Dichloridobis[2-(morpholin-4-yl)ethanamine-κ2N,N′]cadmium

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

doi:10.1107/S1600536811003709

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page m298

doi:10.1107/S1600536811003709

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Dichloridobis[2-(morpholin-4-yl)ethanamine-κ²N,N′]cadmium

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 25 January 2011; accepted 28 January 2011; online 2 February 2011)

In the title compound, [CdCl₂(C₆H₁₄N₂O)₂], the Cl and Cd^II atoms are located on a twofold rotation axis and the Cd^II atom is octahedrally coordinated by two N,N′-bidentate 2-(morpholin-4-yl)ethanamine ligands and two trans-located Cl atoms. In the crystal, adjacent molecules are linked by N—H⋯Cl and C—H⋯O hydrogen bonds into a three-dimensional structure. An intramolecular C—H⋯Cl hydrogen bond is also observed.

Related literature

For the structures of nickel(II) complexes with 4-(2-aminoethyl)morpholine (L), see: Chattopadhyay et al. (2005 ); Laskar et al. (2001 ). For the structures of other metal complexes with the ligand (L), see: Shi et al. (2006 ) and literature cited therein.

Experimental

Crystal data

[CdCl₂(C₆H₁₄N₂O)₂]
M_r = 443.68
Orthorhombic, P c c a
a = 19.6443 (2) Å
b = 10.6159 (1) Å
c = 8.3553 (1) Å
V = 1742.43 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.57 mm⁻¹
T = 100 K
0.18 × 0.16 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.765, T_max = 0.954
20511 measured reflections
2009 independent reflections
1619 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.078
S = 1.28
2009 reflections
103 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.00 e Å⁻³
Δρ_min = −1.06 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N2	2.290 (3)
Cd1—N1	2.537 (3)
Cd1—Cl2	2.6244 (13)
Cd1—Cl1	2.6414 (14)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯Cl2ⁱ	0.88 (3)	2.54 (3)	3.344 (3)	152 (4)
N2—H2D⋯Cl1ⁱⁱ	0.90 (3)	2.46 (3)	3.333 (3)	161 (4)
C1—H1B⋯Cl1	0.99	2.80	3.540 (4)	132
C5—H5B⋯O1ⁱⁱⁱ	0.99	2.57	3.509 (5)	158
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z+1; (iii) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ .

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: 10.1107/S1600536811003709/si2331sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003709/si2331Isup2.hkl

checkCIF report

Comment top

The title compound was obtained upon complexation of 4-(2-aminoethyl)morpholine with CdCl₂. Similar to what was observed in the other metal complexes of 4-(2-aminoethyl)morpholine (Chattopadhyay et al., 2005; Laskar et al., 2001), the morpholine ring adopts a chair conformation and the amine acts as an N,N'-bidentate ligand to form a five-membered chelate ring with the metal center. Within the formed chelate ring, the Cd—N distances are considerably different from one another (Table 1). By contrast, the Pt—N bond lenghts in the square-planar complex of PtCl₂ with the amine ligand (Shi et al., 2006) are only slightly different [2.018 (6) and 2.075 (5) Å]. The Cd^II ion, placed on a 2-fold rotation axis, is six-coordinated by two of the amine ligands and two Cl atoms in a distorted octahedral geometry. The crystal structure is consolidated by intermolecular N—H···Cl and C—H···O and also intramolecular C—H···Cl hydrogen bonding interactions (Table 2).

Related literature top

For the structures of nickel(II) complexes with 4-(2-aminoethyl)morpholine (L), see: Chattopadhyay et al. (2005); Laskar et al. (2001). For the structures of other metal complexes with the ligand (L), see: Shi et al. (2006) and literature cited therein.

Experimental top

A solution of cadmium(II) chloride (0.92 g, 5.0 mmol) in minimum amount of water was added to an ethanolic solution (50 ml) of 4-(2-aminoethyl)morpholine (1.30 g, 10 mmol). The resulting solution was refluxed for 30 min, then left at room temperature. The crystals of the title complex were obtained in a few days.

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. Unlabelled non-H atoms in the complex are related to labelled atoms by [1 - x, y, 1/2 - z].

Dichloridobis[2-(morpholin-4-yl)ethanamine-κ²N,N']cadmium top

Crystal data top

[CdCl₂(C₆H₁₄N₂O)₂]	F(000) = 904
M_r = 443.68	D_x = 1.691 Mg m⁻³
Orthorhombic, Pcca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2ac	Cell parameters from 6671 reflections
a = 19.6443 (2) Å	θ = 3.3–30.4°
b = 10.6159 (1) Å	µ = 1.57 mm⁻¹
c = 8.3553 (1) Å	T = 100 K
V = 1742.43 (3) Å³	Plate, colorless
Z = 4	0.18 × 0.16 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	2009 independent reflections
Radiation source: fine-focus sealed tube	1619 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→24
T_min = 0.765, T_max = 0.954	k = −13→13
20511 measured reflections	l = −10→10

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	w = 1/[σ²(F_o²) + (0.P)² + 9.8151P] where P = (F_o² + 2F_c²)/3
2009 reflections	(Δ/σ)_max < 0.001
103 parameters	Δρ_max = 1.00 e Å⁻³
2 restraints	Δρ_min = −1.06 e Å⁻³

Crystal data top

[CdCl₂(C₆H₁₄N₂O)₂]	V = 1742.43 (3) Å³
M_r = 443.68	Z = 4
Orthorhombic, Pcca	Mo Kα radiation
a = 19.6443 (2) Å	µ = 1.57 mm⁻¹
b = 10.6159 (1) Å	T = 100 K
c = 8.3553 (1) Å	0.18 × 0.16 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	2009 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1619 reflections with I > 2σ(I)
T_min = 0.765, T_max = 0.954	R_int = 0.026
20511 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	2 restraints
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	Δρ_max = 1.00 e Å⁻³
2009 reflections	Δρ_min = −1.06 e Å⁻³
103 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	0.5000	0.74719 (3)	0.2500	0.01253 (10)
Cl1	0.5000	0.49837 (12)	0.2500	0.0181 (3)
Cl2	0.5000	0.99440 (12)	0.2500	0.0173 (3)
O1	0.31029 (15)	0.7816 (3)	−0.0516 (3)	0.0249 (7)
N1	0.37113 (16)	0.7319 (3)	0.2563 (4)	0.0182 (6)
N2	0.47563 (16)	0.7529 (3)	0.5179 (3)	0.0112 (6)
H2C	0.497 (2)	0.815 (3)	0.566 (5)	0.013*
H2D	0.491 (2)	0.682 (3)	0.565 (5)	0.013*
C1	0.3397 (2)	0.6315 (4)	0.1558 (5)	0.0213 (9)
H1A	0.2916	0.6197	0.1878	0.026*
H1B	0.3640	0.5509	0.1736	0.026*
C2	0.3431 (2)	0.6660 (4)	−0.0196 (5)	0.0256 (9)
H2A	0.3913	0.6719	−0.0529	0.031*
H2B	0.3213	0.5986	−0.0836	0.031*
C3	0.3403 (2)	0.8793 (4)	0.0428 (5)	0.0212 (9)
H3A	0.3166	0.9597	0.0206	0.025*
H3B	0.3886	0.8895	0.0114	0.025*
C4	0.3365 (2)	0.8516 (4)	0.2191 (5)	0.0213 (9)
H4A	0.3583	0.9210	0.2796	0.026*
H4B	0.2882	0.8465	0.2524	0.026*
C5	0.3615 (2)	0.6927 (4)	0.4264 (5)	0.0217 (9)
H5A	0.3753	0.6035	0.4383	0.026*
H5B	0.3126	0.6990	0.4542	0.026*
C6	0.4020 (2)	0.7721 (4)	0.5403 (5)	0.0210 (9)
H6A	0.3909	0.8620	0.5230	0.025*
H6B	0.3894	0.7501	0.6516	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01464 (18)	0.01259 (17)	0.01036 (17)	0.000	0.00092 (15)	0.000
Cl1	0.0252 (7)	0.0131 (5)	0.0161 (6)	0.000	−0.0003 (6)	0.000
Cl2	0.0234 (6)	0.0130 (5)	0.0155 (6)	0.000	−0.0011 (5)	0.000
O1	0.0217 (15)	0.0351 (17)	0.0178 (14)	0.0025 (13)	−0.0058 (12)	0.0038 (13)
N1	0.0172 (14)	0.0242 (17)	0.0133 (14)	−0.0006 (13)	0.0010 (13)	0.0038 (16)
N2	0.0181 (14)	0.0074 (13)	0.0082 (13)	0.0010 (12)	−0.0001 (11)	−0.0005 (12)
C1	0.0172 (19)	0.0103 (17)	0.036 (3)	−0.0043 (15)	−0.0047 (18)	0.0025 (18)
C2	0.023 (2)	0.028 (2)	0.026 (2)	−0.0008 (18)	−0.0047 (18)	−0.0127 (19)
C3	0.018 (2)	0.019 (2)	0.026 (2)	−0.0005 (16)	−0.0020 (17)	0.0088 (17)
C4	0.0158 (18)	0.0178 (19)	0.030 (2)	0.0017 (15)	−0.0001 (17)	−0.0073 (17)
C5	0.023 (2)	0.024 (2)	0.017 (2)	−0.0008 (17)	0.0024 (16)	0.0048 (17)
C6	0.019 (2)	0.032 (2)	0.0114 (17)	0.0013 (17)	0.0030 (15)	0.0007 (17)

Geometric parameters (Å, º) top

Cd1—N2	2.290 (3)	C1—H1A	0.9900
Cd1—N2ⁱ	2.290 (3)	C1—H1B	0.9900
Cd1—N1	2.537 (3)	C2—H2A	0.9900
Cd1—N1ⁱ	2.537 (3)	C2—H2B	0.9900
Cd1—Cl2	2.6244 (13)	C3—C4	1.503 (6)
Cd1—Cl1	2.6414 (14)	C3—H3A	0.9900
O1—C2	1.411 (5)	C3—H3B	0.9900
O1—C3	1.430 (5)	C4—H4A	0.9900
N1—C4	1.475 (5)	C4—H4B	0.9900
N1—C1	1.490 (5)	C5—C6	1.500 (6)
N1—C5	1.493 (5)	C5—H5A	0.9900
N2—C6	1.472 (5)	C5—H5B	0.9900
N2—H2C	0.88 (3)	C6—H6A	0.9900
N2—H2D	0.90 (3)	C6—H6B	0.9900
C1—C2	1.513 (6)

N2—Cd1—N2ⁱ	176.95 (15)	C2—C1—H1B	109.5
N2—Cd1—N1	76.88 (11)	H1A—C1—H1B	108.1
N2ⁱ—Cd1—N1	103.32 (11)	O1—C2—C1	112.0 (3)
N2—Cd1—N1ⁱ	103.32 (11)	O1—C2—H2A	109.2
N2ⁱ—Cd1—N1ⁱ	76.88 (11)	C1—C2—H2A	109.2
N1—Cd1—N1ⁱ	172.65 (15)	O1—C2—H2B	109.2
N2—Cd1—Cl2	88.47 (8)	C1—C2—H2B	109.2
N2ⁱ—Cd1—Cl2	88.47 (8)	H2A—C2—H2B	107.9
N1—Cd1—Cl2	93.68 (8)	O1—C3—C4	112.2 (3)
N1ⁱ—Cd1—Cl2	93.68 (8)	O1—C3—H3A	109.2
N2—Cd1—Cl1	91.53 (8)	C4—C3—H3A	109.2
N2ⁱ—Cd1—Cl1	91.53 (8)	O1—C3—H3B	109.2
N1—Cd1—Cl1	86.32 (8)	C4—C3—H3B	109.2
N1ⁱ—Cd1—Cl1	86.32 (8)	H3A—C3—H3B	107.9
Cl2—Cd1—Cl1	180.0	N1—C4—C3	110.6 (3)
C2—O1—C3	109.8 (3)	N1—C4—H4A	109.5
C4—N1—C1	107.9 (3)	C3—C4—H4A	109.5
C4—N1—C5	112.5 (3)	N1—C4—H4B	109.5
C1—N1—C5	106.5 (3)	C3—C4—H4B	109.5
C4—N1—Cd1	113.6 (2)	H4A—C4—H4B	108.1
C1—N1—Cd1	116.6 (2)	N1—C5—C6	112.4 (3)
C5—N1—Cd1	99.4 (2)	N1—C5—H5A	109.1
C6—N2—Cd1	109.5 (2)	C6—C5—H5A	109.1
C6—N2—H2C	108 (3)	N1—C5—H5B	109.1
Cd1—N2—H2C	111 (3)	C6—C5—H5B	109.1
C6—N2—H2D	113 (3)	H5A—C5—H5B	107.9
Cd1—N2—H2D	110 (3)	N2—C6—C5	111.3 (3)
H2C—N2—H2D	106 (4)	N2—C6—H6A	109.4
N1—C1—C2	110.7 (3)	C5—C6—H6A	109.4
N1—C1—H1A	109.5	N2—C6—H6B	109.4
C2—C1—H1A	109.5	C5—C6—H6B	109.4
N1—C1—H1B	109.5	H6A—C6—H6B	108.0

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···Cl2ⁱⁱ	0.88 (3)	2.54 (3)	3.344 (3)	152 (4)
N2—H2D···Cl1ⁱⁱⁱ	0.90 (3)	2.46 (3)	3.333 (3)	161 (4)
C1—H1B···Cl1	0.99	2.80	3.540 (4)	132
C5—H5B···O1^iv	0.99	2.57	3.509 (5)	158

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

Experimental details

Crystal data
Chemical formula	[CdCl₂(C₆H₁₄N₂O)₂]
M_r	443.68
Crystal system, space group	Orthorhombic, Pcca
Temperature (K)	100
a, b, c (Å)	19.6443 (2), 10.6159 (1), 8.3553 (1)
V (Å³)	1742.43 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.57
Crystal size (mm)	0.18 × 0.16 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.765, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	20511, 2009, 1619
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.078, 1.28
No. of reflections	2009
No. of parameters	103
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.00, −1.06

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

Selected bond lengths (Å) top

Cd1—N2	2.290 (3)	Cd1—Cl2	2.6244 (13)
Cd1—N1	2.537 (3)	Cd1—Cl1	2.6414 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···Cl2ⁱ	0.88 (3)	2.54 (3)	3.344 (3)	152 (4)
N2—H2D···Cl1ⁱⁱ	0.90 (3)	2.46 (3)	3.333 (3)	161 (4)
C1—H1B···Cl1	0.99	2.80	3.540 (4)	132
C5—H5B···O1ⁱⁱⁱ	0.99	2.57	3.509 (5)	158

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

Acknowledgements

The authors thank the University of Malaya for funding this study (FRGS grant No. FP004/2010B).

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