Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005354/na6142sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005354/na6142Isup2.hkl |
CCDC reference: 185769
According to the procedure whose detailed description is reported in the literature (Dondela & Sliwa, 2000; Chrzastek et al., 1999; Chrzastek & Sliwa, 2001), a solution of benzo[c]-1,5-naphthyridine (1.8 g, 10 mmol) and ethyl iodide (34.79 g, 223 mmol) in benzene (72 ml) was refluxed for 10 h. The resulting yellow solid was filtered off and recrystallized twice from distilled benzene. Single crystals were grown by slow cooling of a chloroform solution from 313 to 293 K at a rate of ca 0.7 K h-1 in an apparatus described previously by Marciniak (2002). To prevent solvent evaporation, the solution was covered with a practically immiscible layer of demineralized water.
The traditional X-ray photographic methods such as Laue and rotation (camera RKD 86, Mo radiation) and Weissenberg (camera RGNS 2, Cu radiation) were used for the preliminary examination of the crystal structure. For the data collection a four circle DARCH-1 diffractometer with a scintillation detector was used. The positions of the H atoms were generated and refined by the SHELXL97 constraints.
Data collection: DARCH software; cell refinement: DARCH software; data reduction: DARCH software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97.
Fig. 1. The constituent ions of the C14N13N2+·I- compound. | |
Fig. 2. The unit-cell contents viewed along a. |
C14H13N2+·I− | Dx = 1.703 Mg m−3 Dm = not measered Mg m−3 Dm measured by not measured |
Mr = 336.16 | Melting point: 491 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 6.589 (1) Å | Cell parameters from 74 reflections |
b = 13.365 (3) Å | θ = 3.0–25.0° |
c = 14.892 (3) Å | µ = 2.42 mm−1 |
β = 91.62 (3)° | T = 293 K |
V = 1310.9 (4) Å3 | Prism, clear pale yellow |
Z = 4 | 0.45 × 0.18 × 0.10 mm |
F(000) = 656 |
DARCH-1 diffractometer | 2586 independent reflections |
Radiation source: BSW X-ray tube | 2399 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω–2θ scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: empirical (using intensity measurements) (DIFABS; Walker & Stuart, 1983) | h = −8→8 |
Tmin = 0.577, Tmax = 0.785 | k = 0→17 |
2586 measured reflections | l = 0→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.148 | w = 1/[σ2(Fo2) + (0.0748P)2 + 0.56P] where P = (Fo2 + 2Fc2)/3 |
S = 1.34 | (Δ/σ)max = 0.004 |
2586 reflections | Δρmax = 0.65 e Å−3 |
157 parameters | Δρmin = −0.82 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0060 (13) |
C14H13N2+·I− | V = 1310.9 (4) Å3 |
Mr = 336.16 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.589 (1) Å | µ = 2.42 mm−1 |
b = 13.365 (3) Å | T = 293 K |
c = 14.892 (3) Å | 0.45 × 0.18 × 0.10 mm |
β = 91.62 (3)° |
DARCH-1 diffractometer | 2586 independent reflections |
Absorption correction: empirical (using intensity measurements) (DIFABS; Walker & Stuart, 1983) | 2399 reflections with I > 2σ(I) |
Tmin = 0.577, Tmax = 0.785 | Rint = 0.043 |
2586 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.34 | Δρmax = 0.65 e Å−3 |
2586 reflections | Δρmin = −0.82 e Å−3 |
157 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.73326 (6) | 0.34075 (3) | 0.16387 (3) | 0.0839 (2) | |
N1 | 0.1607 (9) | 0.5160 (4) | 0.2667 (3) | 0.0810 (12) | |
N2 | −0.2553 (7) | 0.4824 (4) | 0.4235 (4) | 0.0855 (13) | |
C1 | 0.2731 (9) | 0.4395 (4) | 0.2883 (3) | 0.0760 (13) | |
H1 | 0.3902 | 0.4284 | 0.2563 | 0.091* | |
C2 | 0.2260 (8) | 0.3720 (4) | 0.3584 (4) | 0.0693 (11) | |
C3 | 0.3587 (9) | 0.2943 (5) | 0.3807 (4) | 0.0820 (14) | |
H3 | 0.4797 | 0.2869 | 0.3508 | 0.098* | |
C4 | 0.3092 (10) | 0.2288 (5) | 0.4471 (4) | 0.0898 (16) | |
H4 | 0.3980 | 0.1775 | 0.4638 | 0.108* | |
C5 | 0.1242 (7) | 0.2395 (3) | 0.4897 (3) | 0.0879 (16) | |
H5 | 0.0902 | 0.1938 | 0.5339 | 0.106* | |
C6 | −0.0079 (7) | 0.3148 (3) | 0.4685 (3) | 0.0773 (13) | |
H6 | −0.1307 | 0.3198 | 0.4974 | 0.093* | |
C7 | 0.0423 (8) | 0.3843 (4) | 0.4031 (3) | 0.0678 (11) | |
C8 | −0.0815 (8) | 0.4702 (4) | 0.3786 (3) | 0.0713 (12) | |
C9 | −0.3652 (10) | 0.5629 (6) | 0.4023 (6) | 0.104 (2) | |
H9 | −0.4842 | 0.5740 | 0.4330 | 0.124* | |
C10 | −0.3107 (15) | 0.6325 (6) | 0.3357 (7) | 0.112 (3) | |
H10 | −0.3926 | 0.6879 | 0.3240 | 0.134* | |
C11 | −0.1389 (13) | 0.6187 (5) | 0.2886 (5) | 0.098 (2) | |
H11 | −0.1023 | 0.6630 | 0.2437 | 0.118* | |
C12 | −0.0190 (10) | 0.5347 (4) | 0.3108 (4) | 0.0784 (14) | |
C13 | 0.2335 (17) | 0.5785 (5) | 0.1907 (6) | 0.120 (3) | |
H13A | 0.1751 | 0.6448 | 0.1955 | 0.21 (4)* | |
H13B | 0.3798 | 0.5854 | 0.1971 | 0.21 (4)* | |
C14 | 0.187 (2) | 0.5409 (7) | 0.1054 (5) | 0.151 (5) | |
H14A | 0.2439 | 0.4753 | 0.0997 | 0.23 (4)* | |
H14B | 0.2420 | 0.5843 | 0.0610 | 0.23 (4)* | |
H14C | 0.0420 | 0.5374 | 0.0969 | 0.23 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0805 (3) | 0.0862 (3) | 0.0852 (3) | −0.00962 (17) | 0.00636 (19) | −0.01661 (16) |
N1 | 0.114 (4) | 0.061 (2) | 0.068 (2) | 0.000 (2) | 0.005 (2) | −0.0006 (19) |
N2 | 0.068 (2) | 0.090 (3) | 0.098 (3) | 0.001 (2) | −0.010 (2) | −0.022 (3) |
C1 | 0.096 (4) | 0.067 (3) | 0.066 (3) | −0.007 (3) | 0.006 (2) | −0.011 (2) |
C2 | 0.074 (3) | 0.058 (3) | 0.076 (3) | −0.002 (2) | 0.004 (2) | −0.008 (2) |
C3 | 0.080 (3) | 0.080 (4) | 0.086 (3) | 0.009 (3) | 0.002 (3) | −0.008 (3) |
C4 | 0.101 (4) | 0.076 (4) | 0.092 (4) | 0.022 (3) | −0.003 (3) | 0.004 (3) |
C5 | 0.116 (5) | 0.074 (3) | 0.074 (3) | 0.000 (3) | 0.004 (3) | 0.008 (3) |
C6 | 0.084 (3) | 0.076 (3) | 0.072 (3) | −0.006 (3) | 0.010 (2) | 0.001 (2) |
C7 | 0.068 (3) | 0.067 (3) | 0.068 (2) | −0.004 (2) | −0.0070 (19) | −0.007 (2) |
C8 | 0.073 (3) | 0.065 (3) | 0.075 (3) | −0.001 (2) | −0.011 (2) | −0.014 (2) |
C9 | 0.074 (3) | 0.096 (5) | 0.140 (6) | 0.010 (3) | −0.020 (4) | −0.029 (4) |
C10 | 0.111 (5) | 0.080 (4) | 0.142 (7) | 0.027 (4) | −0.049 (5) | −0.015 (4) |
C11 | 0.116 (5) | 0.075 (4) | 0.102 (4) | 0.012 (4) | −0.042 (4) | −0.005 (3) |
C12 | 0.095 (4) | 0.063 (3) | 0.076 (3) | 0.002 (3) | −0.025 (3) | −0.008 (2) |
C13 | 0.199 (10) | 0.063 (4) | 0.099 (4) | −0.015 (4) | 0.027 (5) | 0.016 (3) |
C14 | 0.271 (14) | 0.104 (6) | 0.080 (4) | −0.028 (7) | 0.028 (6) | 0.014 (4) |
I1—I1 | 0.0000 (9) | C6—C7 | 1.393 (7) |
N1—C1 | 1.297 (8) | C6—H6 | 0.9300 |
N1—C12 | 1.393 (8) | C7—C8 | 1.449 (7) |
N1—C13 | 1.496 (8) | C8—C12 | 1.398 (8) |
N2—C9 | 1.330 (9) | C9—C10 | 1.414 (13) |
N2—C8 | 1.353 (7) | C9—H9 | 0.9300 |
C1—C2 | 1.421 (8) | C10—C11 | 1.361 (13) |
C1—H1 | 0.9300 | C10—H10 | 0.9300 |
C2—C7 | 1.407 (7) | C11—C12 | 1.406 (9) |
C2—C3 | 1.392 (8) | C11—H11 | 0.9300 |
C3—C4 | 1.366 (9) | C13—C14 | 1.392 (13) |
C3—H3 | 0.9300 | C13—H13A | 0.9700 |
C4—C5 | 1.398 (8) | C13—H13B | 0.9700 |
C4—H4 | 0.9300 | C14—H14A | 0.9600 |
C5—C6 | 1.3617 | C14—H14B | 0.9600 |
C5—H5 | 0.9300 | C14—H14C | 0.9600 |
C1—N1—C12 | 120.7 (5) | N2—C8—C7 | 116.7 (5) |
C1—N1—C13 | 115.7 (6) | C12—C8—C7 | 119.7 (5) |
C12—N1—C13 | 123.5 (6) | N2—C9—C10 | 123.4 (7) |
C9—N2—C8 | 116.3 (6) | N2—C9—H9 | 118.3 |
N1—C1—C2 | 123.2 (5) | C10—C9—H9 | 118.3 |
N1—C1—H1 | 118.4 | C11—C10—C9 | 120.3 (7) |
C2—C1—H1 | 118.4 | C11—C10—H10 | 119.9 |
C7—C2—C3 | 121.1 (5) | C9—C10—H10 | 119.9 |
C7—C2—C1 | 118.8 (5) | C10—C11—C12 | 117.2 (7) |
C3—C2—C1 | 120.1 (5) | C10—C11—H11 | 121.4 |
C4—C3—C2 | 119.3 (5) | C12—C11—H11 | 121.4 |
C4—C3—H3 | 120.3 | N1—C12—C11 | 120.8 (6) |
C2—C3—H3 | 120.3 | N1—C12—C8 | 120.1 (5) |
C3—C4—C5 | 119.4 (5) | C11—C12—C8 | 119.1 (6) |
C3—C4—H4 | 120.3 | C14—C13—N1 | 114.9 (7) |
C5—C4—H4 | 120.3 | C14—C13—H13A | 108.5 |
C6—C5—C4 | 122.0 (3) | N1—C13—H13A | 108.5 |
C6—C5—H5 | 119.0 | C14—C13—H13B | 108.5 |
C4—C5—H5 | 119.0 | N1—C13—H13B | 108.5 |
C5—C6—C7 | 119.5 (3) | H13A—C13—H13B | 107.5 |
C5—C6—H6 | 120.3 | C13—C14—H14A | 109.5 |
C7—C6—H6 | 120.3 | C13—C14—H14B | 109.5 |
C6—C7—C2 | 118.5 (5) | H14A—C14—H14B | 109.5 |
C6—C7—C8 | 124.1 (5) | C13—C14—H14C | 109.5 |
C2—C7—C8 | 117.3 (5) | H14A—C14—H14C | 109.5 |
N2—C8—C12 | 123.6 (5) | H14B—C14—H14C | 109.5 |
C12—N1—C1—C2 | −1.7 (8) | C2—C7—C8—N2 | −178.5 (5) |
C13—N1—C1—C2 | −179.6 (6) | C6—C7—C8—C12 | −178.9 (5) |
N1—C1—C2—C7 | 4.3 (8) | C2—C7—C8—C12 | 2.1 (7) |
N1—C1—C2—C3 | −176.9 (5) | C8—N2—C9—C10 | 1.3 (10) |
C7—C2—C3—C4 | 0.0 (9) | N2—C9—C10—C11 | 0.6 (12) |
C1—C2—C3—C4 | −178.7 (6) | C9—C10—C11—C12 | −1.4 (10) |
C2—C3—C4—C5 | 1.7 (9) | C1—N1—C12—C11 | 178.8 (6) |
C3—C4—C5—C6 | −1.4 (8) | C13—N1—C12—C11 | −3.5 (9) |
C4—C5—C6—C7 | −0.7 (4) | C1—N1—C12—C8 | −0.7 (8) |
C5—C6—C7—C2 | 2.4 (5) | C13—N1—C12—C8 | 177.1 (6) |
C5—C6—C7—C8 | −176.6 (3) | C10—C11—C12—N1 | −179.1 (6) |
C3—C2—C7—C6 | −2.1 (8) | C10—C11—C12—C8 | 0.4 (9) |
C1—C2—C7—C6 | 176.7 (5) | N2—C8—C12—N1 | −178.9 (5) |
C3—C2—C7—C8 | 176.9 (5) | C7—C8—C12—N1 | 0.4 (7) |
C1—C2—C7—C8 | −4.3 (7) | N2—C8—C12—C11 | 1.6 (8) |
C9—N2—C8—C12 | −2.4 (8) | C7—C8—C12—C11 | −179.0 (5) |
C9—N2—C8—C7 | 178.2 (5) | C1—N1—C13—C14 | 80.8 (11) |
C6—C7—C8—N2 | 0.5 (7) | C12—N1—C13—C14 | −97.1 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···I1 | 0.93 | 2.92 | 3.832 (6) | 166 |
C10—H10···I1i | 0.93 | 3.04 | 3.937 (8) | 162 |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H13N2+·I− |
Mr | 336.16 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.589 (1), 13.365 (3), 14.892 (3) |
β (°) | 91.62 (3) |
V (Å3) | 1310.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.42 |
Crystal size (mm) | 0.45 × 0.18 × 0.10 |
Data collection | |
Diffractometer | DARCH-1 diffractometer |
Absorption correction | Empirical (using intensity measurements) (DIFABS; Walker & Stuart, 1983) |
Tmin, Tmax | 0.577, 0.785 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2586, 2586, 2399 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.148, 1.34 |
No. of reflections | 2586 |
No. of parameters | 157 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.82 |
Computer programs: DARCH software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2000), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···I1 | 0.93 | 2.92 | 3.832 (6) | 166 |
C10—H10···I1i | 0.93 | 3.04 | 3.937 (8) | 162 |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
Quaternary salts of azaaromatics are the subject of many reports due to their interesting application possibilities, e.g. they may be used in non-linear optics (Struganowa, 2000; Burtman et al., 2000), in the construction of electronic devices (Gittins et al., 2000; Bryce et al., 2001), as photochromic (Sotomayor et al., 2000) and electrochromic (Cummins et al., 2000) materials, as chemosensors (Goodal & Williams, 2000; Maidwell et al., 2000), laser dyes (Nishigaki & Nakamura, 2001; Gawinecki & Trzebiatowska, 2001) and NAD model systems (Zhu et al., 2001; Mikata et al., 2000). Some of these salts are biologically active (Goda & Saito, 2000) and also show anticancer properties (Nakanishi & Suzuki, 2001; Palm et al., 2000). In a number of reactions, they serve as synthons (Bennasar et al., 2001; Kuethe & Comins, 2000); their use in supramolecular chemistry systems should also be mentioned (Balzani et al., 2000; Loeb & Wisner, 2000). The crystal structures of similar compounds with two azaaromatic N atoms which can be unprotonated, mono- or diprotonated are described by (Hensen et al., 2000; Wang et al., 1999a,b). For all these structures, short H···X (X = Cl, I) contacts to aromatic H atoms are found. Furthermore, the crystal packing is stabilized by several short X···H—C contacts (Hensen et al., 2000).