Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038780/hb2497sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038780/hb2497Isup2.hkl |
CCDC reference: 660282
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C)= 0.005 Å
- R factor = 0.031
- wR factor = 0.084
- Data-to-parameter ratio = 19.9
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
The title compound was synthesized by a literature method (Huang et al., 1996; Li & Peng, 1995; Boto et al., 2007). For structural analogues, see: Sax et al. (1974); Kluger et al. (1987).
The title compound was prepared by the method of Boto et al. (2007). Red blocks of (I) were recrystallized from dry methanol/diethyl ether.
The H atoms were located in a difference map but those attached to C atoms were repositioned geometrically. Their positions were refined, initially with restraints, and then as riding, resulting in C—H distances in the range 0.93–1.00 Å and N—H = 0.81–0.84 Å).
As part of our studies of cyanine related dyes, the title compound, (I), (Fig. 1) was obtained as the product of reaction of 2,3,4-trimethyl-thiazol-3-ium iodide, aniline and triethyl orthoformiate. The atoms of the organic molecule (except H12A–H12C/H13A–H13C) are nearly coplanar with the largest deviation of 0.0846 Å for N2. The sum of the bond angles of the quaternary N2 atom is 360.0°. The N1—C7 bond distance of 1.340 (4) Å is indicative of strong π-conjugation.
The crystal packing (Fig. 2) features a π–π stacking interaction with a centroid separation Cg···Cgi (i = 1 - x, -y, 1 - z) = 3.631 (2) Å and a C—H···π interaction with H12A···Cg (ii = 3/2 - x, 1/2 - y, 1 - z) = 2.76 Å (Cg is the ring centroid defined by atoms C1–C6) generate a supramolecular framework with [001] channels.
The I- counter ions are fixed in these channels by means of an N—H···I hydrogen bond (Table 1) and weak S···I interactions [S1···I1iii (iii = 1/2 - x, -1/2 + y, 1/2 - z) = 3.7645 (11) Å].
The title compound was synthesized by a literature method (Huang et al., 1996; Li & Peng, 1995; Boto et al., 2007). For structural analogues, see: Sax et al. (1974); Kluger et al. (1987).
Data collection: XSCANS (Bruker, 1999); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97.
C13H15N2S+·I− | F(000) = 1408 |
Mr = 358.24 | Dx = 1.722 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C2yc | Cell parameters from 842 reflections |
a = 15.830 (3) Å | θ = 2.7–22.5° |
b = 11.3918 (15) Å | µ = 2.45 mm−1 |
c = 16.787 (3) Å | T = 295 K |
β = 114.118 (11)° | Block, red |
V = 2763.0 (8) Å3 | 0.21 × 0.18 × 0.11 mm |
Z = 8 |
Bruker P4 diffractometer | 2530 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 27.5°, θmin = 2.3° |
ω scans | h = −20→1 |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | k = −14→1 |
Tmin = 0.602, Tmax = 0.760 | l = −20→21 |
3886 measured reflections | 7 standard reflections every 99 reflections |
3185 independent reflections | intensity decay: none |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0384P)2 + 2.2252P] where P = (Fo2 + 2Fc2)/3 |
3185 reflections | (Δ/σ)max = 0.001 |
160 parameters | Δρmax = 0.98 e Å−3 |
0 restraints | Δρmin = −0.88 e Å−3 |
C13H15N2S+·I− | V = 2763.0 (8) Å3 |
Mr = 358.24 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.830 (3) Å | µ = 2.45 mm−1 |
b = 11.3918 (15) Å | T = 295 K |
c = 16.787 (3) Å | 0.21 × 0.18 × 0.11 mm |
β = 114.118 (11)° |
Bruker P4 diffractometer | 2530 reflections with I > 2σ(I) |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | Rint = 0.033 |
Tmin = 0.602, Tmax = 0.760 | 7 standard reflections every 99 reflections |
3886 measured reflections | intensity decay: none |
3185 independent reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.98 e Å−3 |
3185 reflections | Δρmin = −0.88 e Å−3 |
160 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 | 0.910963 (14) | 0.004448 (18) | 0.580356 (13) | 0.04055 (9) | |
S1 | 0.60582 (5) | 0.30762 (7) | 0.23224 (5) | 0.03483 (17) | |
N2 | 0.75770 (15) | 0.2168 (2) | 0.24803 (14) | 0.0307 (5) | |
C8 | 0.7179 (2) | 0.1634 (3) | 0.36907 (18) | 0.0342 (6) | |
H8 | 0.7731 | 0.1220 | 0.3955 | 0.041* | |
C7 | 0.6589 (2) | 0.1649 (2) | 0.40926 (18) | 0.0333 (6) | |
H7 | 0.6023 | 0.2029 | 0.3819 | 0.040* | |
C11 | 0.6462 (2) | 0.3346 (3) | 0.15299 (18) | 0.0343 (6) | |
H11 | 0.6147 | 0.3797 | 0.1035 | 0.041* | |
N1 | 0.67922 (19) | 0.1137 (2) | 0.48681 (16) | 0.0366 (6) | |
C10 | 0.7276 (2) | 0.2835 (3) | 0.17069 (18) | 0.0329 (6) | |
C6 | 0.5398 (2) | 0.1630 (3) | 0.5086 (2) | 0.0418 (7) | |
H6 | 0.5172 | 0.2079 | 0.4579 | 0.050* | |
C9 | 0.70041 (19) | 0.2212 (2) | 0.28914 (18) | 0.0300 (6) | |
C2 | 0.6599 (2) | 0.0458 (3) | 0.61312 (19) | 0.0382 (7) | |
H2 | 0.7181 | 0.0112 | 0.6324 | 0.046* | |
C1 | 0.6249 (2) | 0.1085 (2) | 0.53502 (17) | 0.0318 (6) | |
C3 | 0.6082 (3) | 0.0355 (3) | 0.6613 (2) | 0.0441 (8) | |
H3 | 0.6315 | −0.0070 | 0.7132 | 0.053* | |
C5 | 0.4884 (2) | 0.1506 (3) | 0.5578 (2) | 0.0480 (8) | |
H5 | 0.4304 | 0.1857 | 0.5391 | 0.058* | |
C13 | 0.7850 (3) | 0.2912 (3) | 0.1196 (2) | 0.0480 (8) | |
H13A | 0.7552 | 0.3418 | 0.0703 | 0.072* | |
H13B | 0.7920 | 0.2143 | 0.0997 | 0.072* | |
H13C | 0.8448 | 0.3224 | 0.1558 | 0.072* | |
C4 | 0.5222 (2) | 0.0870 (3) | 0.6340 (2) | 0.0459 (8) | |
H4 | 0.4874 | 0.0788 | 0.6668 | 0.055* | |
C12 | 0.8446 (2) | 0.1497 (3) | 0.2817 (2) | 0.0431 (7) | |
H12A | 0.8873 | 0.1849 | 0.3349 | 0.065* | |
H12B | 0.8709 | 0.1501 | 0.2393 | 0.065* | |
H12C | 0.8323 | 0.0703 | 0.2929 | 0.065* | |
H1A | 0.730 (2) | 0.084 (3) | 0.508 (2) | 0.043 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.03565 (13) | 0.04473 (14) | 0.04291 (14) | −0.00040 (9) | 0.01772 (10) | −0.00322 (9) |
S1 | 0.0328 (4) | 0.0414 (4) | 0.0344 (4) | 0.0038 (3) | 0.0180 (3) | 0.0021 (3) |
N2 | 0.0331 (12) | 0.0329 (11) | 0.0295 (11) | 0.0014 (10) | 0.0162 (10) | −0.0025 (10) |
C8 | 0.0366 (15) | 0.0361 (15) | 0.0294 (14) | 0.0005 (12) | 0.0131 (12) | 0.0009 (12) |
C7 | 0.0375 (15) | 0.0322 (14) | 0.0294 (13) | −0.0008 (12) | 0.0131 (12) | 0.0004 (11) |
C11 | 0.0396 (15) | 0.0382 (15) | 0.0270 (13) | 0.0002 (13) | 0.0156 (12) | 0.0014 (12) |
N1 | 0.0366 (14) | 0.0436 (15) | 0.0316 (13) | 0.0041 (12) | 0.0159 (11) | 0.0082 (11) |
C10 | 0.0392 (15) | 0.0350 (15) | 0.0295 (13) | −0.0013 (12) | 0.0190 (12) | −0.0021 (12) |
C6 | 0.0433 (17) | 0.0486 (19) | 0.0360 (16) | 0.0078 (15) | 0.0188 (13) | 0.0118 (14) |
C9 | 0.0325 (14) | 0.0299 (14) | 0.0304 (13) | −0.0036 (12) | 0.0157 (11) | −0.0032 (11) |
C2 | 0.0413 (17) | 0.0407 (16) | 0.0338 (15) | 0.0073 (14) | 0.0165 (13) | 0.0076 (13) |
C1 | 0.0377 (15) | 0.0317 (14) | 0.0290 (13) | −0.0028 (12) | 0.0166 (12) | 0.0007 (11) |
C3 | 0.060 (2) | 0.0401 (16) | 0.0375 (16) | 0.0022 (16) | 0.0259 (16) | 0.0082 (14) |
C5 | 0.0415 (18) | 0.062 (2) | 0.0450 (18) | 0.0098 (16) | 0.0221 (15) | 0.0058 (17) |
C13 | 0.056 (2) | 0.057 (2) | 0.0435 (17) | 0.0092 (17) | 0.0337 (16) | 0.0060 (16) |
C4 | 0.052 (2) | 0.053 (2) | 0.0429 (17) | −0.0006 (16) | 0.0297 (16) | 0.0013 (16) |
C12 | 0.0392 (16) | 0.0488 (18) | 0.0427 (18) | 0.0097 (15) | 0.0182 (14) | 0.0037 (15) |
S1—C9 | 1.719 (3) | C6—C5 | 1.384 (4) |
S1—C11 | 1.722 (3) | C6—H6 | 0.9300 |
N2—C9 | 1.346 (3) | C2—C3 | 1.371 (5) |
N2—C10 | 1.408 (3) | C2—C1 | 1.393 (4) |
N2—C12 | 1.470 (4) | C2—H2 | 0.9300 |
C8—C7 | 1.358 (4) | C3—C4 | 1.377 (5) |
C8—C9 | 1.417 (4) | C3—H3 | 0.9300 |
C8—H8 | 0.9300 | C5—C4 | 1.374 (5) |
C7—N1 | 1.340 (4) | C5—H5 | 0.9300 |
C7—H7 | 0.9300 | C13—H13A | 0.9600 |
C11—C10 | 1.333 (4) | C13—H13B | 0.9600 |
C11—H11 | 0.9300 | C13—H13C | 0.9600 |
N1—C1 | 1.403 (4) | C4—H4 | 0.9300 |
N1—H1A | 0.81 (3) | C12—H12A | 0.9600 |
C10—C13 | 1.485 (4) | C12—H12B | 0.9600 |
C6—C1 | 1.381 (4) | C12—H12C | 0.9600 |
C9—S1—C11 | 91.02 (14) | C3—C2—H2 | 120.2 |
C9—N2—C10 | 114.0 (2) | C1—C2—H2 | 120.2 |
C9—N2—C12 | 122.9 (2) | C6—C1—C2 | 119.6 (3) |
C10—N2—C12 | 123.1 (2) | C6—C1—N1 | 122.9 (3) |
C7—C8—C9 | 123.8 (3) | C2—C1—N1 | 117.5 (3) |
C7—C8—H8 | 118.1 | C2—C3—C4 | 120.9 (3) |
C9—C8—H8 | 118.1 | C2—C3—H3 | 119.6 |
N1—C7—C8 | 122.5 (3) | C4—C3—H3 | 119.6 |
N1—C7—H7 | 118.8 | C4—C5—C6 | 120.6 (3) |
C8—C7—H7 | 118.8 | C4—C5—H5 | 119.7 |
C10—C11—S1 | 112.3 (2) | C6—C5—H5 | 119.7 |
C10—C11—H11 | 123.8 | C10—C13—H13A | 109.5 |
S1—C11—H11 | 123.8 | C10—C13—H13B | 109.5 |
C7—N1—C1 | 128.2 (3) | H13A—C13—H13B | 109.5 |
C7—N1—H1A | 114 (2) | C10—C13—H13C | 109.5 |
C1—N1—H1A | 118 (2) | H13A—C13—H13C | 109.5 |
C11—C10—N2 | 111.9 (2) | H13B—C13—H13C | 109.5 |
C11—C10—C13 | 127.6 (3) | C5—C4—C3 | 119.4 (3) |
N2—C10—C13 | 120.5 (3) | C5—C4—H4 | 120.3 |
C1—C6—C5 | 119.7 (3) | C3—C4—H4 | 120.3 |
C1—C6—H6 | 120.1 | N2—C12—H12A | 109.5 |
C5—C6—H6 | 120.1 | N2—C12—H12B | 109.5 |
N2—C9—C8 | 123.8 (3) | H12A—C12—H12B | 109.5 |
N2—C9—S1 | 110.7 (2) | N2—C12—H12C | 109.5 |
C8—C9—S1 | 125.6 (2) | H12A—C12—H12C | 109.5 |
C3—C2—C1 | 119.7 (3) | H12B—C12—H12C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I1 | 0.81 (3) | 2.77 (3) | 3.573 (3) | 174 (3) |
C12—H12A···Cgi | 0.96 | 2.76 | Missing | Missing |
Symmetry code: (i) −x+3/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C13H15N2S+·I− |
Mr | 358.24 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 15.830 (3), 11.3918 (15), 16.787 (3) |
β (°) | 114.118 (11) |
V (Å3) | 2763.0 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.45 |
Crystal size (mm) | 0.21 × 0.18 × 0.11 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.602, 0.760 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3886, 3185, 2530 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.084, 1.03 |
No. of reflections | 3185 |
No. of parameters | 160 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.98, −0.88 |
Computer programs: XSCANS (Bruker, 1999), XSCANS, SHELXTL (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL, SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I1 | 0.81 (3) | 2.77 (3) | 3.573 (3) | 174 (3) |
C12—H12A···Cgi | 0.96 | 2.76 | Missing | Missing |
Symmetry code: (i) −x+3/2, −y+1/2, −z+1. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
As part of our studies of cyanine related dyes, the title compound, (I), (Fig. 1) was obtained as the product of reaction of 2,3,4-trimethyl-thiazol-3-ium iodide, aniline and triethyl orthoformiate. The atoms of the organic molecule (except H12A–H12C/H13A–H13C) are nearly coplanar with the largest deviation of 0.0846 Å for N2. The sum of the bond angles of the quaternary N2 atom is 360.0°. The N1—C7 bond distance of 1.340 (4) Å is indicative of strong π-conjugation.
The crystal packing (Fig. 2) features a π–π stacking interaction with a centroid separation Cg···Cgi (i = 1 - x, -y, 1 - z) = 3.631 (2) Å and a C—H···π interaction with H12A···Cg (ii = 3/2 - x, 1/2 - y, 1 - z) = 2.76 Å (Cg is the ring centroid defined by atoms C1–C6) generate a supramolecular framework with [001] channels.
The I- counter ions are fixed in these channels by means of an N—H···I hydrogen bond (Table 1) and weak S···I interactions [S1···I1iii (iii = 1/2 - x, -1/2 + y, 1/2 - z) = 3.7645 (11) Å].