Dichloridobis[2-(morpholin-4-yl)ethanamine-κ² N,N′]cadmium

Abstract

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,

• a = 19.6443 (2) Å

• b = 10.6159 (1) Å

• c = 8.3553 (1) Å

• V = 1742.43 (3) ų

• 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[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The C-bound hydrogen atoms were placed at calculated positions (C—H 0.99 Å) and were treated as riding on their parent atoms. The amine hydrogen atoms were located in a difference Fourier map and refined with a restrained N—H distance of 0.91 (3) Å. For all hydrogen atoms Uiso(H) were set to 1.2 times Ueq(carrier atom).

Figures

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].

Crystal data

[CdCl2(C6H14N2O)2]	F(000) = 904
Mr = 443.68	Dx = 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

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

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)] = 0.039	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(Fo2) + (0.P)2 + 9.8151P] where P = (Fo2 + 2Fc2)/3
2009 reflections	(Δ/σ)max < 0.001
103 parameters	Δρmax = 1.00 e Å−3
2 restraints	Δρmin = −1.06 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

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···O1iv	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.