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In the title compound, C13H15N2S+·I, the organic cation is almost planar and the N atoms have nearly trigonal-planar geometry. The crystal packing involves N—H...I hydrogen bonds, aromatic π–π stacking [centroid-to-centroid separation 3.631 (2) Å; symmetry code: -x+1,-y,-z+1], a C—H...π inter­action and a weak S...I inter­action [3.7645 (11) Å; symmetry code: -x+{1 \over 2},y-{1 \over 2},-z+{1 \over 2}].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038780/hb2497sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038780/hb2497Isup2.hkl
Contains datablock I

CCDC reference: 660282

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](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

Comment top

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 ππ 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].

Related literature top

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).

Experimental top

The title compound was prepared by the method of Boto et al. (2007). Red blocks of (I) were recrystallized from dry methanol/diethyl ether.

Refinement top

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).

Structure description top

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 ππ 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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms). The hydrogen bond is indicated as dashed line.
[Figure 2] Fig. 2. Fragment of (I) along the c diraction, showing that the I- ions are trapped within the [001] channels.
(E)-2-(2-Anilinovinyl)-3,4-dimethylthiazol-3-ium iodide top
Crystal data top
C13H15N2S+·IF(000) = 1408
Mr = 358.24Dx = 1.722 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C2ycCell parameters from 842 reflections
a = 15.830 (3) Åθ = 2.7–22.5°
b = 11.3918 (15) ŵ = 2.45 mm1
c = 16.787 (3) ÅT = 295 K
β = 114.118 (11)°Block, red
V = 2763.0 (8) Å30.21 × 0.18 × 0.11 mm
Z = 8
Data collection top
Bruker P4
diffractometer
2530 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.033
Graphite monochromatorθmax = 27.5°, θmin = 2.3°
ω scansh = 201
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
k = 141
Tmin = 0.602, Tmax = 0.760l = 2021
3886 measured reflections7 standard reflections every 99 reflections
3185 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H 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 parametersΔρmax = 0.98 e Å3
0 restraintsΔρmin = 0.88 e Å3
Crystal data top
C13H15N2S+·IV = 2763.0 (8) Å3
Mr = 358.24Z = 8
Monoclinic, C2/cMo Kα radiation
a = 15.830 (3) ŵ = 2.45 mm1
b = 11.3918 (15) ÅT = 295 K
c = 16.787 (3) Å0.21 × 0.18 × 0.11 mm
β = 114.118 (11)°
Data collection top
Bruker P4
diffractometer
2530 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
Rint = 0.033
Tmin = 0.602, Tmax = 0.7607 standard reflections every 99 reflections
3886 measured reflections intensity decay: none
3185 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.98 e Å3
3185 reflectionsΔρmin = 0.88 e Å3
160 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.910963 (14)0.004448 (18)0.580356 (13)0.04055 (9)
S10.60582 (5)0.30762 (7)0.23224 (5)0.03483 (17)
N20.75770 (15)0.2168 (2)0.24803 (14)0.0307 (5)
C80.7179 (2)0.1634 (3)0.36907 (18)0.0342 (6)
H80.77310.12200.39550.041*
C70.6589 (2)0.1649 (2)0.40926 (18)0.0333 (6)
H70.60230.20290.38190.040*
C110.6462 (2)0.3346 (3)0.15299 (18)0.0343 (6)
H110.61470.37970.10350.041*
N10.67922 (19)0.1137 (2)0.48681 (16)0.0366 (6)
C100.7276 (2)0.2835 (3)0.17069 (18)0.0329 (6)
C60.5398 (2)0.1630 (3)0.5086 (2)0.0418 (7)
H60.51720.20790.45790.050*
C90.70041 (19)0.2212 (2)0.28914 (18)0.0300 (6)
C20.6599 (2)0.0458 (3)0.61312 (19)0.0382 (7)
H20.71810.01120.63240.046*
C10.6249 (2)0.1085 (2)0.53502 (17)0.0318 (6)
C30.6082 (3)0.0355 (3)0.6613 (2)0.0441 (8)
H30.63150.00700.71320.053*
C50.4884 (2)0.1506 (3)0.5578 (2)0.0480 (8)
H50.43040.18570.53910.058*
C130.7850 (3)0.2912 (3)0.1196 (2)0.0480 (8)
H13A0.75520.34180.07030.072*
H13B0.79200.21430.09970.072*
H13C0.84480.32240.15580.072*
C40.5222 (2)0.0870 (3)0.6340 (2)0.0459 (8)
H40.48740.07880.66680.055*
C120.8446 (2)0.1497 (3)0.2817 (2)0.0431 (7)
H12A0.88730.18490.33490.065*
H12B0.87090.15010.23930.065*
H12C0.83230.07030.29290.065*
H1A0.730 (2)0.084 (3)0.508 (2)0.043 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.03565 (13)0.04473 (14)0.04291 (14)0.00040 (9)0.01772 (10)0.00322 (9)
S10.0328 (4)0.0414 (4)0.0344 (4)0.0038 (3)0.0180 (3)0.0021 (3)
N20.0331 (12)0.0329 (11)0.0295 (11)0.0014 (10)0.0162 (10)0.0025 (10)
C80.0366 (15)0.0361 (15)0.0294 (14)0.0005 (12)0.0131 (12)0.0009 (12)
C70.0375 (15)0.0322 (14)0.0294 (13)0.0008 (12)0.0131 (12)0.0004 (11)
C110.0396 (15)0.0382 (15)0.0270 (13)0.0002 (13)0.0156 (12)0.0014 (12)
N10.0366 (14)0.0436 (15)0.0316 (13)0.0041 (12)0.0159 (11)0.0082 (11)
C100.0392 (15)0.0350 (15)0.0295 (13)0.0013 (12)0.0190 (12)0.0021 (12)
C60.0433 (17)0.0486 (19)0.0360 (16)0.0078 (15)0.0188 (13)0.0118 (14)
C90.0325 (14)0.0299 (14)0.0304 (13)0.0036 (12)0.0157 (11)0.0032 (11)
C20.0413 (17)0.0407 (16)0.0338 (15)0.0073 (14)0.0165 (13)0.0076 (13)
C10.0377 (15)0.0317 (14)0.0290 (13)0.0028 (12)0.0166 (12)0.0007 (11)
C30.060 (2)0.0401 (16)0.0375 (16)0.0022 (16)0.0259 (16)0.0082 (14)
C50.0415 (18)0.062 (2)0.0450 (18)0.0098 (16)0.0221 (15)0.0058 (17)
C130.056 (2)0.057 (2)0.0435 (17)0.0092 (17)0.0337 (16)0.0060 (16)
C40.052 (2)0.053 (2)0.0429 (17)0.0006 (16)0.0297 (16)0.0013 (16)
C120.0392 (16)0.0488 (18)0.0427 (18)0.0097 (15)0.0182 (14)0.0037 (15)
Geometric parameters (Å, º) top
S1—C91.719 (3)C6—C51.384 (4)
S1—C111.722 (3)C6—H60.9300
N2—C91.346 (3)C2—C31.371 (5)
N2—C101.408 (3)C2—C11.393 (4)
N2—C121.470 (4)C2—H20.9300
C8—C71.358 (4)C3—C41.377 (5)
C8—C91.417 (4)C3—H30.9300
C8—H80.9300C5—C41.374 (5)
C7—N11.340 (4)C5—H50.9300
C7—H70.9300C13—H13A0.9600
C11—C101.333 (4)C13—H13B0.9600
C11—H110.9300C13—H13C0.9600
N1—C11.403 (4)C4—H40.9300
N1—H1A0.81 (3)C12—H12A0.9600
C10—C131.485 (4)C12—H12B0.9600
C6—C11.381 (4)C12—H12C0.9600
C9—S1—C1191.02 (14)C3—C2—H2120.2
C9—N2—C10114.0 (2)C1—C2—H2120.2
C9—N2—C12122.9 (2)C6—C1—C2119.6 (3)
C10—N2—C12123.1 (2)C6—C1—N1122.9 (3)
C7—C8—C9123.8 (3)C2—C1—N1117.5 (3)
C7—C8—H8118.1C2—C3—C4120.9 (3)
C9—C8—H8118.1C2—C3—H3119.6
N1—C7—C8122.5 (3)C4—C3—H3119.6
N1—C7—H7118.8C4—C5—C6120.6 (3)
C8—C7—H7118.8C4—C5—H5119.7
C10—C11—S1112.3 (2)C6—C5—H5119.7
C10—C11—H11123.8C10—C13—H13A109.5
S1—C11—H11123.8C10—C13—H13B109.5
C7—N1—C1128.2 (3)H13A—C13—H13B109.5
C7—N1—H1A114 (2)C10—C13—H13C109.5
C1—N1—H1A118 (2)H13A—C13—H13C109.5
C11—C10—N2111.9 (2)H13B—C13—H13C109.5
C11—C10—C13127.6 (3)C5—C4—C3119.4 (3)
N2—C10—C13120.5 (3)C5—C4—H4120.3
C1—C6—C5119.7 (3)C3—C4—H4120.3
C1—C6—H6120.1N2—C12—H12A109.5
C5—C6—H6120.1N2—C12—H12B109.5
N2—C9—C8123.8 (3)H12A—C12—H12B109.5
N2—C9—S1110.7 (2)N2—C12—H12C109.5
C8—C9—S1125.6 (2)H12A—C12—H12C109.5
C3—C2—C1119.7 (3)H12B—C12—H12C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···I10.81 (3)2.77 (3)3.573 (3)174 (3)
C12—H12A···Cgi0.962.76MissingMissing
Symmetry code: (i) x+3/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC13H15N2S+·I
Mr358.24
Crystal system, space groupMonoclinic, C2/c
Temperature (K)295
a, b, c (Å)15.830 (3), 11.3918 (15), 16.787 (3)
β (°) 114.118 (11)
V3)2763.0 (8)
Z8
Radiation typeMo Kα
µ (mm1)2.45
Crystal size (mm)0.21 × 0.18 × 0.11
Data collection
DiffractometerBruker P4
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.602, 0.760
No. of measured, independent and
observed [I > 2σ(I)] reflections
3886, 3185, 2530
Rint0.033
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.084, 1.03
No. of reflections3185
No. of parameters160
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.98, 0.88

Computer programs: XSCANS (Bruker, 1999), XSCANS, SHELXTL (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL, SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···I10.81 (3)2.77 (3)3.573 (3)174 (3)
C12—H12A···Cgi0.962.76MissingMissing
Symmetry code: (i) x+3/2, y+1/2, z+1.
 

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