Diamminesilver(I) picrate

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metal-organic papers

m1624

You, Zhu and Liu [Ag(NH₃)₂](C₆H₂N₃O₇) doi: 10.1107/S1600536804025425 Acta Cryst.(2004). E60, m1624±m1626 Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

Diamminesilver(I) picrate

Zhong-Lu You,a,b_Hai-Liang

Zhua_{* and Wei-Sheng Liu}b

a_{Department of Chemistry, Fuyang Normal}

College, Fuyang, Anhui 236041, People's Republic of China, andb_{Department of}

Chemistry, Lanzhou University, Lanzhou 730000, People's Republic of China

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 298 K

Mean(C±C) = 0.004 AÊ Disorder in main residue

Rfactor = 0.027

wRfactor = 0.072 Data-to-parameter ratio = 9.4

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

In the title compound, [Ag(NH3)2](C6H2N3O7), the AgIion is

bicoordinated in a linear con®guration by two N atoms from two inversion-related ammine ligands. In the crystal structure, the picrate anions, with twofold rotation symmetry, are linked to the diamminesilver(I) cations through intermolecular NÐ H O hydrogen bonds, forming two-dimensional layers parallel to theacplane.

Comment

The synthesis or construction of supramolecular coordination architecture is currently receiving considerable attention (Melceret al., 2001; Feiet al., 2001; Xuet al., 2001; Zhuet al., 2004). The construction of a wide variety of network cation topologies has been achieved through ligand design and the use of different counter-anions. The balance between the formation of different structures is often subtle. Factors that affect the coordination polymer topology include not only the anion-based interactions but also the con®gurations of the ligands. The latter factor is particularly notable in AgI

coor-dination polymers (You, Zhu et al., 2004; You, Yang et al., 2004). Owing to the ¯exible coordination sphere of AgI_,

coordination numbers from two to six are all possible, and because of the relatively weak nature of many AgI_±ligand

interactions such compounds are particularly susceptible to the in¯uence of weaker supramolecular forces (Khlobystovet al., 2001).

Recently, we have reported a polynuclear AgI_{complex with}

1,2-diaminoethane as the ligand and picrate as the counter-anion, viz. catena-poly[(silver(I)--ethylenediamine)-2,4,6-trinitrophenolate], (II) (Zhuet al., 2003). In order to study the effects of the ligand in the construction of silver(I) coordina-tion polymers, the structure of the title compound, (I), is reported here.

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Compound (I) has a discrete diammine±AgI_{complex cation}

with picrate as the counter-anion (Fig. 1). The asymmetric unit contains half each of a diamminesilver(I) cation and a picrate anion. The diamminesilver(I) cation lies on an inversion centre. The picrate anion has crystallographic twofold symmetry, with atoms O1, C1, C4 and N2 lying on the twofold axis. The AgI_{ion is in a perfectly linear coordination}

envir-onment and is bicoordinated by two N atoms [N3 and N3i_;

symmetry code: (i) 1ÿx, 1ÿy, 1ÿz] from two symmetry-related ammine ligands. Compound (II) is a polymeric ethyl-enediamine±AgI_{complex, with linear coordination geometry}

for the AgI_{ion. In (I), the Ag1ÐN3 bond length [2.113 (2) AÊ]}

is slightly shorter than the average value of 2.124 (5) AÊ observed in (II). All other bond lengths in (I) are within the normal ranges (Allenet al., 1987).

In the crystal structure, cations and anions are linked together by intermolecular NÐH O hydrogen bonds (Table 1). The ammine ligand acts as a multiple hydrogen-bond donor, whereas the phenolate O atom and the O atoms of the 2,6-nitro groups of the picrate anion act as hydrogen-bond acceptors. The same pattern can be observed in complex (II). In (I), the NÐH O hydrogen bonds link the cations and anions into two-dimensional sheets parallel to the ac plane (Fig. 2), while in the crystal packing of (II), the NÐH O hydrogen bonding leads to a three-dimensional network. This may be caused by the different types of ligands present in the two compounds.

Experimental

Ag2O (0.5 mmol, 116.1 mg) and picric acid (1.0 mmol, 229.2 mg) were dissolved in a 30% ammonia solution (20 ml). The mixture was stirred for 20 min to give a clear solution. After allowing the colourless solution to stand in air for 12 d, colourless block-shaped crystals were formed at the bottom of the vessel on slow evaporation of the solvent.

Crystal data

[Ag(NH3)2](C6H2N3O7) Mr= 370.04

Monoclinic,C2=c a= 10.046 (5) AÊ

b= 21.735 (10) AÊ

c= 7.189 (3) AÊ

= 131.879 (4) V= 1168.7 (9) AÊ3 Z= 4

Dx= 2.103 Mg mÿ3

MoKradiation Cell parameters from 2263

re¯ections

= 3.0±26.4

= 1.77 mmÿ1 T= 298 (2) K Block, colourless 0.340.310.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer

!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.585,Tmax= 0.753 3050 measured re¯ections

1038 independent re¯ections 892 re¯ections withI> 2(I)

Rint= 0.029

max= 25.0 h=ÿ10!11

k=ÿ25!19

l=ÿ8!8

Refinement

Re®nement onF2 R[F2_{> 2}₍_F2_{)] = 0.027} wR(F2_{) = 0.072} S= 1.10 1038 re¯ections 110 parameters

H-atom parameters constrained

w= 1/[2₍_F

o2) + (0.0435P)2

+ 0.3947P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.30 e AÊÿ3

min=ÿ0.88 e AÊÿ3

Extinction correction:SHELXL97 Extinction coef®cient: 0.058 (2)

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N3ÐH1 O1i _0.89 _2.42 _{3.294 (3)} ₁₆₉

N3ÐH2 O2ii _0.89 _2.16 _{3.019 (8)} ₁₆₂

N3ÐH2 O20ii _0.89 _2.18 _{3.061 (8)} ₁₇₃

N3ÐH3 O1iii _0.89 _2.28 _{3.149 (3)} ₁₆₅

N3ÐH3 O2iii _0.89 _2.46 _{3.087 (7)} ₁₂₈

N3ÐH3 O20iii _0.89 _2.27 _{2.848 (7)} ₁₂₂ Symmetry codes: (i) 1x;y;1z; (ii) 1ÿx;y;1

2ÿz; (iii) 1ÿx;1ÿy;1ÿz.

After location, all H atoms were placed in idealized positions and constrained to ride on their parent atoms, with NÐH and CÐH distances of 0.89 and 0.93 AÊ, respectively, and withUiso(H) values ®xed at 0.08 AÊ2_{. One of the nitro groups is found to have rotational} disorder; the occupancies of the disordered positions O2 and O20_(or

O3 and O30_{) were initially re®ned to 0.490 (19) and 0.510 (19),}

respectively, and were later ®xed at 0.5.

metal-organic papers

Acta Cryst.(2004). E60, m1624±m1626 You, Zhu and Liu [Ag(NH₃)₂](C₆H₂N₃O₇)

m1625

Figure 1

The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Dashed lines indicate NÐH O hydrogen bonds.

Figure 2

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Data collection:SMART(Bruker, 1998); cell re®nement:SAINT

(Bruker, 1998); data reduction: ; program(s) used to solve structure:

SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:

SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL

(Bruker, 1997); software used to prepare material for publication:

SHELXTL.

The authors thank the Education Of®ce of Anhui Province, the People's Republic of China, for research grant No. 2004kj300zd.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987).J. Chem. Soc. Perkin Trans.2, pp. S1±10.

Bruker (1997). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (1998).SMART(Version 5.628) andSAINT(Version 6.02). Bruker AXS Inc., Madison, Wisconsin, USA.

Fei, B.-L., Sun, W.-Y., Okamura, T., Tang, W.-X. & Ueyama, N. (2001).New J. Chem.25, 210±212.

Khlobystov, A. N., Blake, A. J., Champness, N. R., Lemenovskii, D. A., Majouga, A. G., Zyk, N. V. & SchroÈder, M. (2001).Coord. Chem. Rev.222, 155±192.

Melcer, N. J., Enright, G. D., Ripmeester, J. A. & Shimizu, K. H. (2001).Inorg. Chem.40, 4641±4648.

Sheldrick, G. M. (1996).SADABS.University of GoÈttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

GoÈttingen, Germany.

Xu, A.-W., Su, C.-Y., Zhang, Z.-F., Cai, Y.-P. & Chen, C.-L. (2001).New J. Chem.25, 479±482.

You, Z.-L., Yang, L., Zou, Y., Zeng, W.-J., Liu, W.-S. & Zhu, H.-L. (2004).Acta Cryst.C60, m117±m118.

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metal-organic papers

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sup-1 Acta Cryst. (2004). E60, m1624–m1626

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Acta Cryst. (2004). E60, m1624–m1626 [https://doi.org/10.1107/S1600536804025425]

Diamminesilver(I) picrate

Zhong-Lu You, Hai-Liang Zhu and Wei-Sheng Liu

Diamminesilver(I) picrate

Crystal data

[Ag(NH3)2](C6H2N3O7)

Mr = 370.04

Monoclinic, C2/c Hall symbol: -C 2yc a = 10.046 (5) Å b = 21.735 (10) Å c = 7.189 (3) Å β = 131.879 (4)° V = 1168.7 (9) Å3

Z = 4

F(000) = 728

Dx = 2.103 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2263 reflections θ = 3.0–26.4°

µ = 1.77 mm−1

T = 298 K Block, colourless 0.34 × 0.31 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.585, Tmax = 0.753

3050 measured reflections 1038 independent reflections 892 reflections with I > 2σ(I)

Rint = 0.029

θmax = 25.0°, θmin = 1.9°

h = −10→11 k = −25→19 l = −8→8

Refinement

Refinement on F2

Least-squares matrix: full

R[F2_{> 2σ(F}2_{)] = 0.027}

wR(F2_{) = 0.072}

S = 1.10 1038 reflections 110 parameters 2 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0435P)2 + 0.3947P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.30 e Å−3

Δρmin = −0.88 e Å−3

Extinction correction: SHELXL97,

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

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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 0.5000 0.5000 0.5000 0.0515 (2)

N1 0.1569 (3) 0.65349 (10) 0.0881 (4) 0.0536 (6)

N2 0.0000 0.84349 (14) 0.2500 0.0617 (9)

N3 0.7708 (3) 0.52141 (11) 0.6996 (4) 0.0492 (5)

H1 0.8183 0.5392 0.8439 0.080*

H2 0.7776 0.5470 0.6097 0.080*

H3 0.8304 0.4870 0.7294 0.080*

O1 0.0000 0.58742 (10) 0.2500 0.0511 (7)

O2 0.1160 (10) 0.6018 (3) 0.0165 (14) 0.0604 (17) 0.50

O3 0.2796 (8) 0.6810 (3) 0.1254 (12) 0.0840 (18) 0.50

O2′ 0.1981 (11) 0.5997 (3) 0.1238 (17) 0.091 (3) 0.50

O3′ 0.1640 (11) 0.6841 (2) −0.0515 (12) 0.0882 (18) 0.50

O4 −0.0854 (4) 0.86995 (10) 0.2891 (6) 0.0965 (9)

C1 0.0000 0.64472 (14) 0.2500 0.0366 (7)

C2 0.0738 (3) 0.68265 (10) 0.1713 (4) 0.0389 (5)

C3 0.0746 (3) 0.74556 (11) 0.1717 (4) 0.0433 (6)

H3A 0.1248 0.7671 0.1198 0.080*

C4 0.0000 0.77673 (14) 0.2500 0.0420 (8)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Ag1 0.0480 (3) 0.0423 (3) 0.0681 (3) 0.00044 (10) 0.0404 (2) 0.00279 (11)

N1 0.0690 (16) 0.0461 (13) 0.0715 (14) −0.0071 (12) 0.0575 (14) −0.0075 (12)

N2 0.065 (2) 0.0299 (17) 0.075 (2) 0.000 0.041 (2) 0.000

N3 0.0530 (14) 0.0399 (12) 0.0636 (13) −0.0004 (11) 0.0425 (12) −0.0010 (11)

O1 0.0652 (17) 0.0268 (12) 0.0805 (18) 0.000 0.0566 (16) 0.000

O2 0.084 (5) 0.039 (3) 0.094 (5) 0.001 (2) 0.074 (4) −0.011 (3)

O3 0.085 (4) 0.088 (4) 0.127 (5) −0.032 (3) 0.090 (4) −0.031 (4)

O2′ 0.135 (9) 0.070 (4) 0.135 (8) 0.057 (5) 0.117 (7) 0.046 (5)

O3′ 0.153 (6) 0.059 (3) 0.132 (5) −0.019 (4) 0.127 (5) −0.009 (4)

O4 0.121 (2) 0.0375 (12) 0.154 (2) 0.0082 (13) 0.101 (2) −0.0100 (14)

C1 0.0384 (18) 0.0305 (16) 0.0414 (16) 0.000 0.0269 (15) 0.000

C2 0.0435 (13) 0.0327 (12) 0.0469 (12) −0.0014 (10) 0.0328 (11) −0.0019 (10)

C3 0.0469 (14) 0.0340 (12) 0.0486 (12) −0.0059 (10) 0.0317 (11) 0.0013 (10)

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Geometric parameters (Å, º)

Ag1—N3i _{2.113 (2)} _N3—H1 _0.89

Ag1—N3 2.113 (3) N3—H2 0.89

N1—O2 1.190 (7) N3—H3 0.89

N1—O2′ 1.209 (5) O1—C1 1.246 (4)

N1—O3 1.227 (5) C1—C2ii _{1.452 (3)}

N1—O3′ 1.244 (4) C1—C2 1.452 (3)

N1—C2 1.457 (3) C2—C3 1.367 (3)

N2—O4ii _{1.212 (3)} _C3—C4 _{1.378 (3)}

N2—O4 1.212 (3) C3—H3A 0.93

N2—C4 1.451 (4) C4—C3ii _{1.378 (3)}

N3i_—Ag1—N3 _180.0 _H1—N3—H3 _109.5

O2—N1—O3 124.1 (5) H2—N3—H3 109.5

O2′—N1—O3′ 119.4 (6) O1—C1—C2ii _{124.59 (13)}

O2—N1—C2 117.5 (5) O1—C1—C2 124.59 (13)

O2′—N1—C2 122.8 (5) C2ii_—C1—C2 _{110.8 (3)}

O3—N1—C2 117.7 (3) C3—C2—C1 124.8 (2)

O3′—N1—C2 117.1 (3) C3—C2—N1 115.59 (19)

O4ii_—N2—O4 _{123.3 (3)} _C1—C2—N1 _{119.6 (2)}

O4ii_—N2—C4 _{118.33 (17)} _C2—C3—C4 _{119.3 (2)}

O4—N2—C4 118.33 (17) C2—C3—H3A 120.4

Ag1—N3—H1 109.5 C4—C3—H3A 120.4

Ag1—N3—H2 109.5 C3—C4—C3ii _{121.1 (3)}

H1—N3—H2 109.5 C3—C4—N2 119.44 (15)

Ag1—N3—H3 109.5 C3ii_—C4—N2 _{119.44 (15)}

O1—C1—C2—C3 −179.78 (17) O3—N1—C2—C1 −149.1 (4)

C2ii_{—C1—C2—C3} _{0.22 (17)} _{O3′—N1—C2—C1} _{156.7 (4)}

O1—C1—C2—N1 −0.8 (2) C1—C2—C3—C4 −0.4 (3)

C2ii_{—C1—C2—N1} _{179.2 (2)} _{N1—C2—C3—C4} _{−179.41 (19)}

O2—N1—C2—C3 −158.9 (5) C2—C3—C4—C3ii _{0.20 (16)}

O2′—N1—C2—C3 164.9 (5) C2—C3—C4—N2 −179.80 (16)

O3—N1—C2—C3 29.9 (5) O4ii_{—N2—C4—C3} _{−9.1 (2)}

O3′—N1—C2—C3 −24.2 (5) O4—N2—C4—C3 170.9 (2)

O2—N1—C2—C1 22.1 (5) O4ii_{—N2—C4—C3}ii _{170.9 (2)}

O2′—N1—C2—C1 −14.2 (6) O4—N2—C4—C3ii _{−9.1 (2)}

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

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N3—H1···O1iii _0.89 _2.42 _{3.294 (3)} ₁₆₉

N3—H2···O2iv _0.89 _2.16 _{3.019 (8)} ₁₆₂

N3—H2···O2′iv _0.89 _2.18 _{3.061 (8)} ₁₇₃

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N3—H3···O2i _0.89 _2.46 _{3.087 (7)} ₁₂₈

N3—H3···O2′i _0.89 _2.27 _{2.848 (7)} ₁₂₂