Dichlorido(6,6′-dimethyl-2,2′-bipyridine-κ2N,N′)cadmium(II)

Alizadeh, R.; Mohammadi Eshlaghi, P.; Amani, V.

doi:10.1107/S1600536810029399

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m1024

https://doi.org/10.1107/S1600536810029399

Open

access

Dichlorido(6,6′-dimethyl-2,2′-bipyridine-κ²N,N′)cadmium(II)

Robabeh Alizadeh,^a ^* Parisa Mohammadi Eshlaghi ^a and Vahid Amani ^b

^aSchool of Chemistry, Damghan University, Damghan, Iran, and ^bIslamic Azad University, Shahr-e-Rey Branch, Tehran, Iran
^*Correspondence e-mail: robabeh_alizadeh@yahoo.com

(Received 18 July 2010; accepted 23 July 2010; online 31 July 2010)

In the title compound, [CdCl₂(C₁₂H₁₂N₂)], the Cd^II atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from a 6,6′-dimethyl-2,2′-bipyridine ligand and two terminal Cl atoms. Intermolecular C—H⋯Cl hydrogen bonds and π–π stacking interactions between the pyridyl rings [centroid–centroid distance = 3.7337 (18) Å] are present in the crystal structure.

Related literature

For related structures, see: Alizadeh, Kalateh, Ebadi et al. (2009 ); Alizadeh, Kalateh, Khoshtarkib et al. (2009 ); Alizadeh, Khoshtarkib et al. (2009 ); Itoh et al. (2005 ); Kou et al. (2008 ); Onggo et al. (2005 ).

Experimental

Crystal data

[CdCl₂(C₁₂H₁₂N₂)]
M_r = 367.55
Monoclinic, P 2₁ /c
a = 7.6715 (9) Å
b = 10.0970 (16) Å
c = 17.902 (2) Å
β = 97.474 (9)°
V = 1374.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.96 mm⁻¹
T = 298 K
0.50 × 0.25 × 0.17 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.569, T_max = 0.723
9684 measured reflections
3656 independent reflections
3162 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.086
S = 1.08
3656 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N1	2.268 (2)
Cd1—N2	2.2752 (19)
Cd1—Cl1	2.3919 (9)
Cd1—Cl2	2.3885 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1C⋯Cl1ⁱ	0.96	2.76	3.711 (4)	169
C5—H5⋯Cl1ⁱⁱ	0.93	2.79	3.551 (3)	140
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029399/hy2335sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029399/hy2335Isup2.hkl

checkCIF report

Comment top

6,6'-Dimethyl-2,2'-bipyridine (6,6'-dmbipy) is a good bidentate ligand, and numerous complexes with 6,6'-dmbipy have been prepared, such as those of zinc (Alizadeh, Kalateh, Ebadi et al., 2009; Alizadeh, Kalateh, Khoshtarkib, et al., 2009; Alizadeh, Khoshtarkib et al., 2009), copper (Itoh et al., 2005), nickel (Kou et al., 2008) and ruthenium (Onggo et al., 2005). We report herein the synthesis and crystal structure of the title compound.

In the title compound (Fig. 1), the Cd ^II atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from a 6,6'-dmbipy ligand and two terminal Cl atoms. The Cd—N and Cd—Cl bond lengths and angles are normal (Table 1). In the crystal structure, intermolecular C—H···Cl hydrogen bonds (Table 2) and π–π contacts (Fig. 2) between the pyridyl rings, Cg1···Cg2ⁱ [symmetry code: (i) 1-x, -y, 1-z. Cg1 and Cg2 are centroids of the N1, C2—C6 ring and the N2, C7—C11 ring], stabilize the structure, with a centroid–centroid distance of 3.7337 (18) Å.

Related literature top

For related structures, see: Alizadeh, Kalateh, Ebadi et al. (2009); Alizadeh, Kalateh, Khoshtarkib et al. (2009); Alizadeh, Khoshtarkib et al. (2009); Itoh et al. (2005); Kou et al. (2008); Onggo et al. (2005).

Experimental top

A solution of 6,6'-dimethyl-2,2'-bipyridine (0.25 g, 1.33 mmol) in methanol (10 ml) was added to a solution of CdCl₂.H₂O (0.27 g, 1.33 mmol) in methanol (5 ml) at room temperature. Crystals suitable for X-ray diffraction experiment were obtained by methanol diffusion into a colorless solution of the title compound in DMSO after one week (yield: 0.35 g, 71.6%).

Structure description top

For related structures, see: Alizadeh, Kalateh, Ebadi et al. (2009); Alizadeh, Kalateh, Khoshtarkib et al. (2009); Alizadeh, Khoshtarkib et al. (2009); Itoh et al. (2005); Kou et al. (2008); Onggo et al. (2005).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Crystal packing diagram of the title compound. Dashed lines denote hydrogen bonds.

Dichlorido(6,6'-dimethyl-2,2'-bipyridine-κ²N,N')cadmium(II) top

Crystal data top

[CdCl₂(C₁₂H₁₂N₂)]	F(000) = 720
M_r = 367.55	D_x = 1.776 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 899 reflections
a = 7.6715 (9) Å	θ = 2.3–29.2°
b = 10.0970 (16) Å	µ = 1.96 mm⁻¹
c = 17.902 (2) Å	T = 298 K
β = 97.474 (9)°	Block, colorless
V = 1374.9 (3) Å³	0.50 × 0.25 × 0.17 mm
Z = 4

Data collection top

Bruker APEX CCD diffractometer	3656 independent reflections
Radiation source: fine-focus sealed tube	3162 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
φ and ω scans	θ_max = 29.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.569, T_max = 0.723	k = −11→13
9684 measured reflections	l = −24→24

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0364P)² + 0.7364P] where P = (F_o² + 2F_c²)/3
3656 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

[CdCl₂(C₁₂H₁₂N₂)]	V = 1374.9 (3) Å³
M_r = 367.55	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6715 (9) Å	µ = 1.96 mm⁻¹
b = 10.0970 (16) Å	T = 298 K
c = 17.902 (2) Å	0.50 × 0.25 × 0.17 mm
β = 97.474 (9)°

Data collection top

Bruker APEX CCD diffractometer	3656 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3162 reflections with I > 2σ(I)
T_min = 0.569, T_max = 0.723	R_int = 0.045
9684 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.08	Δρ_max = 0.57 e Å⁻³
3656 reflections	Δρ_min = −0.63 e Å⁻³
154 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3527 (5)	0.0531 (4)	0.26805 (18)	0.0737 (9)
H1A	0.4386	0.1215	0.2805	0.088*
H1B	0.2400	0.0927	0.2526	0.088*
H1C	0.3861	0.0002	0.2277	0.088*
C2	0.3427 (4)	−0.0323 (3)	0.33533 (16)	0.0526 (6)
C3	0.3765 (4)	−0.1659 (3)	0.3346 (2)	0.0690 (9)
H3	0.4058	−0.2060	0.2912	0.083*
C4	0.3668 (5)	−0.2393 (3)	0.3977 (3)	0.0754 (11)
H4	0.3912	−0.3296	0.3978	0.090*
C5	0.3202 (4)	−0.1785 (3)	0.4621 (2)	0.0634 (8)
H5	0.3131	−0.2276	0.5055	0.076*
C6	0.2846 (3)	−0.0442 (2)	0.46048 (15)	0.0451 (5)
C7	0.2319 (3)	0.0282 (3)	0.52617 (13)	0.0435 (5)
C8	0.2145 (4)	−0.0343 (3)	0.59409 (17)	0.0613 (8)
H8	0.2401	−0.1239	0.6005	0.074*
C9	0.1589 (5)	0.0381 (4)	0.65159 (17)	0.0698 (9)
H9	0.1458	−0.0026	0.6971	0.084*
C10	0.1233 (4)	0.1690 (4)	0.64177 (16)	0.0638 (8)
H10	0.0852	0.2183	0.6804	0.077*
C11	0.1442 (4)	0.2293 (3)	0.57342 (15)	0.0512 (6)
C12	0.1080 (6)	0.3718 (3)	0.5588 (2)	0.0744 (9)
H12A	0.0164	0.3811	0.5172	0.089*
H12B	0.2127	0.4146	0.5469	0.089*
H12C	0.0715	0.4120	0.6028	0.089*
N1	0.2975 (3)	0.0269 (2)	0.39745 (11)	0.0432 (4)
N2	0.1971 (3)	0.1583 (2)	0.51688 (10)	0.0416 (4)
Cd1	0.23178 (3)	0.245465 (17)	0.402558 (10)	0.04588 (8)
Cl1	0.47640 (12)	0.38850 (9)	0.39295 (5)	0.0758 (2)
Cl2	−0.03250 (11)	0.31365 (9)	0.32689 (4)	0.0646 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.098 (3)	0.074 (2)	0.0528 (16)	0.0060 (19)	0.0223 (16)	−0.0106 (15)
C2	0.0483 (14)	0.0502 (15)	0.0586 (15)	0.0060 (11)	0.0044 (11)	−0.0126 (12)
C3	0.0651 (18)	0.0542 (17)	0.086 (2)	0.0132 (14)	0.0011 (16)	−0.0255 (17)
C4	0.068 (2)	0.0414 (16)	0.112 (3)	0.0141 (13)	−0.006 (2)	−0.0137 (16)
C5	0.0637 (17)	0.0381 (14)	0.084 (2)	0.0048 (12)	−0.0088 (15)	0.0090 (13)
C6	0.0398 (12)	0.0360 (11)	0.0563 (13)	−0.0014 (9)	−0.0060 (10)	0.0041 (10)
C7	0.0396 (11)	0.0452 (13)	0.0438 (12)	−0.0055 (9)	−0.0017 (9)	0.0094 (10)
C8	0.0597 (16)	0.0636 (18)	0.0590 (16)	−0.0095 (14)	0.0019 (13)	0.0260 (14)
C9	0.0691 (19)	0.096 (3)	0.0444 (14)	−0.0182 (18)	0.0075 (13)	0.0219 (16)
C10	0.0610 (17)	0.092 (3)	0.0399 (13)	−0.0105 (16)	0.0103 (11)	−0.0033 (14)
C11	0.0536 (14)	0.0589 (16)	0.0417 (12)	−0.0037 (12)	0.0078 (10)	−0.0053 (11)
C12	0.106 (3)	0.0579 (19)	0.0631 (18)	0.0082 (18)	0.0232 (18)	−0.0126 (15)
N1	0.0445 (10)	0.0377 (10)	0.0469 (10)	0.0011 (8)	0.0041 (8)	−0.0034 (8)
N2	0.0452 (10)	0.0430 (10)	0.0363 (9)	−0.0023 (8)	0.0040 (7)	0.0022 (8)
Cd1	0.05923 (13)	0.03760 (12)	0.04198 (11)	0.00404 (7)	0.01099 (8)	0.00679 (6)
Cl1	0.0785 (5)	0.0607 (5)	0.0887 (6)	−0.0146 (4)	0.0127 (4)	0.0244 (4)
Cl2	0.0668 (4)	0.0701 (5)	0.0562 (4)	0.0142 (4)	0.0048 (3)	0.0153 (3)

Geometric parameters (Å, º) top

C1—C2	1.491 (5)	C8—C9	1.374 (5)
C1—H1A	0.9600	C8—H8	0.9300
C1—H1B	0.9600	C9—C10	1.357 (6)
C1—H1C	0.9600	C9—H9	0.9300
C2—N1	1.347 (3)	C10—C11	1.394 (4)
C2—C3	1.374 (4)	C10—H10	0.9300
C3—C4	1.361 (6)	C11—N2	1.346 (3)
C3—H3	0.9300	C11—C12	1.482 (4)
C4—C5	1.394 (6)	C12—H12A	0.9600
C4—H4	0.9300	C12—H12B	0.9600
C5—C6	1.383 (4)	C12—H12C	0.9600
C5—H5	0.9300	Cd1—N1	2.268 (2)
C6—N1	1.352 (3)	Cd1—N2	2.2752 (19)
C6—C7	1.485 (4)	Cd1—Cl1	2.3919 (9)
C7—N2	1.345 (3)	Cd1—Cl2	2.3885 (8)
C7—C8	1.392 (3)

C2—C1—H1A	109.5	C10—C9—C8	119.9 (3)
C2—C1—H1B	109.5	C10—C9—H9	120.1
H1A—C1—H1B	109.5	C8—C9—H9	120.1
C2—C1—H1C	109.5	C9—C10—C11	119.7 (3)
H1A—C1—H1C	109.5	C9—C10—H10	120.2
H1B—C1—H1C	109.5	C11—C10—H10	120.2
N1—C2—C3	120.8 (3)	N2—C11—C10	120.5 (3)
N1—C2—C1	117.1 (3)	N2—C11—C12	116.9 (3)
C3—C2—C1	122.0 (3)	C10—C11—C12	122.6 (3)
C4—C3—C2	119.8 (3)	C11—C12—H12A	109.5
C4—C3—H3	120.1	C11—C12—H12B	109.5
C2—C3—H3	120.1	H12A—C12—H12B	109.5
C3—C4—C5	119.6 (3)	C11—C12—H12C	109.5
C3—C4—H4	120.2	H12A—C12—H12C	109.5
C5—C4—H4	120.2	H12B—C12—H12C	109.5
C6—C5—C4	119.1 (3)	C2—N1—C6	120.6 (2)
C6—C5—H5	120.5	C2—N1—Cd1	123.18 (18)
C4—C5—H5	120.5	C6—N1—Cd1	116.24 (16)
N1—C6—C5	120.1 (3)	C7—N2—C11	120.1 (2)
N1—C6—C7	117.2 (2)	C7—N2—Cd1	116.38 (16)
C5—C6—C7	122.7 (3)	C11—N2—Cd1	123.52 (18)
N2—C7—C8	120.7 (3)	N1—Cd1—N2	73.28 (8)
N2—C7—C6	116.9 (2)	N1—Cd1—Cl2	115.75 (6)
C8—C7—C6	122.4 (3)	N2—Cd1—Cl2	115.59 (6)
C9—C8—C7	119.2 (3)	N1—Cd1—Cl1	113.82 (6)
C9—C8—H8	120.4	N2—Cd1—Cl1	118.88 (6)
C7—C8—H8	120.4	Cl2—Cd1—Cl1	113.65 (3)

N1—C2—C3—C4	−1.0 (5)	C5—C6—N1—Cd1	179.2 (2)
C1—C2—C3—C4	179.5 (3)	C7—C6—N1—Cd1	−1.0 (3)
C2—C3—C4—C5	1.0 (5)	C8—C7—N2—C11	−0.3 (4)
C3—C4—C5—C6	0.0 (5)	C6—C7—N2—C11	178.2 (2)
C4—C5—C6—N1	−1.0 (4)	C8—C7—N2—Cd1	−179.97 (19)
C4—C5—C6—C7	179.2 (3)	C6—C7—N2—Cd1	−1.4 (3)
N1—C6—C7—N2	1.6 (3)	C10—C11—N2—C7	−0.5 (4)
C5—C6—C7—N2	−178.6 (2)	C12—C11—N2—C7	−179.8 (3)
N1—C6—C7—C8	−179.9 (2)	C10—C11—N2—Cd1	179.1 (2)
C5—C6—C7—C8	−0.1 (4)	C12—C11—N2—Cd1	−0.2 (4)
N2—C7—C8—C9	0.9 (4)	C2—N1—Cd1—N2	178.4 (2)
C6—C7—C8—C9	−177.6 (3)	C6—N1—Cd1—N2	0.18 (16)
C7—C8—C9—C10	−0.5 (5)	C2—N1—Cd1—Cl2	67.6 (2)
C8—C9—C10—C11	−0.3 (5)	C6—N1—Cd1—Cl2	−110.67 (16)
C9—C10—C11—N2	0.8 (5)	C2—N1—Cd1—Cl1	−66.8 (2)
C9—C10—C11—C12	−179.9 (3)	C6—N1—Cd1—Cl1	114.92 (16)
C3—C2—N1—C6	0.1 (4)	C7—N2—Cd1—N1	0.69 (16)
C1—C2—N1—C6	179.5 (3)	C11—N2—Cd1—N1	−179.0 (2)
C3—C2—N1—Cd1	−178.1 (2)	C7—N2—Cd1—Cl2	111.73 (16)
C1—C2—N1—Cd1	1.4 (4)	C11—N2—Cd1—Cl2	−67.9 (2)
C5—C6—N1—C2	0.9 (4)	C7—N2—Cd1—Cl1	−107.72 (16)
C7—C6—N1—C2	−179.3 (2)	C11—N2—Cd1—Cl1	72.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···Cl1ⁱ	0.96	2.76	3.711 (4)	169
C5—H5···Cl1ⁱⁱ	0.93	2.79	3.551 (3)	140

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

Experimental details

Crystal data
Chemical formula	[CdCl₂(C₁₂H₁₂N₂)]
M_r	367.55
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.6715 (9), 10.0970 (16), 17.902 (2)
β (°)	97.474 (9)
V (Å³)	1374.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.96
Crystal size (mm)	0.50 × 0.25 × 0.17

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.569, 0.723
No. of measured, independent and observed [I > 2σ(I)] reflections	9684, 3656, 3162
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.086, 1.08
No. of reflections	3656
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.63

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cd1—N1	2.268 (2)	Cd1—Cl1	2.3919 (9)
Cd1—N2	2.2752 (19)	Cd1—Cl2	2.3885 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···Cl1ⁱ	0.96	2.76	3.711 (4)	169
C5—H5···Cl1ⁱⁱ	0.93	2.79	3.551 (3)	140

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

Acknowledgements

We are grateful to Damghan University for financial support.

References

Alizadeh, R., Kalateh, K., Ebadi, A., Ahmadi, R. & Amani, V. (2009). Acta Cryst. E65, m1250. Web of Science CSD CrossRef IUCr Journals Google Scholar
Alizadeh, R., Kalateh, K., Khoshtarkib, Z., Ahmadi, R. & Amani, V. (2009). Acta Cryst. E65, m1439–m1440. Web of Science CrossRef CAS IUCr Journals Google Scholar
Alizadeh, R., Khoshtarkib, Z., Chegeni, K., Ebadi, A. & Amani, V. (2009). Acta Cryst. E65, m1311. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Itoh, S., Kishikawa, N., Suzuki, T. & Takagi, H. D. (2005). Dalton Trans. pp. 1066–1078. Web of Science CSD CrossRef Google Scholar
Kou, H. Z., Hishiya, S. & Sato, O. (2008). Inorg. Chim. Acta, 361, 2396–2406. Web of Science CSD CrossRef CAS Google Scholar
Onggo, D., Scudder, M. L., Craig, D. C. & Goodwin, H. A. (2005). J. Mol. Struct. 738, 129–136. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar