Layer and Chain Structures in the Co-Crystals of 18-Crown-6with Aromatic Thiosemicarbazide Derivatives

Yurii A. Simonov,a Marina S. Fonari,a,* Janusz Lipkowski,b

Edward V. Ganinc and Arkadii A. Yavolovskiid

aInstitute of Applied Physics of the Academy of Sciences of Moldova, Chisinau, MoldovabInstitute of Physical Chemistry, Polish Academy of Sciences, ul Kasprzaka 44/52, Warszawa, Poland

cOdessa State Environmental University of the Ministry of Education and Science of Ukraine, Odessa, UkrainedBogatsky Physico-Chemical Institute of the National Academy of Science of Ukraine, Odessa, Ukraine

Abstract—The crystal structures of 1:2 binary complexes of 18-crown-6 with two thiosemicarbazide derivatives, phenylthiosemi-carbazide (PH), (1) and quinoline thiosemicarbazide (QH), (2) are reported. Compound 1 displays a layered structure formed bythe association of PH zigzag chains and crown molecules. In compound 2 centrosymmetric QH dimers alternate with the crownspacers in the chains. Both structures are sustained by N–H. . .O and N–H. . .S hydrogen bonds.# 2003 Elsevier Ltd. All rights reserved.

Introduction

Crown ethers and their complexes have been intensivelystudied during the last 30 years.1 The interest stems notonly from the fact that these systems exhibit a widevariety of structural assemblies but also from the che-mical and biological potential of these compounds asion exchangers and possible agents for transportingionic species in living tissues.

On the other hand, thiosemicarbazides and their deri-vatives are very suitable complexing agents due to highflexibility of their thiosemicarbazide branch. Metalcomplexes and self-assembly of ligands derived fromthese systems have been widely reported.2 So far, inspite of rich exploration, only few examples are knownfor the complexes of thiosemicarbazones and thiosemi-carbazides and their derivatives with crown ethers (bin-ary complexes of acetone thiosemicarbazone with12-crown-4,3 complexes of thioamide hydrazide of2-aminobenzoic acid and thioamide hydrazide of 4-amino-1,2,5-thiodiazole-3-carbonic acid with 18-crown-64).The topology of the networks formed is governed, atleast partially, by the availability of both hydrazine andthioamide moieties in the same molecule that are cap-able of self-association of the molecules in a manner

that directs crystal structures in two or even in threedirections. The aim of these studies is to create newmaterials for applications such as molecular sieves withapplications to green chemistry.

This paper will outline further studies on hydrogen-bonded polymeric networks constructed through theinteraction of crown ether with thiosemicarbazideligands possessing a multi-siteconnecting geometry.

Scheme 1 represents the ligands which have been usedsuccessfully for design of 2D and 3D architectures in thecomplexes with 18-crown-6 (18C6), hydrazide of 2-ami-nobenzoic acid (HA), hydrazide of 5-amine-1-benzyl-1,2,3-triazole-4-carbonic acid (HB),4,5 thioamide hydra-zide of 2-aminobenzoic acid (TB), thioamide hydrazideof 4-amino-1,2,5-thiodiazole-3-carbonic acid (HT),5

phenylhydrazinecarbothioamide (PH), (2-quinoline-2-ylcarbonyl)hydrazinecarbothioamide (QH) (this study).

Experimental

Crystals of 1 and 2 were obtained in nearly quantitativeyield from slow evaporation of the reactants at roomtemperature. Intensity data for both complexes werecollected at room temperature for 1 and at 150 K for 2on a Nonius Kappa CCD diffractometer equipped withgraphite monochromatized MoKa radiation using rota-tion with sample-to-detector distance of 40 mm. Pre-liminary orientation matrix and unit cell parameters

1472-7862/02/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.doi:10.1016/S1472-7862(03)00051-0

Journal of Supramolecular Chemistry 2 (2002) 415–420

Keywords: Crown based binary complexes; Thiosemicarbazide deriva-tives; Hydrogen bonding; X-ray crystallography.*Corresponding author. Tel.: +373-2-738154; fax: +373-2-725887;e-mail: fonari.xray@phys.asm.md

were obtained from the peaks of the first 10 frames,respectively, and refined using the whole data set.Frames were integrated and corrected for Lorentz andpolarization effects using DENZO.6 The scaling andglobal refinement of crystal parameters were performedby SCALEPACK.6 Reflections, which were partly mea-sured on previous and following frames, are used toscale these frames. The structures were solved by directmethods and refined using SHELX977 software pack-age. The non-hydrogen atoms of the asymmetric unitwere refined anisotropically (full-matrix least squaresmethod on F2). C-bound hydrogen atoms were placed incalculated positions with their isotropic displacementparameters riding on those of parent atoms, while theN-bound H-atoms were found from differential Fouriermaps and refined without any constraints. The X-raydata and the details of the refinement for (1) and (2) aregiven in Table 1, the geometric parameters for H-bondsare given in Table 2.

Results and discussion

The 1:2 centrosymmetric binary complex 1 crystallizesin the monoclinic system, space group P21/c. Figure 1displays an ORTEP drawing with the atom labels. Theamine group of each PH molecule is perching above andbelow the crown moiety and is linked to the macrocyclevia two long and appreciably bent N–H. . .O hydrogenbonds with symmetry related crown oxygens,N(11). . .O(4) 3.075(2) and N(11). . .O(4)(�x, �y+1,�z+1) 3.085(2) A (angles subtended at the H atoms158 and 155�, Table 2). The C(26)–N(11) bond is

Scheme 1.

Table 2. Hydrogen bonds for 1 and 2

D-H...A d

(H...A), Ad (D...A), A ˚ (DHA),� Symmetry codefor acceptor

1

N(11)–H(1N1)...O(4)

2.32(2) 3 .075(2) 158(2) N(11)–H(2N1)...O(4) 2.34(2) 3 .085(2) 155(2) � x, �y+1, �z+1 N(12)–H(1N2)...O(1) 2.11(2) 2 .918(2) 163(2) x , �y+1/2, z�1/2 N(13)–H(1N3)...S(11) 2.46(2) 3 .273(2) 174(2) x , �y+1/2, z�1/2 2

N(11)–H(1N1)...O(1)

2.24(2) 3 .077(2) 158(2) � x+1, �y+2, �z N(11)–H(2N1)...O(4) 2.17(2) 2 .965(2) 152(2) N(12)–H(1N2)...O(7) 2.28(2) 3 .081(2) 160(2) x, y�1, z N(13)–H(1N3)...S(11) 2.52(2) 3 .283(2) 150(2) � x+1, �y+1, �z

Table 1. Crystal data and structure refinement for compounds 1, 2

1

2

Empirical formula

C26H42N6O6S2 C34H44N8O8S2 Formula weight 598.78 756.89 Temperature, K 293 (2) 150 (2) Space group P21/c P21/c a (A) 9.996 (3) 10.241 (2) b (A) 14.585 (5) 7.777 (2) c (A) 11.181 (4) 23.848 (6) b(�) 102.11 (2) 95.91 (8) Volume (A3) 1593.8 (9) 1889.3 (8) Z 2 2 Dcalc, (g cm

�3)

1.248 1.331 m, (mm�1) 0.214 0.201 F(000) 640 800 Crystal dimensions,mm

0.15�0.20�0.25

0.20�0.20�0.30

y range for datacollection, deg.

2.08 to 27.49

2.76 to 27.48

Limiting indices

�12<h<12,�15<k<18,�14< l<14

0<h<13,0<k <10,�30< l<30

Reflections collected/unique

6629/3598 4319/4319 Reflections with I>2s(I) 2613 3577 Refinement method Full-matrix least squares on F2

Data/restraints/parameters

3598/0/197 4319/0/251 Goodness-of-fit on F2 1.050 1.108 Final R indices [I>2s(I)] R1=0.0455,

wR2=0.1001

R1=0.0471,wR2=0.0937

R indices (all data)

R1=0.0730,wR2=0.1076

R1=0.0667,wR2=0.0996

Largest diff. peak (hole), e/ 3

0.315 (�0.238) 0.223 (�0.247)

Figure 1. ORTEP view of 1. Thermal ellipsoids are given at 50%probability level. The symmetry related PH molecule is omitted.

416 Y. A. Simonov et al. / Journal of Supramolecular Chemistry 2 (2002) 415–420

practically perpendicular to the crown ether averageplane and nitrogen atom is deviated at 1.90 (1) A fromit. The phenyl ring of the PH molecule is situatedapproximately parallel to the macrocycle, with thedihedral angle between the average planes of the aro-matic ring of PH and 6-O atoms of 18C6 being equalto 2.1(1)�. These units are associated into sheets by twoadditional hydrogen bonds, N–H. . .O and N–H. . .S,originating from both NH groups of hydrazine func-tionality and utilizing the thioureido S atom or a sec-ond crystallographically independent ether O atom asacceptors. The first of these interactions,N(12). . .O(1)(x, �y+1/2, z1/2) 2.918(2) A contributesinto stability of (PH)2

. . .18C6. . .(PH)2 unit which issustained by six N-H. . .O hydrogen bonds. SingleN–H. . .S hydrogen bond, N(13). . .S(11)(x,�y+1/2, z�1/2)3.273(2) A links the PH molecules into zigzag chainsrunning along c direction in the unit cell (Fig. 2a). In the

layer each six PH molecules and two 18C6 are asso-ciated into cages closed by aforementioned hydrogenbonds, each molecule in the layer being shared betweentwo neighboring cages. The layers are propagated par-allel to the (011) plane (Fig. 2b). Two neighboring layersmeet by phenyl substituents that form hydrophobicsurfaces of each layer. The very similar layer organiza-tion has been previously found in the 18C6 complexwith HB4,5 where similar cages are found to be inter-connected by 16 intermolecular hydrogen bonds ofN–H...O(crown) and N–H...O¼C types.

In 1 the sulfur atom contributes only to one N–H. . .Shydrogen bond, responsible for the PH arrangement inchains in distinction to the free PH8 molecule, where achain structure is sustained by two alternating N–H. . ..S,R22(8)9,10 synthons I (Scheme 2) which are very typical

for thiosemicarbazides.

Figure 2. (a). Zigzag chain of PH molecules in 1. (b). Layer in 1. Red: oxygen, blue: nitrogen, yellow: sulfur.

Y. A. Simonov et al. / Journal of Supramolecular Chemistry 2 (2002) 415–420 417

2 crystallizes in the monoclinic system, space group P21/c.An ORTEP drawing with numbering scheme is shownin Fig. 3. Similar to 1, primary amine group of QHyields two weak and essentially bent N–H. . .O hydrogenbonds, N(11). . .O(4) 2.965(2), N(11). . .O(1)(�x+1,�y+2, �z) 3.077(2) A (angles subtended at the H atoms158 and 152, Table 2), one more subsidiary N–H. . .Ointeraction exists with the translated macrocycle,N(12). . .O(7)(x, y�1, �z) 3.283(2) A. Two QH mole-cules are combined into a centrosymmetric dimer viatwo N–H. . .S hydrogen bonds, N(13). . .S(11)(�x+1,�y+1, �z) 3.283(2) A, R2

2(10) graph set,11 II (Scheme2). This H-bonded 10-membered ring is essentially cor-rugated with the deviations (from planar) of the con-tributing atoms falling in the range from 0.456(3) A forC(26) to �0.432(3) A for N(12) and the dihedral anglebetween the average planes of the planar quinoline sys-tem and R2

2(10) synthon itself equal 20.0(1)�. The QHdimers and crown molecules alternate in the chainsalong b direction in the unit cell (Fig. 4). Fig. 5 displaysthe chain packing in 2.

The aforementioned R22(10)11 synthon was previously

found in the associated in chains TB molecules in thecomplex with 18C6. However, the amine group availablein TB in the neighboring to the thiosemicarbazide func-tionality position facilitates the further unification ofTB centrosymmetric dimers into chains via N–H. . .S andN–H. . .O hydrogen bonds. In this case sulfur atom isinvolved in two lying approximately at the straight lineN–H. . .S hydrogen bonds, III, Scheme 2. The combi-nation of TB chains and rows of crown ethers affords

Scheme 2.

Figure 3. ORTEP view of 2. Thermal ellipsoids are given at 50%probability level. The symmetry related QH molecule is omitted.

Figure 4. Chain in 2.

418 Y. A. Simonov et al. / Journal of Supramolecular Chemistry 2 (2002) 415–420

the layer structure, which is depicted in Fig. 6. Thecomparison of these two packing modes reveals someunexpected similarities. First, the unit cell dimensionsare very close for these two compounds, for 18C6.(TB)2:a=10.437(2), b=7.942(3), c=19.958(7) A, b=90.89(2),for 2 see Table 1. Space group P21/c is the same in bothcases. The chains that combine crown molecules andQH(or TB) dimers are running along b direction in the unit

cell in both structures (Figs 5 and 6). Only van der Waalsinteractions bind chains in 2. In 18C6.(TB)2 the layersbuilt of the similar chains and bound by H-bondinginteractions, are propagated in the same plane as thechains in 2. So, one may say that the quinoline systemof two QH molecules that belong to the neighboringchains corresponds in size to the H-bonded TB mole-cules. In the case of 2 the further development of chain

Figure 5. Packing of chains in 2.

Figure 6. Layer in the complex 18C6.(TB)2.

Y. A. Simonov et al. / Journal of Supramolecular Chemistry 2 (2002) 415–420 419

structure into the layered one is impeded by the absenceof the neighboring proton donor group in QH and itprevents the transformation of II to III.

Supporting information

Tables of crystal data, atomic coordinates and thermalparameters, full bond distances and angles, and struc-ture factors may be obtained on request from theauthors. Crystallographic files in CIF format are alsoavailable from the authors and from the CambridgeCrystallographic Data Centre, on quoting the full jour-nal citation and the deposition numbers CCDC 192819and CCDC 192820 for compounds 1 and 2, respectively.

Acknowledgements

Support of this research from MRDA-CRDF (grantMP2-3021) is gratefully acknowledged.

References and notes

1. (a) Pedersen, C. T.; Frensdorff, H. K. Angew. Chem., Int.Ed. Engl. 1972, 11, 16. (b) Lehn, J. M. Acc. Chem. Res. 1978,11, 49. (c) Cram, D. J.; Cram, J. M. Acc. Chem. Res. 1978, 11,8.2. Allen, F. N.; Kennard, O. Chemical Design AutomationNews 1993, 8 (1), 31 The search of thiosemicarbazide deriva-tives gave more than 200 hits for these molecules coordinatedto the metals and free ligands..3. Henschel, D.; Blaschette, A.; Jones, P. G. Acta Cryst. 1997,C53, 1875.4. Fonari, M. S.; Simonov, Yu. A.; Kravtsov, V. Ch.; Lip-kowski, J.; Ganin, E. V.; Yavolovskii, A. A. J. Mol. Str. 2003,647, 129. CIF files are available from the authors and from theCambridge Crystallographic Data Centre, on the depositionnumbers CCDC 182691 and CCDC 175853 for the TB andHT — crown complexes, respectively.5. Simonov, Yu. A.; Fonari, M. S.; Kravtsov, V. Kh.; Lip-

kowski, J.; Ganin, E. V.; Yavolovskii, A. A. Russian Kris-tallografiya 2002, 47, 93 CIF files are available from theauthors and from the Cambridge Crystallographic Data Cen-tre, on the deposition numbers CCDC 160249 and CCDC160250 for the HA and HB — crown complexes, respectively.6. Otwinowski, Z.; Minor, W. In Processing of X-ray Diffrac-tion Data Collected in Oscillation Mode; Carter, C. W., Sweet,R. M., Eds.; Methods in Enzymology, Vol 276, Macro-molecular Crystallography, Part A; Academic Press: NewYork, 1997; pp 307.7. Sheldrick, J.M. SHELX-97 Program for structure determi-nation and refinement, University of Gottingen, Germany, 1997.8. Czugler, M.; Kalman, A.; Argay, G. Cryst. Struct. Com-mun. 1973, 2, 655.9. (a) For information about graph-set notation see: Bern-stein, J.; Davis, R. E.; Shimoni, L.; Chang, N-L. Angew.Chem., Int. Ed. Engl. 1995, 34, 1555. (b) Etter, M. C.; Mac-Donald, J. C.; Bernstein, J. Acta Crystallogr., Sect. B. 1990,B46, 256.10. (a) For some recent examples of R2

2(8) NH. . .S synthon inthiosemicarbazides see: Rabe, G.; Roesky, H. W.; Bohra, R.;Schmidt, H.-G.; Noltemeyer, M. J. Fluorine Chem. 1991, 52,235. (b) Childs, B. J.; Cadogan, J. M.; Craig, D. C.; Scudder,M. L. Goodwin, H. A. Aust. J. Chem. 1998, 51, 273. (c) Per-tlik, F. Monatsh. Chem. 1990, 121, 129. (d) Nesterov, V. N.;Shestopalov, A. M.; Sharanin, Yu. A.; Aitov, I. A.; Shklover,V. E.; Struchkov, Yu. T.; Litvinov, V. P. Izv. Akad. NaukSSSR, Ser. Khim. 1991, 896. (e) Kaiser, D.; Videnov, G.;Maichle-Mossmer, C.; Strahle, J.; Jung, G. J. Chem. Soc.,Perkin Trans. 2 2000, 1081. (f) Hereygers, M. L. B. F.; Des-seyn, H. O.; Perlepes, S. P.; Verhulst, K. A. F.; Lenstra,A. T. H. J. Chem. Cryst. 1995, 25, 181.11. (a) For some recent examples of R2

2(10) NH. . .S synthon inthiosemicarbazides see: (a) Bhatia, S. C.; Gautam, P.; Cha-trath, A. K.; Jain, P. C. Indian J. Chem., Sect. B. 1993, 32,1237. (b) Ferrari, M. B.; Bonardi, A.; Fava, G. G.; Pelizzi, C.;Tarasconi, P. Inorg. Chim. Acta 1994, 223, 77. (c) Chatto-padhyay, D.; Banerjee, T.; Mazumdar, S. K.; Ghosh, S.;Kuroda, R. Acta Crystallogr., Sect. C (Cr. Str. Comm.) 1991,47, 112. (d) Abram, U.; Ortner, K.; Gust, R.; Sommer, K. J.Chem. Soc., Dalton Trans. 2000, 735. (e) Menzies, C. M.;Squattrito, P. J. Inorg. Chim. Acta 2001, 314, 194. (f) Valente,E. J.; Zubkowski, J. D.; Jabalameli, A.; Mazhari, S.; Venka-traman, R.; Sullivan, R. H. J. Chem. Cryst. 1998, 27, 28.

420 Y. A. Simonov et al. / Journal of Supramolecular Chemistry 2 (2002) 415–420