metal-organic compounds

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1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Dichlorido(4,4 0 -di-tert-butyl-2,2 0 -bipyridine-j 2 N,N 0 )palladium(ii) dimethyl sulfoxide monosolvate monohydrate Ricardo A. Gutiérrez-Márquez, Carmela Crisóstomo- Lucas, Reyna Reyes-Martínez,* Simón Hernández-Ortega and David Morales-Morales Instituto de Química, Universidad Nacional Autónoma de México, Circuito exterior, Ciudad Universitaria, México, DF, 04510, Mexico Correspondence rrm@uaem.mx Received 13 April 2014; accepted 26 April 2014 Key indicators: single-crystal X-ray study; T = 298 K; mean (C C) = Å; disorder in solvent or counterion; R factor = 0.028; wr factor = 0.076; data-toparameter ratio = Experimental Crystal data [PdCl 2 (C 18 H 24 N 2 )]C 2 H 6 OSH 2 O M r = Monoclinic, P2 1 =c a = (3) Å b = (8) Å c = (7) Å = (1) V = (17) Å 3 Z =4 Mo K radiation = 1.10 mm 1 T = 298 K mm The title compound, [PdCl 2 (C 18 H 24 N 2 )](CH 3 ) 2 SOH 2 O, the Pd II ion is in a distorted square-planar geometry. The Pd N bond distances are (2) and (2) Å, the Pd Cl bond distances are (7) and (7) Å, and the ligand bite angle is (9). The dimethyl sulfoxide and water molecules form linear chains along [100] by O HO and O HS hydrogen bonds, generating eight- and 12-membered rings. C HCl interactions link the chains, forming a threedimensional arrangement. In addition, the 4,4-di-tert-butyl- 2,2 0 -bipyridine ligand exhibits stacking interactions [centroid centroid distances = (15) and (15) Å]. The DMSO solvent is disordered and was refined with an occupancy ratio of (3):0.134 (3). Related literature For compounds with N N ligands, see: Corona-Rodríguez et al. (2007); Basauri-Molina et al. (2010). For the crystal structure of non-solvated compound, see: Qin et al. (2002); MacLean et al. (2002). For metallomacrocycles, see: Qin et al. (2002); Tzeng et al. (2001). For similar compounds and their crystal structures, see: Jones et al. (2007). Data collection Bruker APEXII CCD area-detector diffractometer Absorption correction: analytical (SADABS; Sheldrick, 2008) T min = 0.780, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 302 parameters 118 restraints Table 1 Hydrogen-bond geometry (Å, ) measured reflections 4343 independent reflections 3766 reflections with I > 2(I) R int = H atoms treated by a mixture of independent and constrained refinement max = 0.39 e Å 3 min = 0.55 e Å 3 D HA D H HA DA D HA O2 H2AO1 i 0.87 (1) 2.11 (2) (7) 165 (7) O2 H2AS1A i 0.87 (1) 2.71 (2) (14) 167 (7) O2 H2AO1A i 0.87 (1) 1.68 (4) 2.51 (3) 157 (8) O2 H2BO1 ii 0.87 (1) 2.20 (2) (9) 171 (7) O2 H2BS1A ii 0.87 (1) 1.84 (4) (12) 146 (7) O2 H2BO1A ii 0.87 (1) 2.30 (4) 3.17 (4) 173 (7) C14 H14BCl2 iii (1) 163 Symmetry codes: (i) x þ 1; y þ 1; z þ 1; (ii) x; y þ 1; z; (iii) x þ 1; y 1 2 ; z þ 3 2. Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009). m200 Gutiérrez-Márquez et al. doi: /s

2 metal-organic compounds Financial support of this research by CONACyT (grant CB ) and PAPIIT (grants IN and IN ) is gratefully acknowledged. Supporting information for this paper is available from the IUCr electronic archives (Reference: PJ2010). References Basauri-Molina, M., Hernández-Ortega, S., Toscano, R. A., Valdés-Martínez, J. & Morales-Morales, D. (2010). Inorg. Chim. Acta, 363, Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Bruker (2012). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Corona-Rodríguez, M., Hernández-Ortega, S., Valdés-Martínez, J. & Morales- Morales, D. (2007). Supramol. Chem. 19, Farrugia, L. J. (2012). J. Appl. Cryst. 45, Jones, P. G., Fernández-Rodríguez, M. J. & Martínez-Martínez, A. J. (2007). Acta Cryst. E63, m2758. MacLean, E. J., Robinson, R. I., Teat, S. J., Wilson, C. & Woodward, S. (2002). J. Chem. Soc. Dalton Trans. pp Qin, Z., Jennings, M. C. & Puddephatt, R. J. (2002). Inorg. Chem. 41, Sheldrick, G. M. (2008). Acta Cryst. A64, Spek, A. L. (2009). Acta Cryst. D65, Tzeng, B., Chan, S., Chan, M. C. W., Che, C., Cheung, K. & Peng, S. (2001). Inorg. Chem. 40, Gutiérrez-Márquez et al. [PdCl 2 (C 18 H 24 N 2 )]C 2 H 6 OSH 2 O m201

3 supporting information [doi: /s ] Dichlorido(4,4 -di-tert-butyl-2,2 -bipyridine-κ 2 N,N )palladium(ii) dimethyl sulfoxide monosolvate monohydrate Ricardo A. Gutiérrez-Márquez, Carmela Crisóstomo-Lucas, Reyna Reyes-Martínez, Simón Hernández-Ortega and David Morales-Morales S1. Introduction The N N chelate ligands have been studied with a variety of transition metals as building blocks in supramolecular chemistry. 2,2 -Bipyridine and its derivatives have been employed as auxiliary ligands in transition metal complexes usually serving as blocking ligands. Thus, given our continuous interest in the synthesis of metal complexes with potential catalytic activities in cross coupling reactions and the use of N N quelate ligands (Corona-Rodríguez et al., 2007; Basauri-Molina et al., 2010), we report here the crystal structure of the compound [PdCl 2 ( t Bubpy)] (CH 3 ) 2 SO) H 2 O ( t Bubpy = 4,4 -di-tert-butyl-2,2 -bipyridine) as a solvated compound. The crystal structure of the non-solvated complex has been reported previously (Qin et al., 2002; MacLean et al., 2002), and this compound has served as precursor in the formation of metallomacrocycles (Qin et al., 2002; Tzeng et al., 2001) and due to its structure may present π interactions like π-π stacking and C H π interactions. S2. Experimental S2.1. Synthesis and crystallization To a solution of [Pd(MeCN) 2 Cl 2 ] (0.13 g, mmol) in ethanol (10 ml), 4,4 -di-tert-butyl-2,2 -bipyridine (0.1 g, mmol) was added under stirring. The resulting orange solution was allowed to react for 4 h under stirring at room temperature. After this time the solution was filtered and the solvent taken off under vacuum to produce a yellow solid. Crystals suitable for X-ray diffraction experiments were obtained from dimethylsulfoxide as solvent at room temperature. 1 H-NMR (300 MHz, DMSO D 6 ): d 1.42 (s, 18H, t Bu), 7.82 (d, 2H, CH), 8.60 (s, 2H, CH), 9.02 (d, 2H, CH). 13 C-NMR (75.6 MHz, DMSO-D 6 ): d 30.3 (s, CH 3 ), 39.9 (s, C(CH 3 ) 3 ), (s, CH), (s, CH), (s, CH), (s, C), (s, C). S2.2. Refinement Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were included in calculated positions (C H = 0.93 Å for aromatic H, C H = 0.96 Å for methyl H), and refined using a riding model with U iso (H) = 1.2Ueq of the carrier atom. H atoms on O were located on the Fourier map and refined isotropically. The DMSO solvent is disordered and was refined in two major positions using a free variable of Site Occupational Factor (SOF), the ratio of disordered atoms was 87/13 of SOF. In the refinement six reflections, (0 0 1), (0 5 1), (1 2 2), (1 2 0), (-1 2 4) and (-2 0 2), were considered as disagreeable and were omitted. sup-1

4 S3. Results and discussion The title compound is formed by a molecule of the complex [PdCl 2 ( t Bubpy)], one molecule of dimethylsulfoxide (disordered) and one molecule of water, the structure is presented in Figure 1. The coordination around the Pd(II) ion adopts a distorted square planar geometry, surrounded by two chloride atoms and one 4,4 -di-tert-butyl-2,2 -bipyridine ligand coordinated in a chelate fashion with a bite angle of (8). The Pd Cl bond distances are (9) and (9) Å which are similar to those found in the non-solvated structure (Qin et al., 2002; MacLean et al., 2002). The Pd N bond distances are (2) and (2) Å which are close in value to those found for the compound [PdCl 2 ( t Bubpy)] and slightly smaller than those observed in the diiodo complex [PdI 2 ( t Bubpy)] (2.047 (4), (4) Å) (Jones et al., 2007). Both the dimethylsulfoxide and water molecules interact via hydrogen bonds (O H O, C H O) forming 8- and 12- member rings that generate a linear chain in the [100] direction (Table 1). The 4,4 -di-tert-butyl-2,2 -bipyridine ligand presents π-π stacking interactions which extend along the a axis [100] generated by the symmetry operations 1-x, 1-y, 1-z and -x, 1-y, 1-z. The two centroid-centroid distances between the ligand rings are (15) and (15) Å respectively. The crystal arrangement is complemented by C H Cl interactions which link the linear arrangement of π- π stacking in layers parallel to (100). Figure 1 The asymmetric unit of the title compound. All non-hydrogen atoms are shown as ellipsoids with probability level of 50%. sup-2

5 Figure 2 Packing of the molecular entities in the structure of the title compound. Hydrogen bonds interaction as shown by dashed lines. Dichlorido(4,4 -di-tert-butyl-2,2 -bipyridine-κ 2 N,N )palladium(ii) dimethyl sulfoxide monosolvate monohydrate Crystal data [PdCl 2 (C 18 H 24 N 2 )] C 2 H 6 OS H 2 O M r = Monoclinic, P2 1 /c a = (3) Å b = (8) Å c = (7) Å β = (1) V = (17) Å 3 Z = 4 Data collection Bruker APEXII CCD area-detector diffractometer Detector resolution: 0.83 pixels mm -1 ω scans Absorption correction: analytical (SADABS; Sheldrick, 2008) T min = 0.780, T max = measured reflections F(000) = 1112 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 9545 reflections θ = µ = 1.10 mm 1 T = 298 K Prism, yellow mm 4343 independent reflections 3766 reflections with I > 2σ(I) R int = θ max = 25.3, θ min = 2.1 h = 9 8 k = l = sup-3

6 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 302 parameters 118 restraints Hydrogen site location: mixed H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.042P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.39 e Å 3 Δρ min = 0.55 e Å 3 Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Occ. (<1) Pd (3) (2) (2) (9) Cl (11) (4) (5) (2) Cl (12) (4) (5) (2) N (3) (10) (12) (5) C (3) (12) (14) (5) C (3) (13) (15) (6) H * C (3) (14) (15) (6) C (4) (14) (16) (6) H * C (4) (14) (15) (6) H * N (3) (10) (12) (5) C (3) (12) (14) (5) C (3) (13) (15) (6) H * C (3) (13) (15) (6) C (4) (14) (15) (6) H * C (3) (13) (15) (6) H * C (4) (14) (17) (6) C (5) (17) (2) (9) H14A * H14B * H14C * C (4) (18) (2) (9) H15A * H15B * H15C * sup-4

7 C (5) (15) (2) (9) H16A * H16B * H16C * C (4) (14) (17) (7) C (5) (19) (2) (11) H18A * H18B * H18C * C (6) (2) (2) (12) H19A * H19B * H19C * C (5) (16) (2) (10) H20A * H20B * H20C * S (19) (6) (7) (4) (3) O (7) (3) (4) (14) (3) C (7) (3) (4) (19) (3) H21A * (3) H21B * (3) H21C * (3) C (10) (3) (4) (2) (3) H22A * (3) H22B * (3) H22C * (3) S1A (17) (7) (7) (3) (3) O1A (4) (17) (2) (5) (3) C21A (2) (19) (2) (5) (3) H21D * (3) H21E * (3) H21F * (3) C22A (5) (9) (3) (6) (3) H22D * (3) H22E * (3) H22F * (3) O (8) (3) (3) (16) H2A (6) (4) (4) 0.187* H2B (10) (4) (18) 0.187* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Pd (14) (12) (13) (8) (9) (7) Cl (5) (4) (5) (3) (4) (3) Cl (6) (4) (5) (4) (4) (3) N (11) (11) (11) (9) (9) (9) sup-5

8 C (12) (13) (12) (10) (10) (10) C (14) (13) (14) (11) (12) (11) C (14) (14) (14) (11) (11) (12) C (15) (16) (13) (12) (12) (12) C (16) (15) (13) (12) (12) (11) N (11) (11) (11) (9) (9) (9) C (13) (13) (12) (10) (10) (10) C (15) (13) (14) (11) (12) (11) C (14) (15) (13) (11) (11) (11) C (15) (16) (13) (12) (12) (12) C (15) (14) (14) (11) (12) (11) C (15) (16) (16) (13) (13) (13) C (2) (2) (2) (17) (18) (17) C (19) (2) (2) (17) (17) (18) C (2) (17) (2) (16) (18) (16) C (17) (16) (15) (13) (13) (13) C (2) (2) (3) (18) (2) (2) C (3) (3) (2) (2) (2) (2) C (3) (18) (2) (17) (2) (16) S (10) (9) (6) (6) (6) (5) O (4) (2) (4) (2) (3) (3) C (4) (6) (3) (3) (3) (4) C (5) (4) (4) (4) (4) (3) S1A (5) (6) (5) (5) (5) (5) O1A (10) (9) (10) (10) (9) (8) C21A (6) (11) (10) (8) (9) (11) C22A (11) (7) (12) (9) (11) (9) O (5) (4) (3) (4) (3) (3) Geometric parameters (Å, º) Pd1 N (2) C16 H16B Pd1 N (2) C16 H16C Pd1 Cl (7) C17 C (4) Pd1 Cl (7) C17 C (4) N1 C (3) C17 C (4) N1 C (3) C18 H18A C2 C (3) C18 H18B C2 C (3) C18 H18C C3 C (3) C19 H19A C3 H C19 H19B C4 C (4) C19 H19C C4 C (4) C20 H20A C5 C (4) C20 H20B C5 H C20 H20C C6 H S1 O (5) N7 C (3) S1 C (5) N7 C (3) S1 C (5) sup-6

9 C8 C (3) C21 H21A C9 C (3) C21 H21B C9 H C21 H21C C10 C (4) C22 H22A C10 C (4) C22 H22B C11 C (4) C22 H22C C11 H S1A O1A (12) C12 H S1A C22A (9) C13 C (4) S1A C21A (9) C13 C (4) C21A H21D C13 C (4) C21A H21E C14 H14A C21A H21F C14 H14B C22A H22D C14 H14C C22A H22E C15 H15A C22A H22F C15 H15B O2 H2A (10) C15 H15C O2 H2B (10) C16 H16A N1 Pd1 N (9) C13 C16 H16B N1 Pd1 Cl (6) H16A C16 H16B N7 Pd1 Cl (6) C13 C16 H16C N1 Pd1 Cl (6) H16A C16 H16C N7 Pd1 Cl (6) H16B C16 H16C Cl2 Pd1 Cl (3) C18 C17 C (3) C6 N1 C (2) C18 C17 C (2) C6 N1 Pd (17) C19 C17 C (2) C2 N1 Pd (16) C18 C17 C (3) N1 C2 C (2) C19 C17 C (3) N1 C2 C (2) C10 C17 C (2) C3 C2 C (2) C17 C18 H18A C2 C3 C (2) C17 C18 H18B C2 C3 H H18A C18 H18B C4 C3 H C17 C18 H18C C5 C4 C (2) H18A C18 H18C C5 C4 C (2) H18B C18 H18C C3 C4 C (2) C17 C19 H19A C6 C5 C (2) C17 C19 H19B C6 C5 H H19A C19 H19B C4 C5 H C17 C19 H19C N1 C6 C (2) H19A C19 H19C N1 C6 H H19B C19 H19C C5 C6 H C17 C20 H20A C12 N7 C (2) C17 C20 H20B C12 N7 Pd (17) H20A C20 H20B C8 N7 Pd (16) C17 C20 H20C N7 C8 C (2) H20A C20 H20C N7 C8 C (2) H20B C20 H20C sup-7

10 C9 C8 C (2) O1 S1 C (3) C8 C9 C (2) O1 S1 C (3) C8 C9 H C21 S1 C (3) C10 C9 H S1 C21 H21A C11 C10 C (2) S1 C21 H21B C11 C10 C (2) H21A C21 H21B C9 C10 C (2) S1 C21 H21C C12 C11 C (2) H21A C21 H21C C12 C11 H H21B C21 H21C C10 C11 H S1 C22 H22A N7 C12 C (2) S1 C22 H22B N7 C12 H H22A C22 H22B C11 C12 H S1 C22 H22C C15 C13 C (2) H22A C22 H22C C15 C13 C (3) H22B C22 H22C C4 C13 C (2) O1A S1A C22A (8) C15 C13 C (3) O1A S1A C21A (8) C4 C13 C (2) C22A S1A C21A 96.0 (7) C16 C13 C (3) S1A C21A H21D C13 C14 H14A S1A C21A H21E C13 C14 H14B H21D C21A H21E H14A C14 H14B S1A C21A H21F C13 C14 H14C H21D C21A H21F H14A C14 H14C H21E C21A H21F H14B C14 H14C S1A C22A H22D C13 C15 H15A S1A C22A H22E C13 C15 H15B H22D C22A H22E H15A C15 H15B S1A C22A H22F C13 C15 H15C H22D C22A H22F H15A C15 H15C H22E C22A H22F H15B C15 H15C H2A O2 H2B 88 (6) C13 C16 H16A Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O2 H2A O1 i 0.87 (1) 2.11 (2) (7) 165 (7) O2 H2A S1A i 0.87 (1) 2.71 (2) (14) 167 (7) O2 H2A O1A i 0.87 (1) 1.68 (4) 2.51 (3) 157 (8) O2 H2B O1 ii 0.87 (1) 2.20 (2) (9) 171 (7) O2 H2B S1A ii 0.87 (1) 1.84 (4) (12) 146 (7) O2 H2B O1A ii 0.87 (1) 2.30 (4) 3.17 (4) 173 (7) C14 H14B Cl2 iii (1) 163 Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z; (iii) x+1, y 1/2, z+3/2. sup-8