1-(Biphenyl-4-ylmethyl-idene)thio-semicarbazide monohydrate.

In the title compound, C(14)H(13)N(3)S·H(2)O, the thio-semicarbazide group is nearly planar, with a maximum deviation of 0.072 (2) Å from the ideal least-squares plane, and shows an E conformation. In the crystal packing, the water mol-ecules are involved in an extensive inter-molecular N-H⋯O hydrogen-bond network, assisted by O-H⋯S inter-actions, which link the independent mol-ecules into chains extended along b axis. An intra-molecular hydrogen N-H⋯N bond helps to stabilize the mol-ecular conformation.

Related literature

For the biological activity and potential medical applications of thio­semicarbazides, see: West et al. (1991 ▶). For thio­semicarbazides as ligands, see: Kowol et al. (2007 ▶).

Experimental

Crystal data

C14H13N3S·H2O

M = 273.36

Monoclinic,

a = 14.428 (5) Å

b = 6.350 (5) Å

c = 15.276 (4) Å

β = 99.750 (5)°

V = 1379.3 (12) Å3

Z = 4

Cu Kα radiation

μ = 2.05 mm−1

T = 293 K

0.28 × 0.22 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur Gemini S diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.659, T max = 1.000

8823 measured reflections

2652 independent reflections

2208 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.145

S = 1.12

2652 reflections

233 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.32 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011888/vm2023sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011888/vm2023Isup2.hkl

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

C14H13N3S·H2O	F(000) = 576
Mr = 273.36	Dx = 1.316 Mg m−3
Monoclinic, P21/c	Melting point: 475 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54180 Å
a = 14.428 (5) Å	Cell parameters from 3594 reflections
b = 6.350 (5) Å	θ = 3.9–71.2°
c = 15.276 (4) Å	µ = 2.05 mm−1
β = 99.750 (5)°	T = 293 K
V = 1379.3 (12) Å3	Needle, yellow
Z = 4	0.28 × 0.22 × 0.19 mm

Oxford Diffraction Xcalibur Gemini S diffractometer	2652 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2208 reflections with I > 2σ(I)
graphite	Rint = 0.035
Detector resolution: 10.2673 pixels mm-1	θmax = 71.3°, θmin = 5.9°
ω scans	h = −17→17
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −6→7
Tmin = 0.659, Tmax = 1.000	l = −17→18
8823 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.145	w = 1/[σ2(Fo2) + (0.0724P)2 + 0.4128P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max = 0.001
2652 reflections	Δρmax = 0.34 e Å−3
233 parameters	Δρmin = −0.32 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0022 (5)

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.9 (release 08-12-2009 CrysAlis171 .NET)(compiled Dec 8 2009,17:31:18). Empirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm.

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 > 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	1.03245 (4)	−0.35800 (9)	0.35948 (4)	0.0569 (2)
N2	0.87783 (13)	−0.1308 (3)	0.31541 (13)	0.0506 (5)
N1	0.79162 (12)	−0.0958 (3)	0.26420 (12)	0.0512 (5)
O1	0.95339 (19)	0.1981 (4)	0.42955 (18)	0.0826 (7)
C9	0.62409 (16)	0.3346 (4)	0.22359 (17)	0.0554 (6)
C14	0.92353 (15)	−0.3091 (4)	0.30268 (15)	0.0518 (5)
N3	0.87879 (17)	−0.4428 (4)	0.24280 (16)	0.0687 (6)
C7	0.48473 (14)	0.2361 (4)	0.12056 (15)	0.0490 (5)
C13	0.75391 (15)	0.0839 (4)	0.27165 (16)	0.0526 (5)
C10	0.66283 (15)	0.1342 (3)	0.21913 (15)	0.0506 (5)
C11	0.61170 (16)	−0.0131 (4)	0.16261 (17)	0.0546 (5)
C8	0.53638 (16)	0.3841 (4)	0.17552 (16)	0.0543 (6)
C6	0.39026 (15)	0.2860 (4)	0.07042 (15)	0.0516 (5)
C12	0.52453 (16)	0.0367 (4)	0.11508 (16)	0.0545 (6)
C5	0.36951 (18)	0.4859 (4)	0.03497 (19)	0.0639 (6)
C1	0.31911 (17)	0.1354 (4)	0.05726 (18)	0.0609 (6)
C2	0.22957 (19)	0.1843 (5)	0.01258 (19)	0.0707 (7)
C4	0.2796 (2)	0.5341 (5)	−0.0100 (2)	0.0748 (8)
C3	0.2100 (2)	0.3841 (6)	−0.02047 (18)	0.0728 (8)
H8	0.5121 (18)	0.525 (5)	0.1814 (18)	0.063 (7)*
H12	0.4912 (18)	−0.064 (4)	0.0746 (17)	0.060 (7)*
H5	0.421 (2)	0.590 (5)	0.041 (2)	0.078 (9)*
H1	0.3329 (17)	−0.005 (4)	0.0831 (18)	0.060 (7)*
H9	0.6583 (17)	0.436 (4)	0.2642 (17)	0.057 (7)*
H13	0.7819 (17)	0.187 (4)	0.3128 (17)	0.052 (6)*
H11	0.638 (2)	−0.147 (4)	0.1583 (19)	0.066 (8)*
H3	0.146 (2)	0.420 (5)	−0.053 (2)	0.085 (9)*
H4	0.267 (2)	0.679 (6)	−0.036 (2)	0.094 (10)*
H2	0.180 (2)	0.076 (6)	0.004 (2)	0.094 (11)*
H14	0.907 (2)	−0.033 (5)	0.3552 (19)	0.066 (8)*
H15	0.825 (2)	−0.392 (5)	0.211 (2)	0.072 (8)*
H16	0.907 (2)	−0.553 (6)	0.229 (2)	0.082 (9)*
H17	0.975 (3)	0.304 (8)	0.404 (3)	0.129 (16)*
H18	0.959 (3)	0.210 (7)	0.481 (3)	0.120 (17)*

	U11	U22	U33	U12	U13	U23
S1	0.0468 (3)	0.0545 (4)	0.0666 (4)	0.0023 (2)	0.0016 (3)	0.0058 (3)
N2	0.0410 (9)	0.0526 (10)	0.0555 (11)	0.0008 (8)	0.0005 (8)	−0.0025 (8)
N1	0.0417 (9)	0.0596 (11)	0.0509 (10)	0.0024 (8)	0.0035 (7)	−0.0017 (8)
O1	0.1079 (17)	0.0666 (12)	0.0679 (14)	−0.0285 (12)	−0.0003 (12)	−0.0015 (11)
C9	0.0459 (12)	0.0556 (13)	0.0621 (14)	−0.0015 (10)	0.0020 (10)	−0.0123 (11)
C14	0.0498 (12)	0.0509 (12)	0.0562 (13)	−0.0018 (9)	0.0134 (10)	0.0014 (10)
N3	0.0610 (13)	0.0635 (14)	0.0759 (15)	0.0105 (11)	−0.0048 (11)	−0.0176 (11)
C7	0.0431 (10)	0.0533 (12)	0.0500 (11)	−0.0014 (9)	0.0066 (9)	−0.0015 (9)
C13	0.0444 (11)	0.0564 (13)	0.0560 (13)	−0.0008 (10)	0.0052 (9)	−0.0058 (11)
C10	0.0422 (11)	0.0541 (12)	0.0552 (12)	−0.0006 (9)	0.0073 (9)	−0.0027 (10)
C11	0.0490 (12)	0.0500 (12)	0.0630 (14)	0.0034 (10)	0.0046 (10)	−0.0039 (10)
C8	0.0485 (12)	0.0516 (13)	0.0614 (14)	0.0038 (10)	0.0057 (10)	−0.0061 (10)
C6	0.0457 (11)	0.0598 (13)	0.0490 (12)	0.0023 (10)	0.0067 (9)	−0.0032 (10)
C12	0.0491 (12)	0.0536 (13)	0.0577 (13)	−0.0037 (10)	0.0004 (10)	−0.0081 (10)
C5	0.0558 (14)	0.0617 (15)	0.0714 (16)	0.0053 (12)	0.0030 (11)	0.0020 (12)
C1	0.0488 (12)	0.0681 (16)	0.0627 (15)	−0.0034 (11)	0.0007 (10)	0.0016 (12)
C2	0.0510 (14)	0.092 (2)	0.0656 (16)	−0.0049 (14)	0.0009 (11)	−0.0072 (14)
C4	0.0709 (17)	0.0776 (19)	0.0721 (18)	0.0199 (15)	0.0007 (13)	0.0035 (14)
C3	0.0559 (15)	0.102 (2)	0.0566 (15)	0.0155 (15)	−0.0005 (11)	−0.0039 (14)

S1—C14	1.690 (2)	C13—H13	0.95 (3)
N2—C14	1.341 (3)	C10—C11	1.396 (3)
N2—N1	1.371 (3)	C11—C12	1.378 (3)
N2—H14	0.92 (3)	C11—H11	0.94 (3)
N1—C13	1.278 (3)	C8—H8	0.97 (3)
O1—H17	0.86 (5)	C6—C1	1.393 (4)
O1—H18	0.77 (5)	C6—C5	1.393 (4)
C9—C8	1.387 (3)	C12—H12	0.96 (3)
C9—C10	1.397 (3)	C5—C4	1.396 (4)
C9—H9	0.97 (3)	C5—H5	0.98 (3)
C14—N3	1.332 (3)	C1—C2	1.390 (4)
N3—H15	0.90 (3)	C1—H1	0.98 (3)
N3—H16	0.86 (4)	C2—C3	1.377 (5)
C7—C8	1.390 (3)	C2—H2	0.98 (4)
C7—C12	1.399 (3)	C4—C3	1.374 (5)
C7—C6	1.480 (3)	C4—H4	1.01 (4)
C13—C10	1.454 (3)	C3—H3	0.99 (3)
C14—N2—N1	118.4 (2)	C10—C11—H11	118.6 (17)
C14—N2—H14	119.4 (17)	C9—C8—C7	121.0 (2)
N1—N2—H14	122.1 (17)	C9—C8—H8	118.1 (16)
C13—N1—N2	116.9 (2)	C7—C8—H8	120.9 (16)
H17—O1—H18	113 (4)	C1—C6—C5	117.7 (2)
C8—C9—C10	121.1 (2)	C1—C6—C7	121.3 (2)
C8—C9—H9	120.6 (15)	C5—C6—C7	121.0 (2)
C10—C9—H9	118.1 (15)	C11—C12—C7	121.5 (2)
N3—C14—N2	116.4 (2)	C11—C12—H12	120.0 (16)
N3—C14—S1	122.39 (19)	C7—C12—H12	118.4 (16)
N2—C14—S1	121.19 (18)	C6—C5—C4	120.8 (3)
C14—N3—H15	114.4 (19)	C6—C5—H5	118.1 (18)
C14—N3—H16	120 (2)	C4—C5—H5	121.1 (18)
H15—N3—H16	124 (3)	C2—C1—C6	121.2 (3)
C8—C7—C12	117.7 (2)	C2—C1—H1	120.6 (15)
C8—C7—C6	121.3 (2)	C6—C1—H1	118.1 (15)
C12—C7—C6	121.0 (2)	C3—C2—C1	120.1 (3)
N1—C13—C10	120.4 (2)	C3—C2—H2	120 (2)
N1—C13—H13	122.5 (15)	C1—C2—H2	120 (2)
C10—C13—H13	117.1 (15)	C3—C4—C5	120.4 (3)
C11—C10—C9	117.8 (2)	C3—C4—H4	121 (2)
C11—C10—C13	121.9 (2)	C5—C4—H4	119 (2)
C9—C10—C13	120.3 (2)	C4—C3—C2	119.7 (3)
C12—C11—C10	120.8 (2)	C4—C3—H3	119.5 (19)
C12—C11—H11	120.6 (17)	C2—C3—H3	120.8 (19)
C14—N2—N1—C13	−173.4 (2)	C12—C7—C6—C1	35.4 (3)
N1—N2—C14—N3	−2.6 (3)	C8—C7—C6—C5	36.1 (3)
N1—N2—C14—S1	176.85 (16)	C12—C7—C6—C5	−144.8 (3)
N2—N1—C13—C10	179.54 (19)	C10—C11—C12—C7	0.9 (4)
C8—C9—C10—C11	1.9 (4)	C8—C7—C12—C11	0.3 (4)
C8—C9—C10—C13	−178.5 (2)	C6—C7—C12—C11	−178.8 (2)
N1—C13—C10—C11	3.1 (4)	C1—C6—C5—C4	1.7 (4)
N1—C13—C10—C9	−176.4 (2)	C7—C6—C5—C4	−178.1 (2)
C9—C10—C11—C12	−2.0 (4)	C5—C6—C1—C2	−1.9 (4)
C13—C10—C11—C12	178.5 (2)	C7—C6—C1—C2	177.9 (2)
C10—C9—C8—C7	−0.7 (4)	C6—C1—C2—C3	0.7 (4)
C12—C7—C8—C9	−0.4 (4)	C6—C5—C4—C3	−0.3 (4)
C6—C7—C8—C9	178.8 (2)	C5—C4—C3—C2	−1.0 (4)
C8—C7—C6—C1	−143.7 (2)	C1—C2—C3—C4	0.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H14···O1	0.92 (3)	1.91 (3)	2.819 (3)	172 (3)
N3—H15···N1	0.91 (3)	2.14 (3)	2.585 (3)	110 (2)
N3—H16···S1i	0.86 (4)	2.59 (4)	3.422 (3)	163 (3)
O1—H17···S1ii	0.86 (5)	2.44 (5)	3.287 (3)	169 (4)
O1—H18···S1iii	0.77 (5)	2.60 (5)	3.352 (3)	164 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H14⋯O1	0.92 (3)	1.91 (3)	2.819 (3)	172 (3)
N3—H15⋯N1	0.91 (3)	2.14 (3)	2.585 (3)	110 (2)
N3—H16⋯S1i	0.86 (4)	2.59 (4)	3.422 (3)	163 (3)
O1—H17⋯S1ii	0.86 (5)	2.44 (5)	3.287 (3)	169 (4)
O1—H18⋯S1iii	0.77 (5)	2.60 (5)	3.352 (3)	164 (5)

Symmetry codes: (i) ; (ii) ; (iii) .