Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801012971/wn6041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801012971/wn6041Isup2.hkl |
CCDC reference: 172206
Key indicators
- Single-crystal X-ray study
- T = 297 K
- Mean (C-C) = 0.003 Å
- R factor = 0.052
- wR factor = 0.150
- Data-to-parameter ratio = 11.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound was prepared by the reaction of a solution of p-phenylazoaniline in ethanol and HCl solution (37% in water) in a molar ratio of 1:1.5, at ambient temperature. Crystals suitable for X-ray diffraction analysis were obtained by very slow evaporation of the solution after several days.
The H atoms of the amine and azonium groups were located from difference Fourier maps and refined with a bond distance constrained to 0.85 Å. The other H atoms were constrained to idealized geometries using the appropriate riding model.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2000).
C12H12N3+·Cl− | F(000) = 488 |
Mr = 233.70 | Dx = 1.375 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3718 (3) Å | Cell parameters from 2394 reflections |
b = 18.5164 (7) Å | θ = 1–25° |
c = 8.9123 (1) Å | µ = 0.31 mm−1 |
β = 111.913 (1)° | T = 297 K |
V = 1128.63 (6) Å3 | Needle, dark-red |
Z = 4 | 0.60 × 0.20 × 0.20 mm |
Siemens SMART CCD diffractometer | 1982 independent reflections |
Radiation source: fine-focus sealed tube | 1476 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 25.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −8→8 |
Tmin = 0.835, Tmax = 0.940 | k = −22→10 |
3608 measured reflections | l = −10→8 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0885P)2 + 0.0439P] where P = (Fo2 + 2Fc2)/3 |
1982 reflections | (Δ/σ)max < 0.001 |
166 parameters | Δρmax = 0.40 e Å−3 |
3 restraints | Δρmin = −0.32 e Å−3 |
C12H12N3+·Cl− | V = 1128.63 (6) Å3 |
Mr = 233.70 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.3718 (3) Å | µ = 0.31 mm−1 |
b = 18.5164 (7) Å | T = 297 K |
c = 8.9123 (1) Å | 0.60 × 0.20 × 0.20 mm |
β = 111.913 (1)° |
Siemens SMART CCD diffractometer | 1982 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 1476 reflections with I > 2σ(I) |
Tmin = 0.835, Tmax = 0.940 | Rint = 0.038 |
3608 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 3 restraints |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.40 e Å−3 |
1982 reflections | Δρmin = −0.32 e Å−3 |
166 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 | ||
Cl | 0.25125 (11) | 0.35094 (3) | 0.25208 (7) | 0.0583 (3) | |
N1 | −0.1796 (3) | 0.69262 (11) | 0.1163 (3) | 0.0450 (5) | |
H2 | −0.227 (4) | 0.6825 (15) | 0.013 (2) | 0.058 (9)* | |
H1 | −0.212 (4) | 0.7331 (11) | 0.151 (3) | 0.055 (8)* | |
N2 | 0.2890 (3) | 0.51264 (9) | 0.5880 (2) | 0.0367 (5) | |
N3 | 0.3509 (3) | 0.44960 (10) | 0.5676 (2) | 0.0363 (5) | |
H3 | 0.322 (4) | 0.4275 (13) | 0.474 (2) | 0.053 (8)* | |
C11 | −0.0719 (3) | 0.64667 (11) | 0.2278 (3) | 0.0357 (6) | |
C12 | −0.0222 (3) | 0.57759 (12) | 0.1830 (3) | 0.0384 (6) | |
H12 | −0.0707 | 0.5641 | 0.0747 | 0.041 (7)* | |
C13 | 0.0940 (3) | 0.53167 (12) | 0.2955 (3) | 0.0379 (6) | |
H13 | 0.1252 | 0.4870 | 0.2640 | 0.042 (6)* | |
C14 | 0.1692 (3) | 0.55117 (11) | 0.4622 (3) | 0.0344 (5) | |
C15 | 0.1147 (3) | 0.61907 (12) | 0.5067 (3) | 0.0394 (6) | |
H15 | 0.1603 | 0.6321 | 0.6153 | 0.041 (7)* | |
C16 | −0.0026 (3) | 0.66536 (12) | 0.3942 (3) | 0.0386 (6) | |
H16 | −0.0376 | 0.7093 | 0.4261 | 0.049 (7)* | |
C21 | 0.4736 (3) | 0.41061 (12) | 0.7048 (3) | 0.0348 (5) | |
C22 | 0.5158 (4) | 0.33944 (13) | 0.6843 (3) | 0.0435 (6) | |
H22 | 0.4691 | 0.3185 | 0.5821 | 0.038 (6)* | |
C23 | 0.6290 (4) | 0.29977 (14) | 0.8188 (3) | 0.0516 (7) | |
H23 | 0.6572 | 0.2517 | 0.8069 | 0.059 (8)* | |
C24 | 0.7000 (4) | 0.33110 (16) | 0.9698 (3) | 0.0555 (7) | |
H24 | 0.7746 | 0.3039 | 1.0594 | 0.078 (9)* | |
C25 | 0.6609 (4) | 0.40211 (16) | 0.9886 (3) | 0.0562 (7) | |
H25 | 0.7110 | 0.4232 | 1.0907 | 0.071 (9)* | |
C26 | 0.5472 (4) | 0.44282 (14) | 0.8565 (3) | 0.0466 (6) | |
H26 | 0.5206 | 0.4910 | 0.8692 | 0.055 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0853 (6) | 0.0381 (4) | 0.0381 (4) | 0.0054 (3) | 0.0076 (4) | −0.0031 (2) |
N1 | 0.0482 (13) | 0.0401 (12) | 0.0390 (14) | 0.0084 (10) | 0.0072 (10) | 0.0050 (9) |
N2 | 0.0323 (11) | 0.0327 (10) | 0.0384 (11) | −0.0019 (8) | 0.0055 (8) | 0.0013 (8) |
N3 | 0.0349 (11) | 0.0338 (10) | 0.0322 (11) | 0.0011 (8) | 0.0031 (9) | 0.0002 (8) |
C11 | 0.0320 (12) | 0.0340 (12) | 0.0394 (13) | −0.0021 (9) | 0.0114 (10) | 0.0038 (9) |
C12 | 0.0398 (13) | 0.0365 (12) | 0.0323 (13) | 0.0010 (10) | 0.0058 (10) | −0.0017 (9) |
C13 | 0.0391 (13) | 0.0321 (11) | 0.0381 (14) | 0.0004 (10) | 0.0096 (10) | −0.0011 (9) |
C14 | 0.0295 (12) | 0.0311 (11) | 0.0358 (13) | −0.0022 (9) | 0.0042 (9) | 0.0029 (9) |
C15 | 0.0442 (14) | 0.0361 (12) | 0.0321 (13) | −0.0038 (10) | 0.0078 (10) | −0.0032 (9) |
C16 | 0.0400 (13) | 0.0318 (11) | 0.0403 (14) | 0.0014 (10) | 0.0104 (11) | −0.0018 (9) |
C21 | 0.0259 (11) | 0.0374 (12) | 0.0351 (13) | 0.0019 (9) | 0.0046 (9) | 0.0044 (9) |
C22 | 0.0391 (13) | 0.0411 (13) | 0.0417 (15) | 0.0018 (10) | 0.0051 (11) | −0.0003 (10) |
C23 | 0.0452 (15) | 0.0427 (14) | 0.0597 (18) | 0.0116 (12) | 0.0112 (12) | 0.0065 (12) |
C24 | 0.0503 (16) | 0.0612 (17) | 0.0478 (16) | 0.0202 (13) | 0.0100 (13) | 0.0194 (13) |
C25 | 0.0533 (17) | 0.0669 (18) | 0.0365 (15) | 0.0169 (14) | 0.0030 (12) | 0.0010 (12) |
C26 | 0.0459 (15) | 0.0473 (14) | 0.0378 (14) | 0.0121 (11) | 0.0056 (11) | −0.0001 (11) |
N1—C11 | 1.324 (3) | C15—C16 | 1.356 (3) |
N1—H2 | 0.878 (17) | C15—H15 | 0.9300 |
N1—H1 | 0.876 (17) | C16—H16 | 0.9300 |
N2—N3 | 1.291 (3) | C21—C22 | 1.382 (3) |
N2—C14 | 1.344 (3) | C21—C26 | 1.389 (3) |
N3—C21 | 1.418 (3) | C22—C23 | 1.388 (3) |
N3—H3 | 0.879 (16) | C22—H22 | 0.9300 |
C11—C16 | 1.420 (3) | C23—C24 | 1.377 (4) |
C11—C12 | 1.428 (3) | C23—H23 | 0.9300 |
C12—C13 | 1.350 (3) | C24—C25 | 1.370 (4) |
C12—H12 | 0.9300 | C24—H24 | 0.9300 |
C13—C14 | 1.425 (3) | C25—C26 | 1.386 (3) |
C13—H13 | 0.9300 | C25—H25 | 0.9300 |
C14—C15 | 1.421 (3) | C26—H26 | 0.9300 |
C11—N1—H2 | 123.0 (19) | C15—C16—C11 | 120.0 (2) |
C11—N1—H1 | 117.0 (18) | C15—C16—H16 | 120.0 |
H2—N1—H1 | 120 (3) | C11—C16—H16 | 120.0 |
N3—N2—C14 | 121.29 (19) | C22—C21—C26 | 120.8 (2) |
N2—N3—C21 | 118.97 (19) | C22—C21—N3 | 118.3 (2) |
N2—N3—H3 | 125.5 (17) | C26—C21—N3 | 120.8 (2) |
C21—N3—H3 | 115.6 (17) | C21—C22—C23 | 118.9 (2) |
N1—C11—C16 | 120.6 (2) | C21—C22—H22 | 120.6 |
N1—C11—C12 | 120.7 (2) | C23—C22—H22 | 120.6 |
C16—C11—C12 | 118.73 (19) | C24—C23—C22 | 120.5 (2) |
C13—C12—C11 | 121.0 (2) | C24—C23—H23 | 119.7 |
C13—C12—H12 | 119.5 | C22—C23—H23 | 119.7 |
C11—C12—H12 | 119.5 | C25—C24—C23 | 120.2 (2) |
C12—C13—C14 | 120.5 (2) | C25—C24—H24 | 119.9 |
C12—C13—H13 | 119.8 | C23—C24—H24 | 119.9 |
C14—C13—H13 | 119.8 | C24—C25—C26 | 120.4 (3) |
N2—C14—C15 | 113.79 (19) | C24—C25—H25 | 119.8 |
N2—C14—C13 | 127.9 (2) | C26—C25—H25 | 119.8 |
C15—C14—C13 | 118.3 (2) | C25—C26—C21 | 119.1 (2) |
C16—C15—C14 | 121.4 (2) | C25—C26—H26 | 120.5 |
C16—C15—H15 | 119.3 | C21—C26—H26 | 120.5 |
C14—C15—H15 | 119.3 | ||
N3—N2—C14—C13 | −0.2 (4) | C21—N3—N2—C14 | −178.7 (2) |
N2—N3—C21—C26 | −8.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cli | 0.88 (2) | 2.41 (2) | 3.273 (2) | 171 (2) |
N1—H2···Clii | 0.88 (2) | 2.38 (2) | 3.227 (2) | 162 (2) |
N3—H3···Cl | 0.88 (2) | 2.33 (2) | 3.200 (2) | 170 (2) |
C13—H13···Cl | 0.93 | 2.70 | 3.609 (2) | 166 |
C22—H22···Cl | 0.93 | 2.84 | 3.617 (3) | 142 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C12H12N3+·Cl− |
Mr | 233.70 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 297 |
a, b, c (Å) | 7.3718 (3), 18.5164 (7), 8.9123 (1) |
β (°) | 111.913 (1) |
V (Å3) | 1128.63 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.60 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.835, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3608, 1982, 1476 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.604 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.150, 1.05 |
No. of reflections | 1982 |
No. of parameters | 166 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.32 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and SADABS (Sheldrick, 2001), SHELXTL (Bruker, 2001), SHELXTL, DIAMOND (Brandenburg, 2000).
N1—C11 | 1.324 (3) | N2—C14 | 1.344 (3) |
N2—N3 | 1.291 (3) | N3—C21 | 1.418 (3) |
N3—N2—C14 | 121.29 (19) | N2—N3—C21 | 118.97 (19) |
N3—N2—C14—C13 | −0.2 (4) | C21—N3—N2—C14 | −178.7 (2) |
N2—N3—C21—C26 | −8.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cli | 0.876 (17) | 2.405 (18) | 3.273 (2) | 171 (2) |
N1—H2···Clii | 0.878 (17) | 2.379 (19) | 3.227 (2) | 162 (2) |
N3—H3···Cl | 0.879 (16) | 2.330 (17) | 3.200 (2) | 170 (2) |
C13—H13···Cl | 0.93 | 2.70 | 3.609 (2) | 165.8 |
C22—H22···Cl | 0.93 | 2.84 | 3.617 (3) | 141.8 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y+1, −z. |
Azo compounds have not only been used in many chemical syntheses but they also constitute an important class of organic dyes with a wide range of industrial applications. Yatsenko et al. (2000) have recently reported the crystal structure of title compound, (I), from powder diffraction data where a constrained model of the organic cation and an isotropic refinement of non-H atoms, except for the chloride ion, were applied during structure refinement. Here we present a redetermination of this structure using single-crystal data from a Siemens SMART CCD diffractometer.
The crystal structure of (I) is shown in Fig. 1 and selected geometrical parameters are given in Table 1. The N═N bond distance of 1.291 (3) Å is significantly larger than the corresponding distances of 1.2493 (13) Å for p-phenylazoanilinium oxalate, and 1.246 (5) and 1.243 (5) Å for p-phenylazoanilinium phenylphosphonate (Mahmoudkhani & Langer, 2001a,b). In these compounds, the amine groups are protonated rather than the azo group. Furthermore, there is a shortening of the N2—C14 and N1—C11 bonds to 1.344 (3) and 1.324 (3) Å, respectively, compared to the C—N(H3) distances of 1.4637 (12) and 1.458 (5) Å, and the (N═)N—-C distances of 1.4303 (14) and 1.427 (6) Å in the above-mentioned compounds. These differences can be attributed to a resonance hybrid of the organic cation, as shown in Scheme 2. The same feature has been reported by Moreiras et al. (1981). The structure exhibits both N—H···Cl and C—H···Cl hydrogen bonds. As shown in Fig. 2 (top), each organic cation is bonded to the chloride anions through hydrogen bonds via C13, C22 and N3. Each ion pair is then linked to another pair through the N1—H2···Cl hydrogen bond, thus forming a dimer. The dimers are connected to each other, in a zigzag fashion, via N1—H1···Cl hydrogen bonds to form sheets [see Fig. 2 (bottom)]. The sheets are stacked along the a axis (see Fig. 3), with chloride ions sandwiched between organic cations. The existence of C—H···Cl hydrogen bonds has recently been reviewed by Aakeröy et al. (1999), though they have not been invoked by Yatsenko et al. (2000).