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Acta Cryst. (2009). E65, m1245    [ doi:10.1107/S1600536809038124 ]

Dichlorido(2,9-dipropoxy-1,10-phenanthroline-[kappa]2N,N')cadmium(II)

C.-Y. Niu, X.-F. Zheng and Y.-L. Dang

Abstract top

In the title complex, [CdCl2(C18H20N2O2)], the CdII ion is coordinated by two N atoms from a bis-chelating 2,9-dipropoxy-1,10-phenanthroline ligand and two Cl atoms in a distorted tetrahedral environment. The two Cd-Cl bond distances are significantly different from each other and the N-Cd-N bond angle is acute. In the crystal structure, there are [pi]-[pi] stacking interactions between symmetry-related phenanthroline ring systems, with a centroid-centroid distance of 3.585 (3) Å.

Comment top

The compound 1,10-phenanthroline and its derivatives have been used with d10 metals to synthesize some luminescent materials (Arpi, et al., 2006; Bie, et al., 2006). The compound 2,9-diethoxy-1,10-phenanthroline has been shown to possesses antimycoplasmal activity in the presence of copper (Pijper, et al., 1984). Herein, we present the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig.1. The CdII ion is four-coordinated to two nitrogen atoms from one 1,10-phenanthroline ring (N1, N2) and two chlorine atoms (Cl1, Cl2), defining a distorted tetrahedral coordination geometry. The two Cd—Cl bond distances are significantly different from each other. The the N—Zn—N bond angle is acute. In the crystal structure, there are π–π stacking interactions between phenanthroline ring systems with centroid to centroid distances of 3.5847 (1) Å (Fig. 2).

Related literature top

For related literature regarding the coordination chemistry of 1,10-phenanthroline derivatives, see: Arpi et al. (2006); Bie et al. (2006). For synthetic details, see: Pijper et al. (1984).

Experimental top

2,9-Dipropoxy-1,10-phenanthroline was prepared according to the literature procedure (Pijper, et al., 1984). Slow evaporation of a mixture of the ligand (0.027 g, 0.1 mmol) and cadmium dichloride (0.016 g, 0.1 mmol) in 30 ml methanol afforded suitable colourless block crystals in about 7 days (yield about 45%).

Refinement top

C-bound H atoms were placed in calculated positions and refined using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for methylene H atoms and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms]. The final difference Fourier map had a highest peak 0.94 Å from atom C17 and a deepest hole at 0.85 Å from atom H18, but were otherwise featureless.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Packing diagram showing the π-π interaction (purple dotted line). All H atoms have been omitted for clarity.
Dichlorido(2,9-dipropoxy-1,10-phenanthroline-κ2N,N')cadmium(II) top
Crystal data top
[CdCl2(C18H20N2O2)]Dx = 1.591 Mg m−3
Mr = 479.66Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 3326 reflections
Hall symbol: -I 4adθ = 2.6–25.5°
a = 31.3159 (10) ŵ = 1.37 mm−1
c = 8.1662 (5) ÅT = 291 K
V = 8008.5 (6) Å3Needle, colourless
Z = 160.18 × 0.07 × 0.04 mm
F(000) = 3840
Data collection top
Bruker APEXII CCD
diffractometer		3722 independent reflections
Radiation source: fine-focus sealed tube2656 reflections with I > 2σ(I)
graphiteRint = 0.051
φ and ω scansθmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −36→37
Tmin = 0.791, Tmax = 0.947k = −37→29
21000 measured reflectionsl = −8→9
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0421P)2 + 20.3768P]
where P = (Fo2 + 2Fc2)/3
3722 reflections(Δ/σ)max = 0.001
228 parametersΔρmax = 0.80 e Å−3
21 restraintsΔρmin = −0.41 e Å−3
Crystal data top
[CdCl2(C18H20N2O2)]Z = 16
Mr = 479.66Mo Kα radiation
Tetragonal, I41/aµ = 1.37 mm−1
a = 31.3159 (10) ÅT = 291 K
c = 8.1662 (5) Å0.18 × 0.07 × 0.04 mm
V = 8008.5 (6) Å3
Data collection top
Bruker APEXII CCD
diffractometer		3722 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		2656 reflections with I > 2σ(I)
Tmin = 0.791, Tmax = 0.947Rint = 0.051
21000 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.039 w = 1/[σ2(Fo2) + (0.0421P)2 + 20.3768P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.101Δρmax = 0.80 e Å−3
S = 1.01Δρmin = −0.41 e Å−3
3722 reflectionsAbsolute structure: ?
228 parametersFlack parameter: ?
21 restraintsRogers parameter: ?
H-atom parameters constrained
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
xyzUiso*/Ueq
Cd10.329113 (11)0.831007 (11)0.02856 (5)0.05269 (15)
N10.26377 (11)0.80406 (11)−0.0466 (4)0.0434 (9)
N20.32414 (12)0.76370 (11)0.1350 (5)0.0498 (9)
Cl10.37894 (5)0.82330 (5)−0.19572 (19)0.0758 (4)
Cl20.33196 (5)0.89205 (5)0.19815 (19)0.0805 (5)
O10.24631 (11)0.86473 (11)−0.1694 (4)0.0632 (9)
O20.38663 (13)0.77153 (12)0.2600 (5)0.0803 (12)
C10.23473 (14)0.82433 (15)−0.1329 (6)0.0497 (11)
C20.19693 (16)0.80477 (18)−0.1842 (6)0.0606 (13)
H20.17680.8200−0.24400.073*
C30.19006 (16)0.76326 (19)−0.1456 (6)0.0640 (14)
H30.16530.7498−0.18150.077*
C40.22027 (16)0.73999 (15)−0.0509 (6)0.0534 (12)
C50.21500 (19)0.69696 (18)−0.0030 (7)0.0678 (16)
H50.19040.6823−0.03280.081*
C60.2456 (2)0.67679 (17)0.0860 (8)0.0715 (16)
H60.24170.64840.11540.086*
C70.28325 (17)0.69825 (15)0.1348 (6)0.0564 (13)
C80.3164 (2)0.67952 (17)0.2272 (7)0.0697 (16)
H80.31420.65100.25720.084*
C90.3512 (2)0.70209 (17)0.2734 (7)0.0659 (15)
H90.37270.68950.33550.079*
C100.35403 (17)0.74526 (16)0.2245 (6)0.0582 (13)
C110.28890 (15)0.74128 (14)0.0899 (6)0.0474 (11)
C120.25695 (14)0.76273 (14)−0.0050 (5)0.0464 (11)
C130.2158 (2)0.8939 (2)−0.2393 (8)0.0847 (19)
H13A0.19920.8794−0.32280.102*
H13B0.23070.9176−0.29030.102*
C140.1869 (3)0.9102 (3)−0.1088 (12)0.118 (3)
H14A0.17060.8865−0.06520.141*
H14B0.16700.9302−0.15720.141*
C150.2103 (3)0.9323 (3)0.0324 (12)0.133 (3)
H15A0.22970.91250.08260.199*
H15B0.18990.94180.11210.199*
H15C0.22590.9564−0.00890.199*
C160.41947 (19)0.7591 (2)0.3744 (9)0.094 (2)
H16A0.43060.73110.34650.112*
H16B0.40810.75800.48480.112*
C170.4545 (3)0.7927 (3)0.3621 (14)0.155 (4)
H17A0.47650.78530.44070.187*
H17B0.46710.79030.25410.187*
C180.4437 (3)0.8368 (3)0.3878 (16)0.182 (4)
H18A0.42410.84590.30450.272*
H18B0.46910.85380.38250.272*
H18C0.43070.84000.49350.272*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0529 (2)0.0449 (2)0.0603 (3)−0.00643 (15)−0.00647 (17)−0.00164 (17)
N10.044 (2)0.041 (2)0.045 (2)0.0000 (16)−0.0002 (17)−0.0051 (17)
N20.056 (2)0.042 (2)0.052 (2)0.0049 (18)−0.0024 (19)−0.0005 (18)
Cl10.0642 (8)0.0880 (10)0.0751 (10)−0.0247 (7)0.0081 (7)−0.0212 (8)
Cl20.0959 (11)0.0639 (9)0.0818 (10)−0.0271 (8)0.0134 (8)−0.0216 (8)
O10.059 (2)0.060 (2)0.071 (2)0.0051 (17)−0.0177 (18)0.0077 (18)
O20.073 (3)0.070 (3)0.098 (3)0.009 (2)−0.033 (2)0.009 (2)
C10.046 (3)0.058 (3)0.045 (3)0.001 (2)−0.003 (2)−0.005 (2)
C20.051 (3)0.074 (4)0.057 (3)0.001 (3)−0.009 (2)−0.010 (3)
C30.050 (3)0.084 (4)0.058 (3)−0.015 (3)0.005 (3)−0.022 (3)
C40.056 (3)0.055 (3)0.049 (3)−0.010 (2)0.013 (2)−0.011 (2)
C50.071 (4)0.060 (3)0.073 (4)−0.022 (3)0.023 (3)−0.018 (3)
C60.094 (4)0.043 (3)0.078 (4)−0.018 (3)0.033 (4)−0.011 (3)
C70.075 (3)0.041 (3)0.053 (3)0.000 (2)0.021 (3)−0.004 (2)
C80.100 (5)0.042 (3)0.067 (4)0.012 (3)0.029 (3)0.005 (3)
C90.082 (4)0.056 (3)0.060 (3)0.024 (3)0.008 (3)0.010 (3)
C100.061 (3)0.055 (3)0.058 (3)0.010 (2)0.001 (3)0.002 (3)
C110.061 (3)0.037 (2)0.044 (3)−0.004 (2)0.015 (2)−0.006 (2)
C120.049 (3)0.046 (3)0.045 (3)−0.005 (2)0.009 (2)−0.008 (2)
C130.080 (4)0.080 (4)0.094 (5)0.018 (3)−0.021 (4)0.017 (4)
C140.101 (6)0.116 (6)0.136 (7)0.036 (5)0.000 (6)0.013 (6)
C150.142 (8)0.119 (7)0.138 (8)0.032 (6)0.017 (6)−0.025 (6)
C160.076 (4)0.101 (5)0.104 (5)0.015 (4)−0.034 (4)0.017 (4)
C170.111 (6)0.151 (6)0.204 (8)0.025 (5)−0.095 (6)−0.038 (6)
C180.170 (8)0.168 (7)0.207 (8)−0.013 (6)−0.038 (7)−0.011 (7)
Geometric parameters (Å, °) top
Cd1—N22.285 (4)C7—C81.411 (8)
Cd1—N12.297 (4)C8—C91.353 (8)
Cd1—Cl22.3623 (14)C8—H80.9300
Cd1—Cl12.4182 (15)C9—C101.412 (7)
N1—C11.314 (5)C9—H90.9300
N1—C121.355 (5)C11—C121.433 (6)
N2—C101.321 (6)C13—C141.488 (10)
N2—C111.359 (6)C13—H13A0.9700
O1—C11.349 (6)C13—H13B0.9700
O1—C131.439 (6)C14—C151.530 (11)
O2—C101.343 (6)C14—H14A0.9700
O2—C161.443 (6)C14—H14B0.9700
C1—C21.397 (7)C15—H15A0.9600
C2—C31.355 (7)C15—H15B0.9600
C2—H20.9300C15—H15C0.9600
C3—C41.423 (7)C16—C171.524 (8)
C3—H30.9300C16—H16A0.9700
C4—C121.403 (6)C16—H16B0.9700
C4—C51.413 (7)C17—C181.436 (8)
C5—C61.358 (8)C17—H17A0.9700
C5—H50.9300C17—H17B0.9700
C6—C71.415 (7)C18—H18A0.9600
C6—H60.9300C18—H18B0.9600
C7—C111.408 (6)C18—H18C0.9600
N2—Cd1—N172.66 (13)O2—C10—C9125.0 (5)
N2—Cd1—Cl2121.73 (11)N2—C11—C7121.7 (5)
N1—Cd1—Cl2119.18 (10)N2—C11—C12118.1 (4)
N2—Cd1—Cl1103.88 (10)C7—C11—C12120.1 (4)
N1—Cd1—Cl1109.63 (9)N1—C12—C4123.1 (4)
Cl2—Cd1—Cl1120.03 (5)N1—C12—C11118.3 (4)
C1—N1—C12119.1 (4)C4—C12—C11118.6 (4)
C1—N1—Cd1125.6 (3)O1—C13—C14109.7 (5)
C12—N1—Cd1115.1 (3)O1—C13—H13A109.7
C10—N2—C11120.0 (4)C14—C13—H13A109.7
C10—N2—Cd1124.4 (3)O1—C13—H13B109.7
C11—N2—Cd1115.4 (3)C14—C13—H13B109.7
C1—O1—C13120.3 (4)H13A—C13—H13B108.2
C10—O2—C16121.0 (4)C13—C14—C15113.8 (7)
N1—C1—O1112.7 (4)C13—C14—H14A108.8
N1—C1—C2122.4 (5)C15—C14—H14A108.8
O1—C1—C2124.9 (5)C13—C14—H14B108.8
C3—C2—C1119.0 (5)C15—C14—H14B108.8
C3—C2—H2120.5H14A—C14—H14B107.7
C1—C2—H2120.5C14—C15—H15A109.5
C2—C3—C4120.8 (5)C14—C15—H15B109.5
C2—C3—H3119.6H15A—C15—H15B109.5
C4—C3—H3119.6C14—C15—H15C109.5
C12—C4—C5120.4 (5)H15A—C15—H15C109.5
C12—C4—C3115.5 (4)H15B—C15—H15C109.5
C5—C4—C3124.1 (5)O2—C16—C17106.4 (5)
C6—C5—C4120.6 (5)O2—C16—H16A110.4
C6—C5—H5119.7C17—C16—H16A110.4
C4—C5—H5119.7O2—C16—H16B110.4
C5—C6—C7121.2 (5)C17—C16—H16B110.4
C5—C6—H6119.4H16A—C16—H16B108.6
C7—C6—H6119.4C18—C17—C16119.1 (8)
C11—C7—C8116.4 (5)C18—C17—H17A107.5
C11—C7—C6119.1 (5)C16—C17—H17A107.5
C8—C7—C6124.5 (5)C18—C17—H17B107.5
C9—C8—C7121.6 (5)C16—C17—H17B107.5
C9—C8—H8119.2H17A—C17—H17B107.0
C7—C8—H8119.2C17—C18—H18A109.5
C8—C9—C10118.2 (5)C17—C18—H18B109.5
C8—C9—H9120.9H18A—C18—H18B109.5
C10—C9—H9120.9C17—C18—H18C109.5
N2—C10—O2113.0 (4)H18A—C18—H18C109.5
N2—C10—C9122.0 (5)H18B—C18—H18C109.5
N2—Cd1—N1—C1179.1 (4)Cd1—N2—C10—O25.6 (6)
Cl2—Cd1—N1—C161.9 (4)C11—N2—C10—C91.4 (7)
Cl1—Cd1—N1—C1−82.0 (4)Cd1—N2—C10—C9−173.5 (4)
N2—Cd1—N1—C12−5.3 (3)C16—O2—C10—N2171.6 (5)
Cl2—Cd1—N1—C12−122.5 (3)C16—O2—C10—C9−9.3 (8)
Cl1—Cd1—N1—C1293.6 (3)C8—C9—C10—N2−0.6 (8)
N1—Cd1—N2—C10−179.2 (4)C8—C9—C10—O2−179.6 (5)
Cl2—Cd1—N2—C10−65.1 (4)C10—N2—C11—C7−0.6 (7)
Cl1—Cd1—N2—C1074.2 (4)Cd1—N2—C11—C7174.7 (3)
N1—Cd1—N2—C115.8 (3)C10—N2—C11—C12179.0 (4)
Cl2—Cd1—N2—C11119.8 (3)Cd1—N2—C11—C12−5.7 (5)
Cl1—Cd1—N2—C11−100.8 (3)C8—C7—C11—N2−0.8 (7)
C12—N1—C1—O1−178.1 (4)C6—C7—C11—N2179.1 (4)
Cd1—N1—C1—O1−2.7 (6)C8—C7—C11—C12179.6 (4)
C12—N1—C1—C2−0.2 (7)C6—C7—C11—C12−0.5 (7)
Cd1—N1—C1—C2175.2 (3)C1—N1—C12—C40.6 (7)
C13—O1—C1—N1−169.7 (5)Cd1—N1—C12—C4−175.3 (3)
C13—O1—C1—C212.5 (7)C1—N1—C12—C11−179.7 (4)
N1—C1—C2—C3−0.8 (8)Cd1—N1—C12—C114.5 (5)
O1—C1—C2—C3176.8 (5)C5—C4—C12—N1−179.8 (4)
C1—C2—C3—C41.5 (8)C3—C4—C12—N10.1 (7)
C2—C3—C4—C12−1.1 (7)C5—C4—C12—C110.5 (7)
C2—C3—C4—C5178.7 (5)C3—C4—C12—C11−179.7 (4)
C12—C4—C5—C6−1.0 (7)N2—C11—C12—N10.8 (6)
C3—C4—C5—C6179.2 (5)C7—C11—C12—N1−179.6 (4)
C4—C5—C6—C70.7 (8)N2—C11—C12—C4−179.4 (4)
C5—C6—C7—C110.0 (8)C7—C11—C12—C40.2 (6)
C5—C6—C7—C8180.0 (5)C1—O1—C13—C1477.9 (7)
C11—C7—C8—C91.5 (7)O1—C13—C14—C1557.3 (9)
C6—C7—C8—C9−178.4 (5)C10—O2—C16—C17170.5 (6)
C7—C8—C9—C10−0.8 (8)O2—C16—C17—C1855.8 (12)
C11—N2—C10—O2−179.6 (4)
Table 1
Selected geometric parameters (Å, °) top
Cd1—N22.285 (4)Cd1—Cl22.3623 (14)
Cd1—N12.297 (4)Cd1—Cl12.4182 (15)
N2—Cd1—N172.66 (13)N2—Cd1—Cl1103.88 (10)
N2—Cd1—Cl2121.73 (11)N1—Cd1—Cl1109.63 (9)
N1—Cd1—Cl2119.18 (10)Cl2—Cd1—Cl1120.03 (5)
Acknowledgements top

The authors are grateful to Mrs Li (Wuhan University) for her assistance with the X-ray crystallographic analysis.

references
References top

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