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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 2| February 2012| Page o544
doi:10.1107/S1600536812002978

N-(5-Eth­­oxy-1,3,4-thia­diazol-2-yl)benzamide

Sung Kwon Kang,a* Nam Sook Choa and Min Kyeong Jeona

aDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
*Correspondence e-mail: skkang@cnu.ac.kr

(Received 20 January 2012; accepted 24 January 2012; online 31 January 2012)

In the title compound, C11H11N3O2S, the dihedral angle between the thia­diazole and phenyl rings is 28.08 (7)°. In the crystal, mol­ecules are linked into an inversion dimer by a pair of inter­molecular N—H⋯N hydrogen bonds with an R22(8) graph-set motif.

Related literature

For the structures and reactivity of thia­diazole derivatives, see: Cho et al. (1996[Cho, N. S., Cho, J. J., Ra, D. Y., Moon, J. H., Song, J. S. & Kang, S. K. (1996). Bull. Korean Chem. Soc. 17, 1170-1174.]); Parkanyi et al. (1989[Parkanyi, C., Yuan, H. L., Cho, N. S., Jaw, J. J., Woodhouse, T. E. & Aung, T. L. (1989). J. Heterocycl. Chem. 26, 1331-1334.]).

[Scheme 1]

Experimental

Crystal data

  • C11H11N3O2S

  • Mr = 249.29

  • Monoclinic, P 21 /c

  • a = 3.9797 (5) Å

  • b = 20.138 (3) Å

  • c = 14.4305 (18) Å

  • β = 92.036 (2)°

  • V = 1155.8 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.27 mm−1

  • T = 296 K

  • 0.27 × 0.12 × 0.11 mm
Data collection

  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2002[Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.956, Tmax = 0.965

  • 22225 measured reflections

  • 2891 independent reflections

  • 1287 reflections with I > 2σ(I)

  • Rint = 0.114
Refinement

  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.081

  • S = 0.74

  • 2891 reflections

  • 158 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.19 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N6—H6⋯N3i 0.86 (2) 2.12 (2) 2.967 (3) 169 (2)
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2002[Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2002[Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812002978/is5058sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812002978/is5058Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812002978/is5058Isup3.cml

checkCIF report


Comment top

5-Amino-2H-1,2,4-thiadiazol-3-one is a five-membered ring analog of cytosine. 5-Amino-3H-1,3,4-thiadiazol-2-one is an isomer of 5-amino-2H-1,2,4-thiadiazol-3-one. The analogs of cytosine have potential to have biological activities (Parkanyi et al., 1989). Thus, we attempted synthesis of derivatives of 5-amino-3H-1,3,4-thiadiazol-2-one (Cho et al., 1996). The title compound, 2-benzoylamino-5-ethoxy-1,3,4-thiadiazole (I) is an intermediate to prepare 5-benzolamino-3H-1,3,4-thiadiazolin-2-one via hydrolysis.

The five-membered 1,3,4-thiadiazol-2-yl unit is planar, with an r.m.s. deviation of 0.003 Å from the corresponding squares plane defined by the seven constituent atoms. The bond distances of C2—N3 and C5—N4 [1.298 (2) and 1.282 (2) Å] in five-membered heterocyclic ring are shorter than those of C2—N6 and C7—N6 [1.379 (2) and 1.369 (2) Å], which is consistent with double bond character. A pair of intermolecular N6—H6···N3i [symmetry code: (i) -x, -y + 1, -z + 1] hydrogen bonds link two molecules into an inversion dimer (Fig. 2 and Table 1), which stabilizes the crystal structure.

Related literature top

For the structures and reactivity of thiadiazole derivatives, see: Cho et al. (1996); Parkanyi et al. (1989).

Experimental top

5-Amino-2-ethoxy-1,3,4-thiadiazole (1 g, 7.4 mmol) was dissolved in anhydrous dioxane (20 ml) at 80 °C. Triethylamine and benzoyl chloride (8.9 mmol) was added respectively to the above solution. The reaction solution was stirred at 80 °C for 40 minutes. TLC was used to determine the completion of the reaction. The reaction mixture was then cooled to room temperature and the ethylamine hydrochloride filtered off. The white solid was remained after the solvent was distilled off. The solid was recrystallized from ethanol to get analytical sample (product yield 55%). Colourless crystals of (I) were obtained from its ethanol solution by slow evaporation of the solvent at room temperature (m.p. 180 °C). IR (KBr, cm-1) 3120 (NH), 3000 (CH), 2950 (CH), 1680 (C=O), 1580 (C=N). -1H NMR (DMSO-d6, p.p.m.): 12.5 (1H, b, NH), 8.3–7.4 (5H, m, Ph), 4.4 (2H, q, CH2), 1.4 (3H, t, CH3). 13C NMR (DMSO-d6, p.p.m.): 170.5 (amide C=O), 165.2 (O—C=N), 153.2 (C=N), 132.9, 131.6, 128.7, 128.4 (Ph), 68.2 (CH2), 14.4 (CH3). Anal. Calcd. For C11H11N3O2S: C 53.00, H 4.456, N 16.86, S 12.86. Found: C 53.07, H 4.46, N 16.83, S 13.29.

Refinement top

Atom H6 of the NH group was located in a difference Fourier map and refined freely [refined distance = 0.86 (2) Å]. Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(carrier C) for aromatic and methylene or 1.5Ueq(carrier C) for methyl H atoms.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme and 30% probability ellipsoids.
[Figure 2] Fig. 2. Part of the crystal structure of the title compound, showing molecules linked by intermolecular N—H···N hydrogen bonds (dashed lines).
N-(5-Ethoxy-1,3,4-thiadiazol-2-yl)benzamide top
Crystal data top
C11H11N3O2SF(000) = 520
Mr = 249.29Dx = 1.433 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1448 reflections
a = 3.9797 (5) Åθ = 2.8–18.7°
b = 20.138 (3) ŵ = 0.27 mm−1
c = 14.4305 (18) ÅT = 296 K
β = 92.036 (2)°Needle, colourless
V = 1155.8 (2) Å30.27 × 0.12 × 0.11 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		1287 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.114
ϕ and ω scansθmax = 28.4°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −5→5
Tmin = 0.956, Tmax = 0.965k = −26→26
22225 measured reflectionsl = −19→19
2891 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 0.74 w = 1/[σ2(Fo2) + (0.0257P)2]
where P = (Fo2 + 2Fc2)/3
2891 reflections(Δ/σ)max < 0.001
158 parametersΔρmax = 0.19 e Å−3
0 restraintsΔρmin = −0.19 e Å−3
Crystal data top
C11H11N3O2SV = 1155.8 (2) Å3
Mr = 249.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 3.9797 (5) ŵ = 0.27 mm−1
b = 20.138 (3) ÅT = 296 K
c = 14.4305 (18) Å0.27 × 0.12 × 0.11 mm
β = 92.036 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2891 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		1287 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.965Rint = 0.114
22225 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 0.74Δρmax = 0.19 e Å−3
2891 reflectionsΔρmin = −0.19 e Å−3
158 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
S10.39663 (15)0.34946 (3)0.62317 (4)0.04682 (18)
C20.2359 (5)0.42298 (9)0.57867 (14)0.0375 (5)
N30.2325 (5)0.42812 (8)0.48901 (12)0.0467 (5)
N40.3654 (5)0.37174 (8)0.44715 (11)0.0473 (5)
C50.4558 (5)0.32859 (10)0.50836 (14)0.0411 (5)
N60.1165 (5)0.47337 (9)0.63320 (12)0.0433 (5)
H60.021 (6)0.5057 (12)0.6040 (16)0.082 (9)*
C70.1183 (5)0.46904 (10)0.72786 (14)0.0398 (5)
O80.2192 (4)0.41880 (7)0.76704 (9)0.0545 (4)
C9−0.0024 (5)0.52767 (10)0.77924 (14)0.0399 (5)
C10−0.1415 (6)0.51700 (12)0.86450 (15)0.0549 (7)
H10−0.16290.47390.88680.066*
C11−0.2486 (6)0.56979 (13)0.91657 (16)0.0608 (7)
H11−0.34390.56230.97360.073*
C12−0.2143 (6)0.63343 (13)0.88413 (16)0.0621 (7)
H12−0.2880.66910.9190.075*
C13−0.0712 (6)0.64450 (11)0.80031 (16)0.0606 (7)
H13−0.04440.68770.77910.073*
C140.0330 (6)0.59171 (10)0.74726 (15)0.0491 (6)
H140.12680.59940.69010.059*
O150.5894 (4)0.26919 (7)0.49063 (10)0.0541 (4)
C160.6596 (6)0.25697 (10)0.39481 (14)0.0516 (6)
H16A0.83590.28650.37510.062*
H16B0.45970.26490.35590.062*
C170.7689 (6)0.18619 (11)0.38643 (15)0.0639 (7)
H17A0.81810.17690.32310.096*
H17B0.59220.15740.40570.096*
H17C0.96660.17890.42510.096*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0621 (4)0.0364 (3)0.0421 (3)0.0089 (3)0.0035 (3)0.0037 (3)
C20.0460 (14)0.0303 (12)0.0362 (12)0.0008 (10)0.0005 (10)−0.0005 (10)
N30.0673 (14)0.0351 (11)0.0377 (11)0.0110 (9)0.0004 (9)−0.0021 (9)
N40.0638 (14)0.0364 (11)0.0417 (11)0.0106 (9)0.0004 (9)−0.0033 (9)
C50.0478 (15)0.0334 (12)0.0420 (13)0.0021 (11)0.0024 (11)−0.0026 (11)
N60.0624 (14)0.0343 (11)0.0330 (11)0.0088 (10)−0.0004 (9)0.0006 (9)
C70.0406 (14)0.0376 (13)0.0411 (13)−0.0021 (10)0.0011 (10)0.0030 (11)
O80.0763 (12)0.0425 (9)0.0445 (9)0.0106 (8)0.0006 (8)0.0078 (7)
C90.0428 (14)0.0421 (13)0.0348 (12)0.0002 (11)−0.0010 (10)−0.0013 (11)
C100.0631 (18)0.0525 (16)0.0492 (15)−0.0006 (13)0.0017 (12)−0.0016 (12)
C110.0647 (18)0.0749 (19)0.0436 (15)−0.0008 (15)0.0128 (12)−0.0064 (14)
C120.0724 (19)0.0667 (19)0.0470 (16)0.0162 (15)−0.0007 (13)−0.0157 (14)
C130.090 (2)0.0438 (15)0.0480 (15)0.0117 (14)−0.0032 (14)−0.0036 (13)
C140.0667 (17)0.0426 (14)0.0381 (13)0.0023 (12)0.0013 (11)−0.0005 (11)
O150.0777 (12)0.0369 (9)0.0483 (10)0.0159 (8)0.0091 (8)−0.0015 (7)
C160.0564 (17)0.0477 (15)0.0510 (15)0.0077 (12)0.0056 (12)−0.0087 (12)
C170.0682 (18)0.0512 (16)0.0720 (18)0.0097 (13)−0.0032 (14)−0.0174 (13)
Geometric parameters (Å, º) top
S1—C21.727 (2)C11—C121.373 (3)
S1—C51.733 (2)C11—H110.93
C2—N31.298 (2)C12—C131.373 (3)
C2—N61.379 (2)C12—H120.93
N3—N41.399 (2)C13—C141.382 (3)
N4—C51.282 (2)C13—H130.93
C5—O151.337 (2)C14—H140.93
N6—C71.368 (2)O15—C161.442 (2)
N6—H60.86 (2)C16—C171.496 (3)
C7—O81.220 (2)C16—H16A0.97
C7—C91.483 (3)C16—H16B0.97
C9—C141.379 (3)C17—H17A0.96
C9—C101.384 (3)C17—H17B0.96
C10—C111.378 (3)C17—H17C0.96
C10—H100.93
C2—S1—C585.05 (10)C10—C11—H11120.1
N3—C2—N6121.25 (18)C11—C12—C13120.1 (2)
N3—C2—S1115.45 (15)C11—C12—H12120
N6—C2—S1123.31 (16)C13—C12—H12120
C2—N3—N4112.03 (16)C12—C13—C14120.3 (2)
C5—N4—N3110.73 (17)C12—C13—H13119.8
N4—C5—O15125.34 (19)C14—C13—H13119.8
N4—C5—S1116.75 (16)C9—C14—C13119.9 (2)
O15—C5—S1117.92 (15)C9—C14—H14120.1
C7—N6—C2122.22 (19)C13—C14—H14120.1
C7—N6—H6121.7 (16)C5—O15—C16115.34 (15)
C2—N6—H6115.7 (16)O15—C16—C17107.87 (17)
O8—C7—N6120.35 (19)O15—C16—H16A110.1
O8—C7—C9122.38 (19)C17—C16—H16A110.1
N6—C7—C9117.26 (19)O15—C16—H16B110.1
C14—C9—C10119.5 (2)C17—C16—H16B110.1
C14—C9—C7122.6 (2)H16A—C16—H16B108.4
C10—C9—C7117.9 (2)C16—C17—H17A109.5
C11—C10—C9120.4 (2)C16—C17—H17B109.5
C11—C10—H10119.8H17A—C17—H17B109.5
C9—C10—H10119.8C16—C17—H17C109.5
C12—C11—C10119.8 (2)H17A—C17—H17C109.5
C12—C11—H11120.1H17B—C17—H17C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N3i0.86 (2)2.12 (2)2.967 (3)169 (2)
Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formulaC11H11N3O2S
Mr249.29
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)3.9797 (5), 20.138 (3), 14.4305 (18)
β (°) 92.036 (2)
V (Å3)1155.8 (2)
Z4
Radiation typeMo Kα
µ (mm−1)0.27
Crystal size (mm)0.27 × 0.12 × 0.11
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.956, 0.965
No. of measured, independent and
observed [I > 2σ(I)] reflections		22225, 2891, 1287
Rint0.114
(sin θ/λ)max (Å−1)0.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.081, 0.74
No. of reflections2891
No. of parameters158
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.19, −0.19

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6···N3i0.86 (2)2.12 (2)2.967 (3)169 (2)
Symmetry code: (i) −x, −y+1, −z+1.
 

References

First citationBruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationCho, N. S., Cho, J. J., Ra, D. Y., Moon, J. H., Song, J. S. & Kang, S. K. (1996). Bull. Korean Chem. Soc. 17, 1170–1174.  CAS Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
 First citationParkanyi, C., Yuan, H. L., Cho, N. S., Jaw, J. J., Woodhouse, T. E. & Aung, T. L. (1989). J. Heterocycl. Chem. 26, 1331–1334.  CAS Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 2| February 2012| Page o544
doi:10.1107/S1600536812002978
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