Related literature

Acta Crystallogr Sect E Struct Rep Online

Acta Cryst. E

Acta Crystallographica Section E: Structure Reports Online

1600-5368

International Union of Crystallography

22969476

3435603

zs2227

10.1107/S1600536812035398

ACSEBH

S1600536812035398

Metal-Organic Papers

Dichlorido(1-{(E)-[phenyl(pyridin-2-yl-κN)methylidene]amino-κN}pyrrolidin-2-one-κO)copper(II) monohydrate

[CuCl₂(C₁₆H₁₅N₃O)]·H₂O

Kunnath

Roji J.

aPrathapachandra Kurup

M.R.

aNg

Seik Weng

bc*aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, IndiabDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, MalaysiacChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia

Correspondence e-mail: seikweng@um.edu.my

0192012

2382012

68Pt 9

e120900

m1181m118103820121082012

2012

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

A full version of this article is available from Crystallography Journals Online.

The Cu^II atom in the title compound, [CuCl₂(C₁₆H₁₅N₃O)]·H₂O, is N,N′,O-chelated by the neutral Schiff base ligand and exists in a square-pyramidal geometry. It is displaced by 0.316 (1) Å out of the square plane (r.m.s. deviation = 0.015 Å) in the direction of the apical Cl atom. The apical Cl atoms of adjacent complex units are hydrogen-bond acceptors to two water molecules, the interaction generating a centrosymmetric dimer through a cyclic R ₄ ²(8) association.

Related literature

For a history of Schiff bases, see: Tidwell (2008 ▶). For graph-set notation, see: Etter et al. (1990 ▶).

Experimental <sec id="sec2.1.1"><title>Crystal data

[CuCl₂(C₁₆H₁₅N₃O)]·H₂O

M _r = 417.77

Triclinic,

a = 9.1289 (2) Å

b = 9.4017 (2) Å

c = 10.6798 (2) Å

α = 90.4349 (6)°

β = 99.1627 (6)°

γ = 105.4911 (6)°

V = 870.84 (3) Å³

Z = 2

Mo Kα radiation

μ = 1.57 mm⁻¹

T = 293 K

0.30 × 0.30 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.650, T _max = 0.650

14839 measured reflections

3987 independent reflections

3761 reflections with I > 2σ(I)

R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.026

wR(F ²) = 0.076

S = 1.07

3987 reflections

225 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρ_max = 0.45 e Å⁻³

Δρ_min = −0.34 e Å⁻³

Data collection: <italic>APEX2</italic> (Bruker, 2010<xref ref-type="bibr" rid="bb2"> ▶</xref>); cell refinement: <italic>SAINT</italic> (Bruker, 2010<xref ref-type="bibr" rid="bb2"> ▶</xref>); data reduction: <italic>SAINT</italic>; program(s) used to solve structure: <italic>SHELXS97</italic> (Sheldrick, 2008<xref ref-type="bibr" rid="bb5"> ▶</xref>); program(s) used to refine structure: <italic>SHELXL97</italic> (Sheldrick, 2008<xref ref-type="bibr" rid="bb5"> ▶</xref>); molecular graphics: <italic>X-SEED</italic> (Barbour, 2001<xref ref-type="bibr" rid="bb1"> ▶</xref>); software used to prepare material for publication: <italic>publCIF</italic> (Westrip, 2010<xref ref-type="bibr" rid="bb7"> ▶</xref>).</sec></sec><sec sec-type="supplementary-material"><title>Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812035398/zs2227sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035398/zs2227Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZS2227).

RJK thanks the University Grants Commission (India) for a Junior Research Fellowship. We thank the Sophisticated Analytical Instruments Facility, Cochin University of Science and Technology, for the diffraction measurements. We also thank the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

supplementary crystallographic information Comment

Among the plethora of Schiff bases that have been synthesized for the purpose of furnishing coordination compounds, some are synthesized in situ, and their formulation is inferred from the crystal structure of the product. Phenyl[(pyridin-2-yl)methylidene]amino]pyrrolidin-2-one is an example of such a Schiff base, which possess a carbonyl group and it forms a monohydrated complex with copper(II) chloride (Scheme I, Fig. 1). The Cu^II atom in this complex is N,N',O-chelated by the neutral Schiff ligand and has a square-pyramidal geometry, with the atom displaced out of the square plane in the direction of the apical Cl atom by 0.316 (1) Å. The apical Cl atoms of adjacent complex units are hydrogen-bond acceptors to two water molecules (Table 1), the interaction generating a centrosymmetric dimer (Fig. 2) through a cyclic R²₄(8) association (Etter et al., 1990).

Experimental

1-[(E)-[Phenyl(pyridin-2-yl)methylidene]amino]pyrrolidin-2-one was synthesized in situ from 2-benzoylpyridine (0.183 g, 1 mmol) and 1-aminopyrrolidin-2-one (0.100 g, 1 mmol) by heating in methanol for 2 h. Copper(II) chloride dihydrate (0.170 g, 1 mmol) was added, and the mixture heated for 5 h. The resulting pale green solid was collected and recrystallized from methanol.

FiguresFig. 1.

Thermal ellipsoid plot (Barbour, 2001) of [CuCl2(C16H15N3O)].H2O at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Fig. 2.

The hydrogen-bonded dimer.

Crystal data

[CuCl₂(C₁₆H₁₅N₃O)]·H₂O	Z = 2
M_r = 417.77	F(000) = 426
Triclinic, P1	D_x = 1.593 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1289 (2) Å	Cell parameters from 9988 reflections
b = 9.4017 (2) Å	θ = 2.3–28.2°
c = 10.6798 (2) Å	µ = 1.57 mm⁻¹
α = 90.4349 (6)°	T = 293 K
β = 99.1627 (6)°	Cube, green
γ = 105.4911 (6)°	0.30 × 0.30 × 0.30 mm
V = 870.84 (3) Å³

Data collection

Bruker Kappa APEXII CCD diffractometer	3987 independent reflections
Radiation source: fine-focus sealed tube	3761 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.650, T_max = 0.650	k = −12→12
14839 measured reflections	l = −13→13

Refinement

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0379P)² + 0.3259P] where P = (F_o² + 2F_c²)/3
3987 reflections	(Δ/σ)_max = 0.001
225 parameters	Δρ_max = 0.45 e Å⁻³
2 restraints	Δρ_min = −0.34 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

	x	y	z	U_iso*/U_eq
Cu1	0.48709 (2)	0.63969 (2)	0.845334 (18)	0.03229 (8)
Cl1	0.54227 (8)	0.72830 (6)	0.64075 (5)	0.06303 (16)
Cl2	0.64240 (5)	0.82061 (5)	0.97595 (4)	0.04703 (12)
O1	0.62811 (14)	0.49646 (15)	0.86442 (14)	0.0478 (3)
O1W	0.2859 (2)	0.5064 (3)	0.4420 (2)	0.0832 (6)
N1	0.28316 (15)	0.68570 (15)	0.84571 (13)	0.0340 (3)
N2	0.33922 (15)	0.44928 (14)	0.77515 (13)	0.0308 (3)
N3	0.40965 (15)	0.34475 (15)	0.75166 (14)	0.0339 (3)
C1	0.2610 (2)	0.81241 (19)	0.88367 (18)	0.0410 (4)
H1A	0.3462	0.8893	0.9176	0.049*
C2	0.1151 (2)	0.8336 (2)	0.8743 (2)	0.0505 (5)
H2A	0.1028	0.9227	0.9030	0.061*
C3	−0.0106 (2)	0.7216 (2)	0.8222 (2)	0.0557 (5)
H3	−0.1094	0.7339	0.8150	0.067*
C4	0.0108 (2)	0.5900 (2)	0.7803 (2)	0.0467 (4)
H4	−0.0729	0.5129	0.7439	0.056*
C5	0.15940 (18)	0.57554 (17)	0.79400 (16)	0.0333 (3)
C6	0.19396 (18)	0.43781 (17)	0.75440 (15)	0.0320 (3)
C7	0.06742 (18)	0.30651 (17)	0.70149 (17)	0.0342 (3)
C8	0.0047 (3)	0.2941 (2)	0.5739 (2)	0.0549 (5)
H8	0.0428	0.3672	0.5202	0.066*
C9	−0.1152 (3)	0.1720 (3)	0.5270 (2)	0.0704 (7)
H9	−0.1575	0.1632	0.4412	0.085*
C10	−0.1720 (2)	0.0643 (2)	0.6054 (3)	0.0614 (6)
H10	−0.2518	−0.0179	0.5726	0.074*
C11	−0.1118 (2)	0.0772 (2)	0.7324 (2)	0.0530 (5)
H11	−0.1516	0.0041	0.7856	0.064*
C12	0.0085 (2)	0.1990 (2)	0.7818 (2)	0.0428 (4)
H12	0.0491	0.2082	0.8680	0.051*
C13	0.3480 (2)	0.19716 (19)	0.68807 (18)	0.0399 (4)
H13A	0.2971	0.2019	0.6019	0.048*
H13B	0.2759	0.1326	0.7344	0.048*
C14	0.4930 (2)	0.1453 (2)	0.6898 (2)	0.0510 (5)
H14A	0.4770	0.0461	0.7198	0.061*
H14B	0.5182	0.1444	0.6049	0.061*
C15	0.6226 (2)	0.2524 (2)	0.7783 (2)	0.0509 (5)
H15A	0.6500	0.2064	0.8563	0.061*
H15B	0.7132	0.2849	0.7382	0.061*
C16	0.5608 (2)	0.3787 (2)	0.80431 (18)	0.0392 (4)
H1	0.355 (3)	0.564 (3)	0.493 (3)	0.100 (12)*
H2	0.330 (4)	0.441 (3)	0.435 (4)	0.114 (15)*

Atomic displacement parameters (Å2)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02431 (11)	0.02906 (11)	0.03759 (12)	0.00025 (8)	0.00019 (7)	−0.00478 (8)
Cl1	0.0821 (4)	0.0500 (3)	0.0433 (3)	−0.0090 (3)	0.0168 (2)	0.0018 (2)
Cl2	0.0366 (2)	0.0455 (2)	0.0467 (2)	−0.00346 (18)	−0.00297 (17)	−0.01499 (18)
O1	0.0300 (6)	0.0431 (7)	0.0650 (9)	0.0087 (5)	−0.0048 (6)	−0.0102 (6)
O1W	0.0539 (11)	0.1031 (17)	0.0784 (13)	0.0071 (11)	−0.0049 (9)	−0.0176 (12)
N1	0.0284 (6)	0.0284 (6)	0.0404 (7)	0.0027 (5)	0.0005 (5)	−0.0031 (5)
N2	0.0270 (6)	0.0253 (6)	0.0374 (7)	0.0043 (5)	0.0027 (5)	−0.0006 (5)
N3	0.0292 (6)	0.0277 (6)	0.0426 (7)	0.0055 (5)	0.0039 (5)	−0.0018 (5)
C1	0.0379 (9)	0.0302 (8)	0.0495 (10)	0.0047 (7)	−0.0003 (7)	−0.0060 (7)
C2	0.0452 (10)	0.0355 (9)	0.0704 (13)	0.0149 (8)	0.0020 (9)	−0.0109 (9)
C3	0.0357 (9)	0.0442 (10)	0.0866 (16)	0.0148 (8)	0.0026 (10)	−0.0097 (10)
C4	0.0281 (8)	0.0363 (9)	0.0696 (12)	0.0042 (7)	−0.0010 (8)	−0.0078 (8)
C5	0.0274 (7)	0.0270 (7)	0.0409 (8)	0.0024 (6)	0.0011 (6)	−0.0019 (6)
C6	0.0281 (7)	0.0272 (7)	0.0357 (8)	0.0016 (6)	0.0013 (6)	−0.0006 (6)
C7	0.0244 (7)	0.0259 (7)	0.0487 (9)	0.0030 (6)	0.0022 (6)	−0.0033 (6)
C8	0.0518 (12)	0.0488 (11)	0.0482 (11)	−0.0085 (9)	0.0008 (9)	−0.0049 (9)
C9	0.0602 (14)	0.0709 (16)	0.0591 (14)	−0.0100 (12)	−0.0031 (11)	−0.0230 (12)
C10	0.0396 (10)	0.0414 (11)	0.0903 (17)	−0.0088 (8)	0.0091 (10)	−0.0261 (11)
C11	0.0368 (9)	0.0295 (8)	0.0926 (16)	0.0040 (7)	0.0193 (10)	0.0060 (9)
C12	0.0334 (8)	0.0344 (8)	0.0578 (11)	0.0056 (7)	0.0058 (7)	0.0058 (7)
C13	0.0404 (9)	0.0314 (8)	0.0460 (9)	0.0073 (7)	0.0060 (7)	−0.0074 (7)
C14	0.0479 (11)	0.0396 (10)	0.0684 (13)	0.0156 (8)	0.0119 (9)	−0.0043 (9)
C15	0.0423 (10)	0.0509 (11)	0.0632 (12)	0.0225 (9)	0.0033 (9)	−0.0043 (9)
C16	0.0321 (8)	0.0392 (9)	0.0461 (9)	0.0102 (7)	0.0048 (7)	0.0014 (7)

Geometric parameters (Å, º)

Cu1—N2	1.9888 (13)	C5—C6	1.486 (2)
Cu1—N1	2.0213 (14)	C6—C7	1.482 (2)
Cu1—O1	2.0878 (13)	C7—C8	1.382 (3)
Cu1—Cl2	2.2125 (4)	C7—C12	1.384 (2)
Cu1—Cl1	2.4240 (5)	C8—C9	1.383 (3)
O1—C16	1.231 (2)	C8—H8	0.9300
O1W—H1	0.834 (10)	C9—C10	1.366 (4)
O1W—H2	0.833 (10)	C9—H9	0.9300
N1—C1	1.331 (2)	C10—C11	1.372 (4)
N1—C5	1.350 (2)	C10—H10	0.9300
N2—C6	1.284 (2)	C11—C12	1.389 (3)
N2—N3	1.3518 (19)	C11—H11	0.9300
N3—C16	1.355 (2)	C12—H12	0.9300
N3—C13	1.466 (2)	C13—C14	1.526 (3)
C1—C2	1.387 (3)	C13—H13A	0.9700
C1—H1A	0.9300	C13—H13B	0.9700
C2—C3	1.371 (3)	C14—C15	1.517 (3)
C2—H2A	0.9300	C14—H14A	0.9700
C3—C4	1.385 (3)	C14—H14B	0.9700
C3—H3	0.9300	C15—C16	1.486 (2)
C4—C5	1.384 (2)	C15—H15A	0.9700
C4—H4	0.9300	C15—H15B	0.9700

N2—Cu1—N1	78.77 (5)	C8—C7—C12	120.20 (17)
N2—Cu1—O1	78.29 (5)	C8—C7—C6	120.33 (16)
N1—Cu1—O1	152.34 (6)	C12—C7—C6	119.42 (16)
N2—Cu1—Cl2	163.34 (4)	C7—C8—C9	119.4 (2)
N1—Cu1—Cl2	100.41 (4)	C7—C8—H8	120.3
O1—Cu1—Cl2	97.17 (4)	C9—C8—H8	120.3
N2—Cu1—Cl1	95.08 (4)	C10—C9—C8	120.6 (2)
N1—Cu1—Cl1	100.24 (4)	C10—C9—H9	119.7
O1—Cu1—Cl1	96.99 (5)	C8—C9—H9	119.7
Cl2—Cu1—Cl1	101.40 (2)	C9—C10—C11	120.19 (19)
C16—O1—Cu1	109.91 (11)	C9—C10—H10	119.9
H1—O1W—H2	98 (3)	C11—C10—H10	119.9
C1—N1—C5	118.68 (14)	C10—C11—C12	120.2 (2)
C1—N1—Cu1	127.24 (12)	C10—C11—H11	119.9
C5—N1—Cu1	113.95 (11)	C12—C11—H11	119.9
C6—N2—N3	127.33 (14)	C7—C12—C11	119.36 (19)
C6—N2—Cu1	119.74 (11)	C7—C12—H12	120.3
N3—N2—Cu1	112.90 (10)	C11—C12—H12	120.3
N2—N3—C16	113.89 (13)	N3—C13—C14	102.37 (15)
N2—N3—C13	131.06 (14)	N3—C13—H13A	111.3
C16—N3—C13	114.85 (14)	C14—C13—H13A	111.3
N1—C1—C2	122.22 (16)	N3—C13—H13B	111.3
N1—C1—H1A	118.9	C14—C13—H13B	111.3
C2—C1—H1A	118.9	H13A—C13—H13B	109.2
C3—C2—C1	119.11 (17)	C15—C14—C13	107.37 (15)
C3—C2—H2A	120.4	C15—C14—H14A	110.2
C1—C2—H2A	120.4	C13—C14—H14A	110.2
C2—C3—C4	119.32 (18)	C15—C14—H14B	110.2
C2—C3—H3	120.3	C13—C14—H14B	110.2
C4—C3—H3	120.3	H14A—C14—H14B	108.5
C5—C4—C3	118.56 (17)	C16—C15—C14	105.17 (15)
C5—C4—H4	120.7	C16—C15—H15A	110.7
C3—C4—H4	120.7	C14—C15—H15A	110.7
N1—C5—C4	122.09 (15)	C16—C15—H15B	110.7
N1—C5—C6	115.32 (14)	C14—C15—H15B	110.7
C4—C5—C6	122.59 (15)	H15A—C15—H15B	108.8
N2—C6—C7	127.44 (14)	O1—C16—N3	122.62 (16)
N2—C6—C5	112.02 (13)	O1—C16—C15	128.59 (17)
C7—C6—C5	120.52 (13)	N3—C16—C15	108.77 (15)

N2—Cu1—O1—C16	12.11 (13)	C3—C4—C5—C6	178.79 (19)
N1—Cu1—O1—C16	46.6 (2)	N3—N2—C6—C7	1.0 (3)
Cl2—Cu1—O1—C16	175.86 (13)	Cu1—N2—C6—C7	179.23 (13)
Cl1—Cu1—O1—C16	−81.66 (13)	N3—N2—C6—C5	179.28 (14)
N2—Cu1—N1—C1	−179.79 (16)	Cu1—N2—C6—C5	−2.54 (19)
O1—Cu1—N1—C1	145.74 (15)	N1—C5—C6—N2	−1.0 (2)
Cl2—Cu1—N1—C1	17.15 (16)	C4—C5—C6—N2	179.64 (17)
Cl1—Cu1—N1—C1	−86.58 (15)	N1—C5—C6—C7	177.33 (15)
N2—Cu1—N1—C5	−3.96 (12)	C4—C5—C6—C7	−2.0 (3)
O1—Cu1—N1—C5	−38.43 (19)	N2—C6—C7—C8	−97.6 (2)
Cl2—Cu1—N1—C5	−167.02 (11)	C5—C6—C7—C8	84.3 (2)
Cl1—Cu1—N1—C5	89.24 (12)	N2—C6—C7—C12	84.8 (2)
N1—Cu1—N2—C6	3.67 (13)	C5—C6—C7—C12	−93.27 (19)
O1—Cu1—N2—C6	168.11 (14)	C12—C7—C8—C9	−1.3 (3)
Cl2—Cu1—N2—C6	92.48 (18)	C6—C7—C8—C9	−178.8 (2)
Cl1—Cu1—N2—C6	−95.78 (13)	C7—C8—C9—C10	0.2 (4)
N1—Cu1—N2—N3	−177.89 (12)	C8—C9—C10—C11	0.8 (4)
O1—Cu1—N2—N3	−13.46 (11)	C9—C10—C11—C12	−0.7 (3)
Cl2—Cu1—N2—N3	−89.09 (17)	C8—C7—C12—C11	1.4 (3)
Cl1—Cu1—N2—N3	82.65 (11)	C6—C7—C12—C11	178.96 (16)
C6—N2—N3—C16	−168.57 (16)	C10—C11—C12—C7	−0.4 (3)
Cu1—N2—N3—C16	13.14 (17)	N2—N3—C13—C14	177.20 (17)
C6—N2—N3—C13	5.9 (3)	C16—N3—C13—C14	−8.4 (2)
Cu1—N2—N3—C13	−172.38 (14)	N3—C13—C14—C15	11.8 (2)
C5—N1—C1—C2	1.4 (3)	C13—C14—C15—C16	−11.4 (2)
Cu1—N1—C1—C2	177.05 (15)	Cu1—O1—C16—N3	−9.2 (2)
N1—C1—C2—C3	−1.2 (3)	Cu1—O1—C16—C15	172.06 (17)
C1—C2—C3—C4	0.1 (4)	N2—N3—C16—O1	−2.2 (3)
C2—C3—C4—C5	0.7 (3)	C13—N3—C16—O1	−177.64 (17)
C1—N1—C5—C4	−0.5 (3)	N2—N3—C16—C15	176.76 (15)
Cu1—N1—C5—C4	−176.76 (15)	C13—N3—C16—C15	1.4 (2)
C1—N1—C5—C6	−179.87 (15)	C14—C15—C16—O1	−174.7 (2)
Cu1—N1—C5—C6	3.92 (18)	C14—C15—C16—N3	6.4 (2)
C3—C4—C5—N1	−0.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1···Cl1	0.83 (1)	2.34 (1)	3.175 (2)	178 (4)
O1w—H2···Cl1ⁱ	0.83 (1)	2.41 (2)	3.221 (3)	165 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2010). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.

Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.

Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Tidwell, T. T. (2008). Angew. Chem. Int. Ed. Engl. 47, 1016–1020.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Table 1Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H1⋯Cl1	0.83 (1)	2.34 (1)	3.175 (2)	178 (4)
O1w—H2⋯Cl1ⁱ	0.83 (1)	2.41 (2)	3.221 (3)	165 (4)

Symmetry code: (i) .