Dichloridobis(2-dimethyl­amino-1,10-phenanthroline)cadmium(II)

Li, H.L.

doi:10.1107/S1600536809032358

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1150

doi:10.1107/S1600536809032358

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Dichloridobis(2-dimethylamino-1,10-phenanthroline)cadmium(II)

Hong Liang Li ^a ^*

^aDepartment of Chemistry, Dezhou University, Dezhou 253023, People's Republic of China
^*Correspondence e-mail: hongliangl1968@yahoo.com.cn

(Received 10 August 2009; accepted 15 August 2009; online 29 August 2009)

In the title complex, [CdCl₂(C₁₄H₁₃N₃)₂], the Cd^II ion lies on a twofold rotation axis and assumes a distorted octahedral CdN₄Cl₂ coordination geometry. There is a π–π stacking interaction between the symmetry-related 1,10-phenanthroline ligands with a centroid–centroid distance of 3.5578 (16) Å and a perpendicular distance of 3.445 (su?) Å between the relevant rings.

Related literature

For background to the use of 1,10-phenanthroline derivatives in coordination chemistry, see: Liu et al. (2008 ). For a related structure, see: Zhang et al. (2008 ).

Experimental

Crystal data

[CdCl₂(C₁₄H₁₃N₃)₂]
M_r = 629.85
Monoclinic, C 2/c
a = 17.161 (2) Å
b = 9.3572 (12) Å
c = 16.805 (2) Å
β = 110.343 (2)°
V = 2530.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.11 mm⁻¹
T = 298 K
0.36 × 0.19 × 0.17 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.692, T_max = 0.834
7147 measured reflections
2741 independent reflections
2512 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.078
S = 1.04
2741 reflections
170 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809032358/bt5029sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032358/bt5029Isup2.hkl

checkCIF report

Comment top

Derivatives of 1,10-phenanthroline play an important role in modern coordination chemistry (Liu et al., 2008), and only one complex with 2-(dimethyl)amine-1,10-phenanthroline as ligand has been published (Zhang et al., 2008) so far. Now the crystal structure of title complex, which is the second complex dealing with 2-(dimethyl)amine-1,10-phenanthroline as ligand, is reported.

Fig. 1 and Table 1 show the coordination structure, with the Cd centre located on a crystallographic twofold axis. It is in a distorted octahedral geometry. There is a π-π stacking interaction involving symmetry related 1,10-phenanthroline ligands, with the relevant distances being Cg1···Cg2ⁱ = 3.5578 (16) Å and Cg1···Cg2ⁱ_perp = 3.445 Å and α = 3.82° [symmetry code: (i) 1-X, -Y, -Z; Cg1 and Cg2 are the centroids of C1C2C5-C7/N2 ring and C6—C11 ring, respectively; Cg1···Cg2¹_perp is the perpendicular distance from ring Cg1 to ring Cg2ⁱ; α is the dihedral between ring plane Cg1 and ring plane Cg2ⁱ].

Related literature top

For background to the use of 1,10-phenanthroline derivatives in coordination chemistry, see: Liu et al. (2008). For a related structure, see: Zhang et al. (2008).

Experimental top

10 ml me thanol solution of 2-(dimethyl)amine-1,10-phenanthroline (0.1438 g, 0.644 mmol) was added into 5 ml H₂O solution of cadmium chloride (0.1485 g, 0.650 mmol), and the mixed solution was stirred for a few minutes. The yellow single crystals were obtained after the filtrate had been allowed to stand at room temperature for two weeks.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

Fig. 1. Coordination diagram of title complex with atom-numbering scheme for only asymmetric unit, and displacement ellipsoids being at the 30% probability level

Dichloridobis(2-dimethylamino-1,10-phenanthroline)cadmium(II) top

Crystal data top

[CdCl₂(C₁₄H₁₃N₃)₂]	F(000) = 1272
M_r = 629.85	D_x = 1.653 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3730 reflections
a = 17.161 (2) Å	θ = 2.5–27.9°
b = 9.3572 (12) Å	µ = 1.11 mm⁻¹
c = 16.805 (2) Å	T = 298 K
β = 110.343 (2)°	Block, yellow
V = 2530.2 (6) Å³	0.36 × 0.19 × 0.17 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2741 independent reflections
Radiation source: fine-focus sealed tube	2512 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −21→21
T_min = 0.692, T_max = 0.834	k = −6→11
7147 measured reflections	l = −21→21

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0465P)² + 0.8626P] where P = (F_o² + 2F_c²)/3
2741 reflections	(Δ/σ)_max = 0.002
170 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[CdCl₂(C₁₄H₁₃N₃)₂]	V = 2530.2 (6) Å³
M_r = 629.85	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.161 (2) Å	µ = 1.11 mm⁻¹
b = 9.3572 (12) Å	T = 298 K
c = 16.805 (2) Å	0.36 × 0.19 × 0.17 mm
β = 110.343 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	2741 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2512 reflections with I > 2σ(I)
T_min = 0.692, T_max = 0.834	R_int = 0.026
7147 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.04	Δρ_max = 0.67 e Å⁻³
2741 reflections	Δρ_min = −0.32 e Å⁻³
170 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
C1	0.53071 (18)	−0.2662 (3)	0.14483 (19)	0.0453 (6)
H1	0.5561	−0.3519	0.1680	0.054*
C2	0.55652 (14)	−0.1339 (3)	0.18970 (16)	0.0366 (5)
C3	0.6672 (2)	−0.2607 (3)	0.3007 (2)	0.0597 (8)
H3A	0.6275	−0.3371	0.2899	0.090*
H3B	0.6916	−0.2451	0.3608	0.090*
H3C	0.7099	−0.2855	0.2785	0.090*
C4	0.67199 (15)	−0.0021 (3)	0.29048 (17)	0.0442 (6)
H4A	0.6495	0.0734	0.2503	0.066*
H4B	0.7293	−0.0169	0.2972	0.066*
H4C	0.6679	0.0237	0.3442	0.066*
C5	0.46892 (18)	−0.2641 (3)	0.0683 (2)	0.0468 (6)
H5	0.4529	−0.3484	0.0377	0.056*
C6	0.42857 (14)	−0.1347 (3)	0.03479 (15)	0.0378 (5)
C7	0.45301 (13)	−0.0134 (2)	0.08600 (14)	0.0324 (5)
C8	0.36608 (16)	−0.1257 (3)	−0.04727 (16)	0.0483 (7)
H8	0.3509	−0.2077	−0.0804	0.058*
C9	0.32884 (17)	−0.0021 (3)	−0.07762 (17)	0.0507 (7)
H9	0.2884	0.0010	−0.1315	0.061*
C10	0.35021 (14)	0.1243 (3)	−0.02876 (15)	0.0410 (6)
C11	0.40983 (14)	0.1189 (3)	0.05419 (14)	0.0346 (5)
C12	0.39202 (17)	0.3585 (3)	0.07410 (18)	0.0488 (6)
H12	0.4049	0.4381	0.1094	0.059*
C13	0.31509 (18)	0.2587 (4)	−0.05904 (18)	0.0499 (7)
H13	0.2766	0.2671	−0.1137	0.060*
C14	0.33721 (18)	0.3755 (3)	−0.00872 (18)	0.0531 (7)
H14	0.3163	0.4652	−0.0290	0.064*
Cd1	0.5000	0.20663 (2)	0.2500	0.03387 (10)
Cl1	0.61434 (4)	0.36432 (7)	0.22647 (5)	0.05136 (18)
N1	0.62589 (13)	−0.1317 (2)	0.26011 (15)	0.0465 (5)
N2	0.51504 (11)	−0.0126 (2)	0.16313 (12)	0.0339 (4)
N3	0.42685 (13)	0.2347 (2)	0.10524 (14)	0.0396 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0450 (15)	0.0335 (13)	0.0594 (17)	0.0015 (11)	0.0208 (13)	0.0007 (12)
C2	0.0310 (11)	0.0353 (12)	0.0446 (13)	−0.0017 (9)	0.0144 (10)	−0.0014 (10)
C3	0.0533 (18)	0.0496 (16)	0.068 (2)	0.0181 (14)	0.0110 (16)	0.0104 (15)
C4	0.0343 (12)	0.0454 (14)	0.0472 (14)	0.0030 (11)	0.0069 (11)	−0.0062 (12)
C5	0.0462 (15)	0.0371 (13)	0.0596 (17)	−0.0105 (11)	0.0216 (14)	−0.0121 (12)
C6	0.0340 (12)	0.0406 (13)	0.0390 (12)	−0.0075 (10)	0.0130 (10)	−0.0056 (11)
C7	0.0285 (11)	0.0375 (12)	0.0322 (11)	−0.0063 (9)	0.0117 (9)	−0.0011 (9)
C8	0.0455 (14)	0.0565 (17)	0.0404 (14)	−0.0104 (13)	0.0118 (12)	−0.0146 (13)
C9	0.0451 (15)	0.0664 (19)	0.0334 (13)	−0.0081 (13)	0.0045 (11)	−0.0037 (13)
C10	0.0317 (12)	0.0576 (16)	0.0340 (12)	−0.0023 (11)	0.0117 (10)	0.0045 (12)
C11	0.0303 (11)	0.0406 (13)	0.0340 (11)	−0.0070 (10)	0.0124 (9)	−0.0019 (10)
C12	0.0505 (15)	0.0382 (14)	0.0493 (15)	0.0040 (12)	0.0066 (12)	0.0062 (12)
C13	0.0396 (14)	0.0670 (18)	0.0368 (14)	0.0022 (13)	0.0053 (11)	0.0113 (13)
C14	0.0520 (16)	0.0485 (16)	0.0535 (16)	0.0080 (13)	0.0115 (13)	0.0168 (14)
Cd1	0.03261 (15)	0.02812 (14)	0.03351 (15)	0.000	0.00217 (10)	0.000
Cl1	0.0486 (4)	0.0394 (4)	0.0652 (4)	−0.0099 (3)	0.0188 (3)	−0.0034 (3)
N1	0.0360 (11)	0.0370 (12)	0.0562 (13)	0.0051 (9)	0.0029 (10)	0.0034 (10)
N2	0.0299 (9)	0.0336 (10)	0.0356 (10)	−0.0019 (8)	0.0080 (8)	−0.0006 (8)
N3	0.0395 (11)	0.0342 (10)	0.0406 (12)	0.0013 (9)	0.0083 (9)	0.0032 (9)

Geometric parameters (Å, º) top

C1—C5	1.353 (4)	C8—C9	1.334 (4)
C1—C2	1.437 (4)	C8—H8	0.9300
C1—H1	0.9300	C9—C10	1.413 (4)
C2—N2	1.332 (3)	C9—H9	0.9300
C2—N1	1.356 (3)	C10—C13	1.412 (4)
C3—N1	1.445 (4)	C10—C11	1.415 (3)
C3—H3A	0.9600	C11—N3	1.349 (3)
C3—H3B	0.9600	C12—N3	1.325 (3)
C3—H3C	0.9600	C12—C14	1.392 (4)
C4—N1	1.441 (3)	C12—H12	0.9300
C4—H4A	0.9600	C13—C14	1.353 (4)
C4—H4B	0.9600	C13—H13	0.9300
C4—H4C	0.9600	C14—H14	0.9300
C5—C6	1.411 (4)	Cd1—N3ⁱ	2.332 (2)
C5—H5	0.9300	Cd1—N3	2.332 (2)
C6—C7	1.398 (3)	Cd1—N2ⁱ	2.582 (2)
C6—C8	1.425 (3)	Cd1—N2	2.582 (2)
C7—N2	1.362 (3)	Cd1—Cl1	2.5928 (7)
C7—C11	1.446 (3)	Cd1—Cl1ⁱ	2.5928 (7)

C5—C1—C2	118.9 (3)	N3—C11—C10	121.4 (2)
C5—C1—H1	120.6	N3—C11—C7	118.8 (2)
C2—C1—H1	120.6	C10—C11—C7	119.8 (2)
N2—C2—N1	118.9 (2)	N3—C12—C14	123.4 (3)
N2—C2—C1	121.8 (2)	N3—C12—H12	118.3
N1—C2—C1	119.2 (2)	C14—C12—H12	118.3
N1—C3—H3A	109.5	C14—C13—C10	120.2 (2)
N1—C3—H3B	109.5	C14—C13—H13	119.9
H3A—C3—H3B	109.5	C10—C13—H13	119.9
N1—C3—H3C	109.5	C13—C14—C12	118.6 (3)
H3A—C3—H3C	109.5	C13—C14—H14	120.7
H3B—C3—H3C	109.5	C12—C14—H14	120.7
N1—C4—H4A	109.5	N3ⁱ—Cd1—N3	167.08 (10)
N1—C4—H4B	109.5	N3ⁱ—Cd1—N2ⁱ	67.85 (7)
H4A—C4—H4B	109.5	N3—Cd1—N2ⁱ	123.76 (7)
N1—C4—H4C	109.5	N3ⁱ—Cd1—N2	123.76 (7)
H4A—C4—H4C	109.5	N3—Cd1—N2	67.85 (7)
H4B—C4—H4C	109.5	N2ⁱ—Cd1—N2	74.81 (9)
C1—C5—C6	120.4 (3)	N3ⁱ—Cd1—Cl1	86.19 (6)
C1—C5—H5	119.8	N3—Cd1—Cl1	86.47 (6)
C6—C5—H5	119.8	N2ⁱ—Cd1—Cl1	140.17 (4)
C7—C6—C5	116.8 (2)	N2—Cd1—Cl1	97.82 (5)
C7—C6—C8	120.8 (2)	N3ⁱ—Cd1—Cl1ⁱ	86.47 (6)
C5—C6—C8	122.5 (2)	N3—Cd1—Cl1ⁱ	86.19 (6)
N2—C7—C6	123.9 (2)	N2ⁱ—Cd1—Cl1ⁱ	97.82 (5)
N2—C7—C11	118.5 (2)	N2—Cd1—Cl1ⁱ	140.17 (4)
C6—C7—C11	117.5 (2)	Cl1—Cd1—Cl1ⁱ	110.63 (3)
C9—C8—C6	121.4 (3)	C2—N1—C4	122.0 (2)
C9—C8—H8	119.3	C2—N1—C3	122.5 (2)
C6—C8—H8	119.3	C4—N1—C3	114.6 (2)
C8—C9—C10	120.7 (2)	C2—N2—C7	117.7 (2)
C8—C9—H9	119.7	C2—N2—Cd1	129.38 (16)
C10—C9—H9	119.7	C7—N2—Cd1	110.11 (14)
C13—C10—C11	117.3 (3)	C12—N3—C11	118.9 (2)
C13—C10—C9	123.0 (2)	C12—N3—Cd1	121.04 (18)
C11—C10—C9	119.7 (2)	C11—N3—Cd1	119.46 (16)

C5—C1—C2—N2	8.2 (4)	N1—C2—N2—Cd1	−30.5 (3)
C5—C1—C2—N1	−170.5 (3)	C1—C2—N2—Cd1	150.79 (19)
C2—C1—C5—C6	−2.3 (4)	C6—C7—N2—C2	2.4 (3)
C1—C5—C6—C7	−2.9 (4)	C11—C7—N2—C2	−177.1 (2)
C1—C5—C6—C8	176.8 (3)	C6—C7—N2—Cd1	−160.33 (18)
C5—C6—C7—N2	3.1 (3)	C11—C7—N2—Cd1	20.2 (2)
C8—C6—C7—N2	−176.6 (2)	N3ⁱ—Cd1—N2—C2	7.3 (2)
C5—C6—C7—C11	−177.4 (2)	N3—Cd1—N2—C2	−179.2 (2)
C8—C6—C7—C11	2.9 (3)	N2ⁱ—Cd1—N2—C2	−42.08 (16)
C7—C6—C8—C9	−0.3 (4)	Cl1—Cd1—N2—C2	97.91 (18)
C5—C6—C8—C9	−180.0 (3)	Cl1ⁱ—Cd1—N2—C2	−126.03 (17)
C6—C8—C9—C10	−0.3 (4)	N3ⁱ—Cd1—N2—C7	167.33 (14)
C8—C9—C10—C13	177.5 (3)	N3—Cd1—N2—C7	−19.10 (14)
C8—C9—C10—C11	−2.0 (4)	N2ⁱ—Cd1—N2—C7	117.98 (17)
C13—C10—C11—N3	6.0 (3)	Cl1—Cd1—N2—C7	−102.02 (14)
C9—C10—C11—N3	−174.5 (2)	Cl1ⁱ—Cd1—N2—C7	34.03 (18)
C13—C10—C11—C7	−174.8 (2)	C14—C12—N3—C11	1.1 (4)
C9—C10—C11—C7	4.7 (4)	C14—C12—N3—Cd1	−169.7 (2)
N2—C7—C11—N3	−6.3 (3)	C10—C11—N3—C12	−5.8 (4)
C6—C7—C11—N3	174.1 (2)	C7—C11—N3—C12	175.0 (2)
N2—C7—C11—C10	174.5 (2)	C10—C11—N3—Cd1	165.14 (17)
C6—C7—C11—C10	−5.1 (3)	C7—C11—N3—Cd1	−14.1 (3)
C11—C10—C13—C14	−1.5 (4)	N3ⁱ—Cd1—N3—C12	−16.5 (2)
C9—C10—C13—C14	179.0 (3)	N2ⁱ—Cd1—N3—C12	135.9 (2)
C10—C13—C14—C12	−2.9 (4)	N2—Cd1—N3—C12	−171.9 (2)
N3—C12—C14—C13	3.2 (5)	Cl1—Cd1—N3—C12	−72.0 (2)
N2—C2—N1—C4	−21.3 (4)	Cl1ⁱ—Cd1—N3—C12	39.0 (2)
C1—C2—N1—C4	157.4 (2)	N3ⁱ—Cd1—N3—C11	172.75 (18)
N2—C2—N1—C3	170.2 (3)	N2ⁱ—Cd1—N3—C11	−34.9 (2)
C1—C2—N1—C3	−11.0 (4)	N2—Cd1—N3—C11	17.35 (17)
N1—C2—N2—C7	170.7 (2)	Cl1—Cd1—N3—C11	117.28 (18)
C1—C2—N2—C7	−8.0 (3)	Cl1ⁱ—Cd1—N3—C11	−131.75 (18)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[CdCl₂(C₁₄H₁₃N₃)₂]
M_r	629.85
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	17.161 (2), 9.3572 (12), 16.805 (2)
β (°)	110.343 (2)
V (Å³)	2530.2 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.11
Crystal size (mm)	0.36 × 0.19 × 0.17

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.692, 0.834
No. of measured, independent and observed [I > 2σ(I)] reflections	7147, 2741, 2512
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.078, 1.04
No. of reflections	2741
No. of parameters	170
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and local programs.

References

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, Q. S., Liu, L. D. & Shi, J. M. (2008). Acta Cryst. C64, m58–m60. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, S. G., Hu, T. Q. & Li, H. (2008). Acta Cryst. E64, m769. Web of Science CSD CrossRef IUCr Journals Google Scholar