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Acta Cryst. (2007). E63, m2957    [ doi:10.1107/S160053680705074X ]

Bis{4-[4-(dimethylamino)styryl]-1-ethylpyridinium} di-[mu]-iodido-bis[iodidocuprate(II)]

Y.-F. Liu, J.-Z. Chen and C.-C. Huang

Abstract top

The title compound, (C17H21N2)2[Cu2I4], consists of an organic cation, 4-[4-(dimethylamino)stryl]-1-ethylpyrdinium, and an inorganic anion, [Cu2I4]2-. The Cu(I) atom exhibits a trigonal coordination. The anions form discrete centrosymmetric dimers about inversion centers and are surrounded by the cations.

Comment top

Organic-inorganic complex materials have received extensive attention in recent years owing to their interesting crystal structure and some special properties, such as nonlinear optical response (Cariati et al., 2001) and luminescence (Guloy et al., 2001). 4-(4-(Dimethylamino) stryl)-1-ethylpyrdinium iodide possesses large conjugation system, which will be beneficial to the nonlinera optical response. In order to understand this phenomenon better, we present here the synthesis and the structure of the title compound, (I).

As shown in Fig. 1, the crystal structure of (I) consists of an organic cation, 4-(4-(dimethylmino)stryl)-1-ethylpridinium and an in-organic anion, [Cu2I4]2−. The configuration of the anion is similar to that of [Cu2I4]2− anion reported in the tetrabutylammonium salt (Asplund et al., 1982). There are, however, somewhat smaller differences between the Cu—Iterminal and Cu—Ibridging ligand distances in the anion reported in tetrabutylammonium salt and in (I), i.e. Cu—Iterminal = 2.514 (2) Å, Cu—Ibridging = 2.566 (2) and 2.592 (2)Å in the tetrabutylammonium salt compared to 2.5019 (9), 2.5731 (9) and 2.5800 (10) Å, respectively, in (I). Moreover, the distance d(Cu—Cu) in (I), 2.8046 (13) Å, is slightly longer than that in the tetrabutylammonium salt. It seems that the Cu···Cu distance is longer than the shortest possible distance for the given coordination, but that the value 2.8046 (13) Å in (I) indicates a weak attractive Cu(I)—Cu(I) interaction (Mehrotra et al., 1978). In the crystal structure, the organic cations are surround by the anions which form centrosymmetric dimers about inversion centers resulting in the organic-inorganic complex structure.

Related literature top

For related literature, see: Asplund et al. (1982); Cariati et al. (2001); Guloy et al. (2001); Mehrotra & Hoffmann (1978).

Experimental top

All chemicals and reagents were analytical grade available commercially and were used without further purfication. The title compound was prepared by self-assembling reaction of CuI with 4-(4-(dimethylmino)stryl)-1-ethyl- pridinium iodide. 4-(4-(Dimethylmino)stryl)-1-ethylpridinium iodide (0.19 g, 0.5 mmol) and CuI (0.095 g, 0.5 mmol) were dissolved in 8 ml dimethylformamide (DMF). The mixed solution was stirred still clear, with the pH value being adjusted to 6 by the addition of 10% HI/DMF solution and then filtered. The resulting solution was kept at room temperature for five days to obtain brown block crystals.

Computing details top

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY (Molecular Structure Corporation, 1999); data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atomic labels and 50% probability displacement ellipsoids for non-H atoms. The codes A in the symmetry related atoms of the anions is generatd by the symmertry operation (−x, −y + 2, −z + 1)
Bis{4-[4-(dimethylamino)styryl]-1-ethylpyridinium} di-µ-iodido-bis[iodidocuprate(II)] top
Crystal data top
(C17H21N2)2[Cu2I4]F000 = 1088.0
Mr = 1141.42Dx = 1.992 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 14979 reflections
a = 10.707 (4) Åθ = 3.2–27.5º
b = 7.367 (4) ŵ = 4.39 mm−1
c = 24.127 (9) ÅT = 293 (2) K
β = 90.908 (14)ºBlock, brown
V = 1902.9 (14) Å30.10 × 0.10 × 0.10 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID Imaging Plate
diffractometer		4356 independent reflections
Radiation source: fine-focus sealed tube3506 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.079
T = 293(2) Kθmax = 27.5º
ω scansθmin = 3.2º
Absorption correction: multi-scan
(Higash, 1995)		h = −13→13
Tmin = 0.645, Tmax = 0.651k = −9→9
18111 measured reflectionsl = −31→31
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.081  w = 1/[σ2(Fo2) + 0.277P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
4356 reflectionsΔρmax = 0.57 e Å−3
199 parametersΔρmin = −0.68 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C17H21N2)2[Cu2I4]V = 1902.9 (14) Å3
Mr = 1141.42Z = 2
Monoclinic, P21/cMo Kα
a = 10.707 (4) ŵ = 4.39 mm−1
b = 7.367 (4) ÅT = 293 (2) K
c = 24.127 (9) Å0.10 × 0.10 × 0.10 mm
β = 90.908 (14)º
Data collection top
Rigaku R-AXIS RAPID Imaging Plate
diffractometer		4356 independent reflections
Absorption correction: multi-scan
(Higash, 1995)		3506 reflections with I > 2σ(I)
Tmin = 0.645, Tmax = 0.651Rint = 0.079
18111 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034199 parameters
wR(F2) = 0.081H-atom parameters constrained
S = 1.05Δρmax = 0.57 e Å−3
4356 reflectionsΔρmin = −0.68 e Å−3
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
Cu1−0.02181 (5)0.88384 (8)0.54486 (2)0.06562 (15)
N10.2231 (2)0.2381 (5)0.60271 (12)0.0512 (7)
N20.7093 (3)0.3834 (5)0.22097 (13)0.0654 (9)
I10.16416 (2)0.84431 (4)0.479695 (11)0.06287 (10)
I2−0.05789 (2)0.69481 (4)0.629255 (10)0.06314 (10)
C10.3368 (3)0.1598 (6)0.60262 (15)0.0605 (10)
H1A0.36210.08890.63260.073*
C20.4154 (3)0.1826 (6)0.55930 (15)0.0594 (10)
H2A0.49450.13080.56080.071*
C30.3792 (3)0.2816 (5)0.51307 (13)0.0465 (7)
C40.2609 (3)0.3617 (5)0.51481 (14)0.0497 (8)
H4A0.23290.43220.48510.060*
C50.1864 (3)0.3379 (5)0.55932 (14)0.0536 (9)
H5A0.10810.39240.55950.064*
C60.4607 (3)0.2970 (5)0.46644 (14)0.0505 (8)
H6A0.54240.25670.47140.061*
C70.4299 (3)0.3635 (5)0.41694 (14)0.0517 (8)
H7A0.34920.40920.41330.062*
C80.5049 (3)0.3738 (5)0.36851 (14)0.0478 (8)
C90.6319 (3)0.3220 (5)0.36681 (14)0.0501 (8)
H9A0.67170.28500.39940.060*
C100.6976 (3)0.3246 (5)0.31940 (14)0.0534 (9)
H10A0.78070.28760.32040.064*
C110.6443 (3)0.3813 (5)0.26860 (14)0.0493 (8)
C120.5181 (3)0.4374 (6)0.27021 (14)0.0591 (10)
H12A0.47860.47860.23800.071*
C130.4540 (3)0.4320 (6)0.31796 (15)0.0605 (10)
H13A0.37110.46940.31710.073*
C140.8395 (4)0.3222 (7)0.21911 (19)0.0844 (15)
H14A0.86810.29150.25580.127*
H14B0.89060.41770.20460.127*
H14C0.84510.21740.19560.127*
C150.6530 (4)0.4375 (8)0.16883 (16)0.0840 (15)
H15A0.56870.47670.17480.126*
H15B0.65260.33640.14370.126*
H15C0.70010.53540.15330.126*
C160.1340 (4)0.2066 (7)0.64840 (17)0.0749 (13)
H16A0.07570.30740.64920.090*
H16B0.08630.09780.64000.090*
C170.1902 (4)0.1865 (8)0.70363 (17)0.0846 (15)
H17A0.12570.16750.73020.127*
H17B0.23600.29460.71300.127*
H17C0.24590.08440.70390.127*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0730 (3)0.0628 (4)0.0608 (3)0.0051 (3)−0.0046 (2)0.0030 (2)
N10.0456 (14)0.057 (2)0.0505 (15)−0.0001 (14)0.0014 (13)0.0024 (14)
N20.0533 (16)0.095 (3)0.0483 (16)−0.0006 (17)0.0045 (15)0.0059 (16)
I10.06111 (15)0.05589 (18)0.07167 (17)0.01157 (12)0.00291 (13)0.00773 (12)
I20.05782 (15)0.0763 (2)0.05521 (15)0.01122 (12)−0.00368 (12)0.00891 (12)
C10.0540 (19)0.073 (3)0.054 (2)0.0093 (19)−0.0013 (17)0.0118 (18)
C20.0445 (17)0.079 (3)0.055 (2)0.0116 (18)−0.0008 (16)0.0060 (19)
C30.0469 (16)0.046 (2)0.0466 (17)−0.0033 (15)−0.0019 (15)−0.0040 (15)
C40.0581 (19)0.047 (2)0.0437 (16)0.0083 (16)−0.0016 (15)−0.0035 (14)
C50.0477 (17)0.060 (3)0.0528 (19)0.0081 (16)−0.0018 (16)−0.0072 (17)
C60.0432 (15)0.058 (2)0.0501 (18)0.0031 (16)−0.0001 (15)−0.0037 (16)
C70.0489 (17)0.054 (2)0.0524 (18)−0.0021 (16)−0.0045 (16)−0.0025 (16)
C80.0448 (16)0.051 (2)0.0471 (17)−0.0007 (15)0.0027 (15)−0.0022 (15)
C90.0481 (16)0.057 (2)0.0456 (17)−0.0023 (16)−0.0063 (15)0.0036 (15)
C100.0418 (15)0.062 (3)0.056 (2)−0.0006 (16)−0.0014 (16)−0.0009 (17)
C110.0454 (16)0.053 (2)0.0499 (18)−0.0024 (15)0.0001 (15)0.0000 (15)
C120.0528 (19)0.078 (3)0.0458 (17)0.0059 (19)−0.0044 (16)0.0065 (17)
C130.0400 (16)0.082 (3)0.060 (2)0.0109 (18)−0.0017 (16)0.005 (2)
C140.061 (2)0.121 (5)0.072 (3)0.014 (3)0.021 (2)0.011 (3)
C150.078 (3)0.121 (5)0.053 (2)0.003 (3)0.007 (2)0.016 (2)
C160.056 (2)0.097 (4)0.072 (3)−0.007 (2)0.017 (2)0.012 (2)
C170.085 (3)0.115 (5)0.054 (2)−0.020 (3)0.015 (2)−0.006 (2)
Geometric parameters (Å, °) top
Cu1—I22.5019 (9)C7—H7A0.9300
Cu1—I12.5731 (9)C8—C131.395 (5)
Cu1—I1i2.5800 (10)C8—C91.414 (5)
Cu1—Cu1i2.8046 (13)C9—C101.352 (4)
N1—C51.333 (5)C9—H9A0.9300
N1—C11.347 (4)C10—C111.407 (5)
N1—C161.488 (4)C10—H10A0.9300
N2—C111.353 (4)C11—C121.414 (5)
N2—C151.443 (5)C12—C131.351 (5)
N2—C141.466 (5)C12—H12A0.9300
I1—Cu1i2.5800 (10)C13—H13A0.9300
C1—C21.362 (5)C14—H14A0.9600
C1—H1A0.9300C14—H14B0.9600
C2—C31.383 (5)C14—H14C0.9600
C2—H2A0.9300C15—H15A0.9600
C3—C41.398 (5)C15—H15B0.9600
C3—C61.439 (4)C15—H15C0.9600
C4—C51.359 (5)C16—C171.461 (6)
C4—H4A0.9300C16—H16A0.9700
C5—H5A0.9300C16—H16B0.9700
C6—C71.328 (5)C17—H17A0.9600
C6—H6A0.9300C17—H17B0.9600
C7—C81.430 (4)C17—H17C0.9600
I2—Cu1—I1124.42 (3)C10—C9—H9A118.9
I2—Cu1—I1i121.38 (3)C8—C9—H9A118.9
I1—Cu1—I1i114.05 (3)C9—C10—C11122.1 (3)
I2—Cu1—Cu1i176.04 (4)C9—C10—H10A118.9
I1—Cu1—Cu1i57.15 (2)C11—C10—H10A118.9
I1i—Cu1—Cu1i56.91 (3)N2—C11—C10122.4 (3)
C5—N1—C1119.3 (3)N2—C11—C12121.7 (3)
C5—N1—C16118.9 (3)C10—C11—C12116.0 (3)
C1—N1—C16121.7 (3)C13—C12—C11120.9 (3)
C11—N2—C15122.0 (3)C13—C12—H12A119.6
C11—N2—C14121.7 (3)C11—C12—H12A119.6
C15—N2—C14116.3 (3)C12—C13—C8123.9 (3)
Cu1—I1—Cu1i65.95 (3)C12—C13—H13A118.0
N1—C1—C2121.2 (3)C8—C13—H13A118.0
N1—C1—H1A119.4N2—C14—H14A109.5
C2—C1—H1A119.4N2—C14—H14B109.5
C1—C2—C3121.0 (3)H14A—C14—H14B109.5
C1—C2—H2A119.5N2—C14—H14C109.5
C3—C2—H2A119.5H14A—C14—H14C109.5
C2—C3—C4116.2 (3)H14B—C14—H14C109.5
C2—C3—C6120.4 (3)N2—C15—H15A109.5
C4—C3—C6123.4 (3)N2—C15—H15B109.5
C5—C4—C3120.8 (3)H15A—C15—H15B109.5
C5—C4—H4A119.6N2—C15—H15C109.5
C3—C4—H4A119.6H15A—C15—H15C109.5
N1—C5—C4121.5 (3)H15B—C15—H15C109.5
N1—C5—H5A119.3C17—C16—N1115.6 (3)
C4—C5—H5A119.3C17—C16—H16A108.4
C7—C6—C3126.0 (3)N1—C16—H16A108.4
C7—C6—H6A117.0C17—C16—H16B108.4
C3—C6—H6A117.0N1—C16—H16B108.4
C6—C7—C8128.3 (3)H16A—C16—H16B107.5
C6—C7—H7A115.9C16—C17—H17A109.5
C8—C7—H7A115.9C16—C17—H17B109.5
C13—C8—C9114.8 (3)H17A—C17—H17B109.5
C13—C8—C7120.9 (3)C16—C17—H17C109.5
C9—C8—C7124.2 (3)H17A—C17—H17C109.5
C10—C9—C8122.3 (3)H17B—C17—H17C109.5
I2—Cu1—I1—Cu1i−175.63 (4)C13—C8—C9—C10−1.7 (6)
I1i—Cu1—I1—Cu1i0.0C7—C8—C9—C10176.3 (4)
C5—N1—C1—C20.8 (6)C8—C9—C10—C110.9 (6)
C16—N1—C1—C2176.8 (4)C15—N2—C11—C10178.4 (4)
N1—C1—C2—C3−2.4 (7)C14—N2—C11—C101.4 (6)
C1—C2—C3—C42.6 (6)C15—N2—C11—C12−1.9 (6)
C1—C2—C3—C6−176.9 (4)C14—N2—C11—C12−178.9 (4)
C2—C3—C4—C5−1.5 (5)C9—C10—C11—N2−179.7 (4)
C6—C3—C4—C5178.0 (3)C9—C10—C11—C120.6 (6)
C1—N1—C5—C40.3 (6)N2—C11—C12—C13179.1 (4)
C16—N1—C5—C4−175.8 (4)C10—C11—C12—C13−1.3 (6)
C3—C4—C5—N10.1 (6)C11—C12—C13—C80.4 (7)
C2—C3—C6—C7169.0 (4)C9—C8—C13—C121.0 (6)
C4—C3—C6—C7−10.5 (6)C7—C8—C13—C12−177.0 (4)
C3—C6—C7—C8−176.6 (4)C5—N1—C16—C17−148.8 (4)
C6—C7—C8—C13173.7 (4)C1—N1—C16—C1735.2 (6)
C6—C7—C8—C9−4.1 (6)
Symmetry codes: (i) −x, −y+2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—I22.5019 (9)Cu1—Cu1i2.8046 (13)
Cu1—I12.5731 (9)I1—Cu1i2.5800 (10)
Cu1—I1i2.5800 (10)
I2—Cu1—I1124.42 (3)I1—Cu1—Cu1i57.15 (2)
I2—Cu1—I1i121.38 (3)I1i—Cu1—Cu1i56.91 (3)
I1—Cu1—I1i114.05 (3)Cu1—I1—Cu1i65.95 (3)
I2—Cu1—Cu1i176.04 (4)
Symmetry codes: (i) −x, −y+2, −z+1.
Acknowledgements top

We are grateful for financial support from the National Natural Science Foundation of China (No.0041814161).

references
References top

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Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.