metal-organic compounds
Tris(pyrrolidin-1-yl)carbenium tri-μ-iodido-bis[triiodidobismuthate(III)]
aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: willi.kantlehner@hs-aalen.de
The 13H24N3)+ [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 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].
of the title compound, 3(CCCDC reference: 1465174
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 et al., 2016). One of them is the here presented title compound.
(SEM), where the contrast and the 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 (KnoblochThe 2I9]3− ion (Fig. 1). All five-membered rings adopt an 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). 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). 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 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.
comprises two tris(pyrrolidin-1-yl)carbenium ions and one half of a [BiSynthesis 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 . The reflections 1 1 1 and 0 2 0 were affected by the beam stop and were omitted in the last steps of the 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, − 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.
details are summarized in Table 1Structural data
CCDC reference: 1465174
10.1107/S2414314616004272/zl4007sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616004272/zl4007Isup2.hkl
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.
Crystal data, data collection and structure
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 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.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.
Crystal data, data collection and structure
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 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.Peralkylated guanidinium ions with complex inorganic anions are considered as organic-inorganic hybrid compounds. Their physical behaviour makes them interesting for application in
(SEM), where the contrast and the 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
comprises two tris(pyrrolidin-1-yl)carbenium ions and one half of a [Bi2I9]3− ion (Fig. 1). All five-membered rings adopt an 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 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.Data collection: APEX2 (Bruker, 2008); cell
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).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]. | |
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]. | |
Fig. 3. The [Bi2I9]3− ion in the crystal structure of the title compound [symmetry code: (i) 1 − x, y, 1/2 − z]. |
(C13H24N3)3[Bi2I9] | F(000) = 4048 |
Mr = 2227.11 | Dx = 2.507 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.1643 (7) Å | Cell parameters from 61942 reflections |
b = 16.7047 (8) Å | θ = 1.6–30.5° |
c = 24.9505 (12) Å | µ = 10.70 mm−1 |
β = 91.601 (2)° | T = 100 K |
V = 5901.2 (5) Å3 | Needle, orange |
Z = 4 | 0.18 × 0.14 × 0.08 mm |
Bruker Kappa APEXII DUO diffractometer | 9039 independent reflections |
Radiation source: fine-focus sealed tube | 8198 reflections with I > 2σ(I) |
Triumph monochromator | Rint = 0.028 |
φ scans, and ω scans | θmax = 30.5°, θmin = 1.6° |
Absorption correction: multi-scan (Blessing, 1995) | h = −17→20 |
Tmin = 0.086, Tmax = 0.276 | k = −23→23 |
61942 measured reflections | l = −35→34 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.018 | H-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 reflections | Δρmax = 0.82 e Å−3 |
314 parameters | Δρmin = −0.96 e Å−3 |
50 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.000096 (3) |
(C13H24N3)3[Bi2I9] | V = 5901.2 (5) Å3 |
Mr = 2227.11 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.1643 (7) Å | µ = 10.70 mm−1 |
b = 16.7047 (8) Å | T = 100 K |
c = 24.9505 (12) Å | 0.18 × 0.14 × 0.08 mm |
β = 91.601 (2)° |
Bruker Kappa APEXII DUO diffractometer | 9039 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 8198 reflections with I > 2σ(I) |
Tmin = 0.086, Tmax = 0.276 | Rint = 0.028 |
61942 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 50 restraints |
wR(F2) = 0.034 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0068P)2 + 14.6985P] where P = (Fo2 + 2Fc2)/3 |
9039 reflections | Δρmax = 0.82 e Å−3 |
314 parameters | Δρmin = −0.96 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Bi1 | 0.53466 (2) | 0.28574 (2) | 0.16937 (2) | 0.01601 (2) | |
I1 | 0.35614 (2) | 0.21736 (2) | 0.22913 (2) | 0.01759 (3) | |
I2 | 0.5000 | 0.43436 (2) | 0.2500 | 0.02276 (5) | |
I3 | 0.71208 (2) | 0.35570 (2) | 0.13006 (2) | 0.02981 (4) | |
I4 | 0.55859 (2) | 0.13174 (2) | 0.11313 (2) | 0.03154 (4) | |
I5 | 0.41065 (2) | 0.34792 (2) | 0.07986 (2) | 0.02754 (4) | |
C1 | 0.03309 (17) | 0.19805 (15) | 0.06915 (9) | 0.0210 (5) | |
N2 | −0.05065 (15) | 0.16115 (13) | 0.06500 (8) | 0.0231 (4) | |
C2 | 0.11229 (19) | 0.32663 (15) | 0.04243 (11) | 0.0270 (5) | |
H2A | 0.1303 | 0.3037 | 0.0076 | 0.032* | |
H2B | 0.1689 | 0.3290 | 0.0665 | 0.032* | |
N3 | 0.11203 (15) | 0.15561 (12) | 0.07760 (8) | 0.0217 (4) | |
C3A | 0.0681 (2) | 0.40961 (16) | 0.03500 (12) | 0.0320 (6) | 0.757 (10) |
H3A1 | 0.0353 | 0.4145 | −0.0004 | 0.038* | 0.757 (10) |
H3A2 | 0.1164 | 0.4523 | 0.0386 | 0.038* | 0.757 (10) |
C4A | −0.0018 (3) | 0.4134 (2) | 0.08058 (19) | 0.0313 (11) | 0.757 (10) |
H4A1 | 0.0310 | 0.4226 | 0.1156 | 0.038* | 0.757 (10) |
H4A2 | −0.0496 | 0.4559 | 0.0743 | 0.038* | 0.757 (10) |
C5A | −0.0459 (3) | 0.3310 (3) | 0.0778 (3) | 0.0286 (12) | 0.757 (10) |
H5A | −0.0746 | 0.3164 | 0.1122 | 0.034* | 0.757 (10) |
H5B | −0.0946 | 0.3276 | 0.0487 | 0.034* | 0.757 (10) |
N1A | 0.03670 (15) | 0.27905 (13) | 0.06662 (9) | 0.0256 (5) | 0.757 (10) |
C3B | 0.0681 (2) | 0.40961 (16) | 0.03500 (12) | 0.0320 (6) | 0.243 (10) |
H3B1 | 0.0697 | 0.4266 | −0.0030 | 0.038* | 0.243 (10) |
H3B2 | 0.1020 | 0.4498 | 0.0575 | 0.038* | 0.243 (10) |
C4B | −0.0351 (8) | 0.3993 (7) | 0.0531 (6) | 0.032 (4) | 0.243 (10) |
H4B1 | −0.0600 | 0.4496 | 0.0682 | 0.039* | 0.243 (10) |
H4B2 | −0.0771 | 0.3815 | 0.0230 | 0.039* | 0.243 (10) |
C5B | −0.0241 (11) | 0.3358 (9) | 0.0951 (5) | 0.030 (4) | 0.243 (10) |
H5B1 | 0.0074 | 0.3565 | 0.1282 | 0.036* | 0.243 (10) |
H5B2 | −0.0854 | 0.3115 | 0.1040 | 0.036* | 0.243 (10) |
N1B | 0.03670 (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 | −0.0515 | 0.0816 | 0.1280 | 0.047* | |
H6B | −0.0438 | 0.0383 | 0.0704 | 0.047* | |
C7 | −0.1801 (2) | 0.0802 (2) | 0.08463 (17) | 0.0546 (10) | |
H7A | −0.2037 | 0.0245 | 0.0858 | 0.065* | |
H7B | −0.2099 | 0.1119 | 0.1131 | 0.065* | |
C8 | −0.1974 (2) | 0.1170 (2) | 0.03040 (15) | 0.0481 (8) | |
H8A | −0.2642 | 0.1335 | 0.0253 | 0.058* | |
H8B | −0.1810 | 0.0793 | 0.0015 | 0.058* | |
C9 | −0.13268 (19) | 0.18854 (18) | 0.03134 (11) | 0.0298 (6) | |
H9A | −0.1131 | 0.2026 | −0.0053 | 0.036* | |
H9B | −0.1635 | 0.2355 | 0.0476 | 0.036* | |
C10 | 0.12569 (18) | 0.07202 (15) | 0.05954 (10) | 0.0222 (5) | |
H10A | 0.0965 | 0.0631 | 0.0235 | 0.027* | |
H10B | 0.0989 | 0.0334 | 0.0851 | 0.027* | |
C11 | 0.23229 (18) | 0.06521 (16) | 0.05838 (11) | 0.0268 (5) | |
H11A | 0.2573 | 0.0895 | 0.0255 | 0.032* | |
H11B | 0.2531 | 0.0087 | 0.0609 | 0.032* | |
C12 | 0.2626 (2) | 0.11214 (18) | 0.10793 (13) | 0.0354 (7) | |
H12A | 0.3304 | 0.1263 | 0.1073 | 0.042* | |
H12B | 0.2502 | 0.0818 | 0.1411 | 0.042* | |
C13 | 0.2004 (2) | 0.18620 (18) | 0.10330 (13) | 0.0360 (7) | |
H13A | 0.1884 | 0.2091 | 0.1391 | 0.043* | |
H13B | 0.2298 | 0.2276 | 0.0808 | 0.043* | |
N4 | 0.07962 (15) | 0.41124 (12) | 0.23848 (10) | 0.0267 (5) | |
C15 | 0.10680 (18) | 0.49321 (14) | 0.25543 (12) | 0.0266 (5) | |
H15A | 0.1011 | 0.5001 | 0.2946 | 0.032* | |
H15B | 0.0673 | 0.5339 | 0.2366 | 0.032* | |
C16 | 0.20983 (19) | 0.49899 (16) | 0.23912 (12) | 0.0303 (6) | |
H16A | 0.2270 | 0.5549 | 0.2305 | 0.036* | |
H16B | 0.2530 | 0.4789 | 0.2680 | 0.036* | |
C17 | 0.2131 (2) | 0.44610 (16) | 0.18978 (12) | 0.0315 (6) | |
H17A | 0.1842 | 0.4729 | 0.1580 | 0.038* | |
H17B | 0.2787 | 0.4305 | 0.1819 | 0.038* | |
C18 | 0.1553 (2) | 0.37471 (16) | 0.20671 (13) | 0.0340 (6) | |
H18A | 0.1286 | 0.3458 | 0.1751 | 0.041* | |
H18B | 0.1939 | 0.3371 | 0.2288 | 0.041* | |
C14 | 0.0012 (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 | −0.1137 | 0.2681 | 0.2080 | 0.031* | 0.5 |
H19B | −0.1231 | 0.2272 | 0.2662 | 0.031* | 0.5 |
C20 | −0.0262 (4) | 0.1674 (3) | 0.2181 (2) | 0.0303 (12) | 0.5 |
H20A | −0.0631 | 0.1183 | 0.2251 | 0.036* | 0.5 |
H20B | −0.0159 | 0.1712 | 0.1792 | 0.036* | 0.5 |
C21 | 0.0675 (6) | 0.1651 (4) | 0.2490 (3) | 0.0506 (17) | 0.5 |
H21A | 0.0708 | 0.1174 | 0.2725 | 0.061* | 0.5 |
H21B | 0.1204 | 0.1628 | 0.2240 | 0.061* | 0.5 |
C22 | 0.0731 (8) | 0.2391 (6) | 0.2815 (3) | 0.0278 (17) | 0.5 |
H22A | 0.0615 | 0.2273 | 0.3196 | 0.033* | 0.5 |
H22B | 0.1360 | 0.2643 | 0.2788 | 0.033* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.01522 (4) | 0.01865 (4) | 0.01416 (4) | 0.00196 (3) | 0.00050 (3) | 0.00034 (3) |
I1 | 0.01442 (7) | 0.01826 (7) | 0.01994 (7) | −0.00191 (5) | −0.00236 (5) | −0.00073 (5) |
I2 | 0.02242 (11) | 0.01260 (9) | 0.03334 (12) | 0.000 | 0.00212 (9) | 0.000 |
I3 | 0.02103 (8) | 0.03904 (10) | 0.02977 (9) | −0.00113 (7) | 0.00787 (7) | 0.00943 (7) |
I4 | 0.02613 (9) | 0.03328 (9) | 0.03497 (9) | 0.00884 (7) | −0.00354 (7) | −0.01672 (7) |
I5 | 0.02761 (9) | 0.03426 (9) | 0.02041 (8) | 0.00227 (7) | −0.00543 (6) | 0.00749 (6) |
C1 | 0.0195 (12) | 0.0265 (12) | 0.0172 (11) | −0.0009 (9) | 0.0021 (9) | 0.0011 (9) |
N2 | 0.0175 (10) | 0.0281 (11) | 0.0238 (10) | −0.0029 (8) | 0.0004 (8) | 0.0057 (8) |
C2 | 0.0210 (13) | 0.0258 (13) | 0.0347 (14) | −0.0035 (10) | 0.0086 (11) | −0.0045 (11) |
N3 | 0.0178 (10) | 0.0247 (10) | 0.0223 (10) | −0.0013 (8) | −0.0036 (8) | −0.0014 (8) |
C3A | 0.0343 (16) | 0.0239 (13) | 0.0377 (15) | −0.0020 (11) | 0.0030 (12) | −0.0039 (11) |
C4A | 0.025 (2) | 0.031 (2) | 0.037 (2) | 0.0020 (15) | 0.0003 (17) | −0.0142 (17) |
C5A | 0.019 (2) | 0.026 (2) | 0.040 (3) | −0.0004 (16) | 0.003 (2) | −0.009 (2) |
N1A | 0.0201 (11) | 0.0243 (11) | 0.0327 (12) | −0.0011 (8) | 0.0068 (9) | −0.0032 (9) |
C3B | 0.0343 (16) | 0.0239 (13) | 0.0377 (15) | −0.0020 (11) | 0.0030 (12) | −0.0039 (11) |
C4B | 0.030 (7) | 0.022 (6) | 0.045 (9) | 0.005 (5) | 0.005 (6) | −0.007 (5) |
C5B | 0.018 (7) | 0.048 (8) | 0.025 (8) | 0.002 (6) | −0.001 (5) | −0.015 (6) |
N1B | 0.0201 (11) | 0.0243 (11) | 0.0327 (12) | −0.0011 (8) | 0.0068 (9) | −0.0032 (9) |
C6 | 0.0251 (15) | 0.0394 (17) | 0.0528 (19) | −0.0031 (12) | 0.0082 (13) | 0.0194 (14) |
C7 | 0.0236 (16) | 0.055 (2) | 0.086 (3) | −0.0070 (14) | 0.0136 (17) | 0.028 (2) |
C8 | 0.0229 (16) | 0.059 (2) | 0.062 (2) | −0.0100 (14) | −0.0043 (15) | −0.0011 (18) |
C9 | 0.0203 (13) | 0.0414 (16) | 0.0275 (13) | 0.0003 (11) | −0.0038 (10) | 0.0004 (12) |
C10 | 0.0229 (12) | 0.0225 (12) | 0.0210 (11) | −0.0013 (9) | −0.0008 (9) | 0.0025 (9) |
C11 | 0.0224 (13) | 0.0279 (13) | 0.0301 (13) | 0.0005 (10) | 0.0013 (10) | −0.0010 (11) |
C12 | 0.0245 (14) | 0.0357 (15) | 0.0450 (17) | 0.0051 (12) | −0.0142 (12) | −0.0086 (13) |
C13 | 0.0235 (14) | 0.0335 (15) | 0.0499 (18) | 0.0024 (11) | −0.0166 (13) | −0.0121 (13) |
N4 | 0.0208 (11) | 0.0124 (9) | 0.0471 (14) | 0.0019 (8) | 0.0030 (10) | −0.0024 (9) |
C15 | 0.0204 (12) | 0.0153 (11) | 0.0441 (15) | −0.0035 (9) | 0.0048 (11) | −0.0043 (10) |
C16 | 0.0183 (12) | 0.0235 (13) | 0.0493 (17) | −0.0005 (10) | 0.0045 (11) | −0.0019 (12) |
C17 | 0.0215 (13) | 0.0295 (14) | 0.0437 (16) | 0.0067 (11) | 0.0052 (12) | −0.0025 (12) |
C18 | 0.0258 (14) | 0.0225 (13) | 0.0539 (18) | 0.0069 (10) | 0.0047 (13) | −0.0082 (12) |
C14 | 0.0231 (18) | 0.0173 (16) | 0.044 (2) | 0.003 (4) | −0.0030 (17) | −0.003 (4) |
N5 | 0.0240 (17) | 0.0140 (14) | 0.031 (4) | −0.004 (2) | −0.006 (4) | −0.0012 (17) |
C19 | 0.030 (3) | 0.019 (3) | 0.029 (4) | −0.002 (2) | −0.004 (3) | −0.005 (3) |
C20 | 0.037 (3) | 0.020 (2) | 0.033 (3) | 0.004 (2) | −0.008 (2) | −0.016 (2) |
C21 | 0.059 (4) | 0.035 (3) | 0.057 (4) | 0.010 (3) | −0.019 (3) | −0.005 (3) |
C22 | 0.027 (3) | 0.017 (3) | 0.038 (4) | 0.005 (2) | −0.010 (4) | 0.004 (4) |
Bi1—I4 | 2.9544 (2) | C7—H7B | 0.9900 |
Bi1—I3 | 2.9633 (2) | C8—C9 | 1.506 (4) |
Bi1—I5 | 2.9889 (2) | C8—H8A | 0.9900 |
Bi1—I1i | 3.1450 (2) | C8—H8B | 0.9900 |
Bi1—I1 | 3.1832 (2) | C9—H9A | 0.9900 |
Bi1—I2 | 3.2414 (2) | C9—H9B | 0.9900 |
I1—Bi1i | 3.1450 (2) | C10—C11 | 1.515 (4) |
I2—Bi1i | 3.2414 (2) | C10—H10A | 0.9900 |
C1—N3 | 1.336 (3) | C10—H10B | 0.9900 |
C1—N2 | 1.338 (3) | C11—C12 | 1.516 (4) |
C1—N1B | 1.356 (3) | C11—H11A | 0.9900 |
C1—N1A | 1.356 (3) | C11—H11B | 0.9900 |
N2—C6 | 1.481 (3) | C12—C13 | 1.521 (4) |
N2—C9 | 1.487 (3) | C12—H12A | 0.9900 |
C2—N1B | 1.476 (3) | C12—H12B | 0.9900 |
C2—N1A | 1.476 (3) | C13—H13A | 0.9900 |
C2—C3A | 1.530 (4) | C13—H13B | 0.9900 |
C2—C3B | 1.530 (4) | N4—C14 | 1.340 (10) |
C2—H2A | 0.9900 | N4—C15 | 1.481 (3) |
C2—H2B | 0.9900 | N4—C18 | 1.483 (3) |
N3—C13 | 1.481 (3) | C15—C16 | 1.529 (4) |
N3—C10 | 1.482 (3) | C15—H15A | 0.9900 |
C3A—C4A | 1.530 (5) | C15—H15B | 0.9900 |
C3A—H3A1 | 0.9900 | C16—C17 | 1.517 (4) |
C3A—H3A2 | 0.9900 | C16—H16A | 0.9900 |
C4A—C5A | 1.513 (6) | C16—H16B | 0.9900 |
C4A—H4A1 | 0.9900 | C17—C18 | 1.513 (4) |
C4A—H4A2 | 0.9900 | C17—H17A | 0.9900 |
C5A—N1A | 1.490 (5) | C17—H17B | 0.9900 |
C5A—H5A | 0.9900 | C18—H18A | 0.9900 |
C5A—H5B | 0.9900 | C18—H18B | 0.9900 |
C3B—C4B | 1.551 (11) | C14—N5 | 1.364 (5) |
C3B—H3B1 | 0.9900 | N5—C22 | 1.463 (14) |
C3B—H3B2 | 0.9900 | N5—C19 | 1.475 (14) |
C4B—C5B | 1.498 (14) | C19—C20 | 1.528 (11) |
C4B—H4B1 | 0.9900 | C19—H19A | 0.9900 |
C4B—H4B2 | 0.9900 | C19—H19B | 0.9900 |
C5B—N1B | 1.476 (13) | C20—C21 | 1.516 (8) |
C5B—H5B1 | 0.9900 | C20—H20A | 0.9900 |
C5B—H5B2 | 0.9900 | C20—H20B | 0.9900 |
C6—C7 | 1.520 (4) | C21—C22 | 1.479 (12) |
C6—H6A | 0.9900 | C21—H21A | 0.9900 |
C6—H6B | 0.9900 | C21—H21B | 0.9900 |
C7—C8 | 1.500 (5) | C22—H22A | 0.9900 |
C7—H7A | 0.9900 | C22—H22B | 0.9900 |
I4—Bi1—I3 | 94.391 (6) | C7—C8—H8A | 111.1 |
I4—Bi1—I5 | 91.172 (6) | C9—C8—H8A | 111.1 |
I3—Bi1—I5 | 95.836 (6) | C7—C8—H8B | 111.1 |
I4—Bi1—I1i | 90.337 (6) | C9—C8—H8B | 111.1 |
I3—Bi1—I1i | 90.414 (6) | H8A—C8—H8B | 109.1 |
I5—Bi1—I1i | 173.438 (5) | N2—C9—C8 | 103.3 (2) |
I4—Bi1—I1 | 90.759 (6) | N2—C9—H9A | 111.1 |
I3—Bi1—I1 | 171.376 (5) | C8—C9—H9A | 111.1 |
I5—Bi1—I1 | 90.962 (6) | N2—C9—H9B | 111.1 |
I1i—Bi1—I1 | 82.632 (6) | C8—C9—H9B | 111.1 |
I4—Bi1—I2 | 169.447 (6) | H9A—C9—H9B | 109.1 |
I3—Bi1—I2 | 92.746 (5) | N3—C10—C11 | 102.4 (2) |
I5—Bi1—I2 | 95.829 (5) | N3—C10—H10A | 111.3 |
I1i—Bi1—I2 | 81.840 (5) | C11—C10—H10A | 111.3 |
I1—Bi1—I2 | 81.260 (4) | N3—C10—H10B | 111.3 |
Bi1i—I1—Bi1 | 82.390 (5) | C11—C10—H10B | 111.3 |
Bi1—I2—Bi1i | 80.022 (7) | H10A—C10—H10B | 109.2 |
N3—C1—N2 | 120.3 (2) | C10—C11—C12 | 101.8 (2) |
N3—C1—N1B | 120.3 (2) | C10—C11—H11A | 111.4 |
N2—C1—N1B | 119.4 (2) | C12—C11—H11A | 111.4 |
N3—C1—N1A | 120.3 (2) | C10—C11—H11B | 111.4 |
N2—C1—N1A | 119.4 (2) | C12—C11—H11B | 111.4 |
C1—N2—C6 | 124.9 (2) | H11A—C11—H11B | 109.3 |
C1—N2—C9 | 125.4 (2) | C11—C12—C13 | 102.0 (2) |
C6—N2—C9 | 109.6 (2) | C11—C12—H12A | 111.4 |
N1A—C2—C3A | 103.8 (2) | C13—C12—H12A | 111.4 |
N1B—C2—C3B | 103.8 (2) | C11—C12—H12B | 111.4 |
N1A—C2—H2A | 111.0 | C13—C12—H12B | 111.4 |
C3A—C2—H2A | 111.0 | H12A—C12—H12B | 109.2 |
N1A—C2—H2B | 111.0 | N3—C13—C12 | 103.5 (2) |
C3A—C2—H2B | 111.0 | N3—C13—H13A | 111.1 |
H2A—C2—H2B | 109.0 | C12—C13—H13A | 111.1 |
C1—N3—C13 | 125.4 (2) | N3—C13—H13B | 111.1 |
C1—N3—C10 | 124.6 (2) | C12—C13—H13B | 111.1 |
C13—N3—C10 | 109.9 (2) | H13A—C13—H13B | 109.0 |
C2—C3A—C4A | 102.6 (2) | C14—N4—C15 | 125.4 (3) |
C2—C3A—H3A1 | 111.2 | C14—N4—C18 | 124.1 (3) |
C4A—C3A—H3A1 | 111.2 | C15—N4—C18 | 110.3 (2) |
C2—C3A—H3A2 | 111.2 | N4—C15—C16 | 103.0 (2) |
C4A—C3A—H3A2 | 111.2 | N4—C15—H15A | 111.2 |
H3A1—C3A—H3A2 | 109.2 | C16—C15—H15A | 111.2 |
C5A—C4A—C3A | 101.8 (3) | N4—C15—H15B | 111.2 |
C5A—C4A—H4A1 | 111.4 | C16—C15—H15B | 111.2 |
C3A—C4A—H4A1 | 111.4 | H15A—C15—H15B | 109.1 |
C5A—C4A—H4A2 | 111.4 | C17—C16—C15 | 103.3 (2) |
C3A—C4A—H4A2 | 111.4 | C17—C16—H16A | 111.1 |
H4A1—C4A—H4A2 | 109.3 | C15—C16—H16A | 111.1 |
N1A—C5A—C4A | 102.3 (3) | C17—C16—H16B | 111.1 |
N1A—C5A—H5A | 111.3 | C15—C16—H16B | 111.1 |
C4A—C5A—H5A | 111.3 | H16A—C16—H16B | 109.1 |
N1A—C5A—H5B | 111.3 | C18—C17—C16 | 101.7 (2) |
C4A—C5A—H5B | 111.3 | C18—C17—H17A | 111.4 |
H5A—C5A—H5B | 109.2 | C16—C17—H17A | 111.4 |
C1—N1A—C2 | 125.8 (2) | C18—C17—H17B | 111.4 |
C1—N1A—C5A | 122.8 (3) | C16—C17—H17B | 111.4 |
C2—N1A—C5A | 110.2 (3) | H17A—C17—H17B | 109.3 |
C2—C3B—C4B | 104.5 (4) | N4—C18—C17 | 103.3 (2) |
C2—C3B—H3B1 | 110.9 | N4—C18—H18A | 111.1 |
C4B—C3B—H3B1 | 110.9 | C17—C18—H18A | 111.1 |
C2—C3B—H3B2 | 110.9 | N4—C18—H18B | 111.1 |
C4B—C3B—H3B2 | 110.9 | C17—C18—H18B | 111.1 |
H3B1—C3B—H3B2 | 108.9 | H18A—C18—H18B | 109.1 |
C5B—C4B—C3B | 101.6 (10) | N4—C14—N5 | 121.7 (9) |
C5B—C4B—H4B1 | 111.4 | C14—N5—C22 | 128.6 (10) |
C3B—C4B—H4B1 | 111.4 | C14—N5—C19 | 122.8 (9) |
C5B—C4B—H4B2 | 111.4 | C22—N5—C19 | 108.3 (3) |
C3B—C4B—H4B2 | 111.4 | N5—C19—C20 | 102.1 (8) |
H4B1—C4B—H4B2 | 109.3 | N5—C19—H19A | 111.3 |
N1B—C5B—C4B | 99.7 (9) | C20—C19—H19A | 111.3 |
N1B—C5B—H5B1 | 111.8 | N5—C19—H19B | 111.3 |
C4B—C5B—H5B1 | 111.8 | C20—C19—H19B | 111.3 |
N1B—C5B—H5B2 | 111.8 | H19A—C19—H19B | 109.2 |
C4B—C5B—H5B2 | 111.8 | C21—C20—C19 | 106.5 (6) |
H5B1—C5B—H5B2 | 109.6 | C21—C20—H20A | 110.4 |
C1—N1B—C2 | 125.8 (2) | C19—C20—H20A | 110.4 |
C1—N1B—C5B | 126.5 (7) | C21—C20—H20B | 110.4 |
C2—N1B—C5B | 106.9 (7) | C19—C20—H20B | 110.4 |
N2—C6—C7 | 102.6 (2) | H20A—C20—H20B | 108.6 |
N2—C6—H6A | 111.3 | C22—C21—C20 | 106.9 (6) |
C7—C6—H6A | 111.3 | C22—C21—H21A | 110.3 |
N2—C6—H6B | 111.3 | C20—C21—H21A | 110.3 |
C7—C6—H6B | 111.3 | C22—C21—H21B | 110.3 |
H6A—C6—H6B | 109.2 | C20—C21—H21B | 110.3 |
C8—C7—C6 | 101.7 (3) | H21A—C21—H21B | 108.6 |
C8—C7—H7A | 111.4 | N5—C22—C21 | 105.3 (7) |
C6—C7—H7A | 111.4 | N5—C22—H22A | 110.7 |
C8—C7—H7B | 111.4 | C21—C22—H22A | 110.7 |
C6—C7—H7B | 111.4 | N5—C22—H22B | 110.7 |
H7A—C7—H7B | 109.3 | C21—C22—H22B | 110.7 |
C7—C8—C9 | 103.1 (3) | H22A—C22—H22B | 108.8 |
N3—C1—N2—C6 | 26.6 (4) | C4B—C5B—N1B—C2 | 46.0 (12) |
N1B—C1—N2—C6 | −151.0 (3) | C1—N2—C6—C7 | 166.3 (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—C8 | 38.2 (4) |
N1B—C1—N2—C9 | 34.2 (4) | C6—C7—C8—C9 | −44.6 (4) |
N1A—C1—N2—C9 | 34.2 (4) | C1—N2—C9—C8 | 166.4 (3) |
N2—C1—N3—C13 | −154.8 (3) | C6—N2—C9—C8 | −9.0 (3) |
N1B—C1—N3—C13 | 22.9 (4) | C7—C8—C9—N2 | 33.2 (3) |
N1A—C1—N3—C13 | 22.9 (4) | C1—N3—C10—C11 | 157.9 (2) |
N2—C1—N3—C10 | 29.1 (3) | C13—N3—C10—C11 | −18.7 (3) |
N1B—C1—N3—C10 | −153.3 (2) | N3—C10—C11—C12 | 39.0 (2) |
N1A—C1—N3—C10 | −153.3 (2) | C10—C11—C12—C13 | −45.0 (3) |
N1A—C2—C3A—C4A | 29.4 (3) | C1—N3—C13—C12 | 174.4 (2) |
C2—C3A—C4A—C5A | −43.2 (4) | C10—N3—C13—C12 | −9.0 (3) |
C3A—C4A—C5A—N1A | 39.8 (5) | C11—C12—C13—N3 | 33.1 (3) |
N3—C1—N1A—C2 | 37.1 (4) | C14—N4—C15—C16 | 167.3 (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—C17 | 31.5 (3) |
N2—C1—N1A—C5A | 21.3 (4) | C15—C16—C17—C18 | −42.8 (3) |
C3A—C2—N1A—C1 | 163.4 (2) | C14—N4—C18—C17 | 166.2 (3) |
C3A—C2—N1A—C5A | −4.6 (4) | C15—N4—C18—C17 | −18.2 (3) |
C4A—C5A—N1A—C1 | 169.3 (3) | C16—C17—C18—N4 | 37.2 (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—N5 | 27.2 (4) |
C2—C3B—C4B—C5B | 31.2 (12) | N4—C14—N5—C22 | 37.8 (9) |
C3B—C4B—C5B—N1B | −46.1 (14) | N4—C14—N5—C19 | −135.8 (8) |
N3—C1—N1B—C2 | 37.1 (4) | C14—N5—C19—C20 | 141.3 (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—C21 | 23.0 (9) |
N2—C1—N1B—C5B | 46.0 (8) | C19—C20—C21—C22 | −5.2 (10) |
C3B—C2—N1B—C1 | 163.4 (2) | C14—N5—C22—C21 | −143.3 (9) |
C3B—C2—N1B—C5B | −26.1 (6) | C19—N5—C22—C21 | 31.1 (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] |
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) |
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 |
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
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
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