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X-ray Structure Analysis Online 2013, VOL. 29 2013 © The Japan Society for Analytical Chemistry 17 X-ray Structure Analysis Online Structural Features of Hexakis-DMSO Nickel(II) Complex Cations: Pseudo-S6- and Pseudo-S4-Propeller-Like Structures Reiji SUDO,* Daisuke YOSHIOKA,** Masahiro MIKURIYA,** and Hiroshi SAKIYAMA*† *Department of Material and Biological Chemistry,Faculty of Science, Yamagata University, 1-4-12 Kojirakawa, Yamagata 990-8560, Japan **Department of Chemistry and Research Center for Coordination Molecule-based Devices, School of Science and Technology, Kwansei Gakuin University, Gakuen 2-1, Sanda 669-1337, Japan The nickel(II) complex [Ni(DMSO)6](BPh4)2 (DMSO = dimethylsulfoxide) [hexakis(dimethylsulfoxide-kO)nickel(II) bis(tetraphenylborate)] was prepared, and characterized by a single-crystal X-ray method. The compound crystallizes in the triclinic space group P1 and Z = 1 with cell parameters a = 12.4224(17)Å, b = 12.5588(18)Å, c = 12.9099(18)Å, a = 61.745(2)˚, b = 89.999(2)˚, g = 63.942(2)˚, V = 1537.8(4)Å3. Six DMSO molecules coordinate to a nickel(II) center to form a [Ni(DMSO)6]2+ cation. In the present crystal, the DMSO molecules are disordered, and two conformers of [Ni(DMSO)6]2+ were found to be superimposed. The NiO6S6 units in both conformers are approximated by an S6propeller-like structure; however, in conformer A, the Ni(DMSO)4 unit in the complex cation is approximated by an S4propeller-like structure, and tetragonal elongation is observed along the pseudo-S4 axis; while in conformer B, the whole structure is approximated as an S6-propeller-like structure, and a trigonal compression is observed along the pseudo-S6 axis. (Received January 23, 2013; Accepted February 20, 2013; Published on web April 10, 2013) It is important to study how the coordination geometry is distorted around a central metal ion in the coordination compounds, because the slight distortion influences the sign of the zero-field splitting, which will determine the magnetic behavior.1 Previously, a crystal structure of hexakis-DMSO cobalt(II) complex [Co(DMSO)6](BPh4)2 (DMSO = dimethylsulfoxide) was determined.2 The CoO6S6 unit in the complex cation was approximated as an S6 point group; however, the coordination geometry—the CoO6 unit—was best described as having a pseudo-C2v symmetry with elongation along an O–Co–O axis. In the present study, we prepared a nickel(II) derivative with the aim of revealing its structural features. The nickel(II) derivative was prepared by refluxing a DMSO solution (5.0 ml) of nickel(II) nitrate hexahydrate (1.0 mmol, 0.29 g) for 10 min; after adding a DMSO solution (1.0 ml) of sodium tetraphenylborate (2.0 mmol, 0.68 g), the solution was refluxed for 1 h; then, upon cooling, green microcrystals were Fig. 1 Chemical structure of [Ni(DMSO)6](BPh4)2. † To whom correspondence should be addressed. E-mail: [email protected] precipitated. Single-crystals suitable for X-ray analysis were obtained by recrystallization of the microcrystals from DMSO. The crystal data are included in Table 1. The structure was solved by direct methods and expanded using Fourier Table 1 Crystal and experimental data Chemical formula: C60H76B2NiO6S6 Formula weight = 1165.90 T = 90 K Crystal system: triclinic Space group: P1 a = 12.4224(17)Å a = 61.745(2)˚ b = 12.5588(18)Å b = 89.999(2)˚ c = 12.9099(18)Å g = 63.942(2)˚ V = 1537.8(4)Å3 Z=1 Dx = 1.259 g/cm3 Radiation: Mo Ka (l = 0.71073 Å) m(Mo Ka) = 0.566 mm–1 F(0 0 0) = 618 Crystal size = 0.35 ¥ 0.35 ¥ 0.31 mm3 No. of reflections collected = 9586 No. of independent reflections = 6820 [R(int) = 0.0158] q range for data cosllection: 1.86 to 28.60˚ Data/Restraints/Parameters = 6820/0/448 Goodness-of-fit on F2 = 1.034 R indices [I > 2s(I)]: R1 = 0.0467, wR2 = 0.1279 R indices (all data): R1 = 0.0508, wR2 = 0.1315 (D/s)max = 0.001 (Dr)min = –0.319 eÅ–3 (Dr)max = 1.525 eÅ–3 Measurement: Bruker Smart APEX CCD diffractometer Program system: SHELXTL Structure determination: Direct methods (SHELXS-97) Refinement: full matrix least-squares (SHELXL-97) CCDC deposition number: 920602 18 Fig. 2 Molecular structure of [Ni(DMSO)6]2+ with atom labeling. Thermal ellipsoids are drawn at the 50% probability level, and hydrogen atoms are omitted for clarity. techniques. The non-hydrogen atoms were refined anisotropically, and hydrogen atoms were refined using the riding model. The final cycle of full-matrix least-squares refinement on F2 was allowed to satisfactory converge with R1 = 0.0467 [I > 2s(I)]. The crystal consists of complex cations, [Ni(DMSO)6]2+, and tetraphenylborate anions in a 1:2 molar ratio. Although the crystal structures of two complexes containing [Ni(DMSO)6]2+ have been reported ([Ni(DMSO)6]Br2·2DMSO and [Ni(DMSO)6] (NO3)2·2DMSO),3,4 the present tetraphenylborate derivative has not been reported. The chemical structure is shown in Fig. 1, and an ORTEP view for the complex cation is shown in Fig. 2. The complex cation is centrosymmetric; the six DMSO molecules in the complex cation are disordered, and two conformers of [Ni(DMSO)6]2+ are found to be superimposed in a 50:50 ratio. Hereafter, we call them conformer A and conformer B. In both conformers six DMSO molecules coordinate to the nickel(II) ion to form an octahedral geometry. If we focus on the NiO6S6 units in the complex cations, the structures are approximated to be S6-propeller-like for both conformers (Figs. 3A-1 and 3B), although the whole structures are different from each other. In conformer A, the orientations of the DMSO moieties are not very symmetrical along the pseudo-S6 axis; however, four of the DMSO moieties in the cation appear to be very symmetrical along the O–Ni–O axis (Fig. 3A-2), and the Ni(DMSO)4 unit in the complex cation is approximated as an S4-propeller-like structure along the pseudo-S4 O(3A)–Ni(1)–O(3A*) axis. When we look at the bond distances around the central nickel(II) ion in conformer A (Tables 2S and 3S), we find a tetragonal elongation along the pseudo-S4 axis. On the other hand, in conformer B the whole X-ray Structure Analysis Online 2013, VOL. 29 Fig. 3 Two types of [Ni(DMSO)6]2+ cations: conformer A along the unique pseudo-S6 axis (A-1) and along the unique pseudo-S4 axis (A-2) and conformer B along the unique pseudo-S6 axis (B). structure is really symmetrical along its pseudo-S6 axis (Fig. 3B), and is approximated as an S6-propeller-like structure. Moreover, judging from the bond angles around the nickel(II) ion (Table 2S) and the distances between the opposite faces of the NiO6 octahedron, typical trigonal compression is observed along the pseudo-S6 axis. In conclusion, the present [Ni(DMSO)6](BPh4)2 complex contains two conformers of [Ni(DMSO)6]2+ complex cations. The NiO6S6 units in both conformers are approximated as an S6-propeller-like structure; however, in conformer A, a Ni(DMSO)4 unit in the complex cation is approximated as an S4-propeller-like structure, and tetragonal elongation is observed along the pseudo-S4 axis, while in conformer B, the whole structure is approximated as an S6-propeller-like structure, and trigonal compression is observed along the pseudo-S6 axis. Supporting Information A CIF format file and Tables 2S and 3S. These materials are available free of charge on the Web at http://www.jsac.or.jp/ xraystruct/. References 1. R. Boba, Coord. Chem. Rev., 2004, 248, 757. 2. R. Sudo, D. Yoshioka, M. Mikuriya, and H. Sakiyama, X-ray Struct. Anal. Online, 2012, 28, 71. 3. D. Bobicz, O. Kristiansen, and I. Persson, J. Chem. Soc., Dalton Trans., 2002, 4201. 4. A. J. Blake, M. Felloni, P. Hubberstey, M. Schroder, and C. Wilson, Acta Crystallogr., Sect E, 2001, 57, m556.