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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): m352.
Published online 2008 January 16. doi:  10.1107/S1600536807063490
PMCID: PMC2960218

catena-Poly[silver(I)-μ-pyrazolato-κ2 N:N′]

Abstract

The title compound, [Ag(C3H3N2)]n, has an infinite helical chain structure in which each pyrazolate group bridges two AgI atoms related by a 21 axis with an intra­chain Ag(...)Ag separation of 3.3718 (7) Å. Each AgI 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 [triangle]).

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Object name is e-64-0m352-scheme1.jpg

Experimental

Crystal data

  • [Ag(C3H3N2)]
  • M r = 174.94
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m352-efi9.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.066
  • S = 1.26
  • 951 reflections
  • 55 parameters
  • H-atom parameters constrained
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.55 e Å−3

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

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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].

Experimental

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.

Refinement

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C,N).

Figures

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]

Crystal data

[Ag(C3H3N2)]F000 = 656
Mr = 174.94Dx = 2.797 Mg m3
Orthorhombic, PbcaMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 6390 reflections
a = 6.4084 (13) Åθ = 3.1–27.7º
b = 6.4989 (13) ŵ = 4.66 mm1
c = 19.948 (4) ÅT = 293 (2) K
V = 830.8 (3) Å3Block, colorless
Z = 80.40 × 0.20 × 0.20 mm

Data collection

Bruker Smart CCD area-detector diffractometer951 independent reflections
Radiation source: fine-focus sealed tube778 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.044
T = 293(2) Kθmax = 27.5º
[var phi] and ω scanθmin = 3.8º
Absorption correction: multi-scan(SADABS; Bruker, 1998)h = −8→7
Tmin = 0.340, Tmax = 0.400k = −8→8
7019 measured reflectionsl = −25→25

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.066  w = 1/[σ2(Fo2) + (0.0145P)2 + 0.695P] where P = (Fo2 + 2Fc2)/3
S = 1.26(Δ/σ)max = 0.004
951 reflectionsΔρmax = 0.38 e Å3
55 parametersΔρmin = −0.55 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
Ag10.23552 (5)0.32951 (6)1.004623 (15)0.04206 (16)
N10.3965 (5)0.3598 (6)0.91516 (17)0.0345 (9)
N20.5800 (5)0.2552 (6)0.90915 (17)0.0364 (9)
C10.3418 (7)0.4213 (7)0.8548 (2)0.0403 (12)
H1A0.22170.49580.84500.048*
C20.4861 (7)0.3606 (7)0.8087 (2)0.0448 (12)
H2A0.48510.38360.76270.054*
C30.6325 (7)0.2581 (7)0.8457 (2)0.0425 (12)
H3A0.75280.19860.82820.051*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ag10.0444 (3)0.0411 (3)0.0407 (2)−0.00048 (16)0.00707 (18)−0.00123 (16)
N10.038 (2)0.032 (2)0.033 (2)0.0036 (18)0.0039 (16)−0.0005 (17)
N20.037 (2)0.037 (2)0.036 (2)0.0002 (17)0.0017 (17)−0.0002 (18)
C10.048 (3)0.026 (3)0.047 (3)0.006 (2)−0.009 (2)0.002 (2)
C20.062 (3)0.040 (3)0.033 (3)−0.010 (3)0.002 (2)0.003 (2)
C30.044 (3)0.036 (3)0.048 (3)−0.001 (2)0.011 (2)−0.006 (2)

Geometric parameters (Å, °)

Ag1—N12.070 (3)N2—C31.310 (5)
Ag1—N2i2.063 (4)C1—C21.362 (6)
Ag1—Ag1ii3.2547 (6)C1—H1A0.9300
Ag1—Ag1i3.3718 (7)C2—C31.367 (6)
N1—C11.316 (5)C2—H2A0.9300
N1—N21.364 (5)C3—H3A0.9300
N2i—Ag1—N1169.98 (14)C1—N1—N2107.5 (3)
N2i—Ag1—Ag1ii76.18 (10)C1—N1—Ag1133.2 (3)
N1—Ag1—Ag1ii93.82 (10)N2—N1—Ag1117.3 (3)
N2i—Ag1—Ag1iii107.09 (10)C3—N2—N1107.4 (3)
N1—Ag1—Ag1iii82.91 (10)C3—N2—Ag1iv133.3 (3)
Ag1ii—Ag1—Ag1iii173.46 (2)N1—N2—Ag1iv118.5 (2)
N2i—Ag1—Ag1i60.31 (10)N1—C1—C2110.4 (4)
N1—Ag1—Ag1i117.09 (10)N1—C1—H1A124.8
Ag1ii—Ag1—Ag1i75.415 (18)C2—C1—H1A124.8
Ag1iii—Ag1—Ag1i111.111 (17)C1—C2—C3104.1 (4)
N2i—Ag1—Ag1iv115.02 (10)C1—C2—H2A128.0
N1—Ag1—Ag1iv60.57 (10)C3—C2—H2A128.0
Ag1ii—Ag1—Ag1iv68.889 (17)N2—C3—C2110.6 (4)
Ag1iii—Ag1—Ag1iv104.585 (18)N2—C3—H3A124.7
Ag1i—Ag1—Ag1iv143.72 (3)C2—C3—H3A124.7
N2i—Ag1—N1—C1108.9 (8)C1—N1—N2—C30.7 (5)
Ag1ii—Ag1—N1—C1112.0 (4)Ag1—N1—N2—C3166.6 (3)
Ag1iii—Ag1—N1—C1−73.6 (4)C1—N1—N2—Ag1iv171.5 (3)
Ag1i—Ag1—N1—C136.5 (5)Ag1—N1—N2—Ag1iv−22.6 (4)
Ag1iv—Ag1—N1—C1175.2 (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—N2124.9 (3)N1—N2—C3—C2−0.8 (5)
Ag1i—Ag1—N1—N2−124.9 (3)Ag1iv—N2—C3—C2−169.6 (3)
Ag1iv—Ag1—N1—N213.7 (2)C1—C2—C3—N20.6 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BQ2042).

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.
  • Masciocchi, N., Moret, M., Cairati, P., Sironi, A., Ardizzoia, G. A. & La Monica, G. (1994). J. Am. Chem. Soc.116, 7668–7676.
  • Sheldrick, G. M. (1997). SHELXL97 and SHELXS97 University of Göttingen, Germany.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography