Poly[[bis­[μ2-N,N′-bis­(2-pyridyl­meth­yl)oxalamide-κ4N,O:N′,O′][μ2-N,N′-bis­(2-pyridyl­meth­yl)oxalamide-κ2N:N′]disilver(I)] bis­(trifluoro­methane­sulfonate)]

Arman, H.D.; Miller, T.; Poplaukhin, P.; Tiekink, E.R.T.

doi:10.1107/S1600536810033611

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 9| September 2010| Pages m1167-m1168

https://doi.org/10.1107/S1600536810033611

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Poly[[bis[μ₂-N,N′-bis(2-pyridylmethyl)oxalamide-κ⁴N,O:N′,O′][μ₂-N,N′-bis(2-pyridylmethyl)oxalamide-κ²N:N′]disilver(I)] bis(trifluoromethanesulfonate)]

Hadi D. Arman,^a Tyler Miller,^a Pavel Poplaukhin ^b and Edward R. T. Tiekink ^c ^*

^aDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, ^bChemical Abstracts Service, 2540 Olentangy River Rd, Columbus, Ohio, 43202, USA, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 18 August 2010; accepted 20 August 2010; online 28 August 2010)

The asymmetric unit of the title salt, [Ag(C₁₄H₁₄N₄O₂)_1.5](CF₃SO₃), comprises a Ag⁺ cation, three half-molecules of N,N′-bis(2-pyridylmethyl)oxalamide (each of which is disposed about a centre of inversion) and a trifluoromethanesulfonate anion. Distinct coordination modes are found for the bridging ligands, i.e., a μ₂,κ²-bridging mode involving pyridine N atoms for one ligand, and a μ₂,κ⁴-bridging mode, employing both pyridine N and amide O atoms for the remaining ligands. The Ag⁺ cations, which are in a distorted square-pyramidal coordination, and the ligands combine to form a two-dimensional array parallel to (101); these arrays are connected into a three-dimensional structure by trifluoromethanesulfonate anions via N—H⋯O, C—H⋯O, and C—F⋯O interactions.

Related literature

For structural diversity in the structures of silver salts, see: Kundu et al. (2010 ). For crystal engineering studies on isomeric N,N′-bis(3-pyridylmethyl)oxalamides, see: Poplaukhin & Tiekink (2010 ). For the structure of the BF₄⁻ salt, see: Schauer et al. (1998 ). For additional structural analysis, see: Addison et al. (1984 ).

Experimental

Crystal data

[Ag(C₁₄H₁₄N₄O₂)_1.5](CF₃SO₃)
M_r = 662.38
Triclinic, $[P \overline 1]$
a = 8.7242 (14) Å
b = 11.1762 (17) Å
c = 14.210 (2) Å
α = 95.977 (1)°
β = 105.948 (2)°
γ = 107.017 (3)°
V = 1247.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 98 K
0.36 × 0.32 × 0.18 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.868, T_max = 1.000
10177 measured reflections
5688 independent reflections
5438 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.079
S = 1.05
5688 reflections
352 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −1.05 e Å⁻³

Table 1
Selected bond lengths (Å)

Ag—N1	2.378 (2)
Ag—N3	2.210 (2)
Ag—N5	2.250 (2)
Ag—O1	2.9665 (19)
Ag—O2	2.7299 (17)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2n⋯O4ⁱ	0.88	2.17	2.992 (4)	156
N4—H4n⋯O3ⁱⁱ	0.88	2.19	2.980 (3)	149
N6—H6n⋯O6ⁱⁱⁱ	0.88	2.22	2.936 (3)	139
C1—H1⋯O5^iv	0.95	2.36	3.197 (3)	146
C17—H17⋯O4	0.95	2.43	3.334 (4)	158
C18—H18⋯F1	0.95	2.45	3.261 (4)	144
N2—H2n⋯O1^v	0.88	2.32	2.697 (3)	106
N4—H4n⋯O2ⁱⁱ	0.88	2.32	2.692 (3)	105
N6—H6n⋯O3^vi	0.88	2.34	2.709 (3)	106
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+2, -z+1; (iii) x-1, y, z; (iv) x, y+1, z; (v) -x, -y+1, -z; (vi) -x+1, -y+1, -z+1.

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810033611/pv2322sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810033611/pv2322Isup2.hkl

checkCIF report

Comment top

For silver salts, the dependence of crystal structure upon counter anions and the presence of solvent is notorious and has ramifications for photoluminescence (Kundu et al., 2010). In connection with crystal engineering studies on the isomeric N,N'-bis(n-pyridylmethyl)oxalamides (Poplaukhin & Tiekink, 2010), the 3:2 reaction between Ag(trifluoromethanesulfonate) and N,N'-bis(2-pyridylmethyl)oxalamide in an ethanol/chloroform solution was investigated, which led to the characterization of the title compound, (I).

The asymmetric unit of (I) comprises a Ag cation, three half molecules of N,N'-bis(2-pyridylmethyl)oxalamide (each of which is disposed about a centre of inversion) and a trifluoromethanesulfonate anion. Each of the ligands coordinates to a Ag atom, one employing the pyridine-N atoms exclusively while the others are µ₂,κ⁴-bridging, employing both pyridine-N and amide-O atoms, leading to non-planar seven-membered chelate rings, Fig. 2. It is noted that the Ag–O bond distances are significantly longer than the Ag–N bond distances, Table 1. The resulting N₃O₂ coordination geometry is distorted square pyramidal based on the value for τ in (I) of 0.02 compared to the ideal values for τ of 0.0 and 1.0 for ideal square pyramidal and trigonal bi-pyramidal geometries, respectively (Addison et al., 1984). In this description, the Ag atoms lies 0.7272 (10) Å out of the plane defined by the O1,O2,N3 and N5 atoms (r.m.s. deviation = 0.0805 Å) in the direction of the N1 atom.

The 2-D structure observed for (I) contrasts the helical coordination polymer observed in the structure of the silver tetrafluoroborate salt containing the same ligand, isolated as a hydrate (Schauer et al., 1998). The N,N'-bis(2-pyridylmethyl)oxalamide ligand acts as a bidentate donor employing both pyridine-N atoms in coordination (Schauer et al., 1998).

The crystal packing in (I) can be envisaged as chains of Ag atoms bridged by the µ₂,κ⁴-ligands linked by the µ₂,κ²-ligands leading to 2-D arrays parallel to (1 0 1), Fig. 3. The layers are connected by contacts involving the trifluoromethanesulfonate anions. Thus, the trifluoromethanesulfonate anions participate in N–H···O hydrogen bonds formed to one layer, and C–H···O and C–H···F interactions to the other, Fig. 4 and Table 2. In addition to the intermolecular interactions, intramolecular N–H···O hydrogen bonds are also noted, Table 2.

Related literature top

For structural diversity in the structures of silver salts, see: Kundu et al. (2010). For crystal engineering studies on isomeric N,N'-bis(3-pyridylmethyl)oxalamides, see: Poplaukhin & Tiekink (2010). For the structure of the BF₄^- salt, see: Schauer et al. (1998). For additional structural analysis, see: Addison et al. (1984).

Experimental top

Colourless crystals of (I) were isolated from the 3:2 reaction of Ag(trifluoromethanesulfonate) (Sigma-Aldrich, 0.06 mmol) and N,N'-bis(2-pyridylmethyl)oxalamide (0.04 mmol) in a warm ethanol/chloroform solution (8 ml).

Structure description top

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. An asymmetric unit of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. Each of the N,N'-bis(2-pyridylmethyl)oxalamide molecules is situated about a centre of inversion.
	Fig. 2. A part of the 2-D grid in (I) showing the µ₂ and µ₄– (twice) modes of coordination of the N,N'-bis(2-pyridylmethyl)oxalamide ligands. The N–H···O hydrogen bonds are shown as orange dashed lines. The trifluoromethanesulfonate anions and the C-bound hydrogen atoms have been omitted for clarity.
	Fig. 3. A view in projection down the a axis of the 2-D grid in (I). The trifluoromethanesulfonate anions have been omitted for clarity.
	Fig. 4. A view in projection down the b axis of the crystal packing in (I). The layers shown in Fig. 3 are interspersed by the trifluoromethanesulfonate anions which are connected by N–H···O hydrogen bonds (orange dashed lines) to one layer, and C–H···O and C–H···F interactions (shown as purple and blue dashed lines, respectively) to the other.

Poly[[bis[µ₂-N,N'-bis(2-pyridylmethyl)oxalamide- κ⁴N,O:N',O'][µ₂-N,N'- bis(2-pyridylmethyl)oxalamide-κ²N:N']disilver(I)] bis(trifluoromethanesulfonate)] top

Crystal data top

[Ag(C₁₄H₁₄N₄O₂)_1.5](CF₃SO₃)	Z = 2
M_r = 662.38	F(000) = 666
Triclinic, P1	D_x = 1.763 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 8.7242 (14) Å	Cell parameters from 5470 reflections
b = 11.1762 (17) Å	θ = 2.7–40.5°
c = 14.210 (2) Å	µ = 0.97 mm⁻¹
α = 95.977 (1)°	T = 98 K
β = 105.948 (2)°	Plate, colourless
γ = 107.017 (3)°	0.36 × 0.32 × 0.18 mm
V = 1247.9 (3) Å³

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	5688 independent reflections
Radiation source: fine-focus sealed tube	5438 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
T_min = 0.868, T_max = 1.000	k = −14→14
10177 measured reflections	l = −18→10

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0295P)² + 1.3977P] where P = (F_o² + 2F_c²)/3
5688 reflections	(Δ/σ)_max = 0.001
352 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −1.05 e Å⁻³

Crystal data top

[Ag(C₁₄H₁₄N₄O₂)_1.5](CF₃SO₃)	γ = 107.017 (3)°
M_r = 662.38	V = 1247.9 (3) Å³
Triclinic, P1	Z = 2
a = 8.7242 (14) Å	Mo Kα radiation
b = 11.1762 (17) Å	µ = 0.97 mm⁻¹
c = 14.210 (2) Å	T = 98 K
α = 95.977 (1)°	0.36 × 0.32 × 0.18 mm
β = 105.948 (2)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	5688 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	5438 reflections with I > 2σ(I)
T_min = 0.868, T_max = 1.000	R_int = 0.029
10177 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.05	Δρ_max = 0.67 e Å⁻³
5688 reflections	Δρ_min = −1.05 e Å⁻³
352 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
Ag	0.18992 (2)	0.789941 (17)	0.198313 (13)	0.01680 (6)
S1	0.83484 (8)	0.26442 (7)	0.26813 (5)	0.02348 (14)
F1	0.6446 (3)	0.3310 (3)	0.36252 (17)	0.0586 (6)
F2	0.8906 (4)	0.4736 (2)	0.39309 (18)	0.0663 (7)
F3	0.8647 (3)	0.3038 (2)	0.45763 (14)	0.0527 (6)
O1	−0.1034 (2)	0.56970 (17)	0.06781 (14)	0.0230 (4)
O2	0.4189 (2)	0.89384 (17)	0.38477 (13)	0.0210 (4)
O3	0.5809 (2)	0.65495 (16)	0.47965 (13)	0.0180 (3)
O4	0.7817 (3)	0.3298 (2)	0.18909 (16)	0.0330 (5)
O5	0.7255 (2)	0.1362 (2)	0.25641 (17)	0.0346 (5)
O6	1.0141 (2)	0.28246 (18)	0.29925 (16)	0.0284 (4)
N1	0.2257 (3)	0.8994 (2)	0.06692 (15)	0.0171 (4)
N2	0.0110 (3)	0.63965 (19)	−0.05116 (15)	0.0183 (4)
H2N	0.0695	0.6247	−0.0898	0.022*
N3	0.0373 (3)	0.8513 (2)	0.28181 (15)	0.0178 (4)
N4	0.3734 (3)	1.07931 (19)	0.42923 (15)	0.0162 (4)
H4N	0.4058	1.1475	0.4765	0.019*
N5	0.3388 (2)	0.65910 (18)	0.18415 (15)	0.0148 (4)
N6	0.3291 (3)	0.49849 (19)	0.39599 (15)	0.0166 (4)
H6N	0.2627	0.4214	0.3942	0.020*
C1	0.3585 (3)	1.0079 (2)	0.09336 (19)	0.0203 (5)
H1	0.4419	1.0246	0.1568	0.024*
C2	0.3804 (3)	1.0972 (2)	0.0328 (2)	0.0229 (5)
H2	0.4757	1.1735	0.0545	0.028*
C3	0.2598 (4)	1.0721 (3)	−0.0599 (2)	0.0257 (6)
H3	0.2707	1.1308	−0.1035	0.031*
C4	0.1235 (3)	0.9603 (2)	−0.08807 (19)	0.0219 (5)
H4	0.0394	0.9414	−0.1516	0.026*
C5	0.1091 (3)	0.8756 (2)	−0.02376 (18)	0.0177 (5)
C6	−0.0395 (3)	0.7529 (2)	−0.0529 (2)	0.0210 (5)
H6A	−0.1056	0.7548	−0.0066	0.025*
H6B	−0.1140	0.7473	−0.1210	0.025*
C7	−0.0292 (3)	0.5578 (2)	0.00759 (18)	0.0168 (5)
C8	−0.1050 (3)	0.7645 (3)	0.2844 (2)	0.0240 (5)
H8	−0.1325	0.6781	0.2532	0.029*
C9	−0.2128 (3)	0.7952 (3)	0.3302 (2)	0.0292 (6)
H9	−0.3111	0.7310	0.3314	0.035*
C10	−0.1752 (3)	0.9210 (3)	0.3744 (2)	0.0286 (6)
H10	−0.2494	0.9452	0.4042	0.034*
C11	−0.0268 (3)	1.0114 (3)	0.37424 (19)	0.0224 (5)
H11	0.0028	1.0983	0.4049	0.027*
C12	0.0774 (3)	0.9732 (2)	0.32879 (17)	0.0159 (4)
C13	0.2458 (3)	1.0686 (2)	0.33435 (17)	0.0173 (5)
H13A	0.2820	1.0402	0.2783	0.021*
H13B	0.2335	1.1531	0.3286	0.021*
C14	0.4416 (3)	0.9886 (2)	0.44598 (17)	0.0155 (4)
C15	0.4180 (3)	0.6709 (2)	0.11494 (17)	0.0180 (5)
H15	0.4053	0.7318	0.0741	0.022*
C16	0.5166 (3)	0.5990 (2)	0.10053 (18)	0.0203 (5)
H16	0.5752	0.6132	0.0532	0.024*
C17	0.5288 (3)	0.5057 (3)	0.15634 (19)	0.0237 (5)
H17	0.5921	0.4522	0.1462	0.028*
C18	0.4466 (3)	0.4921 (2)	0.22738 (19)	0.0207 (5)
H18	0.4524	0.4284	0.2663	0.025*
C19	0.3555 (3)	0.5721 (2)	0.24127 (17)	0.0147 (4)
C20	0.2721 (3)	0.5694 (2)	0.32159 (17)	0.0167 (5)
H20A	0.2964	0.6582	0.3552	0.020*
H20B	0.1480	0.5304	0.2900	0.020*
C21	0.4798 (3)	0.5475 (2)	0.46690 (17)	0.0152 (4)
C22	0.8089 (5)	0.3483 (3)	0.3762 (2)	0.0387 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag	0.01925 (10)	0.01673 (10)	0.01533 (10)	0.00778 (7)	0.00530 (7)	0.00263 (7)
S1	0.0203 (3)	0.0251 (3)	0.0249 (3)	0.0084 (3)	0.0054 (3)	0.0072 (3)
F1	0.0680 (15)	0.0967 (19)	0.0516 (13)	0.0604 (15)	0.0387 (12)	0.0368 (13)
F2	0.108 (2)	0.0355 (12)	0.0527 (14)	0.0256 (13)	0.0241 (14)	−0.0027 (10)
F3	0.0741 (15)	0.0691 (15)	0.0260 (9)	0.0405 (13)	0.0131 (10)	0.0164 (10)
O1	0.0281 (9)	0.0181 (9)	0.0243 (9)	0.0069 (7)	0.0121 (8)	0.0028 (7)
O2	0.0221 (9)	0.0180 (9)	0.0183 (8)	0.0072 (7)	0.0015 (7)	−0.0030 (7)
O3	0.0194 (8)	0.0137 (8)	0.0183 (8)	0.0030 (7)	0.0046 (7)	0.0043 (7)
O4	0.0376 (11)	0.0423 (12)	0.0318 (11)	0.0238 (10)	0.0157 (9)	0.0182 (10)
O5	0.0208 (9)	0.0291 (11)	0.0438 (12)	0.0022 (8)	0.0010 (9)	0.0082 (10)
O6	0.0176 (9)	0.0223 (10)	0.0402 (11)	0.0034 (7)	0.0049 (8)	0.0058 (9)
N1	0.0180 (10)	0.0182 (10)	0.0151 (9)	0.0065 (8)	0.0046 (8)	0.0040 (8)
N2	0.0201 (10)	0.0135 (9)	0.0195 (10)	0.0045 (8)	0.0050 (8)	0.0033 (8)
N3	0.0151 (9)	0.0199 (10)	0.0169 (10)	0.0047 (8)	0.0042 (8)	0.0032 (8)
N4	0.0167 (9)	0.0143 (9)	0.0140 (9)	0.0046 (8)	0.0014 (8)	−0.0005 (8)
N5	0.0152 (9)	0.0131 (9)	0.0156 (9)	0.0043 (7)	0.0047 (8)	0.0022 (7)
N6	0.0174 (9)	0.0128 (9)	0.0171 (9)	0.0024 (8)	0.0032 (8)	0.0064 (8)
C1	0.0179 (11)	0.0223 (12)	0.0186 (11)	0.0054 (10)	0.0054 (10)	0.0008 (10)
C2	0.0238 (13)	0.0166 (12)	0.0259 (13)	0.0015 (10)	0.0108 (11)	0.0017 (10)
C3	0.0358 (15)	0.0180 (12)	0.0259 (13)	0.0079 (11)	0.0132 (12)	0.0100 (10)
C4	0.0273 (13)	0.0203 (12)	0.0176 (12)	0.0095 (10)	0.0040 (10)	0.0058 (10)
C5	0.0193 (11)	0.0152 (11)	0.0183 (11)	0.0063 (9)	0.0053 (9)	0.0025 (9)
C6	0.0193 (12)	0.0157 (12)	0.0244 (12)	0.0062 (10)	0.0014 (10)	0.0039 (10)
C7	0.0148 (10)	0.0133 (11)	0.0160 (11)	0.0020 (9)	−0.0005 (9)	−0.0006 (9)
C8	0.0180 (12)	0.0254 (13)	0.0216 (12)	0.0010 (10)	0.0031 (10)	0.0031 (10)
C9	0.0160 (12)	0.0426 (17)	0.0222 (13)	0.0006 (11)	0.0061 (10)	0.0052 (12)
C10	0.0214 (13)	0.0506 (18)	0.0181 (12)	0.0169 (13)	0.0080 (11)	0.0062 (12)
C11	0.0231 (12)	0.0309 (14)	0.0174 (11)	0.0156 (11)	0.0059 (10)	0.0050 (10)
C12	0.0168 (11)	0.0197 (12)	0.0108 (10)	0.0079 (9)	0.0015 (9)	0.0038 (9)
C13	0.0194 (11)	0.0176 (11)	0.0156 (11)	0.0078 (9)	0.0043 (9)	0.0054 (9)
C14	0.0127 (10)	0.0153 (11)	0.0166 (11)	0.0025 (8)	0.0048 (9)	0.0013 (9)
C15	0.0203 (11)	0.0176 (11)	0.0131 (10)	0.0041 (9)	0.0034 (9)	0.0025 (9)
C16	0.0195 (11)	0.0222 (12)	0.0162 (11)	0.0056 (10)	0.0053 (9)	−0.0027 (9)
C17	0.0256 (13)	0.0245 (13)	0.0201 (12)	0.0127 (11)	0.0039 (10)	−0.0025 (10)
C18	0.0249 (12)	0.0183 (12)	0.0191 (12)	0.0119 (10)	0.0027 (10)	0.0035 (10)
C19	0.0129 (10)	0.0132 (10)	0.0133 (10)	0.0020 (8)	0.0000 (8)	0.0010 (8)
C20	0.0176 (11)	0.0164 (11)	0.0153 (11)	0.0061 (9)	0.0031 (9)	0.0052 (9)
C21	0.0190 (11)	0.0151 (11)	0.0135 (10)	0.0071 (9)	0.0065 (9)	0.0038 (9)
C22	0.0490 (19)	0.0446 (19)	0.0307 (16)	0.0252 (16)	0.0144 (15)	0.0101 (14)

Geometric parameters (Å, º) top

Ag—N1	2.378 (2)	C2—H2	0.9500
Ag—N3	2.210 (2)	C3—C4	1.378 (4)
Ag—N5	2.250 (2)	C3—H3	0.9500
Ag—O1	2.9665 (19)	C4—C5	1.386 (3)
Ag—O2	2.7299 (17)	C4—H4	0.9500
S1—O5	1.433 (2)	C5—C6	1.510 (3)
S1—O4	1.447 (2)	C6—H6A	0.9900
S1—O6	1.4487 (19)	C6—H6B	0.9900
S1—C22	1.818 (3)	C7—C7ⁱ	1.537 (5)
F1—C22	1.344 (4)	C8—C9	1.381 (4)
F2—C22	1.333 (4)	C8—H8	0.9500
F3—C22	1.333 (4)	C9—C10	1.382 (4)
O1—C7	1.225 (3)	C9—H9	0.9500
O2—C14	1.228 (3)	C10—C11	1.391 (4)
O3—C21	1.225 (3)	C10—H10	0.9500
N1—C1	1.341 (3)	C11—C12	1.385 (3)
N1—C5	1.347 (3)	C11—H11	0.9500
N2—C7	1.337 (3)	C12—C13	1.518 (3)
N2—C6	1.457 (3)	C13—H13A	0.9900
N2—H2N	0.8800	C13—H13B	0.9900
N3—C8	1.346 (3)	C14—C14ⁱⁱ	1.538 (5)
N3—C12	1.352 (3)	C15—C16	1.376 (4)
N4—C14	1.329 (3)	C15—H15	0.9500
N4—C13	1.461 (3)	C16—C17	1.386 (4)
N4—H4N	0.8800	C16—H16	0.9500
N5—C19	1.344 (3)	C17—C18	1.387 (4)
N5—C15	1.345 (3)	C17—H17	0.9500
N6—C21	1.334 (3)	C18—C19	1.392 (3)
N6—C20	1.452 (3)	C18—H18	0.9500
N6—H6N	0.8800	C19—C20	1.511 (3)
C1—C2	1.390 (4)	C20—H20A	0.9900
C1—H1	0.9500	C20—H20B	0.9900
C2—C3	1.382 (4)	C21—C21ⁱⁱⁱ	1.543 (4)

N3—Ag—N5	145.64 (8)	O1—C7—N2	125.9 (2)
N3—Ag—N1	114.52 (7)	O1—C7—C7ⁱ	121.7 (3)
N5—Ag—N1	99.84 (7)	N2—C7—C7ⁱ	112.3 (3)
N3—Ag—O2	77.39 (7)	N3—C8—C9	123.0 (3)
N5—Ag—O2	86.55 (6)	N3—C8—H8	118.5
N1—Ag—O2	117.91 (6)	C9—C8—H8	118.5
N3—Ag—O1	92.93 (6)	C8—C9—C10	118.9 (3)
N5—Ag—O1	84.19 (6)	C8—C9—H9	120.5
N1—Ag—O1	94.90 (6)	C10—C9—H9	120.5
O2—Ag—O1	146.99 (5)	C9—C10—C11	118.8 (2)
O5—S1—O4	115.07 (13)	C9—C10—H10	120.6
O5—S1—O6	115.22 (12)	C11—C10—H10	120.6
O4—S1—O6	114.01 (13)	C12—C11—C10	119.1 (3)
O5—S1—C22	102.86 (16)	C12—C11—H11	120.4
O4—S1—C22	104.09 (14)	C10—C11—H11	120.4
O6—S1—C22	103.39 (15)	N3—C12—C11	122.2 (2)
C7—O1—Ag	91.70 (14)	N3—C12—C13	118.0 (2)
C14—O2—Ag	131.58 (16)	C11—C12—C13	119.8 (2)
C1—N1—C5	117.9 (2)	N4—C13—C12	109.80 (19)
C1—N1—Ag	115.41 (16)	N4—C13—H13A	109.7
C5—N1—Ag	125.33 (16)	C12—C13—H13A	109.7
C7—N2—C6	121.8 (2)	N4—C13—H13B	109.7
C7—N2—H2N	119.1	C12—C13—H13B	109.7
C6—N2—H2N	119.1	H13A—C13—H13B	108.2
C8—N3—C12	117.9 (2)	O2—C14—N4	126.2 (2)
C8—N3—Ag	118.87 (18)	O2—C14—C14ⁱⁱ	120.5 (3)
C12—N3—Ag	123.19 (16)	N4—C14—C14ⁱⁱ	113.3 (3)
C14—N4—C13	121.6 (2)	N5—C15—C16	123.1 (2)
C14—N4—H4N	119.2	N5—C15—H15	118.5
C13—N4—H4N	119.2	C16—C15—H15	118.5
C19—N5—C15	118.4 (2)	C15—C16—C17	118.8 (2)
C19—N5—Ag	124.21 (15)	C15—C16—H16	120.6
C15—N5—Ag	117.34 (16)	C17—C16—H16	120.6
C21—N6—C20	121.6 (2)	C16—C17—C18	118.5 (2)
C21—N6—H6N	119.2	C16—C17—H17	120.7
C20—N6—H6N	119.2	C18—C17—H17	120.7
N1—C1—C2	123.4 (2)	C17—C18—C19	119.6 (2)
N1—C1—H1	118.3	C17—C18—H18	120.2
C2—C1—H1	118.3	C19—C18—H18	120.2
C3—C2—C1	118.2 (2)	N5—C19—C18	121.4 (2)
C3—C2—H2	120.9	N5—C19—C20	115.7 (2)
C1—C2—H2	120.9	C18—C19—C20	122.9 (2)
C4—C3—C2	118.8 (2)	N6—C20—C19	113.0 (2)
C4—C3—H3	120.6	N6—C20—H20A	109.0
C2—C3—H3	120.6	C19—C20—H20A	109.0
C3—C4—C5	120.0 (2)	N6—C20—H20B	109.0
C3—C4—H4	120.0	C19—C20—H20B	109.0
C5—C4—H4	120.0	H20A—C20—H20B	107.8
N1—C5—C4	121.7 (2)	O3—C21—N6	125.6 (2)
N1—C5—C6	117.5 (2)	O3—C21—C21ⁱⁱⁱ	121.4 (3)
C4—C5—C6	120.9 (2)	N6—C21—C21ⁱⁱⁱ	113.0 (2)
N2—C6—C5	113.0 (2)	F3—C22—F2	109.1 (3)
N2—C6—H6A	109.0	F3—C22—F1	106.6 (3)
C5—C6—H6A	109.0	F2—C22—F1	107.8 (3)
N2—C6—H6B	109.0	F3—C22—S1	111.0 (2)
C5—C6—H6B	109.0	F2—C22—S1	111.4 (2)
H6A—C6—H6B	107.8	F1—C22—S1	110.8 (2)

N3—Ag—O1—C7	163.63 (15)	Ag—O1—C7—C7ⁱ	111.3 (3)
N5—Ag—O1—C7	−50.71 (15)	C6—N2—C7—O1	−3.3 (4)
N1—Ag—O1—C7	48.71 (15)	C6—N2—C7—C7ⁱ	176.9 (2)
O2—Ag—O1—C7	−125.18 (15)	C12—N3—C8—C9	1.8 (4)
N3—Ag—O2—C14	−39.2 (2)	Ag—N3—C8—C9	−176.6 (2)
N5—Ag—O2—C14	171.4 (2)	N3—C8—C9—C10	1.0 (4)
N1—Ag—O2—C14	72.1 (2)	C8—C9—C10—C11	−2.4 (4)
O1—Ag—O2—C14	−114.8 (2)	C9—C10—C11—C12	0.9 (4)
N3—Ag—N1—C1	87.98 (19)	C8—N3—C12—C11	−3.3 (3)
N5—Ag—N1—C1	−91.61 (18)	Ag—N3—C12—C11	175.01 (18)
O2—Ag—N1—C1	−0.3 (2)	C8—N3—C12—C13	174.4 (2)
O1—Ag—N1—C1	−176.54 (17)	Ag—N3—C12—C13	−7.3 (3)
N3—Ag—N1—C5	−78.4 (2)	C10—C11—C12—N3	2.0 (4)
N5—Ag—N1—C5	102.0 (2)	C10—C11—C12—C13	−175.7 (2)
O2—Ag—N1—C5	−166.73 (18)	C14—N4—C13—C12	74.8 (3)
O1—Ag—N1—C5	17.0 (2)	N3—C12—C13—N4	−95.2 (2)
N5—Ag—N3—C8	−60.0 (2)	C11—C12—C13—N4	82.5 (3)
N1—Ag—N3—C8	120.70 (19)	Ag—O2—C14—N4	−11.8 (4)
O2—Ag—N3—C8	−124.1 (2)	Ag—O2—C14—C14ⁱⁱ	168.21 (18)
O1—Ag—N3—C8	23.97 (19)	C13—N4—C14—O2	6.2 (4)
N5—Ag—N3—C12	121.69 (19)	C13—N4—C14—C14ⁱⁱ	−173.8 (2)
N1—Ag—N3—C12	−57.6 (2)	C19—N5—C15—C16	−0.6 (3)
O2—Ag—N3—C12	57.57 (18)	Ag—N5—C15—C16	178.29 (18)
O1—Ag—N3—C12	−154.33 (18)	N5—C15—C16—C17	3.2 (4)
N3—Ag—N5—C19	2.5 (3)	C15—C16—C17—C18	−2.6 (4)
N1—Ag—N5—C19	−178.21 (18)	C16—C17—C18—C19	−0.4 (4)
O2—Ag—N5—C19	64.05 (18)	C15—N5—C19—C18	−2.5 (3)
O1—Ag—N5—C19	−84.22 (18)	Ag—N5—C19—C18	178.64 (17)
N3—Ag—N5—C15	−176.41 (15)	C15—N5—C19—C20	176.4 (2)
N1—Ag—N5—C15	2.93 (18)	Ag—N5—C19—C20	−2.4 (3)
O2—Ag—N5—C15	−114.81 (17)	C17—C18—C19—N5	3.0 (4)
O1—Ag—N5—C15	96.91 (17)	C17—C18—C19—C20	−175.8 (2)
C5—N1—C1—C2	0.9 (4)	C21—N6—C20—C19	76.1 (3)
Ag—N1—C1—C2	−166.6 (2)	N5—C19—C20—N6	−165.2 (2)
N1—C1—C2—C3	−0.7 (4)	C18—C19—C20—N6	13.7 (3)
C1—C2—C3—C4	0.2 (4)	C20—N6—C21—O3	2.8 (4)
C2—C3—C4—C5	0.1 (4)	C20—N6—C21—C21ⁱⁱⁱ	−175.8 (2)
C1—N1—C5—C4	−0.6 (4)	O5—S1—C22—F3	64.0 (3)
Ag—N1—C5—C4	165.49 (18)	O4—S1—C22—F3	−175.7 (2)
C1—N1—C5—C6	179.8 (2)	O6—S1—C22—F3	−56.3 (3)
Ag—N1—C5—C6	−14.1 (3)	O5—S1—C22—F2	−174.2 (2)
C3—C4—C5—N1	0.2 (4)	O4—S1—C22—F2	−53.9 (3)
C3—C4—C5—C6	179.8 (2)	O6—S1—C22—F2	65.5 (3)
C7—N2—C6—C5	120.3 (2)	O5—S1—C22—F1	−54.3 (3)
N1—C5—C6—N2	−58.2 (3)	O4—S1—C22—F1	66.1 (3)
C4—C5—C6—N2	122.2 (3)	O6—S1—C22—F1	−174.5 (2)
Ag—O1—C7—N2	−68.5 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···O4^iv	0.88	2.17	2.992 (4)	156
N4—H4n···O3ⁱⁱ	0.88	2.19	2.980 (3)	149
N6—H6n···O6^v	0.88	2.22	2.936 (3)	139
C1—H1···O5^vi	0.95	2.36	3.197 (3)	146
C17—H17···O4	0.95	2.43	3.334 (4)	158
C18—H18···F1	0.95	2.45	3.261 (4)	144
N2—H2n···O1ⁱ	0.88	2.32	2.697 (3)	106
N4—H4n···O2ⁱⁱ	0.88	2.32	2.692 (3)	105
N6—H6n···O3ⁱⁱⁱ	0.88	2.34	2.709 (3)	106

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) x−1, y, z; (vi) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Ag(C₁₄H₁₄N₄O₂)_1.5](CF₃SO₃)
M_r	662.38
Crystal system, space group	Triclinic, P1
Temperature (K)	98
a, b, c (Å)	8.7242 (14), 11.1762 (17), 14.210 (2)
α, β, γ (°)	95.977 (1), 105.948 (2), 107.017 (3)
V (Å³)	1247.9 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.36 × 0.32 × 0.18

Data collection
Diffractometer	Rigaku AFC12K/SATURN724
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.868, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10177, 5688, 5438
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.079, 1.05
No. of reflections	5688
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −1.05

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Ag—N1	2.378 (2)	Ag—O1	2.9665 (19)
Ag—N3	2.210 (2)	Ag—O2	2.7299 (17)
Ag—N5	2.250 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···O4ⁱ	0.88	2.17	2.992 (4)	156
N4—H4n···O3ⁱⁱ	0.88	2.19	2.980 (3)	149
N6—H6n···O6ⁱⁱⁱ	0.88	2.22	2.936 (3)	139
C1—H1···O5^iv	0.95	2.36	3.197 (3)	146
C17—H17···O4	0.95	2.43	3.334 (4)	158
C18—H18···F1	0.95	2.45	3.261 (4)	144
N2—H2n···O1^v	0.88	2.32	2.697 (3)	106
N4—H4n···O2ⁱⁱ	0.88	2.32	2.692 (3)	105
N6—H6n···O3^vi	0.88	2.34	2.709 (3)	106

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+2, −z+1; (iii) x−1, y, z; (iv) x, y+1, z; (v) −x, −y+1, −z; (vi) −x+1, −y+1, −z+1.

References

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