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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807063490/bq2042sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807063490/bq2042Isup2.hkl
Contains datablock I

CCDC reference: 677453

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.041
  • wR factor = 0.066
  • Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found




Alert level C PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.29 Ratio
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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.

Refinement top

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).

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
[Figure 1] 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]
[Figure 2] 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
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 = 3.1–27.7°
b = 6.4989 (13) ŵ = 4.66 mm1
c = 19.948 (4) ÅT = 293 K
V = 830.8 (3) Å3Block, colorless
Z = 80.40 × 0.20 × 0.20 mm
Data collection top
Bruker Smart CCD area-detector
diffractometer
951 independent reflections
Radiation source: fine-focus sealed tube778 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
ϕ and ω scanθmax = 27.5°, θmin = 3.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 87
Tmin = 0.340, Tmax = 0.400k = 88
7019 measured reflectionsl = 2525
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 1.26 w = 1/[σ2(Fo2) + (0.0145P)2 + 0.695P]
where P = (Fo2 + 2Fc2)/3
951 reflections(Δ/σ)max = 0.004
55 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.55 e Å3
Crystal data top
[Ag(C3H3N2)]V = 830.8 (3) Å3
Mr = 174.94Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 6.4084 (13) ŵ = 4.66 mm1
b = 6.4989 (13) ÅT = 293 K
c = 19.948 (4) Å0.40 × 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)
Tmin = 0.340, Tmax = 0.400Rint = 0.044
7019 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.066H-atom parameters constrained
S = 1.26Δρmax = 0.38 e Å3
951 reflectionsΔρmin = 0.55 e Å3
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
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) top
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, º) top
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—C173.6 (4)C1—N1—N2—Ag1iv171.5 (3)
Ag1i—Ag1—N1—C136.5 (5)Ag1—N1—N2—Ag1iv22.6 (4)
Ag1iv—Ag1—N1—C1175.2 (5)N2—N1—C1—C20.3 (5)
N2i—Ag1—N1—N252.6 (9)Ag1—N1—C1—C2163.1 (3)
Ag1ii—Ag1—N1—N249.4 (3)N1—C1—C2—C30.1 (6)
Ag1iii—Ag1—N1—N2124.9 (3)N1—N2—C3—C20.8 (5)
Ag1i—Ag1—N1—N2124.9 (3)Ag1iv—N2—C3—C2169.6 (3)
Ag1iv—Ag1—N1—N213.7 (2)C1—C2—C3—N20.6 (6)
Symmetry codes: (i) x1/2, y+1/2, z+2; (ii) x+1/2, y1/2, 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)]
Mr174.94
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)293
a, b, c (Å)6.4084 (13), 6.4989 (13), 19.948 (4)
V3)830.8 (3)
Z8
Radiation typeMo Kα
µ (mm1)4.66
Crystal size (mm)0.40 × 0.20 × 0.20
Data collection
DiffractometerBruker Smart CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.340, 0.400
No. of measured, independent and
observed [I > 2σ(I)] reflections
7019, 951, 778
Rint0.044
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.066, 1.26
No. of reflections951
No. of parameters55
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—N12.070 (3)Ag1—Ag1ii3.2547 (6)
Ag1—N2i2.063 (4)Ag1—Ag1i3.3718 (7)
N2i—Ag1—N1169.98 (14)Ag1ii—Ag1—Ag1i75.415 (18)
N2i—Ag1—Ag1ii76.18 (10)Ag1iii—Ag1—Ag1i111.111 (17)
N1—Ag1—Ag1ii93.82 (10)N2i—Ag1—Ag1iv115.02 (10)
N2i—Ag1—Ag1iii107.09 (10)N1—Ag1—Ag1iv60.57 (10)
N1—Ag1—Ag1iii82.91 (10)Ag1ii—Ag1—Ag1iv68.889 (17)
Ag1ii—Ag1—Ag1iii173.46 (2)Ag1iii—Ag1—Ag1iv104.585 (18)
N2i—Ag1—Ag1i60.31 (10)Ag1i—Ag1—Ag1iv143.72 (3)
N1—Ag1—Ag1i117.09 (10)
Symmetry codes: (i) x1/2, y+1/2, z+2; (ii) x+1/2, y1/2, z; (iii) x+1/2, y+1/2, z; (iv) x+1/2, y+1/2, z+2.
 

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