Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616006781/eg3202sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006781/eg3202Isup2.hkl | |
Microsoft Word (DOC) file https://doi.org/10.1107/S2053229616006781/eg3202sup3.doc | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616006781/eg3202sup3.pdf |
CCDC reference: 1475919
The design, synthesis and study of N-heterocyclic carbene (NHC) based systems have grown exponentially over the last few years. Nowadays, they are assiduously utilized by organic and organometallic chemists, particularly in the exploration of catalytic mechanisms and processes in organocatalysis, and homogeneous and heterogeneous catalysis. However, despite their wide use and the fact that imidazolium salts have been known for many years, their molecular structures have not received adequate attention.
We report here the characterization of the bis(imidazolium) salt methylenebis(N-butylimidazolium) diiodide, [H2BisBuIm]I2, and its isolation as the crystalline material [H2BisBuIm]I2·CH3CN, (I), in combination with a Hirshfeld surface analysis and density functional theory (DFT) calculations. Although the [H2BisBuIm]2+ cation has been frequently utilized, its solid-state structure has not been described previously (see, for example, Poyatos et al., 2003; Quezada et al., 2003, 2004; Jin et al., 2005; Lee et al., 2008; Yang et al., 2008, 2010, 2016; Cheng et al., 2010; Mercs et al., 2011; Sun et al., 2011; Saha et al., 2012; Lai et al., 2013; Zou et al., 2014; Aliaga-Lavrijsen et al., 2015; Cebollada et al., 2015; Li et al., 2015; Krüger et al., 2015; Sun et al., 2015).
[H2BisBuIm]I2 was synthesized according to the method of Cebollada et al. (2015). Colourless crystals of [H2BisBuIm]I2·CH3CN, (I), were obtained from a saturated solution of [H2BisBuIm]I2 in acetonitrile (277 K, 10 ml, one week). Further information is summarized in the Supporting information.
NMR spectra were recorded on a Bruker Avance 300 MHz or a Bruker ARX 300 MHz instruments. To reference chemical shifts (p.p.m.) residual solvent peaks were used. Elemental analyses (C/H/N) were acquired with a PerkinElmer 2400 CHNS/O analyzer. 1H NMR (CD3CN, 300 MHz): δ 9.83 (s, 2H. H2), 8.09 (m, 2H, H5), 7.49 (m, 2H, H4), 6.85 (s, 2H, N–CH2–N bridge), 4.21 (t, 4H, JH–H = 7.3 Hz, N—CH2–C), 1.87 (m, 4H, N—CH2–CH2—C), 1.36 (m, 4H, C—CH2—CH3), 0.95 (t, 6H, JH–H = 7.3 Hz, C—CH3). 13C NMR (CD3CN, 300 MHz): δ 138.1 (C2), 124.0 (C4), 123.4 (C5), 58.5 (N—CH2—N bridge), 50.9 (N—CH2—C), 32.09 (N—CH2—CH2—C), 19.9 (C–CH2–CH3), 13.7 (C—CH3). Analysis calculated for C15H24N4I2: C 34.88, H 5.08, N 10.85%; found: C 34.90, H 4.95, N 10.92. NMR characterization (13C, HMBC and HSQC) is compiled in the Supporting information.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl groups, C–H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for methylene groups, and C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aryl groups. A low-angle reflection (011), with an intensity strongly affected by the beam stop, was omitted from the refinement.
For the preparation of the methylenebis(N-butylimidazolium) cation, [H2BisBuIm]2+, several pathways have been reported over the years. A general synthetic description could be as follows: a mixture of 1-butylimidazole and CH2X2 [X = Cl (Lee et al., 2008; Lai et al., 2013; Li et al., 2015), Br (Cheng et al., 2010; Zou et al., 2014; Sun et al., 2015) or I (Poyatos et al., 2003; Quezada et al., 2003, 2004; Yang et al., 2008, 2010; Mercs et al., 2011; Sun et al., 2011; Aliaga-Lavrijsen et al., 2015)] was stirred in refluxing nonpolar or polar aprotic solvents until a white solid precipitated. This product was then isolated by filtration and washed, obtaining high yields in all cases. Particularly, when X = Cl, dichloromethane was utilized both as solvent and reactant. There, the reaction mixture was heated to 358 K (1 d) using sealed containers. The obtained product was precipitated using either Et2O (Lee et al., 2008; Lai et al., 2013) or a mixture of MeOH and tetrahydrofuran (Li et al., 2015). Good yields were also obtained by refluxing 1-butylimidazole and CH2I2 in acetonitrile, followed by filtration and purification with Et2O (Sun et al., 2015). This last procedure has been applied for the isolation of [H2BisBuIm]I2 in our case (Vellé et al., 2014; Cebollada et al., 2015). Further recrystallization from a saturated solution of [H2BisBuIm]I2 in acetonitrile afforded the corresponding [H2BisBuIm]I2·CH3CN solvate, (I), which was suitable for X-ray structural investigation. Two additional options, used less frequently, are: (i) starting from bis(imidazol-1-yl)methane, which after reacting with the adequate quantity of BuX (X = Br or I; Jin et al., 2005) yields the corresponding bis(imidazolium) salt; (ii) following a ring closure synthetic strategy (Saha et al., 2012), which also offers the possibility of obtaining chiral imidazolium salts (Herrmann et al., 1996).
The resulting structure consists of two imidazole rings bridged through N atoms by a methylene group, which incorporate two additional butyl pendants at their available N-atom sites. A view of the [H2BisBuIm]2+ cation is shown in Fig. 1. Selected bond lengths and angles are summarized in Table 2. Both protonated C12 and C22 atoms form internal N—C—N angles of 108.64 (17) (N13—C12—N11) and 108.14 (18)° (N23—C22—N21), which are not significantly different. This angle is usually strongly affected upon metal coordination and subsequent loss of H+; reported examples exhibit values of 101.9–105.2°. The rest of the geometrical values are not affected to such an extent. Both imidazolium rings are cisoid disposed and display a dihedral angle of 74.71 (7)° between their mean planes.
Regarding the crystal packing, mutual positioning of the iodide anions around the [H2BisBuIm]2+ cation allows for hydrogen-bonding interactions, fashioned in a novel cation–anion interacting pattern (Fig. 2): C12(—H12)···I1 = 3.746 (2) Å, C22(—H22)···I1 = 3.790 (2) Å, C15(—H15)···I2 = 3.957 (2) Å and C25(—H25)···I2 = 3.857 (2) Å. As expected, C···I distances involving the C12 and C22 sites are shorter in comparison with C15 and C25. In addition, the I1 anion exhibits relatively short anion–π interactions: intermolecular distances between I1 and the acidic C12 and C22 sites are 3.5736 (19) and 3.4995 (19) Å, respectively. We have also identified this interaction pattern in chloride and bromide salts, in which methylene-bridged bis(imidazolium) cations with different N-atom pendant groups are involved (Leclercq et al., 2009; Ahrens & Strassner, 2006; Liu et al., 2009).
A Hirshfeld surface analysis (Spackman & Jayatilaka, 2009; Wolff et al., 2012) revealed that hydrogen-bonding interactions in [H2BisBuIm]2+ are associated with 13.8% of the surface area, whereas anion–π contacts cover its 2.7% (Fig. 3). These numbers support the predominance of hydrogen bonding in the crystal packing, but also an important contribution of the anion–π interactions. For comparison, the N-phenyl derivative, i.e. methylenebis(N-phenylimidazolium) (Leclercq et al., 2009), which displays two crystallographically different cations (bearing N-phenyl pendants), two water molecules and four bromide anions in the asymmetric unit, exhibits anion–π interactions associated with ca 2.4% of the surface area, and hydrogen bonding occupying nearly 16% (including water molecules). The N-mesityl cation (Ahrens & Strassner, 2006) interacts with three Cl- anions and exhibits smaller values, of 11.7% (hydrogen bonding) and 1.2% (anion–π), due probably to the bulky pendants, and the smaller size of the chloride anions. In this particular series, it seems to be a correlation between the size of the counteranions and the contribution of the anion–π interactions.
The 1H NMR spectrum (room temperature, CD3CN) of [H2BisBuIm]I2 (see Fig. S1 in the Supporting Information) shows the H2 proton signals (protons at the C12 and C22 atoms in Fig. 1) as a singlet at 9.83 p.p.m., and the H5 (at the C15 and C25 atoms) and H4 (at the C14 and C24 atoms) resonances as two pseudotriplets centred at 8.09 and 7.49 p.p.m., respectively. The methylene bridge signal is observed as a singlet at 6.85 p.p.m., denoting rotation about this position in solution. The CH2 groups of the side arms appear as a triplet, a pseudoquintuplet and a pseudosextuplet centered at 4.21, 1.87 and 1.36 p.p.m., respectively, and the methyl group as a triplet centred at 0.95 p.p.m. (see Fig. S1 in the Supporting Information).
Quantum chemical calculations were performed with the GAUSSIAN09 (Frisch et al., 2009) software using the M11L functional (Peverati & Truhlar, 2012) and the polarizable continuum method (SMD) (Marenich et al., 2009). This combination has demonstrated to reproduce accurately the geometry of the cationic N-heterocyclic hemicytosinium pair (Vellé et al., 2015). Here, we utilized acetonitrile as solvent – as the title compound is an acetonitrile solvate – and the 6-311++G(d,p) and SDD (Andrae et al., 1990; Dolg et al., 1993) basis sets. Salient geometrical parameters of the optimized molecules agree well with the solid-state structure of [H2BisBuIm]2+: intramolecular angles match within the standard deviation (3σ) limits, and bond distances deviate a maximum of 0.01 Å. From the precision exhibited, this theoretical approach is a well suited tool for the study of this kind of heterocyclic cations. However, the anion–π interactions exhibited in the solid-state structure of (I) are not anticipated by these calculations, which result in significantly longer I1···C12 and I1···C22 distances. Coordinates and tables including geometrical records are reported in the Supporting information.
In summary, we have synthesized and fully characterized [H2BisBuIm]I2 and its corresponding [H2BisBuIm]I2·CH3CN solvate. The crystal arrangement of the latter exhibits a cation–anion connection pattern, which can be identified in related methylene-bridged bis(imidazolium) salts incorporating chloride and bromide as counter-anions. A Hirshfeld surface analysis reveals a broader surface area associated to hydrogen bonding in comparison to the relatively close anion–π contacts. Quantum chemical calculations (M11L, SMD acetonitrile) reproduce the molecular geometries exhibited by the [H2BisBuIm]2+ cation in solid state with high precision.
The design, synthesis and study of N-heterocyclic carbene (NHC) based systems have grown exponentially over the last few years. Nowadays, they are assiduously utilized by organic and organometallic chemists, particularly in the exploration of catalytic mechanisms and processes in organocatalysis, and homogeneous and heterogeneous catalysis. However, despite their wide use and the fact that imidazolium salts have been known for many years, their molecular structures have not received adequate attention.
We report here the characterization of the bis(imidazolium) salt methylenebis(N-butylimidazolium) diiodide, [H2BisBuIm]I2, and its isolation as the crystalline material [H2BisBuIm]I2·CH3CN, (I), in combination with a Hirshfeld surface analysis and density functional theory (DFT) calculations. Although the [H2BisBuIm]2+ cation has been frequently utilized, its solid-state structure has not been described previously (see, for example, Poyatos et al., 2003; Quezada et al., 2003, 2004; Jin et al., 2005; Lee et al., 2008; Yang et al., 2008, 2010, 2016; Cheng et al., 2010; Mercs et al., 2011; Sun et al., 2011; Saha et al., 2012; Lai et al., 2013; Zou et al., 2014; Aliaga-Lavrijsen et al., 2015; Cebollada et al., 2015; Li et al., 2015; Krüger et al., 2015; Sun et al., 2015).
NMR spectra were recorded on a Bruker Avance 300 MHz or a Bruker ARX 300 MHz instruments. To reference chemical shifts (p.p.m.) residual solvent peaks were used. Elemental analyses (C/H/N) were acquired with a PerkinElmer 2400 CHNS/O analyzer. 1H NMR (CD3CN, 300 MHz): δ 9.83 (s, 2H. H2), 8.09 (m, 2H, H5), 7.49 (m, 2H, H4), 6.85 (s, 2H, N–CH2–N bridge), 4.21 (t, 4H, JH–H = 7.3 Hz, N—CH2–C), 1.87 (m, 4H, N—CH2–CH2—C), 1.36 (m, 4H, C—CH2—CH3), 0.95 (t, 6H, JH–H = 7.3 Hz, C—CH3). 13C NMR (CD3CN, 300 MHz): δ 138.1 (C2), 124.0 (C4), 123.4 (C5), 58.5 (N—CH2—N bridge), 50.9 (N—CH2—C), 32.09 (N—CH2—CH2—C), 19.9 (C–CH2–CH3), 13.7 (C—CH3). Analysis calculated for C15H24N4I2: C 34.88, H 5.08, N 10.85%; found: C 34.90, H 4.95, N 10.92. NMR characterization (13C, HMBC and HSQC) is compiled in the Supporting information.
For the preparation of the methylenebis(N-butylimidazolium) cation, [H2BisBuIm]2+, several pathways have been reported over the years. A general synthetic description could be as follows: a mixture of 1-butylimidazole and CH2X2 [X = Cl (Lee et al., 2008; Lai et al., 2013; Li et al., 2015), Br (Cheng et al., 2010; Zou et al., 2014; Sun et al., 2015) or I (Poyatos et al., 2003; Quezada et al., 2003, 2004; Yang et al., 2008, 2010; Mercs et al., 2011; Sun et al., 2011; Aliaga-Lavrijsen et al., 2015)] was stirred in refluxing nonpolar or polar aprotic solvents until a white solid precipitated. This product was then isolated by filtration and washed, obtaining high yields in all cases. Particularly, when X = Cl, dichloromethane was utilized both as solvent and reactant. There, the reaction mixture was heated to 358 K (1 d) using sealed containers. The obtained product was precipitated using either Et2O (Lee et al., 2008; Lai et al., 2013) or a mixture of MeOH and tetrahydrofuran (Li et al., 2015). Good yields were also obtained by refluxing 1-butylimidazole and CH2I2 in acetonitrile, followed by filtration and purification with Et2O (Sun et al., 2015). This last procedure has been applied for the isolation of [H2BisBuIm]I2 in our case (Vellé et al., 2014; Cebollada et al., 2015). Further recrystallization from a saturated solution of [H2BisBuIm]I2 in acetonitrile afforded the corresponding [H2BisBuIm]I2·CH3CN solvate, (I), which was suitable for X-ray structural investigation. Two additional options, used less frequently, are: (i) starting from bis(imidazol-1-yl)methane, which after reacting with the adequate quantity of BuX (X = Br or I; Jin et al., 2005) yields the corresponding bis(imidazolium) salt; (ii) following a ring closure synthetic strategy (Saha et al., 2012), which also offers the possibility of obtaining chiral imidazolium salts (Herrmann et al., 1996).
The resulting structure consists of two imidazole rings bridged through N atoms by a methylene group, which incorporate two additional butyl pendants at their available N-atom sites. A view of the [H2BisBuIm]2+ cation is shown in Fig. 1. Selected bond lengths and angles are summarized in Table 2. Both protonated C12 and C22 atoms form internal N—C—N angles of 108.64 (17) (N13—C12—N11) and 108.14 (18)° (N23—C22—N21), which are not significantly different. This angle is usually strongly affected upon metal coordination and subsequent loss of H+; reported examples exhibit values of 101.9–105.2°. The rest of the geometrical values are not affected to such an extent. Both imidazolium rings are cisoid disposed and display a dihedral angle of 74.71 (7)° between their mean planes.
Regarding the crystal packing, mutual positioning of the iodide anions around the [H2BisBuIm]2+ cation allows for hydrogen-bonding interactions, fashioned in a novel cation–anion interacting pattern (Fig. 2): C12(—H12)···I1 = 3.746 (2) Å, C22(—H22)···I1 = 3.790 (2) Å, C15(—H15)···I2 = 3.957 (2) Å and C25(—H25)···I2 = 3.857 (2) Å. As expected, C···I distances involving the C12 and C22 sites are shorter in comparison with C15 and C25. In addition, the I1 anion exhibits relatively short anion–π interactions: intermolecular distances between I1 and the acidic C12 and C22 sites are 3.5736 (19) and 3.4995 (19) Å, respectively. We have also identified this interaction pattern in chloride and bromide salts, in which methylene-bridged bis(imidazolium) cations with different N-atom pendant groups are involved (Leclercq et al., 2009; Ahrens & Strassner, 2006; Liu et al., 2009).
A Hirshfeld surface analysis (Spackman & Jayatilaka, 2009; Wolff et al., 2012) revealed that hydrogen-bonding interactions in [H2BisBuIm]2+ are associated with 13.8% of the surface area, whereas anion–π contacts cover its 2.7% (Fig. 3). These numbers support the predominance of hydrogen bonding in the crystal packing, but also an important contribution of the anion–π interactions. For comparison, the N-phenyl derivative, i.e. methylenebis(N-phenylimidazolium) (Leclercq et al., 2009), which displays two crystallographically different cations (bearing N-phenyl pendants), two water molecules and four bromide anions in the asymmetric unit, exhibits anion–π interactions associated with ca 2.4% of the surface area, and hydrogen bonding occupying nearly 16% (including water molecules). The N-mesityl cation (Ahrens & Strassner, 2006) interacts with three Cl- anions and exhibits smaller values, of 11.7% (hydrogen bonding) and 1.2% (anion–π), due probably to the bulky pendants, and the smaller size of the chloride anions. In this particular series, it seems to be a correlation between the size of the counteranions and the contribution of the anion–π interactions.
The 1H NMR spectrum (room temperature, CD3CN) of [H2BisBuIm]I2 (see Fig. S1 in the Supporting Information) shows the H2 proton signals (protons at the C12 and C22 atoms in Fig. 1) as a singlet at 9.83 p.p.m., and the H5 (at the C15 and C25 atoms) and H4 (at the C14 and C24 atoms) resonances as two pseudotriplets centred at 8.09 and 7.49 p.p.m., respectively. The methylene bridge signal is observed as a singlet at 6.85 p.p.m., denoting rotation about this position in solution. The CH2 groups of the side arms appear as a triplet, a pseudoquintuplet and a pseudosextuplet centered at 4.21, 1.87 and 1.36 p.p.m., respectively, and the methyl group as a triplet centred at 0.95 p.p.m. (see Fig. S1 in the Supporting Information).
Quantum chemical calculations were performed with the GAUSSIAN09 (Frisch et al., 2009) software using the M11L functional (Peverati & Truhlar, 2012) and the polarizable continuum method (SMD) (Marenich et al., 2009). This combination has demonstrated to reproduce accurately the geometry of the cationic N-heterocyclic hemicytosinium pair (Vellé et al., 2015). Here, we utilized acetonitrile as solvent – as the title compound is an acetonitrile solvate – and the 6-311++G(d,p) and SDD (Andrae et al., 1990; Dolg et al., 1993) basis sets. Salient geometrical parameters of the optimized molecules agree well with the solid-state structure of [H2BisBuIm]2+: intramolecular angles match within the standard deviation (3σ) limits, and bond distances deviate a maximum of 0.01 Å. From the precision exhibited, this theoretical approach is a well suited tool for the study of this kind of heterocyclic cations. However, the anion–π interactions exhibited in the solid-state structure of (I) are not anticipated by these calculations, which result in significantly longer I1···C12 and I1···C22 distances. Coordinates and tables including geometrical records are reported in the Supporting information.
In summary, we have synthesized and fully characterized [H2BisBuIm]I2 and its corresponding [H2BisBuIm]I2·CH3CN solvate. The crystal arrangement of the latter exhibits a cation–anion connection pattern, which can be identified in related methylene-bridged bis(imidazolium) salts incorporating chloride and bromide as counter-anions. A Hirshfeld surface analysis reveals a broader surface area associated to hydrogen bonding in comparison to the relatively close anion–π contacts. Quantum chemical calculations (M11L, SMD acetonitrile) reproduce the molecular geometries exhibited by the [H2BisBuIm]2+ cation in solid state with high precision.
[H2BisBuIm]I2 was synthesized according to the method of Cebollada et al. (2015). Colourless crystals of [H2BisBuIm]I2·CH3CN, (I), were obtained from a saturated solution of [H2BisBuIm]I2 in acetonitrile (277 K, 10 ml, one week). Further information is summarized in the Supporting information.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl groups, C–H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for methylene groups, and C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aryl groups. A low-angle reflection (011), with an intensity strongly affected by the beam stop, was omitted from the refinement.
Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2011); software used to prepare material for publication: SHELXTL (Bruker, 2011).
C15H26N42+·2I−·C2H3N | Z = 2 |
Mr = 557.25 | F(000) = 544 |
Triclinic, P1 | Dx = 1.636 Mg m−3 |
a = 5.2513 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.9534 (6) Å | Cell parameters from 9931 reflections |
c = 16.0336 (7) Å | θ = 2.2–28.5° |
α = 101.7655 (5)° | µ = 2.79 mm−1 |
β = 93.2300 (5)° | T = 100 K |
γ = 99.0746 (5)° | Prisms, colourless |
V = 1130.99 (8) Å3 | 0.45 × 0.25 × 0.15 mm |
Bruker APEXII CCD diffractometer | 4794 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.017 |
φ and ω scans | θmax = 28.6°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | h = −6→6 |
Tmin = 0.441, Tmax = 0.658 | k = −18→18 |
14589 measured reflections | l = −20→21 |
5242 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.019 | H-atom parameters constrained |
wR(F2) = 0.047 | w = 1/[σ2(Fo2) + (0.0224P)2 + 0.5576P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
5242 reflections | Δρmax = 0.92 e Å−3 |
220 parameters | Δρmin = −0.42 e Å−3 |
C15H26N42+·2I−·C2H3N | γ = 99.0746 (5)° |
Mr = 557.25 | V = 1130.99 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.2513 (2) Å | Mo Kα radiation |
b = 13.9534 (6) Å | µ = 2.79 mm−1 |
c = 16.0336 (7) Å | T = 100 K |
α = 101.7655 (5)° | 0.45 × 0.25 × 0.15 mm |
β = 93.2300 (5)° |
Bruker APEXII CCD diffractometer | 5242 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | 4794 reflections with I > 2σ(I) |
Tmin = 0.441, Tmax = 0.658 | Rint = 0.017 |
14589 measured reflections |
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.047 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.92 e Å−3 |
5242 reflections | Δρmin = −0.42 e Å−3 |
220 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.42021 (2) | 0.58093 (2) | 0.35311 (2) | 0.01844 (4) | |
I2 | 0.72032 (2) | 0.76194 (2) | 0.00980 (2) | 0.02117 (4) | |
N11 | −0.1149 (3) | 0.36742 (12) | 0.23753 (10) | 0.0182 (3) | |
C12 | −0.1418 (4) | 0.39156 (14) | 0.32081 (12) | 0.0182 (4) | |
H12 | −0.2492 | 0.4357 | 0.3468 | 0.022* | |
N13 | 0.0060 (3) | 0.34381 (12) | 0.36144 (10) | 0.0162 (3) | |
C14 | 0.1377 (4) | 0.28869 (15) | 0.30215 (13) | 0.0195 (4) | |
H14 | 0.2585 | 0.2481 | 0.3140 | 0.023* | |
C15 | 0.0630 (4) | 0.30320 (15) | 0.22457 (13) | 0.0204 (4) | |
H15 | 0.1206 | 0.2750 | 0.1714 | 0.024* | |
C16 | 0.0363 (4) | 0.35405 (15) | 0.45488 (12) | 0.0192 (4) | |
H161 | −0.0679 | 0.4031 | 0.4820 | 0.023* | |
H162 | 0.2201 | 0.3797 | 0.4760 | 0.023* | |
C17 | −0.0480 (4) | 0.25647 (15) | 0.48106 (13) | 0.0201 (4) | |
H171 | −0.0251 | 0.2677 | 0.5442 | 0.024* | |
H172 | 0.0656 | 0.2092 | 0.4576 | 0.024* | |
C18 | −0.3285 (4) | 0.20997 (15) | 0.45049 (13) | 0.0216 (4) | |
H181 | −0.4391 | 0.2614 | 0.4634 | 0.026* | |
H182 | −0.3441 | 0.1853 | 0.3877 | 0.026* | |
C19 | −0.4247 (5) | 0.12446 (17) | 0.49273 (16) | 0.0313 (5) | |
H191 | −0.5990 | 0.0923 | 0.4671 | 0.047* | |
H192 | −0.4298 | 0.1501 | 0.5541 | 0.047* | |
H193 | −0.3073 | 0.0760 | 0.4841 | 0.047* | |
N21 | −0.0729 (3) | 0.49440 (12) | 0.15562 (10) | 0.0196 (3) | |
C22 | −0.0651 (4) | 0.58842 (15) | 0.19695 (13) | 0.0190 (4) | |
H22 | −0.1740 | 0.6105 | 0.2396 | 0.023* | |
N23 | 0.1212 (3) | 0.64552 (13) | 0.16814 (11) | 0.0188 (3) | |
C24 | 0.2411 (4) | 0.58611 (16) | 0.10818 (13) | 0.0237 (4) | |
H24 | 0.3823 | 0.6079 | 0.0782 | 0.028* | |
C25 | 0.1201 (4) | 0.49146 (16) | 0.10025 (13) | 0.0232 (4) | |
H25 | 0.1596 | 0.4340 | 0.0638 | 0.028* | |
C26 | 0.2100 (4) | 0.75326 (15) | 0.19954 (14) | 0.0225 (4) | |
H261 | 0.2452 | 0.7841 | 0.1500 | 0.027* | |
H262 | 0.3748 | 0.7640 | 0.2361 | 0.027* | |
C27 | 0.0177 (4) | 0.80450 (15) | 0.25005 (13) | 0.0219 (4) | |
H271 | −0.0055 | 0.7790 | 0.3029 | 0.026* | |
H272 | −0.1520 | 0.7899 | 0.2157 | 0.026* | |
C28 | 0.1121 (4) | 0.91589 (16) | 0.27323 (16) | 0.0290 (5) | |
H281 | 0.1403 | 0.9404 | 0.2201 | 0.035* | |
H282 | 0.2807 | 0.9298 | 0.3081 | 0.035* | |
C29 | −0.0770 (5) | 0.9724 (2) | 0.3228 (2) | 0.0431 (6) | |
H291 | −0.0081 | 1.0438 | 0.3352 | 0.065* | |
H292 | −0.1005 | 0.9504 | 0.3765 | 0.065* | |
H293 | −0.2441 | 0.9593 | 0.2884 | 0.065* | |
C31 | −0.2422 (4) | 0.40854 (15) | 0.17320 (13) | 0.0232 (4) | |
H311 | −0.4040 | 0.4288 | 0.1937 | 0.028* | |
H312 | −0.2884 | 0.3570 | 0.1198 | 0.028* | |
N41 | 0.4743 (4) | 0.13329 (17) | 0.21320 (14) | 0.0380 (5) | |
C42 | 0.5987 (4) | 0.10146 (17) | 0.16261 (15) | 0.0286 (5) | |
C43 | 0.7612 (5) | 0.06174 (19) | 0.09817 (19) | 0.0414 (6) | |
H431 | 0.7504 | 0.0945 | 0.0498 | 0.062* | |
H432 | 0.7016 | −0.0099 | 0.0782 | 0.062* | |
H433 | 0.9412 | 0.0740 | 0.1231 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.01837 (7) | 0.02001 (7) | 0.01690 (7) | 0.00343 (5) | 0.00282 (5) | 0.00347 (5) |
I2 | 0.02533 (7) | 0.02081 (7) | 0.01639 (7) | 0.00167 (5) | 0.00536 (5) | 0.00265 (5) |
N11 | 0.0206 (8) | 0.0169 (8) | 0.0165 (8) | 0.0000 (6) | 0.0020 (6) | 0.0046 (6) |
C12 | 0.0171 (9) | 0.0172 (9) | 0.0194 (9) | 0.0004 (7) | 0.0034 (7) | 0.0037 (7) |
N13 | 0.0180 (8) | 0.0153 (8) | 0.0163 (8) | 0.0022 (6) | 0.0049 (6) | 0.0050 (6) |
C14 | 0.0200 (9) | 0.0173 (9) | 0.0220 (10) | 0.0034 (7) | 0.0086 (8) | 0.0043 (8) |
C15 | 0.0225 (10) | 0.0178 (10) | 0.0201 (10) | 0.0014 (7) | 0.0074 (8) | 0.0026 (8) |
C16 | 0.0225 (10) | 0.0201 (10) | 0.0145 (9) | 0.0021 (7) | 0.0024 (7) | 0.0035 (7) |
C17 | 0.0215 (10) | 0.0226 (10) | 0.0186 (9) | 0.0046 (8) | 0.0037 (8) | 0.0084 (8) |
C18 | 0.0231 (10) | 0.0200 (10) | 0.0222 (10) | 0.0018 (8) | 0.0045 (8) | 0.0067 (8) |
C19 | 0.0320 (12) | 0.0255 (11) | 0.0400 (13) | 0.0025 (9) | 0.0106 (10) | 0.0154 (10) |
N21 | 0.0243 (9) | 0.0189 (8) | 0.0156 (8) | 0.0010 (7) | 0.0013 (7) | 0.0061 (6) |
C22 | 0.0179 (9) | 0.0227 (10) | 0.0182 (9) | 0.0035 (7) | 0.0031 (7) | 0.0078 (8) |
N23 | 0.0202 (8) | 0.0202 (8) | 0.0179 (8) | 0.0038 (6) | 0.0045 (6) | 0.0074 (6) |
C24 | 0.0275 (11) | 0.0273 (11) | 0.0192 (10) | 0.0073 (8) | 0.0082 (8) | 0.0080 (8) |
C25 | 0.0306 (11) | 0.0232 (11) | 0.0173 (9) | 0.0064 (8) | 0.0049 (8) | 0.0057 (8) |
C26 | 0.0218 (10) | 0.0181 (10) | 0.0280 (11) | 0.0011 (8) | 0.0073 (8) | 0.0064 (8) |
C27 | 0.0215 (10) | 0.0231 (10) | 0.0218 (10) | 0.0029 (8) | 0.0039 (8) | 0.0067 (8) |
C28 | 0.0253 (11) | 0.0234 (11) | 0.0383 (13) | 0.0037 (8) | 0.0071 (9) | 0.0055 (9) |
C29 | 0.0397 (14) | 0.0299 (13) | 0.0573 (17) | 0.0101 (11) | 0.0118 (13) | −0.0013 (12) |
C31 | 0.0239 (10) | 0.0225 (11) | 0.0220 (10) | −0.0025 (8) | −0.0032 (8) | 0.0087 (8) |
N41 | 0.0377 (12) | 0.0404 (12) | 0.0370 (12) | 0.0106 (9) | 0.0096 (10) | 0.0059 (10) |
C42 | 0.0304 (12) | 0.0210 (11) | 0.0337 (12) | 0.0023 (9) | 0.0019 (10) | 0.0059 (9) |
C43 | 0.0442 (15) | 0.0279 (13) | 0.0510 (16) | 0.0065 (11) | 0.0214 (13) | 0.0016 (11) |
N11—C12 | 1.330 (3) | C22—H22 | 0.9500 |
N11—C15 | 1.389 (3) | N23—C24 | 1.384 (3) |
N11—C31 | 1.457 (3) | N23—C26 | 1.475 (3) |
C12—N13 | 1.324 (3) | C24—C25 | 1.350 (3) |
C12—H12 | 0.9500 | C24—H24 | 0.9500 |
N13—C14 | 1.385 (2) | C25—H25 | 0.9500 |
N13—C16 | 1.473 (2) | C26—C27 | 1.507 (3) |
C14—C15 | 1.347 (3) | C26—H261 | 0.9900 |
C14—H14 | 0.9500 | C26—H262 | 0.9900 |
C15—H15 | 0.9500 | C27—C28 | 1.517 (3) |
C16—C17 | 1.513 (3) | C27—H271 | 0.9900 |
C16—H161 | 0.9900 | C27—H272 | 0.9900 |
C16—H162 | 0.9900 | C28—C29 | 1.523 (3) |
C17—C18 | 1.523 (3) | C28—H281 | 0.9900 |
C17—H171 | 0.9900 | C28—H282 | 0.9900 |
C17—H172 | 0.9900 | C29—H291 | 0.9800 |
C18—C19 | 1.522 (3) | C29—H292 | 0.9800 |
C18—H181 | 0.9900 | C29—H293 | 0.9800 |
C18—H182 | 0.9900 | C31—H311 | 0.9900 |
C19—H191 | 0.9800 | C31—H312 | 0.9900 |
C19—H192 | 0.9800 | N41—C42 | 1.134 (3) |
C19—H193 | 0.9800 | C42—C43 | 1.456 (3) |
N21—C22 | 1.337 (3) | C43—H431 | 0.9800 |
N21—C25 | 1.384 (3) | C43—H432 | 0.9800 |
N21—C31 | 1.461 (2) | C43—H433 | 0.9800 |
C22—N23 | 1.327 (3) | ||
C12—N11—C15 | 108.78 (16) | C25—C24—N23 | 107.27 (18) |
N13—C12—N11 | 108.64 (17) | C25—C24—H24 | 126.4 |
N13—C12—H12 | 125.7 | N23—C24—H24 | 126.4 |
N11—C12—H12 | 125.7 | C24—C25—N21 | 106.63 (19) |
C12—N13—C14 | 108.63 (16) | C25—N21—C31 | 126.08 (18) |
C15—C14—N13 | 107.39 (18) | C22—N23—C26 | 126.91 (17) |
C15—C14—H14 | 126.3 | C24—N23—C26 | 123.88 (17) |
N13—C14—H14 | 126.3 | C24—C25—H25 | 126.7 |
C14—C15—N11 | 106.54 (17) | N21—C25—H25 | 126.7 |
C12—N11—C31 | 124.01 (18) | N23—C26—C27 | 113.44 (16) |
C15—N11—C31 | 127.10 (17) | N23—C26—H261 | 108.9 |
C12—N13—C16 | 124.92 (16) | C27—C26—H261 | 108.9 |
C14—N13—C16 | 126.33 (17) | N23—C26—H262 | 108.9 |
C14—C15—H15 | 126.7 | C27—C26—H262 | 108.9 |
N11—C15—H15 | 126.7 | H261—C26—H262 | 107.7 |
N13—C16—C17 | 112.29 (16) | C26—C27—C28 | 110.24 (17) |
N13—C16—H161 | 109.1 | C26—C27—H271 | 109.6 |
C17—C16—H161 | 109.1 | C28—C27—H271 | 109.6 |
N13—C16—H162 | 109.1 | C26—C27—H272 | 109.6 |
C17—C16—H162 | 109.1 | C28—C27—H272 | 109.6 |
H161—C16—H162 | 107.9 | H271—C27—H272 | 108.1 |
C16—C17—C18 | 113.26 (17) | C27—C28—C29 | 112.85 (19) |
C16—C17—H171 | 108.9 | C27—C28—H281 | 109.0 |
C18—C17—H171 | 108.9 | C29—C28—H281 | 109.0 |
C16—C17—H172 | 108.9 | C27—C28—H282 | 109.0 |
C18—C17—H172 | 108.9 | C29—C28—H282 | 109.0 |
H171—C17—H172 | 107.7 | H281—C28—H282 | 107.8 |
C19—C18—C17 | 112.06 (18) | C28—C29—H291 | 109.5 |
N11—C31—N21 | 110.80 (16) | C28—C29—H292 | 109.5 |
C19—C18—H181 | 109.2 | H291—C29—H292 | 109.5 |
C17—C18—H181 | 109.2 | C28—C29—H293 | 109.5 |
C19—C18—H182 | 109.2 | H291—C29—H293 | 109.5 |
C17—C18—H182 | 109.2 | H292—C29—H293 | 109.5 |
H181—C18—H182 | 107.9 | N11—C31—H311 | 109.5 |
C18—C19—H191 | 109.5 | N21—C31—H311 | 109.5 |
C18—C19—H192 | 109.5 | N11—C31—H312 | 109.5 |
H191—C19—H192 | 109.5 | N21—C31—H312 | 109.5 |
C18—C19—H193 | 109.5 | H311—C31—H312 | 108.1 |
H191—C19—H193 | 109.5 | N41—C42—C43 | 179.2 (3) |
H192—C19—H193 | 109.5 | C42—C43—H431 | 109.5 |
C22—N21—C25 | 109.01 (17) | C42—C43—H432 | 109.5 |
C22—N21—C31 | 124.65 (18) | H431—C43—H432 | 109.5 |
N23—C22—N21 | 108.14 (18) | C42—C43—H433 | 109.5 |
N23—C22—H22 | 125.9 | H431—C43—H433 | 109.5 |
N21—C22—H22 | 125.9 | H432—C43—H433 | 109.5 |
C22—N23—C24 | 108.93 (17) | ||
C15—N11—C12—N13 | −1.5 (2) | N21—C22—N23—C24 | −1.6 (2) |
C31—N11—C12—N13 | −177.84 (16) | N21—C22—N23—C26 | −175.68 (18) |
N11—C12—N13—C14 | 1.5 (2) | C22—N23—C24—C25 | 1.0 (2) |
N11—C12—N13—C16 | 177.62 (17) | C26—N23—C24—C25 | 175.23 (18) |
C12—N13—C14—C15 | −0.9 (2) | N23—C24—C25—N21 | 0.1 (2) |
C16—N13—C14—C15 | −176.96 (17) | C22—N21—C25—C24 | −1.1 (2) |
N13—C14—C15—N11 | 0.0 (2) | C31—N21—C25—C24 | −175.36 (18) |
C12—N11—C15—C14 | 0.9 (2) | C22—N23—C26—C27 | −18.8 (3) |
C31—N11—C15—C14 | 177.14 (18) | C24—N23—C26—C27 | 168.00 (18) |
C12—N13—C16—C17 | 119.9 (2) | N23—C26—C27—C28 | −174.97 (18) |
C14—N13—C16—C17 | −64.6 (2) | C26—C27—C28—C29 | 178.7 (2) |
N13—C16—C17—C18 | −58.1 (2) | C12—N11—C31—N21 | 94.2 (2) |
C16—C17—C18—C19 | −168.04 (18) | C15—N11—C31—N21 | −81.5 (2) |
C25—N21—C22—N23 | 1.7 (2) | C22—N21—C31—N11 | −90.3 (2) |
C31—N21—C22—N23 | 176.07 (17) | C25—N21—C31—N11 | 83.1 (2) |
Experimental details
Crystal data | |
Chemical formula | C15H26N42+·2I−·C2H3N |
Mr | 557.25 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 5.2513 (2), 13.9534 (6), 16.0336 (7) |
α, β, γ (°) | 101.7655 (5), 93.2300 (5), 99.0746 (5) |
V (Å3) | 1130.99 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.79 |
Crystal size (mm) | 0.45 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2011) |
Tmin, Tmax | 0.441, 0.658 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14589, 5242, 4794 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.674 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.047, 1.07 |
No. of reflections | 5242 |
No. of parameters | 220 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.92, −0.42 |
Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), SHELXTL (Bruker, 2011).
N11—C12 | 1.330 (3) | N21—C22 | 1.337 (3) |
N11—C15 | 1.389 (3) | N21—C25 | 1.384 (3) |
N11—C31 | 1.457 (3) | N21—C31 | 1.461 (2) |
C12—N13 | 1.324 (3) | C22—N23 | 1.327 (3) |
N13—C14 | 1.385 (2) | N23—C24 | 1.384 (3) |
N13—C16 | 1.473 (2) | N23—C26 | 1.475 (3) |
C14—C15 | 1.347 (3) | C24—C25 | 1.350 (3) |
C16—C17 | 1.513 (3) | C26—C27 | 1.507 (3) |
C17—C18 | 1.523 (3) | C27—C28 | 1.517 (3) |
C18—C19 | 1.522 (3) | C28—C29 | 1.523 (3) |
C12—N11—C15 | 108.78 (16) | N11—C31—N21 | 110.80 (16) |
N13—C12—N11 | 108.64 (17) | C22—N21—C25 | 109.01 (17) |
C12—N13—C14 | 108.63 (16) | N23—C22—N21 | 108.14 (18) |
C15—C14—N13 | 107.39 (18) | C22—N23—C24 | 108.93 (17) |
C14—C15—N11 | 106.54 (17) | C25—C24—N23 | 107.27 (18) |
C12—N11—C31 | 124.01 (18) | C24—C25—N21 | 106.63 (19) |
C15—N11—C31 | 127.10 (17) | C25—N21—C31 | 126.08 (18) |
C12—N13—C16 | 124.92 (16) | C22—N23—C26 | 126.91 (17) |
C14—N13—C16 | 126.33 (17) | C24—N23—C26 | 123.88 (17) |
N13—C16—C17 | 112.29 (16) | N23—C26—C27 | 113.44 (16) |
C16—C17—C18 | 113.26 (17) | C26—C27—C28 | 110.24 (17) |
C19—C18—C17 | 112.06 (18) | C27—C28—C29 | 112.85 (19) |