1-(2,6-Dimethyl­phen­yl)thio­urea

The geometric parameters of the title compound, C₉H₁₂N₂S, are in the usual ranges. The thio­urea group is almost perpendicular to the aromatic ring [dihedral angle = 80.75 (7)°]. The crystal packing is stabilized by N—H...S hydrogen bonds linking the mol­ecules into layers perpendicular to the c axis. Only two of the three amino H atoms are involved in hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.032
• wR factor = 0.086
• Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C9      ..       6.35 su
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2A    ...          ?

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 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

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S1. Comment

Thiourea and its derivatives have been the focus of attention in recent years in view of their interesting physicochemical properties and broad range of applications in several chemical disciplines. Certain thiourea molecules have antiviral activity and might be characterized as prospective inhibitors of many enzymes, particularly, HIV-1 reverse transcriptase As antibacterial and antifungal agents, they have been used in agriculture In technical applications dithioamide compounds are known to be prospective nonlinear optical materials corrosion inhibitors for copper and iron in acidic media and functionalization agents for production of chemically modified resins. Thiourea derivatives have been also reported as potential receptors and ionophores for heavy metal cations building blocks in the synthesis of heterocyclic compounds. Finally, the strong hydrogen-bonding donor capability of the –N(H)—C(=S)—N(H)- group has been widely exploited in supramolecular chemistry, where it has been used as a building block for anion receptors A new thiourea, C₉H₁₂N₂S was synthesized and its crystal structure is reported.

Geometric parameters of the title compound (Fig. 1) are in the usual ranges. The thio-urea moiety is almost perpendicular to the aromatic ring [dihedral angle 80.75 (7)°]. The crystal packing is stabilized by N—H···S hydrogen bonds linking the molecules into layers perpendicular to the c axis (Fig.2). Only two of the three amino H atoms are involved in hydrogen bonding.

Related literature

For related structures, see: Usman et al. (2002); Zhang et al. (2003); Dege et al. (2005). For related literature, see: Ren et al. (2004); Rodriguez-Fernandez et al. (2005); Zhou et al. (2003); Stankovic & Vukovic (1996); Trochimczuk & Kolarz et al. (2000); Castro et al. (2003); Kearney et al. (1998); Nie et al. (2004).

S2. Experimental

2,6-dimethylaniline (0.983 g, 0.0081 mol) was refluxed with potassium thiocyanate (1.4 g, 0.0142 mol) in 20 ml of water and 1.6 ml of conc. HCl for 3 h. The reaction mixture was then cooled to room temperature and stirred overnight. The precipitated product was then filtered, washed with water, dried and recrystallized from acetone (m.p.: 453–455 K). Analysis for C₉H₁₂N₂S: Found (Calculated): C: 59.92 (59.96); H: 6.74 (6.71); N: 15.49 (15.54): S: 17.83% (17.79%).

S3. Refinement

H atoms were found in a difference map, but those bonded to C were refined using a riding model with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for C_aromatic and C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for C_methyl. The methyl group was allowed to rotate but not to tip. The H atoms bonded to N were freely refined.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.
	Fig. 2. Packing diagram of the title compound with view along the c axis. H atoms bonded to C omitted. Hydrogen bonds shown as dashed lines.

1-(2,6-Dimethylphenyl)thiourea

Crystal data

C9H12N2S	F(000) = 384
Mr = 180.27	Dx = 1.222 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6186 reflections
a = 9.8715 (13) Å	θ = 3.6–25.8°
b = 8.3940 (7) Å	µ = 0.28 mm^−1
c = 11.8276 (16) Å	T = 173 K
β = 91.557 (11)°	Block, colourless
V = 979.7 (2) Å^3	0.29 × 0.28 × 0.25 mm
Z = 4

Data collection

Stoe IPDS II two-circle diffractometer	1830 independent reflections
Radiation source: fine-focus sealed tube	1598 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 25.6°, θmin = 3.6°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −11→11
Tmin = 0.934, Tmax = 0.944	k = −10→9
6116 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0421P)^2 + 0.4733P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
1830 reflections	Δρmax = 0.24 e Å^−3
124 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (3)

Special details

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
S1	0.80471 (4)	0.44604 (5)	0.77764 (4)	0.02740 (17)
N1	0.55700 (12)	0.31654 (16)	0.75999 (11)	0.0199 (3)
H1	0.6001 (18)	0.226 (2)	0.7519 (15)	0.029 (5)*
N2	0.56619 (14)	0.58952 (16)	0.77011 (13)	0.0252 (3)
H2A	0.480 (2)	0.596 (2)	0.7641 (17)	0.034 (5)*
H2B	0.613 (2)	0.683 (3)	0.7684 (19)	0.047 (6)*
C1	0.41512 (14)	0.32335 (17)	0.72473 (13)	0.0192 (3)
C2	0.38282 (16)	0.31028 (19)	0.60910 (14)	0.0237 (3)
C3	0.24801 (17)	0.3325 (2)	0.57317 (15)	0.0314 (4)
H3	0.2237	0.3227	0.4952	0.038*
C4	0.14901 (16)	0.3689 (2)	0.65092 (16)	0.0330 (4)
H4	0.0583	0.3879	0.6255	0.040*
C5	0.18274 (16)	0.3775 (2)	0.76508 (15)	0.0303 (4)
H5	0.1141	0.4005	0.8174	0.036*
C6	0.31617 (15)	0.35293 (19)	0.80533 (13)	0.0243 (4)
C7	0.49229 (18)	0.2749 (2)	0.52544 (14)	0.0358 (4)
H7A	0.5599	0.3603	0.5281	0.054*
H7B	0.4518	0.2681	0.4490	0.054*
H7C	0.5360	0.1734	0.5450	0.054*
C8	0.35129 (19)	0.3592 (3)	0.93045 (15)	0.0388 (5)
H8A	0.3435	0.2523	0.9629	0.058*
H8B	0.2888	0.4316	0.9679	0.058*
H8C	0.4444	0.3979	0.9417	0.058*
C9	0.63163 (14)	0.45104 (17)	0.76801 (12)	0.0178 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0138 (2)	0.0166 (2)	0.0516 (3)	0.00035 (14)	−0.00217 (16)	−0.00235 (17)
N1	0.0160 (6)	0.0153 (6)	0.0284 (7)	0.0002 (5)	0.0000 (5)	−0.0009 (5)
N2	0.0149 (7)	0.0157 (7)	0.0451 (9)	0.0000 (5)	0.0010 (6)	−0.0005 (6)
C1	0.0163 (7)	0.0142 (7)	0.0270 (8)	−0.0025 (6)	0.0005 (6)	−0.0001 (6)
C2	0.0231 (8)	0.0212 (8)	0.0268 (8)	−0.0022 (6)	0.0017 (6)	−0.0008 (6)
C3	0.0268 (9)	0.0389 (10)	0.0282 (9)	−0.0052 (7)	−0.0061 (7)	0.0008 (7)
C4	0.0159 (8)	0.0361 (10)	0.0469 (10)	−0.0038 (7)	−0.0030 (7)	0.0046 (8)
C5	0.0183 (8)	0.0327 (9)	0.0403 (10)	−0.0048 (7)	0.0082 (7)	−0.0014 (8)
C6	0.0209 (8)	0.0235 (8)	0.0286 (8)	−0.0064 (6)	0.0045 (6)	−0.0020 (7)
C7	0.0335 (9)	0.0483 (11)	0.0259 (9)	0.0028 (8)	0.0052 (7)	−0.0047 (8)
C8	0.0334 (10)	0.0561 (13)	0.0273 (9)	−0.0071 (9)	0.0077 (7)	−0.0045 (9)
C9	0.0180 (7)	0.0172 (7)	0.0183 (7)	−0.0006 (6)	0.0013 (5)	0.0004 (6)

Geometric parameters (Å, º)

S1—C9	1.7098 (15)	C3—H3	0.9500
N1—C9	1.3500 (19)	C4—C5	1.384 (3)
N1—C1	1.4516 (19)	C4—H4	0.9500
N1—H1	0.88 (2)	C5—C6	1.404 (2)
N2—C9	1.330 (2)	C5—H5	0.9500
N2—H2A	0.86 (2)	C6—C8	1.512 (2)
N2—H2B	0.91 (2)	C7—H7A	0.9800
C1—C2	1.400 (2)	C7—H7B	0.9800
C1—C6	1.405 (2)	C7—H7C	0.9800
C2—C3	1.399 (2)	C8—H8A	0.9800
C2—C7	1.514 (2)	C8—H8B	0.9800
C3—C4	1.394 (2)	C8—H8C	0.9800
C9—N1—C1	120.51 (13)	C6—C5—H5	119.3
C9—N1—H1	117.9 (12)	C5—C6—C1	117.32 (15)
C1—N1—H1	118.0 (12)	C5—C6—C8	121.00 (14)
C9—N2—H2A	122.3 (14)	C1—C6—C8	121.67 (15)
C9—N2—H2B	120.4 (14)	C2—C7—H7A	109.5
H2A—N2—H2B	117 (2)	C2—C7—H7B	109.5
C2—C1—C6	122.17 (14)	H7A—C7—H7B	109.5
C2—C1—N1	118.03 (13)	C2—C7—H7C	109.5
C6—C1—N1	119.67 (14)	H7A—C7—H7C	109.5
C3—C2—C1	118.42 (14)	H7B—C7—H7C	109.5
C3—C2—C7	121.17 (15)	C6—C8—H8A	109.5
C1—C2—C7	120.40 (14)	C6—C8—H8B	109.5
C4—C3—C2	120.47 (16)	H8A—C8—H8B	109.5
C4—C3—H3	119.8	C6—C8—H8C	109.5
C2—C3—H3	119.8	H8A—C8—H8C	109.5
C5—C4—C3	120.05 (15)	H8B—C8—H8C	109.5
C5—C4—H4	120.0	N2—C9—N1	117.89 (13)
C3—C4—H4	120.0	N2—C9—S1	120.33 (12)
C4—C5—C6	121.47 (15)	N1—C9—S1	121.77 (11)
C4—C5—H5	119.3
C9—N1—C1—C2	90.37 (18)	C3—C4—C5—C6	1.1 (3)
C9—N1—C1—C6	−85.50 (18)	C4—C5—C6—C1	1.6 (2)
C6—C1—C2—C3	2.0 (2)	C4—C5—C6—C8	−178.72 (17)
N1—C1—C2—C3	−173.73 (14)	C2—C1—C6—C5	−3.2 (2)
C6—C1—C2—C7	−178.72 (15)	N1—C1—C6—C5	172.46 (14)
N1—C1—C2—C7	5.5 (2)	C2—C1—C6—C8	177.13 (16)
C1—C2—C3—C4	0.9 (3)	N1—C1—C6—C8	−7.2 (2)
C7—C2—C3—C4	−178.39 (17)	C1—N1—C9—N2	16.1 (2)
C2—C3—C4—C5	−2.4 (3)	C1—N1—C9—S1	−164.98 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.88 (2)	2.56 (2)	3.4302 (14)	172.6 (16)
N2—H2B···S1^ii	0.91 (2)	2.42 (2)	3.3073 (15)	164.8 (19)

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