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

Abstract

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,

• a = 17.161 (2) Å

• b = 9.3572 (12) Å

• c = 16.805 (2) Å

• β = 110.343 (2)°

• V = 2530.2 (6) ų

• 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[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 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.

Supplementary Material

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

supplementary crystallographic information

Comment

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].

Experimental

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.

Refinement

All H atoms were placed in calculated positions and refined as riding with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl groups, and C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for other H atoms.

Figures

Fig. 1.

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

Crystal data

[CdCl2(C14H13N3)2]	F(000) = 1272
Mr = 629.85	Dx = 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

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

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0465P)2 + 0.8626P] where P = (Fo2 + 2Fc2)/3
2741 reflections	(Δ/σ)max = 0.002
170 parameters	Δρmax = 0.67 e Å−3
0 restraints	Δρmin = −0.32 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
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 (Ų)

	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, °)

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 codes: (i) −x+1, y, −z+1/2.