Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802023620/ya6149sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802023620/ya6149Isup2.hkl |
CCDC reference: 204676
A solution of furan-2-carboxylic acid hydrazide (0.16 g, 1.40 mmol) in acetone (50 ml) was added dropwise to 50 ml of an acetone solution containing an equimolar amount of benzoyl thiocyanate in a two-neck round-bottomed flask. The solution was refluxed for about one hour and then cooled on ice. The brown precipitate was filtered off and washed with ethanol-distilled water, then dried in a vacuum (yield 76%). Recrystallization from DMF yielded single crystals suitable for X-ray analysis.
After checking their presence in a difference map, all H atoms were included in the refinement in the riding-motion approximation and allowed to ride on the parent C or N atoms, with C—H = 0.97 Å and N—H = 0.89 Å.
Data collection: SMART(Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
C13H11N3O3S | F(000) = 600 |
Mr = 289.31 | Dx = 1.422 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.7902 (14) Å | Cell parameters from 3018 reflections |
b = 7.5505 (8) Å | θ = 1.6–27.5° |
c = 13.9952 (15) Å | µ = 0.25 mm−1 |
β = 90.375 (2)° | T = 299 K |
V = 1351.5 (3) Å3 | Block, brown |
Z = 4 | 0.61 × 0.39 × 0.30 mm |
Bruker SMART APEX CCD area-detector diffractometer | 3065 independent reflections |
Radiation source: fine-focus sealed tube | 2548 reflections with I > 2σ(I)' |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 83.66 pixels mm-1 | θmax = 27.5°, θmin = 1.6° |
ω scans | h = −16→16 |
Absorption correction: empirical (SADABS; Sheldrick, 1996) | k = −9→7 |
Tmin = 0.862, Tmax = 0.929 | l = −17→17 |
7854 measured reflections |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0818P)2 + 0.2233P] where P = (Fo2 + 2Fc2)/3 |
3065 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C13H11N3O3S | V = 1351.5 (3) Å3 |
Mr = 289.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.7902 (14) Å | µ = 0.25 mm−1 |
b = 7.5505 (8) Å | T = 299 K |
c = 13.9952 (15) Å | 0.61 × 0.39 × 0.30 mm |
β = 90.375 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 3065 independent reflections |
Absorption correction: empirical (SADABS; Sheldrick, 1996) | 2548 reflections with I > 2σ(I)' |
Tmin = 0.862, Tmax = 0.929 | Rint = 0.018 |
7854 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.26 e Å−3 |
3065 reflections | Δρmin = −0.24 e Å−3 |
181 parameters |
Experimental. Due to large fraction of weak data at higher angles, the 2θ maximum is limited to 55°. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.32038 (4) | 0.11672 (8) | 0.43803 (3) | 0.0640 (2) | |
O1 | −0.00052 (10) | 0.1927 (2) | 0.55967 (9) | 0.0622 (4) | |
O2 | 0.18606 (10) | 0.0735 (2) | 0.77269 (9) | 0.0585 (4) | |
O3 | 0.42788 (12) | −0.1285 (2) | 0.71557 (11) | 0.0678 (4) | |
N1 | 0.12097 (10) | 0.21639 (19) | 0.44317 (9) | 0.0443 (3) | |
H1A | 0.1318 | 0.2538 | 0.3860 | 0.053* | |
N2 | 0.18874 (11) | 0.0983 (2) | 0.58095 (10) | 0.0489 (4) | |
H2A | 0.1286 | 0.1168 | 0.6062 | 0.059* | |
N3 | 0.26738 (12) | 0.0221 (2) | 0.63375 (11) | 0.0539 (4) | |
H3A | 0.3213 | −0.0206 | 0.6055 | 0.065* | |
C1 | −0.04962 (14) | 0.3110 (3) | 0.31386 (12) | 0.0496 (4) | |
H1B | 0.0098 | 0.2644 | 0.2853 | 0.059* | |
C2 | −0.12924 (15) | 0.3808 (3) | 0.25803 (13) | 0.0545 (5) | |
H2B | −0.1236 | 0.3798 | 0.1918 | 0.065* | |
C3 | −0.21662 (15) | 0.4514 (3) | 0.29990 (14) | 0.0560 (5) | |
H3B | −0.2696 | 0.4994 | 0.2622 | 0.067* | |
C4 | −0.22572 (16) | 0.4509 (3) | 0.39809 (14) | 0.0612 (5) | |
H4A | −0.2848 | 0.4990 | 0.4264 | 0.073* | |
C5 | −0.14789 (16) | 0.3799 (3) | 0.45408 (14) | 0.0538 (5) | |
H5A | −0.1551 | 0.3780 | 0.5202 | 0.065* | |
C6 | −0.05850 (12) | 0.3108 (2) | 0.41250 (11) | 0.0427 (4) | |
C7 | 0.02142 (13) | 0.2348 (2) | 0.47812 (12) | 0.0449 (4) | |
C8 | 0.20562 (13) | 0.1432 (2) | 0.49137 (12) | 0.0442 (4) | |
C9 | 0.26055 (12) | 0.0138 (2) | 0.72926 (12) | 0.0433 (4) | |
C10 | 0.34991 (13) | −0.0723 (2) | 0.77474 (13) | 0.0463 (4) | |
C11 | 0.37363 (18) | −0.1043 (3) | 0.86534 (16) | 0.0725 (6) | |
H11A | 0.3335 | −0.0793 | 0.9188 | 0.087* | |
C12 | 0.47552 (19) | −0.1866 (4) | 0.8629 (2) | 0.0836 (8) | |
H12A | 0.5144 | −0.2253 | 0.9152 | 0.100* | |
C13 | 0.5025 (2) | −0.1965 (4) | 0.7736 (2) | 0.0821 (7) | |
H13A | 0.5653 | −0.2442 | 0.7525 | 0.098* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0465 (3) | 0.1028 (5) | 0.0427 (3) | 0.0105 (2) | 0.00506 (19) | −0.0016 (2) |
O1 | 0.0506 (7) | 0.0935 (10) | 0.0424 (7) | 0.0085 (7) | 0.0093 (5) | 0.0177 (7) |
O2 | 0.0460 (7) | 0.0837 (9) | 0.0459 (7) | 0.0121 (6) | 0.0024 (5) | −0.0071 (6) |
O3 | 0.0606 (9) | 0.0754 (10) | 0.0676 (9) | 0.0212 (7) | 0.0122 (7) | 0.0068 (7) |
N1 | 0.0424 (7) | 0.0573 (8) | 0.0334 (7) | −0.0010 (6) | 0.0023 (5) | 0.0018 (6) |
N2 | 0.0427 (8) | 0.0628 (9) | 0.0413 (8) | 0.0065 (6) | 0.0018 (6) | 0.0052 (6) |
N3 | 0.0507 (8) | 0.0696 (10) | 0.0414 (8) | 0.0157 (7) | 0.0020 (6) | 0.0029 (7) |
C1 | 0.0426 (9) | 0.0641 (11) | 0.0421 (9) | −0.0026 (8) | 0.0057 (7) | −0.0006 (8) |
C2 | 0.0527 (10) | 0.0722 (12) | 0.0387 (9) | −0.0033 (9) | 0.0004 (7) | 0.0044 (8) |
C3 | 0.0548 (10) | 0.0611 (11) | 0.0520 (11) | 0.0052 (9) | −0.0040 (8) | 0.0062 (8) |
C4 | 0.0549 (11) | 0.0719 (13) | 0.0569 (12) | 0.0154 (9) | 0.0059 (8) | −0.0002 (9) |
C5 | 0.0539 (10) | 0.0660 (12) | 0.0416 (9) | 0.0086 (8) | 0.0060 (7) | 0.0006 (8) |
C6 | 0.0418 (8) | 0.0456 (9) | 0.0406 (9) | −0.0043 (7) | 0.0030 (6) | 0.0005 (7) |
C7 | 0.0429 (9) | 0.0522 (9) | 0.0395 (9) | −0.0029 (7) | 0.0038 (6) | 0.0006 (7) |
C8 | 0.0461 (9) | 0.0496 (9) | 0.0370 (8) | −0.0029 (7) | −0.0003 (6) | −0.0047 (7) |
C9 | 0.0412 (8) | 0.0455 (9) | 0.0433 (9) | −0.0019 (7) | −0.0005 (6) | −0.0029 (7) |
C10 | 0.0416 (8) | 0.0508 (9) | 0.0465 (9) | 0.0007 (7) | 0.0027 (7) | 0.0019 (7) |
C11 | 0.0624 (12) | 0.1038 (18) | 0.0513 (12) | 0.0057 (12) | −0.0062 (9) | 0.0137 (11) |
C12 | 0.0659 (14) | 0.1033 (19) | 0.0813 (17) | 0.0148 (13) | −0.0197 (12) | 0.0285 (14) |
C13 | 0.0629 (13) | 0.0875 (17) | 0.096 (2) | 0.0265 (12) | 0.0056 (12) | 0.0216 (14) |
S1—C8 | 1.6631 (18) | C2—C3 | 1.373 (3) |
O1—C7 | 1.219 (2) | C2—H2B | 0.9300 |
O2—C9 | 1.220 (2) | C3—C4 | 1.380 (3) |
O3—C10 | 1.368 (2) | C3—H3B | 0.9300 |
O3—C13 | 1.351 (3) | C4—C5 | 1.372 (3) |
N1—C7 | 1.374 (2) | C4—H4A | 0.9300 |
N1—C8 | 1.387 (2) | C5—C6 | 1.388 (2) |
N1—H1A | 0.8600 | C5—H5A | 0.9300 |
N2—N3 | 1.371 (2) | C6—C7 | 1.485 (2) |
N2—C8 | 1.318 (2) | C9—C10 | 1.457 (2) |
N2—H2A | 0.8600 | C10—C11 | 1.324 (3) |
N3—C9 | 1.342 (2) | C11—C12 | 1.444 (3) |
N3—H3A | 0.8600 | C11—H11A | 0.9300 |
C1—C2 | 1.384 (3) | C12—C13 | 1.300 (4) |
C1—C6 | 1.386 (2) | C12—H12A | 0.9300 |
C1—H1B | 0.9300 | C13—H13A | 0.9300 |
C13—O3—C10 | 105.60 (18) | C1—C6—C5 | 119.35 (16) |
C7—N1—C8 | 126.13 (14) | C1—C6—C7 | 123.78 (15) |
C7—N1—H1A | 116.9 | C5—C6—C7 | 116.84 (15) |
C8—N1—H1A | 116.9 | O1—C7—N1 | 121.75 (16) |
C8—N2—N3 | 119.77 (14) | O1—C7—C6 | 121.19 (14) |
C8—N2—H2A | 120.1 | N1—C7—C6 | 117.05 (14) |
N3—N2—H2A | 120.1 | N2—C8—N1 | 115.66 (14) |
C9—N3—N2 | 120.29 (14) | N2—C8—S1 | 123.14 (13) |
C9—N3—H3A | 119.9 | N1—C8—S1 | 121.20 (12) |
N2—N3—H3A | 119.9 | O2—C9—N3 | 122.36 (15) |
C2—C1—C6 | 119.88 (16) | O2—C9—C10 | 124.06 (16) |
C2—C1—H1B | 120.1 | N3—C9—C10 | 113.58 (14) |
C6—C1—H1B | 120.1 | C11—C10—O3 | 111.08 (17) |
C3—C2—C1 | 120.32 (17) | C11—C10—C9 | 132.35 (18) |
C3—C2—H2B | 119.8 | O3—C10—C9 | 116.54 (15) |
C1—C2—H2B | 119.8 | C10—C11—C12 | 104.9 (2) |
C2—C3—C4 | 119.90 (17) | C10—C11—H11A | 127.6 |
C2—C3—H3B | 120.1 | C12—C11—H11A | 127.6 |
C4—C3—H3B | 120.1 | C13—C12—C11 | 107.0 (2) |
C5—C4—C3 | 120.27 (18) | C13—C12—H12A | 126.5 |
C5—C4—H4A | 119.9 | C11—C12—H12A | 126.5 |
C3—C4—H4A | 119.9 | C12—C13—O3 | 111.4 (2) |
C4—C5—C6 | 120.27 (17) | C12—C13—H13A | 124.3 |
C4—C5—H5A | 119.9 | O3—C13—H13A | 124.3 |
C6—C5—H5A | 119.9 | ||
C8—N2—N3—C9 | 164.33 (16) | N3—N2—C8—S1 | −1.6 (2) |
C6—C1—C2—C3 | 0.7 (3) | C7—N1—C8—N2 | −4.6 (2) |
C1—C2—C3—C4 | −0.8 (3) | C7—N1—C8—S1 | 175.93 (14) |
C2—C3—C4—C5 | −0.1 (3) | N2—N3—C9—O2 | −0.5 (3) |
C3—C4—C5—C6 | 1.2 (3) | N2—N3—C9—C10 | 179.54 (15) |
C2—C1—C6—C5 | 0.4 (3) | C13—O3—C10—C11 | −0.5 (3) |
C2—C1—C6—C7 | 178.34 (16) | C13—O3—C10—C9 | 177.71 (18) |
C4—C5—C6—C1 | −1.3 (3) | O2—C9—C10—C11 | −0.9 (3) |
C4—C5—C6—C7 | −179.39 (18) | N3—C9—C10—C11 | 179.0 (2) |
C8—N1—C7—O1 | 3.2 (3) | O2—C9—C10—O3 | −178.67 (17) |
C8—N1—C7—C6 | −177.63 (15) | N3—C9—C10—O3 | 1.2 (2) |
C1—C6—C7—O1 | −159.43 (18) | O3—C10—C11—C12 | 0.4 (3) |
C5—C6—C7—O1 | 18.6 (3) | C9—C10—C11—C12 | −177.4 (2) |
C1—C6—C7—N1 | 21.4 (2) | C10—C11—C12—C13 | −0.2 (3) |
C5—C6—C7—N1 | −160.64 (16) | C11—C12—C13—O3 | −0.1 (3) |
N3—N2—C8—N1 | 178.88 (15) | C10—O3—C13—C12 | 0.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 2.17 | 2.988 (2) | 158 |
N2—H2A···O1 | 0.86 | 1.86 | 2.5395 (19) | 134 |
N3—H3A···S1 | 0.86 | 2.56 | 2.9148 (16) | 105 |
N3—H3A···O3 | 0.86 | 2.21 | 2.606 (2) | 108 |
C1—H1B···O2i | 0.93 | 2.57 | 3.194 (2) | 124 |
C2—H2B···O1i | 0.93 | 2.49 | 3.284 (2) | 143 |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H11N3O3S |
Mr | 289.31 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 299 |
a, b, c (Å) | 12.7902 (14), 7.5505 (8), 13.9952 (15) |
β (°) | 90.375 (2) |
V (Å3) | 1351.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.61 × 0.39 × 0.30 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Empirical (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.862, 0.929 |
No. of measured, independent and observed [I > 2σ(I)'] reflections | 7854, 3065, 2548 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.141, 1.04 |
No. of reflections | 3065 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.24 |
Computer programs: SMART(Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
S1—C8 | 1.6631 (18) | N1—C7 | 1.374 (2) |
O1—C7 | 1.219 (2) | N1—C8 | 1.387 (2) |
O2—C9 | 1.220 (2) | N2—N3 | 1.371 (2) |
O3—C10 | 1.368 (2) | N2—C8 | 1.318 (2) |
O3—C13 | 1.351 (3) | N3—C9 | 1.342 (2) |
C13—O3—C10 | 105.60 (18) | O1—C7—N1 | 121.75 (16) |
C7—N1—C8 | 126.13 (14) | N1—C7—C6 | 117.05 (14) |
C8—N2—N3 | 119.77 (14) | N2—C8—N1 | 115.66 (14) |
C9—N3—N2 | 120.29 (14) | O2—C9—N3 | 122.36 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 2.17 | 2.988 (2) | 158 |
N2—H2A···O1 | 0.86 | 1.86 | 2.5395 (19) | 134 |
N3—H3A···S1 | 0.86 | 2.56 | 2.9148 (16) | 105 |
N3—H3A···O3 | 0.86 | 2.21 | 2.606 (2) | 108 |
C1—H1B···O2i | 0.93 | 2.57 | 3.194 (2) | 124 |
C2—H2B···O1i | 0.93 | 2.49 | 3.284 (2) | 143 |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Thiourea and dithio compounds, such as dithiocarbazate and dithiocarbamates, are potential biologically active compounds. Some thiourea derivatives, such as N-[2-(2-chlorophenethyl)]-N'-[2-(5-bromopyridyl)]thiourea, have been reported as potent non-nucleoside inhibitors of HIV reverse transcriptase at nanomolar concentrations (Vig et al., 1998; Vankatachalam et al., 2001). Therefore, new thiourea derivatives and their structures are presently the focus of the studies of several research groups. Within the framework of such studies carried out in our group, the suitable quality crystals of the title compound, (I), were obtained and its crystal structure was determined.
As well as the majority of benzoylthiourea derivatives, the title compound, (I) (Fig. 1), adopts a cis–trans conformation where the N3/C9/O2/C10/C11/C12/C13/O3 furoyl moiety and the benzoyl group lie respectively cis and trans relative to to the S atom across the thiourea C—N bonds (Usman et al., 2002; Shanmuga Sundara Raj et al., 1999). The bond lengths and angles in (I) (Table 1) are within normal ranges (Allen et al., 1987). However, the N1==-C8 and N2-==C8 bond lengths of 1.387 (2) and 1.318 (2) Å, respectively are slightly shorter than the analogous bonds in N-benzoyl-N'-(2,6-dimethylphenyl)thiourea with a bulky dimethylphenyl substituent [1.395 (2) and 1.331 (3) Å, respectively (Usman et al., 2002)].
The S1/C8/N1/N2/C7/O1 and the O2/O3/C9/C10/C11/C12/C13 furoyl fragments are almost planar [maximum deviations at N1 and C10 from their respective mean planes are 0.039 (1) and 0.023 (2) Å]. Unlike the bulky N-benzoyl-N'-(2,6-dimethylphenyl)thiourea, where the aromatic rings are almost perpendicular to each other, the present compound shows the dihedral angle between the phenyl and the furoyl O2/O3/C9/C10/C11/C12/C13 planes of only 1.72 (8)°. The dihedral angles between the carbonylthiourea moiety S1/C8/N1/N2/C7/O1 and the phenyl C1/C2/C3/C4/C5/C6/C7 and furoyl O2/O3/C9/C10/C11/C12/C13 fragments are equal to 18.74 (7) and 17.60 (6)°, respectively.
There are three intramolecular hydrogen bonds in the molecule of (I) (N2—H2A···O1, N3—H3A···S1 and N3—H3A···O3; Table 2). As a result, in addition to typical for benzoylthiourea systems six-membered pseudocycle (O1—C7—N1—C8—N2—H2A), two five-membered rings (O3—C10—C9—N3—H3A and S1—C8—N2—N3—H3A) are formed. In the crystal, three intermolecular hydrogen bonds [N1—H1A···O2i, C1—H1B···O2i and C2—H2B···O1i; symmetry code (i): x, 1/2 − y, z − 1/2; Table 2] link the molecules into infinite chains parallel to the c axis (Fig. 2).