catena-Poly[[[2-(pyridin-2-yldisulfan­yl)pyridine-κ2N,S]copper(I)]-μ1,5-dicyanamido]

Wu, S.; Jiang, W.; Li, F.; Liu, L.

doi:10.1107/S1600536811002728

metal-organic compounds

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Volume 67| Part 2| February 2011| Page m285

doi:10.1107/S1600536811002728

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catena-Poly[[[2-(pyridin-2-yldisulfanyl)pyridine-κ²N,S]copper(I)]-μ_1,5-dicyanamido]

Shixi Wu,^a Wei Jiang,^a Fengsheng Li ^a ^* and Li Liu ^a

^aNational Special Superfine Powder Engineering Research Center, Nanjing University of Science and Technology, Nanjing 210094, People's Republic of China
^*Correspondence e-mail: wushixi_308@yahoo.com.cn

(Received 8 January 2011; accepted 20 January 2011; online 29 January 2011)

In the title compound, [Cu(C₂N₃)(C₁₀H₈N₂S₂)]_n, the Cu^I atoms are connected by bridging dicyanamide ligands, forming chains parallel to [100]. Each Cu^I atom displays a tetrahedral coordination environment, formed by one S atom and three N atoms from one 2-(pyridin-2-yldisulfanyl)pyridine and two dicyanamide ligands. The crystal structure is stabilized by C—H⋯N hydrogen bonds, forming a three-dimensional network.

Related literature

For potential applications of metal-organic frameworks, see: Eddaoudi et al. (2001 ). For metal-organic frameworks constructed from flexible ligands, see: Xu et al. (2009 ). For related structures, see: Mal et al. (2006 ); Schlueter et al. (2007 ); Sen et al. (2007 ).

Experimental

Crystal data

[Cu(C₂N₃)(C₁₀H₈N₂S₂)]
M_r = 349.92
Triclinic, $[P \overline 1]$
a = 7.6294 (15) Å
b = 9.5964 (19) Å
c = 10.202 (2) Å
α = 84.19 (3)°
β = 80.63 (3)°
γ = 70.93 (3)°
V = 695.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.87 mm⁻¹
T = 293 K
0.20 × 0.16 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.893, T_max = 1.000
6615 measured reflections
2669 independent reflections
2301 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.081
S = 1.07
2669 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯N3ⁱ	0.93	2.53	3.453 (3)	171
Symmetry code: (i) x+1, y-1, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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/S1600536811002728/zq2085sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002728/zq2085Isup2.hkl

checkCIF report

Comment top

Metal-organic compounds have attracted much attention because of their diverse structures (Eddaoudi et al., 2001). Flexible ligands can play different roles in constructing metal-organic frameworks (Xu et al., 2009). The title compound, {C₁₂H₈CuN₅S₂}_n, is constructed by two kinds of flexible ligands: briding dicyanamide ligands and chelate 2-(pyridin-2-yldisulfanyl)pyridine ligands. In this paper, the crystal structure of the title compound is presented. As illustrated in Fig. 1, the Cu atoms are connected by briding dicyanamide ligands, forming a serrate chain. Each Cu atom displays a tetrahedral coordination environment, formed by one S atom and three N atoms from one 2-(pyridin-2-yldisulfanyl)pyridine and two dicyanamide ligands, where the Cu—S and average Cu—N bonds are 2.472 (1) and 1.969 Å, respectively. The crystal structure is stabilized by C—H···N hydrogen bonds [H9···N3ⁱⁱⁱ = 2.53 Å, C9···N3ⁱⁱⁱ = 3.453 (3) Å, and C9—H9···N3ⁱⁱⁱ = 171°] between the central N atom of the dicyanamide and one H atom of a pyridine ring, forming a three-dimensional network [symmetry code: (iii) x + 1, y - 1, z].

Related literature top

For potential applications of metal-organic frameworks, see: Eddaoudi et al. (2001). For metal-organic frameworks constructed from flexible ligands, see: Xu et al. (2009). For related structures, see: Mal et al. (2006); Schlueter et al. (2007); Sen et al. (2007).

Experimental top

CuN(CN)₂ (0.4 mmol) and NaN(CN)₂ (1.2 mmol) were added into 2 ml DMF with thorough stir for 6 minutes. After filtration, the colorless filtrate was carefully laid on the surface with the solution of bis(2-pyridyl)disulfide (0.5 mmol) in 5 ml i-PrOH. Colorless crystals were obtained after 3 weeks.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. The molecular structure of a portion of the title compound, with atom labels and 30% probability displacement ellipsoids. All H atoms have been omitted [symmetry code: (i) x+1, y, z].

catena-Poly[[[2-(pyridin-2-yldisulfanyl)pyridine- κ²N,S]copper(I)]-µ_1,5-dicyanamido] top

Crystal data top

[Cu(C₂N₃)(C₁₀H₈N₂S₂)]	Z = 2
M_r = 349.92	F(000) = 352
Triclinic, P1	D_x = 1.671 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6294 (15) Å	Cell parameters from 3088 reflections
b = 9.5964 (19) Å	θ = 3.0–28.9°
c = 10.202 (2) Å	µ = 1.87 mm⁻¹
α = 84.19 (3)°	T = 293 K
β = 80.63 (3)°	Block, colourless
γ = 70.93 (3)°	0.20 × 0.16 × 0.12 mm
V = 695.6 (2) Å³

Data collection top

Bruker APEXII CCD diffractometer	2669 independent reflections
Radiation source: fine-focus sealed tube	2301 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 26.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
T_min = 0.893, T_max = 1.000	k = −11→11
6615 measured reflections	l = −12→12

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0478P)² + 0.0204P] where P = (F_o² + 2F_c²)/3
2669 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Cu(C₂N₃)(C₁₀H₈N₂S₂)]	γ = 70.93 (3)°
M_r = 349.92	V = 695.6 (2) Å³
Triclinic, P1	Z = 2
a = 7.6294 (15) Å	Mo Kα radiation
b = 9.5964 (19) Å	µ = 1.87 mm⁻¹
c = 10.202 (2) Å	T = 293 K
α = 84.19 (3)°	0.20 × 0.16 × 0.12 mm
β = 80.63 (3)°

Data collection top

Bruker APEXII CCD diffractometer	2669 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2301 reflections with I > 2σ(I)
T_min = 0.893, T_max = 1.000	R_int = 0.018
6615 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.07	Δρ_max = 0.39 e Å⁻³
2669 reflections	Δρ_min = −0.29 e Å⁻³
181 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	−0.03943 (3)	0.83530 (3)	0.16964 (3)	0.05693 (13)
S1	−0.00326 (7)	0.67390 (7)	0.37486 (5)	0.05609 (17)
S2	0.11161 (9)	0.47767 (7)	0.28919 (5)	0.06255 (18)
N1	−0.3026 (2)	0.9293 (2)	0.16879 (19)	0.0580 (5)
N2	0.1131 (2)	0.9633 (2)	0.17961 (19)	0.0599 (5)
N3	−0.6377 (2)	1.0592 (2)	0.2077 (2)	0.0694 (6)
N4	0.3589 (3)	0.6469 (2)	0.38308 (18)	0.0610 (5)
N5	0.1249 (2)	0.65814 (18)	0.06703 (15)	0.0464 (4)
C1	−0.4605 (3)	0.9840 (2)	0.1839 (2)	0.0489 (5)
C2	0.2361 (3)	1.0016 (2)	0.1905 (2)	0.0480 (5)
C3	0.1841 (3)	0.7106 (2)	0.43562 (18)	0.0452 (4)
C4	0.1311 (3)	0.8103 (3)	0.5330 (2)	0.0612 (6)
H4	0.0059	0.8499	0.5684	0.073*
C5	0.2682 (4)	0.8504 (3)	0.5770 (2)	0.0709 (7)
H5	0.2372	0.9197	0.6414	0.085*
C6	0.4516 (4)	0.7863 (3)	0.5242 (2)	0.0692 (7)
H6	0.5475	0.8109	0.5519	0.083*
C7	0.4889 (3)	0.6858 (3)	0.4302 (2)	0.0695 (7)
H7	0.6136	0.6409	0.3963	0.083*
C8	0.1811 (3)	0.5212 (2)	0.11824 (18)	0.0462 (5)
C9	0.2919 (4)	0.4027 (2)	0.0454 (2)	0.0627 (6)
H9	0.3245	0.3078	0.0850	0.075*
C10	0.3528 (4)	0.4264 (3)	−0.0852 (2)	0.0681 (7)
H10	0.4289	0.3484	−0.1362	0.082*
C11	0.2996 (4)	0.5682 (3)	−0.1403 (2)	0.0660 (6)
H11	0.3402	0.5877	−0.2292	0.079*
C12	0.1868 (3)	0.6795 (2)	−0.0633 (2)	0.0568 (5)
H12	0.1505	0.7748	−0.1019	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03597 (17)	0.0595 (2)	0.0745 (2)	−0.01273 (13)	−0.00278 (13)	−0.01572 (14)
S1	0.0434 (3)	0.0798 (4)	0.0469 (3)	−0.0244 (3)	0.0007 (2)	−0.0063 (3)
S2	0.0847 (4)	0.0645 (4)	0.0502 (3)	−0.0423 (3)	−0.0082 (3)	0.0048 (3)
N1	0.0393 (10)	0.0623 (11)	0.0748 (12)	−0.0157 (9)	−0.0099 (8)	−0.0125 (9)
N2	0.0394 (10)	0.0572 (11)	0.0836 (13)	−0.0155 (9)	−0.0067 (9)	−0.0086 (10)
N3	0.0382 (10)	0.0433 (10)	0.1278 (17)	−0.0077 (8)	−0.0184 (10)	−0.0154 (11)
N4	0.0464 (10)	0.0763 (13)	0.0606 (10)	−0.0187 (9)	0.0016 (8)	−0.0213 (10)
N5	0.0448 (9)	0.0463 (9)	0.0459 (9)	−0.0120 (7)	−0.0051 (7)	−0.0025 (7)
C1	0.0433 (12)	0.0430 (10)	0.0654 (12)	−0.0170 (9)	−0.0154 (10)	−0.0011 (9)
C2	0.0353 (10)	0.0381 (10)	0.0647 (12)	−0.0040 (8)	−0.0064 (9)	−0.0028 (9)
C3	0.0450 (11)	0.0532 (11)	0.0357 (9)	−0.0147 (9)	−0.0049 (8)	0.0008 (9)
C4	0.0542 (13)	0.0674 (14)	0.0528 (11)	−0.0058 (11)	−0.0028 (10)	−0.0145 (11)
C5	0.0843 (18)	0.0700 (15)	0.0601 (13)	−0.0197 (14)	−0.0148 (12)	−0.0186 (12)
C6	0.0719 (16)	0.0802 (17)	0.0667 (14)	−0.0325 (14)	−0.0237 (13)	−0.0036 (13)
C7	0.0453 (12)	0.0879 (18)	0.0762 (15)	−0.0188 (12)	−0.0066 (11)	−0.0184 (14)
C8	0.0496 (11)	0.0484 (11)	0.0467 (10)	−0.0227 (9)	−0.0093 (9)	−0.0022 (9)
C9	0.0802 (17)	0.0417 (11)	0.0665 (14)	−0.0190 (11)	−0.0118 (12)	−0.0030 (11)
C10	0.0834 (18)	0.0525 (13)	0.0635 (14)	−0.0162 (12)	0.0008 (12)	−0.0167 (11)
C11	0.0817 (17)	0.0652 (15)	0.0466 (11)	−0.0200 (13)	0.0006 (11)	−0.0081 (11)
C12	0.0596 (13)	0.0518 (12)	0.0520 (11)	−0.0108 (10)	−0.0056 (10)	0.0024 (10)

Geometric parameters (Å, º) top

Cu1—N1	1.9143 (18)	C3—C4	1.369 (3)
Cu1—N2	1.967 (2)	C4—C5	1.377 (4)
Cu1—N5	2.0244 (18)	C4—H4	0.9300
Cu1—S1	2.4720 (10)	C5—C6	1.373 (4)
S1—C3	1.792 (2)	C5—H5	0.9300
S1—S2	2.0207 (11)	C6—C7	1.361 (4)
S2—C8	1.787 (2)	C6—H6	0.9300
N1—C1	1.138 (3)	C7—H7	0.9300
N2—C2	1.138 (3)	C8—C9	1.378 (3)
N3—C2ⁱ	1.298 (3)	C9—C10	1.360 (3)
N3—C1	1.303 (3)	C9—H9	0.9300
N4—C3	1.319 (3)	C10—C11	1.375 (3)
N4—C7	1.337 (3)	C10—H10	0.9300
N5—C8	1.322 (3)	C11—C12	1.359 (3)
N5—C12	1.356 (3)	C11—H11	0.9300
C2—N3ⁱⁱ	1.298 (3)	C12—H12	0.9300

N1—Cu1—N2	117.16 (8)	C6—C5—C4	118.9 (2)
N1—Cu1—N5	126.58 (8)	C6—C5—H5	120.6
N2—Cu1—N5	107.60 (7)	C4—C5—H5	120.6
N1—Cu1—S1	106.75 (7)	C7—C6—C5	118.1 (2)
N2—Cu1—S1	104.29 (6)	C7—C6—H6	121.0
N5—Cu1—S1	87.90 (5)	C5—C6—H6	121.0
C3—S1—S2	105.95 (8)	N4—C7—C6	124.6 (2)
C3—S1—Cu1	102.35 (7)	N4—C7—H7	117.7
S2—S1—Cu1	98.20 (4)	C6—C7—H7	117.7
C8—S2—S1	105.52 (8)	N5—C8—C9	123.48 (18)
C1—N1—Cu1	172.06 (19)	N5—C8—S2	121.22 (16)
C2—N2—Cu1	161.63 (17)	C9—C8—S2	115.29 (16)
C2ⁱ—N3—C1	120.23 (19)	C10—C9—C8	119.1 (2)
C3—N4—C7	115.9 (2)	C10—C9—H9	120.5
C8—N5—C12	116.52 (18)	C8—C9—H9	120.5
C8—N5—Cu1	124.88 (13)	C9—C10—C11	118.6 (2)
C12—N5—Cu1	118.59 (14)	C9—C10—H10	120.7
N1—C1—N3	173.2 (2)	C11—C10—H10	120.7
N2—C2—N3ⁱⁱ	173.5 (2)	C12—C11—C10	119.2 (2)
N4—C3—C4	124.4 (2)	C12—C11—H11	120.4
N4—C3—S1	119.92 (16)	C10—C11—H11	120.4
C4—C3—S1	115.61 (16)	N5—C12—C11	123.1 (2)
C3—C4—C5	118.1 (2)	N5—C12—H12	118.5
C3—C4—H4	120.9	C11—C12—H12	118.5
C5—C4—H4	120.9

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···N3ⁱⁱⁱ	0.93	2.53	3.453 (3)	171

Symmetry code: (iii) x+1, y−1, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₂N₃)(C₁₀H₈N₂S₂)]
M_r	349.92
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.6294 (15), 9.5964 (19), 10.202 (2)
α, β, γ (°)	84.19 (3), 80.63 (3), 70.93 (3)
V (Å³)	695.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.87
Crystal size (mm)	0.20 × 0.16 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.893, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6615, 2669, 2301
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.081, 1.07
No. of reflections	2669
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···N3ⁱ	0.93	2.53	3.453 (3)	171

Symmetry code: (i) x+1, y−1, z.

Acknowledgements

The authors are grateful for the financial support of the National Natural Science Foundation of China (Nos. 50602024, 50972060) and NUST Research Funding (No. 2010ZDJH06).

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