catena-Poly[[bis­[(dicyanamido)silver(I)](Ag—Ag)]-μ2-4,4′-bipyridine-κ2N:N′]

Zhang, J.

doi:10.1107/S1600536809050491

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1703

doi:10.1107/S1600536809050491

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catena-Poly[[bis[(dicyanamido)silver(I)](Ag—Ag)]-μ₂-4,4′-bipyridine-κ²N:N′]

Jinfang Zhang ^a ^*

^aMolecular Materials Research Center, Scientific Research Academy, School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: zjf260@ujs.edu.cn

(Received 18 November 2009; accepted 24 November 2009; online 28 November 2009)

In the title compound, [Ag₂(C₂N₃)₂(C₁₀H₈N₂)]_n, the Ag atoms, lying on inversion centers, are separated by 3.3226 (12) Å. Each Ag atom is connected by one bridging 4,4′-bipyridine [Ag—N = 2.177 (4)Å] and a terminal dicyanamide [Ag—N = 2.108 (4) Å]. The Ag—Ag interactions play a key role in constructing a unique neutral polymeric chain.

Related literature

For the designed syntheses of metal-organic compounds, see: Eddaoudi et al. (2001 ); Zhang et al. (2008 , 2009a ,b ). For their applications, see: Banerjee et al. (2008 ); Zhang et al. (2007 ).

Experimental

Crystal data

[Ag₂(C₂N₃)₂(C₁₀H₈N₂)]
M_r = 252.01
Triclinic, $[P \overline 1]$
a = 6.1867 (12) Å
b = 7.8344 (16) Å
c = 7.9649 (16) Å
α = 88.83 (3)°
β = 84.09 (3)°
γ = 77.54 (3)°
V = 374.95 (13) Å³
Z = 2
Mo Kα radiation
μ = 2.63 mm⁻¹
T = 293 K
0.2 × 0.16 × 0.12 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.407, T_max = 0.664
2474 measured reflections
1358 independent reflections
1315 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.103
S = 1.24
1358 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050491/pv2240sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050491/pv2240Isup2.hkl

checkCIF report

Comment top

The designed syntheses of metal-organic compounds have attracted great attention in recent years because of not only their intriguing structures (Eddaoudi et al., 2001; Zhang et al., 2008) but also their potential applications.(Banerjee et al., 2008; Zhang et al., 2007). The flexible and rigid bridging ligands can play different roles in constructing metal-organic frameworks. The tilte compound, (I), was constructed by employing a flexible, dicyanamide, and a rigid, 4,4'-bipyridine ligand through diffusion reactions. In this paper, the crystal structure of (I) is presented.

As illustrated in Fig. 1, 4,4'-bipyridine acts as a bridgeing ligand to connect two Ag atoms. Dicyanamide usually acts as a briding ligand to construct metal-organic compounds (Zhang et al., 2009a,b). However, in the tilte compound, it is linked to only one Ag atom. Ag—Ag bonds [3.3226 (12) Å] play a key role in constructing a unique one-dimensional neutral chain.

Related literature top

For the designed syntheses of metal-organic compounds, see: Eddaoudi et al. (2001); Zhang et al. (2008, 2009a,b). For their applications, see: Banerjee et al. (2008); Zhang et al. (2007).

Experimental top

Ag(NO₃) (68.0 mg, 0.4 mmol) and NaN(CN)₂ (178.2 mg, 2 mmol) were added into 3 ml dimethylformamide with thorough stirring for 5 minutes. After filtration, the colorless filtrate was carefully laid on the surface of a solution of 4,4'-bipyridine (78.0 mg, 0.5 mmol) in 8 ml i-PrOH. Colorless prismatic crystals were obtained after five days.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (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 the title compound, with atom labels and 30% probability displacement ellipsoids; H atoms have been omitted for clarity. Symmetry code: ⁱ = -x+2, -y+1, -z+1.

catena-Poly[[bis[(dicyanamido)silver(I)](Ag—Ag)]-µ₂- 4,4'-bipyridine-κ²N:N'] top

Crystal data top

[Ag₂(C₂N₃)₂(C₁₀H₈N₂)]	Z = 2
M_r = 252.01	F(000) = 242
Triclinic, P1	D_x = 2.232 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1867 (12) Å	Cell parameters from 1687 reflections
b = 7.8344 (16) Å	θ = 2.6–28.7°
c = 7.9649 (16) Å	µ = 2.63 mm⁻¹
α = 88.83 (3)°	T = 293 K
β = 84.09 (3)°	Prism, colorless
γ = 77.54 (3)°	0.2 × 0.16 × 0.12 mm
V = 374.95 (13) Å³

Data collection top

Rigaku Saturn724+ diffractometer	1358 independent reflections
Radiation source: fine-focus sealed tube	1315 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
dtprofit.ref scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.407, T_max = 0.664	k = −6→9
2474 measured reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0601P)² + 0.1547P] where P = (F_o² + 2F_c²)/3
S = 1.24	(Δ/σ)_max < 0.001
1358 reflections	Δρ_max = 0.67 e Å⁻³
110 parameters	Δρ_min = −0.70 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.055 (7)

Crystal data top

[Ag₂(C₂N₃)₂(C₁₀H₈N₂)]	γ = 77.54 (3)°
M_r = 252.01	V = 374.95 (13) Å³
Triclinic, P1	Z = 2
a = 6.1867 (12) Å	Mo Kα radiation
b = 7.8344 (16) Å	µ = 2.63 mm⁻¹
c = 7.9649 (16) Å	T = 293 K
α = 88.83 (3)°	0.2 × 0.16 × 0.12 mm
β = 84.09 (3)°

Data collection top

Rigaku Saturn724+ diffractometer	1358 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1315 reflections with I > 2σ(I)
T_min = 0.407, T_max = 0.664	R_int = 0.022
2474 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.24	Δρ_max = 0.67 e Å⁻³
1358 reflections	Δρ_min = −0.70 e Å⁻³
110 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
Ag1	0.83031 (5)	0.39268 (4)	0.61182 (3)	0.0570 (3)
N1	0.6869 (7)	0.6445 (6)	0.3950 (4)	0.0626 (10)
N2	0.7664 (7)	0.5131 (6)	−0.1486 (5)	0.0544 (9)
N3	0.6751 (7)	0.7081 (5)	0.0944 (5)	0.0518 (9)
N4	0.8957 (6)	0.2168 (4)	0.3957 (4)	0.0432 (8)
C1	0.6855 (6)	0.6651 (5)	0.2524 (5)	0.0428 (8)
C2	0.7278 (6)	0.5953 (5)	−0.0277 (5)	0.0416 (8)
C3	0.9785 (6)	0.0426 (5)	0.0830 (5)	0.0367 (8)
C4	0.7354 (7)	0.2209 (6)	0.2947 (6)	0.0521 (10)
H4	0.5933	0.2842	0.3301	0.063*
C5	0.7682 (7)	0.1371 (6)	0.1417 (6)	0.0511 (10)
H5	0.6497	0.1434	0.0772	0.061*
C6	1.0962 (7)	0.1231 (5)	0.3420 (5)	0.0447 (9)
H6	1.2110	0.1175	0.4100	0.054*
C7	1.1423 (6)	0.0341 (5)	0.1914 (5)	0.0431 (8)
H7	1.2844	−0.0324	0.1617	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0661 (4)	0.0685 (3)	0.0347 (3)	−0.0119 (2)	0.00158 (18)	−0.02256 (18)
N1	0.084 (3)	0.067 (2)	0.033 (2)	−0.008 (2)	−0.0024 (19)	−0.0116 (16)
N2	0.064 (2)	0.064 (2)	0.0322 (19)	−0.0080 (18)	−0.0025 (16)	−0.0155 (16)
N3	0.067 (2)	0.0520 (19)	0.0328 (19)	−0.0039 (16)	−0.0054 (16)	−0.0089 (14)
N4	0.0522 (19)	0.0447 (17)	0.0315 (17)	−0.0072 (14)	−0.0042 (14)	−0.0108 (13)
C1	0.046 (2)	0.0467 (19)	0.035 (2)	−0.0082 (15)	−0.0020 (16)	−0.0148 (15)
C2	0.0421 (19)	0.051 (2)	0.0298 (19)	−0.0065 (15)	−0.0029 (15)	−0.0036 (16)
C3	0.0445 (19)	0.0327 (16)	0.0321 (19)	−0.0068 (14)	−0.0026 (15)	−0.0023 (14)
C4	0.043 (2)	0.060 (2)	0.047 (2)	0.0017 (17)	−0.0021 (18)	−0.0214 (19)
C5	0.043 (2)	0.061 (2)	0.045 (2)	0.0015 (17)	−0.0080 (17)	−0.0224 (19)
C6	0.049 (2)	0.049 (2)	0.035 (2)	−0.0064 (16)	−0.0091 (17)	−0.0074 (16)
C7	0.0411 (19)	0.046 (2)	0.038 (2)	0.0005 (15)	−0.0065 (16)	−0.0082 (15)

Geometric parameters (Å, º) top

Ag1—N2ⁱ	2.108 (4)	N4—C4	1.334 (6)
Ag1—N4	2.177 (4)	C3—C7	1.387 (6)
Ag1—N1	2.661 (4)	C3—C5	1.390 (6)
Ag1—Ag1ⁱⁱ	3.3226 (12)	C3—C3^iv	1.467 (8)
N1—C1	1.144 (5)	C4—C5	1.372 (6)
N2—C2	1.145 (6)	C4—H4	0.9300
N2—Ag1ⁱⁱⁱ	2.108 (4)	C5—H5	0.9300
N3—C2	1.296 (6)	C6—C7	1.373 (6)
N3—C1	1.301 (6)	C6—H6	0.9300
N4—C6	1.331 (5)	C7—H7	0.9300

N2ⁱ—Ag1—N4	167.60 (15)	C7—C3—C3^iv	122.8 (4)
N2ⁱ—Ag1—N1	105.43 (14)	C5—C3—C3^iv	121.4 (4)
N4—Ag1—N1	86.07 (12)	N4—C4—C5	123.8 (4)
N2ⁱ—Ag1—Ag1ⁱⁱ	105.25 (12)	N4—C4—H4	118.1
N4—Ag1—Ag1ⁱⁱ	84.71 (10)	C5—C4—H4	118.1
N1—Ag1—Ag1ⁱⁱ	57.43 (10)	C4—C5—C3	120.0 (4)
C1—N1—Ag1	139.3 (4)	C4—C5—H5	120.0
C2—N2—Ag1ⁱⁱⁱ	172.6 (4)	C3—C5—H5	120.0
C2—N3—C1	123.1 (4)	N4—C6—C7	123.4 (4)
C6—N4—C4	116.4 (4)	N4—C6—H6	118.3
C6—N4—Ag1	123.9 (3)	C7—C6—H6	118.3
C4—N4—Ag1	118.8 (3)	C6—C7—C3	120.5 (4)
N1—C1—N3	173.2 (5)	C6—C7—H7	119.7
N2—C2—N3	171.4 (4)	C3—C7—H7	119.7
C7—C3—C5	115.8 (4)

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

Experimental details

Crystal data
Chemical formula	[Ag₂(C₂N₃)₂(C₁₀H₈N₂)]
M_r	252.01
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.1867 (12), 7.8344 (16), 7.9649 (16)
α, β, γ (°)	88.83 (3), 84.09 (3), 77.54 (3)
V (Å³)	374.95 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.63
Crystal size (mm)	0.2 × 0.16 × 0.12

Data collection
Diffractometer	Rigaku Saturn724+ diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.407, 0.664
No. of measured, independent and observed [I > 2σ(I)] reflections	2474, 1358, 1315
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.103, 1.24
No. of reflections	1358
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.70

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Foundation of Jiangsu University (08JDG036).

References

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