Bis[μ-1,4-bis­(4,5-dihydro-1H-imidazol-2-yl)benzene-κ2N3:N3′]silver(I) dinitrate dihydrate

Sun, H.; Ren, C.-X.; Shen, B.; Liu, Z.-Q.; Ding, Y.-Q.

doi:10.1107/S1600536808001633

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages m427-m428

doi:10.1107/S1600536808001633

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Bis[μ-1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene-κ²N³:N^3′]silver(I) dinitrate dihydrate

Hua Sun,^a Chun-Xia Ren,^a Bin Shen,^a Zhi-Qiang Liu ^a and Yu-Qiang Ding ^a ^*

^aSchool of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi, Jiangsu Province 214122, People's Republic of China
^*Correspondence e-mail: yuqiang_ding@yahoo.com

(Received 12 January 2008; accepted 16 January 2008; online 30 January 2008)

The reaction of 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (bib) with silver(I) nitrate in a 1:1 molar ratio generates the metallacyclic title complex, [Ag₂(C₁₂H₁₄N₄)₂](NO₃)₂·2H₂O, in which the bib ligand displays a cis configuration. Each bib ligand acts as a bidentate bridging ligand connecting a pair of Ag^I ions to form a [2 + 2] metallamacrocycle in which the Ag⋯Ag distance is 6.77 (2) Å. Each Ag^I ion has weak contacts (2.91 Å) with the nitrate anion. The uncoordinated water molecules make hydrogen bonds with nitrate O atoms, forming chains. The H atoms attached to the uncoordinated nitrogen interact with these chains through N—H⋯O hydrogen bonds, forming layers parallel to the ( $[\overline{1}]$ 11) plane.

Related literature

For related literature, see: Moulton & Zaworotko (2001 ); Nardelli (1999 ); Ren, Ye, He et al. (2004 ); Ren, Ye, Zhu et al. (2004 ); Ren et al. (2007 ); Toh et al. (2005 ); Zhang et al. (2005 ).

Experimental

Crystal data

[Ag₂(C₁₂H₁₄N₄)₂](NO₃)₂·2H₂O
M_r = 804.34
Triclinic, $[P \overline 1]$
a = 10.3562 (19) Å
b = 11.053 (2) Å
c = 13.282 (2) Å
α = 97.496 (3)°
β = 95.354 (3)°
γ = 101.613 (3)°
V = 1465.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.40 mm⁻¹
T = 273 (2) K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.678, T_max = 0.767
7650 measured reflections
5316 independent reflections
3797 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.143
S = 0.92
5316 reflections
397 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 2.17 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6	0.86	2.12	2.980 (6)	173
N1—H1⋯O5	0.86	2.46	3.029 (6)	124
N3—H3⋯O1	0.86	2.13	2.915 (7)	151
N3—H3⋯O2	0.86	2.64	3.143 (6)	119
N6—H6⋯O1W	0.86	2.13	2.912 (6)	150
N8—H8⋯O4ⁱ	0.86	2.33	3.073 (7)	145
O1W—H11W⋯O2ⁱⁱ	0.85	2.12	2.852 (6)	144
O1W—H12W⋯O5ⁱ	0.85	2.04	2.888 (7)	178
O2W—H21W⋯O1	0.85	2.22	3.021 (7)	157
O2W—H22W⋯O6	0.85	2.21	2.973 (7)	150
Symmetry codes: (i) x+1, y, z+1; (ii) x, y-1, z+1.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001633/dn2312sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808001633/dn2312Isup2.hkl

checkCIF report

Comment top

Controlled assembly and crystallization of supramolecular isomers and polymorphs are an interesting challenges in the field of supramolecular chemistry and crystal engineering (Moulton et al., 2001). One of the simplest example of such supramolecular isomerism may be a discrete molecule forming a one-dimensional polymer assembled in a 1/1 metal-ligand stoichiometry(Toh et al., 2005; Zhang et al., 2005). In our previous work, we have designed and synthesized a number of such metal complexes, including silver(I) complexes with a V-shaped ligand 1,3-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (Ren, Ye, He et al., 2004; Ren, Ye, Zhu et al., 2004; Ren et al., 2007) which has four potential coordinated sites with differently binding abilities. To gain more insight into the structural variation of this type of silver(I) complexes, we became interested in a new imidazole-like ligand 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (bib). Here, we present the syntheses and structural characterizations of a new [2:2] metallocyclic silver(I) complexes, namely [Ag₂(bib)₂](NO₃)₂.2H₂O.

The crystal structure of the title complex consists of dimeric [Ag₂(bib)₂]²⁺ cations, as well as NO₃^- counter anion and lattice water in the solid state. As shown in Fig. 1, each pair of Ag^I ions in the title complex are coordinated by two nitrogen atoms from two different bib ligands resulting in a [2:2] 18-membered metallocycle with a Ag(1)···Ag(2) distance of 6.77 Å. The two bib ligands, acting in a cis, cis mode, are organized in a head-to-tail fashion and joined together by two silver ions through coordination bonds to give the metallocycles. All the Ag—N bond distances are from 2.078 (4) to 2.104 (4) Å, and agree with values found in the literature(Ren et al., 2004a, 2004b, 2007). The bond angles around the Ag^I ion are 164.4 (2) /% and 166.5 (2) /%.

The lattice water molecules form hydrogen bonds with nitrate oxygen atoms yielding chains. The H atoms attached to the uncoordinated nitrogen interact through N—H···O hydrogen bonds with these chains forming layers parallel to the (-1 1 1) plane. (Table 1, Fig. 2).

Related literature top

For related literature, see: Moulton & Zaworotko (2001); Nardelli (1999); Ren, Ye, He et al. (2004); Ren, Ye, Zhu et al. (2004); Ren et al. (2007); Toh et al. (2005); Zhang et al. (2005).

Experimental top

All the reagents and solvents employed were commercially available and used as received without further purification.

Synthesis of Ligand bib. 1,4-Benzenedicarboxylic acid (2.31 g, 13.9 mmol), ethylenediamine (3.70 ml, 50 mmol), ethylenediamine dihydrochloride (6.64 g, 50 mmol) and toluene-p-sulfonic acid (0.208 g, 1.09 mmol) were added to the solvent of ethylene glycol (20 ml), and the mixture solution was refluxed for 3 h. About half of the ehylene glycol solvent was then slowly removed by distillation. The residue was dissolved in a mixture of water (40 ml) and concentrated HCl (11M, 3 ml). The addition of 50% aqueous NaOH gave a yellow precipitate that was purified by recrystallization. The ligand bib was obtained in 89% based on 1,4-benzenedicarboxylic acid (ca 2.68 g). Anal. calc. for C₁₂H₁₄N₄: C, 67.27; H, 6.59; N, 26.15%. Found: C, 67.13; H, 6.87; N, 26.04%.

Synthesis of [Ag₂(bib)₂](NO₃)₂.2H₂O. To a solution of AgNO₃ (0.169 g, 1 mmol) in MeCN-H₂O (v/v 1:1), an aqueous solution (2 ml) of bib (0.214 g, 1 mmol) was added. The pale-yellow solution was allowed to stand at room temperature in air avoiding illumination for a few days by slow evaporation. Colourless prismatic crystals of the title complex were obtained, which were collected by filtration washed with aqueous MeCN and dried in a vacuum desiccator over silica gel (ca 0.108 g, 27% yield based on AgNO₃). Anal. calc. for C₂₄H₃₂Ag₂N₁₀O₈. Main IR bands (KBr, cm_-1): 3340m, 2968w, 2887w, 1615m, 1567m, 1510m, 1473m, 1365 s, 1279 s, 1184m, 1049w, 983w, 693w, 576w, 528w.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of compound (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view of [Ag₂(bib)₂](NO₃)₂.2H₂O showing the hydrogen bond interactions as dashed lines. H atoms not involved in hydrogen bondings have been omitted for clarity.[Symmetry codes: (i) 1 + x, y, 1 + z; (ii) x, y - 1, 1 + z]

Bis[µ-1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene- κ²N³:N^3']silver(I) dinitrate dihydrate top

Crystal data top

[Ag₂(C₁₂H₁₄N₄)₂](NO₃)₂·2H₂O	Z = 2
M_r = 804.34	F(000) = 808
Triclinic, P1	D_x = 1.823 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.3562 (19) Å	Cell parameters from 2137 reflections
b = 11.053 (2) Å	θ = 2.5–23.9°
c = 13.282 (2) Å	µ = 1.40 mm⁻¹
α = 97.496 (3)°	T = 273 K
β = 95.354 (3)°	Block, colourless
γ = 101.613 (3)°	0.30 × 0.25 × 0.20 mm
V = 1465.3 (4) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	5316 independent reflections
Radiation source: fine-focus sealed tube	3797 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 25.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −12→12
T_min = 0.678, T_max = 0.767	k = −11→13
7650 measured reflections	l = −16→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.1055P)²] where P = (F_o² + 2F_c²)/3
5316 reflections	(Δ/σ)_max = 0.001
397 parameters	Δρ_max = 2.17 e Å⁻³
3 restraints	Δρ_min = −0.82 e Å⁻³

Crystal data top

[Ag₂(C₁₂H₁₄N₄)₂](NO₃)₂·2H₂O	γ = 101.613 (3)°
M_r = 804.34	V = 1465.3 (4) Å³
Triclinic, P1	Z = 2
a = 10.3562 (19) Å	Mo Kα radiation
b = 11.053 (2) Å	µ = 1.40 mm⁻¹
c = 13.282 (2) Å	T = 273 K
α = 97.496 (3)°	0.30 × 0.25 × 0.20 mm
β = 95.354 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5316 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	3797 reflections with I > 2σ(I)
T_min = 0.678, T_max = 0.767	R_int = 0.017
7650 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	3 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 0.92	Δρ_max = 2.17 e Å⁻³
5316 reflections	Δρ_min = −0.82 e Å⁻³
397 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

	x	y	z	U_iso*/U_eq
Ag1	0.72496 (4)	0.29100 (4)	0.19588 (3)	0.04584 (17)
Ag2	1.24475 (4)	0.78014 (4)	0.21805 (3)	0.04782 (17)
N1	0.5471 (5)	0.3689 (5)	−0.0866 (4)	0.0556 (13)
H1	0.5461	0.4098	−0.1374	0.067*
N2	0.6169 (4)	0.3282 (4)	0.0656 (3)	0.0444 (11)
N3	1.0950 (5)	0.8764 (5)	−0.0663 (4)	0.0562 (13)
H3	1.0437	0.8590	−0.1234	0.067*
N4	1.1847 (4)	0.8423 (4)	0.0829 (3)	0.0446 (11)
N5	0.7991 (4)	0.2146 (4)	0.3188 (3)	0.0425 (10)
N6	0.9176 (5)	0.1613 (4)	0.4484 (3)	0.0487 (12)
H6	0.9871	0.1636	0.4901	0.058*
N7	1.3532 (4)	0.7500 (4)	0.3484 (3)	0.0443 (11)
N8	1.4423 (4)	0.6791 (4)	0.4819 (4)	0.0510 (12)
H8	1.4496	0.6282	0.5248	0.061*
C1	0.4473 (5)	0.2619 (6)	−0.0755 (4)	0.0510 (14)
H1A	0.4548	0.1880	−0.1209	0.061*
H1B	0.3586	0.2768	−0.0886	0.061*
C2	0.4810 (6)	0.2495 (6)	0.0358 (4)	0.0542 (15)
H2A	0.4184	0.2796	0.0775	0.065*
H2B	0.4796	0.1632	0.0433	0.065*
C3	0.6420 (5)	0.3957 (5)	−0.0059 (4)	0.0389 (12)
C4	0.7598 (5)	0.4977 (5)	−0.0017 (4)	0.0373 (11)
C5	0.7993 (5)	0.5387 (5)	−0.0918 (4)	0.0458 (13)
H5	0.7540	0.4984	−0.1549	0.055*
C6	0.9054 (5)	0.6390 (5)	−0.0876 (4)	0.0478 (14)
H6A	0.9299	0.6661	−0.1479	0.057*
C7	0.9754 (5)	0.6992 (5)	0.0054 (4)	0.0385 (12)
C8	0.9353 (5)	0.6586 (5)	0.0946 (4)	0.0449 (13)
H8A	0.9803	0.6992	0.1576	0.054*
C9	0.8298 (5)	0.5590 (5)	0.0907 (4)	0.0430 (12)
H9	0.8053	0.5327	0.1512	0.052*
C10	1.0863 (5)	0.8076 (5)	0.0097 (4)	0.0391 (12)
C11	1.2038 (6)	0.9842 (6)	−0.0381 (5)	0.0585 (16)
H11A	1.1718	1.0604	−0.0223	0.070*
H11B	1.2607	0.9934	−0.0918	0.070*
C12	1.2758 (6)	0.9513 (5)	0.0572 (4)	0.0529 (15)
H12A	1.3596	0.9307	0.0428	0.064*
H12B	1.2929	1.0206	0.1130	0.064*
C13	0.7201 (6)	0.0958 (5)	0.3396 (4)	0.0517 (14)
H13A	0.7169	0.0290	0.2837	0.062*
H13B	0.6301	0.1034	0.3487	0.062*
C14	0.7918 (6)	0.0695 (5)	0.4389 (4)	0.0488 (14)
H14A	0.7433	0.0841	0.4968	0.059*
H14B	0.8055	−0.0153	0.4319	0.059*
C15	0.9071 (5)	0.2413 (5)	0.3818 (4)	0.0407 (12)
C16	1.0166 (5)	0.3512 (5)	0.3846 (4)	0.0379 (11)
C17	0.9944 (5)	0.4653 (5)	0.3636 (4)	0.0404 (12)
H17	0.9080	0.4733	0.3454	0.048*
C18	1.0980 (5)	0.5674 (4)	0.3691 (4)	0.0349 (11)
H18	1.0814	0.6428	0.3532	0.042*
C19	1.2278 (5)	0.5569 (5)	0.3987 (4)	0.0380 (12)
C20	1.2499 (5)	0.4421 (5)	0.4183 (4)	0.0422 (12)
H20	1.3363	0.4335	0.4360	0.051*
C21	1.1465 (5)	0.3411 (5)	0.4119 (4)	0.0413 (12)
H21	1.1633	0.2651	0.4260	0.050*
C22	1.3392 (5)	0.6637 (5)	0.4076 (4)	0.0359 (11)
C23	1.4810 (6)	0.8388 (6)	0.3862 (5)	0.0539 (15)
H23A	1.4667	0.9226	0.4044	0.065*
H23B	1.5407	0.8402	0.3340	0.065*
C24	1.5388 (5)	0.7930 (5)	0.4794 (4)	0.0530 (14)
H24A	1.6260	0.7763	0.4711	0.064*
H24B	1.5450	0.8528	0.5409	0.064*
N9	0.9177 (6)	0.9780 (5)	−0.2608 (4)	0.0576 (13)
O1	0.8766 (5)	0.8843 (4)	−0.2188 (4)	0.0705 (13)
O2	1.0326 (5)	1.0387 (4)	−0.2346 (4)	0.0724 (13)
O3	0.8422 (6)	1.0092 (5)	−0.3252 (4)	0.0875 (16)
N10	0.4137 (5)	0.4736 (5)	−0.2932 (3)	0.0514 (12)
O4	0.3505 (5)	0.5295 (5)	−0.3486 (3)	0.0719 (13)
O5	0.3607 (4)	0.3683 (5)	−0.2766 (3)	0.0703 (13)
O6	0.5283 (4)	0.5234 (4)	−0.2531 (3)	0.0635 (12)
O1W	1.1003 (4)	0.2239 (4)	0.6372 (3)	0.0721 (13)
H11W	1.0637	0.1943	0.6860	0.108*
H12W	1.1775	0.2658	0.6616	0.108*
O2W	0.5808 (5)	0.7918 (5)	−0.2779 (4)	0.0920 (16)
H21W	0.6639	0.8127	−0.2803	0.138*
H22W	0.5669	0.7283	−0.2473	0.138*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0469 (3)	0.0491 (3)	0.0405 (3)	0.0061 (2)	−0.00367 (19)	0.01590 (19)
Ag2	0.0504 (3)	0.0478 (3)	0.0440 (3)	0.0056 (2)	−0.00285 (19)	0.0163 (2)
N1	0.051 (3)	0.065 (3)	0.045 (3)	−0.005 (2)	−0.012 (2)	0.024 (2)
N2	0.044 (3)	0.051 (3)	0.036 (2)	0.005 (2)	−0.0003 (19)	0.014 (2)
N3	0.059 (3)	0.062 (3)	0.043 (3)	0.000 (3)	−0.007 (2)	0.024 (2)
N4	0.049 (3)	0.041 (3)	0.040 (2)	0.001 (2)	0.000 (2)	0.010 (2)
N5	0.039 (2)	0.044 (3)	0.042 (2)	0.004 (2)	−0.004 (2)	0.012 (2)
N6	0.049 (3)	0.050 (3)	0.046 (3)	0.007 (2)	−0.007 (2)	0.020 (2)
N7	0.042 (3)	0.044 (3)	0.044 (2)	0.005 (2)	−0.005 (2)	0.011 (2)
N8	0.043 (3)	0.052 (3)	0.055 (3)	−0.002 (2)	−0.010 (2)	0.023 (2)
C1	0.045 (3)	0.059 (4)	0.046 (3)	0.005 (3)	−0.006 (3)	0.015 (3)
C2	0.049 (3)	0.060 (4)	0.051 (3)	0.002 (3)	−0.002 (3)	0.019 (3)
C3	0.039 (3)	0.047 (3)	0.031 (3)	0.012 (2)	−0.002 (2)	0.007 (2)
C4	0.040 (3)	0.041 (3)	0.034 (3)	0.013 (2)	0.004 (2)	0.012 (2)
C5	0.052 (3)	0.047 (3)	0.034 (3)	0.003 (3)	−0.001 (2)	0.008 (2)
C6	0.053 (3)	0.058 (4)	0.033 (3)	0.009 (3)	0.006 (2)	0.017 (3)
C7	0.039 (3)	0.042 (3)	0.036 (3)	0.012 (2)	−0.002 (2)	0.009 (2)
C8	0.045 (3)	0.053 (3)	0.034 (3)	0.006 (3)	−0.004 (2)	0.013 (2)
C9	0.044 (3)	0.053 (3)	0.032 (3)	0.003 (3)	0.002 (2)	0.016 (2)
C10	0.044 (3)	0.040 (3)	0.036 (3)	0.010 (2)	0.007 (2)	0.012 (2)
C11	0.058 (4)	0.057 (4)	0.058 (4)	−0.002 (3)	0.004 (3)	0.025 (3)
C12	0.052 (4)	0.051 (3)	0.051 (3)	−0.003 (3)	0.008 (3)	0.015 (3)
C13	0.045 (3)	0.052 (3)	0.055 (4)	−0.001 (3)	−0.002 (3)	0.022 (3)
C14	0.052 (3)	0.049 (3)	0.047 (3)	0.004 (3)	0.008 (3)	0.019 (3)
C15	0.041 (3)	0.041 (3)	0.042 (3)	0.008 (2)	0.004 (2)	0.015 (2)
C16	0.039 (3)	0.041 (3)	0.034 (3)	0.007 (2)	0.001 (2)	0.011 (2)
C17	0.040 (3)	0.046 (3)	0.039 (3)	0.016 (2)	0.004 (2)	0.012 (2)
C18	0.038 (3)	0.027 (2)	0.040 (3)	0.007 (2)	0.001 (2)	0.010 (2)
C19	0.041 (3)	0.043 (3)	0.031 (3)	0.009 (2)	0.004 (2)	0.009 (2)
C20	0.036 (3)	0.045 (3)	0.050 (3)	0.012 (2)	0.004 (2)	0.017 (2)
C21	0.040 (3)	0.037 (3)	0.048 (3)	0.009 (2)	0.000 (2)	0.014 (2)
C22	0.034 (3)	0.040 (3)	0.038 (3)	0.012 (2)	0.005 (2)	0.014 (2)
C23	0.045 (3)	0.047 (3)	0.063 (4)	−0.006 (3)	0.002 (3)	0.013 (3)
C24	0.043 (3)	0.057 (4)	0.052 (3)	−0.001 (3)	−0.007 (3)	0.013 (3)
N9	0.073 (4)	0.060 (3)	0.045 (3)	0.027 (3)	0.003 (3)	0.010 (3)
O1	0.076 (3)	0.061 (3)	0.073 (3)	0.010 (2)	−0.001 (2)	0.020 (2)
O2	0.080 (4)	0.068 (3)	0.070 (3)	0.010 (3)	0.006 (3)	0.024 (3)
O3	0.103 (4)	0.096 (4)	0.069 (3)	0.042 (3)	−0.018 (3)	0.025 (3)
N10	0.049 (3)	0.069 (4)	0.038 (3)	0.017 (3)	0.003 (2)	0.013 (2)
O4	0.069 (3)	0.090 (4)	0.062 (3)	0.029 (3)	−0.009 (2)	0.026 (3)
O5	0.063 (3)	0.078 (3)	0.066 (3)	0.004 (3)	−0.002 (2)	0.026 (3)
O6	0.047 (3)	0.077 (3)	0.062 (3)	0.005 (2)	−0.004 (2)	0.015 (2)
O1W	0.068 (3)	0.077 (3)	0.067 (3)	0.004 (2)	−0.015 (2)	0.031 (3)
O2W	0.079 (3)	0.127 (5)	0.071 (3)	0.016 (3)	0.005 (3)	0.027 (3)

Geometric parameters (Å, º) top

Ag1—N5	2.087 (4)	C8—H8A	0.9300
Ag1—N2	2.104 (4)	C9—H9	0.9300
Ag2—N7	2.076 (4)	C11—C12	1.530 (8)
Ag2—N4	2.089 (4)	C11—H11A	0.9700
N1—C3	1.344 (7)	C11—H11B	0.9700
N1—C1	1.439 (7)	C12—H12A	0.9700
N1—H1	0.8600	C12—H12B	0.9700
N2—C3	1.296 (7)	C13—C14	1.542 (7)
N2—C2	1.486 (7)	C13—H13A	0.9700
N3—C10	1.339 (6)	C13—H13B	0.9700
N3—C11	1.447 (7)	C14—H14A	0.9700
N3—H3	0.8600	C14—H14B	0.9700
N4—C10	1.300 (7)	C15—C16	1.480 (7)
N4—C12	1.473 (7)	C16—C17	1.385 (7)
N5—C15	1.291 (7)	C16—C21	1.390 (7)
N5—C13	1.474 (7)	C17—C18	1.381 (7)
N6—C15	1.343 (6)	C17—H17	0.9300
N6—C14	1.466 (7)	C18—C19	1.397 (7)
N6—H6	0.8600	C18—H18	0.9300
N7—C22	1.308 (7)	C19—C20	1.386 (7)
N7—C23	1.480 (7)	C19—C22	1.459 (7)
N8—C22	1.352 (7)	C20—C21	1.371 (7)
N8—C24	1.447 (7)	C20—H20	0.9300
N8—H8	0.8600	C21—H21	0.9300
C1—C2	1.517 (7)	C23—C24	1.515 (8)
C1—H1A	0.9700	C23—H23A	0.9700
C1—H1B	0.9700	C23—H23B	0.9700
C2—H2A	0.9700	C24—H24A	0.9700
C2—H2B	0.9700	C24—H24B	0.9700
C3—C4	1.475 (7)	N9—O3	1.234 (6)
C4—C9	1.382 (7)	N9—O2	1.236 (7)
C4—C5	1.402 (7)	N9—O1	1.258 (7)
C5—C6	1.386 (7)	N10—O5	1.239 (6)
C5—H5	0.9300	N10—O6	1.240 (6)
C6—C7	1.385 (7)	N10—O4	1.243 (6)
C6—H6A	0.9300	O1W—H11W	0.8499
C7—C8	1.390 (7)	O1W—H12W	0.8500
C7—C10	1.475 (7)	O2W—H21W	0.8500
C8—C9	1.378 (7)	O2W—H22W	0.8499

N5—Ag1—N2	166.51 (18)	N3—C11—H11B	111.5
N7—Ag2—N4	164.37 (18)	C12—C11—H11B	111.5
C3—N1—C1	110.0 (5)	H11A—C11—H11B	109.3
C3—N1—H1	125.0	N4—C12—C11	105.0 (5)
C1—N1—H1	125.0	N4—C12—H12A	110.8
C3—N2—C2	107.1 (4)	C11—C12—H12A	110.8
C3—N2—Ag1	136.2 (4)	N4—C12—H12B	110.8
C2—N2—Ag1	116.2 (3)	C11—C12—H12B	110.8
C10—N3—C11	109.9 (5)	H12A—C12—H12B	108.8
C10—N3—H3	125.1	N5—C13—C14	105.5 (4)
C11—N3—H3	125.1	N5—C13—H13A	110.6
C10—N4—C12	107.7 (4)	C14—C13—H13A	110.6
C10—N4—Ag2	136.8 (4)	N5—C13—H13B	110.6
C12—N4—Ag2	115.5 (3)	C14—C13—H13B	110.6
C15—N5—C13	107.1 (4)	H13A—C13—H13B	108.8
C15—N5—Ag1	135.4 (4)	N6—C14—C13	100.8 (4)
C13—N5—Ag1	117.3 (3)	N6—C14—H14A	111.6
C15—N6—C14	109.1 (4)	C13—C14—H14A	111.6
C15—N6—H6	125.4	N6—C14—H14B	111.6
C14—N6—H6	125.4	C13—C14—H14B	111.6
C22—N7—C23	107.4 (4)	H14A—C14—H14B	109.4
C22—N7—Ag2	134.8 (4)	N5—C15—N6	115.9 (5)
C23—N7—Ag2	117.7 (4)	N5—C15—C16	124.9 (5)
C22—N8—C24	110.8 (4)	N6—C15—C16	119.2 (5)
C22—N8—H8	124.6	C17—C16—C21	118.5 (5)
C24—N8—H8	124.6	C17—C16—C15	122.4 (5)
N1—C1—C2	101.7 (4)	C21—C16—C15	119.1 (4)
N1—C1—H1A	111.4	C18—C17—C16	121.4 (5)
C2—C1—H1A	111.4	C18—C17—H17	119.3
N1—C1—H1B	111.4	C16—C17—H17	119.3
C2—C1—H1B	111.4	C17—C18—C19	119.6 (4)
H1A—C1—H1B	109.3	C17—C18—H18	120.2
N2—C2—C1	104.6 (4)	C19—C18—H18	120.2
N2—C2—H2A	110.8	C20—C19—C18	118.9 (5)
C1—C2—H2A	110.8	C20—C19—C22	120.1 (5)
N2—C2—H2B	110.8	C18—C19—C22	121.1 (4)
C1—C2—H2B	110.8	C21—C20—C19	121.0 (5)
H2A—C2—H2B	108.9	C21—C20—H20	119.5
N2—C3—N1	114.1 (5)	C19—C20—H20	119.5
N2—C3—C4	125.2 (5)	C20—C21—C16	120.6 (5)
N1—C3—C4	120.6 (5)	C20—C21—H21	119.7
C9—C4—C5	118.3 (5)	C16—C21—H21	119.7
C9—C4—C3	121.3 (4)	N7—C22—N8	113.6 (5)
C5—C4—C3	120.3 (5)	N7—C22—C19	126.5 (5)
C6—C5—C4	120.4 (5)	N8—C22—C19	119.9 (4)
C6—C5—H5	119.8	N7—C23—C24	106.2 (4)
C4—C5—H5	119.8	N7—C23—H23A	110.5
C7—C6—C5	120.7 (5)	C24—C23—H23A	110.5
C7—C6—H6A	119.6	N7—C23—H23B	110.5
C5—C6—H6A	119.6	C24—C23—H23B	110.5
C6—C7—C8	118.6 (5)	H23A—C23—H23B	108.7
C6—C7—C10	120.5 (5)	N8—C24—C23	101.8 (4)
C8—C7—C10	120.8 (5)	N8—C24—H24A	111.4
C9—C8—C7	120.8 (5)	C23—C24—H24A	111.4
C9—C8—H8A	119.6	N8—C24—H24B	111.4
C7—C8—H8A	119.6	C23—C24—H24B	111.4
C8—C9—C4	121.1 (5)	H24A—C24—H24B	109.3
C8—C9—H9	119.5	O3—N9—O2	121.3 (6)
C4—C9—H9	119.5	O3—N9—O1	119.7 (6)
N4—C10—N3	114.4 (5)	O2—N9—O1	118.9 (5)
N4—C10—C7	124.5 (5)	O5—N10—O6	120.0 (5)
N3—C10—C7	121.1 (5)	O5—N10—O4	119.6 (5)
N3—C11—C12	101.6 (4)	O6—N10—O4	120.4 (5)
N3—C11—H11A	111.5	H11W—O1W—H12W	107.7
C12—C11—H11A	111.5	H21W—O2W—H22W	107.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6	0.86	2.12	2.980 (6)	173
N1—H1···O5	0.86	2.46	3.029 (6)	124
N3—H3···O1	0.86	2.13	2.915 (7)	151
N3—H3···O2	0.86	2.64	3.143 (6)	119
N6—H6···O1W	0.86	2.13	2.912 (6)	150
N8—H8···O4ⁱ	0.86	2.33	3.073 (7)	145
O1W—H11W···O2ⁱⁱ	0.85	2.12	2.852 (6)	144
O1W—H12W···O5ⁱ	0.85	2.04	2.888 (7)	178
O2W—H21W···O1	0.85	2.22	3.021 (7)	157
O2W—H22W···O6	0.85	2.21	2.973 (7)	150

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

Experimental details

Crystal data
Chemical formula	[Ag₂(C₁₂H₁₄N₄)₂](NO₃)₂·2H₂O
M_r	804.34
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	10.3562 (19), 11.053 (2), 13.282 (2)
α, β, γ (°)	97.496 (3), 95.354 (3), 101.613 (3)
V (Å³)	1465.3 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.40
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.678, 0.767
No. of measured, independent and observed [I > 2σ(I)] reflections	7650, 5316, 3797
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.144, 0.92
No. of reflections	5316
No. of parameters	397
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.17, −0.82

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6	0.86	2.12	2.980 (6)	172.9
N1—H1···O5	0.86	2.46	3.029 (6)	123.8
N3—H3···O1	0.86	2.13	2.915 (7)	150.7
N3—H3···O2	0.86	2.64	3.143 (6)	118.6
N6—H6···O1W	0.86	2.13	2.912 (6)	150.2
N8—H8···O4ⁱ	0.86	2.33	3.073 (7)	145.1
O1W—H11W···O2ⁱⁱ	0.85	2.12	2.852 (6)	144.3
O1W—H12W···O5ⁱ	0.85	2.04	2.888 (7)	178.4
O2W—H21W···O1	0.85	2.22	3.021 (7)	156.5
O2W—H22W···O6	0.85	2.21	2.973 (7)	149.7

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

Acknowledgements

This work was generously supported by the National Natural Science Foundation of China (Nos. 20571033 and 20701016).

References

Bruker, (1998). SMART, SAINT and SADABS. Bruker AXS Inc., ADISON. Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629–1658. Web of Science CrossRef PubMed CAS Google Scholar
Nardelli, M. (1999). J. Appl. Cryst. 32, 563–571. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ren, C.-X., Cheng, L., Ye, B.-H. & Chen, X.-M. (2007). Inorg. Chim. Acta, 360, 3741–3747. Web of Science CSD CrossRef CAS Google Scholar
Ren, C.-X., Ye, B.-H., He, F., Cheng, L. & Chen, X.-M. (2004). CrystEngComm, 6, 220–206. Web of Science CSD CrossRef Google Scholar
Ren, C.-X., Ye, B.-H., Zhu, H.-L., Shi, J.-X. & Chen, X.-M. (2004). Inorg. Chim. Acta, 357, 443–450. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Toh, N. L., Nagarathinam, M. & Vittal, J. J. (2005). Angew. Chem. Int. Ed. 44, 2237–2241. Web of Science CSD CrossRef CAS Google Scholar
Zhang, J.-P., Lin, Y.-Y., Huang, X.-C. & Chen, X.-M. (2005). Chem. Commun. pp. 1258–1260. Web of Science CSD CrossRef Google Scholar

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