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Acta Cryst. (2007). E63, m1782    [ doi:10.1107/S1600536807025329 ]

Bis[iodidobis(1,10-phenanthroline-[kappa]2N,N')copper(II)] tetraiodidocadmate(II)

M.-L. Cao, X. Fang, Y.-J. Zhang, H.-Y. Yu and J.-D. Wang

Abstract top

A new mixed-metal complex, [CuI(C12H8N2)2]2[CdI4], with an asymmetric unit consisting of one [CuI(phen)2]+ cation (phen = 1,10-phenanthroline) and half of a [CdI4]2- anion lying on a twofold rotation axis, has been synthesized. The Cu2+ ion in the [CuI(phen)2]+ cation is five-coordinated by two bidentate phenanthroline ligands and an iodide ligand. The crystal packing is stabilized by intermolecular C-H...I hydrogen bonds.

Comment top

Considerable attention has been paid to heteronuclear metal complexes. At present, a variety of mixed metal complexes have been reported. (Chesnut et al., 1999. Ferbinteanu et al., 1998. Shiren et al., 2002.). Here, a new mixed metal complex is obtained under low temperature conditions. The asymmetric unit of the title compound, (I), contains one [CuI(phen)2]+ cation and a CdI2 subunit of the CdI4 dianion with the cadmium atom observed on a crystallographic twofold axis. In the cation, four N atoms of two bidentate phenanthroline ligands and one iodo ligand form an approximately trigonal-bipyramidal arrangement around the Cu2+ ion, with atoms I3, N1 and N4 occupying equatorial positions whereas N2 and N3 occupy the axial positions (Fig. 1). The equatorial plane (Table 1) is distorted with angles of 124.07 (9)° (N1—Cu1—I3), 125.98 (9)° (N4—Cu1—I3), and 109.94 (13)° (N1—Cu1—N4). In the crystal structure of (I), the crystal packing is stabilized by intermolecular I—H interactions between I atoms of the anion and H atoms of the phenanthroline ligands with distances of 3.15 Å, as listed in Table 1. In addition, one of the iodine atoms of the anion (I1) is positioned over the adjacent ring of one of the phenanthroline ligands (C13—C17—C24) with a distance of 3.535 Å.

Related literature top

For related literature see: Chesnut et al. (1999); Ferbinteanu et al. (1998); Shiren et al. (2002); Bowmaker et al. (1973); Boys (1988); Boys et al. (1981); Healy et al. (1985); Pallenberg et al. (1995); Yang et al. (2004).

Experimental top

The title compound was prepared at room temperature. Firstly, CdI2 (0.0366 g, 0.1 mmol) and phen (0.018 g, 0.1 mmol) were slowly added to 5 ml DMF and stirred for 30 min. Meanwhile, CuI (0.0191 g, 0.1 mmol) was added to another 5 ml of DMF, followed by slow addition of KI (0.0116 g,0.1 mmol) in 10 ml DMF until the solution became clear, and stirred for 30 min. Then the two solutions were mixed, stirred for 20 min, and filtered. After the solvent was slowly evaporated at −5°C, dark-purple crystals of the title compound weres obtained.

Refinement top

All H atoms were located at calculated positions where U parameters were refined.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
Bis[iodidobis(1,10-phenanthroline-κ2N,N')copper(II)] tetraiodidocadmate(II) top
Crystal data top
[CuI(C12H8N2)2]2[CdI4]F000 = 3200
Mr = 1721.70Dx = 2.250 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C2ycCell parameters from 24621 reflections
a = 21.0726 (5) Åθ = 6.1–55.0º
b = 15.4727 (5) ŵ = 4.93 mm−1
c = 15.5907 (4) ÅT = 173 (2) K
β = 90.991 (1)ºBlock, black
V = 5082.6 (2) Å30.66 × 0.41 × 0.36 mm
Z = 4
Data collection top
Rigaku R-AXIS SPIDER
diffractometer		5821 independent reflections
Radiation source: fine-focus sealed tube5537 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.061
Detector resolution: 10 pixels mm-1θmax = 27.5º
T = 173(2) Kθmin = 3.1º
ω oscillation scansh = −27→27
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −20→18
Tmin = 0.10, Tmax = 0.16l = −20→20
24621 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullOnly H-atom displacement parameters refined
R[F2 > 2σ(F2)] = 0.033  w = 1/[σ2(Fo2) + (0.0235P)2 + 27.9995P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.085(Δ/σ)max = 0.002
S = 1.11Δρmax = 2.18 e Å−3
5821 reflectionsΔρmin = −1.31 e Å−3
295 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00044 (4)
Secondary atom site location: difference Fourier map
Crystal data top
[CuI(C12H8N2)2]2[CdI4]V = 5082.6 (2) Å3
Mr = 1721.70Z = 4
Monoclinic, C2/cMo Kα
a = 21.0726 (5) ŵ = 4.93 mm−1
b = 15.4727 (5) ÅT = 173 (2) K
c = 15.5907 (4) Å0.66 × 0.41 × 0.36 mm
β = 90.991 (1)º
Data collection top
Rigaku R-AXIS SPIDER
diffractometer		5821 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		5537 reflections with I > 2σ(I)
Tmin = 0.10, Tmax = 0.16Rint = 0.061
24621 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033Only H-atom displacement parameters refined
wR(F2) = 0.085  w = 1/[σ2(Fo2) + (0.0235P)2 + 27.9995P]
where P = (Fo2 + 2Fc2)/3
S = 1.11Δρmax = 2.18 e Å−3
5821 reflectionsΔρmin = −1.31 e Å−3
295 parameters
Special details top

Experimental. collimator diameter: 0.800000 mm

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
I10.423976 (12)0.574827 (17)0.144226 (16)0.02418 (9)
I20.564820 (16)0.78122 (2)0.13363 (3)0.05017 (13)
I30.851339 (13)0.54118 (2)0.092126 (18)0.03378 (10)
Cd10.50000.67667 (3)0.25000.03004 (12)
Cu10.78535 (2)0.55003 (3)0.23361 (3)0.02163 (12)
N30.70292 (15)0.5289 (2)0.1721 (2)0.0233 (7)
N40.75284 (15)0.4442 (2)0.3055 (2)0.0214 (6)
N20.86250 (15)0.5681 (2)0.3079 (2)0.0239 (7)
N10.75895 (15)0.6662 (2)0.2927 (2)0.0215 (6)
C10.70786 (18)0.7152 (3)0.2834 (3)0.0240 (8)
H10.67740.69940.24250.029*
C20.69748 (19)0.7896 (3)0.3321 (3)0.0261 (8)
H20.66090.82240.32330.031*
C30.7417 (2)0.8138 (3)0.3929 (3)0.0264 (8)
H30.73540.86320.42570.032*
C40.79673 (19)0.7635 (3)0.4054 (2)0.0242 (8)
C50.8465 (2)0.7822 (3)0.4664 (3)0.0278 (8)
H50.84250.83020.50180.033*
C60.8982 (2)0.7332 (3)0.4742 (3)0.0307 (9)
H60.92940.74760.51470.037*
C70.90659 (19)0.6585 (3)0.4211 (3)0.0263 (8)
C80.9604 (2)0.6047 (3)0.4244 (3)0.0334 (10)
H80.99340.61630.46290.040*
C90.9637 (2)0.5352 (3)0.3707 (3)0.0353 (10)
H90.99900.49910.37280.042*
C100.9137 (2)0.5183 (3)0.3123 (3)0.0315 (9)
H100.91660.47100.27580.038*
C110.80319 (18)0.6898 (3)0.3528 (2)0.0211 (7)
C120.85850 (17)0.6375 (3)0.3612 (2)0.0221 (7)
C130.6792 (2)0.5724 (3)0.1061 (3)0.0315 (9)
H130.70190.61910.08510.038*
C140.6213 (2)0.5511 (3)0.0665 (3)0.0359 (10)
H140.60600.58330.02030.043*
C150.5874 (2)0.4826 (3)0.0962 (3)0.0340 (10)
H150.54910.46730.06990.041*
C160.61076 (18)0.4357 (3)0.1666 (3)0.0270 (8)
C170.57891 (19)0.3634 (3)0.2041 (3)0.0317 (9)
H170.54000.34570.18120.038*
C180.6040 (2)0.3205 (3)0.2716 (3)0.0347 (10)
H180.58200.27370.29400.042*
C190.66377 (19)0.3450 (3)0.3098 (3)0.0272 (8)
C200.6931 (2)0.3022 (3)0.3785 (3)0.0344 (10)
H200.67380.25430.40290.041*
C210.7504 (2)0.3312 (3)0.4097 (3)0.0329 (9)
H210.77030.30330.45560.039*
C220.7788 (2)0.4031 (3)0.3716 (3)0.0259 (8)
H220.81740.42270.39370.031*
C230.66964 (18)0.4619 (3)0.2029 (2)0.0223 (8)
C240.69596 (18)0.4160 (3)0.2747 (2)0.0215 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.02396 (14)0.02735 (15)0.02109 (14)−0.00515 (9)−0.00331 (9)0.00105 (10)
I20.04088 (19)0.03983 (18)0.0688 (3)−0.01745 (14)−0.02675 (17)0.02747 (17)
I30.02672 (15)0.04954 (19)0.02509 (15)0.00118 (11)0.00064 (11)0.00351 (12)
Cd10.0284 (2)0.0233 (2)0.0379 (2)0.000−0.01419 (18)0.000
Cu10.0176 (2)0.0273 (2)0.0198 (2)−0.00080 (17)−0.00559 (17)0.00044 (19)
N30.0210 (15)0.0285 (17)0.0203 (15)0.0005 (13)−0.0034 (12)−0.0005 (14)
N40.0221 (15)0.0256 (16)0.0166 (14)0.0007 (12)−0.0001 (12)−0.0032 (13)
N20.0191 (15)0.0297 (17)0.0227 (16)−0.0014 (13)−0.0051 (12)0.0016 (14)
N10.0179 (15)0.0276 (16)0.0189 (15)−0.0030 (12)−0.0015 (12)0.0052 (13)
C10.0188 (17)0.029 (2)0.0241 (18)−0.0022 (14)−0.0010 (14)0.0052 (16)
C20.0236 (19)0.029 (2)0.026 (2)0.0024 (15)0.0033 (15)0.0067 (17)
C30.033 (2)0.0242 (19)0.0220 (19)−0.0041 (16)0.0059 (16)0.0006 (16)
C40.0267 (19)0.0288 (19)0.0170 (17)−0.0076 (15)0.0010 (14)0.0035 (16)
C50.034 (2)0.033 (2)0.0168 (17)−0.0085 (17)−0.0023 (15)−0.0005 (16)
C60.030 (2)0.041 (2)0.0210 (19)−0.0128 (18)−0.0066 (16)0.0003 (18)
C70.0230 (19)0.035 (2)0.0206 (18)−0.0070 (16)−0.0058 (15)0.0044 (17)
C80.023 (2)0.047 (3)0.030 (2)−0.0036 (18)−0.0103 (16)0.004 (2)
C90.022 (2)0.048 (3)0.036 (2)0.0061 (18)−0.0071 (17)0.005 (2)
C100.025 (2)0.037 (2)0.032 (2)0.0023 (17)−0.0036 (17)−0.0007 (19)
C110.0214 (18)0.0264 (18)0.0156 (16)−0.0062 (14)−0.0002 (13)0.0029 (15)
C120.0202 (17)0.0293 (19)0.0167 (16)−0.0047 (14)−0.0030 (14)0.0044 (15)
C130.032 (2)0.037 (2)0.025 (2)−0.0009 (17)−0.0080 (17)0.0003 (18)
C140.029 (2)0.047 (3)0.031 (2)0.0085 (19)−0.0121 (18)0.000 (2)
C150.023 (2)0.047 (3)0.032 (2)0.0059 (18)−0.0073 (17)−0.013 (2)
C160.0177 (18)0.036 (2)0.027 (2)0.0021 (15)0.0010 (15)−0.0142 (18)
C170.0190 (18)0.041 (2)0.035 (2)−0.0043 (17)0.0045 (16)−0.014 (2)
C180.029 (2)0.039 (2)0.036 (2)−0.0108 (18)0.0109 (18)−0.012 (2)
C190.0259 (19)0.030 (2)0.026 (2)−0.0023 (16)0.0066 (15)−0.0067 (17)
C200.042 (3)0.030 (2)0.032 (2)−0.0050 (18)0.0096 (19)−0.0002 (19)
C210.043 (3)0.033 (2)0.022 (2)0.0033 (19)−0.0035 (17)0.0037 (18)
C220.028 (2)0.030 (2)0.0200 (18)0.0020 (16)−0.0019 (15)−0.0018 (16)
C230.0176 (17)0.032 (2)0.0179 (17)0.0024 (14)0.0024 (13)−0.0083 (15)
C240.0204 (17)0.0261 (18)0.0181 (17)0.0019 (14)0.0039 (14)−0.0068 (15)
Geometric parameters (Å, °) top
I1—Cd12.7709 (3)C7—C121.404 (5)
I2—Cd12.8036 (4)C7—C81.407 (6)
I3—Cu12.6314 (6)C8—C91.365 (7)
Cd1—I1i2.7708 (3)C8—H80.9300
Cd1—I2i2.8036 (4)C9—C101.405 (6)
Cu1—N31.996 (3)C9—H90.9300
Cu1—N21.999 (3)C10—H100.9300
Cu1—N12.099 (3)C11—C121.424 (5)
Cu1—N42.105 (3)C13—C141.397 (6)
N3—C131.321 (5)C13—H130.9300
N3—C231.346 (5)C14—C151.362 (7)
N4—C221.321 (5)C14—H140.9300
N4—C241.356 (5)C15—C161.397 (6)
N2—C101.327 (5)C15—H150.9300
N2—C121.362 (5)C16—C231.414 (5)
N1—C11.323 (5)C16—C171.435 (6)
N1—C111.360 (5)C17—C181.344 (7)
C1—C21.399 (6)C17—H170.9300
C1—H10.9300C18—C191.436 (6)
C2—C31.370 (6)C18—H180.9300
C2—H20.9300C19—C201.394 (7)
C3—C41.407 (6)C19—C241.407 (6)
C3—H30.9300C20—C211.370 (7)
C4—C111.413 (6)C20—H200.9300
C4—C51.433 (5)C21—C221.401 (6)
C5—C61.331 (6)C21—H210.9300
C5—H50.9300C22—H220.9300
C6—C71.434 (6)C23—C241.429 (6)
C6—H60.9300
I1—Cd1—I1i110.681 (18)C9—C8—H8120.2
I1—Cd1—I2i115.477 (9)C7—C8—H8120.2
I1i—Cd1—I2i103.070 (9)C8—C9—C10119.8 (4)
I1—Cd1—I2103.070 (9)C8—C9—H9120.1
I1i—Cd1—I2115.477 (9)C10—C9—H9120.1
I2i—Cd1—I2109.52 (2)N2—C10—C9121.8 (4)
N3—Cu1—N2173.27 (14)N2—C10—H10119.1
N3—Cu1—N196.64 (13)C9—C10—H10119.1
N2—Cu1—N181.10 (13)N1—C11—C4123.0 (4)
N3—Cu1—N480.80 (13)N1—C11—C12117.5 (3)
N2—Cu1—N493.96 (13)C4—C11—C12119.5 (3)
N1—Cu1—N4109.94 (13)N2—C12—C7122.5 (4)
N3—Cu1—I393.26 (10)N2—C12—C11116.8 (3)
N2—Cu1—I393.24 (10)C7—C12—C11120.6 (4)
N1—Cu1—I3124.07 (9)N3—C13—C14122.7 (4)
N4—Cu1—I3125.98 (9)N3—C13—H13118.7
C13—N3—C23118.5 (4)C14—C13—H13118.7
C13—N3—Cu1127.3 (3)C15—C14—C13119.4 (4)
C23—N3—Cu1114.2 (3)C15—C14—H14120.3
C22—N4—C24118.2 (4)C13—C14—H14120.3
C22—N4—Cu1131.0 (3)C14—C15—C16119.4 (4)
C24—N4—Cu1110.8 (3)C14—C15—H15120.3
C10—N2—C12119.0 (3)C16—C15—H15120.3
C10—N2—Cu1127.0 (3)C15—C16—C23117.4 (4)
C12—N2—Cu1113.9 (3)C15—C16—C17124.4 (4)
C1—N1—C11117.9 (4)C23—C16—C17118.2 (4)
C1—N1—Cu1131.6 (3)C18—C17—C16121.6 (4)
C11—N1—Cu1110.4 (3)C18—C17—H17119.2
N1—C1—C2123.2 (4)C16—C17—H17119.2
N1—C1—H1118.4C17—C18—C19121.6 (4)
C2—C1—H1118.4C17—C18—H18119.2
C3—C2—C1119.3 (4)C19—C18—H18119.2
C3—C2—H2120.3C20—C19—C24117.4 (4)
C1—C2—H2120.3C20—C19—C18124.6 (4)
C2—C3—C4119.6 (4)C24—C19—C18118.0 (4)
C2—C3—H3120.2C21—C20—C19119.6 (4)
C4—C3—H3120.2C21—C20—H20120.2
C3—C4—C11116.9 (3)C19—C20—H20120.2
C3—C4—C5125.0 (4)C20—C21—C22119.4 (4)
C11—C4—C5118.1 (4)C20—C21—H21120.3
C6—C5—C4122.3 (4)C22—C21—H21120.3
C6—C5—H5118.8N4—C22—C21122.6 (4)
C4—C5—H5118.8N4—C22—H22118.7
C5—C6—C7121.0 (4)C21—C22—H22118.7
C5—C6—H6119.5N3—C23—C16122.5 (4)
C7—C6—H6119.5N3—C23—C24117.7 (3)
C12—C7—C8117.3 (4)C16—C23—C24119.8 (4)
C12—C7—C6118.4 (4)N4—C24—C19122.9 (4)
C8—C7—C6124.3 (4)N4—C24—C23116.5 (4)
C9—C8—C7119.7 (4)C19—C24—C23120.6 (4)
Symmetry codes: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1···I20.933.163.916 (4)140
C5—H5···I1ii0.933.153.884 (4)138
Symmetry codes: (ii) x+1/2, −y+3/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1···I20.933.163.916 (4)140
C5—H5···I1i0.933.153.884 (4)138
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2.
Acknowledgements top

This work was supported by the Foundations of Fujian Province (No. 2006 F5058) and Fuzhou University (No. XRC-0527).

references
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