Dichlorido{N,N-dimethyl-N′-[1-(pyridin-2-yl)ethyl­idene]ethane-1,2-diamine-κ³ N,N′,N′′}cadmium

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.016

• wR(F ²) = 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

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. 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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

Hydrogen atoms were placed at calculated positions at distances C—H = 0.95, 0.98 and 0.99 ° for aryl, methyl and methylene type H-atoms, respectively, and were treated as riding on their parent atoms, with U_iso(H) = 1.2–1.5 times U_eq(C).

Figures

Fig. 1.

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

Crystal data

[CdCl2(C11H17N3)]	Z = 2
Mr = 374.58	F(000) = 372
Triclinic, P1	Dx = 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

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

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)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.038	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0151P)2 + 0.4207P] where P = (Fo2 + 2Fc2)/3
2652 reflections	(Δ/σ)max = 0.001
157 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.39 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	−0.076971 (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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) −x, −y, −z+1.