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

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

doi:10.1107/S160053680705074X

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

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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705074X/pv2032sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680705074X/pv2032Isup2.hkl Contains datablock I

CCDC reference: 672622

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Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.034
wR factor = 0.080
Data-to-parameter ratio = 21.9

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No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT412_ALERT_2_C Short Intra XH3 .. XHn     H10A   ..  H14A    ..       1.83 Ang.
PLAT412_ALERT_2_C Short Intra XH3 .. XHn     H12A   ..  H15A    ..       1.82 Ang.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (1)       0.91

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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—I_terminal and Cu—I_bridging ligand distances in the anion reported in tetrabutylammonium salt and in (I), i.e. Cu—I_terminal = 2.514 (2) Å, Cu—I_bridging = 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

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]	F(000) = 1088.0
M_r = 1141.42	D_x = 1.992 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 14979 reflections
a = 10.707 (4) Å	θ = 3.2–27.5°
b = 7.367 (4) Å	µ = 4.39 mm⁻¹
c = 24.127 (9) Å	T = 293 K
β = 90.908 (14)°	Block, brown
V = 1902.9 (14) Å³	0.10 × 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 tube	3506 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (Higash, 1995)	h = −13→13
T_min = 0.645, T_max = 0.651	k = −9→9
18111 measured reflections	l = −31→31

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + 0.277P] where P = (F_o² + 2F_c²)/3
4356 reflections	(Δ/σ)_max = 0.002
199 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

(C₁₇H₂₁N₂)₂[Cu₂I₄]	V = 1902.9 (14) Å³
M_r = 1141.42	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.707 (4) Å	µ = 4.39 mm⁻¹
b = 7.367 (4) Å	T = 293 K
c = 24.127 (9) Å	0.10 × 0.10 × 0.10 mm
β = 90.908 (14)°

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)
T_min = 0.645, T_max = 0.651	R_int = 0.079
18111 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	Δρ_max = 0.57 e Å⁻³
4356 reflections	Δρ_min = −0.68 e Å⁻³
199 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
Cu1	−0.02181 (5)	0.88384 (8)	0.54486 (2)	0.06562 (15)
N1	0.2231 (2)	0.2381 (5)	0.60271 (12)	0.0512 (7)
N2	0.7093 (3)	0.3834 (5)	0.22097 (13)	0.0654 (9)
I1	0.16416 (2)	0.84431 (4)	0.479695 (11)	0.06287 (10)
I2	−0.05789 (2)	0.69481 (4)	0.629255 (10)	0.06314 (10)
C1	0.3368 (3)	0.1598 (6)	0.60262 (15)	0.0605 (10)
H1A	0.3621	0.0889	0.6326	0.073*
C2	0.4154 (3)	0.1826 (6)	0.55930 (15)	0.0594 (10)
H2A	0.4945	0.1308	0.5608	0.071*
C3	0.3792 (3)	0.2816 (5)	0.51307 (13)	0.0465 (7)
C4	0.2609 (3)	0.3617 (5)	0.51481 (14)	0.0497 (8)
H4A	0.2329	0.4322	0.4851	0.060*
C5	0.1864 (3)	0.3379 (5)	0.55932 (14)	0.0536 (9)
H5A	0.1081	0.3924	0.5595	0.064*
C6	0.4607 (3)	0.2970 (5)	0.46644 (14)	0.0505 (8)
H6A	0.5424	0.2567	0.4714	0.061*
C7	0.4299 (3)	0.3635 (5)	0.41694 (14)	0.0517 (8)
H7A	0.3492	0.4092	0.4133	0.062*
C8	0.5049 (3)	0.3738 (5)	0.36851 (14)	0.0478 (8)
C9	0.6319 (3)	0.3220 (5)	0.36681 (14)	0.0501 (8)
H9A	0.6717	0.2850	0.3994	0.060*
C10	0.6976 (3)	0.3246 (5)	0.31940 (14)	0.0534 (9)
H10A	0.7807	0.2876	0.3204	0.064*
C11	0.6443 (3)	0.3813 (5)	0.26860 (14)	0.0493 (8)
C12	0.5181 (3)	0.4374 (6)	0.27021 (14)	0.0591 (10)
H12A	0.4786	0.4786	0.2380	0.071*
C13	0.4540 (3)	0.4320 (6)	0.31796 (15)	0.0605 (10)
H13A	0.3711	0.4694	0.3171	0.073*
C14	0.8395 (4)	0.3222 (7)	0.21911 (19)	0.0844 (15)
H14A	0.8681	0.2915	0.2558	0.127*
H14B	0.8906	0.4177	0.2046	0.127*
H14C	0.8451	0.2174	0.1956	0.127*
C15	0.6530 (4)	0.4375 (8)	0.16883 (16)	0.0840 (15)
H15A	0.5687	0.4767	0.1748	0.126*
H15B	0.6526	0.3364	0.1437	0.126*
H15C	0.7001	0.5354	0.1533	0.126*
C16	0.1340 (4)	0.2066 (7)	0.64840 (17)	0.0749 (13)
H16A	0.0757	0.3074	0.6492	0.090*
H16B	0.0863	0.0978	0.6400	0.090*
C17	0.1902 (4)	0.1865 (8)	0.70363 (17)	0.0846 (15)
H17A	0.1257	0.1675	0.7302	0.127*
H17B	0.2360	0.2946	0.7130	0.127*
H17C	0.2459	0.0844	0.7039	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0730 (3)	0.0628 (4)	0.0608 (3)	0.0051 (3)	−0.0046 (2)	0.0030 (2)
N1	0.0456 (14)	0.057 (2)	0.0505 (15)	−0.0001 (14)	0.0014 (13)	0.0024 (14)
N2	0.0533 (16)	0.095 (3)	0.0483 (16)	−0.0006 (17)	0.0045 (15)	0.0059 (16)
I1	0.06111 (15)	0.05589 (18)	0.07167 (17)	0.01157 (12)	0.00291 (13)	0.00773 (12)
I2	0.05782 (15)	0.0763 (2)	0.05521 (15)	0.01122 (12)	−0.00368 (12)	0.00891 (12)
C1	0.0540 (19)	0.073 (3)	0.054 (2)	0.0093 (19)	−0.0013 (17)	0.0118 (18)
C2	0.0445 (17)	0.079 (3)	0.055 (2)	0.0116 (18)	−0.0008 (16)	0.0060 (19)
C3	0.0469 (16)	0.046 (2)	0.0466 (17)	−0.0033 (15)	−0.0019 (15)	−0.0040 (15)
C4	0.0581 (19)	0.047 (2)	0.0437 (16)	0.0083 (16)	−0.0016 (15)	−0.0035 (14)
C5	0.0477 (17)	0.060 (3)	0.0528 (19)	0.0081 (16)	−0.0018 (16)	−0.0072 (17)
C6	0.0432 (15)	0.058 (2)	0.0501 (18)	0.0031 (16)	−0.0001 (15)	−0.0037 (16)
C7	0.0489 (17)	0.054 (2)	0.0524 (18)	−0.0021 (16)	−0.0045 (16)	−0.0025 (16)
C8	0.0448 (16)	0.051 (2)	0.0471 (17)	−0.0007 (15)	0.0027 (15)	−0.0022 (15)
C9	0.0481 (16)	0.057 (2)	0.0456 (17)	−0.0023 (16)	−0.0063 (15)	0.0036 (15)
C10	0.0418 (15)	0.062 (3)	0.056 (2)	−0.0006 (16)	−0.0014 (16)	−0.0009 (17)
C11	0.0454 (16)	0.053 (2)	0.0499 (18)	−0.0024 (15)	0.0001 (15)	0.0000 (15)
C12	0.0528 (19)	0.078 (3)	0.0458 (17)	0.0059 (19)	−0.0044 (16)	0.0065 (17)
C13	0.0400 (16)	0.082 (3)	0.060 (2)	0.0109 (18)	−0.0017 (16)	0.005 (2)
C14	0.061 (2)	0.121 (5)	0.072 (3)	0.014 (3)	0.021 (2)	0.011 (3)
C15	0.078 (3)	0.121 (5)	0.053 (2)	0.003 (3)	0.007 (2)	0.016 (2)
C16	0.056 (2)	0.097 (4)	0.072 (3)	−0.007 (2)	0.017 (2)	0.012 (2)
C17	0.085 (3)	0.115 (5)	0.054 (2)	−0.020 (3)	0.015 (2)	−0.006 (2)

Geometric parameters (Å, º) top

Cu1—I2	2.5019 (9)	C7—H7A	0.9300
Cu1—I1	2.5731 (9)	C8—C13	1.395 (5)
Cu1—I1ⁱ	2.5800 (10)	C8—C9	1.414 (5)
Cu1—Cu1ⁱ	2.8046 (13)	C9—C10	1.352 (4)
N1—C5	1.333 (5)	C9—H9A	0.9300
N1—C1	1.347 (4)	C10—C11	1.407 (5)
N1—C16	1.488 (4)	C10—H10A	0.9300
N2—C11	1.353 (4)	C11—C12	1.414 (5)
N2—C15	1.443 (5)	C12—C13	1.351 (5)
N2—C14	1.466 (5)	C12—H12A	0.9300
I1—Cu1ⁱ	2.5800 (10)	C13—H13A	0.9300
C1—C2	1.362 (5)	C14—H14A	0.9600
C1—H1A	0.9300	C14—H14B	0.9600
C2—C3	1.383 (5)	C14—H14C	0.9600
C2—H2A	0.9300	C15—H15A	0.9600
C3—C4	1.398 (5)	C15—H15B	0.9600
C3—C6	1.439 (4)	C15—H15C	0.9600
C4—C5	1.359 (5)	C16—C17	1.461 (6)
C4—H4A	0.9300	C16—H16A	0.9700
C5—H5A	0.9300	C16—H16B	0.9700
C6—C7	1.328 (5)	C17—H17A	0.9600
C6—H6A	0.9300	C17—H17B	0.9600
C7—C8	1.430 (4)	C17—H17C	0.9600

I2—Cu1—I1	124.42 (3)	C10—C9—H9A	118.9
I2—Cu1—I1ⁱ	121.38 (3)	C8—C9—H9A	118.9
I1—Cu1—I1ⁱ	114.05 (3)	C9—C10—C11	122.1 (3)
I2—Cu1—Cu1ⁱ	176.04 (4)	C9—C10—H10A	118.9
I1—Cu1—Cu1ⁱ	57.15 (2)	C11—C10—H10A	118.9
I1ⁱ—Cu1—Cu1ⁱ	56.91 (3)	N2—C11—C10	122.4 (3)
C5—N1—C1	119.3 (3)	N2—C11—C12	121.7 (3)
C5—N1—C16	118.9 (3)	C10—C11—C12	116.0 (3)
C1—N1—C16	121.7 (3)	C13—C12—C11	120.9 (3)
C11—N2—C15	122.0 (3)	C13—C12—H12A	119.6
C11—N2—C14	121.7 (3)	C11—C12—H12A	119.6
C15—N2—C14	116.3 (3)	C12—C13—C8	123.9 (3)
Cu1—I1—Cu1ⁱ	65.95 (3)	C12—C13—H13A	118.0
N1—C1—C2	121.2 (3)	C8—C13—H13A	118.0
N1—C1—H1A	119.4	N2—C14—H14A	109.5
C2—C1—H1A	119.4	N2—C14—H14B	109.5
C1—C2—C3	121.0 (3)	H14A—C14—H14B	109.5
C1—C2—H2A	119.5	N2—C14—H14C	109.5
C3—C2—H2A	119.5	H14A—C14—H14C	109.5
C2—C3—C4	116.2 (3)	H14B—C14—H14C	109.5
C2—C3—C6	120.4 (3)	N2—C15—H15A	109.5
C4—C3—C6	123.4 (3)	N2—C15—H15B	109.5
C5—C4—C3	120.8 (3)	H15A—C15—H15B	109.5
C5—C4—H4A	119.6	N2—C15—H15C	109.5
C3—C4—H4A	119.6	H15A—C15—H15C	109.5
N1—C5—C4	121.5 (3)	H15B—C15—H15C	109.5
N1—C5—H5A	119.3	C17—C16—N1	115.6 (3)
C4—C5—H5A	119.3	C17—C16—H16A	108.4
C7—C6—C3	126.0 (3)	N1—C16—H16A	108.4
C7—C6—H6A	117.0	C17—C16—H16B	108.4
C3—C6—H6A	117.0	N1—C16—H16B	108.4
C6—C7—C8	128.3 (3)	H16A—C16—H16B	107.5
C6—C7—H7A	115.9	C16—C17—H17A	109.5
C8—C7—H7A	115.9	C16—C17—H17B	109.5
C13—C8—C9	114.8 (3)	H17A—C17—H17B	109.5
C13—C8—C7	120.9 (3)	C16—C17—H17C	109.5
C9—C8—C7	124.2 (3)	H17A—C17—H17C	109.5
C10—C9—C8	122.3 (3)	H17B—C17—H17C	109.5

I2—Cu1—I1—Cu1ⁱ	−175.63 (4)	C13—C8—C9—C10	−1.7 (6)
I1ⁱ—Cu1—I1—Cu1ⁱ	0.0	C7—C8—C9—C10	176.3 (4)
C5—N1—C1—C2	0.8 (6)	C8—C9—C10—C11	0.9 (6)
C16—N1—C1—C2	176.8 (4)	C15—N2—C11—C10	178.4 (4)
N1—C1—C2—C3	−2.4 (7)	C14—N2—C11—C10	1.4 (6)
C1—C2—C3—C4	2.6 (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—C5	178.0 (3)	C9—C10—C11—C12	0.6 (6)
C1—N1—C5—C4	0.3 (6)	N2—C11—C12—C13	179.1 (4)
C16—N1—C5—C4	−175.8 (4)	C10—C11—C12—C13	−1.3 (6)
C3—C4—C5—N1	0.1 (6)	C11—C12—C13—C8	0.4 (7)
C2—C3—C6—C7	169.0 (4)	C9—C8—C13—C12	1.0 (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—C13	173.7 (4)	C1—N1—C16—C17	35.2 (6)
C6—C7—C8—C9	−4.1 (6)

Symmetry code: (i) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	(C₁₇H₂₁N₂)₂[Cu₂I₄]
M_r	1141.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.707 (4), 7.367 (4), 24.127 (9)
β (°)	90.908 (14)
V (Å³)	1902.9 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.39
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID Imaging Plate diffractometer
Absorption correction	Multi-scan (Higash, 1995)
T_min, T_max	0.645, 0.651
No. of measured, independent and observed [I > 2σ(I)] reflections	18111, 4356, 3506
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.081, 1.05
No. of reflections	4356
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.68

Computer programs: TEXRAY (Molecular Structure Corporation, 1999), TEXSAN (Molecular Structure Corporation, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), SHELXL97.

Selected geometric parameters (Å, º) top

Cu1—I2	2.5019 (9)	Cu1—Cu1ⁱ	2.8046 (13)
Cu1—I1	2.5731 (9)	I1—Cu1ⁱ	2.5800 (10)
Cu1—I1ⁱ	2.5800 (10)

I2—Cu1—I1	124.42 (3)	I1—Cu1—Cu1ⁱ	57.15 (2)
I2—Cu1—I1ⁱ	121.38 (3)	I1ⁱ—Cu1—Cu1ⁱ	56.91 (3)
I1—Cu1—I1ⁱ	114.05 (3)	Cu1—I1—Cu1ⁱ	65.95 (3)
I2—Cu1—Cu1ⁱ	176.04 (4)