catena-Poly[[iodidocopper(I)]-μ-4,4′,6,6′-tetra­methyl-2,2′-(ethyl­enedithio)dipyrimidine-κ2N:N′]

Lu, H.B.; Li, L.; Lv, G.Q.; Yang, J.X.

doi:10.1107/S1600536809032437

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1123

doi:10.1107/S1600536809032437

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catena-Poly[[iodidocopper(I)]-μ-4,4′,6,6′-tetramethyl-2,2′-(ethylenedithio)dipyrimidine-κ²N:N′]

Hong Bo Lu,^a,^b Lin Li,^c Guo Qiang Lv ^a,^b and Jia Xiang Yang ^c ^*

^aKey Laboratory of Special Display Technology, Hefei University of Technology, Ministry of Education, Hefei 230009, People's Republic of China, ^bAcademy of Opto-Electronic Technology, Hefei University of Technology, Ministry of Education, Hefei 230009, People's Republic of China, and ^cDepartment of Chemistry, Anhui University, Hefei 230039, People's Republic of China
^*Correspondence e-mail: bozhilu@mail.ustc.edu.cn

(Received 20 July 2009; accepted 15 August 2009; online 22 August 2009)

In the title coordination polymer, [CuI(C₁₄H₁₈N₄S₂)]_n, the Cu^I center is trigonally coordinated by two pyrimidine N-atom donors from two distinct dithioether ligands and one iodide anion. The Cu and I atoms are located on a twofold axis, whereas the midpoint of the central C—C bond of the dithioether ligand is located on an inversion center. Each organic ligand, acting in a bidentate mode, bridges two Cu^Iions, resulting in the formation of polymeric zigzag chains. The dihedral angle between the two pyrimidine units bonded to the metal center is 88.01 (2)°. The crystal packing is mainly stabilized by van der Waals forces and π–π stacking interactions, with an interplanar distance between the pyrimidine rings of adjacent chains of 3.638 (3) Å.

Related literature

For applications of closed-shell metal atoms or ions, see: Catalano et al. (2000 ). For applications of conjugated multi-branched molecules in optical materials, see: Nishihara et al. (1989 ); Roberto et al. (2000 ). For the structures of CuI complexes with similar ligands, see: Shi et al. (2008 ).

Experimental

Crystal data

[CuI(C₁₄H₁₈N₄S₂)]
M_r = 496.88
Monoclinic, C 2/c
a = 14.201 (5) Å
b = 8.064 (5) Å
c = 16.940 (5) Å
β = 111.655 (5)°
V = 1803.0 (14) Å³
Z = 4
Mo Kα radiation
μ = 3.16 mm⁻¹
T = 293 K
0.33 × 0.24 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.419, T_max = 0.515
5585 measured reflections
2070 independent reflections
1942 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.053
S = 1.09
2070 reflections
103 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

I1—Cu1	2.5191 (16)
Cu1—N2	2.0327 (16)

N2ⁱ—Cu1—N2	118.55 (10)
N2ⁱ—Cu1—I1	120.72 (5)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809032437/gk2225sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032437/gk2225Isup2.hkl

checkCIF report

Comment top

Previous studies have shown that the bonding interaction between closed-shell metal atoms or ions is gaining increasing attention (Catalano et al., 2000), there are a few reports of similar association in the case of alkyl copper (I) complexes. Heterocycle-based aromatic systems with conjugated multi-branched structure possess potential applications in optical image processing, all-optical switching, and integrated optical devices (Nishihara et al., 1989; Roberto et al., 2000). Pyrimidine is a π-electron deficient with its ionization potential value of 10.41 eV and metal complexes of such ligand has been reported (Shi et al., 2008). On the other hand, pyrimidine ring has well known reactivity in the positions 4 and 6, which can easily undergo reactions with an aromatic aldehyde in solvent-free condition. Therefore we pay our attention to the pyrimidine system. As part of our ongoing investigation on d¹⁰ ions and pyrimidine derivatives, the title compound, has been prepared and its crystal structure is presented here.

The molecular structure of the title compound shows that Cu atom coordinated in a triangle-planar configuration (Fig. 1) with two equal Cu—N and one Cu—I bonds (Table 1). The dihedral angles formed by the two pyrimidine rings (N1, C2, N2, C6, C5, C3 and N1A, C2A, N2A, C6A, C5A, C3A) is 88.01 (2)°. Each ligand, acting in a bidentate mode, bridges two Cu ions, resulting in the formation of polymeric zigzag chains. The crystal packing is mainly stabilized by van der Waals forces and π-π interactions, with the shortest distance of 3.938 (3)Å along c axis.

Related literature top

For applications of closed-shell metal atoms or ions, see: Catalano et al. (2000). For applications of conjugated multi-branched molecules in optical materials, see: Nishihara et al. (1989); Roberto et al. (2000). For the structures of CuI complexes with similar ligands, see: Shi et al. (2008).

Experimental top

A mixture of 4,4',6,6'-tetramethyl-2,2'-(ethylenedithio)dipyrimidine (0.30 mmol) and CuI (0.30 mmol) was heated at 363 K with CHCl₃ (20 ml) as a solvent for 10 h. The red powder of the title compound was filtered and washed thoroughly with water and then air dried (yield 55%). Single crystals suitable for X-ray analysis were obtained by slow evaporation from a dichloromethane/2-propanol (3:1) solution.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. : The molecular structure of the title compound showing 30% probability displacement ellipsoids. Atoms labelled with the suffixes A, B and C are at the symmetry positions (1 - x, y, 0.5 - z), (1 - x, 1 - y, -z) and (x, 1 - y, -1/2 + z), respectively.

catena-Poly[[iodidocopper(I)]-µ-4,4',6,6'-tetramethyl-2,2'- (ethylenedithio)dipyrimidine-κ²N:N'] top

Crystal data top

[CuI(C₁₄H₁₈N₄S₂)]	F(000) = 976
M_r = 496.88	D_x = 1.830 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 4275 reflections
a = 14.201 (5) Å	θ = 3.0–27.5°
b = 8.064 (5) Å	µ = 3.16 mm⁻¹
c = 16.940 (5) Å	T = 293 K
β = 111.655 (5)°	Prism, yellow
V = 1803.0 (14) Å³	0.33 × 0.24 × 0.21 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2070 independent reflections
Radiation source: sealed tube	1942 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
Detector resolution: 0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ϕ and ω scans	h = −18→14
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −10→9
T_min = 0.419, T_max = 0.515	l = −21→21
5585 measured reflections

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.053	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0273P)² + 1.5073P] where P = (F_o² + 2F_c²)/3
2070 reflections	(Δ/σ)_max = 0.001
103 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[CuI(C₁₄H₁₈N₄S₂)]	V = 1803.0 (14) Å³
M_r = 496.88	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.201 (5) Å	µ = 3.16 mm⁻¹
b = 8.064 (5) Å	T = 293 K
c = 16.940 (5) Å	0.33 × 0.24 × 0.21 mm
β = 111.655 (5)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2070 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1942 reflections with I > 2σ(I)
T_min = 0.419, T_max = 0.515	R_int = 0.012
5585 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.053	H-atom parameters constrained
S = 1.09	Δρ_max = 0.51 e Å⁻³
2070 reflections	Δρ_min = −0.37 e Å⁻³
103 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
I1	0.5000	−0.19054 (3)	0.2500	0.04737 (8)
Cu1	0.5000	0.12185 (4)	0.2500	0.03416 (9)
S1	0.52076 (4)	0.34963 (8)	0.11434 (3)	0.04371 (14)
N1	0.32885 (12)	0.4555 (2)	0.05807 (11)	0.0342 (3)
N2	0.38109 (11)	0.2506 (2)	0.16787 (9)	0.0290 (3)
C5	0.21161 (14)	0.3484 (3)	0.11508 (12)	0.0344 (4)
H5	0.1466	0.3468	0.1161	0.041*
C3	0.23460 (14)	0.4530 (2)	0.06006 (12)	0.0340 (4)
C6	0.28616 (14)	0.2463 (3)	0.16853 (11)	0.0317 (4)
C1	0.52381 (15)	0.5214 (3)	0.04659 (12)	0.0366 (4)
H1A	0.4881	0.6149	0.0584	0.044*
H1B	0.5936	0.5545	0.0597	0.044*
C2	0.39619 (13)	0.3559 (2)	0.11190 (11)	0.0298 (3)
C4	0.15807 (18)	0.5669 (3)	0.00052 (16)	0.0505 (5)
H4A	0.1729	0.6791	0.0202	0.076*
H4B	0.0916	0.5374	−0.0017	0.076*
H4C	0.1605	0.5575	−0.0552	0.076*
C7	0.26594 (15)	0.1282 (3)	0.22824 (14)	0.0437 (5)
H7A	0.2754	0.0165	0.2128	0.066*
H7B	0.1975	0.1419	0.2252	0.066*
H7C	0.3119	0.1500	0.2851	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.04987 (13)	0.03860 (12)	0.05587 (13)	0.000	0.02211 (9)	0.000
Cu1	0.03150 (16)	0.0412 (2)	0.03022 (16)	0.000	0.01191 (12)	0.000
S1	0.0306 (2)	0.0610 (3)	0.0444 (3)	0.0086 (2)	0.0194 (2)	0.0221 (2)
N1	0.0331 (8)	0.0374 (9)	0.0338 (8)	0.0040 (6)	0.0144 (6)	0.0047 (6)
N2	0.0270 (7)	0.0335 (7)	0.0272 (7)	−0.0021 (6)	0.0107 (5)	0.0004 (6)
C5	0.0261 (8)	0.0388 (10)	0.0398 (10)	−0.0015 (7)	0.0138 (7)	−0.0044 (8)
C3	0.0315 (9)	0.0344 (10)	0.0346 (9)	0.0022 (7)	0.0106 (7)	−0.0033 (7)
C6	0.0305 (8)	0.0352 (9)	0.0308 (8)	−0.0052 (7)	0.0130 (7)	−0.0036 (7)
C1	0.0331 (9)	0.0444 (11)	0.0337 (10)	−0.0086 (8)	0.0141 (8)	0.0027 (8)
C2	0.0292 (8)	0.0343 (9)	0.0283 (8)	−0.0006 (7)	0.0133 (7)	−0.0001 (7)
C4	0.0399 (11)	0.0518 (13)	0.0563 (13)	0.0140 (10)	0.0136 (10)	0.0122 (11)
C7	0.0338 (10)	0.0531 (13)	0.0470 (11)	−0.0064 (9)	0.0183 (8)	0.0099 (10)

Geometric parameters (Å, º) top

I1—Cu1	2.5191 (16)	C3—C4	1.495 (3)
Cu1—N2ⁱ	2.0327 (16)	C6—C7	1.492 (3)
Cu1—N2	2.0327 (16)	C1—C1ⁱⁱ	1.510 (4)
S1—C2	1.7550 (19)	C1—H1A	0.9700
S1—C1	1.809 (2)	C1—H1B	0.9700
N1—C2	1.322 (2)	C4—H4A	0.9600
N1—C3	1.351 (2)	C4—H4B	0.9600
N2—C2	1.348 (2)	C4—H4C	0.9600
N2—C6	1.353 (2)	C7—H7A	0.9600
C5—C3	1.382 (3)	C7—H7B	0.9600
C5—C6	1.383 (3)	C7—H7C	0.9600
C5—H5	0.9300

N2ⁱ—Cu1—N2	118.55 (10)	S1—C1—H1A	109.1
N2ⁱ—Cu1—I1	120.72 (5)	C1ⁱⁱ—C1—H1B	109.1
N2—Cu1—I1	120.72 (5)	S1—C1—H1B	109.1
C2—S1—C1	102.87 (9)	H1A—C1—H1B	107.8
C2—N1—C3	116.41 (16)	N1—C2—N2	127.28 (16)
C2—N2—C6	116.10 (16)	N1—C2—S1	120.02 (13)
C2—N2—Cu1	119.73 (12)	N2—C2—S1	112.69 (13)
C6—N2—Cu1	124.04 (13)	C3—C4—H4A	109.5
C3—C5—C6	119.38 (17)	C3—C4—H4B	109.5
C3—C5—H5	120.3	H4A—C4—H4B	109.5
C6—C5—H5	120.3	C3—C4—H4C	109.5
N1—C3—C5	120.57 (17)	H4A—C4—H4C	109.5
N1—C3—C4	117.01 (18)	H4B—C4—H4C	109.5
C5—C3—C4	122.42 (18)	C6—C7—H7A	109.5
N2—C6—C5	120.24 (17)	C6—C7—H7B	109.5
N2—C6—C7	117.63 (17)	H7A—C7—H7B	109.5
C5—C6—C7	122.13 (17)	C6—C7—H7C	109.5
C1ⁱⁱ—C1—S1	112.45 (19)	H7A—C7—H7C	109.5
C1ⁱⁱ—C1—H1A	109.1	H7B—C7—H7C	109.5

N2ⁱ—Cu1—N2—C2	59.68 (13)	C3—C5—C6—N2	1.1 (3)
I1—Cu1—N2—C2	−120.32 (13)	C3—C5—C6—C7	−178.78 (19)
N2ⁱ—Cu1—N2—C6	−115.97 (16)	C2—S1—C1—C1ⁱⁱ	−79.7 (2)
I1—Cu1—N2—C6	64.03 (16)	C3—N1—C2—N2	0.9 (3)
C2—N1—C3—C5	−1.1 (3)	C3—N1—C2—S1	179.92 (14)
C2—N1—C3—C4	179.03 (19)	C6—N2—C2—N1	0.3 (3)
C6—C5—C3—N1	0.2 (3)	Cu1—N2—C2—N1	−175.69 (15)
C6—C5—C3—C4	−179.9 (2)	C6—N2—C2—S1	−178.79 (13)
C2—N2—C6—C5	−1.3 (3)	Cu1—N2—C2—S1	5.22 (18)
Cu1—N2—C6—C5	174.53 (14)	C1—S1—C2—N1	9.16 (18)
C2—N2—C6—C7	178.58 (18)	C1—S1—C2—N2	−171.68 (14)
Cu1—N2—C6—C7	−5.6 (2)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[CuI(C₁₄H₁₈N₄S₂)]
M_r	496.88
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.201 (5), 8.064 (5), 16.940 (5)
β (°)	111.655 (5)
V (Å³)	1803.0 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.16
Crystal size (mm)	0.33 × 0.24 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.419, 0.515
No. of measured, independent and observed [I > 2σ(I)] reflections	5585, 2070, 1942
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.053, 1.09
No. of reflections	2070
No. of parameters	103
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.37

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

I1—Cu1	2.5191 (16)	Cu1—N2	2.0327 (16)

N2ⁱ—Cu1—N2	118.55 (10)	N2ⁱ—Cu1—I1	120.72 (5)

Symmetry code: (i) −x+1, y, −z+1/2.

Acknowledgements

We thank Professor W.-T. Yu of Shan Dong University for his assistance with the X-ray structure determinations.

References

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