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

Abstract

In the title compound, [Cu(C(12)H(18)N(2)O(2))]·0.25H(2)O, the coordination of the O,N,N',O'-tetra-dentate ligand results in a cis-CuN(2)O(2) square-planar geometry for the metal ion and the presence of two six-membered and one five-membered chelate rings. The complete complex mol-ecule is close to planar (r.m.s. deviation = 0.047 Å). The uncoordinated water mol-ecule (O-atom site symmetry 2) was modelled as half occupied. In the crystal, C-H⋯O(w) and O(w)-H⋯O (w = water) hydrogen bonds link the components into layers parallel to ab plane.

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[4,40 0 0-(Ethane-1,2-diyldinitrilo)bis(pent-2-
en-2-olato)]copper(II) 0.25-hydrate
Muhammad Aslam,a*‡ Itrat Anis,bNighat Afza,aAjaz
Hussain,cWaseem Ahmeddand Muhammad Nadeem
Arshade*
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, andeDepartment 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
Key indicators: single-crystal X-ray study; T = 296 K; mean ?(C–C) = 0.010 A ˚;
disorder in solvent or counterion; R factor = 0.060; wR factor = 0.190; data-to-
parameter ratio = 20.1.
In the title compound, [Cu(C12H18N2O2)]?0.25H2O, the
coordination of the O,N,N0,O0-tetradentate ligand results in
a cis-CuN2O2square-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 A˚). The uncoordinated water
molecule (O-atom site symmetry 2) was modelled as half
occupied. In the crystal, C—H???Owand 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).
Experimental
Crystal data
[Cu(C12H18N2O2)]?0.25H2O
Mr= 290.33
Orthorhombic, Pbcn
a = 17.0029 (7) A˚
b = 8.0198 (3) A˚
c = 19.6532 (7) A˚
V = 2679.91 (18) A˚3
Z = 8
Mo K? radiation
? = 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)
Tmin= 0.697, Tmax= 0.817
22704 measured reflections
3338 independent reflections
1745 reflections with I > 2?(I)
Rint= 0.042
Refinement
R[F2> 2?(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
??max= 0.56 e A˚?3
??min= ?0.39 e A˚?3
Table 1
Selected bond lengths (A˚).
Cu1—O2
Cu1—O1
1.897 (4)
1.901 (4)
Cu1—N2
Cu1—N1
1.922 (4)
1.926 (4)
Table 2
Hydrogen-bond geometry (A˚,?).
D—H???A
C12—H12A???O1Wi
C6—H6B???O1Wi
O1W—H1WA???O2
Symmetry code: (i) x ?1
D—HH???AD???AD—H???A
0.96
0.97
0.79 (2)
2.58
2.44
2.29 (14)
3.466 (9)
3.303 (11)
2.862 (8)
154
149
130 (13)
2;y ?1
2;?z þ1
2.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT
(Bruker, 2007); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure:SHELXL97(Sheldrick,
PLATON (Spek, 2009); software used to prepare material for
publication: WinGX (Farrugia, 1999) and PLATON.
2008); molecular graphics:
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 acknowl-
edges Professor Helen Stoeckli-Evans, Switzerland, for
guidance about the final refinement.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: HB6739).
References
Aslam, M., Anis, I., Afza, N., Ali, B. & Shah, M. R. (2012). J. Chem. Soc. Pak.
34, 391–395.
Bruker (2007). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison,
Wisconsin, USA.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
metal-organic compounds
m670
Aslam et al.
doi:10.1107/S1600536812017102
Acta Cryst. (2012). E68, m670
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
‡ Department of Chemistry, University of Karachi, Karachi 75270, Pakistan.

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supplementary materials
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Acta Cryst. (2012). E68, m670
supplementary materials
Acta Cryst. (2012). E68, m670 [doi:10.1107/S1600536812017102]
[4,4′-(Ethane-1,2-diyldinitrilo)bis(pent-2-en-2-olato)]copper(II) 0.25-hydrate
Muhammad Aslam, Itrat Anis, Nighat Afza, Ajaz Hussain, Waseem Ahmed and Muhammad
Nadeem Arshad
Comment
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).
Experimental
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
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
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).

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Acta Cryst. (2012). E68, m670
Figure 1
The molecular structure of (I) with 50% displacement ellipsoids.

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Acta Cryst. (2012). E68, m670
Figure 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
Crystal data
[Cu(C12H18N2O2)]·0.25H2O
Mr = 290.33
Orthorhombic, Pbcn
Hall symbol: -P 2n 2ab
a = 17.0029 (7) Å
b = 8.0198 (3) Å
c = 19.6532 (7) Å
V = 2679.91 (18) Å3
Z = 8
F(000) = 1212
Dx = 1.439 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 5532 reflections
θ = 2.4–25.9°
µ = 1.62 mm−1
T = 296 K
Block, dark brown
0.24 × 0.21 × 0.13 mm
Data collection
Bruker Kappa APEXII CCD
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
Tmin = 0.697, Tmax = 0.817
22704 measured reflections
3338 independent reflections
1745 reflections with I > 2σ(I)
Rint = 0.042
θmax = 28.3°, θmin = 2.8°
h = −22→22
k = −8→10
l = −22→26
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.060
wR(F2) = 0.190
S = 1.07
3338 reflections
166 parameters
1 restraint
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0608P)2 + 6.2772P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.56 e Å−3
Δρmin = −0.39 e Å−3
Special details
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)
xyzUiso*/Ueq
Occ. (<1)
Cu10.28720 (4)0.12613 (9) 0.19272 (3)0.0578 (3)

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supplementary materials
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Acta Cryst. (2012). E68, m670
O1
O2
N1
N2
C1
H1A
H1B
H1C
C2
C3
H3
C4
C5
H5A
H5B
C6
H6A
H6B
C7
C8
H8
C9
C10
H10A
H10B
H10C
C11
H11A
H11B
H11C
C12
H12A
H12B
H12C
O1W
H1WA
0.3694 (2)
0.3675 (2)
0.2057 (2)
0.2037 (3)
0.4377 (4)
0.4698
0.4650
0.4272
0.3606 (4)
0.2912 (4)
0.2932
0.2160 (3)
0.1275 (4)
0.1025
0.0963
0.1280 (4)
0.0964
0.1027
0.2129 (4)
0.2866 (5)
0.2871
0.3573 (5)
0.4323 (5)
0.4631
0.4617
0.4199
0.1458 (4)
0.1143
0.1149
0.1637
0.1418 (5)
0.1105
0.1111
0.1585
0.5000
0.484 (9)
0.1823 (5)
0.0653 (6)
0.2001 (5)
0.0604 (5)
0.2870 (10)
0.1885
0.3758
0.3189
0.2520 (7)
0.2910 (7)
0.3401
0.2638 (6)
0.1746 (10)
0.2822
0.1117
0.0880 (11)
0.1507
−0.0193
−0.0013 (8)
−0.0314 (8)
−0.0793
0.0023 (9)
−0.0375 (12)
0.0622
−0.1189
−0.0811
0.3136 (9)
0.3925
0.2166
0.3633
−0.0453 (10)
−0.1259
0.0533
−0.0912
0.2851 (13)
0.205 (9)
0.13133 (18)
0.25492 (19)
0.1317 (2)
0.2529 (2)
0.0361 (3)
0.0365
0.0589
−0.0101
0.0726 (3)
0.0431 (3)
0.0002
0.0715 (3)
0.1597 (4)
0.1659
0.1273
0.2234 (4)
0.2555
0.2169
0.3139 (3)
0.3429 (3)
0.3859
0.3145 (3)
0.3520 (4)
0.3569
0.3269
0.3962
0.0287 (3)
0.0534
0.0186
−0.0129
0.3561 (4)
0.3323
0.3642
0.3988
0.2500
0.269 (6)
0.0729 (11)
0.0791 (12)
0.0557 (10)
0.0609 (11)
0.096 (2)
0.144*
0.144*
0.144*
0.0662 (15)
0.0670 (15)
0.080*
0.0596 (13)
0.094 (2)
0.113*
0.113*
0.109 (3)
0.131*
0.131*
0.0741 (17)
0.084 (2)
0.100*
0.0825 (18)
0.126 (3)
0.189*
0.189*
0.189*
0.094 (2)
0.141*
0.141*
0.141*
0.116 (3)
0.174*
0.174*
0.174*
0.070 (3)
0.105*
0.50
0.50
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Cu1
O1
O2
N1
N2
C1
C2
C3
C4
0.0602 (4)
0.054 (2)
0.071 (2)
0.053 (2)
0.068 (3)
0.088 (5)
0.069 (4)
0.081 (4)
0.072 (3)
0.0703 (5)
0.116 (3)
0.117 (3)
0.059 (2)
0.060 (3)
0.124 (6)
0.079 (4)
0.074 (4)
0.052 (3)
0.0430 (4)
0.049 (2)
0.049 (2)
0.056 (2)
0.055 (3)
0.075 (4)
0.051 (3)
0.047 (3)
0.055 (3)
0.0012 (4)
−0.002 (2)
0.011 (2)
0.002 (2)
−0.006 (2)
−0.022 (5)
−0.011 (3)
−0.002 (3)
0.005 (3)
−0.0011 (3)
−0.0047 (17)
−0.0059 (19)
0.003 (2)
0.004 (2)
0.017 (4)
0.007 (3)
−0.004 (3)
−0.010 (3)
−0.0032 (3)
0.005 (2)
0.006 (2)
−0.010 (2)
−0.008 (2)
0.006 (4)
−0.006 (3)
0.006 (3)
−0.010 (2)