metal-organic compounds
{4,4′-Dimethyl-2,2′-[2,2-dimethylpropane-1,3-diylbis(nitrilomethanylylidene)]diphenolato}copper(II) monohydrate
aDepartment of Chemistry, Payame Noor University, PO Box 19395-3697 Tehran, I. R. of IRAN, bDepartment of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran, and cDepartment of Chemistry, University of Isfahan, 81746-73441 Isfahan, Iran
*Correspondence e-mail: h.kargar@pnu.ac.ir
The 21H24N2O2)]·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 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].
of the title compound, [Cu(CRelated literature
For applications of et al. (1993); Blower (1998). For related structures, see: Ghaemi et al. (2011); Kargar et al. (2011, 2012). For standard bond lengths, see: Allen et al. (1987).
in coordination chemistry, see: GranovskiExperimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT (Bruker, 2005); 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 and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536812034502/su2488sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812034502/su2488Isup2.hkl
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
were recrystallized from ethanol by slow evaporation of the solvents at room temperature over several days.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.
Data collection: APEX2 (Bruker, 2005); cell
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: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).[Cu(C21H24N2O2)]·H2O | F(000) = 876 |
Mr = 417.98 | Dx = 1.342 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 512 reflections |
a = 13.353 (5) Å | θ = 2.5–27.4° |
b = 15.986 (5) Å | µ = 1.08 mm−1 |
c = 10.023 (5) Å | T = 296 K |
β = 104.696 (5)° | Block, dark-green |
V = 2069.5 (14) Å3 | 0.11 × 0.08 × 0.05 mm |
Z = 4 |
Bruker SMART APEXII CCD area-detector diffractometer | 1779 independent reflections |
Radiation source: fine-focus sealed tube | 1053 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.101 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −15→11 |
Tmin = 0.891, Tmax = 0.948 | k = −18→18 |
4967 measured reflections | l = −10→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.084 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.209 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0775P)2] where P = (Fo2 + 2Fc2)/3 |
1779 reflections | (Δ/σ)max < 0.001 |
125 parameters | Δρmax = 1.03 e Å−3 |
0 restraints | Δρmin = −0.96 e Å−3 |
[Cu(C21H24N2O2)]·H2O | V = 2069.5 (14) Å3 |
Mr = 417.98 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.353 (5) Å | µ = 1.08 mm−1 |
b = 15.986 (5) Å | T = 296 K |
c = 10.023 (5) Å | 0.11 × 0.08 × 0.05 mm |
β = 104.696 (5)° |
Bruker SMART APEXII CCD area-detector diffractometer | 1779 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1053 reflections with I > 2σ(I) |
Tmin = 0.891, Tmax = 0.948 | Rint = 0.101 |
4967 measured reflections |
R[F2 > 2σ(F2)] = 0.084 | 0 restraints |
wR(F2) = 0.209 | H-atom parameters constrained |
S = 0.95 | Δρmax = 1.03 e Å−3 |
1779 reflections | Δρmin = −0.96 e Å−3 |
125 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 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) | |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0194 (7) | 0.0263 (6) | 0.0300 (9) | 0.000 | −0.0015 (6) | 0.000 |
O1 | 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) | 0.000 |
C5 | 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) | 0.000 |
Cu1—O1i | 1.914 (4) | C6—C7 | 1.441 (10) |
Cu1—O1 | 1.914 (4) | C7—H7 | 0.9300 |
Cu1—N1i | 1.934 (6) | C8—C9 | 1.527 (10) |
Cu1—N1 | 1.934 (6) | C8—H8A | 0.9700 |
O1—C1 | 1.322 (9) | C8—H8B | 0.9700 |
N1—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 | 0.9300 |
C2—C3 | 1.377 (12) | C11—H11B | 0.9600 |
C2—H2 | 0.9300 | C11—H11A | 0.9600 |
C3—C4 | 1.411 (13) | C11—H11C | 0.9600 |
C3—H3 | 0.9300 | C10—H10B | 0.9600 |
C4—C5 | 1.382 (11) | C10—H10A | 0.9600 |
C4—C11 | 1.507 (12) | C10—H10C | 0.9600 |
C6—C5 | 1.413 (11) | O1W—H1W1 | 0.8513 |
O1i—Cu1—O1 | 91.0 (3) | N1—C8—C9 | 113.9 (7) |
O1i—Cu1—N1i | 93.9 (2) | N1—C8—H8A | 108.8 |
O1—Cu1—N1i | 155.2 (3) | C9—C8—H8A | 108.8 |
O1i—Cu1—N1 | 155.1 (3) | N1—C8—H8B | 108.8 |
O1—Cu1—N1 | 93.9 (2) | C9—C8—H8B | 108.8 |
N1i—Cu1—N1 | 91.9 (4) | H8A—C8—H8B | 107.7 |
C1—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 | 118.3 |
C3—C2—H2 | 119.6 | C6—C5—H5 | 118.3 |
C1—C2—H2 | 119.6 | C4—C11—H11B | 109.5 |
C2—C3—C4 | 122.5 (7) | C4—C11—H11A | 109.5 |
C2—C3—H3 | 118.8 | H11B—C11—H11A | 109.5 |
C4—C3—H3 | 118.8 | C4—C11—H11C | 109.5 |
C5—C4—C3 | 115.8 (8) | H11B—C11—H11C | 109.5 |
C5—C4—C11 | 121.0 (9) | H11A—C11—H11C | 109.5 |
C3—C4—C11 | 123.1 (8) | C9—C10—H10B | 109.5 |
C1—C6—C5 | 119.4 (7) | C9—C10—H10A | 109.5 |
C1—C6—C7 | 123.4 (7) | H10B—C10—H10A | 109.5 |
C5—C6—C7 | 117.1 (7) | C9—C10—H10C | 109.5 |
N1—C7—C6 | 124.9 (7) | H10B—C10—H10C | 109.5 |
N1—C7—H7 | 117.5 | H10A—C10—H10C | 109.5 |
C6—C7—H7 | 117.5 | ||
O1i—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. |
Cg1 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O1 | 0.85 | 2.46 | 2.783 (7) | 103 |
O1W—H1W1···O1i | 0.85 | 2.44 | 2.783 (7) | 105 |
C3—H3···O1Wii | 0.93 | 2.55 | 3.48 (1) | 173 |
C8—H8B···Cg1iii | 0.97 | 2.83 | 3.693 (9) | 148 |
C11—H11B···Cg1iv | 0.96 | 2.98 | 3.850 (12) | 151 |
Symmetry 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. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C21H24N2O2)]·H2O |
Mr | 417.98 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 13.353 (5), 15.986 (5), 10.023 (5) |
β (°) | 104.696 (5) |
V (Å3) | 2069.5 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.08 |
Crystal size (mm) | 0.11 × 0.08 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.891, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4967, 1779, 1053 |
Rint | 0.101 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.084, 0.209, 0.95 |
No. of reflections | 1779 |
No. of parameters | 125 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.03, −0.96 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
Cg1 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O1 | 0.85 | 2.46 | 2.783 (7) | 103 |
O1W—H1W1···O1i | 0.85 | 2.44 | 2.783 (7) | 105 |
C3—H3···O1Wii | 0.93 | 2.55 | 3.48 (1) | 173 |
C8—H8B···Cg1iii | 0.97 | 2.83 | 3.693 (9) | 148 |
C11—H11B···Cg1iv | 0.96 | 2.98 | 3.850 (12) | 151 |
Symmetry 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. |
Acknowledgements
HK and FG thank PNU for financial support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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].