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[4,4′-(Ethane-1,2-diyldi­nitrilo)­bis­­(pent-2-en-2-olato)]copper(II) 0.25-hydrate

aPakistan Council of Scientific and Industrial Research Laboratories Complex, Karachi 75280, Pakistan, bDepartment of Chemistry, University of Karachi, Karachi 75270, Pakistan, cDepartment of Chemistry, GC University, Faisalabad, Pakistan, dDepartment of Biochemistry, Federal Urdu University of Arts Science and Technology, Gulshan-e-Iqbal Campus, Karachi, Pakistan, and eDepartment of Chemistry, University of Gujrat (Hafiz Hayat campus), Gujrat 50781, Pakistan
*Correspondence e-mail: maslamchemist@hotmail.com, mnachemist@hotmail.com

(Received 12 April 2012; accepted 18 April 2012; online 25 April 2012)

In the title compound, [Cu(C12H18N2O2)]·0.25H2O, the coordination of the O,N,N′,O′-tetra­dentate ligand results in a cis-CuN2O2 square-planar geometry for the metal ion and the presence of two six-membered and one five-membered chelate rings. The complete complex mol­ecule is close to planar (r.m.s. deviation = 0.047 Å). The uncoordinated water mol­ecule (O-atom site symmetry 2) was modelled as half occupied. In the crystal, C—H⋯Ow and Ow—H⋯O (w = water) hydrogen bonds link the components into layers parallel to ab plane.

Related literature

For background to Schiff bases and their complexes, see: Aslam et al. (2012[Aslam, M., Anis, I., Afza, N., Ali, B. & Shah, M. R. (2012). J. Chem. Soc. Pak. 34, 391-395.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu(C12H18N2O2)]·0.25H2O

  • Mr = 290.33

  • Orthorhombic, P b c n

  • a = 17.0029 (7) Å

  • b = 8.0198 (3) Å

  • c = 19.6532 (7) Å

  • V = 2679.91 (18) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 1.62 mm−1

  • T = 296 K

  • 0.24 × 0.21 × 0.13 mm

Data collection
  • Bruker Kappa APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2007[Bruker (2007). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.697, Tmax = 0.817

  • 22704 measured reflections

  • 3338 independent reflections

  • 1745 reflections with I > 2σ(I)

  • Rint = 0.042

Refinement
  • R[F2 > 2σ(F2)] = 0.060

  • wR(F2) = 0.190

  • S = 1.07

  • 3338 reflections

  • 166 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.56 e Å−3

  • Δρmin = −0.39 e Å−3

Table 1
Selected bond lengths (Å)

Cu1—O2 1.897 (4)
Cu1—O1 1.901 (4)
Cu1—N2 1.922 (4)
Cu1—N1 1.926 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C12—H12A⋯O1Wi 0.96 2.58 3.466 (9) 154
C6—H6B⋯O1Wi 0.97 2.44 3.303 (11) 149
O1W—H1WA⋯O2 0.79 (2) 2.29 (14) 2.862 (8) 130 (13)
Symmetry code: (i) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and PLATON.

Supporting information


Comment top

Herein we report the crystal structure of title compound, (I), which is a Cu complex of schiff base in countinuation of our studies on synthesis and metal complexation of schiff bases (Aslam et al., 2012). The copper metal bonded to the ligand 4,4'-(ethane-1,2-diyldinitrilo)bispent-2-en-2-ol through Cu—O covelant & Cu—N coordinate covelant bonds in such a way that it causes to produce two six membered rings (C2/C3/C4/Cu1/N1/O1) "A" & (C7/C8/C9/Cu1/N2/O2) "B" and a five membered ring (C5/C6/N1/Cu1/N2) "C". All these three rings are almost planer with the r. m. s. deviation of 0.0114 Å, 0.0061 Å and 0.0273 Å respectively. The molecule as a whole is slightly twisted as the five membered ring is oriented at dihedral angle of 2.54 (23)° and 3.34 (23)° with respect to six membered rings "A" and "B". Both of six membered rings are twisted at angle of 3.47 (16)° which showes the slight nonplaner behaviour of the molecule.

Moreover, a half water molecule have also been identified during refinement which links the molecules in two dimensional network through O—H···O and C—H···O interactions along a & b axes (Table. 2, Fig. 2).

Related literature top

For background to Schiff bases and their complexes, see: Aslam et al. (2012).

Experimental top

A methanolic solution of copper (II) chloride dihydrated (1 mol) (5 ml) was slowly added to a methanolic solution of 4-{[2-((1-methyl-3-oxobutylidene)amino)ethyl]imino}-2-pentanone (1 mol) (100 ml) and refluxed with stirring for 45 min. The pH was gradually raised to achieve the suitable pH for the formulation of the complex by the drop wise addition of 1 M NaOH solution. Now the reaction mixture was refluxed with stirring for 90 min. After cooling, the mixture was concentrated to one third under reduced pressure. The concentrated reaction mixture was kept at room temperature and black crystals were obtained after six days. The crystalline product was collected, washed with cooled methanol, recrystallized from ethylacetate and methanol (1:1) mixture and dried to afford the title compound in 73.1% yield. Slow evaporation of a methanol solution afforded dark brown blocks of (I).

Refinement top

All the C—H and H-atoms were positioned with idealized geometry with C—H = 0.93 Å for aromatic, C—H = 0.97 Å for methylene & C—H = 0.96 Å for methyl group and were refined using a riding model with Uiso(H) = 1.2 Ueq(C) for aromatic & methylene and Uiso(H) = 1.5 Ueq(C) for methyl carbon atoms. The O—H = 0.79 (2) Å & O–H 0.95 (2) Å H atoms were refined using fourier map with Uiso(H) = 1.5 Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with 50% displacement ellipsoids.
[Figure 2] Fig. 2. A view of the unit cell packing showing two dimensional hydrogen bonding network through dashed lines.
[4,4'-(Ethane-1,2-diyldinitrilo)bis(pent-2-en-2-olato)]copper(II) 0.25-hydrate top
Crystal data top
[Cu(C12H18N2O2)]·0.25H2OF(000) = 1212
Mr = 290.33Dx = 1.439 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 5532 reflections
a = 17.0029 (7) Åθ = 2.4–25.9°
b = 8.0198 (3) ŵ = 1.62 mm1
c = 19.6532 (7) ÅT = 296 K
V = 2679.91 (18) Å3Block, dark brown
Z = 80.24 × 0.21 × 0.13 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer
3338 independent reflections
Radiation source: fine-focus sealed tube1745 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
ϕ and ω scansθmax = 28.3°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 2222
Tmin = 0.697, Tmax = 0.817k = 810
22704 measured reflectionsl = 2226
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.190H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0608P)2 + 6.2772P]
where P = (Fo2 + 2Fc2)/3
3338 reflections(Δ/σ)max < 0.001
166 parametersΔρmax = 0.56 e Å3
1 restraintΔρmin = 0.39 e Å3
Crystal data top
[Cu(C12H18N2O2)]·0.25H2OV = 2679.91 (18) Å3
Mr = 290.33Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 17.0029 (7) ŵ = 1.62 mm1
b = 8.0198 (3) ÅT = 296 K
c = 19.6532 (7) Å0.24 × 0.21 × 0.13 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer
3338 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
1745 reflections with I > 2σ(I)
Tmin = 0.697, Tmax = 0.817Rint = 0.042
22704 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0601 restraint
wR(F2) = 0.190H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.56 e Å3
3338 reflectionsΔρmin = 0.39 e Å3
166 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 > 2σ(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) top
xyzUiso*/UeqOcc. (<1)
Cu10.28720 (4)0.12613 (9)0.19272 (3)0.0578 (3)
O10.3694 (2)0.1823 (5)0.13133 (18)0.0729 (11)
O20.3675 (2)0.0653 (6)0.25492 (19)0.0791 (12)
N10.2057 (2)0.2001 (5)0.1317 (2)0.0557 (10)
N20.2037 (3)0.0604 (5)0.2529 (2)0.0609 (11)
C10.4377 (4)0.2870 (10)0.0361 (3)0.096 (2)
H1A0.46980.18850.03650.144*
H1B0.46500.37580.05890.144*
H1C0.42720.31890.01010.144*
C20.3606 (4)0.2520 (7)0.0726 (3)0.0662 (15)
C30.2912 (4)0.2910 (7)0.0431 (3)0.0670 (15)
H30.29320.34010.00020.080*
C40.2160 (3)0.2638 (6)0.0715 (3)0.0596 (13)
C50.1275 (4)0.1746 (10)0.1597 (4)0.094 (2)
H5A0.10250.28220.16590.113*
H5B0.09630.11170.12730.113*
C60.1280 (4)0.0880 (11)0.2234 (4)0.109 (3)
H6A0.09640.15070.25550.131*
H6B0.10270.01930.21690.131*
C70.2129 (4)0.0013 (8)0.3139 (3)0.0741 (17)
C80.2866 (5)0.0314 (8)0.3429 (3)0.084 (2)
H80.28710.07930.38590.100*
C90.3573 (5)0.0023 (9)0.3145 (3)0.0825 (18)
C100.4323 (5)0.0375 (12)0.3520 (4)0.126 (3)
H10A0.46310.06220.35690.189*
H10B0.46170.11890.32690.189*
H10C0.41990.08110.39620.189*
C110.1458 (4)0.3136 (9)0.0287 (3)0.094 (2)
H11A0.11430.39250.05340.141*
H11B0.11490.21660.01860.141*
H11C0.16370.36330.01290.141*
C120.1418 (5)0.0453 (10)0.3561 (4)0.116 (3)
H12A0.11050.12590.33230.174*
H12B0.11110.05330.36420.174*
H12C0.15850.09120.39880.174*
O1W0.50000.2851 (13)0.25000.070 (3)0.50
H1WA0.484 (9)0.205 (9)0.269 (6)0.105*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0602 (4)0.0703 (5)0.0430 (4)0.0012 (4)0.0011 (3)0.0032 (3)
O10.054 (2)0.116 (3)0.049 (2)0.002 (2)0.0047 (17)0.005 (2)
O20.071 (2)0.117 (3)0.049 (2)0.011 (2)0.0059 (19)0.006 (2)
N10.053 (2)0.059 (2)0.056 (2)0.002 (2)0.003 (2)0.010 (2)
N20.068 (3)0.060 (3)0.055 (3)0.006 (2)0.004 (2)0.008 (2)
C10.088 (5)0.124 (6)0.075 (4)0.022 (5)0.017 (4)0.006 (4)
C20.069 (4)0.079 (4)0.051 (3)0.011 (3)0.007 (3)0.006 (3)
C30.081 (4)0.074 (4)0.047 (3)0.002 (3)0.004 (3)0.006 (3)
C40.072 (3)0.052 (3)0.055 (3)0.005 (3)0.010 (3)0.010 (2)
C50.064 (4)0.131 (6)0.088 (5)0.002 (4)0.009 (4)0.012 (4)
C60.074 (5)0.156 (8)0.097 (5)0.013 (5)0.007 (4)0.009 (5)
C70.111 (5)0.057 (3)0.055 (3)0.013 (4)0.016 (4)0.009 (3)
C80.131 (6)0.075 (4)0.045 (3)0.003 (4)0.001 (4)0.004 (3)
C90.105 (5)0.087 (4)0.055 (4)0.014 (4)0.017 (4)0.001 (3)
C100.133 (7)0.167 (8)0.076 (5)0.032 (6)0.043 (5)0.014 (5)
C110.097 (5)0.103 (5)0.082 (4)0.014 (4)0.029 (4)0.009 (4)
C120.156 (7)0.120 (6)0.073 (4)0.041 (6)0.037 (5)0.003 (4)
O1W0.033 (5)0.055 (6)0.122 (10)0.0000.007 (6)0.000
Geometric parameters (Å, º) top
Cu1—O21.897 (4)C5—H5A0.9700
Cu1—O11.901 (4)C5—H5B0.9700
Cu1—N21.922 (4)C6—H6A0.9700
Cu1—N11.926 (4)C6—H6B0.9700
O1—C21.291 (6)C7—C81.398 (8)
O2—C91.287 (7)C7—C121.509 (9)
N1—C41.301 (7)C8—C91.352 (9)
N1—C51.454 (7)C8—H80.9300
N2—C71.307 (7)C9—C101.506 (9)
N2—C61.429 (8)C10—H10A0.9600
C1—C21.521 (8)C10—H10B0.9600
C1—H1A0.9600C10—H10C0.9600
C1—H1B0.9600C11—H11A0.9600
C1—H1C0.9600C11—H11B0.9600
C2—C31.351 (7)C11—H11C0.9600
C3—C41.412 (7)C12—H12A0.9600
C3—H30.9300C12—H12B0.9600
C4—C111.514 (7)C12—H12C0.9600
C5—C61.431 (10)O1W—H1WA0.79 (2)
O2—Cu1—O186.59 (16)H5A—C5—H5B107.7
O2—Cu1—N293.75 (19)N2—C6—C5115.8 (6)
O1—Cu1—N2177.56 (18)N2—C6—H6A108.3
O2—Cu1—N1176.84 (19)C5—C6—H6A108.3
O1—Cu1—N193.48 (17)N2—C6—H6B108.3
N2—Cu1—N186.31 (19)C5—C6—H6B108.3
C2—O1—Cu1125.8 (4)H6A—C6—H6B107.4
C9—O2—Cu1126.2 (5)N2—C7—C8123.2 (6)
C4—N1—C5121.5 (5)N2—C7—C12119.8 (7)
C4—N1—Cu1126.2 (4)C8—C7—C12117.0 (6)
C5—N1—Cu1112.3 (4)C9—C8—C7126.5 (6)
C7—N2—C6122.7 (6)C9—C8—H8116.8
C7—N2—Cu1125.4 (4)C7—C8—H8116.8
C6—N2—Cu1112.0 (4)O2—C9—C8124.9 (6)
C2—C1—H1A109.5O2—C9—C10114.5 (7)
C2—C1—H1B109.5C8—C9—C10120.6 (6)
H1A—C1—H1B109.5C9—C10—H10A109.5
C2—C1—H1C109.5C9—C10—H10B109.5
H1A—C1—H1C109.5H10A—C10—H10B109.5
H1B—C1—H1C109.5C9—C10—H10C109.5
O1—C2—C3125.9 (5)H10A—C10—H10C109.5
O1—C2—C1113.6 (5)H10B—C10—H10C109.5
C3—C2—C1120.5 (5)C4—C11—H11A109.5
C2—C3—C4125.8 (5)C4—C11—H11B109.5
C2—C3—H3117.1H11A—C11—H11B109.5
C4—C3—H3117.1C4—C11—H11C109.5
N1—C4—C3122.8 (5)H11A—C11—H11C109.5
N1—C4—C11120.2 (5)H11B—C11—H11C109.5
C3—C4—C11117.0 (5)C7—C12—H12A109.5
C6—C5—N1113.2 (6)C7—C12—H12B109.5
C6—C5—H5A108.9H12A—C12—H12B109.5
N1—C5—H5A108.9C7—C12—H12C109.5
C6—C5—H5B108.9H12A—C12—H12C109.5
N1—C5—H5B108.9H12B—C12—H12C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···O1Wi0.962.583.466 (9)154
C6—H6B···O1Wi0.972.443.303 (11)149
O1W—H1WA···O20.79 (2)2.29 (14)2.862 (8)130 (13)
Symmetry code: (i) x1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu(C12H18N2O2)]·0.25H2O
Mr290.33
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)296
a, b, c (Å)17.0029 (7), 8.0198 (3), 19.6532 (7)
V3)2679.91 (18)
Z8
Radiation typeMo Kα
µ (mm1)1.62
Crystal size (mm)0.24 × 0.21 × 0.13
Data collection
DiffractometerBruker Kappa APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.697, 0.817
No. of measured, independent and
observed [I > 2σ(I)] reflections
22704, 3338, 1745
Rint0.042
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.060, 0.190, 1.07
No. of reflections3338
No. of parameters166
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.56, 0.39

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected bond lengths (Å) top
Cu1—O21.897 (4)Cu1—N21.922 (4)
Cu1—O11.901 (4)Cu1—N11.926 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···O1Wi0.962.583.466 (9)154
C6—H6B···O1Wi0.972.443.303 (11)149
O1W—H1WA···O20.79 (2)2.29 (14)2.862 (8)130 (13)
Symmetry code: (i) x1/2, y1/2, z+1/2.
 

Footnotes

Department of Chemistry, University of Karachi, Karachi 75270, Pakistan.

Acknowledgements

MA expresses his gratitude to the PCSIR Laboratories Complex, Karachi, the Department of Chemistry, University of Karachi, and the Department of Chemistry, GC University, Lahore, for providing financial support, research facilities and X-ray diffraction facilities, respectively. MNA also acknowledges Professor Helen Stoeckli-Evans, Switzerland, for guidance about the final refinement.

References

First citationAslam, M., Anis, I., Afza, N., Ali, B. & Shah, M. R. (2012). J. Chem. Soc. Pak. 34, 391–395.  CAS Google Scholar
First citationBruker (2007). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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