Dichlorido{2-morpholino-N-[1-(2-pyri­dyl)ethyl­idene]ethanamine-κ3N,N′,N′′}cadmium

Ikmal Hisham, N.; Suleiman Gwaram, N.; Khaledi, H.; Mohd Ali, H.

doi:10.1107/S1600536810043163

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page m1471

https://doi.org/10.1107/S1600536810043163

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Dichlorido{2-morpholino-N-[1-(2-pyridyl)ethylidene]ethanamine-κ³N,N′,N′′}cadmium

Nurulazimah Ikmal Hisham,^a Nura Suleiman Gwaram,^a Hamid Khaledi ^a ^* and Hapipah Mohd Ali ^a

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: khaledi@siswa.um.edu.my

(Received 21 October 2010; accepted 22 October 2010; online 30 October 2010)

In the title compound, [CdCl₂(C₁₃H₁₉N₃O)], the Cd^II ion is five-coordinate, with the N,N′,N′′-tridentate Schiff base ligand 2-morpholino-N-[1-(2-pyridyl)ethylidene]ethanamine and two Cl atoms in a distorted square-pyramidal geometry. In the crystal structure, C—H⋯Cl hydrogen-bonding interactions connect the molecules into a three-dimensional network.

Related literature

For the crystal structures of similar compounds, see: Ikmal Hisham et al. (2009 ); Cai (2009 ).

Experimental

Crystal data

[CdCl₂(C₁₃H₁₉N₃O)]
M_r = 416.61
Monoclinic, P 2₁ /n
a = 9.6357 (12) Å
b = 13.9300 (18) Å
c = 12.2514 (17) Å
β = 106.776 (2)°
V = 1574.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.73 mm⁻¹
T = 100 K
0.23 × 0.10 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.692, T_max = 0.934
9407 measured reflections
3437 independent reflections
2646 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.117
S = 1.08
3437 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −1.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯Cl1ⁱ	0.95	2.69	3.603 (6)	161
C7—H7C⋯Cl2ⁱⁱ	0.98	2.73	3.607 (6)	149
C8—H8A⋯Cl2ⁱⁱⁱ	0.99	2.82	3.730 (6)	153
C11—H11B⋯Cl1	0.99	2.80	3.654 (6)	144
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+2, -y, -z+1; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810043163/pv2344sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043163/pv2344Isup2.hkl

checkCIF report

Comment top

The title compound has been obtained via the complexation of cadmium(II) chloride by the N,N,N-tridentate ligand, 2-morpholino-N-[1-(2-pyridyl)ethylidene]ethanamine, which had itself been prepared from the condensation of 4-(2-aminoethyl)morpholine and 2-acetylpyridine. The geometry of the complex can be defined as distorted square-pyramidal (τ = 0.18) with one of the chloride ligands in the apical position. Like the similar structures reported in the literature [Ikmal Hisham et al., 2009; Cai, 2009], the morpholine ring in the present complex adopts a chair conformation. In the crystal structure, the molecules are linked together through C—H···Cl interactions into a three dimensional network.

Related literature top

For the crystal structures of similar compounds, see: Ikmal Hisham et al. (2009); Cai (2009).

Experimental top

A mixture of 4-(2-aminoethyl)morpholine (0.65 g, 5 mmol) and 2-acetylpyridine (0.61 g, 5 mmol) in ethanol (50 ml) was refluxed for 2 h followed by addition of a solution of cadmium(II) chloride (0.92 g, 5 mmol) in a minimum amount of water. The resulting solution was refluxed for 30 min, then evaporated partially and set aside at room temperature. The crystals of the cadmium(II) complex were obtained after a week.

Structure description top

For the crystal structures of similar compounds, see: Ikmal Hisham et al. (2009); Cai (2009).

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: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot of the title compound at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Dichlorido{2-morpholino-N-[1-(2-pyridyl)ethylidene]ethanamine- κ³N,N',N''}cadmium(II) top

Crystal data top

[CdCl₂(C₁₃H₁₉N₃O)]	F(000) = 832
M_r = 416.61	D_x = 1.758 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2378 reflections
a = 9.6357 (12) Å	θ = 2.3–27.3°
b = 13.9300 (18) Å	µ = 1.73 mm⁻¹
c = 12.2514 (17) Å	T = 100 K
β = 106.776 (2)°	Lath, colorless
V = 1574.5 (4) Å³	0.23 × 0.10 × 0.04 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3437 independent reflections
Radiation source: fine-focus sealed tube	2646 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
φ and ω scans	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→12
T_min = 0.692, T_max = 0.934	k = −10→17
9407 measured reflections	l = −15→15

Refinement top

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0488P)² + 6.1933P] where P = (F_o² + 2F_c²)/3
3437 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −1.16 e Å⁻³

Crystal data top

[CdCl₂(C₁₃H₁₉N₃O)]	V = 1574.5 (4) Å³
M_r = 416.61	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6357 (12) Å	µ = 1.73 mm⁻¹
b = 13.9300 (18) Å	T = 100 K
c = 12.2514 (17) Å	0.23 × 0.10 × 0.04 mm
β = 106.776 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3437 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2646 reflections with I > 2σ(I)
T_min = 0.692, T_max = 0.934	R_int = 0.043
9407 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.08	Δρ_max = 0.81 e Å⁻³
3437 reflections	Δρ_min = −1.16 e Å⁻³
182 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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

	x	y	z	U_iso*/U_eq
Cd1	0.77057 (4)	0.09902 (3)	0.33319 (3)	0.01533 (13)
Cl1	0.52520 (14)	0.14366 (10)	0.21865 (11)	0.0195 (3)
Cl2	0.96418 (15)	0.21768 (10)	0.36618 (11)	0.0210 (3)
O1	0.8174 (4)	0.0583 (3)	−0.0120 (3)	0.0235 (9)
N1	0.7320 (5)	0.1178 (3)	0.5165 (4)	0.0180 (10)
N2	0.7579 (5)	−0.0471 (3)	0.4170 (4)	0.0173 (10)
N3	0.8461 (5)	−0.0170 (3)	0.2128 (4)	0.0177 (10)
C1	0.7366 (6)	0.2002 (4)	0.5727 (4)	0.0194 (11)
H1	0.7649	0.2567	0.5413	0.023*
C2	0.7020 (6)	0.2073 (4)	0.6749 (4)	0.0205 (12)
H2	0.7079	0.2672	0.7131	0.025*
C3	0.6588 (7)	0.1252 (5)	0.7199 (4)	0.0261 (14)
H3	0.6321	0.1281	0.7886	0.031*
C4	0.6552 (6)	0.0378 (4)	0.6629 (5)	0.0214 (12)
H4	0.6271	−0.0195	0.6927	0.026*
C5	0.6932 (6)	0.0363 (4)	0.5621 (4)	0.0153 (11)
C6	0.7049 (6)	−0.0549 (4)	0.4993 (4)	0.0154 (11)
C7	0.6593 (6)	−0.1485 (4)	0.5389 (5)	0.0225 (12)
H7A	0.6077	−0.1870	0.4726	0.034*
H7B	0.5951	−0.1362	0.5866	0.034*
H7C	0.7452	−0.1836	0.5834	0.034*
C8	0.7876 (6)	−0.1294 (4)	0.3538 (4)	0.0200 (12)
H8A	0.6972	−0.1515	0.2978	0.024*
H8B	0.8274	−0.1830	0.4067	0.024*
C9	0.8969 (6)	−0.0984 (4)	0.2929 (5)	0.0204 (12)
H9A	0.9881	−0.0795	0.3504	0.024*
H9B	0.9188	−0.1538	0.2499	0.024*
C10	0.7321 (6)	−0.0497 (4)	0.1112 (4)	0.0210 (12)
H10A	0.6446	−0.0677	0.1334	0.025*
H10B	0.7662	−0.1074	0.0794	0.025*
C11	0.6935 (6)	0.0277 (4)	0.0212 (5)	0.0209 (12)
H11A	0.6187	0.0031	−0.0465	0.025*
H11B	0.6521	0.0834	0.0511	0.025*
C12	0.9219 (6)	0.0938 (4)	0.0846 (5)	0.0228 (12)
H12A	0.8806	0.1489	0.1158	0.027*
H12B	1.0065	0.1174	0.0619	0.027*
C13	0.9722 (6)	0.0184 (4)	0.1767 (5)	0.0234 (13)
H13A	1.0175	−0.0357	0.1473	0.028*
H13B	1.0456	0.0464	0.2430	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0202 (2)	0.0147 (2)	0.01291 (19)	0.00042 (16)	0.00765 (14)	0.00102 (15)
Cl1	0.0196 (6)	0.0200 (7)	0.0194 (6)	0.0030 (5)	0.0065 (5)	0.0031 (5)
Cl2	0.0217 (7)	0.0215 (7)	0.0208 (6)	−0.0038 (5)	0.0076 (5)	0.0009 (5)
O1	0.028 (2)	0.029 (2)	0.0161 (18)	−0.0047 (19)	0.0109 (17)	−0.0021 (17)
N1	0.020 (2)	0.023 (3)	0.011 (2)	0.0020 (19)	0.0050 (18)	0.0010 (18)
N2	0.023 (2)	0.015 (2)	0.014 (2)	0.0009 (19)	0.0050 (18)	0.0000 (18)
N3	0.018 (2)	0.023 (3)	0.013 (2)	0.0012 (19)	0.0057 (18)	−0.0006 (18)
C1	0.025 (3)	0.017 (3)	0.016 (2)	−0.004 (2)	0.005 (2)	0.001 (2)
C2	0.026 (3)	0.016 (3)	0.018 (3)	0.006 (2)	0.004 (2)	−0.004 (2)
C3	0.029 (3)	0.039 (4)	0.010 (2)	0.007 (3)	0.006 (2)	0.002 (2)
C4	0.025 (3)	0.025 (3)	0.017 (3)	0.000 (2)	0.011 (2)	0.003 (2)
C5	0.015 (3)	0.017 (3)	0.013 (2)	0.001 (2)	0.003 (2)	0.004 (2)
C6	0.013 (2)	0.018 (3)	0.015 (2)	0.002 (2)	0.003 (2)	0.003 (2)
C7	0.025 (3)	0.021 (3)	0.021 (3)	−0.002 (2)	0.007 (2)	0.005 (2)
C8	0.032 (3)	0.010 (3)	0.019 (3)	0.006 (2)	0.008 (2)	0.001 (2)
C9	0.029 (3)	0.012 (3)	0.021 (3)	0.009 (2)	0.009 (2)	0.001 (2)
C10	0.026 (3)	0.022 (3)	0.015 (2)	0.000 (2)	0.006 (2)	−0.004 (2)
C11	0.024 (3)	0.024 (3)	0.017 (3)	−0.003 (2)	0.008 (2)	−0.001 (2)
C12	0.026 (3)	0.024 (3)	0.023 (3)	−0.012 (3)	0.014 (2)	−0.008 (2)
C13	0.022 (3)	0.031 (4)	0.021 (3)	0.002 (3)	0.012 (2)	−0.006 (2)

Geometric parameters (Å, º) top

Cd1—N2	2.298 (5)	C4—H4	0.9500
Cd1—N1	2.394 (4)	C5—C6	1.506 (8)
Cd1—N3	2.437 (4)	C6—C7	1.501 (8)
Cd1—Cl2	2.4374 (14)	C7—H7A	0.9800
Cd1—Cl1	2.4557 (14)	C7—H7B	0.9800
O1—C12	1.404 (7)	C7—H7C	0.9800
O1—C11	1.432 (6)	C8—C9	1.519 (8)
N1—C1	1.332 (7)	C8—H8A	0.9900
N1—C5	1.364 (7)	C8—H8B	0.9900
N2—C6	1.261 (7)	C9—H9A	0.9900
N2—C8	1.458 (7)	C9—H9B	0.9900
N3—C10	1.474 (7)	C10—C11	1.510 (8)
N3—C9	1.487 (7)	C10—H10A	0.9900
N3—C13	1.492 (7)	C10—H10B	0.9900
C1—C2	1.390 (7)	C11—H11A	0.9900
C1—H1	0.9500	C11—H11B	0.9900
C2—C3	1.385 (8)	C12—C13	1.515 (8)
C2—H2	0.9500	C12—H12A	0.9900
C3—C4	1.398 (8)	C12—H12B	0.9900
C3—H3	0.9500	C13—H13A	0.9900
C4—C5	1.385 (7)	C13—H13B	0.9900

N2—Cd1—N1	68.60 (16)	C6—C7—H7B	109.5
N2—Cd1—N3	75.33 (15)	H7A—C7—H7B	109.5
N1—Cd1—N3	142.63 (15)	C6—C7—H7C	109.5
N2—Cd1—Cl2	131.54 (12)	H7A—C7—H7C	109.5
N1—Cd1—Cl2	95.10 (12)	H7B—C7—H7C	109.5
N3—Cd1—Cl2	101.67 (11)	N2—C8—C9	107.9 (5)
N2—Cd1—Cl1	108.24 (12)	N2—C8—H8A	110.1
N1—Cd1—Cl1	97.11 (11)	C9—C8—H8A	110.1
N3—Cd1—Cl1	103.21 (11)	N2—C8—H8B	110.1
Cl2—Cd1—Cl1	119.18 (5)	C9—C8—H8B	110.1
C12—O1—C11	108.6 (4)	H8A—C8—H8B	108.4
C1—N1—C5	118.5 (4)	N3—C9—C8	113.5 (4)
C1—N1—Cd1	126.0 (4)	N3—C9—H9A	108.9
C5—N1—Cd1	115.4 (3)	C8—C9—H9A	108.9
C6—N2—C8	123.0 (5)	N3—C9—H9B	108.9
C6—N2—Cd1	121.3 (4)	C8—C9—H9B	108.9
C8—N2—Cd1	114.6 (3)	H9A—C9—H9B	107.7
C10—N3—C9	110.2 (4)	N3—C10—C11	111.2 (5)
C10—N3—C13	108.9 (4)	N3—C10—H10A	109.4
C9—N3—C13	107.8 (4)	C11—C10—H10A	109.4
C10—N3—Cd1	115.9 (3)	N3—C10—H10B	109.4
C9—N3—Cd1	101.9 (3)	C11—C10—H10B	109.4
C13—N3—Cd1	111.8 (3)	H10A—C10—H10B	108.0
N1—C1—C2	123.1 (5)	O1—C11—C10	111.7 (5)
N1—C1—H1	118.4	O1—C11—H11A	109.3
C2—C1—H1	118.4	C10—C11—H11A	109.3
C3—C2—C1	118.6 (5)	O1—C11—H11B	109.3
C3—C2—H2	120.7	C10—C11—H11B	109.3
C1—C2—H2	120.7	H11A—C11—H11B	107.9
C2—C3—C4	119.1 (5)	O1—C12—C13	112.4 (5)
C2—C3—H3	120.5	O1—C12—H12A	109.1
C4—C3—H3	120.5	C13—C12—H12A	109.1
C5—C4—C3	118.9 (5)	O1—C12—H12B	109.1
C5—C4—H4	120.5	C13—C12—H12B	109.1
C3—C4—H4	120.5	H12A—C12—H12B	107.9
N1—C5—C4	121.8 (5)	N3—C13—C12	109.7 (5)
N1—C5—C6	115.0 (4)	N3—C13—H13A	109.7
C4—C5—C6	123.1 (5)	C12—C13—H13A	109.7
N2—C6—C7	123.9 (5)	N3—C13—H13B	109.7
N2—C6—C5	116.3 (5)	C12—C13—H13B	109.7
C7—C6—C5	119.8 (4)	H13A—C13—H13B	108.2
C6—C7—H7A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cl1ⁱ	0.95	2.69	3.603 (6)	161
C7—H7C···Cl2ⁱⁱ	0.98	2.73	3.607 (6)	149
C8—H8A···Cl2ⁱⁱⁱ	0.99	2.82	3.730 (6)	153
C11—H11B···Cl1	0.99	2.80	3.654 (6)	144

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+1; (iii) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[CdCl₂(C₁₃H₁₉N₃O)]
M_r	416.61
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.6357 (12), 13.9300 (18), 12.2514 (17)
β (°)	106.776 (2)
V (Å³)	1574.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.73
Crystal size (mm)	0.23 × 0.10 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.692, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	9407, 3437, 2646
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.117, 1.08
No. of reflections	3437
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −1.16

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cl1ⁱ	0.95	2.69	3.603 (6)	160.9
C7—H7C···Cl2ⁱⁱ	0.98	2.73	3.607 (6)	149.3
C8—H8A···Cl2ⁱⁱⁱ	0.99	2.82	3.730 (6)	152.6
C11—H11B···Cl1	0.99	2.80	3.654 (6)	144.4

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+1; (iii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

The authors thank the University of Malaya for funding this study (UMRG grant RG024/09BIO).

References

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