2-Amino-4-(4-chloro-3-methyl­phen­yl)-5-propyl-1,3-thia­zolium iodide

In the crystal structure of the title compound, C₁₃H₁₆ClN₂S⁺·I⁻, the mol­ecule of 2-amino-4-(4-chloro-3-methyl­phen­yl)-5-propyl-1,3-thia­zole is protonated on the ring N atom. The angle between the planes formed by the 1,3-thia­zole and benzene rings is 39.3 (1)°, and this conformation is caused by the presence of the propyl group in position 5 of the heterocyclic ring. The packing in the crystal structure is mainly stabilized by ⁺NH...I⁻ and NH...I⁻ hydrogen bonds and stacking of 2-amino-4-(4-chloro-3-methyl­phen­yl)-5-propyl-1,3-thia­zolium cations.

Key indicators

• Single-crystal X-ray study
• T = 103 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.027
• wR factor = 0.072
• Data-to-parameter ratio = 93.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) .        100 Ang.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           52.30
           From the CIF: _reflns_number_total              16560
           Count of symmetry unique reflns         9541
           Completeness (_total/calc)            173.57%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      7019
           Fraction of Friedel pairs measured     0.736
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: HKL-2000 (Otwinowski & Minor, 1997); cell refinement: HKL-2000; data reduction: HKL-2000; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) and HKL-3000SM (Minor et al., 2006); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and HKL-3000SM; molecular graphics: HKL-3000SM, ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: HKL-3000SM.

2-Amino-4-(4-chloro-3-methylphenyl)-5-propyl-1,3-thiazolium iodide

Crystal data

C13H16ClN2S^+·I^−	F(000) = 776
Mr = 394.69	Dx = 1.736 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71074 Å
Hall symbol: P 2ac 2ab	Cell parameters from 107797 reflections
a = 7.761 (1) Å	θ = 2.3–52.3°
b = 9.659 (1) Å	µ = 2.42 mm^−1
c = 20.145 (1) Å	T = 103 K
V = 1510.1 (3) Å^3	Block, yellow
Z = 4	0.53 × 0.26 × 0.26 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	16521 independent reflections
Radiation source: fine-focus sealed tube	14434 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 10 pixels mm^-1	θmax = 52.3°, θmin = 2.3°
ω scans with χ offset	h = −16→16
Absorption correction: multi-scan (Otwinowski et al., 2003)	k = −21→21
Tmin = 0.47, Tmax = 0.53	l = −44→44
107797 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0474P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.072	(Δ/σ)max = 0.001
S = 1.01	Δρmax = 1.24 e Å^−3
16517 reflections	Δρmin = −0.98 e Å^−3
176 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0111 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 7019 Friedel pairs?
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.001 (6)

Special details

Experimental. NMR spectra were recorded using a Varian-300 spectrometer for ¹H (300 MHz) and ¹³C (75 MHz). Chemical shifts (δ) are given in p.p.m. downfield from tetramethylsilane as internal standard, and coupling constants (J values) are in hertz. Mass spectra data were collected on a Finnigan MAT LC—Q mass spectrometer system using electrospray ionization (ESI). Elemental analyses were performed by Atlantic Microlabs. Melting points were obtained using an electrothermal digital melting point apparatus and are uncorrected. All purifications by flash chromatography were performed using Geduran silica gel 60, 35–75µm (VWR).

For (1): ¹H NMR (CDCl₃) δ 2.28 (s, 3H), 7.33 (d, J = 8.1 Hz), 7.49 (d, J = 8.1 Hz), 7.57 (s, 1H), 9.81 (s, 1H).

For (2): ¹H NMR (CDCl₃) δ 0.88 (t, J = 7.2, 6.9 Hz, 3H), 1.28 - 1.40 (m, 2H), 1.65 - 1.94 (m, 3H), 2.37 (s, 3H), 4.58 - 4.63 (m, 1H), 7.08 - 7.15 (m, 1H), 7.16 - 7.33 (m, 2H).

For (3): ¹H NMR (CDCl₃) δ 0.88 (t, J = 7.2, 7.2 Hz, 3H), 1.26 - 1.39 (m, 2H), 1.57 - 1.67 (m, 2H), 2.32 (s, 3H), 2.83 (t, J = 6.9, 7.8 Hz, 2H), 7.29 (d, J = 8.1 Hz, 1H), 7.61 (d, J = 8.1 Hz, 1H), 7.73 (s, 1H); ¹³C NMR (CDCl₃) δ 13.94, 20.03, 22.45, 26.37, 38.23, 126.77, 129.16, 130.40, 135.44, 136.36, 139.28, 199.27; APCI m/z 211 [M+H]⁺.

For (I): ¹H NMR (DMSO-d₆) δ 0.86 (t, J = 7.5, 7.2 Hz, 3H), 1.48 - 1.60 (m, 2H), 2.39 (s, 3H), 2.62 (t, J = 7.5, 7.5 Hz, 2H), 7.34 (dd, J = 2.1, 2.1 Hz, 1H), 7.49 (d, J = 1.8 Hz, 1H), 7.57 (d, J = 8.4 Hz, 1H), 8.80 (br s, 2H); APCI m/z 395 [M+H]⁺; Anal. Calcd. for C₁₃H₁₆ClIN₂S: C, 39.56; H, 4.09; N, 7.10. Found: C, 39.64; H, 4.14; N, 7.06.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
I1	0.435396 (9)	0.147814 (6)	0.129970 (3)	0.02266 (2)
S1	0.66083 (3)	0.59544 (2)	0.176000 (11)	0.02010 (4)
Cl1	0.68767 (4)	0.90064 (3)	−0.220879 (12)	0.02924 (5)
C7	0.61921 (12)	0.66781 (9)	−0.05937 (4)	0.01859 (11)
H7	0.5837	0.5784	−0.0490	0.022*
N1	0.60319 (11)	0.81119 (8)	0.10852 (3)	0.01909 (11)
C5	0.69493 (12)	0.58856 (9)	0.08993 (4)	0.01833 (11)
C6	0.66899 (11)	0.75651 (9)	−0.00818 (4)	0.01716 (10)
C4	0.65752 (11)	0.71285 (8)	0.06174 (4)	0.01732 (11)
C9	0.68185 (12)	0.84269 (10)	−0.13947 (4)	0.02040 (12)
C12	0.75770 (13)	0.45677 (9)	0.05918 (5)	0.02171 (13)
H12A	0.8290	0.4793	0.0211	0.026*
H12B	0.6592	0.4047	0.0432	0.026*
C2	0.59492 (12)	0.76502 (9)	0.17101 (4)	0.01943 (12)
N2	0.54162 (15)	0.84122 (9)	0.22153 (4)	0.02564 (15)
C8	0.62112 (12)	0.70931 (9)	−0.12589 (4)	0.01944 (11)
C13	0.86102 (13)	0.36576 (10)	0.10630 (5)	0.02203 (13)
H13A	0.7871	0.3348	0.1422	0.026*
H13B	0.9540	0.4196	0.1255	0.026*
C15	0.55685 (17)	0.61508 (12)	−0.17990 (5)	0.02696 (17)
H15A	0.5209	0.5287	−0.1609	0.040*	0.50
H15B	0.6476	0.5987	−0.2113	0.040*	0.50
H15C	0.4610	0.6577	−0.2020	0.040*	0.50
H15D	0.5655	0.6614	−0.2219	0.040*	0.50
H15E	0.4387	0.5914	−0.1715	0.040*	0.50
H15F	0.6253	0.5323	−0.1808	0.040*	0.50
C11	0.72521 (12)	0.89064 (9)	−0.02353 (4)	0.01973 (12)
H11	0.7564	0.9511	0.0103	0.024*
C14	0.9360 (2)	0.24007 (13)	0.07063 (7)	0.0350 (2)
H14A	1.0002	0.1849	0.1016	0.052*	0.50
H14B	1.0108	0.2705	0.0356	0.052*	0.50
H14C	0.8440	0.1857	0.0522	0.052*	0.50
H14D	0.9032	0.2425	0.0247	0.052*	0.50
H14E	0.8925	0.1569	0.0907	0.052*	0.50
H14F	1.0593	0.2417	0.0741	0.052*	0.50
C10	0.73433 (13)	0.93341 (10)	−0.08942 (5)	0.02122 (13)
H10	0.7749	1.0213	−0.1000	0.025*
H1	0.560 (2)	0.888 (2)	0.0987 (9)	0.022 (4)*
H2	0.509 (3)	0.917 (2)	0.2157 (9)	0.025 (4)*
H3	0.563 (2)	0.815 (3)	0.2619 (10)	0.034 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.02939 (3)	0.01897 (2)	0.01962 (2)	−0.00002 (2)	−0.00221 (2)	−0.00087 (2)
S1	0.02722 (9)	0.01763 (7)	0.01543 (6)	0.00181 (7)	0.00103 (6)	0.00167 (5)
Cl1	0.03470 (12)	0.03387 (12)	0.01915 (7)	0.00243 (10)	0.00104 (8)	0.00982 (8)
C7	0.0230 (3)	0.0174 (3)	0.0154 (2)	−0.0003 (2)	0.0000 (2)	0.00054 (18)
N1	0.0260 (3)	0.0161 (2)	0.0152 (2)	0.0017 (2)	0.0016 (2)	0.00017 (17)
C5	0.0232 (3)	0.0159 (2)	0.0159 (2)	0.0005 (2)	0.0009 (2)	0.00060 (18)
C6	0.0198 (3)	0.0164 (2)	0.0153 (2)	0.0002 (2)	0.0003 (2)	0.00057 (18)
C4	0.0215 (3)	0.0158 (2)	0.0146 (2)	0.0004 (2)	0.0008 (2)	−0.00011 (18)
C9	0.0218 (3)	0.0222 (3)	0.0173 (2)	0.0033 (3)	0.0011 (2)	0.0044 (2)
C12	0.0279 (4)	0.0175 (3)	0.0198 (3)	0.0034 (3)	−0.0001 (3)	−0.0010 (2)
C2	0.0261 (4)	0.0176 (3)	0.0146 (2)	0.0004 (2)	0.0006 (2)	0.00009 (19)
N2	0.0404 (4)	0.0202 (3)	0.0164 (2)	0.0038 (3)	0.0039 (2)	−0.0012 (2)
C8	0.0229 (3)	0.0203 (3)	0.0151 (2)	0.0027 (2)	−0.0002 (2)	−0.0001 (2)
C13	0.0236 (3)	0.0178 (3)	0.0248 (3)	0.0013 (2)	−0.0005 (3)	0.0013 (2)
C15	0.0350 (5)	0.0273 (4)	0.0186 (3)	0.0033 (4)	−0.0041 (3)	−0.0035 (3)
C11	0.0226 (3)	0.0173 (3)	0.0193 (3)	−0.0008 (2)	−0.0001 (2)	0.0012 (2)
C14	0.0429 (6)	0.0236 (4)	0.0385 (6)	0.0130 (5)	−0.0009 (5)	−0.0018 (4)
C10	0.0236 (3)	0.0191 (3)	0.0209 (3)	−0.0006 (3)	0.0008 (2)	0.0047 (2)

Geometric parameters (Å, º)

S1—C2	1.719 (1)	N2—H3	0.87 (2)
S1—C5	1.755 (1)	C8—C15	1.5037 (13)
Cl1—C9	1.733 (1)	C13—C14	1.5260 (15)
C7—C6	1.395 (1)	C13—H13A	0.9700
C7—C8	1.399 (1)	C13—H13B	0.9700
C7—H7	0.9300	C15—H15A	0.9600
N1—C2	1.337 (1)	C15—H15B	0.9600
N1—C4	1.403 (1)	C15—H15C	0.9600
N1—H1	0.835 (19)	C15—H15D	0.9600
C5—C4	1.359 (1)	C15—H15E	0.9600
C5—C12	1.4971 (12)	C15—H15F	0.9600
C6—C11	1.4016 (12)	C11—C10	1.3919 (12)
C6—C4	1.473 (1)	C11—H11	0.9300
C9—C10	1.3965 (14)	C14—H14A	0.9600
C9—C8	1.3989 (13)	C14—H14B	0.9600
C12—C13	1.5222 (13)	C14—H14C	0.9600
C12—H12A	0.9700	C14—H14D	0.9600
C12—H12B	0.9700	C14—H14E	0.9600
C2—N2	1.322 (1)	C14—H14F	0.9600
N2—H2	0.78 (2)	C10—H10	0.9300
C2—S1—C5	91.33 (4)	H15A—C15—H15C	109.5
C6—C7—C8	121.95 (8)	H15B—C15—H15C	109.5
C6—C7—H7	119.0	C8—C15—H15D	109.5
C8—C7—H7	119.0	H15A—C15—H15D	141.1
C2—N1—C4	114.90 (7)	H15B—C15—H15D	56.3
C2—N1—H1	119.9 (12)	H15C—C15—H15D	56.3
C4—N1—H1	124.1 (12)	C8—C15—H15E	109.5
C4—C5—C12	130.36 (7)	H15A—C15—H15E	56.3
C4—C5—S1	110.30 (6)	H15B—C15—H15E	141.1
C12—C5—S1	119.34 (6)	H15C—C15—H15E	56.3
C7—C6—C11	119.39 (7)	H15D—C15—H15E	109.5
C7—C6—C4	120.94 (7)	C8—C15—H15F	109.5
C11—C6—C4	119.63 (7)	H15A—C15—H15F	56.3
C5—C4—N1	112.43 (7)	H15B—C15—H15F	56.3
C5—C4—C6	129.74 (7)	H15C—C15—H15F	141.1
N1—C4—C6	117.82 (7)	H15D—C15—H15F	109.5
C10—C9—C8	122.34 (7)	H15E—C15—H15F	109.5
C10—C9—Cl1	118.22 (7)	C10—C11—C6	120.04 (8)
C8—C9—Cl1	119.42 (7)	C10—C11—H11	120.0
C5—C12—C13	113.85 (8)	C6—C11—H11	120.0
C5—C12—H12A	108.8	C13—C14—H14A	109.5
C13—C12—H12A	108.8	C13—C14—H14B	109.5
C5—C12—H12B	108.8	H14A—C14—H14B	109.5
C13—C12—H12B	108.8	C13—C14—H14C	109.5
H12A—C12—H12B	107.7	H14A—C14—H14C	109.5
N2—C2—N1	123.64 (8)	H14B—C14—H14C	109.5
N2—C2—S1	125.34 (7)	C13—C14—H14D	109.5
N1—C2—S1	111.02 (6)	H14A—C14—H14D	141.1
C2—N2—H2	120.3 (14)	H14B—C14—H14D	56.3
C2—N2—H3	119.9 (16)	H14C—C14—H14D	56.3
H2—N2—H3	118 (2)	C13—C14—H14E	109.5
C9—C8—C7	117.06 (8)	H14A—C14—H14E	56.3
C9—C8—C15	121.85 (8)	H14B—C14—H14E	141.1
C7—C8—C15	121.08 (9)	H14C—C14—H14E	56.3
C12—C13—C14	111.50 (9)	H14D—C14—H14E	109.5
C12—C13—H13A	109.3	C13—C14—H14F	109.5
C14—C13—H13A	109.3	H14A—C14—H14F	56.3
C12—C13—H13B	109.3	H14B—C14—H14F	56.3
C14—C13—H13B	109.3	H14C—C14—H14F	141.1
H13A—C13—H13B	108.0	H14D—C14—H14F	109.5
C8—C15—H15A	109.5	H14E—C14—H14F	109.5
C8—C15—H15B	109.5	C11—C10—C9	119.17 (8)
H15A—C15—H15B	109.5	C11—C10—H10	120.4
C8—C15—H15C	109.5	C9—C10—H10	120.4
C2—S1—C5—C4	0.65 (8)	C4—N1—C2—N2	−177.89 (10)
C2—S1—C5—C12	−179.66 (8)	C4—N1—C2—S1	1.71 (11)
C8—C7—C6—C11	−0.98 (14)	C5—S1—C2—N2	178.26 (10)
C8—C7—C6—C4	176.87 (8)	C5—S1—C2—N1	−1.33 (8)
C12—C5—C4—N1	−179.48 (10)	C10—C9—C8—C7	−1.75 (13)
S1—C5—C4—N1	0.16 (10)	Cl1—C9—C8—C7	179.99 (7)
C12—C5—C4—C6	−0.64 (17)	C10—C9—C8—C15	176.96 (10)
S1—C5—C4—C6	179.01 (8)	Cl1—C9—C8—C15	−1.30 (12)
C2—N1—C4—C5	−1.23 (12)	C6—C7—C8—C9	2.45 (14)
C2—N1—C4—C6	179.78 (8)	C6—C7—C8—C15	−176.26 (9)
C7—C6—C4—C5	40.3 (1)	C5—C12—C13—C14	−174.56 (10)
C11—C6—C4—C5	−141.9 (1)	C7—C6—C11—C10	−1.29 (14)
C7—C6—C4—N1	−141.0 (1)	C4—C6—C11—C10	−179.17 (8)
C11—C6—C4—N1	36.9 (1)	C6—C11—C10—C9	1.97 (14)
C4—C5—C12—C13	153.03 (10)	C8—C9—C10—C11	−0.43 (14)
S1—C5—C12—C13	−26.59 (12)	Cl1—C9—C10—C11	177.85 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···I1^i	0.84 (2)	2.77 (2)	3.529 (1)	153 (2)
N2—H2···I1^i	0.78 (2)	2.88 (2)	3.585 (1)	152 (2)
N2—H3···I1^ii	0.87 (2)	2.71 (2)	3.531 (1)	158 (2)

Symmetry codes: (i) x, y+1, z; (ii) −x+1, y+1/2, −z+1/2.