Crystal structure of [(E)-({2-[3-(2-{(1E)-[(carbamo-thioyl-amino)-imino]-meth-yl}phen-oxy)prop-oxy]phen-yl}methyl-idene)amino]-thio-urea with an unknown solvate.

The title mol-ecule, C19H22N6O2S2, has crystallographically imposed C 2 symmetry, with the central C atom lying on the rotation axis. The O-C-C-C torsion angle for the central chain is -59.22 (16)° and the dihedral angle between the planes of the benzene rings is 75.20 (7)°. In the crystal, N-H⋯O and N-H⋯S inter-actions link the mol-ecules, forming a three-dimensional network encompassing channels running parallel to the c axis, which account for about 20% of the unit-cell volume. The contribution to the scattering from the highly disordered solvent mol-ecules in these channels was removed with the SQUEEZE routine [Spek (2015). Acta Cryst. C71, 9-18] in PLATON. The stated crystal data for M r, μ etc. do not take these into account.

Related literature

For the various biological activities of bis-thio­semicarbazones, see: Singh et al. (2001 ▸); Offiong & Martelli (1997 ▸). For general synthesis and assessment of the pharmaceutical properties of thio­semicarbazone scaffold compounds, see: Greenbaum et al. (2004 ▸); Finch et al. (1999 ▸); Wilson et al. (1974 ▸); Du et al. (2002 ▸); Desai et al. (1984 ▸); Shucla et al. (1984 ▸); Vrdoljak et al. (2010 ▸); Belicchi-Ferrari et al. (2010 ▸); Marzano et al. (2009 ▸). For use of the SQUEEZE routine in PLATON to remove the contribution of disordered solvents, see: Spek (2009 ▸, 2015 ▸).

Experimental

Crystal data

C19H22N6O2S2

M = 430.55

Monoclinic,

a = 19.3941 (5) Å

b = 12.7110 (3) Å

c = 10.1450 (3) Å

β = 103.306 (2)°

V = 2433.79 (11) Å3

Z = 4

Cu Kα radiation

μ = 2.19 mm−1

T = 150 K

0.44 × 0.23 × 0.05 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T min = 0.71, T max = 0.91

8997 measured reflections

2365 independent reflections

1886 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.112

S = 1.06

2365 reflections

135 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸) and ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸) and WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015012074/hb7453sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012074/hb7453Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015012074/hb7453Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015012074/hb7453fig1.tif

The title mol­ecule with labeling scheme and 50% probability ellipsoids. Atoms with the suffix a are related to their counterparts by the crystallographic twofold axis passing through C10.

Click here for additional data file.

b . DOI: 10.1107/S2056989015012074/hb7453fig2.tif

Packing viewed down the b axis. N—H⋯O and N—H⋯S hydrogen bonds are shown, respectively, as blue and purple dotted lines.

Click here for additional data file.

c . DOI: 10.1107/S2056989015012074/hb7453fig3.tif

Packing viewed down the the c axis showing the one-dimensonal channels.

CCDC reference: 1408451

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H22N6O2S2	F(000) = 904
Mr = 430.55	Dx = 1.175 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 5935 reflections
a = 19.3941 (5) Å	θ = 4.2–72.3°
b = 12.7110 (3) Å	µ = 2.19 mm−1
c = 10.1450 (3) Å	T = 150 K
β = 103.306 (2)°	Plate, colourless
V = 2433.79 (11) Å3	0.44 × 0.23 × 0.05 mm
Z = 4

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2365 independent reflections
Radiation source: INCOATEC IµS micro–focus source	1886 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.042
Detector resolution: 10.4167 pixels mm-1	θmax = 72.4°, θmin = 4.7°
ω scans	h = −23→21
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −15→15
Tmin = 0.71, Tmax = 0.91	l = −12→11
8997 measured reflections

Refinement on F2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.112	w = 1/[σ2(Fo2) + (0.0642P)2 + 0.5713P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2365 reflections	Δρmax = 0.24 e Å−3
135 parameters	Δρmin = −0.22 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	0.16947 (3)	0.37583 (4)	1.00065 (5)	0.0410 (2)
O1	0.41803 (6)	0.15260 (9)	0.63827 (14)	0.0374 (4)
N1	0.18026 (8)	0.48300 (11)	0.78226 (16)	0.0378 (5)
N2	0.24940 (8)	0.33630 (12)	0.82840 (15)	0.0362 (5)
N3	0.27239 (8)	0.35523 (11)	0.71219 (16)	0.0355 (4)
C1	0.20151 (9)	0.40093 (13)	0.86192 (18)	0.0338 (5)
C2	0.31703 (9)	0.28864 (13)	0.68644 (18)	0.0343 (5)
C3	0.34370 (10)	0.29762 (13)	0.56355 (19)	0.0356 (5)
C4	0.31914 (10)	0.37535 (16)	0.4677 (2)	0.0437 (6)
C5	0.34321 (11)	0.38278 (17)	0.3499 (2)	0.0493 (7)
C6	0.39290 (12)	0.31119 (18)	0.3267 (2)	0.0499 (7)
C7	0.41864 (11)	0.23341 (16)	0.4199 (2)	0.0443 (6)
C8	0.39431 (10)	0.22645 (13)	0.53912 (19)	0.0358 (5)
C9	0.47639 (10)	0.08725 (14)	0.6228 (2)	0.0421 (6)
C10	0.50000	0.0236 (2)	0.75000	0.0468 (9)
H1A	0.19900	0.49480	0.70920	0.0450*
H1B	0.15310	0.53380	0.80830	0.0450*
H2	0.33300	0.23270	0.74800	0.0410*
H2A	0.26650	0.27530	0.87040	0.0430*
H4	0.28500	0.42450	0.48350	0.0520*
H5	0.32590	0.43640	0.28560	0.0590*
H6	0.40940	0.31570	0.24570	0.0600*
H7	0.45280	0.18470	0.40310	0.0530*
H9A	0.51590	0.13150	0.60780	0.0500*
H9B	0.46130	0.04000	0.54380	0.0500*
H10A	0.4614 (9)	−0.0236 (16)	0.755 (2)	0.0560*

	U11	U22	U33	U12	U13	U23
S1	0.0497 (3)	0.0379 (3)	0.0406 (3)	0.0112 (2)	0.0209 (2)	0.0037 (2)
O1	0.0372 (7)	0.0318 (6)	0.0488 (8)	0.0044 (5)	0.0212 (6)	−0.0030 (5)
N1	0.0403 (9)	0.0350 (8)	0.0413 (9)	0.0098 (6)	0.0161 (7)	0.0036 (6)
N2	0.0410 (9)	0.0330 (7)	0.0378 (9)	0.0080 (6)	0.0158 (7)	0.0024 (6)
N3	0.0367 (8)	0.0332 (7)	0.0393 (8)	0.0023 (6)	0.0146 (7)	−0.0007 (6)
C1	0.0325 (9)	0.0315 (8)	0.0385 (10)	0.0019 (7)	0.0107 (7)	−0.0044 (7)
C2	0.0339 (9)	0.0283 (8)	0.0418 (10)	0.0015 (7)	0.0110 (8)	−0.0017 (7)
C3	0.0353 (9)	0.0333 (9)	0.0399 (10)	−0.0033 (7)	0.0121 (7)	−0.0043 (7)
C4	0.0433 (11)	0.0426 (11)	0.0467 (11)	0.0020 (8)	0.0134 (9)	0.0004 (8)
C5	0.0510 (12)	0.0548 (12)	0.0437 (11)	−0.0029 (9)	0.0143 (9)	0.0068 (9)
C6	0.0555 (13)	0.0580 (13)	0.0411 (11)	−0.0120 (10)	0.0215 (9)	−0.0062 (9)
C7	0.0452 (11)	0.0439 (10)	0.0493 (12)	−0.0058 (8)	0.0224 (9)	−0.0119 (9)
C8	0.0361 (9)	0.0316 (9)	0.0415 (10)	−0.0068 (7)	0.0128 (8)	−0.0078 (7)
C9	0.0348 (10)	0.0339 (9)	0.0626 (13)	0.0007 (7)	0.0217 (9)	−0.0127 (8)
C10	0.0335 (14)	0.0252 (12)	0.086 (2)	0.0000	0.0227 (14)	0.0000

S1—C1	1.6945 (19)	C5—C6	1.384 (3)
O1—C8	1.375 (2)	C6—C7	1.380 (3)
O1—C9	1.441 (2)	C7—C8	1.399 (3)
N1—C1	1.326 (2)	C9—C10	1.503 (2)
N2—N3	1.374 (2)	C2—H2	0.9500
N2—C1	1.341 (2)	C4—H4	0.9500
N3—C2	1.280 (2)	C5—H5	0.9500
N1—H1A	0.9100	C6—H6	0.9500
N1—H1B	0.9100	C7—H7	0.9500
C2—C3	1.460 (3)	C9—H9A	0.9900
N2—H2A	0.9100	C9—H9B	0.9900
C3—C4	1.391 (3)	C10—H10A	0.970 (19)
C3—C8	1.398 (3)	C10—H10Ai	0.970 (19)
C4—C5	1.383 (3)
C8—O1—C9	116.91 (14)	O1—C9—C10	107.97 (14)
N3—N2—C1	119.38 (15)	C9—C10—C9i	114.84 (19)
N2—N3—C2	115.31 (15)	N3—C2—H2	120.00
S1—C1—N1	122.17 (14)	C3—C2—H2	120.00
S1—C1—N2	120.20 (13)	C3—C4—H4	119.00
N1—C1—N2	117.62 (16)	C5—C4—H4	119.00
H1A—N1—H1B	119.00	C4—C5—H5	120.00
C1—N1—H1B	120.00	C6—C5—H5	120.00
C1—N1—H1A	120.00	C5—C6—H6	120.00
C1—N2—H2A	127.00	C7—C6—H6	120.00
N3—N2—H2A	113.00	C6—C7—H7	120.00
N3—C2—C3	120.78 (16)	C8—C7—H7	120.00
C4—C3—C8	118.49 (17)	O1—C9—H9A	110.00
C2—C3—C8	120.12 (16)	O1—C9—H9B	110.00
C2—C3—C4	121.38 (17)	C10—C9—H9A	110.00
C3—C4—C5	121.55 (19)	C10—C9—H9B	110.00
C4—C5—C6	119.26 (19)	H9A—C9—H9B	108.00
C5—C6—C7	120.71 (19)	C9—C10—H10A	107.0 (12)
C6—C7—C8	119.81 (19)	C9—C10—H10Ai	112.0 (12)
O1—C8—C3	116.25 (16)	C9i—C10—H10A	112.0 (12)
C3—C8—C7	120.18 (17)	H10A—C10—H10Ai	103.6 (17)
O1—C8—C7	123.57 (17)	C9i—C10—H10Ai	107.0 (12)
C9—O1—C8—C3	−172.46 (16)	C2—C3—C8—O1	−2.2 (3)
C9—O1—C8—C7	6.8 (3)	C2—C3—C8—C7	178.46 (18)
C8—O1—C9—C10	172.29 (14)	C4—C3—C8—O1	178.61 (16)
C1—N2—N3—C2	−178.70 (16)	C4—C3—C8—C7	−0.7 (3)
N3—N2—C1—S1	177.07 (13)	C3—C4—C5—C6	0.0 (3)
N3—N2—C1—N1	−2.2 (2)	C4—C5—C6—C7	−0.3 (3)
N2—N3—C2—C3	177.81 (16)	C5—C6—C7—C8	0.1 (3)
N3—C2—C3—C4	−3.1 (3)	C6—C7—C8—O1	−178.85 (18)
N3—C2—C3—C8	177.76 (17)	C6—C7—C8—C3	0.4 (3)
C2—C3—C4—C5	−178.67 (18)	O1—C9—C10—C9i	−59.22 (16)
C8—C3—C4—C5	0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3	0.91	2.27	2.631 (2)	103
N1—H1A···S1ii	0.91	2.64	3.3393 (16)	135
N1—H1B···O1iii	0.91	2.20	3.1046 (19)	176
N2—H2A···S1iv	0.91	2.49	3.3909 (16)	171

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1AN3	0.91	2.27	2.631(2)	103
N1H1AS1i	0.91	2.64	3.3393(16)	135
N1H1BO1ii	0.91	2.20	3.1046(19)	176
N2H2AS1iii	0.91	2.49	3.3909(16)	171

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