The asymmetric unit of the title compound, [Cu(C21H24N2O2)]·H2O, comprises half of a Schiff base complex and half of a water mol­ecule. The whole compound is generated by crystallographic twofold rotation symmetry. The geometry around the CuII atom, located on a twofold axis, is distorted square-planar, which is supported by the N2O2 donor atoms of the coordinating Schiff base ligand. The dihedral angle between the symmetry-related benzene rings is 47.5 (4)°. In the crystal, the water mol­ecule that is hydrogen bonded to the coordinated O atoms links the mol­ecules via O—H⋯O inter­actions into chains parallel to [001]. The crystal structure is further stabilized by C—H⋯π inter­actions, and by π–π inter­actions involving inversion-related chelate rings [centroid–centroid distance = 3.480 (4) Å]

Ganji, F.

Kargar, H.

Kia, R.

Mirkhani, V.

English

MPG.PuRe

{4,40-Dimethyl-2,20-[2,2-dimethyl-propane-1,3-diylbis(nitrilomethanylyl-idene)]diphenolato}copper(II)monohydrateHadi Kargar,a* Reza Kia,b Fatemeh Ganjia and ValiollahMirkhanicaDepartment of Chemistry, Payame Noor University, PO Box 19395-3697 Tehran,I. R. of IRAN, bDepartment of Chemistry, Science and Research Branch, Islamic AzadUniversity, Tehran, Iran, and cDepartment of Chemistry, University of Isfahan,81746-73441 Isfahan, IranCorrespondence e-mail: h.kargar@pnu.ac.irReceived 23 July 2012; accepted 2 August 2012Key indicators: single-crystal X-ray study; T = 296 K; mean (C–C) = 0.012 A˚;R factor = 0.084; wR factor = 0.209; data-to-parameter ratio = 14.2.The asymmetric unit of the title compound, [Cu(C21H24-N2O2)]H2O, comprises half of a Schiff base complex and halfof a water molecule. The whole compound is generated bycrystallographic twofold rotation symmetry. The geometryaround the CuII atom, located on a twofold axis, is distortedsquare-planar, which is supported by the N2O2 donor atoms ofthe coordinating Schiff base ligand. The dihedral anglebetween the symmetry-related benzene rings is 47.5 (4). Inthe crystal, the water molecule that is hydrogen bonded to thecoordinated O atoms links the molecules via O—H  Ointeractions into chains parallel to [001]. The crystal structureis further stabilized by C—H   interactions, and by –interactions involving inversion-related chelate rings[centroid–centroid distance = 3.480 (4) A˚].Related literatureFor applications of Schiff bases in coordination chemistry, see:Granovski et al. (1993); Blower (1998). For related structures,see: Ghaemi et al. (2011); Kargar et al. (2011, 2012). Forstandard bond lengths, see: Allen et al. (1987).ExperimentalCrystal data[Cu(C21H24N2O2)]H2OMr = 417.98Monoclinic, C2=ca = 13.353 (5) A˚b = 15.986 (5) A˚c = 10.023 (5) A˚ = 104.696 (5)V = 2069.5 (14) A˚3Z = 4Mo K radiation = 1.08 mm1T = 296 K0.11  0.08  0.05 mmData collectionBruker SMART APEXII CCDarea-detector diffractometerAbsorption correction: multi-scan(SADABS; Bruker, 2005)Tmin = 0.891, Tmax = 0.9484967 measured reflections1779 independent reflections1053 reflections with I > 2(I)Rint = 0.101RefinementR[F 2 > 2(F 2)] = 0.084wR(F 2) = 0.209S = 0.951779 reflections125 parametersH-atom parameters constrainedmax = 1.03 e A˚3min = 0.96 e A˚3Table 1Hydrogen-bond geometry (A˚, ).Cg1 is the centroid of the C1–C6 ring.D—H  A D—H H  A D  A D—H  AO1W—H1W1  O1 0.85 2.46 2.783 (7) 103O1W—H1W1  O1i 0.85 2.44 2.783 (7) 105C3—H3  O1W ii 0.93 2.55 3.48 (1) 173C8—H8B  Cg1iii 0.97 2.83 3.693 (9) 148C11—H11B  Cg1iv 0.96 2.98 3.850 (12) 151Symmetry codes: (i) xþ 1; y;z 12; (ii) xþ 12;y 12;z 1; (iii)x þ 32; yþ 12; z 1; (iv) xþ 12; yþ 12;z 12.Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT(Bruker, 2005); data reduction: SAINT; program(s) used to solvestructure: SHELXS97 (Sheldrick, 2008); program(s) used to refinestructure: SHELXL97 (Sheldrick, 2008); molecular graphics:SHELXTL (Sheldrick, 2008); software used to prepare material forpublication: SHELXTL and PLATON (Spek, 2009).HK and FG thank PNU for financial support.Supplementary data and figures for this paper are available from theIUCr electronic archives (Reference: SU2488).ReferencesAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.Blower, P. J. (1998). Transition Met. Chem. 23, 109–112.Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.Ghaemi, A., Rayati, S., Elahi, E., Ng, S. W. & Tiekink, E. R. T. (2011). ActaCryst. E67, m1445–m1446.Granovski, A. D., Nivorozhkin, A. L. & Minkin, V. I. (1993). Coord. Chem.Rev. 126, 1–69.Kargar, H., Kia, R., Pahlavani, E. & Tahir, M. N. (2011). Acta Cryst. E67, m941.Kargar, H., Kia, R., Sharafi, Z. & Tahir, M. N. (2012). Acta Cryst. E68, m82.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Spek, A. L. (2009). Acta Cryst. D65, 148–155.metal-organic compoundsm1172 Kargar et al. doi:10.1107/S1600536812034502 Acta Cryst. (2012). E68, m1172Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368supplementary materialssup-1Acta Cryst. (2012). E68, m1172    supplementary materialsActa Cryst. (2012). E68, m1172    [doi:10.1107/S1600536812034502]{4,4′-Dimethyl-2,2′-[2,2-dimethylpropane-1,3-diylbis(nitrilomethanylyl-idene)]diphenolato}copper(II) monohydrateHadi Kargar, Reza Kia, Fatemeh Ganji and Valiollah MirkhaniComment Schiff base complexes are one of the most important stereochemical models in transition metal coordination chemistry, with the ease of preparation and structural variations (Granovski et al., 1993; Blower, 1998). In continuation of our work on the structural analysis of Schiff base metal complexes (Kargar et al., 2012; Kargar et al., 2011; Ghaemi, et al., (2011), we synthesized the title compound and report herein on its crystal structure.The asymmetric unit of the title compound, Fig. 1, comprises half of a Schiff base complex and half a water molecule. The Cu1 and C9 atoms of the complex and the O atom of the water molecule lie on a two-fold rotation axis which generates the whole complex. The bond lengths (Allen et al., 1987) and angles are within the normal ranges and are comparable to those reported for related structures (Kargar et al., 2012; Kargar et al., 2011; Ghaemi et al., (2011). The geometry around the CuII atom is distorted square-planar which is supported by the N2O2 donor atoms of the coordinated Schiff base ligand. The dihedral angle between the substituted benzene rings is 47.5 (4)°.In the crystal, the water molecule that is hydrogen bonded to the coordinated O atoms, O1, mediates linking of molecules by C—H···O interactions (Table 1 and Fig. 2). The crystal structure is further stabilized by C-H···π interactions (Table 1), and by π-π interactions involving inversion related chelate rings [Cg···Cgi = 3.480 (4) Å; Cg is the centroid of the Cu1/O1/C1/C6/C7/N1 ring; symmetry code: (i) 1 - x, -y, -1 - z].Experimental The title compound was synthesized by adding 5-methyl-salicylaldehyde-2,2-dimethyl-1,3-propanediamine (2 mmol) to a solution of CuCl2. 4H2O (2.1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for 30 min. The resultant solution was filtered. Dark-green single crystals of the title compound suitable for X-ray structure determination were recrystallized from ethanol by slow evaporation of the solvents at room temperature over several days.Refinement The water H atom was located in a difference Fourier map and refined as a riding atom with Uiso(H) = 1.5Ueq(O). The C-bound H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.93, 0.96 and 0.97 Å for CH, CH3 and CH2 H-atoms, respectively, with Uiso (H) = k x Ueq(C), where k = 1.5 for CH3 H-atoms, and = 1.2 for other H-atoms.Computing details Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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: supplementary materialssup-2Acta Cryst. (2012). E68, m1172    SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).Figure 1A view of the molecular structure of the title compound, with the atom numbering. The displacement ellipsoids are drawn at the 40% probability level. The O-H···O hydrogen bonds are shown as dashed lines (see Table 1 for details; symmetry code for suffix A = -x+1, y, -z-1/2). supplementary materialssup-3Acta Cryst. (2012). E68, m1172    Figure 2A view along the b axis of the crystal packing of the title compound showing the C—H···O interactions as dashed lines [see Table 1 for details; only the H atoms involved in these interactions are shown]. {4,4′-Dimethyl-2,2′-[2,2-dimethylpropane-1,3- diylbis(nitrilomethanylylidene)]diphenolato}copper(II) monohydrate Crystal data [Cu(C21H24N2O2)]·H2OMr = 417.98Monoclinic, C2/cHall symbol: -C 2yca = 13.353 (5) Åb = 15.986 (5) Åc = 10.023 (5) Åβ = 104.696 (5)°V = 2069.5 (14) Å3Z = 4F(000) = 876Dx = 1.342 Mg m−3Mo Kα radiation, λ = 0.71073 ÅCell parameters from 512 reflectionsθ = 2.5–27.4°µ = 1.08 mm−1T = 296 KBlock, dark-green0.11 × 0.08 × 0.05 mmsupplementary materialssup-4Acta Cryst. (2012). E68, m1172    Data collection Bruker SMART APEXII CCD area-detector diffractometerRadiation source: fine-focus sealed tubeGraphite monochromatorφ and ω scansAbsorption correction: multi-scan (SADABS; Bruker, 2005)Tmin = 0.891, Tmax = 0.9484967 measured reflections1779 independent reflections1053 reflections with I > 2σ(I)Rint = 0.101θmax = 25.0°, θmin = 2.0°h = −15→11k = −18→18l = −10→11Refinement Refinement on F2Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.084wR(F2) = 0.209S = 0.951779 reflections125 parameters0 restraintsPrimary atom site location: structure-invariant direct methodsSecondary atom site location: difference Fourier mapHydrogen site location: inferred from neighbouring sitesH-atom parameters constrainedw = 1/[σ2(Fo2) + (0.0775P)2] where P = (Fo2 + 2Fc2)/3(Δ/σ)max < 0.001Δρmax = 1.03 e Å−3Δρmin = −0.96 e Å−3Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 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 (Å2) x y z Uiso*/UeqCu1 0.5000 0.01026 (6) −0.2500 0.0266 (5)O1 0.4089 (4) −0.0737 (2) −0.3499 (6) 0.0312 (14)N1 0.4554 (5) 0.0944 (3) −0.3912 (7) 0.0305 (16)C1 0.3331 (6) −0.0612 (4) −0.4620 (9) 0.0293 (19)C2 0.2617 (6) −0.1276 (4) −0.5073 (10) 0.042 (3)H2 0.2662 −0.1758 −0.4541 0.050*C3 0.1860 (7) −0.1214 (5) −0.6291 (11) 0.046 (3)H3 0.1375 −0.1642 −0.6530 0.055*C4 0.1790 (6) −0.0526 (5) −0.7191 (10) 0.045 (2)C6 0.3222 (6) 0.0109 (4) −0.5441 (9) 0.0311 (19)C7 0.3854 (6) 0.0845 (4) −0.5067 (10) 0.032 (2)H7 0.3753 0.1282 −0.5699 0.038*C8 0.5166 (6) 0.1727 (4) −0.3691 (9) 0.036 (2)H8A 0.4984 0.2056 −0.4531 0.043*H8B 0.5894 0.1587 −0.3512 0.043*C9 0.5000 0.2260 (6) −0.2500 0.048 (4)C5 0.2449 (6) 0.0134 (5) −0.6699 (10) 0.042 (2)supplementary materialssup-5Acta Cryst. (2012). E68, m1172    H5 0.2380 0.0621 −0.7224 0.051*C11 0.1004 (8) −0.0471 (7) −0.8564 (12) 0.069 (3)H11B 0.1206 −0.0042 −0.9113 0.104*H11A 0.0338 −0.0338 −0.8421 0.104*H11C 0.0968 −0.0999 −0.9032 0.104*C10 0.4033 (10) 0.2806 (6) −0.2988 (13) 0.087 (5)H10B 0.3947 0.3149 −0.2238 0.130*H10A 0.3436 0.2455 −0.3299 0.130*H10C 0.4110 0.3157 −0.3733 0.130*O1W 0.5000 −0.2254 (4) −0.2500 0.091 (5)H1W1 0.5281 −0.1936 −0.2981 0.137*Atomic displacement parameters (Å2) U11 U22 U33 U12 U13 U23Cu1 0.0194 (7) 0.0263 (6) 0.0300 (9) 0.000 −0.0015 (6) 0.000O1 0.026 (3) 0.026 (2) 0.031 (4) −0.0008 (18) −0.012 (3) −0.005 (2)N1 0.033 (4) 0.032 (3) 0.030 (5) −0.005 (2) 0.016 (4) 0.003 (3)C1 0.018 (4) 0.038 (4) 0.030 (5) 0.001 (3) 0.003 (4) −0.005 (3)C2 0.031 (5) 0.037 (4) 0.049 (7) 0.000 (3) −0.007 (5) 0.000 (4)C3 0.020 (5) 0.060 (5) 0.052 (7) −0.007 (3) 0.001 (5) −0.014 (5)C4 0.017 (4) 0.068 (5) 0.046 (7) −0.005 (4) −0.003 (5) −0.003 (5)C6 0.022 (4) 0.036 (3) 0.032 (5) 0.007 (3) 0.001 (4) 0.001 (3)C7 0.030 (5) 0.029 (3) 0.036 (6) 0.007 (3) 0.006 (5) 0.011 (3)C8 0.026 (5) 0.032 (4) 0.044 (6) −0.007 (3) −0.002 (5) 0.004 (3)C9 0.046 (9) 0.025 (5) 0.073 (12) 0.000 0.018 (8) 0.000C5 0.026 (5) 0.052 (4) 0.043 (6) 0.005 (3) −0.002 (4) 0.007 (4)C11 0.036 (6) 0.113 (8) 0.049 (8) −0.013 (5) −0.007 (6) 0.000 (6)C10 0.123 (12) 0.058 (6) 0.089 (11) 0.050 (6) 0.045 (9) 0.034 (6)O1W 0.106 (10) 0.033 (5) 0.106 (11) 0.000 −0.026 (8) 0.000Geometric parameters (Å, º) Cu1—O1i 1.914 (4) C6—C7 1.441 (10)Cu1—O1 1.914 (4) C7—H7 0.9300Cu1—N1i 1.934 (6) C8—C9 1.527 (10)Cu1—N1 1.934 (6) C8—H8A 0.9700O1—C1 1.322 (9) C8—H8B 0.9700N1—C7 1.300 (10) C9—C8i 1.527 (10)N1—C8 1.480 (8) C9—C10 1.533 (10)C1—C6 1.403 (10) C9—C10i 1.533 (10)C1—C2 1.423 (10) C5—H5 0.9300C2—C3 1.377 (12) C11—H11B 0.9600C2—H2 0.9300 C11—H11A 0.9600C3—C4 1.411 (13) C11—H11C 0.9600C3—H3 0.9300 C10—H10B 0.9600C4—C5 1.382 (11) C10—H10A 0.9600C4—C11 1.507 (12) C10—H10C 0.9600C6—C5 1.413 (11) O1W—H1W1 0.8513supplementary materialssup-6Acta Cryst. (2012). E68, m1172    O1i—Cu1—O1 91.0 (3) N1—C8—C9 113.9 (7)O1i—Cu1—N1i 93.9 (2) N1—C8—H8A 108.8O1—Cu1—N1i 155.2 (3) C9—C8—H8A 108.8O1i—Cu1—N1 155.1 (3) N1—C8—H8B 108.8O1—Cu1—N1 93.9 (2) C9—C8—H8B 108.8N1i—Cu1—N1 91.9 (4) H8A—C8—H8B 107.7C1—O1—Cu1 125.9 (4) C8—C9—C8i 112.2 (8)C7—N1—C8 118.8 (6) C8—C9—C10 110.2 (6)C7—N1—Cu1 125.8 (4) C8i—C9—C10 106.9 (6)C8—N1—Cu1 115.0 (5) C8—C9—C10i 106.9 (6)O1—C1—C6 124.5 (6) C8i—C9—C10i 110.2 (6)O1—C1—C2 117.8 (7) C10—C9—C10i 110.5 (11)C6—C1—C2 117.6 (8) C4—C5—C6 123.4 (8)C3—C2—C1 120.8 (8) C4—C5—H5 118.3C3—C2—H2 119.6 C6—C5—H5 118.3C1—C2—H2 119.6 C4—C11—H11B 109.5C2—C3—C4 122.5 (7) C4—C11—H11A 109.5C2—C3—H3 118.8 H11B—C11—H11A 109.5C4—C3—H3 118.8 C4—C11—H11C 109.5C5—C4—C3 115.8 (8) H11B—C11—H11C 109.5C5—C4—C11 121.0 (9) H11A—C11—H11C 109.5C3—C4—C11 123.1 (8) C9—C10—H10B 109.5C1—C6—C5 119.4 (7) C9—C10—H10A 109.5C1—C6—C7 123.4 (7) H10B—C10—H10A 109.5C5—C6—C7 117.1 (7) C9—C10—H10C 109.5N1—C7—C6 124.9 (7) H10B—C10—H10C 109.5N1—C7—H7 117.5 H10A—C10—H10C 109.5C6—C7—H7 117.5O1i—Cu1—O1—C1 −166.5 (8) C2—C1—C6—C5 −2.8 (12)N1i—Cu1—O1—C1 92.1 (9) O1—C1—C6—C7 −7.9 (13)N1—Cu1—O1—C1 −10.9 (7) C2—C1—C6—C7 176.4 (8)O1i—Cu1—N1—C7 101.3 (8) C8—N1—C7—C6 178.2 (8)O1—Cu1—N1—C7 0.5 (8) Cu1—N1—C7—C6 5.8 (13)N1i—Cu1—N1—C7 −155.3 (9) C1—C6—C7—N1 −3.6 (14)O1i—Cu1—N1—C8 −71.3 (8) C5—C6—C7—N1 175.7 (8)O1—Cu1—N1—C8 −172.1 (6) C7—N1—C8—C9 116.3 (8)N1i—Cu1—N1—C8 32.1 (4) Cu1—N1—C8—C9 −70.5 (7)Cu1—O1—C1—C6 15.7 (11) N1—C8—C9—C8i 35.3 (4)Cu1—O1—C1—C2 −168.6 (6) N1—C8—C9—C10 −83.7 (9)O1—C1—C2—C3 −174.8 (8) N1—C8—C9—C10i 156.2 (8)C6—C1—C2—C3 1.2 (14) C3—C4—C5—C6 6.1 (15)C1—C2—C3—C4 4.2 (15) C11—C4—C5—C6 −177.9 (9)C2—C3—C4—C5 −7.7 (15) C1—C6—C5—C4 −1.0 (14)C2—C3—C4—C11 176.4 (10) C7—C6—C5—C4 179.7 (9)O1—C1—C6—C5 172.9 (8)Symmetry code: (i) −x+1, y, −z−1/2.supplementary materialssup-7Acta Cryst. (2012). E68, m1172    Hydrogen-bond geometry (Å, º) Cg1 is the centroid of the C1–C6 ring.D—H···A D—H H···A D···A D—H···AO1W—H1W1···O1 0.85 2.46 2.783 (7) 103O1W—H1W1···O1i 0.85 2.44 2.783 (7) 105C3—H3···O1Wii 0.93 2.55 3.48 (1) 173C8—H8B···Cg1iii 0.97 2.83 3.693 (9) 148C11—H11B···Cg1iv 0.96 2.98 3.850 (12) 151Symmetry codes: (i) −x+1, y, −z−1/2; (ii) −x+1/2, −y−1/2, −z−1; (iii) x+3/2, y+1/2, z−1; (iv) −x+1/2, y+1/2, −z−1/2.

{4,4'-Dimethyl-2,2'-[2,2-dimethylpropane-1,3-diylbis(nitrilomethanylylidene)]diphenolato}copper(II) monohydrate.

Abstract

Similar works

Full text

Available Versions

MPG.PuRe