catena-Poly[silver(I)-μ-pyrazolato-κ2N:N′]

Zhang, C.-Y.; Feng, J.-B.; Gao, Q.; Xie, Y.-B.

doi:10.1107/S1600536807063490

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page m352

doi:10.1107/S1600536807063490

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catena-Poly[silver(I)-μ-pyrazolato-κ²N:N′]

Chao-Yan Zhang,^a Jian-Bo Feng,^a Qian Gao ^a and Ya-Bo Xie ^a ^*

^aCollege of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100022, People's Republic of China
^*Correspondence e-mail: xieyabo@eyou.com

(Received 29 October 2007; accepted 26 November 2007; online 16 January 2008)

The title compound, [Ag(C₃H₃N₂)]_n, has an infinite helical chain structure in which each pyrazolate group bridges two Ag^I atoms related by a 2₁ axis with an intrachain Ag⋯Ag separation of 3.3718 (7) Å. Each Ag^I center is linearly coordinated by two N atoms [N—Ag—N angle = 169.98 (14)°]. The chains are held together by interchain Ag⋯Ag interactions [3.2547 (6) Å], forming a two-dimensional layer. The X-ray single-crystal diffraction result is consonant with that of the ab initio X-ray powder diffraction reported by Masciocchi, Moret, Cairati, Sironi, Ardizzoia & La Monica [J. Am. Chem. Soc. (1994). 116, 7668–7676], with only minor deviations of structural parameters.

Related literature

For related literature, see: Masciocchi et al. (1994 ).

Experimental

Crystal data

[Ag(C₃H₃N₂)]
M_r = 174.94
Orthorhombic, P b c a
a = 6.4084 (13) Å
b = 6.4989 (13) Å
c = 19.948 (4) Å
V = 830.8 (3) Å³
Z = 8
Mo Kα radiation
μ = 4.66 mm⁻¹
T = 293 (2) K
0.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.340, T_max = 0.400
7019 measured reflections
951 independent reflections
778 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.066
S = 1.26
951 reflections
55 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ag1—N1	2.070 (3)
Ag1—N2ⁱ	2.063 (4)
Ag1⋯Ag1ⁱⁱ	3.2547 (6)
Ag1⋯Ag1ⁱ	3.3718 (7)

N2ⁱ—Ag1—N1	169.98 (14)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063490/bq2042sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807063490/bq2042Isup2.hkl

checkCIF report

Comment top

The synthesis and structure of silver(I)-pyrazolate, i.e. the title compound, [Ag(C₃H₃N₂)]_n (I) has been reported by Masciocchi et al. (1994). In this work, the crystal structure was determined by the Ab-initio X-ray powder diffraction method and refined with the Rietveld technique in the space group of Pbca with a = 6.5295 (4), b = 20.059 (2) and c = 6.4675 (4) %A. The result is almost consistent with the structural determination by the single-crystal diffraction reported herein, with only minor structure parameter deviations.

Compound (I) has an infinite helical chain structure, in which each pyrazolate group bridges two Ag(I) atoms related by a 2₁ axis and each Ag(I) is linearly coordinated by two N atoms from distinct pyrazolate moieties with the N-Ag-N angle of 169.98 (14) °, being larger than reported 165.5 (1) °, (Figure 1). The bond distances and angles are listed in Table 1. The torsion angle of Ag(1)-N(1)-N(2)-Ag(1B) is 22.6 (4) ° and the dihedral angle between two pyrazoly rings around one Ag(I) center is 60.3 (2) °. Furthermore, such chains are linked by interchain Ag—Ag interactions to form a 2D layer (Figure 2). The intrachain and interaction Ag—Ag separations are 3.3718 (7) [Ag(1)-Ag(1A)] and 3.2547 (6) Å [Ag(1)-Ag(1B)], respectively, which are comparable well with those reported [3.40 (1) and 3.273 (1) Å, respectively].

Related literature top

For related literature, see: Masciocchi et al. (1994).

Experimental top

AgNO₃ (85 mg, 0.5 mmol) and pyrazole (34 mg, 0.5 mmol) were dissolved in ammonium hydroxide (20%, 10 ml). The solution was filtered and filtrate was allowed to stand for 15 days. Colorless crystals of (I) were collected, in about 50% yield.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top

	Fig. 1. Displacement ellipsoid plot (30% probability) of (I). [symmetry codes: (A) x - 1/2, 1/2 - y, 2 - z; (B) x + 1/2, 1/2 - y, 2 - z]
	Fig. 2. Two-dimensional network in (I) linked by Ag—Ag interactions. [symmetry codes: (A) x + 1/2, 1/2 - y, 2 - z; (B) 1/2 - x, y - 1/2, z]

catena-Poly[silver(I)-µ-pyrazolato-κ²N:N'] top

Crystal data top

[Ag(C₃H₃N₂)]	F(000) = 656
M_r = 174.94	D_x = 2.797 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6390 reflections
a = 6.4084 (13) Å	θ = 3.1–27.7°
b = 6.4989 (13) Å	µ = 4.66 mm⁻¹
c = 19.948 (4) Å	T = 293 K
V = 830.8 (3) Å³	Block, colorless
Z = 8	0.40 × 0.20 × 0.20 mm

Data collection top

Bruker Smart CCD area-detector diffractometer	951 independent reflections
Radiation source: fine-focus sealed tube	778 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scan	θ_max = 27.5°, θ_min = 3.8°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −8→7
T_min = 0.340, T_max = 0.400	k = −8→8
7019 measured reflections	l = −25→25

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H-atom parameters constrained
S = 1.26	w = 1/[σ²(F_o²) + (0.0145P)² + 0.695P] where P = (F_o² + 2F_c²)/3
951 reflections	(Δ/σ)_max = 0.004
55 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Ag(C₃H₃N₂)]	V = 830.8 (3) Å³
M_r = 174.94	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 6.4084 (13) Å	µ = 4.66 mm⁻¹
b = 6.4989 (13) Å	T = 293 K
c = 19.948 (4) Å	0.40 × 0.20 × 0.20 mm

Data collection top

Bruker Smart CCD area-detector diffractometer	951 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	778 reflections with I > 2σ(I)
T_min = 0.340, T_max = 0.400	R_int = 0.044
7019 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 1.26	Δρ_max = 0.38 e Å⁻³
951 reflections	Δρ_min = −0.55 e Å⁻³
55 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	0.23552 (5)	0.32951 (6)	1.004623 (15)	0.04206 (16)
N1	0.3965 (5)	0.3598 (6)	0.91516 (17)	0.0345 (9)
N2	0.5800 (5)	0.2552 (6)	0.90915 (17)	0.0364 (9)
C1	0.3418 (7)	0.4213 (7)	0.8548 (2)	0.0403 (12)
H1A	0.2217	0.4958	0.8450	0.048*
C2	0.4861 (7)	0.3606 (7)	0.8087 (2)	0.0448 (12)
H2A	0.4851	0.3836	0.7627	0.054*
C3	0.6325 (7)	0.2581 (7)	0.8457 (2)	0.0425 (12)
H3A	0.7528	0.1986	0.8282	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0444 (3)	0.0411 (3)	0.0407 (2)	−0.00048 (16)	0.00707 (18)	−0.00123 (16)
N1	0.038 (2)	0.032 (2)	0.033 (2)	0.0036 (18)	0.0039 (16)	−0.0005 (17)
N2	0.037 (2)	0.037 (2)	0.036 (2)	0.0002 (17)	0.0017 (17)	−0.0002 (18)
C1	0.048 (3)	0.026 (3)	0.047 (3)	0.006 (2)	−0.009 (2)	0.002 (2)
C2	0.062 (3)	0.040 (3)	0.033 (3)	−0.010 (3)	0.002 (2)	0.003 (2)
C3	0.044 (3)	0.036 (3)	0.048 (3)	−0.001 (2)	0.011 (2)	−0.006 (2)

Geometric parameters (Å, º) top

Ag1—N1	2.070 (3)	N2—C3	1.310 (5)
Ag1—N2ⁱ	2.063 (4)	C1—C2	1.362 (6)
Ag1—Ag1ⁱⁱ	3.2547 (6)	C1—H1A	0.9300
Ag1—Ag1ⁱ	3.3718 (7)	C2—C3	1.367 (6)
N1—C1	1.316 (5)	C2—H2A	0.9300
N1—N2	1.364 (5)	C3—H3A	0.9300

N2ⁱ—Ag1—N1	169.98 (14)	C1—N1—N2	107.5 (3)
N2ⁱ—Ag1—Ag1ⁱⁱ	76.18 (10)	C1—N1—Ag1	133.2 (3)
N1—Ag1—Ag1ⁱⁱ	93.82 (10)	N2—N1—Ag1	117.3 (3)
N2ⁱ—Ag1—Ag1ⁱⁱⁱ	107.09 (10)	C3—N2—N1	107.4 (3)
N1—Ag1—Ag1ⁱⁱⁱ	82.91 (10)	C3—N2—Ag1^iv	133.3 (3)
Ag1ⁱⁱ—Ag1—Ag1ⁱⁱⁱ	173.46 (2)	N1—N2—Ag1^iv	118.5 (2)
N2ⁱ—Ag1—Ag1ⁱ	60.31 (10)	N1—C1—C2	110.4 (4)
N1—Ag1—Ag1ⁱ	117.09 (10)	N1—C1—H1A	124.8
Ag1ⁱⁱ—Ag1—Ag1ⁱ	75.415 (18)	C2—C1—H1A	124.8
Ag1ⁱⁱⁱ—Ag1—Ag1ⁱ	111.111 (17)	C1—C2—C3	104.1 (4)
N2ⁱ—Ag1—Ag1^iv	115.02 (10)	C1—C2—H2A	128.0
N1—Ag1—Ag1^iv	60.57 (10)	C3—C2—H2A	128.0
Ag1ⁱⁱ—Ag1—Ag1^iv	68.889 (17)	N2—C3—C2	110.6 (4)
Ag1ⁱⁱⁱ—Ag1—Ag1^iv	104.585 (18)	N2—C3—H3A	124.7
Ag1ⁱ—Ag1—Ag1^iv	143.72 (3)	C2—C3—H3A	124.7

N2ⁱ—Ag1—N1—C1	108.9 (8)	C1—N1—N2—C3	0.7 (5)
Ag1ⁱⁱ—Ag1—N1—C1	112.0 (4)	Ag1—N1—N2—C3	166.6 (3)
Ag1ⁱⁱⁱ—Ag1—N1—C1	−73.6 (4)	C1—N1—N2—Ag1^iv	171.5 (3)
Ag1ⁱ—Ag1—N1—C1	36.5 (5)	Ag1—N1—N2—Ag1^iv	−22.6 (4)
Ag1^iv—Ag1—N1—C1	175.2 (5)	N2—N1—C1—C2	−0.3 (5)
N2ⁱ—Ag1—N1—N2	−52.6 (9)	Ag1—N1—C1—C2	−163.1 (3)
Ag1ⁱⁱ—Ag1—N1—N2	−49.4 (3)	N1—C1—C2—C3	−0.1 (6)
Ag1ⁱⁱⁱ—Ag1—N1—N2	124.9 (3)	N1—N2—C3—C2	−0.8 (5)
Ag1ⁱ—Ag1—N1—N2	−124.9 (3)	Ag1^iv—N2—C3—C2	−169.6 (3)
Ag1^iv—Ag1—N1—N2	13.7 (2)	C1—C2—C3—N2	0.6 (6)

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

Experimental details

Crystal data
Chemical formula	[Ag(C₃H₃N₂)]
M_r	174.94
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	6.4084 (13), 6.4989 (13), 19.948 (4)
V (Å³)	830.8 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.66
Crystal size (mm)	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Smart CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.340, 0.400
No. of measured, independent and observed [I > 2σ(I)] reflections	7019, 951, 778
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.066, 1.26
No. of reflections	951
No. of parameters	55
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.55

Computer programs: SMART (Bruker, 1998), SHELXTL (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).

Selected geometric parameters (Å, º) top

Ag1—N1	2.070 (3)	Ag1—Ag1ⁱⁱ	3.2547 (6)
Ag1—N2ⁱ	2.063 (4)	Ag1—Ag1ⁱ	3.3718 (7)

N2ⁱ—Ag1—N1	169.98 (14)	Ag1ⁱⁱ—Ag1—Ag1ⁱ	75.415 (18)
N2ⁱ—Ag1—Ag1ⁱⁱ	76.18 (10)	Ag1ⁱⁱⁱ—Ag1—Ag1ⁱ	111.111 (17)
N1—Ag1—Ag1ⁱⁱ	93.82 (10)	N2ⁱ—Ag1—Ag1^iv	115.02 (10)
N2ⁱ—Ag1—Ag1ⁱⁱⁱ	107.09 (10)	N1—Ag1—Ag1^iv	60.57 (10)
N1—Ag1—Ag1ⁱⁱⁱ	82.91 (10)	Ag1ⁱⁱ—Ag1—Ag1^iv	68.889 (17)
Ag1ⁱⁱ—Ag1—Ag1ⁱⁱⁱ	173.46 (2)	Ag1ⁱⁱⁱ—Ag1—Ag1^iv	104.585 (18)
N2ⁱ—Ag1—Ag1ⁱ	60.31 (10)	Ag1ⁱ—Ag1—Ag1^iv	143.72 (3)
N1—Ag1—Ag1ⁱ	117.09 (10)

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

Acknowledgements

This work was supported by the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality.

References

Bruker (1998). SMART (Version 5.051), SAINT (Version 5.01), SADABS (Version 2.03) and SHELXTL (Version 6.1). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Masciocchi, N., Moret, M., Cairati, P., Sironi, A., Ardizzoia, G. A. & La Monica, G. (1994). J. Am. Chem. Soc. 116, 7668–7676. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar