Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039803/lh2477sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039803/lh2477Isup2.hkl |
CCDC reference: 660314
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.004 Å
- R factor = 0.030
- wR factor = 0.071
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.88 PLAT480_ALERT_4_C Long H...A H-Bond Reported H3B .. S1 .. 2.95 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.878 Tmax scaled 0.417 Tmin scaled 0.385
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 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 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
2-Bromo-5-methoxybenzohydrazide (1.98 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 4 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 a mixture of dimethylformamide and methylethylketone (1:1) (m.p.: 472–474 K). Analysis for C9H10BrN3O2S: Found (Calculated): C:35.46 (35.54); H: 3.27 (3.31); N:13.72 (13.81): S: 10.43% (10.54%).
H atoms were found in a difference map, but those bonded to C atom 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 refined isotropically.
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 (Ren et al., 2000; Onderwater et al., 2004). As antibacterial and antifungal agents, they have been used in agriculture (Rodriguez-Fernandez et al., 2005). In technical applications, dithioamide compounds are known to be prospective nonlinear optical materials (Zhou et al., 2003), corrosion inhibitors for copper and iron in acidic media (Stankovic et al., 1996) and functionalization agents for production of chemically modified resins (Trochimczuk et al., 2000). Thiourea derivatives have been also reported as potential receptors and ionophores for heavy metal cations (Castro et al., 2003), building blocks in the synthesis of heterocyclic compounds (Kearney et al., 1998). 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 (Nie et al., 2004). A new carbothioamide, C9H10BrN3O2S, has been synthesized and its crystal structure is reported herein.
Geometric parameters of the title molecule (Fig. 1) are in the usual ranges. The plane of the thiourea moiety is almost coparallel to the plane of the aromatic ring [dihedral angle = 8.40 (12)°]. Only the torsion angles about the Ccarbonyl—Caromatic bond [N1—C1—C11—C12 = 114.0 (3)°] and N—N bond [C1—N1—N2—C2 = -100.9 (3)°] differ significantly from 0 or 180°. The crystal packing is stabilized by N—H···O and N—H···S hydrogen bonds.
For related crystal structures, see: Chattopadhyay et al. (1987, 1989, 1991); Fonari et al. (2003); Jian et al. (2005); Sarojini et al. (2007). For related literature, see: Ren et al. (2000); Onderwater et al. (2004); Rodriguez-Fernandez et al. (2005); Zhou et al. (2003); Stankovic & Vukovic (1996); Trochimczuk & Kolarz (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 [Or X-RED?]; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. The molecular structure with the atom numbering; displacement ellipsoids are at the 50% probability level. |
C9H10BrN3O2S | F(000) = 608 |
Mr = 304.17 | Dx = 1.711 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 10030 reflections |
a = 15.6156 (17) Å | θ = 3.7–25.9° |
b = 7.7312 (15) Å | µ = 3.65 mm−1 |
c = 9.8876 (9) Å | T = 173 K |
β = 98.531 (8)° | Block, colourless |
V = 1180.5 (3) Å3 | 0.27 × 0.25 × 0.24 mm |
Z = 4 |
Stoe IPDSII two-circle diffractometer | 2266 independent reflections |
Radiation source: fine-focus sealed tube | 1931 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
ω scans | θmax = 25.8°, θmin = 3.7° |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | h = −19→17 |
Tmin = 0.439, Tmax = 0.475 | k = −9→8 |
10501 measured reflections | l = −12→12 |
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)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.0379P)2 + 0.1127P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2266 reflections | Δρmax = 0.52 e Å−3 |
163 parameters | Δρmin = −0.56 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: 0.0071 (8) |
C9H10BrN3O2S | V = 1180.5 (3) Å3 |
Mr = 304.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.6156 (17) Å | µ = 3.65 mm−1 |
b = 7.7312 (15) Å | T = 173 K |
c = 9.8876 (9) Å | 0.27 × 0.25 × 0.24 mm |
β = 98.531 (8)° |
Stoe IPDSII two-circle diffractometer | 2266 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | 1931 reflections with I > 2σ(I) |
Tmin = 0.439, Tmax = 0.475 | Rint = 0.063 |
10501 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.52 e Å−3 |
2266 reflections | Δρmin = −0.56 e Å−3 |
163 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 | ||
Br1 | 0.85433 (2) | 0.12212 (4) | 0.47258 (3) | 0.03109 (12) | |
S1 | 0.39720 (4) | 0.17481 (10) | 0.55281 (7) | 0.02750 (18) | |
O1 | 0.65985 (12) | 0.3225 (2) | 0.41909 (16) | 0.0221 (4) | |
O2 | 0.86654 (13) | 0.8137 (3) | 0.75887 (19) | 0.0295 (5) | |
N1 | 0.64664 (14) | 0.2785 (3) | 0.6421 (2) | 0.0181 (4) | |
H1 | 0.669 (3) | 0.269 (5) | 0.726 (4) | 0.043 (10)* | |
N2 | 0.56775 (14) | 0.1932 (3) | 0.6095 (2) | 0.0185 (4) | |
H2 | 0.570 (2) | 0.103 (4) | 0.569 (3) | 0.026 (8)* | |
N3 | 0.49439 (18) | 0.4348 (3) | 0.6639 (2) | 0.0267 (5) | |
H3A | 0.447 (2) | 0.491 (5) | 0.660 (3) | 0.033 (9)* | |
H3B | 0.543 (3) | 0.476 (5) | 0.695 (3) | 0.038 (10)* | |
C1 | 0.69051 (16) | 0.3331 (3) | 0.5411 (2) | 0.0161 (5) | |
C2 | 0.49182 (17) | 0.2770 (3) | 0.6114 (2) | 0.0181 (5) | |
C11 | 0.77712 (16) | 0.4120 (3) | 0.5912 (2) | 0.0164 (5) | |
C12 | 0.85456 (17) | 0.3356 (3) | 0.5681 (2) | 0.0195 (5) | |
C13 | 0.93357 (17) | 0.4171 (4) | 0.6103 (2) | 0.0237 (6) | |
H13 | 0.9860 | 0.3632 | 0.5955 | 0.028* | |
C14 | 0.93542 (18) | 0.5765 (4) | 0.6738 (3) | 0.0257 (6) | |
H14 | 0.9893 | 0.6326 | 0.7019 | 0.031* | |
C15 | 0.85812 (17) | 0.6559 (3) | 0.6970 (2) | 0.0210 (5) | |
C16 | 0.77910 (16) | 0.5724 (3) | 0.6580 (2) | 0.0181 (5) | |
H16 | 0.7269 | 0.6240 | 0.6765 | 0.022* | |
C17 | 0.7887 (2) | 0.9056 (4) | 0.7737 (3) | 0.0307 (6) | |
H17A | 0.7513 | 0.9115 | 0.6850 | 0.046* | |
H17B | 0.8033 | 1.0231 | 0.8066 | 0.046* | |
H17C | 0.7582 | 0.8451 | 0.8395 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.03588 (19) | 0.02696 (17) | 0.03174 (16) | 0.00653 (14) | 0.00934 (11) | −0.00653 (11) |
S1 | 0.0147 (3) | 0.0272 (4) | 0.0387 (4) | 0.0010 (3) | −0.0021 (3) | −0.0109 (3) |
O1 | 0.0232 (10) | 0.0288 (10) | 0.0133 (8) | −0.0023 (8) | −0.0001 (7) | −0.0017 (7) |
O2 | 0.0228 (10) | 0.0300 (11) | 0.0351 (10) | −0.0058 (9) | 0.0021 (8) | −0.0124 (9) |
N1 | 0.0157 (11) | 0.0247 (12) | 0.0137 (9) | −0.0040 (9) | 0.0014 (8) | 0.0004 (8) |
N2 | 0.0139 (11) | 0.0196 (11) | 0.0222 (10) | −0.0028 (9) | 0.0035 (8) | −0.0043 (9) |
N3 | 0.0187 (13) | 0.0253 (13) | 0.0352 (12) | 0.0015 (11) | 0.0013 (10) | −0.0121 (10) |
C1 | 0.0174 (12) | 0.0159 (12) | 0.0151 (10) | 0.0022 (10) | 0.0030 (9) | 0.0000 (9) |
C2 | 0.0199 (13) | 0.0214 (13) | 0.0129 (10) | 0.0004 (11) | 0.0017 (9) | 0.0007 (9) |
C11 | 0.0181 (12) | 0.0195 (13) | 0.0117 (10) | −0.0005 (10) | 0.0026 (9) | 0.0032 (8) |
C12 | 0.0231 (13) | 0.0213 (13) | 0.0148 (10) | 0.0023 (10) | 0.0048 (9) | 0.0026 (9) |
C13 | 0.0154 (13) | 0.0356 (16) | 0.0209 (11) | 0.0033 (11) | 0.0051 (10) | 0.0061 (10) |
C14 | 0.0153 (13) | 0.0371 (16) | 0.0239 (12) | −0.0037 (12) | 0.0005 (10) | 0.0011 (11) |
C15 | 0.0193 (13) | 0.0256 (14) | 0.0178 (10) | −0.0025 (11) | 0.0014 (9) | 0.0015 (10) |
C16 | 0.0165 (13) | 0.0230 (13) | 0.0151 (10) | −0.0009 (10) | 0.0035 (9) | −0.0008 (9) |
C17 | 0.0310 (16) | 0.0282 (16) | 0.0338 (14) | −0.0035 (13) | 0.0080 (12) | −0.0126 (12) |
Br1—C12 | 1.901 (3) | C1—C11 | 1.499 (3) |
S1—C2 | 1.700 (3) | C11—C12 | 1.395 (4) |
O1—C1 | 1.233 (3) | C11—C16 | 1.403 (3) |
O2—C15 | 1.363 (3) | C12—C13 | 1.393 (4) |
O2—C17 | 1.434 (4) | C13—C14 | 1.382 (4) |
N1—C1 | 1.359 (3) | C13—H13 | 0.9500 |
N1—N2 | 1.392 (3) | C14—C15 | 1.403 (4) |
N1—H1 | 0.85 (4) | C14—H14 | 0.9500 |
N2—C2 | 1.354 (3) | C15—C16 | 1.395 (4) |
N2—H2 | 0.81 (3) | C16—H16 | 0.9500 |
N3—C2 | 1.324 (3) | C17—H17A | 0.9800 |
N3—H3A | 0.86 (4) | C17—H17B | 0.9800 |
N3—H3B | 0.84 (4) | C17—H17C | 0.9800 |
C15—O2—C17 | 117.6 (2) | C13—C12—Br1 | 118.54 (19) |
C1—N1—N2 | 120.13 (19) | C11—C12—Br1 | 120.74 (19) |
C1—N1—H1 | 124 (3) | C14—C13—C12 | 119.8 (2) |
N2—N1—H1 | 114 (3) | C14—C13—H13 | 120.1 |
C2—N2—N1 | 121.1 (2) | C12—C13—H13 | 120.1 |
C2—N2—H2 | 122 (2) | C13—C14—C15 | 120.2 (2) |
N1—N2—H2 | 115 (2) | C13—C14—H14 | 119.9 |
C2—N3—H3A | 118 (2) | C15—C14—H14 | 119.9 |
C2—N3—H3B | 118 (2) | O2—C15—C16 | 124.1 (2) |
H3A—N3—H3B | 124 (3) | O2—C15—C14 | 115.9 (2) |
O1—C1—N1 | 122.2 (2) | C16—C15—C14 | 120.0 (2) |
O1—C1—C11 | 123.4 (2) | C15—C16—C11 | 119.7 (2) |
N1—C1—C11 | 114.32 (19) | C15—C16—H16 | 120.1 |
N3—C2—N2 | 118.1 (2) | C11—C16—H16 | 120.1 |
N3—C2—S1 | 122.4 (2) | O2—C17—H17A | 109.5 |
N2—C2—S1 | 119.45 (19) | O2—C17—H17B | 109.5 |
C12—C11—C16 | 119.5 (2) | H17A—C17—H17B | 109.5 |
C12—C11—C1 | 122.4 (2) | O2—C17—H17C | 109.5 |
C16—C11—C1 | 118.1 (2) | H17A—C17—H17C | 109.5 |
C13—C12—C11 | 120.7 (2) | H17B—C17—H17C | 109.5 |
C1—N1—N2—C2 | −100.9 (3) | C1—C11—C12—Br1 | −1.0 (3) |
N2—N1—C1—O1 | 5.9 (4) | C11—C12—C13—C14 | −1.1 (4) |
N2—N1—C1—C11 | −176.1 (2) | Br1—C12—C13—C14 | 176.76 (18) |
N1—N2—C2—N3 | −9.6 (3) | C12—C13—C14—C15 | 0.6 (4) |
N1—N2—C2—S1 | 172.75 (17) | C17—O2—C15—C16 | −5.7 (4) |
O1—C1—C11—C12 | −68.1 (3) | C17—O2—C15—C14 | 174.8 (2) |
N1—C1—C11—C12 | 114.0 (3) | C13—C14—C15—O2 | −179.3 (2) |
O1—C1—C11—C16 | 108.9 (3) | C13—C14—C15—C16 | 1.1 (4) |
N1—C1—C11—C16 | −69.1 (3) | O2—C15—C16—C11 | 178.2 (2) |
C16—C11—C12—C13 | −0.1 (3) | C14—C15—C16—C11 | −2.3 (3) |
C1—C11—C12—C13 | 176.8 (2) | C12—C11—C16—C15 | 1.8 (3) |
C16—C11—C12—Br1 | −177.87 (17) | C1—C11—C16—C15 | −175.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.85 (4) | 2.06 (3) | 2.825 (3) | 148 (4) |
N2—H2···S1ii | 0.81 (3) | 2.55 (3) | 3.351 (2) | 171 (3) |
N3—H3A···O1iii | 0.86 (4) | 2.25 (4) | 3.068 (3) | 159 (3) |
N3—H3B···S1iv | 0.84 (4) | 2.95 (4) | 3.570 (3) | 132 (3) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C9H10BrN3O2S |
Mr | 304.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 15.6156 (17), 7.7312 (15), 9.8876 (9) |
β (°) | 98.531 (8) |
V (Å3) | 1180.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.65 |
Crystal size (mm) | 0.27 × 0.25 × 0.24 |
Data collection | |
Diffractometer | Stoe IPDSII two-circle |
Absorption correction | Multi-scan (MULABS; Spek, 2003; Blessing, 1995) |
Tmin, Tmax | 0.439, 0.475 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10501, 2266, 1931 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.613 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.071, 1.05 |
No. of reflections | 2266 |
No. of parameters | 163 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.52, −0.56 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA [Or X-RED?], SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.85 (4) | 2.06 (3) | 2.825 (3) | 148 (4) |
N2—H2···S1ii | 0.81 (3) | 2.55 (3) | 3.351 (2) | 171 (3) |
N3—H3A···O1iii | 0.86 (4) | 2.25 (4) | 3.068 (3) | 159 (3) |
N3—H3B···S1iv | 0.84 (4) | 2.95 (4) | 3.570 (3) | 132 (3) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, 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 (Ren et al., 2000; Onderwater et al., 2004). As antibacterial and antifungal agents, they have been used in agriculture (Rodriguez-Fernandez et al., 2005). In technical applications, dithioamide compounds are known to be prospective nonlinear optical materials (Zhou et al., 2003), corrosion inhibitors for copper and iron in acidic media (Stankovic et al., 1996) and functionalization agents for production of chemically modified resins (Trochimczuk et al., 2000). Thiourea derivatives have been also reported as potential receptors and ionophores for heavy metal cations (Castro et al., 2003), building blocks in the synthesis of heterocyclic compounds (Kearney et al., 1998). 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 (Nie et al., 2004). A new carbothioamide, C9H10BrN3O2S, has been synthesized and its crystal structure is reported herein.
Geometric parameters of the title molecule (Fig. 1) are in the usual ranges. The plane of the thiourea moiety is almost coparallel to the plane of the aromatic ring [dihedral angle = 8.40 (12)°]. Only the torsion angles about the Ccarbonyl—Caromatic bond [N1—C1—C11—C12 = 114.0 (3)°] and N—N bond [C1—N1—N2—C2 = -100.9 (3)°] differ significantly from 0 or 180°. The crystal packing is stabilized by N—H···O and N—H···S hydrogen bonds.