Chloro­tris­(3 methyl­pyridine κN)silver(I)

metal-organic papers

m1678

Structure Reports Online

ISSN 1600-5368

Chlorotris(3-methylpyridine-

j

N

)silver(I)

Christian NaÈther* and Andreas Beck

Institut fuÈr Anorganische Chemie, Christian-Albrechts-UniversitaÈt Kiel, Olshausenstraûe 40, D-24098 Kiel, Germany

Correspondence e-mail: cnaether@ac.uni-kiel.de

Key indicators Single-crystal X-ray study T= 170 K

Mean(C±C) = 0.007 AÊ Disorder in main residue Rfactor = 0.029 wRfactor = 0.068

Data-to-parameter ratio = 16.1

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

In the crystal structure of the title compound, [AgCl(C6H7N)3], each Ag atom is surrounded by one Cl atom and three N atoms of 4-methylpyridine ligands within a distorted tetrahedron. The Ag and Cl atom are located on special positions of site symmetry 3m, whereas all atoms of the 3-methylpyridine ligand, except for the three disordered methyl H atoms, are located on a mirror plane.

Comment

The structure determination of the title compound was undertaken as a part of a project on the synthesis, structure and thermal reactivity of silver halide coordination polymers with nitrogen-donor ligands (NaÈther & Beck, 2004a,b). With 3-methylpyridine and silver halides only two compounds are known. These are catena[(

3-bromo)(3-methylpyridine-N)silver(I)] (Healy et al., 1985) and catena[( 3-bromo)(3-methylpyridine-N)silver(I)] (Healyet al., 1983).

In the crystal structure of the title compound, (I), the Ag atom is coordinated by one Cl atom and three symmetry-related 3-methylpyridine ligands within a distorted tetra-hedron. The asymmetric unit contain 1/6 Ag and 1/6 Cl atom on special positions of site-symmetry 3m, as well as half a 3-methylpyridine ligand which is located on a mirror plane. The CÐN and AgÐCl bond lengths are in the ranges of those observed in related structures retrieved from the Cambridge Structural Database (Allen, 2002; ConQuest Version 1.6 of 2003). In the crystal structure, the complexes are closely packed such that each 3-methylpyridine ligand of one complex points into an aperture of a neighbouring complex.

Experimental

AgCl (288.5 mg, 2.00 mmol) was reacted with 3-methylpyridine (2.0 ml, 20.0 mmol) in a glass container. After 7 d, colourless crystals suitable for X-ray structure analysis had grown. Pure crystalline

powder could be obtained if AgCl (289.4 mg, 2.01 mmol) was reacted with it under stirring in 3-methylpyridine (2.0 ml, 20.0 mmol) in a glass container for 3 d. The product was ®ltered off and washed with diethyl ether (yield: 212.03 mg, 44.4% based on AgCl). The homo-geneity was checked by X-ray powder diffraction. All steps must be carried out in the dark.

Crystal data

[AgCl(C6H7N)3]

Mr= 422.70 Trigonal,R3m a= 14.6795 (10) AÊ

c= 7.5114 (4) AÊ

V= 1401.76 (15) AÊ3

Z= 3

Dx= 1.502 Mg mÿ3

MoKradiation Cell parameters from 4495

re¯ections

= 3±28

= 1.22 mmÿ1

T= 170 (2) K Block, colourless 0.100.090.09 mm

Data collection

Stoe IPDS diffractometer

'scans

Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998)

Tmin= 0.879,Tmax= 0.888

3908 measured re¯ections 823 independent re¯ections

811 re¯ections withI> 2(I)

Rint= 0.046

max= 28.0

h=ÿ19!19

k=ÿ19!17

l=ÿ9!9

Refinement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.029}

wR(F2_{) = 0.068}

S= 1.09 823 re¯ections 51 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(Fo2_{) + (0.0397P)}2

+ 1.7193P]

whereP= (Fo2_{+ 2Fc}2_)/3

(/)max< 0.001 max= 0.70 e AÊÿ3 min=ÿ0.56 e AÊÿ3

Extinction correction:SHELXL97 Extinction coef®cient: 0.0105 (11) Absolute structure: Flack (1983),

397 Friedel re¯ections Flack parameter = 0.01 (6)

Table 1

Selected geometric parameters (AÊ,_).

Ag1ÐN1 2.306 (4) Ag1ÐCl1 2.6066 (18) N1ÐC5 1.327 (6) N1ÐC1 1.327 (6)

C1ÐC2 1.409 (7) C2ÐC3 1.373 (9) C2ÐC6 1.499 (9) C3ÐC4 1.389 (9) N1ÐAg1ÐN1i _{112.88 (8)}

N1ÐAg1ÐCl1 105.80 (10) C5ÐN1ÐC1 117.8 (4) C5ÐN1ÐAg1 116.9 (3) C1ÐN1ÐAg1 125.3 (3) N1ÐC1ÐC2 124.1 (5)

C3ÐC2ÐC1 117.1 (5) C3ÐC2ÐC6 123.3 (5) C1ÐC2ÐC6 119.6 (6) C2ÐC3ÐC4 119.6 (5) C3ÐC4ÐC5 118.5 (5) N1ÐC5ÐC4 122.8 (5)

Symmetry code: (i) 1ÿy;xÿyÿ1;z.

The aromatic H atoms were positioned with idealized geometry (CÐH = 0.95 AÊ) and re®ned with ®xed isotropic displacement parameters [Uiso(H) = 1.2Ueq(C)] using the riding model. The

posi-tions of the methyl H atoms were idealized (CÐH = 0.98 AÊ) then re®ned with ®xed isotropic displacement parameters [Uiso(H) =

1.5Ueq(C)] as rigid groups allowed to rotate but not tip. The absolute

polarity was determined and is in agreement with the selected setting. In addition, re®nement of the inverse structure leads to signi®cantly poorer reliability factors [R1 for 811Fo> 4(Fo) = 0.0340 andwR2 for

all data = 0.0826]. Due to symmetry, the methyl H atoms are disor-dered over two orientations. In a space group of lower symmetry,e.g. R3, these H atoms do not necessarily have to be disordered. However, since all the other atoms could be successfully re®ned in space groupR3m, re®nement was performed in this space group.

Data collection:IPDS Program Package(Stoe & Cie, 1998); cell re®nement:IPDS Program Package; data reduction:IPDS Program Package; program(s) used to solve structure:SHELXS97 (Sheldrick, 1997; program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:XPinSHELXTL(Bruker, 1998); software used to prepare material for publication:XCIFinSHELXTL.

This work is supported by the state of Schleswig-Holstein. We are very thankful to Professor Dr Wolfgang Bensch for ®nancial support and the opportunity to use his experimental equipment.

metal-organic papers

Acta Cryst.(2004). E60, m1678±m1680 NaÈther and Beck [AgCl(C₆H₇N)₃]

m1679

Figure 1

The molecular structure of the title compound, with labelling and displacement ellipsoids drawn at the 50% probability level. The disordered H atoms are displayed with solid and open bonds. [Symmetry codes: (i) 1ÿy,xÿyÿ1,z; (ii) 2ÿx+y, 1ÿx,z.]

Figure 2

References

Allen, F. H. (2002).Acta Cryst.B58, 380±388.

Bruker (1998). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983).Acta Cryst.A39, 876±881.

Healy, P. C., Mills, N. K. & White, A. H. (1983).Aust. J. Chem.36, 1851±1864.

Healy, P. C., Mills, N. K. & White, A. H. (1985).J. Chem. Soc. Dalton Trans.pp. 111±116.

NaÈther, C. & Beck, A. (2004a).Z. Naturforsch. Teil B,59, 992±998. NaÈther, C. & Beck, A. (2004b).Acta Cryst.E60, m1608±m1610.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.

Stoe & Cie (1998).X-SHAPE(Version 1.03) andIPDS Program Package

(Version 2.89). Stoe & Cie, Darmstadt, Germany.

metal-organic papers

supporting information

sup-1 Acta Cryst. (2004). E60, m1678–m1680

supporting information

Acta Cryst. (2004). E60, m1678–m1680 [https://doi.org/10.1107/S1600536804026121]

Chlorotris(3-methylpyridine-

κ

N

)silver(I)

Christian N

ä

ther and Andreas Beck

Chlorotris(3-methylpyridine-κN)silver(I)

Crystal data [AgCl(C6H7N)3] Mr = 422.70 Trigonal, R3m Hall symbol: R3 -2" a = 14.6795 (10) Å c = 7.5114 (4) Å V = 1401.76 (15) Å3 Z = 3

F(000) = 642

Dx = 1.502 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4495 reflections θ = 3–28°

µ = 1.22 mm−1 T = 170 K Block, colourless 0.1 × 0.09 × 0.09 mm

Data collection Stoe IPDS

diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ scans

Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998) Tmin = 0.879, Tmax = 0.888

3908 measured reflections 823 independent reflections 811 reflections with I > 2σ(I) Rint = 0.046

θmax = 28.0°, θmin = 2.8° h = −19→19

k = −19→17 l = −9→9

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.029} wR(F2_{) = 0.068} S = 1.09 823 reflections 51 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0397P)2 + 1.7193P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.70 e Å−3

Δρmin = −0.56 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.0105 (11)

Absolute structure: Flack (1983), 397 Friedel reflections

supporting information

sup-2 Acta Cryst. (2004). E60, m1678–m1680

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq Occ. (<1)

Ag1 1.0000 0.0000 0.9994 0.0302 (2) Cl1 1.0000 0.0000 1.3464 (2) 0.0274 (4) N1 0.91274 (14) 0.08726 (14) 0.9158 (5) 0.0299 (8) C1 0.89529 (19) 0.10471 (19) 0.7493 (7) 0.0316 (9) H1 0.9205 0.0795 0.6560 0.038* C2 0.8417 (2) 0.1583 (2) 0.7022 (8) 0.0341 (12) C3 0.8058 (2) 0.1942 (2) 0.8388 (8) 0.0414 (12) H3 0.7691 0.2309 0.8137 0.050* C4 0.8233 (2) 0.1767 (2) 1.0140 (8) 0.0474 (17) H4 0.7990 0.2010 1.1101 0.057* C5 0.8774 (2) 0.1226 (2) 1.0457 (7) 0.0386 (11) H5 0.8894 0.1106 1.1655 0.046* C6 0.8263 (3) 0.1737 (3) 0.5095 (9) 0.0535 (18)

H6A 0.7731 0.1950 0.4986 0.080* 0.50 H6B 0.8029 0.1076 0.4450 0.080* 0.50 H6C 0.8929 0.2285 0.4591 0.080* 0.50

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Ag1 0.0269 (2) 0.0269 (2) 0.0368 (4) 0.01343 (11) 0.000 0.000 Cl1 0.0282 (6) 0.0282 (6) 0.0259 (10) 0.0141 (3) 0.000 0.000 N1 0.0328 (14) 0.0328 (14) 0.029 (2) 0.0203 (16) −0.0007 (7) 0.0007 (7) C1 0.0367 (18) 0.0367 (18) 0.028 (2) 0.023 (2) 0.0011 (9) −0.0011 (9) C2 0.040 (2) 0.040 (2) 0.025 (4) 0.022 (2) −0.0018 (12) 0.0018 (12) C3 0.051 (2) 0.051 (2) 0.042 (3) 0.040 (3) −0.0017 (10) 0.0017 (10) C4 0.069 (3) 0.069 (3) 0.035 (3) 0.056 (4) 0.0043 (10) −0.0043 (10) C5 0.051 (2) 0.051 (2) 0.028 (3) 0.037 (3) −0.0005 (9) 0.0005 (9) C6 0.069 (4) 0.069 (4) 0.038 (4) 0.045 (4) −0.0048 (14) 0.0048 (14)

Geometric parameters (Å, º)

Ag1—N1i _{2.306 (4) C2—C6 1.499 (9)}

Ag1—N1ii _{2.306 (4) C3—C4 1.389 (9)}

supporting information

sup-3 Acta Cryst. (2004). E60, m1678–m1680

Ag1—Cl1 2.6066 (18) C4—C5 1.395 (7) N1—C5 1.327 (6) C4—H4 0.9500 N1—C1 1.327 (6) C5—H5 0.9500 C1—C2 1.409 (7) C6—H6A 0.9800 C1—H1 0.9500 C6—H6B 0.9800 C2—C3 1.373 (9) C6—H6C 0.9800

N1i_—Ag1—N1ii _{112.88 (8) C2—C3—C4 119.6 (5)}

N1i_{—Ag1—N1 112.88 (8) C2—C3—H3 120.2}

N1ii_{—Ag1—N1 112.88 (8) C4—C3—H3 120.2}

N1i_{—Ag1—Cl1 105.80 (10) C3—C4—C5 118.5 (5)}

N1ii_{—Ag1—Cl1 105.80 (10) C3—C4—H4 120.7}

N1—Ag1—Cl1 105.80 (10) C5—C4—H4 120.7 C5—N1—C1 117.8 (4) N1—C5—C4 122.8 (5) C5—N1—Ag1 116.9 (3) N1—C5—H5 118.6 C1—N1—Ag1 125.3 (3) C4—C5—H5 118.6 N1—C1—C2 124.1 (5) C2—C6—H6A 109.5 N1—C1—H1 118.0 C2—C6—H6B 109.5 C2—C1—H1 118.0 H6A—C6—H6B 109.5 C3—C2—C1 117.1 (5) C2—C6—H6C 109.5 C3—C2—C6 123.3 (5) H6A—C6—H6C 109.5 C1—C2—C6 119.6 (6) H6B—C6—H6C 109.5