C—I⋯N and C—I⋯π halogen bonding in the structures of 1-benzyl­iodo­imidazole derivatives

Nwachukwu, C.I.; Bowling, N.P.; Bosch, E.

doi:10.1107/S2053229616018702

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 73| Part 1| January 2017| Pages 2-8

https://doi.org/10.1107/S2053229616018702

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C—I⋯N and C—I⋯π halogen bonding in the structures of 1-benzyliodoimidazole derivatives

Chideraa I. Nwachukwu,^a Nathan P. Bowling ^b and Eric Bosch ^a ^*

^aChemistry, Missouri State University, 901 South National Avenue, Springfield, MO 65897, USA, and ^bDepartment of Chemistry, University of Wisconsin–Stevens Point, 2001 Fourth Avenue, Stevens Point, WI 54481, USA
^*Correspondence e-mail: ericbosch@missouristate.edu

Edited by M. Kubicki, Adam Mickiewicz University, Poland (Received 19 August 2016; accepted 22 November 2016; online 1 January 2017)

Halogen bonding is a well-established and intensively studied intermolecular interaction that has also been used in the preparation of functional materials. While polyfluoroiodo- and polyfluorobromobenzenes have been widely used as aromatic halogen-bond donors, there have been very few studies of iodoimidazoles with regard to halogen bonding. We describe here the X-ray structures of three iodoimidazole derivatives, namely 1-benzyl-2-iodo-1H-imidazole, C₁₀H₉IN₂, (1), 1-benzyl-4-iodo-1H-imidazole, C₁₀H₉IN₂, (2), and 1-benzyl-2-iodo-1H-benzimidazole, C₁₄H₁₁IN₂, (3), and the halogen bonds that dominate the intermolecular interactions in each of these three structures. The three-dimensional structure of (1) is dominated by a strong C—I⋯N halogen bond, with an N⋯I distance of 2.8765 (2) Å, that connects the molecules into one-dimensional zigzag ribbons of molecules. In contrast, the three-dimensional structures of (2) and (3) both feature C—I⋯π halogen-bonded dimers.

Keywords: halogen bonding; intermolecular interactions; iodoimidazole; crystal structure; halogen-bonded dimer; computational chemistry; molecular electrostatic potential.

CCDC references: 1518622; 1518621; 1518620

1. Introduction

Halogen bonding is now a well-established and intensively studied intermolecular interaction that has also been used in the preparation of functional materials (Cavallo et al., 2016 ; Gilday et al., 2015 ). While polyfluoroiodo- and polyfluorobromobenzenes have been widely used as aromatic halogen-bond donors, there have been very few studies of iodoimidazoles with regard to halogen bonding. Indeed, a search of the Cambridge Structural Database (CSD; Version 5.37; Groom et al., 2016 ) using Conquest (Bruno et al., 2002 ) revealed 74 examples involving iodoimidazoles. It is noteworthy, however, that only 18 of the 74 structures contained neutral iodinated imidazole derivatives. Furthermore, 14 of these 18 structures do not exhibit any close contacts to the I atoms. The structures of five neutral N-unsubstituted iodoimidazoles are dominated by N—H⋯N hydrogen bonds [refcodes BOWREM, BOWRUC and BOWSAJ (Andrzejewski et al., 2015 ), GARJUG (Chlupatý et al., 2012 ), and WISBUL (Ding et al., 2012 )] and one structure features N—H⋯O hydrogen bonds (KOZLIW; Jansa et al., 2015 ), while seven more sterically hindered imidazole derivatives do not display any major intermolecular interactions and the three-dimensional structures presumably have controlled close packing based on size, shape, and polarity [GOGYOR (Delest et al., 2008 ), IGUANM (Al-Mukhtar & Wilson, 1978 ), KIRYEQ (Poverlein et al., 2007 ), UJOCIF (Tschamber et al., 2003 ), NUCRAE (Phillips et al., 1997 ), UNIFUS (Terinek & Vasella, 2003 ), and UXOXOV (Li et al., 2011 )]. In contrast, three unhindered N-substituted iodoimidazoles do display C—I⋯N halogen bonding as the major intermolecular interaction [BEQWEB (Mukai & Nishikawa, 2013 ), GOGYIL (Delest et al., 2008) and HUDSUW (Byrne, 2015 )]. A particularly striking example is the identification of a trimeric halogen-bonded unit by Mukai & Nishikawa (2013). The

reported halogen bonds have N⋯I distances between 2.884 and 2.953 Å, corresponding to 81.7–83.7% of the sum of the van der Waals radii of 3.53 Å (Bondi, 1964

), and are essentially linear, with C—I⋯N angles between 171.38 and 174.86°. In this study, we present the structures of three iodoimidazole derivatives, namely 1-benzyl-2-iodo-1H-imidazole, (1), 1-benzyl-4-iodo-1H-imidazole, (2), and 1-benzyl-2-iodo-1H-benzimidazole, (3), and discuss the intermolecular halogen-bonding interactions and other nonbonding interactions that dominate the crystal structures.

2. Experimental

2.1. Synthesis and crystallization

2.1.1. 1-Benzyl-2-iodo-1H-imidazole, (1)

1-Benzyl-1H-imidazole was synthesized according to the procedure of Salvio et al. (2011 ). Compound (1) was synthesized from 1-benzyl-1H-imidazole using a modification of the procedure of de Figueiredo (2007 ). Thus, 1-benzyl-1H-imidazole (2 g, 12.64 mmol) and anhydrous tetrahydrofuran (35 ml) were added to a three-necked 250 ml round-bottomed flask under an argon atmosphere. The mixture was cooled to 195 K and stirred at this temperature for 7 min. 1.6 M n-BuLi (8 ml, 12.64 mmol, 1 equivalent) was added dropwise over a period of 2 mins and the resultant mixture stirred at 195 K for 45 min. Iodine (4.81 g, 18.96 mmol, 1.5 equivalents) was crushed and added to the stirred mixture. The cooling bath was removed and the mixture stirred at room temperature for 3 h under argon. The mixture was extracted with CH₂Cl₂ (300 ml) and the excess I₂ was quenched with 10% Na₂SO₃ (200 ml). The organic layer was separated, washed twice with H₂O (200 ml) and twice with brine (200 ml), and then dried over Na₂SO₄. The solvent was removed in vacuo and the crude product purified by flash column chromatography using a 10:1 (v/v) mixture of hexane and ethyl acetate to afford 2.23 g of the compound as a white solid (yield 7.85 mmol, 62%). R_F = 0.27 (hexane/EtOAc, 2:1 v/v). The solid was crystallized from a 9:1 (v/v) mixture of hexane and ethyl acetate to give white needle-like crystals [m.p. 373.5–375.9 K; literature 372–374 K (Moreno-Manas et al., 1990 )]. ¹H NMR (400 MHz, CDCl₃): δ 5.10 (s, 2H), 7.01 (d, J = 1.6 Hz, 1H), 7.12–7.15 (m, 3H), 7.32–7.38 (m, 3H).

2.1.2. 1-Benzyl-4-iodo-1H-imidazole, (2)

Compound (2) was synthesized from commercially available 4-iodo-1H-imidazole using a similar procedure to that used to synthesize 1-benzyl-1H-imidazole (see Supporting information).

2.1.3. 1-Benzyl-2-iodo-1H-benzimidazole, (3)

1-Benzyl-1H-benzimidazole and the iodinated compound (3) were synthesized using the modified procedure used for the preparation of (1) (see Supporting information).

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic) or 0.98 Å (methylene) and U_iso(H) = kU_iso(C), where k = 1.5 for the methylene group and 1.2 for all aromatic H atoms. The correct absolute configuration for the molecules of compound (1) in the crystal selected for data collection was determined by the Flack x parameter (Flack, 1983 ) of −0.002 (13) by a classical fit to all intensities and was calculated using 913 quotients [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)] (Parsons et al., 2013 ).

Table 1
Experimental details

	(1)	(2)	(3)
Crystal data
Chemical formula	C₁₀H₉IN₂	C₁₀H₉IN₂	C₁₄H₁₁IN₂
M_r	284.09	284.09	334.15
Crystal system, space group	Orthorhombic, P2₁2₁2₁	Monoclinic, P2₁/n	Triclinic, P $[\overline{1}]$
Temperature (K)	100	100	100
a, b, c (Å)	8.7561 (5), 9.0016 (5), 12.8869 (7)	8.4574 (5), 6.1526 (3), 19.4261 (10)	6.4606 (8), 8.2346 (10), 12.3451 (14)
α, β, γ (°)	90, 90, 90	90, 96.362 (1), 90	108.064 (1), 94.174 (2), 95.366 (2)
V (Å³)	1015.73 (10)	1004.61 (9)	618.05 (13)
Z	4	4	2
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	3.11	3.14	2.57
Crystal size (mm)	0.30 × 0.20 × 0.05	0.22 × 0.22 × 0.22	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )	Multi-scan (SADABS; Bruker, 2014)	Multi-scan (SADABS; Bruker, 2014)
T_min, T_max	0.622, 0.746	0.594, 0.746	0.588, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	13262, 2228, 2202	12374, 2207, 2114	8079, 2777, 2725
R_int	0.030	0.021	0.016
(sin θ/λ)_max (Å⁻¹)	0.641	0.641	0.645

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.013, 0.030, 1.05	0.016, 0.037, 1.11	0.015, 0.039, 1.09
No. of reflections	2228	2207	2777
No. of parameters	118	118	154
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.27	0.73, −0.52	0.74, −0.35
Absolute structure	See §2.2	–	–
Computer programs: SMART (Bruker, 2014), SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and X-SEED (Barbour, 2001 ).

2.3. Electrostatic potential calculations

All molecules were geometry optimized using the Spartan'10 (Wavefunction, 2010 ) molecular modeling program with density functional theory (DFT) at the B3LYP/6-311+G** level, and the corresponding molecular electrostatic potential energy surface was determined also using Spartan'10. The initial geometry for the optimization corresponded to that observed in the corresponding crystal structure. In the optimized geometry (gas phase), the benzyl group is rotated relative to the imidazole ring and minor conformation-based differences in the electrostatic potentials may be expected between the two conformations. The differences between the observed conformation and the optimized conformation of each of (1), (2), and (3) are collected in Table S1 in the Supporting information.

3. Results and discussion

The asymmetric unit of the X-ray structure of (1) contains a single molecule. The phenyl group is essentially orthogonal to the imidazole group, with a dihedral angle between the planes defined by the phenyl C atoms and the imidazole N and C atoms of 84°. Phenyl atom H6 is positioned above imidazole atom N1, with an N1—C4—C5—C6 torsion angle of 13.0 (4)° and an H6⋯N1 distance of 2.58 Å, compared to the sum of the van der Waals radii of 2.75 Å (Bondi, 1964). There is also a close contact between one of the benzyl H atoms and the I atom, with an H4B⋯I1 distance of 3.04 Å, compared to the sum of the van der Waals radii of 3.18 Å. The three-dimensional structure of (1) features an imidazole N⋯I halogen bond, as shown in Fig. 1. The N2⋯I1ⁱ distance [symmetry code: (i) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1] is 2.8765 (2) Å, which is 81% of the sum of the van der Waals radii of 3.53 Å (Bondi, 1964). The halogen bond is almost linear, with a C—I⋯N angle of 174.42 (9)°.

Figure 1
The molecular structure of (1), showing the imidazole N⋯I halogen bond (dashed line). Displacement ellipsoids for the non-H atoms are drawn at the 50% probability level.

Linear one-dimensional ribbons of zigzag halogen-bonded molecules of (1) dominate the three-dimensional structure, as shown in Fig. 2. These one-dimensional ribbons run parallel to the a axis and are close packed with no other significant intermolecular interactions.

Figure 2
The one-dimensional zigzag halogen-bonded ribbon of molecules in the single-crystal X-ray structure of (1).

The X-ray structure of (2) also contains a single molecule in the asymmetric unit having a bent shape. The phenyl group is also almost orthogonal to the imidazole group, with a dihedral angle between the planes defined by the phenyl and imidazole rings of 84°. The phenyl ring is not oriented above the imidazole ring; the C6—C5—C4—N1 torsion angle is −52.0 (2)°. The three-dimensional structure has a weak iodo–π interaction involving the pendant phenyl ring of an adjacent molecule that results in the formation of C—I⋯π halogen-bonded dimers, as shown in Fig. 3.

Figure 3
The molecular structure of (2), showing (a) the atom labeling and the C—I⋯π(phenyl) interactions (dashed lines), with displacement ellipsoids drawn at the 50% probability level, and (b) a space-filling model.

In the C—I⋯π-bonded dimer of (2), the C—I bond is directed towards phenyl atoms C7ⁱ and C8ⁱ [symmetry code: (i) −x + 1, −y + 1, −z + 2] of an adjacent molecule, with I1⋯C7ⁱ and I1⋯C8ⁱ distances of 3.551 (2) and 3.5534 (2) Å, respectively, both approximately 96% of the sum of the van der Waals radii of 3.68 Å (Bondi, 1964). The C2—I1⋯C7ⁱ and C2—I1⋯C8ⁱ angles are 152.99 (1) and 171.24 (1)°, respectively. The C—I⋯Cg1ⁱ distance is 3.5861 (2) Å (Cg1 is the centroid of the C5–C10 phenyl ring) and the C—I⋯Cg1ⁱ angle is 162.82 (1)°. There are two other close contacts in the three-dimensional structure of (2). One of these is a nonconventional C—H⋯N hydrogen bond between atom N2 and a benzylic H atom of an adjacent molecule, with an N2⋯H4Bⁱⁱ [symmetry code: (ii) x, y − 1, z] distance of 2.55 Å, which is 93% of the sum of the van der Waals radii of 2.75 Å (Bondi, 1964); the C—H⋯N angle is 158°. There is a close H⋯H contact of 2.26 Å between atoms H4A and H7ⁱⁱⁱ [symmetry code: (iii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ] of an adjacent molecule.

The structure of (3) also contains a single molecule in the asymmetric unit, with a dihedral angle between the imidazole and benzyl rings of 86°. In this structure, phenyl atom H9 is positioned above atom N1, with an N1—C8—C9—C14 torsion angle of −13.4 (2)°. There is also a C—I⋯π interaction to the phenyl ring of an adjacent molecule, resulting in a C—I⋯π-bonded molecular dimeric motif similar to that observed in (2) (Fig. 4).

Figure 4
The structure of the C—I⋯π halogen-bonded dimers formed in the structure of (3), showing (a) the atom labeling and the C—I⋯π(phenyl) interactions (dashed lines), with displacement ellipsoids drawn at the 50% probability level, and (b) a space-filling model.

In the C—I⋯π-bonded dimer of (3), the C—I bond is directed towards phenyl atom C13ⁱ [symmetry code: (i) −x + 1, −y + 1, −z] of the adjacent molecule, with a C1—I1⋯C13ⁱ angle of 178.66 (1)° and an I3⋯C13ⁱ distance of 3.3929 (4) Å. This distance is 92% of the sum of the van der Waals radii of 3.68 Å (Bondi, 1964). The C—I⋯Cg1ⁱ distance is 3.4562 (4) Å (Cg1 is the centroid of the C9–C14 phenyl ring) and the C—I⋯Cg1ⁱ angle is 156.94 (1)°. There is an intramolecular C—H⋯π interaction since benzyl atom H14 lies above the imidazole ring, with an N1—C8—C9—C14 torsion angle of −13.4 (2)°. This interaction is labeled `x' in Fig. 5. The H14⋯N1 distance is 2.51 Å and the C14—H14⋯N1 angle is 101°. The H14⋯Cg2 distance is 2.82 Å (Cg2 is the centroid of the N1/C1/N2/C2/C7 imidazole ring) and the C14—H14⋯Cg2 angle is 125°.

Figure 5
A partial view of the three-dimensional packing of (3), viewed along the a axis. The C—I⋯π interaction is labeled as Iπ, the C—H⋯π interactions are labeled as x, y and z, and the π-stacking is labeled as ππ.

The three-dimensional packing of (3) involves multiple cohesive interactions, namely two intermolecular C—H⋯π interactions and two π–π interactions. Benzimidazole atom H5 is involved in a C—H⋯π interaction with the pendant phenyl ring, labeled `y' in Fig. 5; the H5⋯Cg1ⁱⁱ distance is 2.78 Å and the C—H⋯Cg1ⁱⁱ angle is 149° [Cg1 is the centroid of C9–C14 ring; symmetry code: (ii) −x + 2, −y + 1, −z + 1]. Benzyl atom H13 is involved in an interaction with the benzimidazole benzene ring, labeled `z' in Fig. 5, with an H13⋯Cg3ⁱⁱⁱ distance of 2.94 Å and a C13—H13⋯Cg3ⁱⁱⁱ angle of 141° [Cg3 is the centroid of the benzimidazole C2–C7 ring; symmetry code: (iii) x, y + 1, z]. The benzimidazole groups are alternately π-stacked (labeled ππ in Fig. 5), with the benzene rings overlaid and slightly offset. The Cg3⋯Cg3^iv distance is 4.5536 (6) Å, the perpendicular distance between the benzene rings is 4.3405 Å and the slippage is 1.377 Å [symmetry code: (iv) −x + 1, −y + 1, −z + 1].

In order to place these C—I⋯N and C—I⋯π interactions in context, two searches of the Cambridge Structural Database (CSD, Version 5.37; Groom et al., 2016) using Conquest (Bruno et al., 2002) were made. The first search, for crystal structures containing C—I⋯N contacts with I⋯N distances equal to or less than the sum of the van der Waals radii (3.53 Å), yielded 763 structures with a total of 1082 contacts that met the criteria. Several of these structures corresponded to parallel-displaced π-stacked aromatics, with very short contacts and C—I⋯N angles less than 90°, which we deemed as significantly different to not include in the analysis. Accordingly, the search was modified to include those structures in which the C—I⋯N angle was between 120 and 180°, resulting in 752 structures with 1058 distinct interactions that are displayed in the scatterplot of N⋯I distance versus C—I⋯N angle in Fig. 6. The N⋯I distance reported here for (1) [2.876 (3) Å] is less than the median (2.973 Å) of the 1058 reported N⋯I distances and is clearly in the group of shorter C—I⋯N interactions. The almost linear C—I⋯N angle is consistent with the majority of the shorter N⋯I distances which are clustered at C—I⋯N angles above 165°.

Figure 6
A scatterplot of the N⋯I distances and C—I⋯N angles corresponding to all results of a search of the CSD using Conquest for C—I⋯N contacts with an I⋯N distance less than or equal to 3.53 Å, i.e. the sum of the van der Waals radii, and an C—I⋯N angle between 120 and 180°.

The second search of the CSD using Conquest probed C—I⋯π interactions specifically between an I atom bonded to carbon and a benzene ring as the π-system in which the I⋯Cg (Cg is the centroid of the benzene ring) distance was less than 3.68 Å (the sum of the van der Waals radii of C and I) and the C—I⋯π angles were between 120 and 180°. The restrictive angle was chosen to exclude parallel-displaced π-stacked systems. The shortest C—I⋯Cg distance from the search (3.215 Å) was recorded from a crystal of 2-(2-fluoropyridin-3-yl)-2-(4-iodophenyl)-2H-3λ⁵,2λ⁵-[1,3,2]oxazaborolo[5,4,3-ij]quinolone under a pressure of 4.88 GPa at ambient temperature (Wesela-Bauman et al., 2014 ). In fact, four of the five shortest C—I⋯Cg distances reported correspond to that study. The C—I⋯Cg distance for the same compound at 100 K and under atmospheric pressure is 3.525 Å. Accordingly, the data corresponding to pressurized crystals from that study are not included in the scatterplot of I⋯Cg distances versus C—I⋯Cg angles displayed in Fig. 7.

Figure 7
A scatterplot showing the C—I⋯Cg contacts (Cg is the centroid of the benzene ring) to benzene derivatives, with an I⋯Cg distance less than or equal to 3.68 Å, i.e. the sum of the van der Waals radii, and an C—I⋯Cg angle between 120 and 180°.

The shortest C—I⋯Cg distance of 3.272 Å in Fig. 7 corresponds to the structure of the p-xylene solvate of hexakis(4-iodophenyl)benzene that includes an iodo–π interaction between one of the iodobenzene molecules and the included p-xylene solvent molecule (Kobayashi et al., 2005 ). The next six close contacts have C—I⋯Cg distances between 3.376 and 3.400 Å. The C—I⋯Cg distance of 3.4562 (4) Å reported here for (3) is clearly amongst the shorter C—I⋯Cg distances reported to date.

In order to better understand the halogen-bonding behavior of (1), (2), and (3), the molecular electrostatic potentials of these three compounds were calculated and the plots showing the molecular electrostatic potential surfaces are shown in Fig. 8.

Figure 8
The molecular electrostatic potential maps of compounds (1), (2), and (3), shown on the same scale (right).

The calculated positive electrostatic potential associated with the positive σ-hole on the I atom of compounds (1), (2), and (3) were determined to be 123, 81, and 129 kJ mol⁻¹, respectively. These modest values associated with the positive σ-hole are considerably lower than the values reported for the better known halogen-bond donors. For example, iodopentafluorobenzene has a calculated positive electrostatic potential associated with the σ-hole on the I atom of 166 kJ mol⁻¹ (Aakeröy et al., 2014 ). The positive electrostatic potential associated with the σ-hole on the I atom of 1,3,5-triiodo-2,4,6-trinitrobenzene has recently been reported as 213 kJ mol⁻¹, which is the most positive value calculated to date (Goud et al., 2016 ). Nevertheless, the 2-iodoimidazole derivatives are distinctly better halogen-bond donors than iodobenzene, with a calculated electrostatic potential of 103 kJ mol⁻¹ (Aakeröy et al., 2014), while the 4-iodoimidazole derivative is a poorer halogen-bond acceptor than iodobenzene. The negative electrostatic potential on the unsubstituted N atom of compounds (1), (2), and (3) are −204, −210, and −193 kJ mol⁻¹, respectively. These values are similar to the values reported for a series of N-substituted imidazole derivatives (Aakeröy et al., 2016 ). Thus, while the relatively weak halogen-bonding interaction of (2) can be ascribed to the low positive electrostatic potential on the I atom, rationalizing the other two results is difficult. The conundrum is that compounds (1) and (3) have similar halogen-bond-donor properties and similar halogen-bond-acceptor properties on the unsubstituted imidazole N atom, yet form different types of halogen bonds (C—I⋯N versus C—I⋯π).

In conclusion, we have demonstrated that 2-iodoimidazoles are effective halogen-bond donors and acceptors and may form C—I⋯N or C—I⋯π halogen bonds but we are, as yet, unable to rationalize the factors that control the type of halogen bonding. In our future work, we plan to explore intra- and intermolecular C—I⋯π interactions.

Supporting information

CCDC references: 1518622; 1518621; 1518620

Crystal structure: contains datablocks 1, 2, 3. DOI: https://doi.org/10.1107/S2053229616018702/ku3188sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2053229616018702/ku31881sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2053229616018702/ku31882sup3.hkl

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S2053229616018702/ku31883sup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2053229616018702/ku31881sup5.cml

Supporting information file. DOI: https://doi.org/10.1107/S2053229616018702/ku31882sup6.cml

Supporting information file. DOI: https://doi.org/10.1107/S2053229616018702/ku31883sup7.cml

Additional synthesis details and comparison of torsion angles. DOI: https://doi.org/10.1107/S2053229616018702/ku3188sup8.pdf

Computing details top

For all structures, data collection: SMART (Bruker, 2014); cell refinement: SMART (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED (Barbour, 2001).

1-Benzyl-2-iodo-1H-imidazole (1) top

Crystal data top

C₁₀H₉IN₂	D_x = 1.858 Mg m⁻³
M_r = 284.09	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 7864 reflections
a = 8.7561 (5) Å	θ = 2.8–27.1°
b = 9.0016 (5) Å	µ = 3.11 mm⁻¹
c = 12.8869 (7) Å	T = 100 K
V = 1015.73 (10) Å³	Irregular, colourless
Z = 4	0.30 × 0.20 × 0.05 mm
F(000) = 544

Data collection top

Bruker APEXII CCD diffractometer	2228 independent reflections
Radiation source: fine-focus sealed tube	2202 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 8.3660 pixels mm^-1	θ_max = 27.1°, θ_min = 2.8°
phi and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −11→11
T_min = 0.622, T_max = 0.746	l = −16→16
13262 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.013	w = 1/[σ²(F_o²) + (0.0131P)² + 0.0966P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.030	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.25 e Å⁻³
2228 reflections	Δρ_min = −0.27 e Å⁻³
118 parameters	Absolute structure: Flack x determined using 913 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.002 (13)

Special details top

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

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

	x	y	z	U_iso*/U_eq
I1	0.23697 (2)	0.28234 (2)	0.52915 (2)	0.01308 (5)
N1	0.1137 (3)	0.4336 (3)	0.72457 (18)	0.0140 (5)
C1	0.0779 (3)	0.3510 (3)	0.6399 (2)	0.0126 (6)
N2	−0.0686 (3)	0.3169 (3)	0.63687 (19)	0.0153 (5)
C2	−0.1294 (3)	0.3814 (3)	0.7256 (2)	0.0175 (6)
H1	−0.2337	0.3759	0.7456	0.021*
C3	−0.0203 (3)	0.4526 (3)	0.7792 (2)	0.0173 (6)
H9	−0.0329	0.5057	0.8423	0.021*
C4	0.2632 (4)	0.4913 (3)	0.7544 (2)	0.0163 (6)
H7	0.2484	0.5859	0.7923	0.020*
H8	0.3218	0.5138	0.6906	0.020*
C5	0.3573 (3)	0.3881 (3)	0.8214 (2)	0.0145 (6)
C6	0.3217 (3)	0.2395 (3)	0.8364 (2)	0.0165 (6)
H3	0.2345	0.1980	0.8035	0.020*
C7	0.4136 (3)	0.1504 (4)	0.8995 (2)	0.0210 (7)
H4	0.3885	0.0487	0.9094	0.025*
C8	0.5407 (3)	0.2094 (4)	0.9477 (2)	0.0215 (7)
H2	0.6027	0.1487	0.9909	0.026*
C9	0.5776 (4)	0.3587 (4)	0.9327 (2)	0.0222 (7)
H5	0.6647	0.4001	0.9658	0.027*
C10	0.4869 (3)	0.4463 (3)	0.8693 (2)	0.0177 (6)
H6	0.5134	0.5474	0.8583	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01264 (8)	0.01415 (9)	0.01244 (8)	0.00140 (7)	0.00028 (7)	−0.00020 (6)
N1	0.0139 (12)	0.0132 (12)	0.0150 (12)	0.0009 (10)	−0.0017 (10)	−0.0015 (10)
C1	0.0138 (14)	0.0102 (13)	0.0138 (14)	0.0027 (11)	−0.0002 (11)	0.0008 (11)
N2	0.0134 (11)	0.0163 (14)	0.0161 (12)	0.0017 (9)	−0.0001 (9)	0.0000 (9)
C2	0.0153 (14)	0.0183 (16)	0.0189 (15)	0.0027 (12)	0.0024 (12)	−0.0005 (12)
C3	0.0206 (16)	0.0178 (15)	0.0135 (14)	0.0043 (13)	0.0023 (13)	−0.0010 (12)
C4	0.0169 (14)	0.0147 (13)	0.0172 (12)	−0.0036 (12)	−0.0032 (15)	−0.0006 (10)
C5	0.0142 (14)	0.0182 (15)	0.0110 (14)	0.0018 (12)	0.0021 (11)	−0.0028 (11)
C6	0.0148 (13)	0.0173 (16)	0.0174 (13)	−0.0015 (11)	−0.0003 (11)	−0.0018 (12)
C7	0.0222 (16)	0.0204 (15)	0.0203 (15)	0.0022 (13)	0.0067 (13)	0.0026 (13)
C8	0.0211 (14)	0.0277 (17)	0.0156 (14)	0.0087 (15)	−0.0008 (11)	0.0024 (14)
C9	0.0171 (15)	0.0285 (18)	0.0210 (16)	0.0039 (14)	−0.0034 (12)	−0.0039 (14)
C10	0.0169 (15)	0.0168 (15)	0.0195 (15)	−0.0010 (12)	0.0007 (13)	−0.0037 (13)

Geometric parameters (Å, º) top

I1—C1	2.088 (3)	C5—C6	1.387 (4)
N1—C1	1.357 (4)	C5—C10	1.394 (4)
N1—C3	1.379 (3)	C6—C7	1.397 (4)
N1—C4	1.461 (4)	C6—H3	0.9500
C1—N2	1.319 (3)	C7—C8	1.381 (4)
N2—C2	1.389 (4)	C7—H4	0.9500
C2—C3	1.341 (4)	C8—C9	1.395 (5)
C2—H1	0.9500	C8—H2	0.9500
C3—H9	0.9500	C9—C10	1.386 (4)
C4—C5	1.512 (4)	C9—H5	0.9500
C4—H7	0.9900	C10—H6	0.9500
C4—H8	0.9900

C1—N1—C3	106.4 (2)	C6—C5—C10	118.9 (3)
C1—N1—C4	127.8 (2)	C6—C5—C4	123.4 (3)
C3—N1—C4	125.8 (2)	C10—C5—C4	117.7 (3)
N2—C1—N1	112.1 (2)	C5—C6—C7	120.4 (3)
N2—C1—I1	124.0 (2)	C5—C6—H3	119.8
N1—C1—I1	123.9 (2)	C7—C6—H3	119.8
C1—N2—C2	104.5 (2)	C8—C7—C6	120.3 (3)
C3—C2—N2	110.5 (3)	C8—C7—H4	119.8
C3—C2—H1	124.7	C6—C7—H4	119.8
N2—C2—H1	124.7	C7—C8—C9	119.7 (3)
C2—C3—N1	106.5 (3)	C7—C8—H2	120.2
C2—C3—H9	126.8	C9—C8—H2	120.2
N1—C3—H9	126.8	C10—C9—C8	119.8 (3)
N1—C4—C5	114.8 (2)	C10—C9—H5	120.1
N1—C4—H7	108.6	C8—C9—H5	120.1
C5—C4—H7	108.6	C9—C10—C5	120.9 (3)
N1—C4—H8	108.6	C9—C10—H6	119.5
C5—C4—H8	108.6	C5—C10—H6	119.5
H7—C4—H8	107.5

C3—N1—C1—N2	0.2 (3)	C3—N1—C4—C5	90.2 (3)
C4—N1—C1—N2	179.7 (2)	N1—C4—C5—C6	13.0 (4)
C3—N1—C1—I1	−178.7 (2)	N1—C4—C5—C10	−167.7 (2)
C4—N1—C1—I1	0.9 (4)	C10—C5—C6—C7	0.8 (4)
N1—C1—N2—C2	−0.3 (3)	C4—C5—C6—C7	−179.9 (3)
I1—C1—N2—C2	178.5 (2)	C5—C6—C7—C8	0.0 (4)
C1—N2—C2—C3	0.3 (3)	C6—C7—C8—C9	−0.3 (4)
N2—C2—C3—N1	−0.2 (3)	C7—C8—C9—C10	−0.2 (4)
C1—N1—C3—C2	0.1 (3)	C8—C9—C10—C5	1.1 (4)
C4—N1—C3—C2	−179.5 (3)	C6—C5—C10—C9	−1.4 (4)
C1—N1—C4—C5	−89.3 (3)	C4—C5—C10—C9	179.3 (3)

1-Benzyl-4-iodo-1H-benzimidazole (2) top

Crystal data top

C₁₀H₉IN₂	F(000) = 544
M_r = 284.09	D_x = 1.878 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.4574 (5) Å	Cell parameters from 7481 reflections
b = 6.1526 (3) Å	θ = 2.5–27.1°
c = 19.4261 (10) Å	µ = 3.14 mm⁻¹
β = 96.362 (1)°	T = 100 K
V = 1004.61 (9) Å³	Cut irregular cube, colourless
Z = 4	0.22 × 0.22 × 0.22 mm

Data collection top

Bruker APEXII CCD diffractometer	2207 independent reflections
Radiation source: fine-focus sealed tube	2114 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 8.3660 pixels mm^-1	θ_max = 27.1°, θ_min = 2.1°
phi and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −7→7
T_min = 0.594, T_max = 0.746	l = −24→24
12374 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.016	H-atom parameters constrained
wR(F²) = 0.037	w = 1/[σ²(F_o²) + (0.0133P)² + 0.8316P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.002
2207 reflections	Δρ_max = 0.73 e Å⁻³
118 parameters	Δρ_min = −0.52 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
I1	0.78435 (2)	0.28882 (2)	0.99037 (2)	0.02415 (5)
N1	0.62017 (18)	0.7607 (3)	0.84311 (8)	0.0184 (3)
C1	0.6885 (2)	0.6133 (3)	0.80429 (9)	0.0193 (4)
H1	0.6911	0.6269	0.7557	0.023*
N2	0.75130 (18)	0.4480 (3)	0.84125 (8)	0.0202 (3)
C2	0.7195 (2)	0.4950 (3)	0.90773 (9)	0.0176 (4)
C3	0.6390 (2)	0.6861 (3)	0.91019 (9)	0.0202 (4)
H3	0.6035	0.7533	0.9497	0.024*
C4	0.5408 (2)	0.9614 (3)	0.81736 (10)	0.0234 (4)
H4A	0.5420	0.9692	0.7665	0.028*
H4B	0.6011	1.0876	0.8381	0.028*
C5	0.3709 (2)	0.9758 (3)	0.83403 (9)	0.0180 (4)
C6	0.2651 (2)	0.8056 (3)	0.81699 (10)	0.0212 (4)
H6	0.3005	0.6781	0.7958	0.025*
C7	0.1081 (2)	0.8218 (3)	0.83096 (10)	0.0256 (4)
H7	0.0365	0.7048	0.8197	0.031*
C8	0.0554 (2)	1.0088 (4)	0.86130 (10)	0.0265 (4)
H8	−0.0523	1.0201	0.8705	0.032*
C9	0.1594 (3)	1.1779 (3)	0.87815 (11)	0.0277 (4)
H9	0.1231	1.3058	0.8988	0.033*
C10	0.3176 (2)	1.1619 (3)	0.86495 (10)	0.0240 (4)
H10	0.3891	1.2783	0.8771	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02821 (8)	0.02566 (8)	0.01895 (7)	0.00504 (5)	0.00421 (5)	0.00451 (5)
N1	0.0185 (8)	0.0183 (8)	0.0193 (8)	0.0004 (6)	0.0055 (6)	0.0031 (6)
C1	0.0177 (9)	0.0255 (10)	0.0152 (8)	0.0006 (7)	0.0038 (7)	−0.0016 (7)
N2	0.0198 (8)	0.0235 (8)	0.0177 (7)	0.0025 (6)	0.0045 (6)	−0.0027 (6)
C2	0.0171 (8)	0.0191 (9)	0.0167 (8)	0.0005 (7)	0.0027 (7)	0.0004 (7)
C3	0.0248 (10)	0.0203 (10)	0.0167 (9)	0.0003 (7)	0.0075 (7)	0.0000 (7)
C4	0.0248 (10)	0.0186 (9)	0.0281 (10)	0.0021 (8)	0.0089 (8)	0.0080 (8)
C5	0.0211 (9)	0.0178 (9)	0.0151 (8)	0.0028 (7)	0.0022 (7)	0.0043 (7)
C6	0.0259 (10)	0.0184 (9)	0.0190 (9)	0.0042 (7)	0.0009 (7)	−0.0028 (7)
C7	0.0212 (10)	0.0305 (12)	0.0236 (10)	−0.0015 (8)	−0.0045 (8)	−0.0048 (8)
C8	0.0195 (9)	0.0380 (12)	0.0216 (9)	0.0078 (8)	0.0004 (7)	−0.0019 (8)
C9	0.0314 (11)	0.0263 (11)	0.0257 (10)	0.0106 (9)	0.0050 (8)	−0.0037 (8)
C10	0.0279 (10)	0.0185 (10)	0.0254 (10)	0.0007 (8)	0.0015 (8)	−0.0010 (8)

Geometric parameters (Å, º) top

I1—C2	2.0717 (18)	C5—C10	1.391 (3)
N1—C1	1.349 (2)	C5—C6	1.393 (3)
N1—C3	1.374 (2)	C6—C7	1.388 (3)
N1—C4	1.467 (2)	C6—H6	0.9500
C1—N2	1.322 (2)	C7—C8	1.388 (3)
C1—H1	0.9500	C7—H7	0.9500
N2—C2	1.379 (2)	C8—C9	1.378 (3)
C2—C3	1.362 (3)	C8—H8	0.9500
C3—H3	0.9500	C9—C10	1.394 (3)
C4—C5	1.510 (3)	C9—H9	0.9500
C4—H4A	0.9900	C10—H10	0.9500
C4—H4B	0.9900

C1—N1—C3	107.09 (15)	C10—C5—C6	119.40 (17)
C1—N1—C4	125.67 (16)	C10—C5—C4	120.18 (18)
C3—N1—C4	127.24 (16)	C6—C5—C4	120.39 (17)
N2—C1—N1	112.62 (16)	C7—C6—C5	120.18 (18)
N2—C1—H1	123.7	C7—C6—H6	119.9
N1—C1—H1	123.7	C5—C6—H6	119.9
C1—N2—C2	103.82 (15)	C8—C7—C6	120.08 (19)
C3—C2—N2	111.35 (16)	C8—C7—H7	120.0
C3—C2—I1	126.28 (13)	C6—C7—H7	120.0
N2—C2—I1	122.34 (13)	C9—C8—C7	120.02 (19)
C2—C3—N1	105.11 (16)	C9—C8—H8	120.0
C2—C3—H3	127.4	C7—C8—H8	120.0
N1—C3—H3	127.4	C8—C9—C10	120.24 (19)
N1—C4—C5	112.76 (15)	C8—C9—H9	119.9
N1—C4—H4A	109.0	C10—C9—H9	119.9
C5—C4—H4A	109.0	C5—C10—C9	120.08 (19)
N1—C4—H4B	109.0	C5—C10—H10	120.0
C5—C4—H4B	109.0	C9—C10—H10	120.0
H4A—C4—H4B	107.8

C3—N1—C1—N2	−0.3 (2)	N1—C4—C5—C10	129.69 (19)
C4—N1—C1—N2	179.94 (17)	N1—C4—C5—C6	−52.0 (2)
N1—C1—N2—C2	0.3 (2)	C10—C5—C6—C7	−0.2 (3)
C1—N2—C2—C3	−0.1 (2)	C4—C5—C6—C7	−178.49 (18)
C1—N2—C2—I1	178.38 (13)	C5—C6—C7—C8	0.7 (3)
N2—C2—C3—N1	0.0 (2)	C6—C7—C8—C9	−0.6 (3)
I1—C2—C3—N1	−178.47 (13)	C7—C8—C9—C10	−0.1 (3)
C1—N1—C3—C2	0.2 (2)	C6—C5—C10—C9	−0.5 (3)
C4—N1—C3—C2	179.96 (17)	C4—C5—C10—C9	177.82 (18)
C1—N1—C4—C5	123.20 (19)	C8—C9—C10—C5	0.7 (3)
C3—N1—C4—C5	−56.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···N2ⁱ	0.99	2.55	3.488 (3)	158
C4—H4B···N2ⁱ	0.99	2.55	3.488 (3)	158
C4—H4B···N2ⁱ	0.99	2.55	3.488 (3)	158
C4—H4B···N2ⁱ	0.99	2.55	3.488 (3)	158

Symmetry code: (i) x, y+1, z.

1-Benzyl-2-iodo-1H-benzimidazole (3) top

Crystal data top

C₁₄H₁₁IN₂	Z = 2
M_r = 334.15	F(000) = 324
Triclinic, P1	D_x = 1.796 Mg m⁻³
a = 6.4606 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2346 (10) Å	Cell parameters from 6682 reflections
c = 12.3451 (14) Å	θ = 2.6–27.3°
α = 108.064 (1)°	µ = 2.57 mm⁻¹
β = 94.174 (2)°	T = 100 K
γ = 95.366 (2)°	Cut irregular cube, colourless
V = 618.05 (13) Å³	0.20 × 0.20 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	2777 independent reflections
Radiation source: fine-focus sealed tube	2725 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
Detector resolution: 8.3660 pixels mm^-1	θ_max = 27.3°, θ_min = 1.8°
phi and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −10→10
T_min = 0.588, T_max = 0.746	l = −15→15
8079 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.015	H-atom parameters constrained
wR(F²) = 0.039	w = 1/[σ²(F_o²) + (0.0194P)² + 0.3329P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2777 reflections	Δρ_max = 0.74 e Å⁻³
154 parameters	Δρ_min = −0.35 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
I1	0.36505 (2)	0.21176 (2)	−0.00445 (2)	0.01647 (5)
N1	0.6779 (2)	0.27787 (17)	0.20512 (12)	0.0120 (3)
C1	0.4707 (3)	0.2345 (2)	0.16333 (14)	0.0128 (3)
N2	0.3471 (2)	0.20232 (18)	0.23569 (12)	0.0150 (3)
C2	0.4817 (3)	0.2263 (2)	0.33480 (14)	0.0139 (3)
C3	0.4394 (3)	0.2054 (2)	0.43956 (15)	0.0182 (3)
H3	0.3012	0.1724	0.4531	0.022*
C4	0.6071 (3)	0.2349 (2)	0.52297 (15)	0.0194 (4)
H4	0.5828	0.2201	0.5945	0.023*
C5	0.8118 (3)	0.2859 (2)	0.50456 (15)	0.0175 (3)
H5	0.9221	0.3057	0.5641	0.021*
C6	0.8566 (3)	0.3081 (2)	0.40127 (15)	0.0151 (3)
H6	0.9943	0.3438	0.3885	0.018*
C7	0.6875 (3)	0.2749 (2)	0.31748 (14)	0.0122 (3)
C8	0.8525 (3)	0.3389 (2)	0.15353 (14)	0.0132 (3)
H8B	0.8223	0.2938	0.0691	0.016*
H8A	0.9799	0.2929	0.1749	0.016*
C9	0.8940 (3)	0.5343 (2)	0.19092 (13)	0.0117 (3)
C10	1.0811 (3)	0.6095 (2)	0.16685 (15)	0.0158 (3)
H10	1.1789	0.5383	0.1290	0.019*
C11	1.1250 (3)	0.7877 (2)	0.19790 (15)	0.0177 (3)
H11	1.2523	0.8376	0.1811	0.021*
C12	0.9832 (3)	0.8928 (2)	0.25341 (15)	0.0160 (3)
H12	1.0129	1.0144	0.2742	0.019*
C13	0.7972 (3)	0.8192 (2)	0.27853 (14)	0.0150 (3)
H13	0.7006	0.8907	0.3173	0.018*
C14	0.7526 (3)	0.6401 (2)	0.24673 (14)	0.0136 (3)
H14	0.6250	0.5904	0.2633	0.016*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01853 (7)	0.01995 (7)	0.01172 (6)	0.00853 (4)	0.00073 (4)	0.00460 (4)
N1	0.0124 (6)	0.0118 (6)	0.0118 (6)	0.0009 (5)	0.0018 (5)	0.0038 (5)
C1	0.0145 (8)	0.0118 (7)	0.0120 (7)	0.0031 (6)	0.0003 (6)	0.0036 (6)
N2	0.0129 (7)	0.0168 (7)	0.0161 (7)	0.0012 (5)	0.0005 (5)	0.0069 (6)
C2	0.0138 (8)	0.0130 (7)	0.0157 (8)	0.0018 (6)	0.0016 (6)	0.0058 (6)
C3	0.0155 (8)	0.0236 (9)	0.0182 (8)	0.0018 (7)	0.0050 (7)	0.0099 (7)
C4	0.0229 (9)	0.0238 (9)	0.0144 (8)	0.0035 (7)	0.0036 (7)	0.0098 (7)
C5	0.0193 (9)	0.0179 (8)	0.0144 (8)	0.0025 (7)	−0.0026 (7)	0.0048 (6)
C6	0.0133 (8)	0.0136 (7)	0.0170 (8)	0.0005 (6)	0.0001 (6)	0.0038 (6)
C7	0.0158 (8)	0.0099 (7)	0.0113 (7)	0.0021 (6)	0.0025 (6)	0.0035 (6)
C8	0.0121 (7)	0.0135 (7)	0.0148 (8)	0.0016 (6)	0.0046 (6)	0.0049 (6)
C9	0.0130 (7)	0.0128 (7)	0.0102 (7)	0.0022 (6)	0.0003 (6)	0.0051 (6)
C10	0.0142 (8)	0.0165 (8)	0.0174 (8)	0.0040 (6)	0.0051 (6)	0.0049 (6)
C11	0.0155 (8)	0.0190 (8)	0.0194 (8)	−0.0008 (6)	0.0040 (7)	0.0078 (7)
C12	0.0199 (8)	0.0129 (7)	0.0151 (8)	0.0010 (6)	0.0011 (6)	0.0048 (6)
C13	0.0161 (8)	0.0142 (8)	0.0150 (8)	0.0045 (6)	0.0028 (6)	0.0043 (6)
C14	0.0122 (7)	0.0159 (8)	0.0141 (8)	0.0021 (6)	0.0029 (6)	0.0063 (6)

Geometric parameters (Å, º) top

I1—C1	2.0787 (16)	C6—H6	0.9500
N1—C1	1.372 (2)	C8—C9	1.522 (2)
N1—C7	1.392 (2)	C8—H8B	0.9900
N1—C8	1.459 (2)	C8—H8A	0.9900
C1—N2	1.310 (2)	C9—C14	1.392 (2)
N2—C2	1.398 (2)	C9—C10	1.399 (2)
C2—C3	1.399 (2)	C10—C11	1.392 (2)
C2—C7	1.403 (2)	C10—H10	0.9500
C3—C4	1.388 (3)	C11—C12	1.389 (2)
C3—H3	0.9500	C11—H11	0.9500
C4—C5	1.406 (3)	C12—C13	1.394 (2)
C4—H4	0.9500	C12—H12	0.9500
C5—C6	1.390 (2)	C13—C14	1.399 (2)
C5—H5	0.9500	C13—H13	0.9500
C6—C7	1.393 (2)	C14—H14	0.9500

C1—N1—C7	105.30 (13)	N1—C8—C9	112.67 (13)
C1—N1—C8	129.42 (14)	N1—C8—H8B	109.1
C7—N1—C8	124.77 (14)	C9—C8—H8B	109.1
N2—C1—N1	114.90 (14)	N1—C8—H8A	109.1
N2—C1—I1	122.95 (12)	C9—C8—H8A	109.1
N1—C1—I1	122.10 (12)	H8B—C8—H8A	107.8
C1—N2—C2	103.99 (14)	C14—C9—C10	119.12 (15)
N2—C2—C3	130.02 (16)	C14—C9—C8	122.54 (14)
N2—C2—C7	110.06 (14)	C10—C9—C8	118.33 (14)
C3—C2—C7	119.90 (16)	C11—C10—C9	120.50 (16)
C4—C3—C2	117.39 (16)	C11—C10—H10	119.8
C4—C3—H3	121.3	C9—C10—H10	119.8
C2—C3—H3	121.3	C12—C11—C10	120.19 (16)
C3—C4—C5	121.86 (16)	C12—C11—H11	119.9
C3—C4—H4	119.1	C10—C11—H11	119.9
C5—C4—H4	119.1	C11—C12—C13	119.71 (15)
C6—C5—C4	121.53 (16)	C11—C12—H12	120.1
C6—C5—H5	119.2	C13—C12—H12	120.1
C4—C5—H5	119.2	C12—C13—C14	120.09 (16)
C5—C6—C7	116.04 (16)	C12—C13—H13	120.0
C5—C6—H6	122.0	C14—C13—H13	120.0
C7—C6—H6	122.0	C9—C14—C13	120.39 (15)
N1—C7—C6	131.00 (15)	C9—C14—H14	119.8
N1—C7—C2	105.74 (14)	C13—C14—H14	119.8
C6—C7—C2	123.26 (15)

C7—N1—C1—N2	−0.68 (19)	C5—C6—C7—C2	1.7 (2)
C8—N1—C1—N2	−172.65 (15)	N2—C2—C7—N1	−0.90 (18)
C7—N1—C1—I1	−178.20 (11)	C3—C2—C7—N1	177.77 (15)
C8—N1—C1—I1	9.8 (2)	N2—C2—C7—C6	179.92 (15)
N1—C1—N2—C2	0.12 (19)	C3—C2—C7—C6	−1.4 (3)
I1—C1—N2—C2	177.62 (11)	C1—N1—C8—C9	93.38 (19)
C1—N2—C2—C3	−178.00 (18)	C7—N1—C8—C9	−77.17 (19)
C1—N2—C2—C7	0.49 (18)	N1—C8—C9—C14	−13.4 (2)
N2—C2—C3—C4	178.48 (17)	N1—C8—C9—C10	167.25 (14)
C7—C2—C3—C4	0.1 (3)	C14—C9—C10—C11	−0.2 (2)
C2—C3—C4—C5	0.8 (3)	C8—C9—C10—C11	179.10 (15)
C3—C4—C5—C6	−0.5 (3)	C9—C10—C11—C12	0.1 (3)
C4—C5—C6—C7	−0.7 (3)	C10—C11—C12—C13	0.4 (3)
C1—N1—C7—C6	−179.98 (17)	C11—C12—C13—C14	−0.8 (3)
C8—N1—C7—C6	−7.5 (3)	C10—C9—C14—C13	−0.1 (2)
C1—N1—C7—C2	0.92 (17)	C8—C9—C14—C13	−179.45 (15)
C8—N1—C7—C2	173.37 (14)	C12—C13—C14—C9	0.6 (3)
C5—C6—C7—N1	−177.29 (16)

Acknowledgements

We thank the National Science Foundation for financial support of this research (RUI grant No. 1606556), the Missouri State University Provost Incentive Fund that funded the purchase of the X-ray diffractometer, and the Missouri State University Graduate College for funding CIN.

References

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Volume 73| Part 1| January 2017| Pages 2-8

https://doi.org/10.1107/S2053229616018702

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

C—I⋯N and C—I⋯π halogen bonding in the structures of 1-benzyl­iodo­imidazole derivatives

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

2.1.1. 1-Benzyl-2-iodo-1H-imidazole, (1)

2.1.2. 1-Benzyl-4-iodo-1H-imidazole, (2)

2.1.3. 1-Benzyl-2-iodo-1H-benz­imidazole, (3)

2.2. Refinement

2.3. Electrostatic potential calculations

3. Results and discussion

Supporting information

Acknowledgements

References

research papers

C—I⋯N and C—I⋯π halogen bonding in the structures of 1-benzyliodoimidazole derivatives

2.1.3. 1-Benzyl-2-iodo-1H-benzimidazole, (3)