2-Hydroxy-imino-1-phenyl-ethanone thio-semicarbazone monohydrate.

In the title thio-semicarbazone derivative, C(9)H(10)N(4)OS·H(2)O, intra-molecular N-H⋯N hydrogen bonds result in the formation of two nearly coplanar five- and six-membered rings, which are also almost coplanar with the adjacent phenyl ring. The oxime group has an E configuration and is involved in inter-molecular O-H⋯O hydrogen bonding as a donor. In the crystal structure, intra-molecular O-H⋯S and N-H⋯N and inter-molecular O-H⋯O and N-H⋯S hydrogen bonds generate edge-fused R(2) (2)(8) and R(4) (1)(11) ring motifs. The hydrogen-bonded motifs are linked to each other to form a three-dimensional supra-molecular network.

Related literature

For general backgroud, see: Lukevics et al. (1995 ▶); Liberta & West (1992 ▶); Hagenbach & Gysin (1952 ▶); Jones et al. (1965 ▶); Brockman & Thomson (1956 ▶); Klayman et al. (1979 ▶); Petering & van Giesen (1966 ▶); Sevagapandian et al. (2000 ▶); Forman (1964 ▶); Holan et al. (1984 ▶); Balsamo et al. (1990 ▶); Marsman et al. (1999 ▶); Karle et al. (1996 ▶); Etter et al. (1990 ▶); Chertanova et al. (1994 ▶); Bernstein et al. (1995 ▶). For related structures, see: Sarıkavaklı et al. (2007 ▶); Özel Güven et al. (2007 ▶); Hökelek, Batı et al. (2001 ▶); Hökelek, Zülfikaroğlu & Batı (2001 ▶); Büyükgüngör et al. (2003 ▶); Hökelek et al. (2004a ▶,b ▶); Hökelek et al. (2004 ▶). For the synthesis, see: El-Shazly et al. (2005 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C9H10N4OS·H2O

M = 240.29

Monoclinic,

a = 28.5615 (3) Å

b = 4.6805 (3) Å

c = 22.0977 (4) Å

β = 127.24 (2)°

V = 2351.8 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.27 mm−1

T = 294 (2) K

0.30 × 0.20 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.940, T max = 0.960

31269 measured reflections

3607 independent reflections

2146 reflections with I > 2σ(I)

R int = 0.090

Refinement

R[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.154

S = 1.04

3607 reflections

193 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.14 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004947/xu2403sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808004947/xu2403Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C9H10N4OS·H2O	F(000) = 1008
Mr = 240.29	Dx = 1.357 Mg m−3
Monoclinic, C2/c	Melting point: 443 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 28.5615 (3) Å	Cell parameters from 2893 reflections
b = 4.6805 (3) Å	θ = 2.3–30.5°
c = 22.0977 (4) Å	µ = 0.27 mm−1
β = 127.24 (2)°	T = 294 K
V = 2351.8 (6) Å3	Prism, yellow
Z = 8	0.30 × 0.20 × 0.15 mm

Rigaku R-AXIS RAPID-S diffractometer	3607 independent reflections
Radiation source: fine-focus sealed tube	2146 reflections with I > 2σ(I)
graphite	Rint = 0.090
ω scans	θmax = 30.5°, θmin = 2.3°
Absorption correction: multi-scan (Blessing, 1995)	h = −40→40
Tmin = 0.940, Tmax = 0.960	k = −6→5
31269 measured reflections	l = −31→31

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0474P)2 + 0.9027P] where P = (Fo2 + 2Fc2)/3
3607 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.14 e Å−3
8 restraints	Δρmin = −0.31 e Å−3

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	0.08587 (3)	0.69943 (16)	0.58554 (3)	0.0693 (2)
O1	0.24428 (8)	0.9359 (4)	0.88734 (10)	0.0740 (5)
H1A	0.2527 (12)	1.022 (6)	0.8584 (15)	0.100 (10)*
O2	0.22848 (8)	0.6577 (4)	0.70204 (11)	0.0720 (5)
H21	0.1878 (8)	0.692 (7)	0.6673 (16)	0.133 (14)*
H22	0.2445 (13)	0.817 (5)	0.7313 (16)	0.113 (12)*
N1	0.19953 (8)	0.7460 (4)	0.83853 (10)	0.0576 (5)
N2	0.09978 (8)	0.3607 (4)	0.75639 (10)	0.0577 (5)
N3	0.10929 (9)	0.5206 (5)	0.71329 (10)	0.0619 (5)
H3A	0.1412 (9)	0.641 (5)	0.7347 (14)	0.077 (8)*
N4	0.02448 (9)	0.3422 (5)	0.60650 (11)	0.0654 (6)
H41	−0.0011 (10)	0.316 (5)	0.5550 (10)	0.076 (8)*
H42	0.0210 (12)	0.238 (5)	0.6394 (14)	0.084 (9)*
C1	0.07415 (11)	0.0295 (6)	0.83508 (14)	0.0644 (6)
H1	0.0517 (11)	0.012 (5)	0.7826 (15)	0.074 (8)*
C2	0.06113 (12)	−0.1405 (6)	0.87378 (17)	0.0721 (7)
H2	0.0280 (11)	−0.257 (5)	0.8455 (15)	0.071 (8)*
C3	0.09577 (13)	−0.1362 (6)	0.95201 (17)	0.0724 (7)
H3	0.0859 (12)	−0.245 (6)	0.9780 (16)	0.083 (9)*
C4	0.14393 (14)	0.0388 (6)	0.99041 (16)	0.0742 (7)
H4	0.1666 (12)	0.036 (6)	1.0426 (16)	0.092 (9)*
C5	0.15737 (13)	0.2112 (6)	0.95211 (14)	0.0639 (6)
H5	0.1913 (13)	0.330 (6)	0.9810 (17)	0.089 (9)*
C6	0.12248 (9)	0.2111 (5)	0.87338 (12)	0.0521 (5)
C7	0.13487 (9)	0.3927 (5)	0.82959 (11)	0.0516 (5)
C8	0.18351 (10)	0.5985 (5)	0.87101 (13)	0.0580 (6)
H8	0.2005 (11)	0.621 (5)	0.9241 (15)	0.080 (8)*
C9	0.07134 (10)	0.5057 (5)	0.63645 (11)	0.0556 (5)

	U11	U22	U33	U12	U13	U23
S1	0.0632 (4)	0.0943 (5)	0.0452 (3)	−0.0096 (3)	0.0301 (3)	0.0036 (3)
O1	0.0703 (11)	0.0827 (12)	0.0573 (10)	−0.0268 (9)	0.0324 (9)	−0.0116 (9)
O2	0.0630 (11)	0.0814 (13)	0.0698 (12)	0.0040 (10)	0.0393 (10)	−0.0022 (10)
N1	0.0518 (10)	0.0649 (12)	0.0491 (10)	−0.0074 (9)	0.0269 (9)	−0.0074 (8)
N2	0.0588 (11)	0.0704 (12)	0.0439 (10)	−0.0070 (9)	0.0311 (9)	−0.0025 (8)
N3	0.0611 (12)	0.0780 (14)	0.0419 (9)	−0.0147 (10)	0.0287 (9)	−0.0037 (9)
N4	0.0628 (12)	0.0832 (15)	0.0449 (11)	−0.0118 (11)	0.0299 (10)	−0.0060 (10)
C1	0.0567 (13)	0.0777 (17)	0.0544 (14)	−0.0031 (12)	0.0313 (12)	0.0037 (12)
C2	0.0633 (15)	0.0771 (18)	0.0776 (18)	−0.0037 (14)	0.0436 (15)	0.0078 (14)
C3	0.0841 (19)	0.0761 (18)	0.0785 (19)	0.0119 (15)	0.0603 (17)	0.0164 (14)
C4	0.093 (2)	0.0816 (18)	0.0567 (15)	0.0102 (16)	0.0496 (15)	0.0081 (14)
C5	0.0737 (16)	0.0693 (15)	0.0500 (13)	−0.0021 (13)	0.0381 (12)	−0.0023 (11)
C6	0.0534 (12)	0.0566 (12)	0.0491 (11)	0.0061 (10)	0.0325 (10)	0.0012 (9)
C7	0.0503 (11)	0.0596 (13)	0.0429 (11)	0.0026 (10)	0.0272 (9)	−0.0009 (9)
C8	0.0563 (13)	0.0668 (14)	0.0435 (11)	−0.0018 (11)	0.0263 (10)	−0.0028 (10)
C9	0.0549 (12)	0.0657 (14)	0.0438 (11)	−0.0008 (11)	0.0286 (10)	−0.0044 (10)

S1—C9	1.681 (2)	C2—H2	0.93 (3)
O1—H1A	0.903 (18)	C3—C2	1.378 (4)
O2—H21	0.940 (17)	C3—C4	1.368 (4)
O2—H22	0.907 (18)	C3—H3	0.93 (3)
N1—O1	1.385 (2)	C4—H4	0.92 (3)
N1—C8	1.264 (3)	C5—C4	1.381 (4)
N2—N3	1.362 (3)	C5—H5	0.95 (3)
N2—C7	1.297 (3)	C6—C1	1.389 (3)
N3—H3A	0.923 (17)	C6—C5	1.386 (3)
N4—C9	1.320 (3)	C6—C7	1.483 (3)
N4—H41	0.915 (17)	C7—C8	1.469 (3)
N4—H42	0.930 (17)	C8—H8	0.97 (3)
C1—C2	1.374 (3)	C9—N3	1.355 (3)
C1—H1	0.93 (2)
N1—O1—H1A	104.6 (19)	C3—C4—C5	121.2 (3)
H21—O2—H22	106 (3)	C3—C4—H4	116.6 (19)
C8—N1—O1	112.88 (19)	C5—C4—H4	122.2 (19)
C7—N2—N3	118.58 (19)	C4—C5—C6	120.9 (3)
C9—N3—N2	120.1 (2)	C4—C5—H5	118.5 (18)
C9—N3—H3A	117.9 (16)	C6—C5—H5	120.6 (18)
N2—N3—H3A	122.0 (17)	C1—C6—C7	119.6 (2)
C9—N4—H41	120.3 (17)	C5—C6—C1	117.3 (2)
C9—N4—H42	117.9 (17)	C5—C6—C7	123.0 (2)
H41—N4—H42	121 (2)	N2—C7—C8	125.4 (2)
C2—C1—C6	121.2 (2)	N2—C7—C6	116.00 (19)
C2—C1—H1	118.9 (16)	C8—C7—C6	118.60 (18)
C6—C1—H1	119.7 (16)	N1—C8—C7	122.4 (2)
C1—C2—C3	120.9 (3)	N1—C8—H8	122.8 (16)
C1—C2—H2	118.0 (16)	C7—C8—H8	114.7 (16)
C3—C2—H2	121.1 (16)	N4—C9—N3	117.2 (2)
C4—C3—C2	118.4 (3)	N4—C9—S1	124.28 (17)
C4—C3—H3	120.7 (18)	N3—C9—S1	118.46 (18)
C2—C3—H3	120.8 (18)
O1—N1—C8—C7	177.1 (2)	C1—C6—C5—C4	−0.6 (4)
C7—N2—N3—C9	−175.9 (2)	C7—C6—C5—C4	179.8 (2)
N3—N2—C7—C8	2.8 (3)	C5—C6—C7—N2	177.2 (2)
N3—N2—C7—C6	−179.56 (19)	C1—C6—C7—N2	−2.4 (3)
C6—C1—C2—C3	−0.1 (4)	C5—C6—C7—C8	−5.0 (3)
C4—C3—C2—C1	−0.8 (4)	C1—C6—C7—C8	175.4 (2)
C2—C3—C4—C5	1.0 (4)	N2—C7—C8—N1	−7.6 (4)
C6—C5—C4—C3	−0.3 (4)	C6—C7—C8—N1	174.8 (2)
C5—C6—C1—C2	0.8 (4)	S1—C9—N3—N2	−178.23 (16)
C7—C6—C1—C2	−179.6 (2)	N4—C9—N3—N2	3.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2i	0.90 (3)	1.83 (3)	2.728 (3)	174 (3)
O2—H21···S1	0.94 (3)	2.32 (3)	3.250 (3)	171 (3)
O2—H22···O2i	0.91 (3)	1.98 (3)	2.886 (3)	172 (4)
N3—H3A···N1	0.92 (3)	1.91 (2)	2.604 (3)	130 (2)
N4—H41···S1ii	0.92 (2)	2.53 (2)	3.434 (2)	169 (3)
N4—H42···N2	0.93 (3)	2.24 (3)	2.643 (3)	105 (2)

Bond/Angle	(I)	(II)	(III)	(IV)	(V)	(VI)	(VII)
N1-O1	1.385 (2)	1.403 (2)	1.423 (3)	1.417 (1)	1.429 (4)	1.424 (2)	1.416 (3)
		1.396 (2)	1.396 (3)				1.397 (3)
N1-C8	1.264 (3)	1.281 (2)	1.290 (3)	1.290 (1)	1.241 (6)	1.289 (2)	1.282 (3)
		1.281 (2)	1.282 (3)				1.289 (3)
C7-C8	1.469 (3)	1.477 (3)	1.489 (3)	1.510 (1)	1.551 (7)	1.513 (2)	1.501 (4)
		1.473 (3)					1.502 (4)
C7-C8-N1	122.4 (2)	115.2 (2)	116.6 (2)	114.3 (1)	118.3 (5)	113.2 (1)	114.4 (2)
		115.0 (2)	115.0 (2)				113.4 (2)
C8-N1-O1	112.9 (2)	112.4 (1)	109.4 (2)	110.7 (1)	112.2 (4)	110.6 (1)	110.7 (2)
		112.2 (1)	111.5 (2)				111.1 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2i	0.90 (3)	1.83 (3)	2.728 (3)	174 (3)
O2—H21⋯S1	0.94 (3)	2.32 (3)	3.250 (3)	171 (3)
O2—H22⋯O2i	0.91 (3)	1.98 (3)	2.886 (3)	172 (4)
N3—H3A⋯N1	0.92 (3)	1.91 (2)	2.604 (3)	130 (2)
N4—H41⋯S1ii	0.92 (2)	2.53 (2)	3.434 (2)	169 (3)
N4—H42⋯N2	0.93 (3)	2.24 (3)	2.643 (3)	105 (2)

Symmetry codes: (i) ; (ii) .