Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005378/na6144sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005378/na6144Isup2.hkl |
CCDC reference: 185771
The title compound was synthesized from benzo[f][1,7]naphthyridine and 2-bromoethanol. The mixture containing 1.80 g (10 mmol) of benzo[f][1,7]naphthyridine and 1.25 g (10 mmol) of 2-bromoethanol was dissolved in 54 ml acetonitrile and then refluxed for 30 h. The solid which formed was filtered off and after the first recrystallization from absolute ethanol was dissolved in acetonitrile under reflux and left at room temperature. The melting point of the obtained final product measured by means of electrothermal IA 910 apparatus was 514–515 K. The crystals were grown from nucleated spontaneously supercooled solution in acetonitrile at a constant temperature of 298 K in an apparatus described previously by Marciniak (2002).
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 C14N13N2O+·Br- compound. | |
Fig. 2. The unit-cell contents viewed along a. |
C14H13N2O+·Br− | Melting point: 514 K |
Mr = 305.17 | Mo Kα radiation, λ = 0.71069 Å |
Trigonal, P31 | Cell parameters from 45 reflections |
a = 7.057 (1) Å | θ = 3.0–24.0° |
c = 22.372 (4) Å | µ = 3.18 mm−1 |
V = 964.9 (3) Å3 | T = 293 K |
Z = 3 | Tablet, clear pale yellow |
F(000) = 462 | 0.25 × 0.25 × 0.12 mm |
Dx = 1.576 Mg m−3 |
DARCH-1 diffractometer | 1416 independent reflections |
Radiation source: BSW X-ray tube | 1250 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω–2θ scans | θmax = 27.4°, θmin = 2.7° |
Absorption correction: empirical (using intensity measurements) (DIFABS; Walker & Stuart, 1983) | h = −9→4 |
Tmin = 0.431, Tmax = 0.682 | k = 0→8 |
1416 measured reflections | l = 0→26 |
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)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.024P)2 + 0.0222P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.031 |
1416 reflections | Δρmax = 0.12 e Å−3 |
168 parameters | Δρmin = −0.11 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.025 (15) |
C14H13N2O+·Br− | Z = 3 |
Mr = 305.17 | Mo Kα radiation |
Trigonal, P31 | µ = 3.18 mm−1 |
a = 7.057 (1) Å | T = 293 K |
c = 22.372 (4) Å | 0.25 × 0.25 × 0.12 mm |
V = 964.9 (3) Å3 |
DARCH-1 diffractometer | 1416 independent reflections |
Absorption correction: empirical (using intensity measurements) (DIFABS; Walker & Stuart, 1983) | 1250 reflections with I > 2σ(I) |
Tmin = 0.431, Tmax = 0.682 | Rint = 0.021 |
1416 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.068 | Δρmax = 0.12 e Å−3 |
S = 1.04 | Δρmin = −0.11 e Å−3 |
1416 reflections | Absolute structure: Flack (1983) |
168 parameters | Absolute structure parameter: 0.025 (15) |
1 restraint |
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 | ||
Br | 0.50948 (10) | 0.34260 (9) | 0.33326 (3) | 0.09973 (19) | |
O | 0.7126 (8) | 0.1043 (8) | 0.41541 (19) | 0.1154 (13) | |
H0 | 0.8246 | 0.2108 | 0.4030 | 0.053 (4)* | |
N1 | 0.9073 (7) | 0.1169 (8) | 0.29451 (17) | 0.0870 (10) | |
N2 | 1.1740 (8) | 0.6903 (8) | 0.2816 (2) | 0.0950 (13) | |
C1 | 1.0229 (10) | 0.3283 (13) | 0.3058 (3) | 0.1074 (18) | |
H1 | 1.0837 | 0.3757 | 0.3435 | 0.129* | |
C2 | 1.0555 (9) | 0.4838 (9) | 0.2612 (2) | 0.0878 (13) | |
C3 | 1.2145 (10) | 0.8416 (11) | 0.2434 (3) | 0.1036 (18) | |
H3 | 1.3000 | 0.9873 | 0.2548 | 0.124* | |
C4 | 1.1308 (12) | 0.7910 (12) | 0.1835 (3) | 0.117 (2) | |
H4 | 1.1606 | 0.9075 | 0.1583 | 0.140* | |
C5 | 1.0127 (12) | 0.5879 (10) | 0.1612 (3) | 0.1049 (18) | |
H5 | 0.9628 | 0.5566 | 0.1220 | 0.126* | |
C6 | 0.9717 (10) | 0.4194 (9) | 0.2072 (3) | 0.0928 (14) | |
C7 | 0.8368 (10) | 0.1816 (10) | 0.1946 (3) | 0.0955 (16) | |
C8 | 0.7443 (8) | 0.0976 (8) | 0.1361 (2) | 0.0817 (12) | |
H8 | 0.7646 | 0.1940 | 0.1052 | 0.098* | |
C9 | 0.6302 (8) | −0.1175 (9) | 0.1266 (2) | 0.0945 (15) | |
H9 | 0.5737 | −0.1687 | 0.0887 | 0.113* | |
C10 | 0.5919 (11) | −0.2728 (11) | 0.1734 (2) | 0.0984 (18) | |
H10 | 0.5101 | −0.4226 | 0.1664 | 0.118* | |
C11 | 0.6808 (9) | −0.1918 (10) | 0.2291 (3) | 0.0965 (15) | |
H11 | 0.6563 | −0.2889 | 0.2602 | 0.116* | |
C12 | 0.8075 (10) | 0.0346 (9) | 0.2396 (2) | 0.0916 (15) | |
C13 | 0.8691 (7) | −0.0325 (8) | 0.3457 (2) | 0.0787 (12) | |
H13A | 0.9981 | 0.0319 | 0.3709 | 0.053 (4)* | |
H13B | 0.8500 | −0.1696 | 0.3304 | 0.053 (4)* | |
C14 | 0.6734 (10) | −0.0802 (10) | 0.3833 (2) | 0.0910 (15) | |
H14A | 0.5468 | −0.1259 | 0.3577 | 0.053 (4)* | |
H14B | 0.6420 | −0.1989 | 0.4107 | 0.053 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.1085 (4) | 0.0948 (4) | 0.0962 (3) | 0.0510 (3) | −0.0064 (3) | −0.0019 (3) |
O | 0.138 (4) | 0.111 (3) | 0.096 (3) | 0.061 (3) | 0.017 (3) | −0.009 (2) |
N1 | 0.086 (3) | 0.102 (3) | 0.067 (2) | 0.043 (2) | 0.0114 (18) | 0.017 (2) |
N2 | 0.120 (3) | 0.095 (3) | 0.080 (3) | 0.062 (3) | 0.020 (2) | 0.018 (2) |
C1 | 0.095 (4) | 0.128 (5) | 0.087 (3) | 0.046 (4) | 0.011 (3) | 0.009 (4) |
C2 | 0.100 (3) | 0.085 (3) | 0.079 (3) | 0.047 (3) | −0.009 (3) | −0.005 (2) |
C3 | 0.088 (4) | 0.106 (4) | 0.125 (5) | 0.055 (3) | −0.004 (3) | −0.032 (4) |
C4 | 0.141 (6) | 0.123 (5) | 0.091 (4) | 0.071 (5) | 0.027 (4) | 0.015 (4) |
C5 | 0.136 (5) | 0.106 (4) | 0.101 (4) | 0.081 (4) | −0.006 (4) | −0.013 (3) |
C6 | 0.101 (4) | 0.090 (3) | 0.088 (3) | 0.049 (3) | 0.013 (3) | 0.003 (3) |
C7 | 0.112 (4) | 0.108 (4) | 0.090 (3) | 0.073 (4) | −0.011 (3) | −0.010 (3) |
C8 | 0.091 (3) | 0.087 (3) | 0.060 (3) | 0.039 (3) | −0.005 (2) | −0.004 (2) |
C9 | 0.080 (3) | 0.102 (4) | 0.077 (3) | 0.027 (3) | −0.011 (2) | −0.014 (3) |
C10 | 0.135 (5) | 0.116 (4) | 0.066 (3) | 0.079 (4) | 0.027 (3) | 0.008 (3) |
C11 | 0.107 (4) | 0.098 (4) | 0.094 (4) | 0.058 (3) | −0.011 (3) | −0.011 (3) |
C12 | 0.126 (5) | 0.097 (4) | 0.060 (2) | 0.062 (3) | 0.018 (3) | 0.005 (2) |
C13 | 0.075 (3) | 0.075 (3) | 0.057 (2) | 0.016 (2) | −0.0098 (19) | −0.0065 (19) |
C14 | 0.117 (4) | 0.106 (4) | 0.079 (3) | 0.078 (4) | 0.009 (3) | 0.011 (3) |
O—C14 | 1.389 (6) | C6—C7 | 1.485 (8) |
O—H0 | 0.8200 | C7—C12 | 1.385 (8) |
N1—C1 | 1.318 (8) | C7—C8 | 1.450 (7) |
N1—C12 | 1.390 (7) | C8—C9 | 1.333 (7) |
N1—C13 | 1.487 (6) | C8—H8 | 0.9300 |
N2—C3 | 1.283 (8) | C9—C10 | 1.439 (8) |
N2—C2 | 1.347 (7) | C9—H9 | 0.9300 |
C1—C2 | 1.414 (8) | C10—C11 | 1.384 (8) |
C1—H1 | 0.9300 | C10—H10 | 0.9300 |
C2—C6 | 1.321 (7) | C11—C12 | 1.407 (8) |
C3—C4 | 1.436 (10) | C11—H11 | 0.9300 |
C3—H3 | 0.9300 | C13—C14 | 1.504 (7) |
C4—C5 | 1.343 (9) | C13—H13A | 0.9700 |
C4—H4 | 0.9300 | C13—H13B | 0.9700 |
C5—C6 | 1.487 (8) | C14—H14A | 0.9700 |
C5—H5 | 0.9300 | C14—H14B | 0.9700 |
C14—O—H0 | 109.5 | C9—C8—H8 | 119.9 |
C1—N1—C12 | 122.7 (5) | C7—C8—H8 | 119.9 |
C1—N1—C13 | 116.4 (4) | C8—C9—C10 | 121.8 (5) |
C12—N1—C13 | 120.6 (4) | C8—C9—H9 | 119.1 |
C3—N2—C2 | 115.8 (5) | C10—C9—H9 | 119.1 |
N1—C1—C2 | 120.8 (5) | C11—C10—C9 | 117.8 (6) |
N1—C1—H1 | 119.6 | C11—C10—H10 | 121.1 |
C2—C1—H1 | 119.6 | C9—C10—H10 | 121.1 |
C6—C2—N2 | 127.6 (5) | C10—C11—C12 | 121.3 (6) |
C6—C2—C1 | 120.5 (6) | C10—C11—H11 | 119.4 |
N2—C2—C1 | 111.9 (5) | C12—C11—H11 | 119.4 |
N2—C3—C4 | 121.5 (6) | C7—C12—N1 | 118.3 (5) |
N2—C3—H3 | 119.3 | C7—C12—C11 | 120.1 (5) |
C4—C3—H3 | 119.3 | N1—C12—C11 | 121.6 (5) |
C5—C4—C3 | 124.8 (7) | N1—C13—C14 | 114.2 (4) |
C5—C4—H4 | 117.6 | N1—C13—H13A | 108.7 |
C3—C4—H4 | 117.6 | C14—C13—H13A | 108.7 |
C4—C5—C6 | 111.4 (6) | N1—C13—H13B | 108.7 |
C4—C5—H5 | 124.3 | C14—C13—H13B | 108.7 |
C6—C5—H5 | 124.3 | H13A—C13—H13B | 107.6 |
C2—C6—C7 | 119.1 (5) | O—C14—C13 | 110.5 (5) |
C2—C6—C5 | 118.9 (5) | O—C14—H14A | 109.6 |
C7—C6—C5 | 122.1 (5) | C13—C14—H14A | 109.6 |
C12—C7—C8 | 118.8 (5) | O—C14—H14B | 109.6 |
C12—C7—C6 | 118.7 (5) | C13—C14—H14B | 109.6 |
C8—C7—C6 | 122.5 (5) | H14A—C14—H14B | 108.1 |
C9—C8—C7 | 120.2 (5) | ||
C12—N1—C1—C2 | −1.6 (8) | C12—C7—C8—C9 | 1.1 (9) |
C13—N1—C1—C2 | −175.6 (5) | C6—C7—C8—C9 | 177.8 (5) |
C3—N2—C2—C6 | −2.0 (9) | C7—C8—C9—C10 | 0.9 (9) |
C3—N2—C2—C1 | 178.7 (5) | C8—C9—C10—C11 | −1.0 (8) |
N1—C1—C2—C6 | −0.5 (9) | C9—C10—C11—C12 | −1.0 (8) |
N1—C1—C2—N2 | 178.9 (5) | C8—C7—C12—N1 | 176.4 (5) |
C2—N2—C3—C4 | 2.2 (9) | C6—C7—C12—N1 | −0.4 (8) |
N2—C3—C4—C5 | −2.6 (11) | C8—C7—C12—C11 | −3.1 (9) |
C3—C4—C5—C6 | 2.0 (10) | C6—C7—C12—C11 | −179.9 (5) |
N2—C2—C6—C7 | −177.3 (5) | C1—N1—C12—C7 | 2.0 (8) |
C1—C2—C6—C7 | 2.0 (8) | C13—N1—C12—C7 | 175.8 (5) |
N2—C2—C6—C5 | 1.7 (9) | C1—N1—C12—C11 | −178.5 (5) |
C1—C2—C6—C5 | −179.0 (6) | C13—N1—C12—C11 | −4.8 (8) |
C4—C5—C6—C2 | −1.6 (8) | C10—C11—C12—C7 | 3.1 (9) |
C4—C5—C6—C7 | 177.4 (6) | C10—C11—C12—N1 | −176.4 (5) |
C2—C6—C7—C12 | −1.5 (8) | C1—N1—C13—C14 | 86.0 (5) |
C5—C6—C7—C12 | 179.5 (6) | C12—N1—C13—C14 | −88.2 (6) |
C2—C6—C7—C8 | −178.2 (6) | N1—C13—C14—O | −70.1 (5) |
C5—C6—C7—C8 | 2.8 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Bri | 0.93 | 2.80 | 3.676 (6) | 157 |
C5—H5···Brii | 0.93 | 2.84 | 3.773 (7) | 176 |
C10—H10···Oiii | 0.93 | 2.59 | 3.378 (8) | 142 |
C11—H11···Briv | 0.93 | 2.80 | 3.704 (6) | 166 |
Symmetry codes: (i) x+1, y+1, z; (ii) −x+y+1, −x+1, z−1/3; (iii) −x+y+1, −x, z−1/3; (iv) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C14H13N2O+·Br− |
Mr | 305.17 |
Crystal system, space group | Trigonal, P31 |
Temperature (K) | 293 |
a, c (Å) | 7.057 (1), 22.372 (4) |
V (Å3) | 964.9 (3) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 3.18 |
Crystal size (mm) | 0.25 × 0.25 × 0.12 |
Data collection | |
Diffractometer | DARCH-1 diffractometer |
Absorption correction | Empirical (using intensity measurements) (DIFABS; Walker & Stuart, 1983) |
Tmin, Tmax | 0.431, 0.682 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1416, 1416, 1250 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.068, 1.04 |
No. of reflections | 1416 |
No. of parameters | 168 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.12, −0.11 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.025 (15) |
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 |
C3—H3···Bri | 0.93 | 2.80 | 3.676 (6) | 157 |
C5—H5···Brii | 0.93 | 2.84 | 3.773 (7) | 176 |
C10—H10···Oiii | 0.93 | 2.59 | 3.378 (8) | 142 |
C11—H11···Briv | 0.93 | 2.80 | 3.704 (6) | 166 |
Symmetry codes: (i) x+1, y+1, z; (ii) −x+y+1, −x+1, z−1/3; (iii) −x+y+1, −x, z−1/3; (iv) x, y−1, z. |
Quaternary salts of azaaromatics currently receive increasing attention due to their possible applications in the construction of electronic devices (Suzuki et al., 2001; Gittins et al., 2000; Metzger, 2000), in non-linear optics (Teppner et al., 2000; Burtman et al., 2000; Andreu et al., 2000) and as electrochromic (Cummins et al., 2000) and photochromic [Manasawa et al., 2000) materials; they can serve as laser dyes (Gawinecki & Trzebiatowska, 2001; Nishigaki & Nakamura, 2001), surfactants (Viscardi et al., 2000), supramolecular switches and devices (Bryce et al., 2001; Macias et al., 2000), as well as chemosensors (Sotiriou-Leventis et al., 2000; Wright et al., 2000) and biological diagnostic agents (Revesz & Waelchli, 2001). Some show biological activities, e.g. as antidiabetic (Sankaranarayanan, 2001a,b) and anticancer (Saito et al., 2001) therapeutics. The present report is a continuation of our study concerning benzonaphthyridinium quaternary salts (Dondela & Sliwa, 2000; Bachowska & Zujewska, 2001; Matusiak, 1999). The crystal structures of similar compounds with two azaaromatic N atoms which can be unprotonated, mono- or diprotonated have been 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).