3-Methyl-1-{(E)-[1-(4-methyl­pyridin-2-yl)ethyl­idene]amino}­thio­urea: crystal structure and Hirshfeld surface analysis

The title mol­ecule is twisted, with the dihedral angles between the imine core (C₃N) and thio­urea and methyl­pyridyl residues being 20.25 (8) and 7.60 (9)°, respectively. In the crystal, corrugated supra­molecular layers in the bc plane are mediated by amine-N—H...N(pyrid­yl) and thio­amide-N—H...S(thione) hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.035
• wR factor = 0.097
• Data-to-parameter ratio = 15.1

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Computing details

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

3-Methyl-1-{(E)-[1-(4-methylpyridin-2-yl)ethylidene]amino}thiourea

Crystal data

C10H14N4S	F(000) = 472
Mr = 222.31	Dx = 1.309 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.5418 Å
a = 8.8108 (3) Å	Cell parameters from 9894 reflections
b = 14.9044 (4) Å	θ = 3.0–71.2°
c = 9.3583 (3) Å	µ = 2.33 mm^−1
β = 113.391 (4)°	T = 100 K
V = 1127.93 (7) Å^3	Plate, brown
Z = 4	0.15 × 0.13 × 0.03 mm

Data collection

Rigaku Oxford Diffraction Gemini E diffractometer	2184 independent reflections
Radiation source: Enhance X-ray source	1995 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.034
Detector resolution: 16.1952 pixels mm^-1	θmax = 71.3°, θmin = 5.5°
ω scan	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −18→17
Tmin = 0.852, Tmax = 1.000	l = −11→11
21767 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.063P)^2 + 0.4965P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
2184 reflections	Δρmax = 0.41 e Å^−3
145 parameters	Δρmin = −0.23 e Å^−3
2 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	1.01197 (4)	0.43326 (2)	0.80392 (4)	0.01660 (14)
N1	0.78625 (16)	0.52040 (9)	0.56429 (14)	0.0167 (3)
H1N	0.728 (2)	0.5689 (9)	0.527 (2)	0.020*
N2	0.85960 (15)	0.58621 (8)	0.80403 (14)	0.0151 (3)
H2N	0.908 (2)	0.5811 (12)	0.9041 (11)	0.018*
N3	0.73527 (15)	0.64746 (8)	0.73280 (14)	0.0151 (3)
N4	0.57917 (15)	0.85680 (9)	0.79338 (14)	0.0169 (3)
C1	0.87633 (17)	0.51659 (10)	0.71665 (16)	0.0142 (3)
C2	0.7888 (2)	0.45156 (11)	0.45507 (18)	0.0206 (3)
H2A	0.9018	0.4289	0.4860	0.031*
H2B	0.7508	0.4772	0.3502	0.031*
H2C	0.7155	0.4022	0.4554	0.031*
C3	0.73564 (17)	0.72169 (10)	0.80323 (16)	0.0137 (3)
C4	0.86453 (18)	0.75205 (10)	0.95558 (17)	0.0176 (3)
H4A	0.8263	0.7403	1.0389	0.026*
H4B	0.8841	0.8165	0.9508	0.026*
H4C	0.9676	0.7192	0.9768	0.026*
C5	0.59425 (17)	0.78267 (10)	0.71764 (16)	0.0144 (3)
C6	0.45183 (19)	0.91141 (11)	0.71570 (19)	0.0201 (3)
H6	0.4387	0.9638	0.7675	0.024*
C7	0.33818 (18)	0.89648 (11)	0.56488 (18)	0.0198 (3)
H7	0.2515	0.9381	0.5154	0.024*
C8	0.35303 (17)	0.81950 (10)	0.48712 (16)	0.0168 (3)
C9	0.48424 (17)	0.76211 (10)	0.56638 (16)	0.0153 (3)
H9	0.4989	0.7089	0.5175	0.018*
C10	0.23240 (19)	0.79716 (11)	0.32435 (18)	0.0205 (3)
H10A	0.2929	0.7874	0.2576	0.031*
H10B	0.1546	0.8470	0.2830	0.031*
H10C	0.1714	0.7426	0.3267	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0203 (2)	0.0138 (2)	0.0143 (2)	0.00414 (13)	0.00545 (15)	0.00082 (13)
N1	0.0217 (6)	0.0131 (6)	0.0134 (6)	0.0032 (5)	0.0050 (5)	0.0000 (5)
N2	0.0174 (6)	0.0140 (6)	0.0111 (6)	0.0029 (5)	0.0028 (5)	0.0006 (5)
N3	0.0158 (6)	0.0148 (6)	0.0144 (6)	0.0029 (5)	0.0057 (5)	0.0017 (5)
N4	0.0178 (6)	0.0160 (7)	0.0171 (6)	0.0018 (5)	0.0072 (5)	−0.0005 (5)
C1	0.0152 (7)	0.0125 (7)	0.0161 (7)	−0.0017 (5)	0.0073 (5)	0.0008 (5)
C2	0.0278 (8)	0.0167 (8)	0.0158 (7)	0.0015 (6)	0.0072 (6)	−0.0027 (6)
C3	0.0158 (7)	0.0143 (7)	0.0126 (7)	0.0000 (5)	0.0073 (5)	0.0008 (5)
C4	0.0193 (7)	0.0141 (7)	0.0166 (7)	0.0020 (6)	0.0042 (6)	−0.0023 (6)
C5	0.0161 (7)	0.0134 (7)	0.0156 (7)	−0.0002 (5)	0.0082 (6)	0.0013 (5)
C6	0.0216 (7)	0.0157 (8)	0.0228 (8)	0.0035 (6)	0.0086 (6)	−0.0022 (6)
C7	0.0174 (7)	0.0185 (8)	0.0223 (8)	0.0043 (6)	0.0067 (6)	0.0022 (6)
C8	0.0162 (7)	0.0189 (8)	0.0158 (7)	0.0000 (6)	0.0069 (6)	0.0033 (6)
C9	0.0182 (7)	0.0143 (7)	0.0149 (7)	0.0005 (6)	0.0081 (6)	0.0000 (5)
C10	0.0204 (7)	0.0221 (8)	0.0166 (7)	0.0028 (6)	0.0050 (6)	0.0028 (6)

Geometric parameters (Å, º)

S1—C1	1.6920 (15)	C4—H4A	0.9800
N1—C1	1.3295 (18)	C4—H4B	0.9800
N1—C2	1.4547 (19)	C4—H4C	0.9800
N1—H1N	0.873 (9)	C5—C9	1.396 (2)
N2—C1	1.3649 (19)	C6—C7	1.386 (2)
N2—N3	1.3776 (17)	C6—H6	0.9500
N2—H2N	0.864 (9)	C7—C8	1.392 (2)
N3—C3	1.2872 (19)	C7—H7	0.9500
N4—C5	1.3474 (19)	C8—C9	1.392 (2)
N4—C6	1.342 (2)	C8—C10	1.508 (2)
C2—H2A	0.9800	C9—H9	0.9500
C2—H2B	0.9800	C10—H10A	0.9800
C2—H2C	0.9800	C10—H10B	0.9800
C3—C5	1.4923 (19)	C10—H10C	0.9800
C3—C4	1.4971 (19)
C1—N1—C2	123.66 (13)	H4A—C4—H4C	109.5
C1—N1—H1N	117.9 (13)	H4B—C4—H4C	109.5
C2—N1—H1N	118.3 (13)	N4—C5—C9	122.66 (13)
C1—N2—N3	117.92 (12)	N4—C5—C3	116.91 (12)
C1—N2—H2N	117.3 (12)	C9—C5—C3	120.42 (13)
N3—N2—H2N	122.4 (12)	N4—C6—C7	124.37 (14)
C3—N3—N2	118.81 (12)	N4—C6—H6	117.8
C5—N4—C6	116.62 (12)	C7—C6—H6	117.8
N1—C1—N2	116.71 (13)	C6—C7—C8	118.98 (14)
N1—C1—S1	123.75 (11)	C6—C7—H7	120.5
N2—C1—S1	119.50 (11)	C8—C7—H7	120.5
N1—C2—H2A	109.5	C7—C8—C9	117.28 (13)
N1—C2—H2B	109.5	C7—C8—C10	122.34 (14)
H2A—C2—H2B	109.5	C9—C8—C10	120.38 (14)
N1—C2—H2C	109.5	C8—C9—C5	120.08 (14)
H2A—C2—H2C	109.5	C8—C9—H9	120.0
H2B—C2—H2C	109.5	C5—C9—H9	120.0
N3—C3—C5	114.63 (12)	C8—C10—H10A	109.5
N3—C3—C4	126.45 (13)	C8—C10—H10B	109.5
C5—C3—C4	118.89 (12)	H10A—C10—H10B	109.5
C3—C4—H4A	109.5	C8—C10—H10C	109.5
C3—C4—H4B	109.5	H10A—C10—H10C	109.5
H4A—C4—H4B	109.5	H10B—C10—H10C	109.5
C3—C4—H4C	109.5
C1—N2—N3—C3	−167.44 (13)	N3—C3—C5—C9	−6.6 (2)
C2—N1—C1—N2	−179.61 (13)	C4—C3—C5—C9	171.34 (13)
C2—N1—C1—S1	2.5 (2)	C5—N4—C6—C7	−0.5 (2)
N3—N2—C1—N1	9.20 (19)	N4—C6—C7—C8	1.0 (2)
N3—N2—C1—S1	−172.80 (10)	C6—C7—C8—C9	−0.8 (2)
N2—N3—C3—C5	−178.98 (11)	C6—C7—C8—C10	178.57 (15)
N2—N3—C3—C4	3.2 (2)	C7—C8—C9—C5	0.1 (2)
C6—N4—C5—C9	−0.3 (2)	C10—C8—C9—C5	−179.24 (13)
C6—N4—C5—C3	179.94 (13)	N4—C5—C9—C8	0.4 (2)
N3—C3—C5—N4	173.16 (12)	C3—C5—C9—C8	−179.77 (13)
C4—C3—C5—N4	−8.85 (19)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the (N4,C5–C9) ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N3	0.88 (2)	2.23 (2)	2.6148 (18)	106 (1)
N1—H1N···N4^i	0.88 (2)	2.33 (2)	3.0714 (18)	142 (1)
N2—H2N···S1^ii	0.87 (1)	2.55 (1)	3.3955 (13)	168 (2)
C10—H10A···Cg1^i	0.98	2.89	3.7546 (18)	147

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+2, −y+1, −z+2.