Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616002576/eg3198sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616002576/eg3198Isup2.hkl |
CCDC reference: 1453091
\ Consideration of electrostatic interactions between localized integral charges, being either repulsive or attractive in nature, makes the stability and structure of highly charged small and rigid organics intriguing; the issue is how σ/π-electron delocalization can compensate reduced conformational freedom by lowering the repulsion between identical charges. In this spirit, heteroaromatic systems provide both π-conjugation and rigidity features. The issue is hereafter addressed within the context of two neighbouring imidazolium rings at a rigid o-phenylene core; N,N'-dimethylation of 1,2-bis(1H-imidazol-1-yl)benzene, (1) (So, 1992), affords the corresponding bis-imidazolium salt 1,1'-(1,2-phenylene)bis(3-methyl-1H-imidazol-3-ium) bis(trifluoromethanesulfonate), (2) (see Scheme 1). The latter was used as the conjugated acid of a neutral bis-N-heterocyclic carbene (NHC) acting as a cis-chelating ligand in PdII (Tubaro et al., 2006) and RhI complexes such as (3) (Canac et al., 2008). The two positive charges of (2) can, however, be preserved in the coordination sphere of metal centres upon prior C2-phosphinylation of the imidazolium rings: the resulting bis-imidazoliophosphine, 1,1'-(1,2-phenylene)bis-2-(diphenylphosphanyl)-3-methyl-1H-imidazol-3-\ ium] bis(trifluoromethanesulfonate), (4) (Canac et al., 2009), was shown to act as a trans-coordinating ligand in both PdII (Canac et al., 2011) and RhI complexes, such as the carbonylchloridorhodium(I) complex (5) (Canac et al., 2009) (Scheme 1).
The results of a single-crystal X-ray diffraction experiment on (2) are presented. The structure is compared to that of the related bis-imidazoliophosphine (4) reported recently (Canac et al., 2011).
The preparation and analytical data (1H and 13C NMR spectroscopy, HRMS and melting point) of (2) and (4) have been reported previously [see Canac et al. (2008) and Canac et al. (2009), respectively]. Colourless crystals were obtained by recrystallization from CH2Cl2/Et2O at 273 K for (2) and from CH3CN/Et2O at 253 K for (4).
Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms were all located in a difference map, but those attached to C atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H = 0.93–0.98 Å) and Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints (Cooper et al., 2010). The molecular view and local ionic association of (2) are shown in Fig. 1.
The title salt (2) crystallizes in the centrosymmetric space group P21/c with one bisimidazolium dication and two trifluoromethanesulfonate anions in the asymmetric unit (Fig. 1). Data collection at low temperature (100 K) allowed minimization of the displacement parameters, especially for the trifluoromethanesulfonate anions. Both the molecular conformation and the crystal packing are sequentially discussed below.
In the dication of salt (2), the planes of the two imidazolium rings, denoted A (atoms N2/C1/N1/C2/C3) and B (atoms N3/C12/N4/C11/C10) are nearly planar, the maximum deviations from the mean planes being 0.0038 (8) Å for ring A (atom C2) and 0.0021 (8) Å for ring B (atom C11). Phenylene ring C is also nearly planar, with a maximum deviation from the mean plane of 0.0188 (8) Å (atom C9). The anticipated aromatic character of phenylene ring C is further confirmed by a mean C—C bond length of 1.394 Å {corresponding to the value of the harmonic oscillator model for equivalent Kékulé structures: ([1.54 + 2(1.33)]/3 = 1.40 Å} (Kruszewski & Krygowski, 1972). The geometric aromatic character of imidazolium rings A and B is less pronounced, with quasi-equalized bond lengths in the N—C—N units (Table 2), but much greater lengths for the four other C—N bonds (1.390±0.003 Å; Table 2). It is also noticeable that the C═ C bond lengths (C2═C3 and C10═C11; Table 2) in the A and B rings are slightly elongated with respect to related C—C bonds in imidazolium salts of the general type N-aryl-N'-R-1H-imidazolium; mean value = 1.343 Å for 121 structures found in the Cambridge Structural Database (CSD, Version 5.36; Groom & Allen, 2014).
Regarding strain and conformational features, the formal +/+ electrostatic repulsion between imidazolium rings A and B has no significant effect on the standard valence shell electron pair repulsion (VSEPR) bond angles at the aromatic C atoms C4 and C9 (Table 2). The dihedral angles between the mean plane of ring C and those of imidazolium rings A and B are 48.52 (4) and 57.50 (3)°, respectively, and the angle between the mean planes of rings A and B is 56.90 (4)°, with an anti orientation of the two imidazolium rings (the N-methyl groups at C13 and C14 are located on opposite sides of the mean plane of ring C). The contacts of the dication with two different pairs of trifluoromethanesulfonate anions occur at the amidinium centres C1—H11 and C12—H121; the interactions of the O atoms correspond to tight van der Waals contacts with both C atoms [C1···O3 = 3.009 (1) Å, C1···O4 = 2.907 (2) Å, C12···O2v = 2.918 (2) Å and C12···O5ii = 3.363 (2) Å; symmetry codes: (ii) x, −y + 1/2, z − 1/2; (v) −x + 2, −y + 1, −z + 1] and H atoms [H11···O3 = 2.61 Å and C1—H11···O3 = 108°; H11···O4 = 2.66 Å and C1—H11···O4 = 96°; H121···O2v = 2.45 Å and C12—H121···O2v = 112°; H121···O5ii = 2.52 Å and C12—H121···O5ii = 153°]. In spite of the negative charge of the O atoms and the acidic character of the amidinium H atoms, no true C—H···O hydrogen bond is thus evidenced.
The structure of (2) deserves comparison with the previously reported X-ray crystal structure of the bis-diphenylphosphin derivative (4) (Fig. 2; Canac et al., 2011). In contrast to (2), the imidazolium rings of (4) are in a syn orientation with respect to the central phenylene ring [here also without a significant strain effect of the +/+ formal electrostatic repulsion: N3—C9—C4 = 121.6 (4)° and N2—C4—C9 = 120.2 (4)°]. Although a syn–anti equilibrium was evidenced in solution (Canac et al., 2009), the syn conformation found in the solid state was interpreted to be driven by a PN2C+···O−···+CN2P electrostatic pincer interaction at one of the O atoms of the two trifluoromethanesulfonate anions [O5···C1 = 3.382 (6) Å and O5···C10 = 3.261 (6) Å; see Scheme 2 and Fig. 2]. No significant interaction occurs with the second trifluoromethanesulfonate (TfO) anion [minimum nonbonding TfO···C distance O2A···C10iii = 3.831 (7) Å; symmetry code: (iii) −x + 1/2, y − 1/2, −z + 1/2].
In the crystal structure of (2), an anti orientation of imidazolium rings A and B with respect to phenylene ring C (see above) induces a pleated (zigzag) layer pattern (Fig. 3). In addition to the formal electrostatic attraction between the imidazolium and the trifluoromethanesulfonate anions, weak C—H···O interactions [with a minimum C···O distance of 3.1280 (11) Å; Table 2] and weak C—H···F interactions [with a minimum C···F distance of 3.144 (2) Å; Table 3] contribute to the global stabilization of the three-dimensional network.
In the case of (4), weak C—H···O interactions between the bis-imidazolium and trifluoromethanesulfonate ions [with a minimum C···O distance of 3.086 (7) Å; Fig. 4 and Table 4] allow the identification of planar layers along the a and b axes. The crystal packing is further stabilized by weak C—H···F interactions [with a minimum C···F distance of 3.301 (9) Å; Fig. 2 and Table 4]. In spite of the occurrence of five phenylene or phenyl rings and face-to-face positioning between them in the crystal structure of (4), an analysis by PLATON (Spek, 2009) does not give any evidence of significant π–π interactions.
The behaviour of 1,2-bis(1H-imidazol-1-yl)benzene, (1), and its analogues as ligands of transition metal centres has been extensively explored, especially for catalytic purposes (Albrecht et al., 2002; Rentzsch et al., 2009; Subramanium et al., 2011; Munz et al., 2013; Howell et al., 2014). However, despite the report of its symmetric salt [one step on from (1)], the structure of the 3,3'-dimethylated 1,1'-(1,2-phenylene)bis(3-methyl-1H-imidazol-3-ium)dication seen in (2) has not been reported in the CSD. It is finally noteworthy that in spite of a looser local ionic association in (2), the crystal density of (2) (Dx = 1.69 Mg m−3) is significantly greater than the crystal density of the 2,2'-bis (diphenylphosphanyl) analogue, (4) (Dx = 1.17 Mg m−3). The tight electrostatic pincer association occurring in the solid-state structure of (4) is indeed compensated and globally diluted by large voids contributing for a total of ca 25–30% of the crystal volume.
\ Consideration of electrostatic interactions between localized integral charges, being either repulsive or attractive in nature, makes the stability and structure of highly charged small and rigid organics intriguing; the issue is how σ/π-electron delocalization can compensate reduced conformational freedom by lowering the repulsion between identical charges. In this spirit, heteroaromatic systems provide both π-conjugation and rigidity features. The issue is hereafter addressed within the context of two neighbouring imidazolium rings at a rigid o-phenylene core; N,N'-dimethylation of 1,2-bis(1H-imidazol-1-yl)benzene, (1) (So, 1992), affords the corresponding bis-imidazolium salt 1,1'-(1,2-phenylene)bis(3-methyl-1H-imidazol-3-ium) bis(trifluoromethanesulfonate), (2) (see Scheme 1). The latter was used as the conjugated acid of a neutral bis-N-heterocyclic carbene (NHC) acting as a cis-chelating ligand in PdII (Tubaro et al., 2006) and RhI complexes such as (3) (Canac et al., 2008). The two positive charges of (2) can, however, be preserved in the coordination sphere of metal centres upon prior C2-phosphinylation of the imidazolium rings: the resulting bis-imidazoliophosphine, 1,1'-(1,2-phenylene)bis-2-(diphenylphosphanyl)-3-methyl-1H-imidazol-3-\ ium] bis(trifluoromethanesulfonate), (4) (Canac et al., 2009), was shown to act as a trans-coordinating ligand in both PdII (Canac et al., 2011) and RhI complexes, such as the carbonylchloridorhodium(I) complex (5) (Canac et al., 2009) (Scheme 1).
The results of a single-crystal X-ray diffraction experiment on (2) are presented. The structure is compared to that of the related bis-imidazoliophosphine (4) reported recently (Canac et al., 2011).
The title salt (2) crystallizes in the centrosymmetric space group P21/c with one bisimidazolium dication and two trifluoromethanesulfonate anions in the asymmetric unit (Fig. 1). Data collection at low temperature (100 K) allowed minimization of the displacement parameters, especially for the trifluoromethanesulfonate anions. Both the molecular conformation and the crystal packing are sequentially discussed below.
In the dication of salt (2), the planes of the two imidazolium rings, denoted A (atoms N2/C1/N1/C2/C3) and B (atoms N3/C12/N4/C11/C10) are nearly planar, the maximum deviations from the mean planes being 0.0038 (8) Å for ring A (atom C2) and 0.0021 (8) Å for ring B (atom C11). Phenylene ring C is also nearly planar, with a maximum deviation from the mean plane of 0.0188 (8) Å (atom C9). The anticipated aromatic character of phenylene ring C is further confirmed by a mean C—C bond length of 1.394 Å {corresponding to the value of the harmonic oscillator model for equivalent Kékulé structures: ([1.54 + 2(1.33)]/3 = 1.40 Å} (Kruszewski & Krygowski, 1972). The geometric aromatic character of imidazolium rings A and B is less pronounced, with quasi-equalized bond lengths in the N—C—N units (Table 2), but much greater lengths for the four other C—N bonds (1.390±0.003 Å; Table 2). It is also noticeable that the C═ C bond lengths (C2═C3 and C10═C11; Table 2) in the A and B rings are slightly elongated with respect to related C—C bonds in imidazolium salts of the general type N-aryl-N'-R-1H-imidazolium; mean value = 1.343 Å for 121 structures found in the Cambridge Structural Database (CSD, Version 5.36; Groom & Allen, 2014).
Regarding strain and conformational features, the formal +/+ electrostatic repulsion between imidazolium rings A and B has no significant effect on the standard valence shell electron pair repulsion (VSEPR) bond angles at the aromatic C atoms C4 and C9 (Table 2). The dihedral angles between the mean plane of ring C and those of imidazolium rings A and B are 48.52 (4) and 57.50 (3)°, respectively, and the angle between the mean planes of rings A and B is 56.90 (4)°, with an anti orientation of the two imidazolium rings (the N-methyl groups at C13 and C14 are located on opposite sides of the mean plane of ring C). The contacts of the dication with two different pairs of trifluoromethanesulfonate anions occur at the amidinium centres C1—H11 and C12—H121; the interactions of the O atoms correspond to tight van der Waals contacts with both C atoms [C1···O3 = 3.009 (1) Å, C1···O4 = 2.907 (2) Å, C12···O2v = 2.918 (2) Å and C12···O5ii = 3.363 (2) Å; symmetry codes: (ii) x, −y + 1/2, z − 1/2; (v) −x + 2, −y + 1, −z + 1] and H atoms [H11···O3 = 2.61 Å and C1—H11···O3 = 108°; H11···O4 = 2.66 Å and C1—H11···O4 = 96°; H121···O2v = 2.45 Å and C12—H121···O2v = 112°; H121···O5ii = 2.52 Å and C12—H121···O5ii = 153°]. In spite of the negative charge of the O atoms and the acidic character of the amidinium H atoms, no true C—H···O hydrogen bond is thus evidenced.
The structure of (2) deserves comparison with the previously reported X-ray crystal structure of the bis-diphenylphosphin derivative (4) (Fig. 2; Canac et al., 2011). In contrast to (2), the imidazolium rings of (4) are in a syn orientation with respect to the central phenylene ring [here also without a significant strain effect of the +/+ formal electrostatic repulsion: N3—C9—C4 = 121.6 (4)° and N2—C4—C9 = 120.2 (4)°]. Although a syn–anti equilibrium was evidenced in solution (Canac et al., 2009), the syn conformation found in the solid state was interpreted to be driven by a PN2C+···O−···+CN2P electrostatic pincer interaction at one of the O atoms of the two trifluoromethanesulfonate anions [O5···C1 = 3.382 (6) Å and O5···C10 = 3.261 (6) Å; see Scheme 2 and Fig. 2]. No significant interaction occurs with the second trifluoromethanesulfonate (TfO) anion [minimum nonbonding TfO···C distance O2A···C10iii = 3.831 (7) Å; symmetry code: (iii) −x + 1/2, y − 1/2, −z + 1/2].
In the crystal structure of (2), an anti orientation of imidazolium rings A and B with respect to phenylene ring C (see above) induces a pleated (zigzag) layer pattern (Fig. 3). In addition to the formal electrostatic attraction between the imidazolium and the trifluoromethanesulfonate anions, weak C—H···O interactions [with a minimum C···O distance of 3.1280 (11) Å; Table 2] and weak C—H···F interactions [with a minimum C···F distance of 3.144 (2) Å; Table 3] contribute to the global stabilization of the three-dimensional network.
In the case of (4), weak C—H···O interactions between the bis-imidazolium and trifluoromethanesulfonate ions [with a minimum C···O distance of 3.086 (7) Å; Fig. 4 and Table 4] allow the identification of planar layers along the a and b axes. The crystal packing is further stabilized by weak C—H···F interactions [with a minimum C···F distance of 3.301 (9) Å; Fig. 2 and Table 4]. In spite of the occurrence of five phenylene or phenyl rings and face-to-face positioning between them in the crystal structure of (4), an analysis by PLATON (Spek, 2009) does not give any evidence of significant π–π interactions.
The behaviour of 1,2-bis(1H-imidazol-1-yl)benzene, (1), and its analogues as ligands of transition metal centres has been extensively explored, especially for catalytic purposes (Albrecht et al., 2002; Rentzsch et al., 2009; Subramanium et al., 2011; Munz et al., 2013; Howell et al., 2014). However, despite the report of its symmetric salt [one step on from (1)], the structure of the 3,3'-dimethylated 1,1'-(1,2-phenylene)bis(3-methyl-1H-imidazol-3-ium)dication seen in (2) has not been reported in the CSD. It is finally noteworthy that in spite of a looser local ionic association in (2), the crystal density of (2) (Dx = 1.69 Mg m−3) is significantly greater than the crystal density of the 2,2'-bis (diphenylphosphanyl) analogue, (4) (Dx = 1.17 Mg m−3). The tight electrostatic pincer association occurring in the solid-state structure of (4) is indeed compensated and globally diluted by large voids contributing for a total of ca 25–30% of the crystal volume.
The preparation and analytical data (1H and 13C NMR spectroscopy, HRMS and melting point) of (2) and (4) have been reported previously [see Canac et al. (2008) and Canac et al. (2009), respectively]. Colourless crystals were obtained by recrystallization from CH2Cl2/Et2O at 273 K for (2) and from CH3CN/Et2O at 253 K for (4).
Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms were all located in a difference map, but those attached to C atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H = 0.93–0.98 Å) and Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints (Cooper et al., 2010). The molecular view and local ionic association of (2) are shown in Fig. 1.
Data collection: GEMINI (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2002); data reduction: CrysAlis PRO (Oxford Diffraction, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).
C14H16N42+·2CF3O3S− | F(000) = 1096 |
Mr = 538.45 | Dx = 1.692 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25125 reflections |
a = 11.37505 (13) Å | θ = 3–31° |
b = 16.09785 (17) Å | µ = 0.35 mm−1 |
c = 11.60677 (14) Å | T = 100 K |
β = 96.0475 (11)° | Stick, colorless |
V = 2113.53 (4) Å3 | 0.30 × 0.15 × 0.15 mm |
Z = 4 |
Oxford Diffraction Gemini diffractometer | 5692 reflections with I > 2.0σ(I) |
Graphite monochromator | Rint = 0.024 |
φ & ω scans | θmax = 30.8°, θmin = 3.1° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2002) | h = −16→16 |
Tmin = 0.83, Tmax = 0.95 | k = −22→22 |
63741 measured reflections | l = −16→16 |
6255 independent reflections |
Refinement on F | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.037 | Method, part 1, Chebychev polynomial
(Watkin, 1994; Prince, 1982)
[weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 7.87 5.71 6.74 1.57 |
S = 1.03 | (Δ/σ)max = 0.002 |
5521 reflections | Δρmax = 0.43 e Å−3 |
307 parameters | Δρmin = −0.38 e Å−3 |
0 restraints |
C14H16N42+·2CF3O3S− | V = 2113.53 (4) Å3 |
Mr = 538.45 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.37505 (13) Å | µ = 0.35 mm−1 |
b = 16.09785 (17) Å | T = 100 K |
c = 11.60677 (14) Å | 0.30 × 0.15 × 0.15 mm |
β = 96.0475 (11)° |
Oxford Diffraction Gemini diffractometer | 6255 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2002) | 5692 reflections with I > 2.0σ(I) |
Tmin = 0.83, Tmax = 0.95 | Rint = 0.024 |
63741 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.037 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.43 e Å−3 |
5521 reflections | Δρmin = −0.38 e Å−3 |
307 parameters |
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1 K. Cosier, J. & Glazer, A·M., 1986. J. Appl. Cryst. 105–107. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.71376 (7) | 0.35843 (5) | 0.83935 (7) | 0.0132 | |
C2 | 0.55425 (7) | 0.43368 (5) | 0.78613 (7) | 0.0146 | |
C3 | 0.61222 (7) | 0.42296 (5) | 0.69102 (7) | 0.0137 | |
C4 | 0.79606 (7) | 0.34484 (5) | 0.65289 (7) | 0.0115 | |
C5 | 0.82570 (7) | 0.26087 (5) | 0.65653 (7) | 0.0150 | |
C6 | 0.90347 (8) | 0.23055 (5) | 0.58135 (8) | 0.0184 | |
C7 | 0.94882 (8) | 0.28305 (6) | 0.50108 (8) | 0.0195 | |
C8 | 0.92075 (8) | 0.36740 (6) | 0.49951 (8) | 0.0164 | |
C9 | 0.84620 (7) | 0.39814 (5) | 0.57686 (7) | 0.0118 | |
C10 | 0.84737 (7) | 0.53768 (5) | 0.67478 (7) | 0.0129 | |
C11 | 0.81580 (7) | 0.61555 (5) | 0.63821 (7) | 0.0140 | |
C12 | 0.77834 (7) | 0.53111 (5) | 0.48792 (7) | 0.0140 | |
C13 | 0.58510 (9) | 0.38273 (6) | 0.99477 (8) | 0.0208 | |
C14 | 0.72682 (9) | 0.67888 (6) | 0.44805 (8) | 0.0211 | |
C15 | 1.18412 (8) | 0.43699 (7) | 0.94517 (9) | 0.0234 | |
C16 | 0.46626 (8) | 0.19381 (5) | 0.75764 (7) | 0.0157 | |
N1 | 0.61880 (7) | 0.39242 (5) | 0.87714 (6) | 0.0144 | |
N2 | 0.71225 (6) | 0.37591 (4) | 0.72599 (6) | 0.0109 | |
N3 | 0.82313 (6) | 0.48571 (4) | 0.57938 (6) | 0.0114 | |
N4 | 0.77371 (6) | 0.60978 (5) | 0.52187 (6) | 0.0143 | |
O1 | 1.13344 (7) | 0.30817 (4) | 0.81942 (7) | 0.0239 | |
O2 | 1.11338 (7) | 0.44402 (5) | 0.72643 (7) | 0.0255 | |
O3 | 0.97278 (6) | 0.40083 (4) | 0.85946 (6) | 0.0178 | |
O4 | 0.63883 (7) | 0.19745 (5) | 0.91846 (7) | 0.0254 | |
O5 | 0.63356 (7) | 0.08472 (5) | 0.77742 (7) | 0.0263 | |
O6 | 0.49371 (7) | 0.08631 (5) | 0.92308 (6) | 0.0226 | |
S1 | 1.090136 (17) | 0.392408 (12) | 0.823237 (17) | 0.0124 | |
S2 | 0.570075 (18) | 0.133562 (13) | 0.855416 (17) | 0.0143 | |
F1 | 1.16670 (8) | 0.39882 (6) | 1.04432 (6) | 0.0425 | |
F2 | 1.29916 (6) | 0.42872 (5) | 0.93033 (8) | 0.0391 | |
F3 | 1.16272 (7) | 0.51768 (5) | 0.95785 (8) | 0.0407 | |
F4 | 0.39334 (5) | 0.14513 (4) | 0.68946 (5) | 0.0248 | |
F5 | 0.39988 (6) | 0.24389 (4) | 0.81657 (6) | 0.0258 | |
F6 | 0.52463 (5) | 0.24220 (4) | 0.68822 (5) | 0.0209 | |
H11 | 0.7709 | 0.3296 | 0.8827 | 0.0163* | |
H21 | 0.4839 | 0.4618 | 0.7940 | 0.0207* | |
H31 | 0.5916 | 0.4404 | 0.6173 | 0.0165* | |
H51 | 0.7928 | 0.2267 | 0.7071 | 0.0184* | |
H61 | 0.9264 | 0.1745 | 0.5825 | 0.0217* | |
H71 | 0.9983 | 0.2623 | 0.4487 | 0.0249* | |
H81 | 0.9510 | 0.4043 | 0.4462 | 0.0210* | |
H101 | 0.8792 | 0.5185 | 0.7463 | 0.0170* | |
H111 | 0.8218 | 0.6644 | 0.6783 | 0.0177* | |
H121 | 0.7549 | 0.5107 | 0.4155 | 0.0171* | |
H132 | 0.5670 | 0.4362 | 1.0262 | 0.0350* | |
H131 | 0.6469 | 0.3570 | 1.0431 | 0.0345* | |
H133 | 0.5138 | 0.3486 | 0.9907 | 0.0342* | |
H142 | 0.7531 | 0.6725 | 0.3738 | 0.0331* | |
H143 | 0.7583 | 0.7297 | 0.4814 | 0.0345* | |
H141 | 0.6434 | 0.6791 | 0.4448 | 0.0334* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0138 (3) | 0.0135 (3) | 0.0124 (3) | −0.0022 (3) | 0.0012 (3) | 0.0022 (3) |
C2 | 0.0143 (3) | 0.0138 (3) | 0.0159 (4) | 0.0021 (3) | 0.0033 (3) | 0.0009 (3) |
C3 | 0.0135 (3) | 0.0134 (3) | 0.0144 (3) | 0.0028 (3) | 0.0019 (3) | 0.0031 (3) |
C4 | 0.0108 (3) | 0.0115 (3) | 0.0123 (3) | −0.0002 (2) | 0.0013 (2) | −0.0013 (2) |
C5 | 0.0152 (3) | 0.0108 (3) | 0.0184 (4) | 0.0001 (3) | −0.0009 (3) | −0.0007 (3) |
C6 | 0.0154 (4) | 0.0129 (4) | 0.0261 (4) | 0.0021 (3) | −0.0007 (3) | −0.0063 (3) |
C7 | 0.0153 (4) | 0.0187 (4) | 0.0249 (4) | −0.0002 (3) | 0.0049 (3) | −0.0098 (3) |
C8 | 0.0146 (3) | 0.0172 (4) | 0.0182 (4) | −0.0025 (3) | 0.0060 (3) | −0.0051 (3) |
C9 | 0.0118 (3) | 0.0105 (3) | 0.0133 (3) | −0.0008 (2) | 0.0018 (3) | −0.0027 (2) |
C10 | 0.0142 (3) | 0.0121 (3) | 0.0125 (3) | −0.0004 (3) | 0.0025 (3) | −0.0016 (3) |
C11 | 0.0142 (3) | 0.0132 (3) | 0.0150 (3) | 0.0002 (3) | 0.0032 (3) | −0.0005 (3) |
C12 | 0.0148 (3) | 0.0151 (4) | 0.0123 (3) | −0.0020 (3) | 0.0030 (3) | 0.0017 (3) |
C13 | 0.0235 (4) | 0.0258 (4) | 0.0142 (4) | −0.0009 (3) | 0.0073 (3) | 0.0007 (3) |
C14 | 0.0233 (4) | 0.0184 (4) | 0.0218 (4) | 0.0046 (3) | 0.0028 (3) | 0.0087 (3) |
C15 | 0.0155 (4) | 0.0271 (5) | 0.0267 (5) | 0.0004 (3) | −0.0020 (3) | −0.0079 (4) |
C16 | 0.0141 (3) | 0.0167 (4) | 0.0159 (3) | −0.0013 (3) | 0.0000 (3) | 0.0030 (3) |
N1 | 0.0150 (3) | 0.0161 (3) | 0.0124 (3) | −0.0013 (2) | 0.0032 (2) | 0.0011 (2) |
N2 | 0.0112 (3) | 0.0102 (3) | 0.0114 (3) | 0.0001 (2) | 0.0018 (2) | 0.0011 (2) |
N3 | 0.0131 (3) | 0.0104 (3) | 0.0112 (3) | −0.0012 (2) | 0.0029 (2) | −0.0004 (2) |
N4 | 0.0142 (3) | 0.0142 (3) | 0.0148 (3) | 0.0007 (2) | 0.0032 (2) | 0.0033 (2) |
O1 | 0.0270 (3) | 0.0134 (3) | 0.0324 (4) | 0.0020 (2) | 0.0086 (3) | −0.0019 (3) |
O2 | 0.0292 (4) | 0.0275 (4) | 0.0213 (3) | −0.0013 (3) | 0.0101 (3) | 0.0095 (3) |
O3 | 0.0115 (3) | 0.0229 (3) | 0.0191 (3) | −0.0008 (2) | 0.0026 (2) | 0.0022 (2) |
O4 | 0.0251 (3) | 0.0211 (3) | 0.0270 (3) | −0.0059 (3) | −0.0109 (3) | 0.0011 (3) |
O5 | 0.0284 (4) | 0.0251 (4) | 0.0259 (3) | 0.0096 (3) | 0.0059 (3) | 0.0010 (3) |
O6 | 0.0302 (4) | 0.0201 (3) | 0.0174 (3) | −0.0059 (3) | 0.0020 (3) | 0.0054 (2) |
S1 | 0.01286 (9) | 0.01196 (9) | 0.01260 (9) | −0.00093 (6) | 0.00293 (7) | 0.00085 (6) |
S2 | 0.01589 (10) | 0.01231 (9) | 0.01404 (9) | −0.00015 (6) | −0.00162 (7) | 0.00201 (6) |
F1 | 0.0398 (4) | 0.0681 (6) | 0.0173 (3) | 0.0038 (4) | −0.0074 (3) | 0.0004 (3) |
F2 | 0.0126 (3) | 0.0463 (4) | 0.0569 (5) | −0.0003 (3) | −0.0035 (3) | −0.0123 (4) |
F3 | 0.0329 (4) | 0.0295 (4) | 0.0587 (5) | −0.0020 (3) | −0.0004 (3) | −0.0264 (3) |
F4 | 0.0207 (3) | 0.0309 (3) | 0.0210 (3) | −0.0088 (2) | −0.0065 (2) | 0.0014 (2) |
F5 | 0.0222 (3) | 0.0270 (3) | 0.0289 (3) | 0.0091 (2) | 0.0057 (2) | 0.0017 (2) |
F6 | 0.0225 (3) | 0.0198 (3) | 0.0202 (2) | −0.0025 (2) | 0.0020 (2) | 0.0083 (2) |
N1—C1 | 1.3261 (11) | C8—C9 | 1.3894 (11) |
N1—C2 | 1.3903 (11) | C8—H81 | 0.949 |
N1—C13 | 1.4647 (11) | C10—H101 | 0.923 |
N2—C1 | 1.3438 (10) | C11—H111 | 0.913 |
N2—C3 | 1.3913 (10) | C12—H121 | 0.915 |
N2—C4 | 1.4317 (10) | C13—H132 | 0.967 |
N3—C9 | 1.4347 (10) | C13—H131 | 0.948 |
N3—C10 | 1.3921 (10) | C13—H133 | 0.977 |
N3—C12 | 1.3441 (10) | C14—H142 | 0.947 |
N4—C11 | 1.3874 (11) | C14—H143 | 0.958 |
N4—C12 | 1.3290 (11) | C14—H141 | 0.945 |
N4—C14 | 1.4696 (11) | C15—S1 | 1.8282 (10) |
C2—C3 | 1.3552 (11) | C15—F1 | 1.3376 (14) |
C10—C11 | 1.3597 (11) | C15—F2 | 1.3443 (11) |
C1—H11 | 0.907 | C15—F3 | 1.3325 (13) |
C2—H21 | 0.932 | C16—S2 | 1.8277 (9) |
C3—H31 | 0.908 | C16—F4 | 1.3379 (10) |
C4—C5 | 1.3927 (11) | C16—F5 | 1.3405 (10) |
C4—C9 | 1.3951 (11) | C16—F6 | 1.3452 (10) |
C5—C6 | 1.3945 (12) | O1—S1 | 1.4450 (7) |
C5—H51 | 0.913 | O2—S1 | 1.4440 (7) |
C6—C7 | 1.3962 (14) | O3—S1 | 1.4475 (7) |
C6—H61 | 0.939 | O4—S2 | 1.4437 (7) |
C7—C8 | 1.3946 (13) | O5—S2 | 1.4480 (8) |
C7—H71 | 0.932 | O6—S2 | 1.4469 (7) |
N1—C1—N2 | 108.10 (7) | N4—C14—H142 | 108.6 |
N1—C1—H11 | 126.1 | N4—C14—H143 | 108.3 |
N2—C1—H11 | 125.8 | H142—C14—H143 | 108.6 |
C3—C2—N1 | 107.14 (7) | N4—C14—H141 | 109.1 |
C3—C2—H21 | 129.7 | H142—C14—H141 | 112.1 |
N1—C2—H21 | 123.2 | H143—C14—H141 | 110.1 |
C2—C3—N2 | 106.55 (7) | S1—C15—F1 | 110.98 (7) |
C2—C3—H31 | 129.0 | S1—C15—F2 | 111.08 (7) |
N2—C3—H31 | 124.4 | F1—C15—F2 | 107.41 (9) |
C5—C4—C9 | 120.16 (7) | S1—C15—F3 | 111.68 (7) |
C5—C4—N2 | 119.69 (7) | F1—C15—F3 | 107.90 (9) |
N2—C4—C9 | 120.14 (7) | F2—C15—F3 | 107.60 (9) |
C4—C5—C6 | 119.21 (8) | S2—C16—F4 | 112.10 (6) |
C4—C5—H51 | 119.3 | S2—C16—F5 | 111.35 (6) |
C6—C5—H51 | 121.4 | F4—C16—F5 | 107.85 (7) |
C5—C6—C7 | 120.60 (8) | S2—C16—F6 | 110.60 (6) |
C5—C6—H61 | 121.4 | F4—C16—F6 | 107.42 (7) |
C7—C6—H61 | 118.0 | F5—C16—F6 | 107.31 (7) |
C6—C7—C8 | 119.85 (8) | C13—N1—C2 | 126.16 (7) |
C6—C7—H71 | 120.6 | C13—N1—C1 | 124.52 (8) |
C8—C7—H71 | 119.6 | C2—N1—C1 | 109.22 (7) |
C7—C8—C9 | 119.53 (8) | C4—N2—C3 | 126.33 (7) |
C7—C8—H81 | 121.3 | C4—N2—C1 | 124.51 (7) |
C9—C8—H81 | 119.1 | C3—N2—C1 | 108.99 (7) |
C4—C9—C8 | 120.50 (7) | C9—N3—C10 | 125.83 (7) |
N3—C9—C4 | 120.24 (7) | C9—N3—C12 | 124.97 (7) |
C8—C9—N3 | 119.24 (7) | C10—N3—C12 | 109.16 (7) |
C11—C10—N3 | 106.39 (7) | C14—N4—C11 | 125.70 (8) |
C11—C10—H101 | 131.0 | C14—N4—C12 | 124.87 (8) |
N3—C10—H101 | 122.7 | C11—N4—C12 | 109.39 (7) |
C10—C11—N4 | 107.15 (7) | C15—S1—O3 | 102.73 (4) |
C10—C11—H111 | 129.2 | C15—S1—O1 | 102.63 (5) |
N4—C11—H111 | 123.6 | O3—S1—O1 | 115.12 (4) |
N3—C12—N4 | 107.91 (7) | C15—S1—O2 | 103.68 (5) |
N3—C12—H121 | 125.3 | O3—S1—O2 | 114.97 (4) |
N4—C12—H121 | 126.7 | O1—S1—O2 | 115.16 (5) |
N1—C13—H132 | 110.2 | C16—S2—O5 | 103.42 (4) |
N1—C13—H131 | 110.3 | C16—S2—O6 | 103.32 (4) |
H132—C13—H131 | 109.9 | O5—S2—O6 | 114.92 (5) |
N1—C13—H133 | 108.2 | C16—S2—O4 | 102.52 (4) |
H132—C13—H133 | 108.1 | O5—S2—O4 | 115.12 (5) |
H131—C13—H133 | 110.1 | O6—S2—O4 | 115.06 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H21···O5i | 0.93 | 2.48 | 3.2692 (12) | 142 |
C3—H31···O6ii | 0.91 | 2.44 | 3.2600 (11) | 150 |
C10—H101···O3 | 0.92 | 2.48 | 3.2922 (12) | 147 |
C11—H111···O1iii | 0.91 | 2.37 | 3.1827 (12) | 148 |
C12—H121···O5ii | 0.92 | 2.52 | 3.3632 (12) | 153 |
C2—H21···F2iv | 0.93 | 2.81 | 3.5001 (11) | 132 |
C13—H132···F2v | 0.97 | 2.67 | 3.3854 (13) | 131 |
C13—H133···F6vi | 0.98 | 2.71 | 3.1440 (11) | 107 |
C14—H141···F6vii | 0.95 | 2.65 | 3.3680 (12) | 133 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+1/2, z−1/2; (iii) −x+2, y+1/2, −z+3/2; (iv) x−1, y, z; (v) −x+2, −y+1, −z+2; (vi) x, −y+1/2, z+1/2; (vii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H16N42+·2CF3O3S− |
Mr | 538.45 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 11.37505 (13), 16.09785 (17), 11.60677 (14) |
β (°) | 96.0475 (11) |
V (Å3) | 2113.53 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.30 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2002) |
Tmin, Tmax | 0.83, 0.95 |
No. of measured, independent and observed [I > 2.0σ(I)] reflections | 63741, 6255, 5692 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.721 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.037, 1.03 |
No. of reflections | 5521 |
No. of parameters | 307 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.38 |
Computer programs: GEMINI (Oxford Diffraction, 2006), CrysAlis PRO (Oxford Diffraction, 2002), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).
N1—C1 | 1.3261 (11) | N3—C10 | 1.3921 (10) |
N1—C2 | 1.3903 (11) | N3—C12 | 1.3441 (10) |
N1—C13 | 1.4647 (11) | N4—C11 | 1.3874 (11) |
N2—C1 | 1.3438 (10) | N4—C12 | 1.3290 (11) |
N2—C3 | 1.3913 (10) | N4—C14 | 1.4696 (11) |
N2—C4 | 1.4317 (10) | C2—C3 | 1.3552 (11) |
N3—C9 | 1.4347 (10) | C10—C11 | 1.3597 (11) |
N2—C4—C9 | 120.14 (7) | N3—C9—C4 | 120.24 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H21···O5i | 0.932 | 2.481 | 3.2692 (12) | 142.0 |
C3—H31···O6ii | 0.908 | 2.445 | 3.2600 (11) | 150.0 |
C10—H101···O3 | 0.923 | 2.480 | 3.2922 (12) | 147.0 |
C11—H111···O1iii | 0.913 | 2.369 | 3.1827 (12) | 148.0 |
C12—H121···O5ii | 0.915 | 2.523 | 3.3632 (12) | 153.0 |
C2—H21···F2iv | 0.932 | 2.811 | 3.5001 (11) | 131.6 |
C13—H132···F2v | 0.967 | 2.672 | 3.3854 (13) | 131.1 |
C13—H133···F6vi | 0.977 | 2.711 | 3.1440 (11) | 107.4 |
C14—H141···F6vii | 0.945 | 2.650 | 3.3680 (12) | 133.2 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+1/2, z−1/2; (iii) −x+2, y+1/2, −z+3/2; (iv) x−1, y, z; (v) −x+2, −y+1, −z+2; (vi) x, −y+1/2, z+1/2; (vii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A | |
C2—H2···O3A | 0.93 | 2.451 (5) | 3.086 (7) | 125.6 (4) | |
C11—H11···O4i | 0.93 | 2.245 (6) | 3.145 (9) | 162.2 (4) | |
C14—H14···O2Ai | 0.93 | 2.608 (5) | 3.486 (8) | 157.6 (4) | |
C21—H21···O2Aii | 0.93 | 2.518 (5) | 3.274 (8) | 138.6 (4) | |
C24—H24···O5 | 0.93 | 2.540 (4) | 3.376 (8) | 149.9 (4) | |
C7—H7···F5iii | 0.93 | 2.446 (4) | 3.181 (7) | 135.7 (4) | |
C8—H8···F5iii | 0.93 | 2.947 (4) | 3.418 (7) | 113.0 (4) | |
C34—H34···F2Aiv | 0.93 | 2.685 (7) | 3.301 (9) | 124.5 (4) | |
C38—H38A···F4 | 0.93 | 2.528 (4) | 3.459 (7) | 163.8 (4) |
Symmetry codes: (i) −x + 1/2, y + 1/2, −z + 1/2; (ii) x + 1/2, y + 1/2, z. (iii) x, y + 1, z; (iv) −x, −y + 1, −z. |
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