Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037543/ci2428sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037543/ci2428Isup2.hkl |
CCDC reference: 653947
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.003 Å
- R factor = 0.038
- wR factor = 0.110
- Data-to-parameter ratio = 16.6
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A mixture of 3-bromopentane-2,4-dione (1.79 g, 0.01 mol) and 1-(4-nitrophenyl)thiourea (1.97 g, 0.01 mol) in acetone (20 ml) was refluxed for 1 h. The mixture was cooled to room temperature, then it was neutralized with 15% sodium carbonate aqueous solution to a pH of 8, to obtain a yellow precipitate. The precipitate was filtered off and recrystallized from acetone to give the crude product. The solid product was dissolved in ethanol evaporated gradually at room temperature to afford single crystals of the title compound (m.p. 441–441.5 K). 1HNMR(CDCl3)σp.p.m.: 8.42(d,2H,Ar), 7.50(d,2H,Ar), 2.36(s,1H,CH3), 2.25(s,3H,CH3). MS.(m/z,%): 276(M+,100), 262 (15), 230 (20), 163 (80), 117 (55), 76 (30).
Atom H6 was located in a difference Fourier map and refined isotropically with the N—H bond restraint of 0.86 (2) Å. Methyl H atoms were placed in calculated positions, with C—H = 0.96 Å, and torsion angles were refined to fit the electron density [Uiso(H) = 1.5Ueq(C)]. Other H atoms were placed in calculated positions, with C—H = 0.93 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C).
The title compound, (I), was obtained as a by-product during the attempted preparation of a thiazolone (Patil et al., 1978). We report here the crystal structure of (I).
The molecule structure of (I) is illustrated in Fig. 1. The benzene ring is twisted out of the central thiazole ring by 85.36 (5)°. The ethanone group is coplanar with the thiazole ring [dihedral angle = 2.6 (1)°] whereas the nitro group forms a dihedral angle of 10.7 (2)° with the attached benzene ring.
In the crystal structure, weak intermolecular C—H···O and N—H···O hydrogen bonds (Table 1), involving the ethanone oxygen atom, link the molecules into a two-dimensional network parallel to the bc plane (Fig. 2).
For synthesis of thiazolone, see: Patil et al. (1978).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. | |
Fig. 2. The crystal structure of (I), viewed down the a axis. Hydrogen bonds are shown as dashed lines. |
C12H11N3O3S | F(000) = 576 |
Mr = 277.30 | Dx = 1.409 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2619 reflections |
a = 11.446 (2) Å | θ = 2.6–26.9° |
b = 11.1475 (19) Å | µ = 0.26 mm−1 |
c = 10.5155 (18) Å | T = 296 K |
β = 103.108 (2)° | Prism, colourless |
V = 1306.8 (4) Å3 | 0.25 × 0.20 × 0.20 mm |
Z = 4 |
Bruker SMART APEX II CCD area-detector diffractometer | 2957 independent reflections |
Radiation source: fine-focus sealed tube | 2218 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
φ and ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→12 |
Tmin = 0.939, Tmax = 0.941 | k = −14→14 |
8104 measured reflections | l = −13→12 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0564P)2 + 0.1727P] where P = (Fo2 + 2Fc2)/3 |
2957 reflections | (Δ/σ)max = 0.001 |
178 parameters | Δρmax = 0.22 e Å−3 |
1 restraint | Δρmin = −0.21 e Å−3 |
C12H11N3O3S | V = 1306.8 (4) Å3 |
Mr = 277.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.446 (2) Å | µ = 0.26 mm−1 |
b = 11.1475 (19) Å | T = 296 K |
c = 10.5155 (18) Å | 0.25 × 0.20 × 0.20 mm |
β = 103.108 (2)° |
Bruker SMART APEX II CCD area-detector diffractometer | 2957 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2218 reflections with I > 2σ(I) |
Tmin = 0.939, Tmax = 0.941 | Rint = 0.020 |
8104 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.22 e Å−3 |
2957 reflections | Δρmin = −0.21 e Å−3 |
178 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 | 0.41478 (4) | 0.47752 (4) | 0.66509 (4) | 0.05007 (16) | |
C2 | 0.29327 (16) | 0.54805 (15) | 0.55964 (15) | 0.0474 (4) | |
N3 | 0.25911 (13) | 0.47702 (12) | 0.44709 (13) | 0.0454 (3) | |
C4 | 0.32876 (14) | 0.37655 (14) | 0.44183 (14) | 0.0419 (4) | |
C5 | 0.41624 (14) | 0.36138 (14) | 0.55179 (14) | 0.0423 (4) | |
N6 | 0.24008 (16) | 0.64488 (15) | 0.57377 (17) | 0.0654 (4) | |
H6 | 0.271 (2) | 0.677 (2) | 0.6472 (18) | 0.089 (8)* | |
C7 | 0.15721 (15) | 0.51090 (14) | 0.34560 (16) | 0.0452 (4) | |
C8 | 0.17215 (16) | 0.59002 (17) | 0.25130 (18) | 0.0588 (5) | |
H8 | 0.2475 | 0.6223 | 0.2534 | 0.071* | |
C9 | 0.07504 (17) | 0.62214 (17) | 0.15259 (19) | 0.0606 (5) | |
H9 | 0.0837 | 0.6769 | 0.0886 | 0.073* | |
C10 | −0.03356 (15) | 0.57147 (17) | 0.15162 (18) | 0.0548 (4) | |
C11 | −0.05053 (18) | 0.4921 (2) | 0.2445 (2) | 0.0701 (6) | |
H11 | −0.1257 | 0.4589 | 0.2410 | 0.084* | |
C12 | 0.04649 (18) | 0.46203 (19) | 0.3440 (2) | 0.0646 (5) | |
H12 | 0.0370 | 0.4092 | 0.4093 | 0.078* | |
C13 | 0.30315 (17) | 0.30545 (17) | 0.31897 (16) | 0.0571 (5) | |
H13A | 0.3336 | 0.3471 | 0.2535 | 0.086* | |
H13B | 0.2181 | 0.2949 | 0.2893 | 0.086* | |
H13C | 0.3412 | 0.2284 | 0.3348 | 0.086* | |
C14 | 0.50708 (14) | 0.27027 (15) | 0.59324 (15) | 0.0450 (4) | |
C15 | 0.52307 (18) | 0.16729 (18) | 0.50871 (18) | 0.0623 (5) | |
H15A | 0.5914 | 0.1210 | 0.5514 | 0.093* | |
H15B | 0.5354 | 0.1968 | 0.4270 | 0.093* | |
H15C | 0.4527 | 0.1177 | 0.4932 | 0.093* | |
N16 | −0.13660 (16) | 0.60437 (19) | 0.04487 (18) | 0.0728 (5) | |
O1 | 0.57196 (11) | 0.27919 (12) | 0.70342 (11) | 0.0597 (3) | |
O2 | −0.22880 (14) | 0.5470 (2) | 0.0333 (2) | 0.1050 (6) | |
O3 | −0.12451 (16) | 0.6876 (2) | −0.02542 (17) | 0.1007 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0592 (3) | 0.0519 (3) | 0.0348 (2) | −0.00628 (19) | 0.00156 (18) | −0.00343 (16) |
C2 | 0.0545 (10) | 0.0450 (9) | 0.0408 (8) | −0.0065 (7) | 0.0066 (7) | −0.0018 (7) |
N3 | 0.0502 (8) | 0.0432 (7) | 0.0383 (7) | 0.0004 (6) | 0.0004 (6) | −0.0012 (5) |
C4 | 0.0466 (9) | 0.0424 (8) | 0.0352 (8) | −0.0016 (7) | 0.0060 (6) | 0.0009 (6) |
C5 | 0.0474 (9) | 0.0453 (8) | 0.0328 (7) | −0.0059 (7) | 0.0062 (6) | 0.0006 (6) |
N6 | 0.0786 (12) | 0.0523 (10) | 0.0596 (10) | 0.0051 (8) | 0.0038 (9) | −0.0137 (8) |
C7 | 0.0458 (9) | 0.0431 (8) | 0.0427 (8) | 0.0009 (7) | 0.0017 (7) | −0.0014 (6) |
C8 | 0.0470 (10) | 0.0600 (11) | 0.0622 (11) | −0.0121 (8) | −0.0030 (8) | 0.0143 (9) |
C9 | 0.0577 (11) | 0.0585 (11) | 0.0584 (11) | −0.0020 (9) | −0.0016 (9) | 0.0127 (9) |
C10 | 0.0447 (9) | 0.0580 (10) | 0.0548 (10) | 0.0081 (8) | −0.0029 (8) | −0.0104 (8) |
C11 | 0.0416 (10) | 0.0887 (15) | 0.0775 (14) | −0.0101 (10) | 0.0082 (10) | 0.0033 (11) |
C12 | 0.0563 (11) | 0.0737 (13) | 0.0631 (12) | −0.0104 (10) | 0.0117 (9) | 0.0119 (10) |
C13 | 0.0647 (11) | 0.0601 (11) | 0.0396 (9) | 0.0086 (9) | −0.0027 (8) | −0.0083 (8) |
C14 | 0.0407 (8) | 0.0554 (10) | 0.0374 (8) | −0.0043 (7) | 0.0060 (7) | 0.0063 (7) |
C15 | 0.0595 (11) | 0.0651 (11) | 0.0567 (11) | 0.0144 (9) | 0.0012 (9) | −0.0005 (9) |
N16 | 0.0548 (11) | 0.0859 (13) | 0.0671 (11) | 0.0176 (9) | −0.0084 (8) | −0.0193 (10) |
O1 | 0.0527 (7) | 0.0779 (9) | 0.0418 (6) | 0.0014 (6) | −0.0036 (5) | 0.0048 (6) |
O2 | 0.0463 (9) | 0.1384 (17) | 0.1146 (14) | 0.0024 (10) | −0.0146 (9) | −0.0233 (12) |
O3 | 0.0961 (13) | 0.1092 (14) | 0.0755 (11) | 0.0222 (11) | −0.0251 (9) | 0.0102 (10) |
S1—C2 | 1.7558 (18) | C10—C11 | 1.364 (3) |
S1—C5 | 1.7620 (16) | C10—N16 | 1.478 (2) |
C2—N6 | 1.264 (2) | C11—C12 | 1.383 (3) |
C2—N3 | 1.404 (2) | C11—H11 | 0.93 |
N3—C4 | 1.383 (2) | C12—H12 | 0.93 |
N3—C7 | 1.441 (2) | C13—H13A | 0.96 |
C4—C5 | 1.358 (2) | C13—H13B | 0.96 |
C4—C13 | 1.487 (2) | C13—H13C | 0.96 |
C5—C14 | 1.448 (2) | C14—O1 | 1.2303 (19) |
N6—H6 | 0.85 (2) | C14—C15 | 1.488 (2) |
C7—C8 | 1.367 (2) | C15—H15A | 0.96 |
C7—C12 | 1.376 (3) | C15—H15B | 0.96 |
C8—C9 | 1.385 (2) | C15—H15C | 0.96 |
C8—H8 | 0.93 | N16—O3 | 1.214 (3) |
C9—C10 | 1.363 (3) | N16—O2 | 1.216 (3) |
C9—H9 | 0.93 | ||
C2—S1—C5 | 91.70 (8) | C11—C10—N16 | 119.07 (18) |
N6—C2—N3 | 122.08 (16) | C10—C11—C12 | 118.58 (18) |
N6—C2—S1 | 129.91 (14) | C10—C11—H11 | 120.7 |
N3—C2—S1 | 108.00 (12) | C12—C11—H11 | 120.7 |
C4—N3—C2 | 115.95 (13) | C7—C12—C11 | 119.52 (18) |
C4—N3—C7 | 124.02 (13) | C7—C12—H12 | 120.2 |
C2—N3—C7 | 120.02 (13) | C11—C12—H12 | 120.2 |
C5—C4—N3 | 112.78 (13) | C4—C13—H13A | 109.5 |
C5—C4—C13 | 129.46 (15) | C4—C13—H13B | 109.5 |
N3—C4—C13 | 117.68 (14) | H13A—C13—H13B | 109.5 |
C4—C5—C14 | 133.17 (15) | C4—C13—H13C | 109.5 |
C4—C5—S1 | 111.48 (12) | H13A—C13—H13C | 109.5 |
C14—C5—S1 | 115.34 (11) | H13B—C13—H13C | 109.5 |
C2—N6—H6 | 110.6 (17) | O1—C14—C5 | 117.75 (15) |
C8—C7—C12 | 120.87 (16) | O1—C14—C15 | 119.67 (16) |
C8—C7—N3 | 119.53 (15) | C5—C14—C15 | 122.57 (14) |
C12—C7—N3 | 119.59 (16) | C14—C15—H15A | 109.5 |
C7—C8—C9 | 119.96 (17) | C14—C15—H15B | 109.5 |
C7—C8—H8 | 120.0 | H15A—C15—H15B | 109.5 |
C9—C8—H8 | 120.0 | C14—C15—H15C | 109.5 |
C10—C9—C8 | 118.30 (17) | H15A—C15—H15C | 109.5 |
C10—C9—H9 | 120.9 | H15B—C15—H15C | 109.5 |
C8—C9—H9 | 120.9 | O3—N16—O2 | 123.9 (2) |
C9—C10—C11 | 122.76 (17) | O3—N16—C10 | 118.08 (19) |
C9—C10—N16 | 118.17 (19) | O2—N16—C10 | 118.0 (2) |
C5—S1—C2—N6 | −178.16 (19) | C2—N3—C7—C12 | −95.0 (2) |
C5—S1—C2—N3 | 1.87 (12) | C12—C7—C8—C9 | 0.1 (3) |
N6—C2—N3—C4 | 176.94 (16) | N3—C7—C8—C9 | 179.31 (16) |
S1—C2—N3—C4 | −3.09 (17) | C7—C8—C9—C10 | −1.0 (3) |
N6—C2—N3—C7 | −2.8 (3) | C8—C9—C10—C11 | 0.9 (3) |
S1—C2—N3—C7 | 177.17 (12) | C8—C9—C10—N16 | −178.98 (17) |
C2—N3—C4—C5 | 3.0 (2) | C9—C10—C11—C12 | 0.2 (3) |
C7—N3—C4—C5 | −177.31 (14) | N16—C10—C11—C12 | −179.94 (19) |
C2—N3—C4—C13 | −174.16 (15) | C8—C7—C12—C11 | 1.0 (3) |
C7—N3—C4—C13 | 5.6 (2) | N3—C7—C12—C11 | −178.22 (17) |
N3—C4—C5—C14 | 177.98 (16) | C10—C11—C12—C7 | −1.1 (3) |
C13—C4—C5—C14 | −5.3 (3) | C4—C5—C14—O1 | −177.10 (17) |
N3—C4—C5—S1 | −1.33 (17) | S1—C5—C14—O1 | 2.19 (19) |
C13—C4—C5—S1 | 175.36 (15) | C4—C5—C14—C15 | 2.2 (3) |
C2—S1—C5—C4 | −0.36 (13) | S1—C5—C14—C15 | −178.54 (14) |
C2—S1—C5—C14 | −179.80 (12) | C9—C10—N16—O3 | −10.8 (3) |
C4—N3—C7—C8 | −94.0 (2) | C11—C10—N16—O3 | 169.3 (2) |
C2—N3—C7—C8 | 85.8 (2) | C9—C10—N16—O2 | 169.77 (19) |
C4—N3—C7—C12 | 85.2 (2) | C11—C10—N16—O2 | −10.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···O1i | 0.85 (2) | 2.39 (2) | 3.174 (2) | 153 (2) |
C8—H8···O1ii | 0.93 | 2.29 | 3.209 (2) | 168 |
C15—H15B···O1iii | 0.96 | 2.49 | 3.434 (2) | 166 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H11N3O3S |
Mr | 277.30 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 11.446 (2), 11.1475 (19), 10.5155 (18) |
β (°) | 103.108 (2) |
V (Å3) | 1306.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX II CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.939, 0.941 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8104, 2957, 2218 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.110, 1.03 |
No. of reflections | 2957 |
No. of parameters | 178 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.21 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2005), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···O1i | 0.85 (2) | 2.39 (2) | 3.174 (2) | 153 (2) |
C8—H8···O1ii | 0.93 | 2.29 | 3.209 (2) | 168 |
C15—H15B···O1iii | 0.96 | 2.49 | 3.434 (2) | 166 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2. |
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The title compound, (I), was obtained as a by-product during the attempted preparation of a thiazolone (Patil et al., 1978). We report here the crystal structure of (I).
The molecule structure of (I) is illustrated in Fig. 1. The benzene ring is twisted out of the central thiazole ring by 85.36 (5)°. The ethanone group is coplanar with the thiazole ring [dihedral angle = 2.6 (1)°] whereas the nitro group forms a dihedral angle of 10.7 (2)° with the attached benzene ring.
In the crystal structure, weak intermolecular C—H···O and N—H···O hydrogen bonds (Table 1), involving the ethanone oxygen atom, link the molecules into a two-dimensional network parallel to the bc plane (Fig. 2).