metal-organic compounds

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1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN a = (11) Å b = (2) Å c = (3) Å = (2) V = (7) Å 3 Z =4 Mo K radiation = 0.72 mm 1 T = 293 (2) K mm (Benzoato-j 2 O,O 0 )(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-j 4 N,N 0,N 00,N 000 )nickel(ii) perchlorate benzoic acid solvate Guang-Chuan Ou,* Min Zhang, Xian-You Yuan and Yong-Qiang Dai Department of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou, Hunan , People s Republic of China Correspondence ouguangchuan@yahoo.com.cn Received 27 October 2008; accepted 16 November 2008 Key indicators: single-crystal X-ray study; T = 293 K; mean (C C) = Å; R factor = 0.042; wr factor = 0.126; data-to-parameter ratio = In the title compound, [Ni(C 7 H 5 O 2 )(C 16 H 36 N 4 )]ClO 4 C 7 H 6 O 2, the Ni atom displays a distorted octahedral coordination geometry with four N atoms of the ligand rac-5,5,7,12,12,14- hexamethyl-1,4,8,11-tetraazacyclotetradecane (L) in a folded configuration and two benzoate (bz) O atoms. The [Ni(rac- L)(bz)] + complex cation, perchlorate anion and benzoic acid molecules engage in hydrogen bonding, with NO distances between (3) and (3) Å and an OO distance of (3) Å. Related literature For related background, see: Tait & Busch (1976); Curtis (1965). For related structures, see: Ou et al. (2008); Basiuk et al. (2001); Jiang et al. (2005). Data collection Bruker SMART CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.725, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections Table 1 Hydrogen-bond geometry (Å, ) measured reflections 7304 independent reflections 5272 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.58 e Å 3 min = 0.42 e Å 3 D HA D H HA DA D HA N1 H1CO4 i (3) 171 N4 H4DO6 ii (3) 161 O3 H3BO1 iii (3) 174 N3 H3CO (3) 166 N2 H2CO6 ii (3) 160 Symmetry codes: (i) x þ 1; y þ 1 2 ; z þ 3 2 ; (ii) x þ 1; y; z; (iii) x þ 1; y 1 2 ; z þ 3 2. Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL. The authors thank the Key Subject Construction Project of Hunan Province (grant No ), the Scientific Research Project of the Hunan Provincial Finance Bureau and Education Department (grant No. 08C366), and the Foundation for University Key Teachers of the Education Department of Hunan Province for supporting this study. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2117). Experimental Crystal data [Ni(C 7 H 5 O 2 )(C 16 H 36 N 4 )]ClO 4 - C 7 H 6 O 2 M r = Monoclinic, P2 1 =c References Basiuk, E. V., Basiuk, V. A., Hernández-Ortega, S., Martínez-García, M. & Saniger-Blesa, J.-M. (2001). Acta Cryst. C57, Bruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (2003). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Curtis, N. F. (1965). J. Chem. Soc. A, pp Jiang, L., Feng, X. L. & Lu, T. B. (2005). Cryst. Growth Des.. 5, Ou, G.-C., Zhang, M. & Yuan, X.-Y. (2008a). Acta Cryst. E64, m1010. Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, Tait, A. M. & Busch, D. H. (1976). Inorg. Synth. 18, 4 7. m1588 Ou et al. doi: /s

2 supporting information [doi: /s ] (Benzoato-κ 2 O,O )(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ 4 N,N,N,N )nickel(ii) perchlorate benzoic acid solvate Guang-Chuan Ou, Min Zhang, Xian-You Yuan and Yong-Qiang Dai S1. Comment It is important to control the geometries of ML 2+ [M = Ni(II), Co(II), Cu(II)] with cis- or trans-conformation, since they form different structures and show different properties (Tait & Busch, 1976; Curtis, 1965). Continuing our research (Ou et al., 2008), we have synthesized the title compound, (I), which is presented in this paper. The asymmetric unit of the title compouind, (I), contains one [Ni(rac-L)(bz)] + cation, one [ClO 4 ] - anion and one benzoic acid molecule (Fig. 1). The six-coordinated Ni 2+ of the complex [Ni(rac-L)(bz)] + cation displays a distorted octahedral geometry by coordination with four nitrogen atoms of the macrocyclic ligand L in a folded configuration, and two carboxylate oxygen atoms of benzoic acid in cis-position. The Ni N distances range between (2) to (2) Å, and are slightly shorter than the Ni O distance (2.116 (2) and (2) Å). The neighbouring cations, anions and benzoic acid are connected to each other through intermolecular hydrogen bond of the types N H O and O H O (Table 1, Fig. 2). The crystal structures of a few compound closely related to (I) have been reported (Ou et al., 2008a,b; Basiuk et al. 2001; Jiang et al., 2005). S2. Experimental Benzoic acid (0.36 g, 3 mmol) and NaOH (0.08 g, 2 mmol) were dissolved in 15 ml of water. To this solution was added [Ni(rac-L)](ClO 4 ) 2 (0.54 g, 1 mmol) dissolved in 2 ml of CH 3 CN. The solution was left to stand at room temperature and blue crystals formed after several weeks. S3. Refinement H atoms bound to C, O and N atoms were positioned geometrically and refined using the riding model, and with C H = 0.93, 0.96, 0.97 and 0.98 Å, for aryl, methyl, methylene and methine H-atoms, O H = 0.82 Å and N H = 0.91 Å, and with U iso (H) set to 1.5U eq (methyl C) and 1.2U eq (the rest of the parent atoms). sup-1

3 Figure 1 The molecular structure of (I), showing displacement ellipsoids at the 30% probability level; H-atoms have been excluded for clarity. Figure 2 A view of the packing of the title compound along a axis. sup-2

4 (Benzoato-κ 2 O,O )(5,5,7,12,12,14-hexamethyl-1,4,8,11- tetraazacyclotetradecane- κ 4 N,N,N,N )nickel(ii) perchlorate benzoic acid solvate Crystal data [Ni(C 7 H 5 O 2 )(C 16 H 36 N 4 )]ClO 4 C 7 H 6 O 2 M r = Monoclinic, P2 1 /c a = (11) Å b = (2) Å c = (3) Å β = (2) V = (7) Å 3 Z = 4 Data collection Bruker SMART CCD area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.725, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 404 parameters 0 restraints Primary atom site location: structure-invariant direct methods F(000) = 1456 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 7647 reflections θ = µ = 0.72 mm 1 T = 293 K Prism, light-blue mm measured reflections 7304 independent reflections 5272 reflections with I > 2σ(I) R int = θ max = 27.1, θ min = 1.5 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0643P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.58 e Å 3 Δρ min = 0.42 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. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Ni (4) (17) (14) (11) Cl (7) (4) (3) (16) N (2) (11) (9) (5) H3C * sup-3

5 N (2) (12) (9) (5) H1C * O (2) (10) (8) (4) O (2) (10) (8) (4) N (2) (12) (10) (5) H4D * O (3) (13) (12) (6) O (3) (12) (10) (6) N (2) (12) (10) (5) H2C * O (3) (15) (11) (6) C (3) (15) (12) (6) C (3) (14) (12) (6) C (3) (14) (12) (6) H9A * H9B * C (3) (14) (11) (6) C (3) (14) (11) (5) O (4) (15) (11) (8) C (3) (17) (12) (7) H7A * H7B * H7C * C (3) (15) (12) (6) H3A * C (3) (15) (12) (6) H5A * H5B * C (4) (16) (14) (7) H * C (3) (16) (13) (7) H15A * H15B * H15C * C (3) (15) (12) (6) H10A * H10B * C (3) (16) (13) (6) H1A * H1B * C (3) (16) (12) (6) H2A * H2B * C (3) (15) (12) (6) H13A * H13B * C (4) (16) (13) (7) H8A * sup-4

6 H8B * H8C * C (3) (16) (12) (6) H * C (4) (16) (14) (7) H4A * H4B * H4C * C (3) (16) (13) (7) H16A * H16B * H16C * C (3) (14) (12) (6) H * C (4) (16) (15) (8) H12A * H12B * H12C * C (3) (18) (13) (7) H * C (4) (19) (15) (8) H * C (4) (19) (15) (8) H * O (3) (10) (9) (5) H3B * O (3) (12) (10) (7) C (3) (15) (13) (6) H * C (3) (16) (14) (7) H * C (3) (16) (13) (6) C (3) (15) (12) (6) C (3) (16) (13) (7) H * C (4) (18) (13) (7) H * C (4) (17) (14) (7) H * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Ni (19) (18) (16) (13) (12) (13) Cl (4) (4) (3) (3) (3) (3) N (11) (12) (10) (9) (8) (9) N (12) (12) (10) (9) (9) (9) O (10) (10) (8) (8) (7) (7) sup-5

7 O (11) (10) (9) (8) (8) (8) N (12) (12) (10) (9) (9) (9) O (14) (15) (16) (11) (12) (12) O (14) (13) (11) (11) (10) (10) N (12) (12) (11) (9) (9) (9) O (14) (17) (14) (12) (11) (12) C (15) (15) (12) (11) (11) (11) C (15) (14) (12) (11) (11) (11) C (16) (14) (12) (12) (11) (10) C (14) (14) (12) (11) (10) (10) C (14) (14) (11) (11) (10) (10) O (2) (17) (12) (16) (14) (12) C (17) (17) (13) (13) (12) (12) C (16) (14) (14) (12) (12) (11) C (16) (14) (13) (12) (11) (11) C (19) (17) (15) (14) (14) (13) C (18) (16) (13) (13) (12) (12) C (15) (15) (13) (11) (11) (11) C (14) (17) (13) (12) (11) (12) C (15) (16) (13) (12) (11) (12) C (16) (15) (13) (12) (11) (11) C (18) (16) (14) (13) (12) (12) C (17) (16) (13) (13) (12) (12) C (18) (17) (17) (13) (14) (14) C (18) (17) (14) (14) (12) (12) C (16) (14) (13) (11) (11) (11) C (2) (16) (16) (15) (16) (13) C (17) (2) (14) (14) (12) (13) C (2) (19) (19) (15) (16) (15) C (18) (2) (17) (16) (14) (15) O (14) (11) (10) (10) (9) (8) O (2) (13) (11) (12) (12) (9) C (16) (15) (14) (12) (12) (12) C (17) (15) (17) (12) (13) (13) C (17) (16) (14) (13) (12) (12) C (16) (15) (13) (11) (11) (11) C (18) (16) (14) (13) (12) (12) C (19) (18) (13) (14) (12) (13) C (18) (19) (15) (14) (13) (13) Geometric parameters (Å, º) Ni1 N (2) C15 H15C Ni1 N (2) C10 H10A Ni1 O (2) C10 H10B Ni1 N (2) C1 C (4) Ni1 N (2) C1 H1A Ni1 O (2) C1 H1B sup-6

8 Cl1 O (2) C2 H2A Cl1 O (2) C2 H2B Cl1 O (2) C13 C (4) Cl1 O (2) C13 H13A N3 C (3) C13 H13B N3 C (3) C8 H8A N3 H3C C8 H8B N1 C (3) C8 H8C N1 C (3) C19 C (4) N1 H1C C19 H O1 C (3) C4 H4A O2 C (3) C4 H4B N4 C (3) C4 H4C N4 C (3) C16 H16A N4 H4D C16 H16B N2 C (3) C16 H16C N2 C (3) C11 C (4) N2 H2C C11 H C6 C (4) C12 H12A C6 C (4) C12 H12B C6 C (3) C12 H12C C14 C (4) C20 C (5) C14 C (4) C20 H C14 C (4) C22 C (5) C9 C (4) C22 H C9 H9A C21 H C9 H9B O3 C (3) C18 C (4) O3 H3B C18 C (4) O4 C (3) C18 C (4) C30 C (4) C7 H7A C30 C (4) C7 H7B C30 H C7 H7C C29 C (4) C3 C (4) C29 H C3 C (4) C24 C (4) C3 H3A C25 C (4) C5 H5A C26 C (4) C5 H5B C26 H C23 C (4) C27 C (4) C23 H C27 H C15 H15A C28 H C15 H15B N2 Ni1 N (8) C14 C15 H15B N2 Ni1 O (8) H15A C15 H15B N4 Ni1 O (8) C14 C15 H15C N2 Ni1 N (8) H15A C15 H15C N4 Ni1 N (8) H15B C15 H15C sup-7

9 O2 Ni1 N (8) N4 C10 C (2) N2 Ni1 N (8) N4 C10 H10A N4 Ni1 N (8) C9 C10 H10A O2 Ni1 N (8) N4 C10 H10B N1 Ni1 N (8) C9 C10 H10B N2 Ni1 O (8) H10A C10 H10B N4 Ni1 O (8) N1 C1 C (2) O2 Ni1 O (7) N1 C1 H1A N1 Ni1 O (7) C2 C1 H1A N3 Ni1 O (7) N1 C1 H1B O7 Cl1 O (14) C2 C1 H1B O7 Cl1 O (18) H1A C1 H1B O5 Cl1 O (15) N2 C2 C (2) O7 Cl1 O (18) N2 C2 H2A O5 Cl1 O (14) C1 C2 H2A O8 Cl1 O (14) N2 C2 H2B C9 N3 C (19) C1 C2 H2B C9 N3 Ni (14) H2A C2 H2B C6 N3 Ni (15) C11 C13 C (2) C9 N3 H3C C11 C13 H13A C6 N3 H3C C14 C13 H13A Ni1 N3 H3C C11 C13 H13B C1 N1 C (2) C14 C13 H13B C1 N1 Ni (15) H13A C13 H13B C14 N1 Ni (15) C6 C8 H8A C1 N1 H1C C6 C8 H8B C14 N1 H1C H8A C8 H8B Ni1 N1 H1C C6 C8 H8C C17 O1 Ni (15) H8A C8 H8C C17 O2 Ni (16) H8B C8 H8C C11 N4 C (2) C20 C19 C (3) C11 N4 Ni (15) C20 C19 H C10 N4 Ni (15) C18 C19 H C11 N4 H4D C3 C4 H4A C10 N4 H4D C3 C4 H4B Ni1 N4 H4D H4A C4 H4B C2 N2 C (2) C3 C4 H4C C2 N2 Ni (15) H4A C4 H4C C3 N2 Ni (16) H4B C4 H4C C2 N2 H2C C14 C16 H16A C3 N2 H2C C14 C16 H16B Ni1 N2 H2C H16A C16 H16B N3 C6 C (2) C14 C16 H16C N3 C6 C (2) H16A C16 H16C C8 C6 C (2) H16B C16 H16C N3 C6 C (2) N4 C11 C (2) C8 C6 C (2) N4 C11 C (2) C5 C6 C (2) C12 C11 C (2) sup-8

10 N1 C14 C (2) N4 C11 H N1 C14 C (2) C12 C11 H C13 C14 C (2) C13 C11 H N1 C14 C (2) C11 C12 H12A C13 C14 C (2) C11 C12 H12B C15 C14 C (2) H12A C12 H12B N3 C9 C (2) C11 C12 H12C N3 C9 H9A H12A C12 H12C C10 C9 H9A H12B C12 H12C N3 C9 H9B C21 C20 C (3) C10 C9 H9B C21 C20 H H9A C9 H9B C19 C20 H C19 C18 C (3) C21 C22 C (3) C19 C18 C (2) C21 C22 H C23 C18 C (2) C23 C22 H O2 C17 O (2) C22 C21 C (3) O2 C17 C (2) C22 C21 H O1 C17 C (2) C20 C21 H C6 C7 H7A C24 O3 H3B C6 C7 H7B C25 C30 C (3) H7A C7 H7B C25 C30 H C6 C7 H7C C29 C30 H H7A C7 H7C C28 C29 C (3) H7B C7 H7C C28 C29 H N2 C3 C (2) C30 C29 H N2 C3 C (2) O4 C24 O (2) C5 C3 C (2) O4 C24 C (2) N2 C3 H3A O3 C24 C (2) C5 C3 H3A C26 C25 C (2) C4 C3 H3A C26 C25 C (2) C3 C5 C (2) C30 C25 C (2) C3 C5 H5A C25 C26 C (3) C6 C5 H5A C25 C26 H C3 C5 H5B C27 C26 H C6 C5 H5B C28 C27 C (3) H5A C5 H5B C28 C27 H C18 C23 C (3) C26 C27 H C18 C23 H C29 C28 C (3) C22 C23 H C29 C28 H C14 C15 H15A C27 C28 H N2 Ni1 N3 C (16) Ni1 N1 C14 C (2) N4 Ni1 N3 C (16) C1 N1 C14 C (3) O2 Ni1 N3 C (16) Ni1 N1 C14 C (17) N1 Ni1 N3 C (8) C6 N3 C9 C (2) O1 Ni1 N3 C (15) Ni1 N3 C9 C (2) N2 Ni1 N3 C (19) Ni1 O2 C17 O1 4.4 (2) N4 Ni1 N3 C (19) Ni1 O2 C17 C (19) sup-9

11 O2 Ni1 N3 C (18) Ni1 O1 C17 O2 4.2 (2) N1 Ni1 N3 C (8) Ni1 O1 C17 C (2) O1 Ni1 N3 C (19) C19 C18 C17 O (4) N2 Ni1 N1 C (16) C23 C18 C17 O (3) N4 Ni1 N1 C (16) C19 C18 C17 O (2) O2 Ni1 N1 C (16) C23 C18 C17 O (4) N3 Ni1 N1 C (8) C2 N2 C3 C (2) O1 Ni1 N1 C (16) Ni1 N2 C3 C (3) N2 Ni1 N1 C (19) C2 N2 C3 C (3) N4 Ni1 N1 C (19) Ni1 N2 C3 C (17) O2 Ni1 N1 C (19) N2 C3 C5 C (3) N3 Ni1 N1 C (8) C4 C3 C5 C (2) O1 Ni1 N1 C (18) N3 C6 C5 C (3) N2 Ni1 O1 C (13) C8 C6 C5 C (3) N4 Ni1 O1 C (3) C7 C6 C5 C (2) O2 Ni1 O1 C (13) C19 C18 C23 C (4) N1 Ni1 O1 C (14) C17 C18 C23 C (3) N3 Ni1 O1 C (14) C11 N4 C10 C (2) N2 Ni1 O2 C (3) Ni1 N4 C10 C (2) N4 Ni1 O2 C (14) N3 C9 C10 N (3) N1 Ni1 O2 C (15) C14 N1 C1 C (2) N3 Ni1 O2 C (14) Ni1 N1 C1 C (2) O1 Ni1 O2 C (13) C3 N2 C2 C (2) N2 Ni1 N4 C (18) Ni1 N2 C2 C (2) O2 Ni1 N4 C (18) N1 C1 C2 N (3) N1 Ni1 N4 C (18) N1 C14 C13 C (3) N3 Ni1 N4 C (18) C15 C14 C13 C (3) O1 Ni1 N4 C (3) C16 C14 C13 C (2) N2 Ni1 N4 C (16) C23 C18 C19 C (4) O2 Ni1 N4 C (16) C17 C18 C19 C (2) N1 Ni1 N4 C (16) C10 N4 C11 C (3) N3 Ni1 N4 C (16) Ni1 N4 C11 C (2) O1 Ni1 N4 C (3) C10 N4 C11 C (2) N4 Ni1 N2 C (16) Ni1 N4 C11 C (2) O2 Ni1 N2 C (3) C14 C13 C11 N (3) N1 Ni1 N2 C (16) C14 C13 C11 C (2) N3 Ni1 N2 C (16) C18 C19 C20 C (4) O1 Ni1 N2 C (16) C18 C23 C22 C (5) N4 Ni1 N2 C (17) C23 C22 C21 C (5) O2 Ni1 N2 C (3) C19 C20 C21 C (5) N1 Ni1 N2 C (18) C25 C30 C29 C (4) N3 Ni1 N2 C (18) C29 C30 C25 C (4) O1 Ni1 N2 C (18) C29 C30 C25 C (3) C9 N3 C6 C (2) O4 C24 C25 C (5) Ni1 N3 C6 C (2) O3 C24 C25 C (3) C9 N3 C6 C (3) O4 C24 C25 C (3) Ni1 N3 C6 C (3) O3 C24 C25 C (4) C9 N3 C6 C (3) C30 C25 C26 C (4) sup-10

12 Ni1 N3 C6 C (17) C24 C25 C26 C (3) C1 N1 C14 C (3) C25 C26 C27 C (5) Ni1 N1 C14 C (3) C30 C29 C28 C (5) C1 N1 C14 C (2) C26 C27 C28 C (5) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A N1 H1C O4 i (3) 171 N4 H4D O6 ii (3) 161 O3 H3B O1 iii (3) 174 N3 H3C O (3) 166 N2 H2C O6 ii (3) 160 Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y, z; (iii) x+1, y 1/2, z+3/2. sup-11