Dichlorido{N,N-dimethyl-N′-[1-(pyridin-2-yl)ethyl­idene]ethane-1,2-diamine-κ3N,N′,N′′}cadmium

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

doi:10.1107/S1600536811005538

metal-organic compounds

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Volume 67| Part 3| March 2011| Page m348

doi:10.1107/S1600536811005538

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Dichlorido{N,N-dimethyl-N′-[1-(pyridin-2-yl)ethylidene]ethane-1,2-diamine-κ³N,N′,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 9 February 2011; accepted 15 February 2011; online 19 February 2011)

In the title compound, [CdCl₂(C₁₁H₁₇N₃)], the Schiff base acts as an N,N′,N′′-tridentate ligand towards the Cd^II ion. Two Cl atoms complete a distorted square-pyramidal geometry around the metal atom. In the crystal, a C—H⋯Cl interaction connects pairs of molecules into centrosymetric dimers.

Related literature

For the structure of a CuCl₂ complex of the same Schiff base, see: Saleh Salga et al. (2010 ). For the structure of a similar Cd^II complex, see: Bian et al. (2003 ). For a description of the geometry of complexes with five-coordinate metal atoms, see: Addison et al. (1984 ).

Experimental

Crystal data

[CdCl₂(C₁₁H₁₇N₃)]
M_r = 374.58
Triclinic, $[P \overline 1]$
a = 8.0276 (2) Å
b = 9.6048 (2) Å
c = 10.0851 (2) Å
α = 102.534 (1)°
β = 103.365 (1)°
γ = 97.850 (1)°
V = 724.09 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.86 mm⁻¹
T = 100 K
0.23 × 0.11 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.674, T_max = 0.929
5023 measured reflections
2652 independent reflections
2547 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.038
S = 1.08
2652 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯Cl2ⁱ	0.98	2.77	3.679 (2)	155
Symmetry code: (i) -x, -y, -z+1.

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/S1600536811005538/pv2387sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005538/pv2387Isup2.hkl

checkCIF report

Comment top

The title compound was obtained via the complexation of CdCl₂ by N,N-dimethyl-N'-[methyl(2-pyridyl)methylene]ethane-1,2-diamine. Similar to the structure of the analogous copper(II) complex (Saleh Salga et al., 2010), the cadmium(II) ion is penta-coordinated by the N,N',N"-tridentate Schiff base ligand and two Cl atoms in a distorted square-pyramidal geometry, the τ value (Addison et al., 1984) being 0.17. This arrangement is similar to what was observed in the structure of [CdCl₂(C₁₀H₁₅N₃)], the closest analogous cadmium complex (Bian et al., 2003). In the crystal, pairs of the molecules, related by symmetry -x, -y, -z + 1, are bonded into centrosymmetric dimers via C7—H7B···Cl2 interaction.

Related literature top

For the structure of a CuCl₂ complex of the same Schiff base, see: Saleh Salga et al. (2010). For the structure of a similar Cd^II complex, see: Bian et al. (2003). For a description of the geometry of five-coordinate metal complexes, see: Addison et al. (1984).

Experimental top

A mixture of 2-acetylpyridine (0.61 g, 5 mmol) and N,N-dimethylethyldiamine (0.44 g, 5 mmol) in ethanol (50 ml) was refluxed for 2 hr 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 set aside at room temperature. The colorless crystals of the title compound were obtained after 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. Hydrogen atoms are drawn as spheres of arbitrary radius.

Dichlorido{N,N-dimethyl-N'- [1-(pyridin-2-yl)ethylidene]ethane-1,2-diamine- κ³N,N',N''}cadmium top

Crystal data top

[CdCl₂(C₁₁H₁₇N₃)]	Z = 2
M_r = 374.58	F(000) = 372
Triclinic, P1	D_x = 1.718 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0276 (2) Å	Cell parameters from 5105 reflections
b = 9.6048 (2) Å	θ = 2.2–29.7°
c = 10.0851 (2) Å	µ = 1.86 mm⁻¹
α = 102.534 (1)°	T = 100 K
β = 103.365 (1)°	Plate, colorless
γ = 97.850 (1)°	0.23 × 0.11 × 0.04 mm
V = 724.09 (3) Å³

Data collection top

Bruker APEXII CCD diffractometer	2652 independent reflections
Radiation source: fine-focus sealed tube	2547 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.674, T_max = 0.929	k = −11→11
5023 measured reflections	l = −12→12

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)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.038	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0151P)² + 0.4207P] where P = (F_o² + 2F_c²)/3
2652 reflections	(Δ/σ)_max = 0.001
157 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[CdCl₂(C₁₁H₁₇N₃)]	γ = 97.850 (1)°
M_r = 374.58	V = 724.09 (3) Å³
Triclinic, P1	Z = 2
a = 8.0276 (2) Å	Mo Kα radiation
b = 9.6048 (2) Å	µ = 1.86 mm⁻¹
c = 10.0851 (2) Å	T = 100 K
α = 102.534 (1)°	0.23 × 0.11 × 0.04 mm
β = 103.365 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2652 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2547 reflections with I > 2σ(I)
T_min = 0.674, T_max = 0.929	R_int = 0.014
5023 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	0 restraints
wR(F²) = 0.038	H-atom parameters constrained
S = 1.08	Δρ_max = 0.29 e Å⁻³
2652 reflections	Δρ_min = −0.39 e Å⁻³
157 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	−0.076971 (16)	0.190459 (13)	0.205336 (13)	0.01438 (5)
Cl1	−0.19397 (6)	0.14396 (5)	−0.04976 (5)	0.02368 (11)
Cl2	−0.21885 (7)	0.34705 (5)	0.35214 (5)	0.02337 (11)
N1	−0.1880 (2)	−0.04027 (16)	0.23109 (16)	0.0155 (3)
N2	0.1417 (2)	0.10346 (17)	0.33828 (16)	0.0171 (3)
N3	0.1925 (2)	0.34724 (17)	0.22918 (16)	0.0187 (3)
C1	−0.3543 (3)	−0.1088 (2)	0.1769 (2)	0.0193 (4)
H1	−0.4351	−0.0611	0.1283	0.023*
C2	−0.4143 (3)	−0.2472 (2)	0.1886 (2)	0.0214 (4)
H2	−0.5330	−0.2941	0.1471	0.026*
C3	−0.2973 (3)	−0.3147 (2)	0.2619 (2)	0.0233 (4)
H3	−0.3346	−0.4091	0.2719	0.028*
C4	−0.1247 (3)	−0.2432 (2)	0.3208 (2)	0.0202 (4)
H4	−0.0429	−0.2874	0.3732	0.024*
C5	−0.0729 (2)	−0.1063 (2)	0.30211 (19)	0.0166 (4)
C6	0.1124 (2)	−0.0244 (2)	0.35613 (19)	0.0173 (4)
C7	0.2517 (3)	−0.0968 (2)	0.4217 (2)	0.0244 (4)
H7A	0.2968	−0.1510	0.3482	0.037*
H7B	0.2025	−0.1639	0.4697	0.037*
H7C	0.3470	−0.0229	0.4902	0.037*
C8	0.3182 (2)	0.1896 (2)	0.3762 (2)	0.0212 (4)
H8A	0.3840	0.1458	0.3117	0.025*
H8B	0.3803	0.1910	0.4737	0.025*
C9	0.3074 (3)	0.3439 (2)	0.3656 (2)	0.0211 (4)
H9A	0.2626	0.3932	0.4431	0.025*
H9B	0.4260	0.3985	0.3773	0.025*
C10	0.2668 (3)	0.2957 (2)	0.1115 (2)	0.0246 (4)
H10A	0.3822	0.3559	0.1282	0.037*
H10B	0.1898	0.3027	0.0233	0.037*
H10C	0.2779	0.1942	0.1045	0.037*
C11	0.1656 (3)	0.4971 (2)	0.2359 (2)	0.0286 (5)
H11A	0.2779	0.5613	0.2511	0.043*
H11B	0.1150	0.5301	0.3140	0.043*
H11C	0.0860	0.4995	0.1470	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01536 (8)	0.01317 (8)	0.01511 (8)	0.00330 (5)	0.00430 (5)	0.00417 (5)
Cl1	0.0233 (2)	0.0301 (3)	0.0159 (2)	0.0048 (2)	0.00258 (18)	0.00570 (19)
Cl2	0.0298 (3)	0.0205 (2)	0.0265 (2)	0.0112 (2)	0.0154 (2)	0.00792 (19)
N1	0.0182 (8)	0.0151 (7)	0.0148 (7)	0.0045 (6)	0.0055 (6)	0.0048 (6)
N2	0.0165 (8)	0.0180 (8)	0.0158 (8)	0.0040 (6)	0.0032 (6)	0.0031 (6)
N3	0.0202 (8)	0.0168 (8)	0.0194 (8)	0.0030 (6)	0.0076 (7)	0.0029 (6)
C1	0.0193 (10)	0.0203 (10)	0.0203 (9)	0.0059 (8)	0.0072 (8)	0.0063 (8)
C2	0.0200 (10)	0.0221 (10)	0.0230 (10)	0.0011 (8)	0.0091 (8)	0.0063 (8)
C3	0.0294 (11)	0.0165 (9)	0.0289 (11)	0.0041 (8)	0.0149 (9)	0.0084 (8)
C4	0.0264 (10)	0.0196 (10)	0.0211 (10)	0.0107 (8)	0.0114 (8)	0.0095 (8)
C5	0.0220 (10)	0.0162 (9)	0.0141 (9)	0.0075 (8)	0.0081 (7)	0.0033 (7)
C6	0.0205 (10)	0.0200 (9)	0.0129 (9)	0.0080 (8)	0.0056 (7)	0.0036 (7)
C7	0.0222 (10)	0.0253 (10)	0.0275 (11)	0.0083 (8)	0.0044 (9)	0.0107 (9)
C8	0.0169 (10)	0.0226 (10)	0.0218 (10)	0.0035 (8)	0.0028 (8)	0.0038 (8)
C9	0.0206 (10)	0.0194 (10)	0.0198 (10)	−0.0004 (8)	0.0057 (8)	−0.0001 (8)
C10	0.0239 (11)	0.0297 (11)	0.0202 (10)	0.0027 (9)	0.0100 (8)	0.0032 (8)
C11	0.0326 (12)	0.0171 (10)	0.0388 (12)	0.0030 (9)	0.0150 (10)	0.0083 (9)

Geometric parameters (Å, º) top

Cd1—N2	2.3188 (15)	C4—C5	1.390 (3)
Cd1—N1	2.3644 (15)	C4—H4	0.9500
Cd1—N3	2.3909 (16)	C5—C6	1.499 (3)
Cd1—Cl1	2.4434 (5)	C6—C7	1.497 (3)
Cd1—Cl2	2.4561 (5)	C7—H7A	0.9800
N1—C1	1.335 (2)	C7—H7B	0.9800
N1—C5	1.350 (2)	C7—H7C	0.9800
N2—C6	1.277 (2)	C8—C9	1.522 (3)
N2—C8	1.459 (2)	C8—H8A	0.9900
N3—C10	1.471 (2)	C8—H8B	0.9900
N3—C11	1.474 (2)	C9—H9A	0.9900
N3—C9	1.478 (2)	C9—H9B	0.9900
C1—C2	1.389 (3)	C10—H10A	0.9800
C1—H1	0.9500	C10—H10B	0.9800
C2—C3	1.379 (3)	C10—H10C	0.9800
C2—H2	0.9500	C11—H11A	0.9800
C3—C4	1.388 (3)	C11—H11B	0.9800
C3—H3	0.9500	C11—H11C	0.9800

N2—Cd1—N1	69.42 (5)	N1—C5—C6	115.96 (16)
N2—Cd1—N3	73.39 (5)	C4—C5—C6	122.77 (17)
N1—Cd1—N3	141.34 (5)	N2—C6—C7	123.96 (18)
N2—Cd1—Cl1	131.13 (4)	N2—C6—C5	116.71 (16)
N1—Cd1—Cl1	98.62 (4)	C7—C6—C5	119.29 (16)
N3—Cd1—Cl1	97.82 (4)	C6—C7—H7A	109.5
N2—Cd1—Cl2	112.49 (4)	C6—C7—H7B	109.5
N1—Cd1—Cl2	100.86 (4)	H7A—C7—H7B	109.5
N3—Cd1—Cl2	102.71 (4)	C6—C7—H7C	109.5
Cl1—Cd1—Cl2	116.315 (17)	H7A—C7—H7C	109.5
C1—N1—C5	119.09 (16)	H7B—C7—H7C	109.5
C1—N1—Cd1	124.01 (12)	N2—C8—C9	109.01 (16)
C5—N1—Cd1	116.87 (12)	N2—C8—H8A	109.9
C6—N2—C8	121.86 (16)	C9—C8—H8A	109.9
C6—N2—Cd1	120.70 (13)	N2—C8—H8B	109.9
C8—N2—Cd1	116.44 (11)	C9—C8—H8B	109.9
C10—N3—C11	110.06 (16)	H8A—C8—H8B	108.3
C10—N3—C9	111.56 (15)	N3—C9—C8	112.34 (15)
C11—N3—C9	108.99 (15)	N3—C9—H9A	109.1
C10—N3—Cd1	110.95 (11)	C8—C9—H9A	109.1
C11—N3—Cd1	110.21 (12)	N3—C9—H9B	109.1
C9—N3—Cd1	104.94 (11)	C8—C9—H9B	109.1
N1—C1—C2	122.72 (18)	H9A—C9—H9B	107.9
N1—C1—H1	118.6	N3—C10—H10A	109.5
C2—C1—H1	118.6	N3—C10—H10B	109.5
C3—C2—C1	118.40 (18)	H10A—C10—H10B	109.5
C3—C2—H2	120.8	N3—C10—H10C	109.5
C1—C2—H2	120.8	H10A—C10—H10C	109.5
C2—C3—C4	119.34 (18)	H10B—C10—H10C	109.5
C2—C3—H3	120.3	N3—C11—H11A	109.5
C4—C3—H3	120.3	N3—C11—H11B	109.5
C3—C4—C5	119.17 (18)	H11A—C11—H11B	109.5
C3—C4—H4	120.4	N3—C11—H11C	109.5
C5—C4—H4	120.4	H11A—C11—H11C	109.5
N1—C5—C4	121.26 (17)	H11B—C11—H11C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···Cl2ⁱ	0.98	2.77	3.679 (2)	155

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[CdCl₂(C₁₁H₁₇N₃)]
M_r	374.58
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.0276 (2), 9.6048 (2), 10.0851 (2)
α, β, γ (°)	102.534 (1), 103.365 (1), 97.850 (1)
V (Å³)	724.09 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.86
Crystal size (mm)	0.23 × 0.11 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.674, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	5023, 2652, 2547
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.038, 1.08
No. of reflections	2652
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.39

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
C7—H7B···Cl2ⁱ	0.98	2.77	3.679 (2)	155

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

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

References

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