data reports
ISSN 2414-3146
1-((E)-{2-[4-(2-{(1E)-[(carbamothioylamino)imino]methyl}phenoxy)butoxy]benzylidene}amino)thiourea dimethyl sulfoxide disolvate Joel T. Mague,a Shaaban K. Mohamed,b,c Mehmet Akkurt,d Eman M. M. AbdelRaheeme and Mustafa R. Albayatif*
Received 9 June 2016 Accepted 11 June 2016
Edited by P. C. Healy, Griffith University, Australia Keywords: crystal structure; bis(dimethylsulfoxide) solvate; thiourea. CCDC reference: 1484676 Structural data: full structural data are available from iucrdata.iucr.org
a
Department of Chemistry, Tulane University, New Orleans, LA 70118, USA, bChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, cChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, eChemistry Department, Faculty of Science, Sohag University, 82524-Sohag, Egypt, and fKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq. *Correspondence e-mail:
[email protected]
The title compound, C20H24N6O2S22C2H6OS, has crystallographically imposed centrosymmetry. The packing is assisted by N—H O, C—H O and N— H S interactions with the lattice solvent molecules, forming a two-dimensional network parallel to (110). The lattice dimethyl sulfoxide molecules (except for the S atoms) were modelled over two sites with refined occupancies of 0.831 (3):0.169 (3).
Structure description Thiosemicarbazones and their metal complexes have been known and interest to chemists for over fifty years due to their wide spectrum of biological activity such as antitumor, antibiotic and antiviral properties (Adelstein, 1973; Pandeya & Dimmock, 1993; Quiroga, et al., 1998; Christlieb & Dilworth, 2006). The synthesis of bis functionalized compounds are considered as significant precursors for building blocks of vital molecules such as nanoscience and supramolecular chemistry (Holland et al., 2007), and binucleating ligand designs (Gavrilova & Bosnich, 2004). In this context we report in this study the synthesis and crystal structure of the title compound. The title molecule (Fig. 1) has crystallographically imposed centrosymmetry. In the crystal, the packing is assisted by N—H O, C—H O and N—H S interactions with the lattice DMSO molecules (Table 1 and Fig. 2), forming a two-dimensional network parallel to (110)
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data reports Table 1 ˚ , ). Hydrogen-bond geometry (A D—H A i
N2—H2A S1 N3—H3A O2 N3—H3B O2ii C7—H7B O2iii
D—H
H A
D A
D—H A
0.91 0.91 0.91 0.99
2.49 2.14 2.04 2.49
3.371 (2) 2.887 (3) 2.885 (3) 3.471 (3)
163 139 153 174
Symmetry codes: (i) x þ 1; y þ 1; z þ 1.
x; y; z;
(ii)
x þ 1; y þ 1; z;
(iii)
Table 2 Experimental details.
Figure 1 The title molecule, showing the atom-labeling scheme and 50% probability displacement ellipsoids [symmetry code: (i) x, y, 1 z].
Synthesis and crystallization Salicyldehyde 122 mg (1 mmol) in hot ethanolic potassium hydroxide solution (prepared by dissolving 56 mg (1 mmol) of KOH in 10 ml of absolute ethanol) was stirred until a clear solution was obtained. The solution was evaporated under vacuum and the residue was dissolved in 5 ml DMF and then 119.4 ml (0.5 mmol) of 1,4-dibromobutane was added. The reaction mixture was refluxed for 5 minutes. The resulted potassium bromide was separated by filtration and the filtrate was then evaporated under vacuum. The remaining solid was washed with water and crystallized from ethanol to give high quality crystals (m.p. 513 K) suitable for X-ray analysis in a good yield (90%).
Refinement Crystal data, data collection and structure refinement details are summarized in Table 2. The lattice DMSO molecules (except S atoms) were modelled over two sites with refined occupancies of 0.831 (3):0.169 (3).
Crystal data Chemical formula Mr Crystal system, space group Temperature (K) ˚) a, b, c (A , , ( ) ˚ 3) V (A Z Radiation type (mm1) Crystal size (mm) Data collection Diffractometer Absorption correction
C20H24N6O2S22C2H6OS 600.83 Triclinic, P1 150 7.2571 (2), 9.7909 (2), 12.0060 (2) 112.984 (1), 98.163 (1), 96.909 (1) 762.80 (3) 1 Cu K 3.19 0.24 0.15 0.09
Bruker D8 VENTURE PHOTON 100 CMOS Multi-scan (SADABS; Bruker, 2015) 0.65, 0.76 8374, 2932, 2679
Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint ˚ 1) (sin /)max (A
0.023 0.617
Refinement R[F 2 > 2(F 2)], wR(F 2), S No. of reflections No. of parameters No. of restraints H-atom treatment ˚ 3) max, min (e A
0.056, 0.162, 1.08 2932 183 27 H-atom parameters constrained 0.88, 0.68
Computer programs: APEX2 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Brandenburg & Putz, 2012) and SHELXTL (Sheldrick, 2008).
Acknowledgements The support of NSF-MRI Grant #1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.
References
Figure 2 Packing viewed down the a axis. Intermolecular N—H O, C—H O and N—H S hydrogen bonds are shown, respectively, as blue, black and purple dotted lines.
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Adelstein, W. (1973). J. Med. Chem. 16, 309–312. Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Bruker (2015). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Christlieb, M. & Dilworth, J. R. (2006). Chem. Eur. J. 12, 6194–6206. Gavrilova, A. L. & Bosnich, B. (2004). Chem. Rev. 104, 349–383. Holland, J. P., Aigbirhio, F. I., Betts, H. M., Bonnitcha, P. D., Burke, P., Christlieb, M., Churchill, G. C., Cowley, A. R., Dilworth, J. R., Donnelly, P. S., Green, J. C., Peach, J. M., Vasudevan, S. R. & Warren, J. E. (2007). Inorg. Chem. 46, 465–485. IUCrData (2016). 1, x160946
data reports Pandeya, S. N. & Dimmock, J. R. (1993). Pharmazie, 48, 659–666. Quiroga, A. G., Pe´rez, J. M., Lo´pez-Solera, I., Masaguer, J. R., Luque, A., Roma´n, P., Edwards, A., Alonso, C. & Navarro-Ranninger, C. (1998). J. Med. Chem. 41, 1399–1408.
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
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full crystallographic data IUCrData (2016). 1, x160946
[doi:10.1107/S2414314616009469]
1-((E)-{2-[4-(2-{(1E)-[(carbamothioylamino)imino]methyl}phenoxy)butoxy]benzylidene}amino)thiourea dimethyl sulfoxide disolvate Joel T. Mague, Shaaban K. Mohamed, Mehmet Akkurt, Eman M. M. Abdel-Raheem and Mustafa R. Albayati 1-((E)-{2-[4-(2-{(1E)-[(Carbamothioylamino)imino]methyl}phenoxy)butoxy]benzylidene}amino)thiourea dimethyl sulfoxide disolvate Crystal data C20H24N6O2S2·2C2H6OS Mr = 600.83 Triclinic, P1 a = 7.2571 (2) Å b = 9.7909 (2) Å c = 12.0060 (2) Å α = 112.984 (1)° β = 98.163 (1)° γ = 96.909 (1)° V = 762.80 (3) Å3
Z=1 F(000) = 318 Dx = 1.308 Mg m−3 Cu Kα radiation, λ = 1.54178 Å Cell parameters from 6799 reflections θ = 4.1–72.1° µ = 3.19 mm−1 T = 150 K Thick plate, colourless 0.24 × 0.15 × 0.09 mm
Data collection Bruker D8 VENTURE PHOTON 100 CMOS diffractometer Radiation source: INCOATEC IµS micro–focus source Mirror monochromator Detector resolution: 10.4167 pixels mm-1 ω scans Absorption correction: multi-scan (SADABS; Bruker, 2015)
Tmin = 0.65, Tmax = 0.76 8374 measured reflections 2932 independent reflections 2679 reflections with I > 2σ(I) Rint = 0.023 θmax = 72.1°, θmin = 5.0° h = −8→8 k = −12→11 l = −14→14
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.056 wR(F2) = 0.162 S = 1.08 2932 reflections 183 parameters 27 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map
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Hydrogen site location: mixed H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0905P)2 + 0.766P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.002 Δρmax = 0.88 e Å−3 Δρmin = −0.68 e Å−3 Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 Extinction coefficient: 0.0061 (13)
data-1
data reports 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. Hatoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) while those attached to nitrogen were placed in locations derived from a difference map and their parameters adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
S1 O1 N1 N2 H2A N3 H3A H3B C1 C2 H2 C3 H3 C4 H4 C5 H5 C6 C7 H7A H7B C8 H8A H8B C9 H9 C10 S2 O2 C11 H11A H11B H11C
x
y
z
Uiso*/Ueq
Occ. (
