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Acta Cryst. (2007). E63, m3071    [ doi:10.1107/S160053680705845X ]

(2,2'-Bipyridine)saccharinatosilver(I)

V. T. Yilmaz, S. Hamamci and W. T. A. Harrison

Abstract top

The title complex, [Ag(C7H4NO3S)(C10H8N2)], has a mononuclear structure in which the AgI ion is coordinated by two N atoms from 2,2'-bipyridine and one N atom from saccharinate, forming a distorted T-shaped (or trigonal-planar) AgN3 arrangement. The bite angle of bpy is 71.69 (6)°, which contributes significantly to the distortion of the coordination geometry. Molecules are connected by C-H...O and [pi](bpy)-[pi](bpy) interactions with a centroid-centroid separation of 3.6741 (13) Å.

Comment top

Saccharin is a well known artificial sweetener and it readily coordinates metal ions in the deprotonated form, saccharinate (sac) (Baran & Yilmaz 2006). The first silver(I) complexes of sac were reported by Weber et al. (1993) and Yilmaz et al. (2004). In this paper, the structure of the title compound, (I) (Fig. 1), containing a 2,2'-bipyridine (bpy) molecule and a sac anion is described.

In (I), Ag(I)I ion is coordinated by two N atoms from 2,2'-bipyridine and one N atom from saccharinate, forming a highly distorted T-shaped (or trigonal planar) coordination geometry (Table 1). The small bite angle of bpy [71.69 (6)°] is responsible for the distortion of the coordination geometry similar to that of a silver(I) complex of bpy (Liu et al., 2006). Both ligands are essentially planar and the dihedral angle between the two pyridine rings of the bipy ligand is only 2.48 (11)°, while the dihedral angle between the sac benzene ring and sac 5-membered ring is 0.50 (8)°. The sac ion makes a dihedral angle of 7.20 (8)° with the complete bipy molecule.

The closest Ag···Agi contact is 4.0838 (3)Å (i = 1 − x, 2 − y, −z). There are two intramolecular CH···O hydrogen bonds involving the sac and bpy ring H atoms and sulfonly and carbony O atoms (Table 2). Furthermore, the molecules are further linked by π(bpy)···π(bpy) interactions with a Cg—Cgi separation of 3.6741 (13)Å (i = 1 − x, 1 − y, −z).

Related literature top

For related literature, see: Weber et al. (1993); Yilmaz et al. (2004); Liu et al. (2006); Baran & Yilmaz (2006).

Experimental top

Na(sac)·2H2O (0.24 g, 1 mmol) was added to a 320 ml solution of AgNO3 (0.17 g, 1 mmol) dissolved in a mixture of water, methanol and dichloromethane (1:1:1, v/v) with stirring. The solution immediately became milky and the addition of bpy (0.16 g, 1 mmol) to the milky suspension resulted in a clear solution. The resulting solution was stirred for 30 min at room temperature and was allowed to stand in darkness at room temperature. Colorless crystals of the title compound were obtained after a week.

Refinement top

All hydrogen atoms were placed in idealized locations and refined by riding, with C—H = 0.95 Å and Uiso(H) = 1.2 x Ueq(C).

Computing details top

Data collection: COLLECT (Enraf–Nonius, 1999); cell refinement: COLLECT (Enraf–Nonius, 1999); data reduction: COLLECT (Enraf–Nonius, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 40% displacement ellipsoids (arbitrary spheres for the H atoms). C—H hydrogen atoms were removed for clarity.
(2,2'-Bipyridine)saccharinatosilver(I) top
Crystal data top
[Ag(C7H4NO3S)(C10H8N2)]F000 = 888
Mr = 446.23Dx = 1.831 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3928 reflections
a = 10.7803 (2) Åθ = 2.9–27.5º
b = 9.76830 (10) ŵ = 1.40 mm−1
c = 15.6176 (2) ÅT = 120 (2) K
β = 100.1975 (8)ºNeedle, colourless
V = 1618.64 (4) Å30.40 × 0.04 × 0.02 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer		3713 independent reflections
Radiation source: fine-focus sealed tube3194 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.038
T = 120(2) Kθmax = 27.5º
ω and φ scansθmin = 3.3º
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		h = −14→13
Tmin = 0.605, Tmax = 0.973k = −12→12
25291 measured reflectionsl = −20→20
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.025  w = 1/[σ2(Fo2) + (0.0156P)2 + 1.822P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.056(Δ/σ)max = 0.001
S = 1.08Δρmax = 0.43 e Å−3
3713 reflectionsΔρmin = −0.46 e Å−3
227 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00128 (18)
Secondary atom site location: difference Fourier map
Crystal data top
[Ag(C7H4NO3S)(C10H8N2)]V = 1618.64 (4) Å3
Mr = 446.23Z = 4
Monoclinic, P21/nMo Kα
a = 10.7803 (2) ŵ = 1.40 mm−1
b = 9.76830 (10) ÅT = 120 (2) K
c = 15.6176 (2) Å0.40 × 0.04 × 0.02 mm
β = 100.1975 (8)º
Data collection top
Nonius KappaCCD
diffractometer		3713 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		3194 reflections with I > 2σ(I)
Tmin = 0.605, Tmax = 0.973Rint = 0.038
25291 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025227 parameters
wR(F2) = 0.056H-atom parameters constrained
S = 1.08Δρmax = 0.43 e Å−3
3713 reflectionsΔρmin = −0.46 e Å−3
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 > 2sigma(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
xyzUiso*/Ueq
Ag10.501633 (17)0.793746 (18)0.021427 (11)0.02327 (7)
C10.4298 (2)1.0121 (2)0.15235 (13)0.0158 (4)
C20.33090 (19)1.1138 (2)0.16617 (13)0.0145 (4)
C30.3360 (2)1.2084 (2)0.23278 (14)0.0185 (4)
H30.40931.21690.27630.022*
C40.2318 (2)1.2901 (2)0.23427 (14)0.0229 (5)
H40.23391.35610.27920.028*
C50.1232 (2)1.2772 (2)0.17078 (15)0.0221 (5)
H50.05261.33410.17350.026*
C60.1172 (2)1.1826 (2)0.10380 (14)0.0190 (5)
H60.04391.17290.06050.023*
C70.2232 (2)1.1032 (2)0.10334 (13)0.0144 (4)
N10.39147 (17)0.93554 (19)0.07890 (11)0.0182 (4)
O10.53026 (15)0.99921 (17)0.20193 (10)0.0240 (4)
O20.16452 (15)0.85874 (16)0.03892 (11)0.0271 (4)
O30.24637 (18)1.02164 (18)−0.05562 (10)0.0295 (4)
S10.24856 (5)0.97131 (6)0.03116 (3)0.01733 (12)
C80.7656 (2)0.6447 (2)0.08002 (15)0.0244 (5)
H80.77340.71130.12500.029*
C90.8607 (2)0.5498 (2)0.08214 (15)0.0237 (5)
H90.93240.55090.12730.028*
C100.8489 (2)0.4530 (2)0.01676 (15)0.0224 (5)
H100.91240.38570.01650.027*
C110.7438 (2)0.4551 (2)−0.04827 (14)0.0182 (5)
H110.73450.3894−0.09380.022*
C120.6517 (2)0.5545 (2)−0.04641 (13)0.0147 (4)
C130.5363 (2)0.5625 (2)−0.11505 (13)0.0158 (4)
C140.5170 (2)0.4753 (3)−0.18644 (15)0.0248 (5)
H140.57740.4070−0.19270.030*
C150.4087 (2)0.4890 (3)−0.24846 (15)0.0283 (6)
H150.39430.4307−0.29790.034*
C160.3221 (2)0.5881 (3)−0.23762 (15)0.0268 (5)
H160.24640.5986−0.27870.032*
C170.3481 (2)0.6718 (3)−0.16543 (16)0.0265 (5)
H170.28880.7408−0.15810.032*
N20.66271 (17)0.64772 (19)0.01771 (11)0.0184 (4)
N30.45297 (17)0.6604 (2)−0.10520 (12)0.0197 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.02769 (11)0.01844 (10)0.02661 (11)0.00675 (7)0.01280 (7)−0.00129 (7)
C10.0157 (11)0.0180 (11)0.0142 (10)−0.0019 (9)0.0041 (8)0.0016 (8)
C20.0166 (10)0.0129 (10)0.0144 (10)0.0002 (8)0.0039 (8)0.0027 (8)
C30.0216 (11)0.0183 (11)0.0149 (10)−0.0024 (9)0.0016 (9)−0.0011 (9)
C40.0347 (13)0.0165 (11)0.0189 (11)0.0021 (10)0.0082 (10)−0.0039 (9)
C50.0256 (12)0.0180 (12)0.0240 (11)0.0085 (10)0.0084 (10)0.0026 (9)
C60.0180 (11)0.0178 (11)0.0204 (11)0.0027 (9)0.0017 (9)0.0025 (9)
C70.0183 (11)0.0116 (10)0.0135 (10)−0.0004 (8)0.0034 (8)0.0004 (8)
N10.0172 (9)0.0196 (10)0.0173 (9)0.0048 (8)0.0018 (7)−0.0030 (7)
O10.0152 (8)0.0314 (10)0.0235 (8)0.0034 (7)−0.0015 (7)−0.0012 (7)
O20.0234 (9)0.0167 (8)0.0379 (10)−0.0006 (7)−0.0040 (7)−0.0056 (7)
O30.0416 (11)0.0304 (10)0.0147 (8)0.0090 (8)0.0002 (7)−0.0023 (7)
S10.0194 (3)0.0152 (3)0.0157 (2)0.0030 (2)−0.0016 (2)−0.0033 (2)
C80.0290 (13)0.0225 (12)0.0195 (11)0.0017 (10)−0.0014 (10)−0.0054 (9)
C90.0233 (12)0.0214 (12)0.0230 (12)0.0017 (10)−0.0057 (9)0.0012 (10)
C100.0201 (12)0.0173 (11)0.0289 (12)0.0058 (9)0.0020 (10)0.0021 (9)
C110.0202 (11)0.0151 (11)0.0195 (11)0.0004 (9)0.0037 (9)−0.0024 (9)
C120.0158 (11)0.0138 (10)0.0152 (10)−0.0015 (9)0.0042 (8)0.0014 (8)
C130.0167 (11)0.0150 (10)0.0163 (10)−0.0027 (9)0.0044 (8)0.0019 (8)
C140.0239 (12)0.0254 (13)0.0238 (12)0.0005 (10)0.0004 (10)−0.0054 (10)
C150.0291 (14)0.0314 (14)0.0221 (12)−0.0062 (11)−0.0020 (10)−0.0048 (10)
C160.0186 (12)0.0366 (15)0.0228 (12)−0.0070 (11)−0.0028 (9)0.0063 (10)
C170.0181 (12)0.0334 (14)0.0274 (12)0.0049 (10)0.0023 (10)0.0046 (11)
N20.0204 (10)0.0164 (9)0.0177 (9)0.0035 (8)0.0017 (8)−0.0021 (7)
N30.0166 (9)0.0236 (10)0.0184 (9)0.0030 (8)0.0018 (7)0.0000 (8)
Geometric parameters (Å, °) top
C1—O11.221 (3)C9—H90.9500
C1—N11.370 (3)C10—C111.381 (3)
C1—C21.500 (3)C10—H100.9500
C2—C71.385 (3)C11—C121.393 (3)
C2—C31.385 (3)C11—H110.9500
C3—C41.382 (3)C12—N21.343 (3)
C3—H30.9500C12—C131.493 (3)
C4—C51.399 (3)C13—N31.339 (3)
C4—H40.9500C13—C141.389 (3)
C5—C61.389 (3)C14—C151.385 (3)
C5—H50.9500C14—H140.9500
C6—C71.383 (3)C15—C161.375 (4)
C6—H60.9500C15—H150.9500
C7—S11.764 (2)C16—C171.381 (3)
N1—S11.6262 (18)C16—H160.9500
O2—S11.4434 (17)C17—N31.341 (3)
O3—S11.4379 (17)C17—H170.9500
C8—N21.340 (3)Ag1—N12.1241 (18)
C8—C91.378 (3)Ag1—N22.2559 (18)
C8—H80.9500Ag1—N32.3488 (18)
C9—C101.381 (3)
O1—C1—N1125.2 (2)C10—C9—H9120.9
O1—C1—C2123.36 (19)C9—C10—C11119.3 (2)
N1—C1—C2111.43 (18)C9—C10—H10120.3
C7—C2—C3119.95 (19)C11—C10—H10120.3
C7—C2—C1112.09 (18)C10—C11—C12119.3 (2)
C3—C2—C1127.95 (19)C10—C11—H11120.3
C4—C3—C2118.3 (2)C12—C11—H11120.3
C4—C3—H3120.9N2—C12—C11121.25 (19)
C2—C3—H3120.9N2—C12—C13116.89 (18)
C3—C4—C5121.1 (2)C11—C12—C13121.86 (19)
C3—C4—H4119.4N3—C13—C14121.4 (2)
C5—C4—H4119.4N3—C13—C12116.45 (18)
C6—C5—C4121.0 (2)C14—C13—C12122.1 (2)
C6—C5—H5119.5C15—C14—C13119.4 (2)
C4—C5—H5119.5C15—C14—H14120.3
C7—C6—C5116.7 (2)C13—C14—H14120.3
C7—C6—H6121.7C16—C15—C14119.2 (2)
C5—C6—H6121.7C16—C15—H15120.4
C6—C7—C2122.98 (19)C14—C15—H15120.4
C6—C7—S1129.37 (16)C15—C16—C17118.2 (2)
C2—C7—S1107.61 (15)C15—C16—H16120.9
C1—N1—S1112.78 (15)C17—C16—H16120.9
C1—N1—Ag1126.97 (14)N3—C17—C16123.2 (2)
S1—N1—Ag1120.10 (10)N3—C17—H17118.4
O3—S1—O2115.70 (11)C16—C17—H17118.4
O3—S1—N1111.21 (10)C8—N2—C12118.60 (19)
O2—S1—N1110.83 (10)C8—N2—Ag1122.51 (15)
O3—S1—C7111.97 (10)C12—N2—Ag1118.75 (14)
O2—S1—C7109.39 (10)C13—N3—C17118.6 (2)
N1—S1—C796.03 (10)C13—N3—Ag1115.99 (14)
N2—C8—C9123.3 (2)C17—N3—Ag1125.41 (16)
N2—C8—H8118.3N1—Ag1—N2156.02 (7)
C9—C8—H8118.3N1—Ag1—N3131.25 (7)
C8—C9—C10118.2 (2)N2—Ag1—N371.69 (6)
C8—C9—H9120.9
O1—C1—C2—C7−176.8 (2)N2—C8—C9—C10−0.1 (4)
N1—C1—C2—C72.0 (3)C8—C9—C10—C110.5 (4)
O1—C1—C2—C31.4 (4)C9—C10—C11—C12−0.2 (3)
N1—C1—C2—C3−179.7 (2)C10—C11—C12—N2−0.5 (3)
C7—C2—C3—C40.0 (3)C10—C11—C12—C13179.7 (2)
C1—C2—C3—C4−178.1 (2)N2—C12—C13—N3−1.4 (3)
C2—C3—C4—C50.6 (3)C11—C12—C13—N3178.4 (2)
C3—C4—C5—C6−0.5 (3)N2—C12—C13—C14177.3 (2)
C4—C5—C6—C7−0.2 (3)C11—C12—C13—C14−2.9 (3)
C5—C6—C7—C20.8 (3)N3—C13—C14—C15−0.6 (4)
C5—C6—C7—S1178.26 (17)C12—C13—C14—C15−179.2 (2)
C3—C2—C7—C6−0.7 (3)C13—C14—C15—C16−0.5 (4)
C1—C2—C7—C6177.67 (19)C14—C15—C16—C171.0 (4)
C3—C2—C7—S1−178.69 (17)C15—C16—C17—N3−0.6 (4)
C1—C2—C7—S1−0.3 (2)C9—C8—N2—C12−0.5 (4)
O1—C1—N1—S1175.89 (18)C9—C8—N2—Ag1175.15 (18)
C2—C1—N1—S1−2.9 (2)C11—C12—N2—C80.8 (3)
O1—C1—N1—Ag1−8.7 (3)C13—C12—N2—C8−179.33 (19)
C2—C1—N1—Ag1172.54 (14)C11—C12—N2—Ag1−175.03 (16)
N2—Ag1—N1—C121.5 (3)C13—C12—N2—Ag14.8 (2)
N3—Ag1—N1—C1−177.96 (16)N1—Ag1—N2—C8−15.4 (3)
N2—Ag1—N1—S1−163.35 (13)N3—Ag1—N2—C8179.9 (2)
N3—Ag1—N1—S1−2.81 (17)N1—Ag1—N2—C12160.26 (17)
C1—N1—S1—O3118.83 (16)N3—Ag1—N2—C12−4.44 (15)
Ag1—N1—S1—O3−56.97 (14)C14—C13—N3—C171.0 (3)
C1—N1—S1—O2−110.97 (16)C12—C13—N3—C17179.76 (19)
Ag1—N1—S1—O273.23 (14)C14—C13—N3—Ag1178.83 (17)
C1—N1—S1—C72.44 (17)C12—C13—N3—Ag1−2.5 (2)
Ag1—N1—S1—C7−173.36 (11)C16—C17—N3—C13−0.5 (4)
C6—C7—S1—O365.3 (2)C16—C17—N3—Ag1−178.04 (18)
C2—C7—S1—O3−116.97 (16)N1—Ag1—N3—C13−168.24 (14)
C6—C7—S1—O2−64.4 (2)N2—Ag1—N3—C133.56 (15)
C2—C7—S1—O2113.41 (15)N1—Ag1—N3—C179.4 (2)
C6—C7—S1—N1−179.0 (2)N2—Ag1—N3—C17−178.8 (2)
C2—C7—S1—N1−1.19 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.952.513.458 (3)173
C16—H16···O1ii0.952.493.235 (3)136
Symmetry codes: (i) −x, −y+2, −z; (ii) x−1/2, −y+3/2, z−1/2.
Selected geometric parameters (Å, °) top
Ag1—N12.1241 (18)Ag1—N32.3488 (18)
Ag1—N22.2559 (18)
N1—Ag1—N2156.02 (7)N2—Ag1—N371.69 (6)
N1—Ag1—N3131.25 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.952.513.458 (3)173
C16—H16···O1ii0.952.493.235 (3)136
Symmetry codes: (i) −x, −y+2, −z; (ii) x−1/2, −y+3/2, z−1/2.
references
References top

Baran, E. J. & Yilmaz, V. T. (2006). Coord. Chem. Rev. 250, 1980–1999.

Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Enraf–Nonius (1999). COLLECT. Enraf–Nonius, Delft, The Netherlands.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Liu, H.-Y., Wu, H. & Ma, J.-F. (2006). Acta Cryst. E62, m325–m326.

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

Weber, R., Gilles, M. & Bergerhoff, G. (1993). Z. Kristallogr. 206, 273–274.

Yilmaz, V. T., Hamamci, S. & Thone, C. (2004). Z. Anorg. Allg. Chem. 630, 1641–1644.