5-Acetyl-3-(5-phenyl-1H-pyrazol-3-yl)-1,3,4-thia­diazol-2(3H)-one monohydrate

In the title hydrate, C₁₃H₁₀N₄O₂S·H₂O, the dihedral angles between the central pyrazole ring and its pendant phenyl and thia­diazole rings are 9.93 (8) and 4.56 (7)°, respectively. In the crystal, the components are linked by N—H...O, O—H...N and O—H...O hydrogen bonds, generating [100] chains incorporating R₄⁴(10) loops. A weak C—H...O inter­action helps to consolidate the packing.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.106
• Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT390_ALERT_3_C Deviating Methyl C13     X-C-H Bond Angle ......        116 Deg.
PLAT391_ALERT_3_C Deviating Methyl C13     H-C-H Bond Angle ......        101 Deg.
PLAT391_ALERT_3_C Deviating Methyl C13     H-C-H Bond Angle ......        101 Deg.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1
PLAT922_ALERT_1_C wR2 in the CIF and FCF Differ by ...............    -0.0035
PLAT923_ALERT_1_C S    values in the CIF and FCF Differ by .......     -0.036

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         41
PLAT982_ALERT_1_G The  C-f'=     0.003 Deviates from the  IT-value      0.018
PLAT982_ALERT_1_G The  N-f'=     0.006 Deviates from the  IT-value      0.031

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   7 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   5 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
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

In the title compound (I), shown in Fig. 1, the aromatic ring is inclined at angles of 9.93 (8)° & 6.36 (7)° with respect to pyrazole and thiadiazole rings. The pyrazole and thiadiazole rings are oriented at dihedral angle of 4.56 (7)°. The acetyl group is inclined at dihedral angle of 6.00 (2)° with thiadiazole ring. The water molecule as usual is involved in classical hydrogen bonding interactions. The interactions through N1—H1···O3w, and O3w—H3a···N2 give rise to inversion dimers forming ten membered ring motif R₄⁴(10). These dimers further connected through O3w—H3b···O1 interaction to make infinite one dimensional chain along a axis. Another non-classical interaction (C8—H8···O1) generates twelve membered ring motif R₁¹(12) loops; for symmetry detail, see; Table. 1, Fig. 2.

Related literature

For the synthesis of the title compound, see: Abdelhamid et al. (2001). For a related structure, see: Ge (2006).

S2. Experimental

The title compound was synthesised according to literature (Abdelhamid et al., 2001 ) procedure and recrystalized from methanol solution under slow evaporation to yield brown plates.

S3. Refinement

All the hydrogen atoms found from a Fourier difference map and allowed to refine freely with appropriate riding models.

Computing details

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and X-SEED (Barbour, 2001).

Figures

	Fig. 1. The molecular structure of title compound with 50% probability displacement ellipsoids.
	Fig. 2. The packing diagram showing inversion dimers through hydrogen bonds, drawn using dashed lines.

5-Acetyl-3-(5-phenyl-1H-pyrazol-3-yl)-1,3,4-thiadiazol-2(3H)-one monohydrate

Crystal data

C13H10N4O2S·H2O	F(000) = 632
Mr = 304.33	Dx = 1.464 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 5915 reflections
a = 7.6084 (2) Å	θ = 3.5–74.7°
b = 25.5788 (4) Å	µ = 2.25 mm^−1
c = 7.6524 (2) Å	T = 296 K
β = 111.974 (3)°	Plate, brown
V = 1381.07 (6) Å^3	0.35 × 0.19 × 0.06 mm
Z = 4

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas, CCD) diffractometer	2806 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2498 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.032
ω scans	θmax = 74.8°, θmin = 3.5°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −9→9
Tmin = 0.778, Tmax = 1.000	k = −31→31
10797 measured reflections	l = −9→6

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0609P)^2 + 0.1856P] where P = (Fo^2 + 2Fc^2)/3
2806 reflections	(Δ/σ)max = 0.002
238 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
S12	0.59223 (6)	0.644569 (15)	0.75319 (6)	0.05072 (15)
O1	0.5175 (2)	0.55662 (5)	0.90067 (17)	0.0659 (4)
N3	0.40123 (17)	0.56623 (4)	0.57705 (17)	0.0362 (3)
O2	0.5725 (2)	0.72711 (5)	0.4716 (2)	0.0757 (4)
N4	0.39508 (17)	0.60041 (4)	0.43842 (17)	0.0375 (3)
N1	0.11453 (18)	0.46444 (5)	0.33689 (18)	0.0408 (3)
N2	0.19673 (18)	0.51164 (5)	0.34177 (17)	0.0398 (3)
C10	0.4991 (2)	0.58140 (6)	0.7612 (2)	0.0439 (3)
C7	0.15808 (19)	0.44351 (5)	0.5095 (2)	0.0361 (3)
C9	0.29698 (18)	0.51911 (5)	0.52301 (19)	0.0338 (3)
C11	0.4876 (2)	0.64236 (5)	0.5106 (2)	0.0398 (3)
C1	0.08453 (19)	0.39258 (5)	0.5408 (2)	0.0383 (3)
C8	0.2800 (2)	0.47822 (5)	0.6365 (2)	0.0387 (3)
C12	0.4979 (2)	0.68747 (6)	0.3918 (3)	0.0487 (4)
C2	0.1125 (2)	0.37673 (7)	0.7226 (3)	0.0505 (4)
H2	0.177 (3)	0.3992 (9)	0.834 (3)	0.068 (6)*
C6	−0.0130 (2)	0.35941 (6)	0.3906 (3)	0.0480 (4)
H6	−0.037 (3)	0.3691 (8)	0.264 (3)	0.052 (5)*
C13	0.4163 (3)	0.68076 (8)	0.1839 (3)	0.0589 (5)
H13B	0.364 (5)	0.7089 (14)	0.126 (5)	0.116 (11)*
H13C	0.501 (6)	0.6663 (17)	0.145 (7)	0.165 (17)*
H13A	0.313 (4)	0.6562 (12)	0.135 (4)	0.099 (9)*
C4	−0.0469 (3)	0.29574 (6)	0.6054 (3)	0.0599 (5)
H4	−0.085 (3)	0.2633 (9)	0.629 (3)	0.071 (6)*
C3	0.0476 (3)	0.32821 (7)	0.7542 (3)	0.0600 (5)
H3	0.071 (3)	0.3194 (9)	0.876 (4)	0.072 (7)*
C5	−0.0788 (3)	0.31131 (6)	0.4244 (3)	0.0570 (4)
H5	−0.140 (4)	0.2917 (9)	0.319 (4)	0.078 (7)*
H1	0.025 (3)	0.4545 (8)	0.221 (3)	0.059 (6)*
H8	0.337 (3)	0.4743 (7)	0.766 (3)	0.046 (5)*
O3W	0.8281 (2)	0.44007 (6)	0.0009 (2)	0.0683 (4)
H3A	0.816 (4)	0.4505 (10)	−0.110 (4)	0.089 (8)*
H3B	0.722 (6)	0.4442 (16)	0.006 (5)	0.145 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S12	0.0611 (3)	0.0453 (2)	0.0392 (2)	−0.01426 (16)	0.01118 (19)	−0.00717 (15)
O1	0.0838 (9)	0.0722 (8)	0.0307 (6)	−0.0271 (7)	0.0087 (6)	0.0042 (6)
N3	0.0429 (6)	0.0336 (5)	0.0290 (6)	−0.0032 (4)	0.0100 (5)	0.0016 (4)
O2	0.0992 (11)	0.0428 (6)	0.0740 (10)	−0.0249 (7)	0.0196 (8)	−0.0011 (6)
N4	0.0448 (6)	0.0321 (5)	0.0341 (6)	−0.0010 (4)	0.0131 (5)	0.0029 (4)
N1	0.0482 (6)	0.0376 (6)	0.0334 (7)	−0.0080 (5)	0.0116 (5)	−0.0008 (5)
N2	0.0483 (6)	0.0368 (6)	0.0322 (6)	−0.0070 (5)	0.0125 (5)	0.0003 (5)
C10	0.0480 (8)	0.0467 (8)	0.0335 (8)	−0.0085 (6)	0.0114 (6)	−0.0010 (6)
C7	0.0384 (6)	0.0333 (6)	0.0354 (7)	0.0021 (5)	0.0124 (6)	0.0029 (5)
C9	0.0373 (6)	0.0322 (6)	0.0306 (7)	−0.0002 (5)	0.0112 (5)	0.0006 (5)
C11	0.0441 (7)	0.0348 (7)	0.0385 (8)	−0.0018 (5)	0.0133 (6)	−0.0009 (6)
C1	0.0378 (6)	0.0330 (6)	0.0428 (8)	0.0019 (5)	0.0134 (6)	0.0040 (5)
C8	0.0435 (7)	0.0368 (7)	0.0324 (8)	−0.0010 (5)	0.0103 (6)	0.0035 (6)
C12	0.0530 (8)	0.0359 (7)	0.0551 (10)	−0.0045 (6)	0.0179 (7)	0.0042 (7)
C2	0.0521 (8)	0.0465 (8)	0.0471 (10)	−0.0060 (7)	0.0118 (7)	0.0093 (7)
C6	0.0551 (9)	0.0385 (7)	0.0506 (10)	−0.0026 (6)	0.0199 (8)	−0.0019 (7)
C13	0.0727 (12)	0.0511 (10)	0.0503 (11)	−0.0066 (9)	0.0198 (9)	0.0124 (8)
C4	0.0581 (9)	0.0373 (8)	0.0833 (15)	−0.0030 (7)	0.0253 (10)	0.0121 (8)
C3	0.0608 (10)	0.0536 (9)	0.0599 (12)	−0.0052 (8)	0.0161 (9)	0.0203 (8)
C5	0.0623 (10)	0.0363 (8)	0.0720 (13)	−0.0058 (7)	0.0246 (9)	−0.0068 (8)
O3W	0.0807 (10)	0.0829 (10)	0.0325 (7)	−0.0270 (8)	0.0112 (6)	0.0031 (6)

Geometric parameters (Å, º)

S12—C11	1.7254 (16)	C1—C6	1.398 (2)
S12—C10	1.7744 (15)	C8—H8	0.92 (2)
O1—C10	1.2038 (19)	C12—C13	1.486 (3)
N3—N4	1.3619 (16)	C2—C3	1.390 (2)
N3—C10	1.3804 (19)	C2—H2	0.99 (2)
N3—C9	1.4170 (17)	C6—C5	1.388 (2)
O2—C12	1.210 (2)	C6—H6	0.95 (2)
N4—C11	1.2887 (18)	C13—H13B	0.86 (4)
N1—C7	1.3466 (19)	C13—H13C	0.89 (5)
N1—N2	1.3538 (16)	C13—H13A	0.96 (3)
N1—H1	0.93 (2)	C4—C5	1.372 (3)
N2—C9	1.3229 (19)	C4—C3	1.375 (3)
C7—C8	1.385 (2)	C4—H4	0.92 (2)
C7—C1	1.4724 (18)	C3—H3	0.91 (3)
C9—C8	1.3960 (19)	C5—H5	0.92 (3)
C11—C12	1.489 (2)	O3W—H3A	0.86 (3)
C1—C2	1.387 (2)	O3W—H3B	0.83 (4)
C11—S12—C10	88.73 (7)	C9—C8—H8	129.2 (12)
N4—N3—C10	117.57 (11)	O2—C12—C13	124.48 (16)
N4—N3—C9	117.81 (11)	O2—C12—C11	117.62 (16)
C10—N3—C9	124.49 (12)	C13—C12—C11	117.90 (14)
C11—N4—N3	110.27 (12)	C1—C2—C3	120.31 (17)
C7—N1—N2	112.70 (12)	C1—C2—H2	122.2 (13)
C7—N1—H1	130.7 (13)	C3—C2—H2	117.5 (13)
N2—N1—H1	115.8 (13)	C5—C6—C1	120.13 (17)
C9—N2—N1	103.70 (11)	C5—C6—H6	118.6 (12)
O1—C10—N3	126.60 (14)	C1—C6—H6	121.3 (12)
O1—C10—S12	126.50 (12)	C12—C13—H13B	113 (2)
N3—C10—S12	106.89 (10)	C12—C13—H13C	110 (3)
N1—C7—C8	106.73 (12)	H13B—C13—H13C	115 (4)
N1—C7—C1	122.84 (13)	C12—C13—H13A	116.2 (19)
C8—C7—C1	130.42 (14)	H13B—C13—H13A	101 (3)
N2—C9—C8	113.13 (12)	H13C—C13—H13A	101 (3)
N2—C9—N3	117.96 (12)	C5—C4—C3	120.03 (16)
C8—C9—N3	128.89 (13)	C5—C4—H4	120.7 (15)
N4—C11—C12	121.91 (14)	C3—C4—H4	119.3 (15)
N4—C11—S12	116.53 (11)	C4—C3—C2	120.32 (19)
C12—C11—S12	121.52 (11)	C4—C3—H3	122.7 (15)
C2—C1—C6	118.83 (14)	C2—C3—H3	116.9 (15)
C2—C1—C7	119.80 (14)	C4—C5—C6	120.37 (18)
C6—C1—C7	121.37 (14)	C4—C5—H5	124.8 (15)
C7—C8—C9	103.72 (13)	C6—C5—H5	114.8 (16)
C7—C8—H8	127.1 (12)	H3A—O3W—H3B	105 (3)
C10—N3—N4—C11	0.25 (18)	N1—C7—C1—C2	−170.77 (14)
C9—N3—N4—C11	176.34 (12)	C8—C7—C1—C2	10.4 (2)
C7—N1—N2—C9	1.40 (16)	N1—C7—C1—C6	9.5 (2)
N4—N3—C10—O1	179.14 (16)	C8—C7—C1—C6	−169.31 (15)
C9—N3—C10—O1	3.3 (3)	N1—C7—C8—C9	0.87 (16)
N4—N3—C10—S12	−0.66 (16)	C1—C7—C8—C9	179.81 (14)
C9—N3—C10—S12	−176.46 (10)	N2—C9—C8—C7	−0.03 (17)
C11—S12—C10—O1	−179.15 (18)	N3—C9—C8—C7	178.50 (13)
C11—S12—C10—N3	0.65 (11)	N4—C11—C12—O2	173.25 (16)
N2—N1—C7—C8	−1.46 (17)	S12—C11—C12—O2	−4.4 (2)
N2—N1—C7—C1	179.50 (12)	N4—C11—C12—C13	−6.8 (2)
N1—N2—C9—C8	−0.80 (16)	S12—C11—C12—C13	175.50 (14)
N1—N2—C9—N3	−179.51 (12)	C6—C1—C2—C3	1.3 (3)
N4—N3—C9—N2	−1.44 (18)	C7—C1—C2—C3	−178.47 (16)
C10—N3—C9—N2	174.35 (14)	C2—C1—C6—C5	−0.6 (2)
N4—N3—C9—C8	−179.92 (13)	C7—C1—C6—C5	179.19 (14)
C10—N3—C9—C8	−4.1 (2)	C5—C4—C3—C2	−0.4 (3)
N3—N4—C11—C12	−177.47 (13)	C1—C2—C3—C4	−0.8 (3)
N3—N4—C11—S12	0.32 (16)	C3—C4—C5—C6	1.1 (3)
C10—S12—C11—N4	−0.59 (13)	C1—C6—C5—C4	−0.7 (3)
C10—S12—C11—C12	177.22 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3W^i	0.93 (2)	1.83 (2)	2.749 (2)	173 (2)
O3W—H3A···N2^ii	0.86 (3)	1.99 (3)	2.8402 (19)	169 (2)
O3W—H3B···O1^iii	0.83 (5)	2.19 (5)	2.995 (2)	163 (4)
C8—H8···O1^iv	0.93 (2)	2.50 (2)	3.4100 (19)	167.8 (15)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z+2.