Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039165/ng2304sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039165/ng2304Isup2.hkl |
CCDC reference: 660247
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%).
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 Uiso(H) = 1.2Ueq(C) for Caromatic and C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for Cmethyl. The methyl group was allowed to rotate but not to tip. The H atoms bonded to N were freely refined.
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.
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).
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.
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) Å3 | 0.29 × 0.28 × 0.25 mm |
Z = 4 |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0421P)2 + 0.4733P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.032 (3) |
C9H12N2S | V = 979.7 (2) Å3 |
Mr = 180.27 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.8715 (13) Å | µ = 0.28 mm−1 |
b = 8.3940 (7) Å | T = 173 K |
c = 11.8276 (16) Å | 0.29 × 0.28 × 0.25 mm |
β = 91.557 (11)° |
Stoe IPDS II two-circle diffractometer | 1830 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | 1598 reflections with I > 2σ(I) |
Tmin = 0.934, Tmax = 0.944 | Rint = 0.034 |
6116 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.24 e Å−3 |
1830 reflections | Δρmin = −0.27 e Å−3 |
124 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.88 (2) | 2.56 (2) | 3.4302 (14) | 172.6 (16) |
N2—H2B···S1ii | 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. |
Experimental details
Crystal data | |
Chemical formula | C9H12N2S |
Mr | 180.27 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 9.8715 (13), 8.3940 (7), 11.8276 (16) |
β (°) | 91.557 (11) |
V (Å3) | 979.7 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.29 × 0.28 × 0.25 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle |
Absorption correction | Multi-scan (MULABS; Spek, 2003; Blessing, 1995) |
Tmin, Tmax | 0.934, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6116, 1830, 1598 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.607 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.087, 1.04 |
No. of reflections | 1830 |
No. of parameters | 124 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.27 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.88 (2) | 2.56 (2) | 3.4302 (14) | 172.6 (16) |
N2—H2B···S1ii | 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. |
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.