N-Methyl-4-(4-nitro­phen­yl)-N-nitroso-1,3-thia­zol-2-amine

Jezuita, A.; Spaleniak, G.; Ejsmont, K.; Zaleski, J.; Zarychta, B.

doi:10.1107/S241431461701121X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 8| August 2017| x171121

https://doi.org/10.1107/S241431461701121X

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N-Methyl-4-(4-nitrophenyl)-N-nitroso-1,3-thiazol-2-amine

Anna Jezuita,^a Grzegorz Spaleniak,^a Krzysztof Ejsmont,^a Jacek Zaleski ^a and Bartosz Zarychta ^a ^*

^aFaculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
^*Correspondence e-mail: bzarychta@uni.opole.pl

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 27 July 2017; accepted 30 July 2017; online 8 August 2017)

The title compound, C₁₀H₈N₄O₃S, is almost planar [dihedral angle between the rings = 2.2 (2)°; r.m.s. deviation for the non-H atoms = 0.050 Å]. In the crystal, C—H⋯O and C—H⋯N hydrogen bonds link the molecules into (10-2) layers.

Keywords: crystal structure; thiazole; N-nitrosamines.

CCDC reference: 1565676

Structure description

The chemistry of N-nitrosamines is a subject of considerable interest with regard to their strong carcinogenic and mutagenic properties (Szyrszyng et al., 2001 ; Loeppky & Outram, 1994 ; Loeppky et al., 1987 ). As part of our studies in this area, the synthesis and crystal structure of the title compound are now reported.

There is one independent molecule in the asymmetric unit of the title compound (Fig. 1). The molecule is nearly planar: dihedral angle between the rings = 2.2 (2)°; r.m.s. deviation for the 18 non-hydrogen atoms = 0.050 Å.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

The crystal structure features four weak hydrogen bonds (Table 1, Fig. 2), which link the molecules into (10 $[\overline{2}]$ ) layers. The layers interact only by weak van der Waals interactions.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.66	3.182 (6)	117
C2—H2⋯N3ⁱ	0.93	2.48	3.280 (6)	144
C4—H4A⋯O2ⁱⁱ	0.96	2.60	3.525 (5)	163
C4—H4B⋯O3ⁱⁱⁱ	0.96	2.52	3.065 (6)	116
Symmetry codes: (i) $[x-1, -y+2, z-{\script{1\over 2}}]$ ; (ii) $[x+1, -y+1, z+{\script{1\over 2}}]$ ; (iii) x+2, y, z+1.

Figure 2
The crystal packing of the title compound, viewed along the b-axis direction.

Synthesis and crystallization

N-methyl-4-(4-nitrophenyl)1,3-thiazol-2-amine (2.0 g, 0.08 mol) was suspended in acetic acid (30 ml). Then, sodium nitrate was added dropwise (0.7 g). After 30 min. the crude yellow precipitate was separated and recrystallized from a solvent mixture of dichloromethane and petrol to yield irregular yellow crystals (0.95 g; melting point = 160–161°C).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₈N₄O₃S
M_r	264.26
Crystal system, space group	Monoclinic, Pc
Temperature (K)	85
a, b, c (Å)	4.7729 (3), 13.7362 (8), 8.5391 (4)
β (°)	96.576 (5)
V (Å³)	556.15 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.30
Crystal size (mm)	0.28 × 0.17 × 0.15

Data collection
Diffractometer	Oxford Diffraction Xcalibur
No. of measured, independent and observed [I > 2σ(I)] reflections	2950, 1557, 1320
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.092, 1.01
No. of reflections	1557
No. of parameters	164
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.36
Computer programs: CrysAlis CCD (Oxford Diffraction Ltd, 2008 $[Oxford Diffraction Ltd. (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXS2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1565676

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S241431461701121X/hb4161sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461701121X/hb4161Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461701121X/hb4161Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction Ltd, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction Ltd, 2008); data reduction: CrysAlis CCD (Oxford Diffraction Ltd, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

N-Methyl-4-(4-nitrophenyl)-N-nitroso-1,3-thiazol-2-amine top

Crystal data top

C₁₀H₈N₄O₃S	F(000) = 272
M_r = 264.26	D_x = 1.578 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 4.7729 (3) Å	Cell parameters from 2950 reflections
b = 13.7362 (8) Å	θ = 3.8–25.9°
c = 8.5391 (4) Å	µ = 0.30 mm⁻¹
β = 96.576 (5)°	T = 85 K
V = 556.15 (5) Å³	Irregular, yellow
Z = 2	0.28 × 0.17 × 0.15 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	1320 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θ_max = 25.9°, θ_min = 3.8°
ω scan	h = −5→5
2950 measured reflections	k = −15→16
1557 independent reflections	l = −10→10

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.061P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1557 reflections	Δρ_max = 0.29 e Å⁻³
164 parameters	Δρ_min = −0.36 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. All H atoms were found in a difference map but set to idealized positions and treated as riding with C_Ar—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) and with C—H₃ = 0.96 Å and U_iso(H) = 1.5U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	1.4840 (8)	0.8638 (2)	0.9230 (4)	0.0325 (8)
O2	−0.3222 (7)	0.4737 (2)	0.2371 (4)	0.0354 (9)
O3	−0.4836 (8)	0.5884 (2)	0.0786 (4)	0.0351 (8)
N1	0.7254 (8)	0.7692 (3)	0.5950 (4)	0.0224 (8)
N2	1.1208 (8)	0.8118 (2)	0.7699 (4)	0.0232 (8)
N3	1.2871 (9)	0.8869 (3)	0.8228 (5)	0.0292 (9)
N4	−0.3161 (8)	0.5566 (3)	0.1862 (4)	0.0264 (9)
S1	0.8523 (3)	0.95119 (7)	0.57753 (16)	0.0281 (3)
C1	0.9010 (9)	0.8347 (3)	0.6527 (5)	0.0234 (9)
C2	0.5680 (10)	0.9071 (3)	0.4564 (6)	0.0259 (10)
H2	0.4532	0.9446	0.3845	0.031*
C3	0.5332 (9)	0.8101 (3)	0.4796 (5)	0.0232 (10)
C4	1.1769 (10)	0.7131 (3)	0.8266 (6)	0.0283 (11)
H4A	1.0292	0.6707	0.7816	0.042*
H4B	1.1844	0.7119	0.9394	0.042*
H4C	1.3541	0.6914	0.7962	0.042*
C5	0.3134 (9)	0.7463 (3)	0.3993 (5)	0.0226 (9)
C6	0.1112 (10)	0.7803 (3)	0.2801 (5)	0.0245 (10)
H6	0.1161	0.8449	0.2479	0.029*
C7	−0.0955 (10)	0.7190 (3)	0.2098 (5)	0.0239 (10)
H7	−0.2308	0.7417	0.1313	0.029*
C8	−0.0967 (9)	0.6235 (3)	0.2586 (5)	0.0239 (9)
C9	0.1000 (10)	0.5865 (3)	0.3759 (5)	0.0251 (10)
H9	0.0933	0.5218	0.4071	0.030*
C10	0.3061 (10)	0.6486 (3)	0.4452 (5)	0.0240 (10)
H10	0.4414	0.6252	0.5231	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.028 (2)	0.0342 (18)	0.0326 (18)	0.0001 (15)	−0.0093 (15)	−0.0021 (13)
O2	0.035 (2)	0.0262 (18)	0.041 (2)	−0.0025 (15)	−0.0119 (17)	−0.0011 (14)
O3	0.031 (2)	0.0381 (18)	0.0320 (18)	−0.0002 (15)	−0.0151 (15)	−0.0006 (14)
N1	0.0174 (19)	0.0251 (17)	0.0237 (19)	0.0004 (15)	−0.0017 (15)	−0.0020 (14)
N2	0.022 (2)	0.0225 (18)	0.0244 (19)	−0.0031 (15)	−0.0008 (16)	−0.0009 (15)
N3	0.028 (2)	0.029 (2)	0.0294 (19)	−0.0030 (18)	−0.0044 (18)	−0.0019 (16)
N4	0.021 (2)	0.030 (2)	0.028 (2)	0.0011 (17)	−0.0035 (16)	−0.0048 (16)
S1	0.0237 (6)	0.0235 (5)	0.0356 (6)	−0.0012 (5)	−0.0033 (4)	0.0000 (5)
C1	0.015 (2)	0.024 (2)	0.031 (2)	0.0013 (18)	0.0042 (18)	−0.0007 (18)
C2	0.017 (3)	0.031 (2)	0.029 (2)	0.0019 (19)	−0.0001 (19)	0.0019 (19)
C3	0.019 (3)	0.024 (2)	0.027 (2)	0.0019 (18)	0.0043 (19)	0.0015 (18)
C4	0.027 (3)	0.026 (2)	0.031 (2)	−0.0021 (19)	−0.004 (2)	−0.0017 (19)
C5	0.016 (2)	0.030 (2)	0.021 (2)	0.0036 (18)	0.0023 (18)	0.0014 (16)
C6	0.024 (2)	0.023 (2)	0.027 (2)	0.0039 (18)	0.0051 (19)	0.0049 (18)
C7	0.021 (2)	0.027 (2)	0.023 (2)	0.0029 (19)	−0.0018 (18)	0.0015 (17)
C8	0.017 (2)	0.030 (2)	0.024 (2)	0.0011 (18)	−0.0027 (18)	−0.0032 (18)
C9	0.028 (3)	0.022 (2)	0.025 (2)	0.002 (2)	0.0001 (19)	−0.0019 (17)
C10	0.019 (3)	0.025 (2)	0.026 (2)	0.0030 (18)	−0.0040 (18)	−0.0016 (17)

Geometric parameters (Å, º) top

O1—N3	1.238 (5)	C4—H4A	0.9600
O2—N4	1.220 (4)	C4—H4B	0.9600
O3—N4	1.227 (5)	C4—H4C	0.9600
N1—C1	1.288 (6)	C5—C10	1.399 (6)
N1—C3	1.386 (6)	C5—C6	1.400 (6)
N2—N3	1.348 (5)	C6—C7	1.381 (6)
N2—C1	1.401 (5)	C6—H6	0.9300
N2—C4	1.454 (5)	C7—C8	1.376 (6)
N4—C8	1.475 (5)	C7—H7	0.9300
S1—C2	1.720 (5)	C8—C9	1.388 (6)
S1—C1	1.730 (4)	C9—C10	1.383 (6)
C2—C3	1.359 (6)	C9—H9	0.9300
C2—H2	0.9300	C10—H10	0.9300
C3—C5	1.475 (6)

C1—N1—C3	109.7 (3)	N2—C4—H4C	109.5
N3—N2—C1	115.6 (3)	H4A—C4—H4C	109.5
N3—N2—C4	121.6 (4)	H4B—C4—H4C	109.5
C1—N2—C4	122.8 (3)	C10—C5—C6	119.1 (4)
O1—N3—N2	114.0 (3)	C10—C5—C3	118.6 (4)
O2—N4—O3	124.0 (4)	C6—C5—C3	122.3 (4)
O2—N4—C8	118.5 (4)	C7—C6—C5	120.7 (4)
O3—N4—C8	117.5 (4)	C7—C6—H6	119.6
C2—S1—C1	87.7 (2)	C5—C6—H6	119.6
N1—C1—N2	121.2 (4)	C8—C7—C6	118.5 (4)
N1—C1—S1	116.8 (4)	C8—C7—H7	120.7
N2—C1—S1	122.0 (3)	C6—C7—H7	120.7
C3—C2—S1	111.0 (4)	C7—C8—C9	122.7 (4)
C3—C2—H2	124.5	C7—C8—N4	119.6 (4)
S1—C2—H2	124.5	C9—C8—N4	117.6 (4)
C2—C3—N1	114.8 (4)	C10—C9—C8	118.2 (4)
C2—C3—C5	127.4 (4)	C10—C9—H9	120.9
N1—C3—C5	117.8 (3)	C8—C9—H9	120.9
N2—C4—H4A	109.5	C9—C10—C5	120.7 (4)
N2—C4—H4B	109.5	C9—C10—H10	119.6
H4A—C4—H4B	109.5	C5—C10—H10	119.6

C1—N2—N3—O1	−178.1 (4)	C2—C3—C5—C6	2.2 (6)
C4—N2—N3—O1	−0.9 (6)	N1—C3—C5—C6	−179.4 (4)
C3—N1—C1—N2	−178.9 (3)	C10—C5—C6—C7	0.9 (6)
C3—N1—C1—S1	0.8 (5)	C3—C5—C6—C7	−178.5 (4)
N3—N2—C1—N1	−178.8 (4)	C5—C6—C7—C8	−0.5 (6)
C4—N2—C1—N1	4.1 (6)	C6—C7—C8—C9	0.4 (6)
N3—N2—C1—S1	1.6 (5)	C6—C7—C8—N4	179.6 (4)
C4—N2—C1—S1	−175.6 (4)	O2—N4—C8—C7	−176.1 (4)
C2—S1—C1—N1	−0.1 (4)	O3—N4—C8—C7	3.3 (6)
C2—S1—C1—N2	179.5 (4)	O2—N4—C8—C9	3.2 (6)
C1—S1—C2—C3	−0.6 (4)	O3—N4—C8—C9	−177.4 (4)
S1—C2—C3—N1	1.2 (5)	C7—C8—C9—C10	−0.5 (6)
S1—C2—C3—C5	179.7 (3)	N4—C8—C9—C10	−179.8 (4)
C1—N1—C3—C2	−1.3 (5)	C8—C9—C10—C5	0.8 (6)
C1—N1—C3—C5	−179.9 (4)	C6—C5—C10—C9	−1.0 (6)
C2—C3—C5—C10	−177.2 (4)	C3—C5—C10—C9	178.4 (4)
N1—C3—C5—C10	1.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.66	3.182 (6)	117
C2—H2···N3ⁱ	0.93	2.48	3.280 (6)	144
C4—H4A···O2ⁱⁱ	0.96	2.60	3.525 (5)	163
C4—H4B···O3ⁱⁱⁱ	0.96	2.52	3.065 (6)	116

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

References

Loeppky, R. N. & Outram, J. R. (1994). In N-Nitrosamines and Related N-Nitroso Compounds. Washington, DC: American Chemical Society. Google Scholar
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