Science Google Scholar
First citationMitzi, D. B. (1999). Progress in Inorganic Chemistry, Vol. 48, edited by K. D. Karlin. New York: Wiley & Sons Inc.  Google Scholar
First citationMitzi, D. B. (2001). J. Chem. Soc. Dalton Trans. pp. 1–12.  Web of Science CrossRef Google Scholar
First citationMitzi, D. B. (2004). J. Mater. Chem. 14, 2355–2365.  Web of Science CrossRef CAS Google Scholar
First citationMitzi, D. B., Dimitrakopoulos, C. D. & Kosbar, L. L. (2001). Chem. Mater. 13, 3728–3740.  Web of Science CSD CrossRef CAS Google Scholar
First citationMitzi, D. B., Medeiros, D. R. & Malenfant, R. L. (2002). Inorg. Chem. 41, 2134–2145.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationMomma, K. & Izumi, F. (2011). J. Appl. Cryst. 44, 1272–1276.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationMouchaham, G., Roques, N., Imaz, I., Duhayon, C. & Sutter, J.-P. (2010). Cryst. Growth Des. 10, 4906–4919.  CSD CrossRef CAS Google Scholar
First citationPradeesh, K., Rao, K. N. & Prakash, G. V. (2013). J. Appl. Phys. 113, 083523–9.  Web of Science CrossRef Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSourisseau, S., Louvain, N., Bi, W., Mercier, N., Rondeau, D., Boucher, F., Buzaré, J.-Y. & Legein, C. (2007). Chem. Mater. 19, 600–607.  Web of Science CSD CrossRef CAS Google Scholar
First citationTakahashi, Y., Obara, R., Nakagawa, K., Nakano, M., Tokita, J. & Inabe, T. (2007). Chem. Mater. 19, 6312–6316.  Web of Science CSD CrossRef CAS Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhengtao, X., Mitzi, D. B., Dimitrakopoulos, C. D. & Maxcy, K. R. (2003b). Inorg. Chem. 42, 2031–2039.  Web of Science PubMed Google Scholar
First citationZhengtao, X., Mitzi, D. B. & Medeiros, D. R. (2003a). Inorg. Chem. 42, 1400–1402.  Web of Science PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages 178-182
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds