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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoIUCrDATA
ISSN: 2414-3146
Volume 1| Part 3| March 2016| x160427
doi:10.1107/S2414314616004272

Tris(pyrrolidin-1-yl)carbenium tri-μ-iodido-bis­­[tri­iodido­bis­­muthate(III)]

Ioannis Tiritiris,a Georg Knobloch,a Stefan Saura and Willi Kantlehnera*

aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: willi.kantlehner@hs-aalen.de

Edited by M. Zeller, Purdue University, USA (Received 7 March 2016; accepted 13 March 2016; online 22 March 2016)

The asymmetric unit of the title compound, 3(C13H24N3)+ [Bi2I9]3−, comprises two cations and one half of a [Bi2I9]3− ion. The C—N bond lengths of the CN3 units in both cations range from 1.336 (3) to 1.364 (5) Å, indicating partial double-bond character pointing towards charge delocalization within the NCN planes. All five-membered rings adopt an envelope conformation with the C atoms as the flap. One of the pyrrolidine rings (cation I) is disordered over two alternative envelope conformations. Two sets of positions were found for two of the methyl­ene groups with an occupancy ratio of 0.757 (10):0.243 (10). The second disordered pyrrolidine moiety (cation II) is disordered around a twofold rotation axis and exhibits two half-occupied symmetry equivalent counterparts. The two BiIII ions are coordinated by six iodide ions in a distorted octa­hedral manner, with the Bi–I bond lengths ranging from 2.9544 (2) to 3.2414 (2) Å. Two [BiI6]3− octa­hedra are fused together through face-sharing, forming a dinuclear [Bi2I9]3− unit. The bond lengths of bis­muth to the terminal iodides [2.9544 (2)–2.9889 (2) Å] are shorter than the bridging ones [3.1450 (2)–3.2414 (2) Å].

CCDC reference: 1465174

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

Peralkyl­ated guanidinium ions with complex inorganic anions are considered as organic-inorganic hybrid compounds. Their physical behaviour makes them inter­esting for application in scanning electron microscopy (SEM), where the contrast and the brightness of the obtained pictures depend on the heaviest atom present in the anions. By testing various guanidinium salts with different inorganic complex anions, we found out that guanidinium iodo­bis­muthates(III) are very suitable candidates for this purpose (Knobloch et al., 2016[Knobloch, G., Saur, S., Gentner, A. R., Tussetschläger, S., Stein, T., Hader, B. & Kantlehner, W. (2016). Z. Naturforsch. Teil B, 71. Accepted.]). One of them is the here presented title compound.

The asymmetric unit comprises two tris­(pyrrolidin-1-yl)carbenium ions and one half of a [Bi2I9]3− ion (Fig. 1[link]). All five-membered rings adopt an envelope conformation with the C atoms as the flap. One of the pyrrolidine rings (cation I) is disordered over two alternative envelope conformations (details of the disorder are described in Refinement). The second pyrrolidine moiety (cation II) is also disordered (Fig. 2[link]). The C—N bond lengths of the CN3 units in both cations range from 1.336 (3) to 1.364 (5) Å, indicating partial double-bond character. The N—C—N angles range from 119.4 (2) to 121.7 (9)°, indicating nearly ideal trigonal–planar surroundings of the carbon atoms C1 and C14 by the nitro­gen atoms. The positive charge is completely delocalized on the CN3 planes. The two BiIII ions are coordinated by six iodide ions in a distorted octa­hedral manner, with the Bi—I bond lengths ranging from 2.9544 (2) to 3.2414 (2) Å. Two [BiI6]3− octa­hedra are fused together through face-sharing, forming a dinuclear [Bi2I9]3− unit (Fig. 3[link]). The bond lengths of bis­muth to the terminal iodides [2.9544 (2)–2.9889 (2) Å] are shorter than the bridging ones [3.1450 (2)–3.2414 (2) Å]. The same anionic arrangement was observed in the crystal structure of (CH3NH3)3[Bi2I9], where the Bi—I bond lengths range from 2.9529 (15) to 3.2286 (15) Å (Eckhardt et al., 2016[Eckhardt, K., Bon, V., Getzschmann, J., Grothe, J., Wisser, F. M. & Kaskel, S. (2016). Chem. Commun. 52, 3058-3060.]). Since no significant hydrogen bonding exists in the title compound, the crystal packing is dominated by electrostatic inter­actions between cations and anions.

[Figure 1]
Figure 1
The structures of the molecular entities of the title compound, with displacement ellipsoids at the 50% probability level. All H atoms have been omitted for clarity. Only one moiety of the disordered pyrrolidine ring of cation II and the major orientation of the disordered pyrrolidine ring of cation I are shown [symmetry codes: (i) 1 − x, y, [{1\over 2}] − z; (ii) −x, y, [{1\over 2}] − z].
[Figure 2]
Figure 2
The tris­(pyrrolidin-1-yl)carbenium ions in the crystal structure of the title compound. The methyl­ene C atoms of the pyrrolidine ring (cation I) are disordered between the opaque and dark positions. The second disordered pyrrolidine moiety (cation II) exhibits two symmetry equivalent counterparts (dark and opaque positions). All H atoms have been omitted for clarity [symmetry code: (i) −x, y, [{1\over 2}] − z].
[Figure 3]
Figure 3
The [Bi2I9]3− ion in the crystal structure of the title compound [symmetry code: (i) 1 − x, y, [{1\over 2}] − z].

Synthesis and crystallization

The title compound was obtained by mixing an aqueous solution of tris­(pyrrolidin-1-yl)carbenium chloride with BiI3/KI dissolved in water at room temperature. The orange colored precipitate was removed by filtration and washed with water and ethanol. The product was crystallized from an aceto­nitrile solution. After evaporation of the solvent at ambient temperature, orange single crystals suitable for X-ray analysis emerged.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1[link]. The reflections 1 1 1 and 0 2 0 were affected by the beam stop and were omitted in the last steps of the refinement. The atoms C4 and C5 of cation I are disordered over two sets of sites (C4A/C4B, C5A/C5B) with refined occupancies of 0.757 (10):0.243 (10). The disordered pyrrol­idine moiety at the cation II (N5, C14 and C19–C22) exhibits two half-occupied symmetry-equivalent counterparts related to each other by a twofold rotation axis. The two moieties of both disordered units were restrained to have similar geometries. The atoms N4, N5, C14, and N4i were restrained to be coplanar [symmetry operator: (i) −x, y, [{1\over 2}] − z]. The Uij components of the ADPs of atoms of the second disordered pyrrolidine ring were restrained to be similar if closer than 1.7 Å, and carbon atom C14 was restrained to be close to isotropic.

Table 1
Experimental details

Crystal data
Chemical formula (C13H24N3)3[Bi2I9]
Mr 2227.11
Crystal system, space group Monoclinic, C2/c
Temperature (K) 100
a, b, c (Å) 14.1643 (7), 16.7047 (8), 24.9505 (12)
β (°) 91.601 (2)
V (Å3) 5901.2 (5)
Z 4
Radiation type Mo Kα
μ (mm−1) 10.70
Crystal size (mm) 0.18 × 0.14 × 0.08
 
Data collection
Diffractometer Bruker Kappa APEXII DUO
Absorption correction Multi-scan [Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]; SADABS (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])]
Tmin, Tmax 0.086, 0.276
No. of measured, independent and observed [I > 2σ(I)] reflections 61942, 9039, 8198
Rint 0.028
(sin θ/λ)max (Å−1) 0.715
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.018, 0.034, 1.09
No. of reflections 9039
No. of parameters 314
No. of restraints 50
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.82, −0.96
Computer programs: APEX2 (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SAINT (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), DIAMOND (Brandenburg & Putz, 2005[Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.]).

Structural data

CCDC reference: 1465174

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616004272/zl4007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616004272/zl4007Isup2.hkl

checkCIF report


Synthesis and crystallization top

The title compound was obtained by mixing an aqueous solution of tris­(pyrrolidin-1-yl)carbenium chloride with BiI3/KI dissolved in water at room temperature. The orange colored precipitate was removed by filtration and washed with water and ethanol. The product was crystallized from an aceto­nitrile solution. After evaporation of the solvent at ambient temperature, orange single crystals suitable for X-ray analysis emerged.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The reflections 1 1 1 and 0 2 0 were affected by the beam stop and were omitted in the last steps of the refinement. The atoms C4 and C5 of cation I are disordered over two sets of sites (C4A/C4B, C5A/C5B) with refined occupancies of 0.757 (10):0.243 (10). The disordered pyrrolidine moiety at the cation II (N5, C14 and C19–C22) exhibits two half-occupied symmetry equivalent counterparts related to each other through a twofold rotation axis. The two moieties of both disordered units were restrained to have similar geometries. The atoms N4, N5, C14, and N4(i) were restrained to be coplanar (symmetry operator (i): −x, y, 1/2 − z). The Uij components of the ADPs of atoms of the second disordered pyrrolidine ring were restrained to be similar if closer than 1.7 Å, and carbon atom C14 was restrained to be close to isotropic.

Experimental top

The title compound was obtained by mixing an aqueous solution of tris(pyrrolidin-1-yl)carbenium chloride with BiI3/KI dissolved in water at room temperature. The orange colored precipitate was removed by filtration and washed with water and ethanol. The product was crystallized from an acetonitrile solution. After evaporation of the solvent at ambient temperature, orange single crystals suitable for X-ray analysis emerged.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The reflections 1 1 1 and 0 2 0 were affected by the beam stop and were omitted in the last steps of the refinement. The atoms C4 and C5 of cation I are disordered over two sets of sites (C4A/C4B, C5A/C5B) with refined occupancies of 0.757 (10):0.243 (10). The disordered pyrrolidine moiety at the cation II (N5, C14 and C19–C22) exhibits two half-occupied symmetry-equivalent counterparts related to each other by a twofold rotation axis. The two moieties of both disordered units were restrained to have similar geometries. The atoms N4, N5, C14, and N4i were restrained to be coplanar [symmetry operator: (i) −x, y, 1/2 − z]. The Uij components of the ADPs of atoms of the second disordered pyrrolidine ring were restrained to be similar if closer than 1.7 Å, and carbon atom C14 was restrained to be close to isotropic.

Structure description top

Peralkylated guanidinium ions with complex inorganic anions are considered as organic-inorganic hybrid compounds. Their physical behaviour makes them interesting for application in scanning electron microscopy (SEM), where the contrast and the brightness of the obtained pictures depend on the heaviest atom present in the anions. By testing various guanidinium salts with different inorganic complex anions, we found out that guanidinium iodobismuthates are very suitable candidates for this purpose (Knobloch et al., 2016). One of them is the here presented title compound.

The asymmetric unit comprises two tris(pyrrolidin-1-yl)carbenium ions and one half of a [Bi2I9]3− ion (Fig. 1). All five-membered rings adopt an envelope conformation with the C atoms as the flap. One of the pyrrolidine rings (cation I) is disordered over two alternative envelope conformations. Two sets of positions were found for two of the methylene groups with an occupancy ratio of 0.757 (10):0.243 (10) (Fig. 2). The second disordered pyrrolidine moiety (cation II) is disordered around a twofold rotation axis and exhibits two half-occupied symmetry equivalent counterparts (Fig. 2). The C—N bond lengths of the CN3 units in both cations range from 1.336 (3) to 1.364 (5) Å, indicating partial double-bond character. The N—C—N angles range from 119.4 (2) to 121.7 (9)°, indicating nearly ideal trigonal–planar surroundings of the carbon centres C1 and C14 by the nitrogen atoms. The positive charge is completely delocalized on the CN3 planes. The two BiIII ions are coordinated by six iodide ions in a distorted octahedral manner, with the Bi—I bond lengths ranging from 2.9544 (2) to 3.2414 (2) Å. Two [BiI6]3− octahedra are fused together through face-sharing, forming a dinuclear [Bi2I9]3− unit (Fig. 3). The bond lengths of bismuth to the terminal iodides [2.9544 (2)–2.9889 (2) Å] are shorter than the bridging ones [3.1450 (2)–3.2414 (2) Å]. The same anionic arrangement was observed in the crystal structure of (CH3NH3)3[Bi2I9], where the Bi—I bond lengths range from 2.9529 (15) to 3.2286 (15) Å (Eckhardt et al., 2016). Since no significant hydrogen bonding exists in the title compound, the crystal packing is dominated by electrostatic interactions between cations and anions.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, with displacement ellipsoids at the 50% probability level. All H atoms have been omitted for clarity. Only one moiety of the disordered pyrrolidine ring of cation II and the major orientation of the disordered pyrrolidine ring of cation I are shown [symmetry codes: (i) 1 − x, y, 1/2 − z; (ii) −x, y, 1/2 − z].
[Figure 2] Fig. 2. The tris(pyrrolidin-1-yl)carbenium ions in the crystal structure of the title compound. The methylene C atoms of the pyrrolidine ring (cation I) are disordered between the opaque and dark positions. The second disordered pyrrolidine moiety (cation II) exhibits two symmetry equivalent counterparts (dark and opaque positions). All H atoms have been omitted for clarity [symmetry code: (i) −x, y, 1/2 − z].
[Figure 3] Fig. 3. The [Bi2I9]3− ion in the crystal structure of the title compound [symmetry code: (i) 1 − x, y, 1/2 − z].
Tris(pyrrolidin-1-yl)carbenium tri-µ-iodido-bis[triiodidobismuthate(III)] top
Crystal data top
(C13H24N3)3[Bi2I9]F(000) = 4048
Mr = 2227.11Dx = 2.507 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 14.1643 (7) ÅCell parameters from 61942 reflections
b = 16.7047 (8) Åθ = 1.6–30.5°
c = 24.9505 (12) ŵ = 10.70 mm−1
β = 91.601 (2)°T = 100 K
V = 5901.2 (5) Å3Needle, orange
Z = 40.18 × 0.14 × 0.08 mm
Data collection top
Bruker Kappa APEXII DUO
diffractometer		9039 independent reflections
Radiation source: fine-focus sealed tube8198 reflections with I > 2σ(I)
Triumph monochromatorRint = 0.028
φ scans, and ω scansθmax = 30.5°, θmin = 1.6°
Absorption correction: multi-scan
(Blessing, 1995)		h = −17→20
Tmin = 0.086, Tmax = 0.276k = −23→23
61942 measured reflectionsl = −35→34
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.018H-atom parameters constrained
wR(F2) = 0.034 w = 1/[σ2(Fo2) + (0.0068P)2 + 14.6985P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
9039 reflectionsΔρmax = 0.82 e Å−3
314 parametersΔρmin = −0.96 e Å−3
50 restraintsExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.000096 (3)
Crystal data top
(C13H24N3)3[Bi2I9]V = 5901.2 (5) Å3
Mr = 2227.11Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.1643 (7) ŵ = 10.70 mm−1
b = 16.7047 (8) ÅT = 100 K
c = 24.9505 (12) Å0.18 × 0.14 × 0.08 mm
β = 91.601 (2)°
Data collection top
Bruker Kappa APEXII DUO
diffractometer		9039 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)		8198 reflections with I > 2σ(I)
Tmin = 0.086, Tmax = 0.276Rint = 0.028
61942 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.01850 restraints
wR(F2) = 0.034H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0068P)2 + 14.6985P]
where P = (Fo2 + 2Fc2)/3
9039 reflectionsΔρmax = 0.82 e Å−3
314 parametersΔρmin = −0.96 e Å−3
Special details top

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

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 > σ(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
xyzUiso*/UeqOcc. (<1)
Bi10.53466 (2)0.28574 (2)0.16937 (2)0.01601 (2)
I10.35614 (2)0.21736 (2)0.22913 (2)0.01759 (3)
I20.50000.43436 (2)0.25000.02276 (5)
I30.71208 (2)0.35570 (2)0.13006 (2)0.02981 (4)
I40.55859 (2)0.13174 (2)0.11313 (2)0.03154 (4)
I50.41065 (2)0.34792 (2)0.07986 (2)0.02754 (4)
C10.03309 (17)0.19805 (15)0.06915 (9)0.0210 (5)
N2−0.05065 (15)0.16115 (13)0.06500 (8)0.0231 (4)
C20.11229 (19)0.32663 (15)0.04243 (11)0.0270 (5)
H2A0.13030.30370.00760.032*
H2B0.16890.32900.06650.032*
N30.11203 (15)0.15561 (12)0.07760 (8)0.0217 (4)
C3A0.0681 (2)0.40961 (16)0.03500 (12)0.0320 (6)0.757 (10)
H3A10.03530.4145−0.00040.038*0.757 (10)
H3A20.11640.45230.03860.038*0.757 (10)
C4A−0.0018 (3)0.4134 (2)0.08058 (19)0.0313 (11)0.757 (10)
H4A10.03100.42260.11560.038*0.757 (10)
H4A2−0.04960.45590.07430.038*0.757 (10)
C5A−0.0459 (3)0.3310 (3)0.0778 (3)0.0286 (12)0.757 (10)
H5A−0.07460.31640.11220.034*0.757 (10)
H5B−0.09460.32760.04870.034*0.757 (10)
N1A0.03670 (15)0.27905 (13)0.06662 (9)0.0256 (5)0.757 (10)
C3B0.0681 (2)0.40961 (16)0.03500 (12)0.0320 (6)0.243 (10)
H3B10.06970.4266−0.00300.038*0.243 (10)
H3B20.10200.44980.05750.038*0.243 (10)
C4B−0.0351 (8)0.3993 (7)0.0531 (6)0.032 (4)0.243 (10)
H4B1−0.06000.44960.06820.039*0.243 (10)
H4B2−0.07710.38150.02300.039*0.243 (10)
C5B−0.0241 (11)0.3358 (9)0.0951 (5)0.030 (4)0.243 (10)
H5B10.00740.35650.12820.036*0.243 (10)
H5B2−0.08540.31150.10400.036*0.243 (10)
N1B0.03670 (15)0.27905 (13)0.06662 (9)0.0256 (5)0.243 (10)
C6−0.0730 (2)0.08320 (19)0.08990 (14)0.0390 (7)
H6A−0.05150.08160.12800.047*
H6B−0.04380.03830.07040.047*
C7−0.1801 (2)0.0802 (2)0.08463 (17)0.0546 (10)
H7A−0.20370.02450.08580.065*
H7B−0.20990.11190.11310.065*
C8−0.1974 (2)0.1170 (2)0.03040 (15)0.0481 (8)
H8A−0.26420.13350.02530.058*
H8B−0.18100.07930.00150.058*
C9−0.13268 (19)0.18854 (18)0.03134 (11)0.0298 (6)
H9A−0.11310.2026−0.00530.036*
H9B−0.16350.23550.04760.036*
C100.12569 (18)0.07202 (15)0.05954 (10)0.0222 (5)
H10A0.09650.06310.02350.027*
H10B0.09890.03340.08510.027*
C110.23229 (18)0.06521 (16)0.05838 (11)0.0268 (5)
H11A0.25730.08950.02550.032*
H11B0.25310.00870.06090.032*
C120.2626 (2)0.11214 (18)0.10793 (13)0.0354 (7)
H12A0.33040.12630.10730.042*
H12B0.25020.08180.14110.042*
C130.2004 (2)0.18620 (18)0.10330 (13)0.0360 (7)
H13A0.18840.20910.13910.043*
H13B0.22980.22760.08080.043*
N40.07962 (15)0.41124 (12)0.23848 (10)0.0267 (5)
C150.10680 (18)0.49321 (14)0.25543 (12)0.0266 (5)
H15A0.10110.50010.29460.032*
H15B0.06730.53390.23660.032*
C160.20983 (19)0.49899 (16)0.23912 (12)0.0303 (6)
H16A0.22700.55490.23050.036*
H16B0.25300.47890.26800.036*
C170.2131 (2)0.44610 (16)0.18978 (12)0.0315 (6)
H17A0.18420.47290.15800.038*
H17B0.27870.43050.18190.038*
C180.1553 (2)0.37471 (16)0.20671 (13)0.0340 (6)
H18A0.12860.34580.17510.041*
H18B0.19390.33710.22880.041*
C140.0012 (8)0.3727 (2)0.25269 (17)0.0282 (8)0.5
N5−0.0006 (11)0.2916 (2)0.2589 (3)0.0230 (15)0.5
C19−0.0786 (8)0.2412 (6)0.2378 (3)0.0259 (16)0.5
H19A−0.11370.26810.20800.031*0.5
H19B−0.12310.22720.26620.031*0.5
C20−0.0262 (4)0.1674 (3)0.2181 (2)0.0303 (12)0.5
H20A−0.06310.11830.22510.036*0.5
H20B−0.01590.17120.17920.036*0.5
C210.0675 (6)0.1651 (4)0.2490 (3)0.0506 (17)0.5
H21A0.07080.11740.27250.061*0.5
H21B0.12040.16280.22400.061*0.5
C220.0731 (8)0.2391 (6)0.2815 (3)0.0278 (17)0.5
H22A0.06150.22730.31960.033*0.5
H22B0.13600.26430.27880.033*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Bi10.01522 (4)0.01865 (4)0.01416 (4)0.00196 (3)0.00050 (3)0.00034 (3)
I10.01442 (7)0.01826 (7)0.01994 (7)−0.00191 (5)−0.00236 (5)−0.00073 (5)
I20.02242 (11)0.01260 (9)0.03334 (12)0.0000.00212 (9)0.000
I30.02103 (8)0.03904 (10)0.02977 (9)−0.00113 (7)0.00787 (7)0.00943 (7)
I40.02613 (9)0.03328 (9)0.03497 (9)0.00884 (7)−0.00354 (7)−0.01672 (7)
I50.02761 (9)0.03426 (9)0.02041 (8)0.00227 (7)−0.00543 (6)0.00749 (6)
C10.0195 (12)0.0265 (12)0.0172 (11)−0.0009 (9)0.0021 (9)0.0011 (9)
N20.0175 (10)0.0281 (11)0.0238 (10)−0.0029 (8)0.0004 (8)0.0057 (8)
C20.0210 (13)0.0258 (13)0.0347 (14)−0.0035 (10)0.0086 (11)−0.0045 (11)
N30.0178 (10)0.0247 (10)0.0223 (10)−0.0013 (8)−0.0036 (8)−0.0014 (8)
C3A0.0343 (16)0.0239 (13)0.0377 (15)−0.0020 (11)0.0030 (12)−0.0039 (11)
C4A0.025 (2)0.031 (2)0.037 (2)0.0020 (15)0.0003 (17)−0.0142 (17)
C5A0.019 (2)0.026 (2)0.040 (3)−0.0004 (16)0.003 (2)−0.009 (2)
N1A0.0201 (11)0.0243 (11)0.0327 (12)−0.0011 (8)0.0068 (9)−0.0032 (9)
C3B0.0343 (16)0.0239 (13)0.0377 (15)−0.0020 (11)0.0030 (12)−0.0039 (11)
C4B0.030 (7)0.022 (6)0.045 (9)0.005 (5)0.005 (6)−0.007 (5)
C5B0.018 (7)0.048 (8)0.025 (8)0.002 (6)−0.001 (5)−0.015 (6)
N1B0.0201 (11)0.0243 (11)0.0327 (12)−0.0011 (8)0.0068 (9)−0.0032 (9)
C60.0251 (15)0.0394 (17)0.0528 (19)−0.0031 (12)0.0082 (13)0.0194 (14)
C70.0236 (16)0.055 (2)0.086 (3)−0.0070 (14)0.0136 (17)0.028 (2)
C80.0229 (16)0.059 (2)0.062 (2)−0.0100 (14)−0.0043 (15)−0.0011 (18)
C90.0203 (13)0.0414 (16)0.0275 (13)0.0003 (11)−0.0038 (10)0.0004 (12)
C100.0229 (12)0.0225 (12)0.0210 (11)−0.0013 (9)−0.0008 (9)0.0025 (9)
C110.0224 (13)0.0279 (13)0.0301 (13)0.0005 (10)0.0013 (10)−0.0010 (11)
C120.0245 (14)0.0357 (15)0.0450 (17)0.0051 (12)−0.0142 (12)−0.0086 (13)
C130.0235 (14)0.0335 (15)0.0499 (18)0.0024 (11)−0.0166 (13)−0.0121 (13)
N40.0208 (11)0.0124 (9)0.0471 (14)0.0019 (8)0.0030 (10)−0.0024 (9)
C150.0204 (12)0.0153 (11)0.0441 (15)−0.0035 (9)0.0048 (11)−0.0043 (10)
C160.0183 (12)0.0235 (13)0.0493 (17)−0.0005 (10)0.0045 (11)−0.0019 (12)
C170.0215 (13)0.0295 (14)0.0437 (16)0.0067 (11)0.0052 (12)−0.0025 (12)
C180.0258 (14)0.0225 (13)0.0539 (18)0.0069 (10)0.0047 (13)−0.0082 (12)
C140.0231 (18)0.0173 (16)0.044 (2)0.003 (4)−0.0030 (17)−0.003 (4)
N50.0240 (17)0.0140 (14)0.031 (4)−0.004 (2)−0.006 (4)−0.0012 (17)
C190.030 (3)0.019 (3)0.029 (4)−0.002 (2)−0.004 (3)−0.005 (3)
C200.037 (3)0.020 (2)0.033 (3)0.004 (2)−0.008 (2)−0.016 (2)
C210.059 (4)0.035 (3)0.057 (4)0.010 (3)−0.019 (3)−0.005 (3)
C220.027 (3)0.017 (3)0.038 (4)0.005 (2)−0.010 (4)0.004 (4)
Geometric parameters (Å, º) top
Bi1—I42.9544 (2)C7—H7B0.9900
Bi1—I32.9633 (2)C8—C91.506 (4)
Bi1—I52.9889 (2)C8—H8A0.9900
Bi1—I1i3.1450 (2)C8—H8B0.9900
Bi1—I13.1832 (2)C9—H9A0.9900
Bi1—I23.2414 (2)C9—H9B0.9900
I1—Bi1i3.1450 (2)C10—C111.515 (4)
I2—Bi1i3.2414 (2)C10—H10A0.9900
C1—N31.336 (3)C10—H10B0.9900
C1—N21.338 (3)C11—C121.516 (4)
C1—N1B1.356 (3)C11—H11A0.9900
C1—N1A1.356 (3)C11—H11B0.9900
N2—C61.481 (3)C12—C131.521 (4)
N2—C91.487 (3)C12—H12A0.9900
C2—N1B1.476 (3)C12—H12B0.9900
C2—N1A1.476 (3)C13—H13A0.9900
C2—C3A1.530 (4)C13—H13B0.9900
C2—C3B1.530 (4)N4—C141.340 (10)
C2—H2A0.9900N4—C151.481 (3)
C2—H2B0.9900N4—C181.483 (3)
N3—C131.481 (3)C15—C161.529 (4)
N3—C101.482 (3)C15—H15A0.9900
C3A—C4A1.530 (5)C15—H15B0.9900
C3A—H3A10.9900C16—C171.517 (4)
C3A—H3A20.9900C16—H16A0.9900
C4A—C5A1.513 (6)C16—H16B0.9900
C4A—H4A10.9900C17—C181.513 (4)
C4A—H4A20.9900C17—H17A0.9900
C5A—N1A1.490 (5)C17—H17B0.9900
C5A—H5A0.9900C18—H18A0.9900
C5A—H5B0.9900C18—H18B0.9900
C3B—C4B1.551 (11)C14—N51.364 (5)
C3B—H3B10.9900N5—C221.463 (14)
C3B—H3B20.9900N5—C191.475 (14)
C4B—C5B1.498 (14)C19—C201.528 (11)
C4B—H4B10.9900C19—H19A0.9900
C4B—H4B20.9900C19—H19B0.9900
C5B—N1B1.476 (13)C20—C211.516 (8)
C5B—H5B10.9900C20—H20A0.9900
C5B—H5B20.9900C20—H20B0.9900
C6—C71.520 (4)C21—C221.479 (12)
C6—H6A0.9900C21—H21A0.9900
C6—H6B0.9900C21—H21B0.9900
C7—C81.500 (5)C22—H22A0.9900
C7—H7A0.9900C22—H22B0.9900
I4—Bi1—I394.391 (6)C7—C8—H8A111.1
I4—Bi1—I591.172 (6)C9—C8—H8A111.1
I3—Bi1—I595.836 (6)C7—C8—H8B111.1
I4—Bi1—I1i90.337 (6)C9—C8—H8B111.1
I3—Bi1—I1i90.414 (6)H8A—C8—H8B109.1
I5—Bi1—I1i173.438 (5)N2—C9—C8103.3 (2)
I4—Bi1—I190.759 (6)N2—C9—H9A111.1
I3—Bi1—I1171.376 (5)C8—C9—H9A111.1
I5—Bi1—I190.962 (6)N2—C9—H9B111.1
I1i—Bi1—I182.632 (6)C8—C9—H9B111.1
I4—Bi1—I2169.447 (6)H9A—C9—H9B109.1
I3—Bi1—I292.746 (5)N3—C10—C11102.4 (2)
I5—Bi1—I295.829 (5)N3—C10—H10A111.3
I1i—Bi1—I281.840 (5)C11—C10—H10A111.3
I1—Bi1—I281.260 (4)N3—C10—H10B111.3
Bi1i—I1—Bi182.390 (5)C11—C10—H10B111.3
Bi1—I2—Bi1i80.022 (7)H10A—C10—H10B109.2
N3—C1—N2120.3 (2)C10—C11—C12101.8 (2)
N3—C1—N1B120.3 (2)C10—C11—H11A111.4
N2—C1—N1B119.4 (2)C12—C11—H11A111.4
N3—C1—N1A120.3 (2)C10—C11—H11B111.4
N2—C1—N1A119.4 (2)C12—C11—H11B111.4
C1—N2—C6124.9 (2)H11A—C11—H11B109.3
C1—N2—C9125.4 (2)C11—C12—C13102.0 (2)
C6—N2—C9109.6 (2)C11—C12—H12A111.4
N1A—C2—C3A103.8 (2)C13—C12—H12A111.4
N1B—C2—C3B103.8 (2)C11—C12—H12B111.4
N1A—C2—H2A111.0C13—C12—H12B111.4
C3A—C2—H2A111.0H12A—C12—H12B109.2
N1A—C2—H2B111.0N3—C13—C12103.5 (2)
C3A—C2—H2B111.0N3—C13—H13A111.1
H2A—C2—H2B109.0C12—C13—H13A111.1
C1—N3—C13125.4 (2)N3—C13—H13B111.1
C1—N3—C10124.6 (2)C12—C13—H13B111.1
C13—N3—C10109.9 (2)H13A—C13—H13B109.0
C2—C3A—C4A102.6 (2)C14—N4—C15125.4 (3)
C2—C3A—H3A1111.2C14—N4—C18124.1 (3)
C4A—C3A—H3A1111.2C15—N4—C18110.3 (2)
C2—C3A—H3A2111.2N4—C15—C16103.0 (2)
C4A—C3A—H3A2111.2N4—C15—H15A111.2
H3A1—C3A—H3A2109.2C16—C15—H15A111.2
C5A—C4A—C3A101.8 (3)N4—C15—H15B111.2
C5A—C4A—H4A1111.4C16—C15—H15B111.2
C3A—C4A—H4A1111.4H15A—C15—H15B109.1
C5A—C4A—H4A2111.4C17—C16—C15103.3 (2)
C3A—C4A—H4A2111.4C17—C16—H16A111.1
H4A1—C4A—H4A2109.3C15—C16—H16A111.1
N1A—C5A—C4A102.3 (3)C17—C16—H16B111.1
N1A—C5A—H5A111.3C15—C16—H16B111.1
C4A—C5A—H5A111.3H16A—C16—H16B109.1
N1A—C5A—H5B111.3C18—C17—C16101.7 (2)
C4A—C5A—H5B111.3C18—C17—H17A111.4
H5A—C5A—H5B109.2C16—C17—H17A111.4
C1—N1A—C2125.8 (2)C18—C17—H17B111.4
C1—N1A—C5A122.8 (3)C16—C17—H17B111.4
C2—N1A—C5A110.2 (3)H17A—C17—H17B109.3
C2—C3B—C4B104.5 (4)N4—C18—C17103.3 (2)
C2—C3B—H3B1110.9N4—C18—H18A111.1
C4B—C3B—H3B1110.9C17—C18—H18A111.1
C2—C3B—H3B2110.9N4—C18—H18B111.1
C4B—C3B—H3B2110.9C17—C18—H18B111.1
H3B1—C3B—H3B2108.9H18A—C18—H18B109.1
C5B—C4B—C3B101.6 (10)N4—C14—N5121.7 (9)
C5B—C4B—H4B1111.4C14—N5—C22128.6 (10)
C3B—C4B—H4B1111.4C14—N5—C19122.8 (9)
C5B—C4B—H4B2111.4C22—N5—C19108.3 (3)
C3B—C4B—H4B2111.4N5—C19—C20102.1 (8)
H4B1—C4B—H4B2109.3N5—C19—H19A111.3
N1B—C5B—C4B99.7 (9)C20—C19—H19A111.3
N1B—C5B—H5B1111.8N5—C19—H19B111.3
C4B—C5B—H5B1111.8C20—C19—H19B111.3
N1B—C5B—H5B2111.8H19A—C19—H19B109.2
C4B—C5B—H5B2111.8C21—C20—C19106.5 (6)
H5B1—C5B—H5B2109.6C21—C20—H20A110.4
C1—N1B—C2125.8 (2)C19—C20—H20A110.4
C1—N1B—C5B126.5 (7)C21—C20—H20B110.4
C2—N1B—C5B106.9 (7)C19—C20—H20B110.4
N2—C6—C7102.6 (2)H20A—C20—H20B108.6
N2—C6—H6A111.3C22—C21—C20106.9 (6)
C7—C6—H6A111.3C22—C21—H21A110.3
N2—C6—H6B111.3C20—C21—H21A110.3
C7—C6—H6B111.3C22—C21—H21B110.3
H6A—C6—H6B109.2C20—C21—H21B110.3
C8—C7—C6101.7 (3)H21A—C21—H21B108.6
C8—C7—H7A111.4N5—C22—C21105.3 (7)
C6—C7—H7A111.4N5—C22—H22A110.7
C8—C7—H7B111.4C21—C22—H22A110.7
C6—C7—H7B111.4N5—C22—H22B110.7
H7A—C7—H7B109.3C21—C22—H22B110.7
C7—C8—C9103.1 (3)H22A—C22—H22B108.8
N3—C1—N2—C626.6 (4)C4B—C5B—N1B—C246.0 (12)
N1B—C1—N2—C6−151.0 (3)C1—N2—C6—C7166.3 (3)
N1A—C1—N2—C6−151.0 (3)C9—N2—C6—C7−18.2 (3)
N3—C1—N2—C9−148.2 (2)N2—C6—C7—C838.2 (4)
N1B—C1—N2—C934.2 (4)C6—C7—C8—C9−44.6 (4)
N1A—C1—N2—C934.2 (4)C1—N2—C9—C8166.4 (3)
N2—C1—N3—C13−154.8 (3)C6—N2—C9—C8−9.0 (3)
N1B—C1—N3—C1322.9 (4)C7—C8—C9—N233.2 (3)
N1A—C1—N3—C1322.9 (4)C1—N3—C10—C11157.9 (2)
N2—C1—N3—C1029.1 (3)C13—N3—C10—C11−18.7 (3)
N1B—C1—N3—C10−153.3 (2)N3—C10—C11—C1239.0 (2)
N1A—C1—N3—C10−153.3 (2)C10—C11—C12—C13−45.0 (3)
N1A—C2—C3A—C4A29.4 (3)C1—N3—C13—C12174.4 (2)
C2—C3A—C4A—C5A−43.2 (4)C10—N3—C13—C12−9.0 (3)
C3A—C4A—C5A—N1A39.8 (5)C11—C12—C13—N333.1 (3)
N3—C1—N1A—C237.1 (4)C14—N4—C15—C16167.3 (3)
N2—C1—N1A—C2−145.3 (3)C18—N4—C15—C16−8.3 (3)
N3—C1—N1A—C5A−156.4 (4)N4—C15—C16—C1731.5 (3)
N2—C1—N1A—C5A21.3 (4)C15—C16—C17—C18−42.8 (3)
C3A—C2—N1A—C1163.4 (2)C14—N4—C18—C17166.2 (3)
C3A—C2—N1A—C5A−4.6 (4)C15—N4—C18—C17−18.2 (3)
C4A—C5A—N1A—C1169.3 (3)C16—C17—C18—N437.2 (3)
C4A—C5A—N1A—C2−22.2 (5)C15—N4—C14—N5−147.8 (3)
N1B—C2—C3B—C4B−3.7 (7)C18—N4—C14—N527.2 (4)
C2—C3B—C4B—C5B31.2 (12)N4—C14—N5—C2237.8 (9)
C3B—C4B—C5B—N1B−46.1 (14)N4—C14—N5—C19−135.8 (8)
N3—C1—N1B—C237.1 (4)C14—N5—C19—C20141.3 (9)
N2—C1—N1B—C2−145.3 (3)C22—N5—C19—C20−33.5 (8)
N3—C1—N1B—C5B−131.7 (8)N5—C19—C20—C2123.0 (9)
N2—C1—N1B—C5B46.0 (8)C19—C20—C21—C22−5.2 (10)
C3B—C2—N1B—C1163.4 (2)C14—N5—C22—C21−143.3 (9)
C3B—C2—N1B—C5B−26.1 (6)C19—N5—C22—C2131.1 (9)
C4B—C5B—N1B—C1−143.5 (9)C20—C21—C22—N5−15.1 (10)
Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula(C13H24N3)3[Bi2I9]
Mr2227.11
Crystal system, space groupMonoclinic, C2/c
Temperature (K)100
a, b, c (Å)14.1643 (7), 16.7047 (8), 24.9505 (12)
β (°) 91.601 (2)
V (Å3)5901.2 (5)
Z4
Radiation typeMo Kα
µ (mm−1)10.70
Crystal size (mm)0.18 × 0.14 × 0.08
Data collection
DiffractometerBruker Kappa APEXII DUO
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.086, 0.276
No. of measured, independent and
observed [I > 2σ(I)] reflections		61942, 9039, 8198
Rint0.028
(sin θ/λ)max (Å−1)0.715
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.018, 0.034, 1.09
No. of reflections9039
No. of parameters314
No. of restraints50
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0068P)2 + 14.6985P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å−3)0.82, −0.96

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg & Putz, 2005).

 

Acknowledgements

The authors thank Dr W. Frey (Institut für Organische Chemie, Universität Stuttgart) for measuring the diffraction data.

References

First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationBrandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
 First citationBruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationEckhardt, K., Bon, V., Getzschmann, J., Grothe, J., Wisser, F. M. & Kaskel, S. (2016). Chem. Commun. 52, 3058–3060.  CSD CrossRef CAS Google Scholar
 First citationKnobloch, G., Saur, S., Gentner, A. R., Tussetschläger, S., Stein, T., Hader, B. & Kantlehner, W. (2016). Z. Naturforsch. Teil B, 71. Accepted.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals 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 logoIUCrDATA
ISSN: 2414-3146
Volume 1| Part 3| March 2016| x160427
doi:10.1107/S2414314616004272
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