Supramolecular Assemblies of Nucleobase Derivative 1-Mecyt with

Supramolecular Assemblies of Nucleobase Derivative 1-Mecyt with Mg(II) and Ni(II) and Solid-State Transformation of Ni(II) Phase: A Comprehensive Evidence of Their Different Reactivity toward 1-Mecyt [1-Mecyt ) 1-Methylcytosine] Teresa F. Mastropietro,§ Donatella Armentano,§ Nadia Marino,§ Giovanni De Munno,*,§ Jane Anastassopoulou,† and Theophilos Theophanides†

CRYSTAL GROWTH & DESIGN 2007 VOL. 7, NO. 4 609-612

Dipartimento di Chimica, UniVersita` della Calabria, 87030 ArcaVacata di Rende, Cosenza, Italy, and Chemical, Engineering, Radiation Chemistry and Biospectroscopy, National Technical UniVersity of Athens, Zografu 15780, Athens, Greece ReceiVed December 7, 2006; ReVised Manuscript ReceiVed January 15, 2007

ABSTRACT: The synthesis and crystal structure of the compounds [Mg(H2O)6(1-Mecyt)2]Cl2 (1), [Ni(H2O)6(1-Mecyt)2]Cl2 (2), and [Ni(1-Mecyt)2Cl2] (3) (where 1-Mecyt ) 1-Methylcytosine) are reported. Compounds 1 and 2 consist of hexaaquo ions, 1-Mecyt molecules, and chloride ions self-assembled through an extended network of hydrogen-bonding interactions. Compound 3 is made of [Ni(1-Mecyt)2Cl2] units, with the 1-Mecyt molecules directly coordinated to the metal centers through the N(3) and O(2) atoms. When crystals of compound 2 are allowed to stand in air for 1 week, a solid transformation occurs. The results of our investigation clearly suggest that a solid-state reaction takes place in 2, leading to 3. Studies on metal ion-nucleic acid interactions are of great current interest because metal ions play a crucial role in the structure and function of nucleic acid and genetic information transfer.1 Many research efforts based on crystallographic studies have been dedicated to the rational design and elaboration of biomimetic systems based on the interaction of nucleobases and their derivatives with a wide range of metal ions.2 The binding mode of a specific nucleobase toward a metal ion depends essentially on the metal ion hardness or softness, the basicity of the donor site of the nucleobase, and eventually on auxiliary ligands coordinated to the metal center.3 The binding patterns have been often established with pyrimidine base blocked at N1 and purine base blocked at N9 to make them biologically relevant. In particular, with cytosine (Cyt) and the substituted nucleobase 1-methylcytosine (1-Mecyt), the metal binding can occur via N3, O2, N4, and simultaneously via N3-O2 or N3-N4. The N4 and N3-N4 coordination modes are reported for Pt(II)-containing 1-Mecyt compounds.4 Binding to N3 or O2 is favored, depending on the softness or hardness of the metal ion and probably steric aspects. Most metal ions prefer the N3 coordination mode.5,6 Only few complexes with the O2 binding mode are known, but for most of them, the simultaneous presence of the N3 coordination is observed.7,8 Merely in the compounds of formula [M(II)(Cyt)2(H2O)4][ClO4]‚2Cyt‚2H2O (M(II) ) Mg,9 Co,5g Mn,5g Ni)10 and [Ni(en)2(Cyt)2][B(C6H5)4],11 whose structures have been determined by X-ray analysis, Cyt shows the O2 coordination mode. The unique example of 1-Mecyt complex showing exclusively the O2 coordination mode is represented by the compound of formula [Mg(H2O)4(1-Mecyt)2]‚2(1-Mecyt).9 This species has been obtained together with a supramolecular assembly of formula [Mg(H2O)6(1-Mecyt)6][ClO4]2‚(H2O), which has been considered its precursor.9 Two supramolecular assemblies isostructural to the previous one have been obtained employing Mn(II) and Co(II) as metal ions.5g Once more, in the case of Co(II), the supramolecular species has been considered the precursor of a second complex of formula [Co(1-Mecyt)4][ClO4], showing the direct metal-base coordination Via N3. Here we present synthesis,12 X-ray structural determination,13 and spectroscopic characterization14 of three new complexes of formula [Mg(H2O)6(1-Mecyt)2]Cl2 (1), [Ni(H2O)6(1-Mecyt)2]Cl2 (2) * To whom correspondence should be addressed. E-mail: demunno@ unical.it. § Universita ` della Calabria. †National Technical University of Athens.

Figure 1. Ortep drawing and atomic labeling scheme of compound 1 (M ) MgII) and 2 (M ) NiII). Thermal ellipsoids are drawn at the 30% probability level.

and [Ni(1-Mecyt)2Cl2] (3). The first two isostructural compounds constitute additional examples of supramolecular assemblies containing M(II) hexaaquo ions. As far as we know, compounds 2 and 3 are the first 1-Mecyt compounds containing Ni(II) as metal ion to be authenticated by X-ray studies. The main novelty of this work is that it gives evidence that a spontaneous solid-state transformation, at air and room temperature, occurs in 2. Our investigation proves that it is associated with the loss of water molecules from nickel inner-coordination sphere and subsequent coordination of 1-Mecyt ligand. Crystal structures of compounds 1 and 2 consist of hexaaquo ions [M(H2O)6]2+ (M ) Mg(II) (1) or Ni(II) (2)), 1-Mecyt molecules, and chloride ions, self-assembled by means of an extended network of hydrogen bonds and π-π stacking interactions. No crystallization water molecules are present, in contrast with the Mg(II),9 Mn(II), and Co(II)5g analogues. The asymmetric unit contains a chlorine atom together with three coordinated water molecules, a 1-Mecyt ligand, and the M(II) ion lying on a crystallographic inversion center, with a 0.5 occupancy factor. Each Mg(II) and Ni(II) metal ion is in a distorted octahedral environment, being bonded to six water molecules. The M(II)-O bond distances (mean value 2.092(2) (1) and 2.049(2) (2)) are in agreement with the values reported for other similar Mg(II)9,15 or Ni(II)16 hexaaquo complexes. Each [M(H2O)6]2+ ion is linked through four hydrogen bonds to two molecules of 1-Mecyt, involving two cis-coordinated water molecules [O(1w) and O(2w)] and the O(2) and N(3) atoms of the nucleobase derivative (O(1w)‚‚‚N(3a) ) 2.811(2)Å (1) and 2.786(2) Å (2); O(2w)‚‚‚O(2) ) 2.738(2) Å (1) and 2.711(2) Å

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610 Crystal Growth & Design, Vol. 7, No. 4, 2007

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Figure 3. Crystal packing of (a) compound 2 (view along the x-axis) and (b) compound 3 (view along the y-axis).

Figure 2. (a) View along z axes of H-bonds within inorganic layers defined by the [M(H2O)6]2+ ions; (b) view along y axes of H-bonding net between inorganic and organic layers in 1 and 2.

(2); a ) -x, -y, -z) (Figure 1). The supramolecular architecture is built up by means of H-bonding and stacking interactions. Chloride anions are held with the cationic moiety [M(H2O)6(1Mecyt)2]2+ by means of H-bonds involving the oxygen atoms of the coordinated water molecules (O(1w)‚‚‚Cl(1) ) 3.238(2) Å (1) and 3.178(2) Å (2); O(2w)‚‚‚Cl(1) ) 3.191(2) Å (1) and 3.127(2) Å (2); O(3w)‚‚‚Cl(1b) ) 3.326(2) Å (1) and 3.234(2) Å (2), b ) x, y + 1, z; O(3w)‚‚‚Cl(1c) ) 3.180(2) Å (1) and 3.145(2) Å (2); c ) -x + 1, -y, -z), generating layers developing in the xy plane, wherein the inorganic planes defined by the [M(H2O)6]2+ ions (Figure 2a) are sandwiched between planes defined by the 1-Mecyt molecules (Figure 2b). These latter are linked to each other by H-bond interactions between O(2) and the N(4) atoms, developing along the x direction (N(4)‚‚‚O(2d) ) 3.072(2) Å (1) and 2.998(3) Å (2), d ) x - 1, y, z). The 3D arrangement is realized by π-stacking interactions between pyrimidine rings, the interplanar distances being 3.58 (1) and 3.42 Å. (2) (Figure 3a).

Figure 4. Ortep drawing and atomic labeling scheme of compound 3. Thermal ellipsoids are drawn at the 30% probability level.

Compound 3 contains two chloride ions and two 1-Mecyt directly linked to Ni(II) via O(2) and N(3) (Figure 4). No water molecules are present. The Ni-O2 coordination has been previously observed for Cyt-containing complexes.10,11 However, there are no structural records in literature reporting on complexes containing Cyt or its derivatives in which the Ni-N3 bond has been observed. Each Ni(II) ions presents a distorted octahedral environment, being coordinated by two chloride ions, two nitrogen (N(3) and N(3)′), and two oxygen (O(2) and O(2)′) atoms from two 1-Mecyt ligands. As usual, the metal-O2 bond length is weaker (Ni(1)-O(2)′ ) 2.234(1) Å and Ni(1)‚‚‚O2 ) 2.575(1) Å) than the metal-N3 one (Ni(1)-N(3)′ ) 2.061(1) Å; Ni(1)-N(3) ) 2.029(1) Å). In

Communications

Figure 5. Perspective drawing of H-bonding network in 3.

particular, the exocyclic O(2) atom of a 1-Mecyt molecule shows a longer bond length, reasonably due to the presence of an intermolecular hydrogen bonding (N(4)‚‚‚O(2b) ) 2.861(1), b ) x, y-1, z) (Figure 5). This latter interaction and the Cl(1)‚‚‚N(4) one (Cl(1a)‚‚‚N(4) ) 3.415(1), a ) -x + 1/2, y + 1/2, -z + 1/2) realize a supramolecular array in the xy plane, whereas stacking between the pyrimidine rings ensures the 3D cohesion (the distance between planes being 3.69 Å) (Figure 3b). Complexes 2 and 3 are obtained together as a mixture. It is reasonable to suppose that, in solution, an equilibrium exists between [Ni(H2O)6]2+, surrounded by 1-Mecyt ligands and chloride anions, and the directly coordinated [Ni(1-Mecyt)2Cl2] complex, as previously stated for Mg(II)9 and Co(II)5g compounds. Keeping in mind their structures, compound 3 can practically be obtained from compound 2 through the mechanism illustrated herein: The coordinated water molecules are progressively removed, allowing the direct coordination of two chloride anions and two 1-Mecyt molecules. Coordination of 1-Mecyt would initially take place through both N3 and O2 for a molecule, and just through N3 for the second one. In fact, before involving its O(2) atom in coordination, the second pyrimidine ring must rotate 82.9° along the direction of its Ni-N(3) bond, a value that corresponds to the dihedral angle between the 1-Mecyt ligands in 3. Curiously, a reaction leading from 2 to 3 also occurs in the solid state. Actually, when the green crystals of compound 2 are allowed to stand in air for 1 week, a solid transformation accompanied by a color change and loss of crystallinity occurs, leading to a brown powder. FT-IR spectra and X-ray powder diffraction patterns have been collected on the brown powder in order to authenticate its composition. The analysis of the IR spectra performed on brown powder and orange-brown crystals of 3 show that both samples have analogous absorption bands, their spectra being essentially superimposable. The microanalysis prove that powder and crystals have the same composition. Finally, the complete correspondence was revealed by XRPD analysis of brown powder and crystals of 3. An accurate analysis of the crystal structures of compounds 2 and 3 points out the structural changes following transformation. Going from 2 to 3, the breaking of 50% of the H-bonding interactions between O(2) and N(4) atoms and the loss of 50% of π-stacking interactions are observed, consequently to the rotation of the pyrimidine rings of alternated planes, as shown in Figure 3. The rest of the O(2)‚‚‚N(4) H-bonds become stronger, with the O(2)‚‚‚N(4) distances passing from 2.997(3) to 2.861(1) Å. The opposite trend is observed in the remaining stacking interactions, where interplanar distances pass from 3.42 to 3.60 Å. The shorter Ni‚‚‚Ni distances are 7.502 Å in 2 and 7.357 Å in 3, values corresponding to the a and b crystallographic axes, respectively. In conclusion, these studies support the hypothesis that the complex formation between Ni(II) and 1-Mecyt undoubtedly passes

Crystal Growth & Design, Vol. 7, No. 4, 2007 611 through a precursor, containing hexaaquo nickel ion in aqueous solution, detachable by itself in solid state. This hypothesis is for the first time supported by the experimental evidence of a transformation that takes place in the solid state, concerning the Ni(II) complex. No compounds other than 1 have been obtained from the MgCl2-containing solution. It is noticeable that in the Mg(II) case, the supramolecular assembly does not evolve toward the species containing direct metal-base links. Such results reasonably suggest the greater reactivity of Ni(II) ion toward 1-Mecyt when compared with Mg(II) ion. It is interesting to compare compound 3 with the Mg(II)9 and Co(II)5g analogues containing direct metal-base bonds. The magnesium complex shows an octahedral environment with coordination of 1-Mecyt via O2, whereas the Co(II) complex is tetrahedral, showing four Co-N(3) bonds. In compound 3, Ni(II) is in a distorted octahedral environment, with 1-Mecyt molecules coordinated via N3 and O2, showing an “intermediate character” between the “hard” ion Mg2+ and the “soft” ion Co2+. Thanks are due to the Italian MIUR, the Universita` della Calabria, and Regione Calabria (POR Calabria 2000/2006, misura 3.16, progetto PROSICA) for financial support. We are also grateful to Dr. Patrizia Rossi for XRPD analysis. Supporting Information Available: X-ray crystallographic files of compounds 1-3 in CIF format, 2D H-bonding net of 1 and 2 showing layers developing along the xy plane (Figure S1), FT-IR spectra (Figure S2) and XRPD profiles (Figure S3) of orange crystals of 3 and brown powder. This material is available free of charge via the Internet at http:// pubs.acs.org.

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L. G.; Kistenmacher, T. J. Inorg. Chem. 1975, 14, 2076. (f) Bruning, W.; Freisinger, E.; Sabat, M.; Sigel, R. K. O.; Lippert, B. Chem.s Eur. J. 2002, 8, 4681. (g) Palaniandavar, M.; Somasundaram, I.; Lakshminarayanan, M.; Monohar, H. J. Chem. Soc., Dalton Trans. 1996, 1333. (a) Gagnon, C.; Beauchamp, A. L.; Tranqui, D. Can. J. Chem. 1979, 57, 1372. (b) Lippert, B.; Thewalt, U.; Schollhorn, H.; Godgame, D. M. L.; Rollins, R. W. Inorg. Chem. 1984, 23, 2807. (c) Schollhorn, H.; Thewalt, U.; Lippert, B. Inorg. Chim. Acta 1987, 135, 155. (d) Kistenmacher, T. J.; Rossi, M.; Marzilli, L. G. Inorg. Chem. 1979, 18, 234. (e) Smith, D. P.; Olmstead, M. M.; Noll, B. C.; Maestre, M. F.; Fish, R. H. Organometallics 1993, 12, 1593. (f) Freisinger, E.; Scheider, A.; Drumm, M.; Hegmans, A.; Meier, S.; Lippert, B. J. Chem. Soc., Dalton Trans. 2000, 3281. (g) Fush, E. C.; Lippert, B. J. Am. Chem. Soc. 1994, 116, 7204. (h) Renn, O.; Preut, H.; Lippert, B. Inorg. Chim. Acta 1991, 188, 133. (a) Tran Qui, D.; Palacios, E. Acta Crystallogr., Sect. C 1990, 46, 1220. (b) Muthiah, P. T.; Robert, J. J.; Ray, S. B.; Bocelli, G.; Olla, L. Acta Crystallogr., Sect. E 2001, 57, m558. (c) Capllonch, M. C.; Garcia-Raso, A.; Terron, A.; Apella, M. C.; Espinosa, E.; Molins, E. J. Inorg. Biochem. 2001, 85, 173. (d) Aoki, K.; Salam, M. A. Inorg. Chim. Acta 2001, 316, 50. Qui, D. T.; Bagieu, M. Acta Crystallogr., Sect. C 1990, 46, 1645. Geday, M. A.; De Munno, G.; Medaglia, M.; Anastassopoulou, J.; Theophanides, T. Angew. Chem., Int. Ed. 1997, 36, 511. De Munno, G. Unpublished results. Cervantes, G.; Fiol, J. J.; Terron, A.; Moreno, V.; Alabart, J. R.; Aguilo, M.; Gomez, M.; Solans, X. Inorg. Chem. 1990, 29, 5168. Single crystals of 1 (colourless parallelepipeds), 2 (green parallelepipeds), or 3 (orange-brown parallelepipeds) have been obtained by slow evaporation of equimolar aqueous solutions of MCl2 (M ) Mg2+ or Ni2+) and 1-Mecyt. Compounds 2 and 3 have been obtained in the Ni2+ solution as a mixture. Yields: 70% (1) and 75% for 2 and 3 (ca. 35 and 40% for 2 and 3, respectively). When crystals of compound 2 are allowed to stand in air for 1 week, a solid transformation accompanied by a color change from green to brown and a loss of crystallinity occurs, leading to a brown powder. Analytical data: Anal. Calcd for C10H26Cl2MgN4O8 (1): C, 28.22; H, 6.16; N, 13.17. Found: C, 28.45; H, 5.98; N, 13.01. Anal. Calcd for C10H26Cl2NiN4O8 (2): C, 26.11; H, 5.70; N, 12.18. Found: C, 26.36; H, 5.47; N, 11.89. Anal. Calcd for C10H14Cl2NiN4O2 (3): C, 34.14; H, 4.01; N, 15.92. Found: C, 34.45; H, 4.36; N, 15.77. Found for the brown powder of 3: C, 34.43; H, 4.39; N, 15.82. X-ray crystallography: the data were collected with Bruker R3m/V automatic four-circle (1,2) and Bruker-Nonius X8APEXII CCD area detector (3) diffractometers using monochromatized MoKR radiation. They were collected over the ranges 2.06° > ϑ > 26.98° (1), 2.08° > ϑ > 27.06° (2), and 2.86° > ϑ > 30.86° (3), and corrected for absorption. Data were processed using the SHELXTL package (SHELXTL; Bruker Analytical X-ray Instruments: Madison, WI, 1998). Solution and refinement were performed through the programs SHELXS97 (Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467) and SHELXL97 (Sheldrick, G. M. SHELXL-97. Program for

Communications the Solution and Refinement of Crystal structures; University of Go¨ttingen: Go¨ttingen, Germany, 1997). Crystal data of 1: M ) 226.78, triclinic, a ) 7.608(2) Å, b ) 7.987(2) Å, c ) 10.443(2) Å, R ) 104.50(3)°, β ) 94.35(3)°, γ ) 116.79(3)°, V ) 535.2(2) Å3, T ) 293(2) K, space group P1h, Z ) 2, F ) 1.407 g/cm3, µ ) 3.79 mm-1; 2487 reflections measured, 2252 unique; R1 [I > 2σ(I)] ) 0.0431, wR2 ) 0.1150. Crystal data of 2: M ) 243.98, triclinic, a ) 7.502(1) Å, b ) 7.584(1) Å, c ) 10.383(1) Å, R ) 104.85(1)°, β ) 94.05(1)°, γ ) 116.11(1)°, V ) 501.2(1) Å3, T ) 293(2) K, space group P1h, Z ) 2, F ) 1.617 g/cm3, µ ) 12.84 mm-1; 2668 reflections measured, 2201 unique; R1 [I > 2σ(I)] ) 0.0380, wR2 ) 0.1029. Crystal data of 3: M ) 379.88, monoclinic, a ) 27.6819(6) Å, b ) 7.3574(2) Å, c ) 14.5039(4) Å, β ) 101.251(2)°, V ) 2897.2(1) Å3, T ) 293(2) K, space group C2/c, Z ) 8, F ) 1.742 g/cm3, µ ) 17.21 mm-1; 26594 reflections measured, 4549 unique; R1 [I > 2σ(I)] ) 0.0231, wR2 ) 0.0924. Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC 629028-629030. Copies of the data can be obtained free of charge on application to CCDC, 12 union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033.; e-mail: [email protected]). (14) Fourier transform infrared (FT-IR) spectra were recorded in a frequency range of 4000-400 cm-1 using an FTS 3000 MX BioRad Excalibur Series Spectrophotometer, with a resolution of 4 cm-1 and 32 scans per spectrum and were processed with the Bio-Rad WinIR Pro 3.0 Software. X-ray powder diffraction profiles were recorded at room temperature on a Bruker-AXS D5005 ϑ-ϑ diffractometer, using Cu-KR radiation operating at 40 kV and 30 mA in grazing incidence (0.5) mode. (15) (a) Liu, J. W.; Gao, S.; Huo, L. H.; Dong, Y.; Zhao, H. Acta Crystallogr., Sect. E 2004, 60, m845. (b) Liu, W. L.; Zou, Y.; Ni, C. L.; Ni, Z. P.; Li, Y. Z.; Yao, Y. G.; Meng, O. J. Polyhedron 2004, 23, 849. (c) Yang, Q.; Gao, S.; Huo, L. H. Acta Crystallogr., Sect. E 2005, 61, m277. (d) Arranz Mascaros, P.; Cobo Domingo, J.; Godino Salido, M.; Gutierrez Valero, M. D.; Lopez Garzon, R.; Low, J. N. Acta Crystallogr., Sect. C 2000, 56, e4. (e) Henke, K. R.; Hutchison, A. R.; Krepps, M. K.; Parkin, S.; Atwood, D. A. Inorg. Chem. 2001, 40, 4443. (f) Michal, G.; Wojciech, S.; Janusz, L. Acta Crystallogr., Sect. E 2005, 61, m1920. (g) Rychlewska, U.; Guresic, D. M.; Warzajtis, B.; Radanovic, D. D.; Djuran, M. I. Polyhedron 2005, 24, 2009. (16) (a) Zheng, Y. Q.; Kong, Z. P. J. Coord. Chem., 2003, 56, 967. (b) Piggot, P. M. T.; Hall, L. A.; White, A. J. P.; Williams, D. J.; Thompson, L. K. Inorg. Chem. 2004, 43, 1167. (c) Junk, P. C.; Smith, M. K.; Steed, J. W. Polyhedron 2001, 20, 2979. (d) Morris, J. E.; Squattrito, P. J.; Kirschbaum, K.; Pinkerton, A. A. J. Chem. Cryst. 2003, 33, 307. (e) Xu, B.; Zhang, Y. Y.; Liu, W. L.; Hu, X. Y. Acta Crystallogr., Sect. E2006, 62, m1508. (f) SeethaLekshmi, N.; Pedireddi, V. R. Inorg. Chem. 2006, 45, 2400.

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