The infinite one-dimensional chain polymer...

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metal-organic papers Acta Cryst. (2007). E63, m1063–m1065 doi:10.1107/S1600536807010835 Qu and Wu [Ag(C 6 H 12 N 2 )](C 7 H 3 N 2 O 7 ) m1063 Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 The infinite one-dimensional chain polymer catena-poly[[silver(I)-l-1,4-diazabicyclo[2.2.2]- octane-j 2 N:N 0 ] 2-hydroxy-3,5-dinitrobenzoate]] Yang Qu* and Jin Wu Institute of Biochemistry, Department of Chem- istry, Huazhong Agricultural University, Wuhan, 430070, People’s Republic of China Correspondence e-mail: [email protected] Key indicators Single-crystal X-ray study T = 293 K Mean (C–C) = 0.005 A ˚ H-atom completeness 81% Disorder in solvent or counterion R factor = 0.032 wR factor = 0.087 Data-to-parameter ratio = 8.2 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e. Received 15 February 2007 Accepted 7 March 2007 # 2007 International Union of Crystallography All rights reserved In the title compound, {[Ag(C 6 H 12 N 2 )](C 7 H 3 N 2 O 7 )} n , the Ag atom is coordinated by two N atoms from the two symmetry- related 1,4-diazabicyclo[2.2.2]octane ligands, giving linear polymeric chains with a [–silver–ligand–] backbone running parallel to the c direction. In the crystal packing, the polymeric chains are interconnected by weak AgO nitro van der Waals forces, resulting in a three-dimensional supramolecular network in the solid. Comment Crystal engineering of coordination polymers has attracted great attention in recent years owing to their potential as functional materials as well as their interesting compositions and topologies (Yaghi et al., 1995; Stumpt et al., 1993). Our study of the crystal structures of metal–triethylenediamine coordination concerns the molecular factors that determine their network structure frameworks (Qu et al., 2005). Triethylenediamine, a bidentate ligand that can coordinate to metal ions via two N atoms, has a very versatile coordination behavior since it can form bridges between metallic centers, generating varied and sometimes surprising molecular archi- tectures (Zhu et al., 2003). Here we report the preparation and crystal structure of [Ag(dabco) 2 ](C 7 H 3 N 2 O 7 ) (dabco is 1,4-diazabicyclo[2.2.2]- octane), (I). Complex (I) is a polymeric Ag I complex. O1,O2,N2,C4 lie on sites of symmetry m; Ag1, N1 lie on sites of symmetry 3m. In the crystal structure of (I), the smallest repeat unit contains an [Ag-(dabco) 2 ] + cation and a 3,5-dini- trosalicylate counter-ion, as shown in Fig. 1. The Ag atom in
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Page 1: The infinite one-dimensional chain polymer catena-poly[[silver(I)-μ-1,4-diazabicyclo[2.2.2]octane-κ2N:N′] 2-hydroxy-3,5-dinitrobenzoate]]

metal-organic papers

Acta Cryst. (2007). E63, m1063–m1065 doi:10.1107/S1600536807010835 Qu and Wu � [Ag(C6H12N2)](C7H3N2O7) m1063

Acta Crystallographica Section E

Structure ReportsOnline

ISSN 1600-5368

The infinite one-dimensional chain polymercatena-poly[[silver(I)-l-1,4-diazabicyclo[2.2.2]-octane-j2N:N000] 2-hydroxy-3,5-dinitrobenzoate]]

Yang Qu* and Jin Wu

Institute of Biochemistry, Department of Chem-

istry, Huazhong Agricultural University, Wuhan,

430070, People’s Republic of China

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T = 293 K

Mean �(C–C) = 0.005 A

H-atom completeness 81%

Disorder in solvent or counterion

R factor = 0.032

wR factor = 0.087

Data-to-parameter ratio = 8.2

For details of how these key indicators were

automatically derived from the article, see

http://journals.iucr.org/e.

Received 15 February 2007

Accepted 7 March 2007

# 2007 International Union of Crystallography

All rights reserved

In the title compound, {[Ag(C6H12N2)](C7H3N2O7)}n, the Ag

atom is coordinated by two N atoms from the two symmetry-

related 1,4-diazabicyclo[2.2.2]octane ligands, giving linear

polymeric chains with a [–silver–ligand–] backbone running

parallel to the c direction. In the crystal packing, the polymeric

chains are interconnected by weak Ag� � �Onitro van der Waals

forces, resulting in a three-dimensional supramolecular

network in the solid.

Comment

Crystal engineering of coordination polymers has attracted

great attention in recent years owing to their potential as

functional materials as well as their interesting compositions

and topologies (Yaghi et al., 1995; Stumpt et al., 1993). Our

study of the crystal structures of metal–triethylenediamine

coordination concerns the molecular factors that determine

their network structure frameworks (Qu et al., 2005).

Triethylenediamine, a bidentate ligand that can coordinate to

metal ions via two N atoms, has a very versatile coordination

behavior since it can form bridges between metallic centers,

generating varied and sometimes surprising molecular archi-

tectures (Zhu et al., 2003).

Here we report the preparation and crystal structure of

[Ag(dabco)2](C7H3N2O7) (dabco is 1,4-diazabicyclo[2.2.2]-

octane), (I). Complex (I) is a polymeric AgI complex.

O1,O2,N2,C4 lie on sites of symmetry m; Ag1, N1 lie on sites

of symmetry 3m. In the crystal structure of (I), the smallest

repeat unit contains an [Ag-(dabco)2]+ cation and a 3,5-dini-

trosalicylate counter-ion, as shown in Fig. 1. The Ag atom in

Page 2: The infinite one-dimensional chain polymer catena-poly[[silver(I)-μ-1,4-diazabicyclo[2.2.2]octane-κ2N:N′] 2-hydroxy-3,5-dinitrobenzoate]]

(I) is coordinated by two N atoms from two different dabco

ligands in a linear geometry [N1—Ag—N1A = 180�; N1A

symmetry code: �y, �x, 12 � z]. The Ag—N bond (Table 1) is

comparable to those [2.186 (4)–2.199 (2) A] in related struc-

tures (Tong et al., 1998; Tong & Chen, 2000). Orientational

disorder is observed in the 3,5-dinitrosalicylate anion. The –

NO2 and –CO2 groups cannot be distinguished in the crystal

structure. The linear N1—Ag—N1A formation gives rise to a

linear polymer of the title complex, running parallel to the c

direction and having a [–silver–(dabco)]n backbone, resulting

in a polymeric chain (Fig. 2). Adjacent [Ag(dabco)2]+ cations

are interlinked through weak Ag� � �O(anion) coordination

[mean Ag� � �O(3,5-dinitrosalicylate) = 3.174 (2) A]. A three-

dimensional network structure is formed via weak Ag� � �O and

Ag� � �N interactions.

Experimental

All reagents and solvents were used as obtained without further

purification. AgO (1 mmol, 124 mg), 3,5-dinitrosalicylic acid (1 mmol,

211 mg) and 1,4-diazabicyclo[2.2.2]octane (1 mmol, 112 mg) were

dissolved in an ammonia solution (10 ml, 30%), and the mixture was

stirred for about 20 min at room temperature. The resulting clear

solution was kept in air and after slow evaporation of the solvent over

a period of a week, large colorless crystals of (I) formed at the bottom

of the vessel. The crystals were isolated, washed three times with

water and dried in a vacuum desiccator using anhydrous CaCl2 (yield

53%). Elemental analysis found: C 35.12, H 3.03, N 12.49%; calcu-

lated for C13H15AgN4O7: C 34.92, H 3.38, N 12.53%.

Crystal data

[Ag(C6H12N2)](C7H3N2O7)Mr = 447Hexagonal, P63=mmca = 11.1991 (16) Ac = 6.9696 (14) AV = 757.0 (2) A3

Z = 2Mo K� radiation� = 1.38 mm�1

T = 293 (2) K0.51 � 0.30 � 0.26 mm

Data collection

Siemens SMART CCD area-detector diffractometer

Absorption correction: multi-scan(SADABS; Sheldrick, 1996)Tmin = 0.600, Tmax = 0.700

3755 measured reflections288 independent reflections279 reflections with I > 2�(I)Rint = 0.023

Refinement

R[F 2 > 2�(F 2)] = 0.032wR(F 2) = 0.087S = 1.00288 reflections

35 parametersH-atom parameters constrained��max = 0.54 e A�3

��min = �0.38 e A�3

Table 1Selected geometric parameters (A, �).

Ag1—N1 2.190 (6)N1—C1 1.485 (4)N2—O2 1.235 (5)N2—C3 1.473 (7)

O1—C2 1.160 (11)C1—C1ii 1.541 (8)C2—C3 1.400 (4)

N1i—Ag1—N1 180C1iii—N1—C1 108.3 (3)C1—N1—Ag1 110.7 (2)

O2—N2—C3 120.3 (3)O1—C2—C3 121.3 (3)C2—C3—N2 118.7 (3)

Symmetry codes: (i) x; y;�z þ 52; (ii) x; y;�zþ 3

2; (iii) �xþ y;�xþ 1; z.

The H atoms bonded to atom C1 were placed in calculated posi-

tions, with a C—H distance of 0.97 A and Uiso(H) values of 1.2 times

Ueq of the parent atom. The H atom of the OH group was not

included because of its orientational disorder. Atoms C2 and N2

atoms share the same site, with 1:2 occupancy.

Data collection: SMART (Siemens, 1996); cell refinement: SAINT

(Siemens, 1996); data reduction: SAINT; program(s) used to solve

structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine

metal-organic papers

m1064 Qu and Wu � [Ag(C6H12N2)](C7H3N2O7) Acta Cryst. (2007). E63, m1063–m1065

Figure 2Crystal packing of (I), viewed along the c axis. The dashed lines showweak Ag� � �O short contacts.

Figure 1A fragment of the polymeric structure of the title compound.Displacement ellipsoids for non-H atoms are drawn at the 30%probability level. [Symmetry codes: (A) �y, x � y, z; (B) �x + y, �x, z;(C) �x, �y, z + 1

2; (D) y, �x + y, z + 12; (E) x � y, x, z + 1

2; (F) �y, �x, z;(G) �x + y, y, z; (H) x, x � y, z.]

Page 3: The infinite one-dimensional chain polymer catena-poly[[silver(I)-μ-1,4-diazabicyclo[2.2.2]octane-κ2N:N′] 2-hydroxy-3,5-dinitrobenzoate]]

structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

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

publication: SHELXTL.

References

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

Qu, Y., Liu, Z.-D., Tan, M.-Y. & Zhu, H.-L. (2005). Acta Cryst. E61, m420–m422.

Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.

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

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Systems Inc.,Madison, Wisconsin, USA.

Stumpt, H. O., Pei, L. Y., Grandjean, D. & Kahn, O. (1993). Science, 261, 447–449.

Tong, M.-L. & Chen, X.-M. (2000). Acta Cryst. C56, 1075–1076.Tong, M.-L., Chen, X.-M., Ye, B.-H. & Ng, S. W. (1998). Inorg. Chem. 37, 5278–

5281.Yaghi, O. M., Li, G. & Li, H. (1995). Nature (London), 378, 703–706.Zhu, H. L., Zhang, X. M., Liu, G. F. & Wang, D. Q. (2003). Z. Anorg. Allg.

Chem. 629, 1059–1062.

metal-organic papers

Acta Cryst. (2007). E63, m1063–m1065 Qu and Wu � [Ag(C6H12N2)](C7H3N2O7) m1065