Poly[{μ2-1,2-bis­[4-(3-pyrid­yl)pyrimidin-2-ylsulfan­yl]ethane}di-μ2-cyanido-dicopper(I)]

Zhang, Y.-W.; Dong, H.-Z.; Cheng, L.

doi:10.1107/S1600536808013172

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m868

doi:10.1107/S1600536808013172

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Poly[{μ₂-1,2-bis[4-(3-pyridyl)pyrimidin-2-ylsulfanyl]ethane}di-μ₂-cyanido-dicopper(I)]

Ya-Wen Zhang,^a Hua-Ze Dong ^b and Lin Cheng ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing, People's Republic of China, and ^bDepartment of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, People's Republic of China
^*Correspondence e-mail: cep02chl@yahoo.com.cn

(Received 12 April 2008; accepted 5 May 2008; online 7 June 2008)

The asymmetric unit of the title complex, [Cu₂(CN)₂(C₂₀H₁₆N₆S₂)]_n, contains one Cu^I cation, one cyanide ligand and half of a centrosymmetric 1,2-bis[4-(3-pyridyl)pyrimidin-2-ylsulfanyl]ethane (bppe) ligand. The Cu^I atom displays a trigonal coordination geometry, being surrounded by one C atom from one cyanide anion and two N atoms from one cyanide and one bppe ligand. In the complex, each cyanide anion links two Cu^I atoms in a bis-monodentate mode into a zigzag [–Cu—CN–]_n chain. Two parallel chains are linked by bppe ligands into a ladder chain.

Related literature

For related literature, see: Awaleh et al. (2005 ); Bu et al. (2003 ); Chen et al. (2003 ); Su et al. (2000 ); Xie et al. (2005 ).

Experimental

Crystal data

[Cu₂(CN)₂(C₂₀H₁₆N₆S₂)]
M_r = 291.81
Monoclinic, C 2/c
a = 16.025 (4) Å
b = 16.296 (7) Å
c = 9.3103 (17) Å
β = 105.660 (19)°
V = 2341.1 (12) Å³
Z = 8
Mo Kα radiation
μ = 2.02 mm⁻¹
T = 153 (2) K
0.50 × 0.20 × 0.10 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.431, T_max = 0.823
6130 measured reflections
2290 independent reflections
1925 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.083
S = 1.09
2290 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 2000 ); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013172/hg2393sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013172/hg2393Isup2.hkl

checkCIF report

Comment top

There has been current significant interest in the rational design and synthesis of metal-organic coordination architectures by using flexible bridging units due that the flexibility and conformational freedoms of such ligands offer the possibility for the construction of unprecedented frameworks (Su et al., 2000). Recently, flexible thioethers have been well established ligands in coordination and metallosupramolecular chemistry because of their rich structural information (Awaleh et al., 2005, Bu et al., 2003, Chen et al., 2003, Xie et al., 2005). Herein, we report the crystal structure of the title compound, [Cu₂(CN)₂(C₂₀H₁₆N₆S₂)]_n, based on a pyridyl dithioether ligand–1,2-bis(4-(pyridinyl-4-)pyrimidin-2-ylthio)ethane. The asymmetric unit of the title complex, contains one Cu^I cation, one cyano and half a bppe (bppe = 1,2-bis(4-(pyridinyl-4-)pyrimidin -2-ylthio)ethane) ligand. The Cu^I atom displays a triangular geometry, being surrounded by one carbon atom (Cu1—C11a 1.873 (3) Å) from one cyano anion and two nitrogen atoms from one cyano (Cu1—N4 1.916 (2) Å) and one bppe ligand (Cu1—N3 1.873 (3) Å). In the complex, each cyano aion links two Cu^I atoms in a bis-monodentate mode into a zigzag (CuCN)_n chain. The shortest intrachain Cu—Cu distance is 4.894 (2) Å. Two parallel zigzag chains were linked by bppe ligands into a one-dimensional ladder chain, in which the Cu—Cu distance separated by bppe is 11.648 (3) Å. The ladder chain is stabilized by the intraladder C–H···N hydrogen bonds (C9—N1 2.810 (3) Å; C8—N2 3.398 (4) Å). Finally, the ladder chains were constructed into a three-dimensional supramolecular network by the interladder C10–H···N1c (c = -1/2 + x,1/2 - y,1/2 + z) hydrogen bond with the C···N distance 2.891 (4) Å.

Related literature top

For related literature, see: Awaleh et al. (2005); Bu et al. (2003); Chen et al. (2003); Su et al. (2000); Xie et al. (2005).

Experimental top

A mixture of bppe (0.040 g, 0.1 mmol), CuCN (0.018 g, 0.2 mmol), and water (6 ml) were heated in a 15-ml Teflon-lined vessel at 403 K for 3 days, followed by slow cooling (5 K/hr) to room temperature. After filtration and washing with H2O, colorless needle-like crystals were collected and dried in air (0.019 g, yield ca 32% based on bppe).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Local coordination environment of the title compound with 30% thermal ellipsoids. All the hydrogen atoms are omitted for clarity. Symmetry codes for 1, a: x, -y, 1/2 + z; b: 1 - x, -y,1 - z.
	Fig. 2. The zigzag (CuCN)_n chain in the title compound.
	Fig. 3. The one-dimensional ladder chain of the title compound.

Poly[{µ₂-1,2-bis[4-(3-pyridyl)pyrimidin-2-ylsulfanyl]ethane}di-µ₂- cyanido-dicopper(I)] top

Crystal data top

[Cu₂(CN)₂(C₂₀H₁₆N₆S₂)]	F(000) = 1176
M_r = 291.81	D_x = 1.656 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 765 reflections
a = 16.025 (4) Å	θ = 2.5–28.0°
b = 16.296 (7) Å	µ = 2.02 mm⁻¹
c = 9.3103 (17) Å	T = 153 K
β = 105.660 (19)°	Needle-like, colorless
V = 2341.1 (12) Å³	0.50 × 0.20 × 0.10 mm
Z = 8

Data collection top

Bruker APEX CCD diffractometer	2290 independent reflections
Radiation source: fine-focus sealed tube	1925 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −19→9
T_min = 0.431, T_max = 0.823	k = −20→19
6130 measured reflections	l = −11→11

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0456P)² + 0.02P] where P = (F_o² + 2F_c²)/3
2290 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Cu₂(CN)₂(C₂₀H₁₆N₆S₂)]	V = 2341.1 (12) Å³
M_r = 291.81	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 16.025 (4) Å	µ = 2.02 mm⁻¹
b = 16.296 (7) Å	T = 153 K
c = 9.3103 (17) Å	0.50 × 0.20 × 0.10 mm
β = 105.660 (19)°

Data collection top

Bruker APEX CCD diffractometer	2290 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	1925 reflections with I > 2σ(I)
T_min = 0.431, T_max = 0.823	R_int = 0.036
6130 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.09	Δρ_max = 0.41 e Å⁻³
2290 reflections	Δρ_min = −0.32 e Å⁻³
154 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	0.200534 (18)	0.046307 (17)	0.73287 (3)	0.04397 (13)
S1	0.58681 (4)	0.09504 (5)	0.45165 (9)	0.0681 (2)
N1	0.46673 (11)	0.17752 (12)	0.5455 (2)	0.0424 (4)
N2	0.55869 (14)	0.25077 (17)	0.4267 (2)	0.0624 (6)
N3	0.25417 (11)	0.16006 (11)	0.71533 (19)	0.0379 (4)
N4	0.18704 (14)	0.00114 (12)	0.5379 (2)	0.0506 (5)
C1	0.52978 (14)	0.18272 (17)	0.4778 (3)	0.0496 (6)
C2	0.52069 (18)	0.3195 (2)	0.4501 (3)	0.0661 (8)
H2	0.5387	0.3684	0.4167	0.079*
C3	0.45586 (16)	0.32250 (16)	0.5214 (3)	0.0539 (6)
H3	0.4308	0.3719	0.5373	0.065*
C4	0.42959 (13)	0.24839 (14)	0.5686 (2)	0.0386 (5)
C5	0.35930 (13)	0.24308 (13)	0.6430 (2)	0.0355 (5)
C6	0.33133 (15)	0.31071 (14)	0.7073 (3)	0.0452 (5)
H6	0.3570	0.3617	0.7045	0.054*
C7	0.26579 (16)	0.30235 (15)	0.7749 (3)	0.0514 (6)
H7	0.2461	0.3475	0.8174	0.062*
C8	0.22945 (14)	0.22636 (15)	0.7791 (3)	0.0442 (5)
H8	0.1862	0.2206	0.8279	0.053*
C9	0.31811 (13)	0.16915 (13)	0.6502 (2)	0.0367 (5)
H9	0.3361	0.1233	0.6071	0.044*
C10	0.54252 (17)	0.01639 (19)	0.5480 (3)	0.0632 (7)
H10A	0.5837	−0.0283	0.5753	0.076*
H10B	0.5337	0.0392	0.6390	0.076*
C11	0.18755 (15)	−0.01827 (14)	0.4207 (3)	0.0432 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0547 (2)	0.0449 (2)	0.04047 (19)	−0.00041 (12)	0.02691 (14)	0.00271 (11)
S1	0.0465 (4)	0.0949 (6)	0.0744 (5)	0.0002 (4)	0.0360 (3)	−0.0228 (4)
N1	0.0357 (10)	0.0536 (12)	0.0422 (10)	−0.0013 (8)	0.0179 (8)	−0.0022 (9)
N2	0.0467 (13)	0.0923 (19)	0.0555 (14)	−0.0152 (12)	0.0262 (11)	0.0025 (12)
N3	0.0387 (10)	0.0410 (10)	0.0402 (10)	−0.0013 (8)	0.0212 (8)	−0.0016 (8)
N4	0.0740 (14)	0.0401 (11)	0.0468 (11)	0.0020 (10)	0.0320 (10)	0.0010 (9)
C1	0.0354 (13)	0.0772 (18)	0.0396 (12)	−0.0048 (11)	0.0163 (10)	−0.0068 (12)
C2	0.0510 (16)	0.082 (2)	0.0691 (18)	−0.0173 (15)	0.0228 (14)	0.0213 (16)
C3	0.0458 (14)	0.0561 (15)	0.0623 (16)	−0.0030 (11)	0.0190 (12)	0.0152 (12)
C4	0.0291 (11)	0.0495 (13)	0.0379 (11)	−0.0011 (9)	0.0101 (9)	0.0048 (9)
C5	0.0325 (11)	0.0379 (12)	0.0370 (11)	0.0017 (8)	0.0113 (9)	0.0054 (8)
C6	0.0444 (13)	0.0359 (12)	0.0571 (14)	−0.0006 (9)	0.0167 (11)	0.0006 (10)
C7	0.0514 (15)	0.0442 (14)	0.0643 (16)	0.0045 (11)	0.0253 (12)	−0.0131 (12)
C8	0.0409 (13)	0.0515 (14)	0.0474 (13)	0.0023 (10)	0.0241 (10)	−0.0046 (11)
C9	0.0390 (12)	0.0361 (11)	0.0401 (11)	0.0028 (9)	0.0193 (9)	0.0003 (9)
C10	0.0495 (15)	0.0784 (19)	0.0614 (16)	0.0148 (14)	0.0144 (12)	−0.0181 (15)
C11	0.0614 (15)	0.0351 (11)	0.0401 (12)	0.0082 (10)	0.0259 (11)	0.0038 (10)

Geometric parameters (Å, º) top

Cu1—C11ⁱ	1.873 (2)	C3—H3	0.9300
Cu1—N4	1.916 (2)	C4—C5	1.476 (3)
Cu1—N3	2.0683 (19)	C5—C9	1.384 (3)
S1—C1	1.748 (3)	C5—C6	1.385 (3)
S1—C10	1.815 (3)	C6—C7	1.369 (4)
N1—C1	1.330 (3)	C6—H6	0.9300
N1—C4	1.343 (3)	C7—C8	1.374 (3)
N2—C2	1.321 (4)	C7—H7	0.9300
N2—C1	1.338 (3)	C8—H8	0.9300
N3—C9	1.332 (3)	C9—H9	0.9300
N3—C8	1.343 (3)	C10—C10ⁱⁱ	1.511 (5)
N4—C11	1.138 (3)	C10—H10A	0.9700
C2—C3	1.376 (4)	C10—H10B	0.9700
C2—H2	0.9300	C11—Cu1ⁱⁱⁱ	1.873 (2)
C3—C4	1.389 (3)

C11ⁱ—Cu1—N4	141.12 (9)	C9—C5—C6	117.2 (2)
C11ⁱ—Cu1—N3	116.47 (8)	C9—C5—C4	120.5 (2)
N4—Cu1—N3	102.27 (8)	C6—C5—C4	122.2 (2)
C1—S1—C10	102.68 (12)	C7—C6—C5	119.8 (2)
C1—N1—C4	116.6 (2)	C7—C6—H6	120.1
C2—N2—C1	115.1 (2)	C5—C6—H6	120.1
C9—N3—C8	117.83 (19)	C6—C7—C8	119.1 (2)
C9—N3—Cu1	121.50 (14)	C6—C7—H7	120.4
C8—N3—Cu1	120.50 (15)	C8—C7—H7	120.4
C11—N4—Cu1	170.7 (2)	N3—C8—C7	122.3 (2)
N1—C1—N2	127.0 (2)	N3—C8—H8	118.8
N1—C1—S1	120.4 (2)	C7—C8—H8	118.8
N2—C1—S1	112.58 (18)	N3—C9—C5	123.65 (19)
N2—C2—C3	123.5 (3)	N3—C9—H9	118.2
N2—C2—H2	118.3	C5—C9—H9	118.2
C3—C2—H2	118.3	C10ⁱⁱ—C10—S1	111.6 (3)
C2—C3—C4	117.0 (3)	C10ⁱⁱ—C10—H10A	109.3
C2—C3—H3	121.5	S1—C10—H10A	109.3
C4—C3—H3	121.5	C10ⁱⁱ—C10—H10B	109.3
N1—C4—C3	120.8 (2)	S1—C10—H10B	109.3
N1—C4—C5	116.88 (19)	H10A—C10—H10B	108.0
C3—C4—C5	122.3 (2)	N4—C11—Cu1ⁱⁱⁱ	173.9 (2)

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

Experimental details

Crystal data
Chemical formula	[Cu₂(CN)₂(C₂₀H₁₆N₆S₂)]
M_r	291.81
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	153
a, b, c (Å)	16.025 (4), 16.296 (7), 9.3103 (17)
β (°)	105.660 (19)
V (Å³)	2341.1 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.02
Crystal size (mm)	0.50 × 0.20 × 0.10

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.431, 0.823
No. of measured, independent and observed [I > 2σ(I)] reflections	6130, 2290, 1925
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.083, 1.09
No. of reflections	2290
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.32

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

References

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