Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105036334/gd1419sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105036334/gd1419Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105036334/gd1419IIsup3.hkl |
CCDC references: 296322; 296323
Nasac·2H2O (0.24 g, 1 mmol) was added to a solution of AgNO3 (0.17 g, 1 mmol) in water (5 ml), and the solution immediately became milky. The white precipitate was dissolved in acetonitrile (15 ml), and pydz (0.08 g, 1 mmol) was added to dropwise to the solution, which was then allowed to stand in darkness at room temperature. Colourless crystals consisting of both mono- and triclinic forms were obtained after four days. Yield 94%. IR (KBr, cm-1): ν(C═O) 1651; νas(S═O) 1286, 1257; νs(S═O) 1151.
All H atoms were refined with a riding model, with C—H distances of 0.93 Å and Uiso(H) = 1.2 Ueq(C).
Saccharin, alternatively named 1,2-benzisothiazoline-3(2H)-one-1,1-dioxide, is one of the best known and most widely used non-caloric sweeteners and food additives. Owing to its potential harmfulness and especially its suspected carcinogenic nature (Cohen-Addad et al., 1986; Suzuki & Suzuki, 1995), saccharin is probably one of the most studied components of the food supply. Simultaneously, it was shown that the deprotonated form of saccharin, saccharinate (sac), acts as a polyfunctional ligand through four sites, viz. the negatively charged imine N atom, and one carbonyl and two sulfonyl O atoms. The sac ligand can behave as a mono-, bi- or tridentate ligand, and in some cases also as a bridging ligand between metal ions (Baran, 2005; Baran & Yilmaz, 2005). As a part of our study on the synthesis, spectral, thermal and crystallographic characterization of metal complexes of sac, an attempt to synthesize a silver(I) complex of sac with pyridazine (pydz) resulted in the concurrent crystallization, from acetonitrile, of monoclinic, (I), and triclinic, (II), forms of bis(pyridazine)bis(saccharinato)disilver(I) as concomitant polymorphs (Fig. 1, and Tables 1 and 3).
Visual examination of the crystals under a microscope indicated that most of the crystals (ca 90%) consisted of (I). Data collections performed at 293 K also produced the same outcome, indicating that the polymorphism observed in the title compound is not associated with a temperature phase transition. In both (I) and (II), the silver(I) ions have a slightly distorted trigonal AgN3 coordination geometry, and are doubly bridged by two neutral pyridazine (pydz) ligands, forming a centrosymmetric dimeric structure. The anionic sac ligands are N-coordinated. The sac (atoms C1–C7, N1 and S1) and pydz (atoms C8–C11, N2 and N3) ligands are both essentially planar, and the dihedral angles between the mean planes of these ligands are 8.43 (7) and 7.94 (8)° in (I) and (II), respectively, suggesting that the dimeric molecules is nearly flat. The bond geometry is similar in both polymorphs. The average intra-dimer Ag···Ag distance of 3.706 (2) Å in (I) and (II) is much longer than the upper limit of 3.30 Å, reported by Jansen (1987), for an Ag···Ag contact in silver(I) complexes. The Ag—Nsac bond distances in (I) and (II) are similar to those found in [Ag2(sac)2(hep)2]n [2.1718 (17) and 2.1819 (17) Å; hep is N-(2-hydroxyethyl)piperazine; Hamamci, et al., 2005a], [Ag2(sac)2(pyet)2] [2.1444 (12) Å; pyet is 2-pyridylethanol; Yilmaz et al., 2005] and [Ag(sac)(py)]n [2.084 (2) Å; py is pyridine; Hamamci et al., 2005b], but significantly shorter than those reported for [Ag2(sac)2(aepy)2] [2.449 (2) Å; aepy is 2-(2-aminoethyl)pyridine; Hamamci et al., 2005c)].
The molecular packing in (I) and (II) is shown in Figs. 2 and 3. The most obvious difference between the two polymorphs is clearly seen in their intermolecular interactions (Tables 2 and 4). In the monoclinic polymorph, (I), two types of interactions (π–π and C—H···O interactions) stabilize the structure. There are two aromatic π–π stacking interactions between the closely associated pairs of both sac and pydz aromatic rings [Cg1···Cg1i = 3.6955 Å and Cg1···Cg1ii = 3.8277 Å; symmetry codes: (i) 2 - x, -y, 2 - z; (ii) 1 - x, -y, -z], leading to two-dimensional layers, which are further cross-linked by two weak C—H···O interactions (Fig. 2). Although the C—H···O interactions in (II) are similar to (I), (II) also exhibits a π–π interaction between the aromatic rings of sac and pydz [Cg1···Cg1i = 3.7008 Å; symmetry code: (i) 1 - x, 1 - y, 1 - z] and a C—H···π interaction [C10—H10···Cgi = 3.2755 Å; symmetry code: (i) 2 - x,1 - y,1 - z], and a π···M interaction between the aromatic ring of sac and the silver(I) ion [Cg···Agi = 3.879 Å; symmetry code: (i) x, -1 + y, z]. In addition to other interactions, these extra weak intermolecular interactions stabilize the triclinic polymorphic structure.
For both compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); 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: WinGX (Farrugia, 1999).
[Ag2(C7H4NO3S)2(C4H4N2)2] | F(000) = 728 |
Mr = 740.27 | Dx = 2.070 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 15455 reflections |
a = 7.2388 (5) Å | θ = 1.8–27.3° |
b = 22.3068 (11) Å | µ = 1.88 mm−1 |
c = 7.7746 (5) Å | T = 100 K |
β = 108.884 (5)° | Prismatic plate, colourless |
V = 1187.83 (13) Å3 | 0.42 × 0.28 × 0.17 mm |
Z = 2 |
STOE IPDS-2 diffractometer | 2602 independent reflections |
Radiation source: fine-focus sealed tube | 2458 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.086 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.1°, θmin = 1.8° |
ω scans | h = −9→9 |
Absorption correction: integration (X-RED; Stoe & Cie, 2002) | k = −28→28 |
Tmin = 0.552, Tmax = 0.741 | l = −9→9 |
15455 measured reflections |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0278P)2 + 1.2187P] where P = (Fo2 + 2Fc2)/3 |
2602 reflections | (Δ/σ)max = 0.002 |
172 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.85 e Å−3 |
[Ag2(C7H4NO3S)2(C4H4N2)2] | V = 1187.83 (13) Å3 |
Mr = 740.27 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.2388 (5) Å | µ = 1.88 mm−1 |
b = 22.3068 (11) Å | T = 100 K |
c = 7.7746 (5) Å | 0.42 × 0.28 × 0.17 mm |
β = 108.884 (5)° |
STOE IPDS-2 diffractometer | 2602 independent reflections |
Absorption correction: integration (X-RED; Stoe & Cie, 2002) | 2458 reflections with I > 2σ(I) |
Tmin = 0.552, Tmax = 0.741 | Rint = 0.086 |
15455 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.50 e Å−3 |
2602 reflections | Δρmin = −0.85 e Å−3 |
172 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7094 (3) | 0.65178 (10) | 0.7564 (3) | 0.0176 (4) | |
C2 | 0.7278 (4) | 0.69917 (10) | 0.8754 (3) | 0.0207 (4) | |
H2 | 0.6863 | 0.7376 | 0.8344 | 0.025* | |
C3 | 0.8116 (4) | 0.68651 (11) | 1.0601 (3) | 0.0224 (5) | |
H3 | 0.8252 | 0.7170 | 1.1448 | 0.027* | |
C4 | 0.8751 (4) | 0.62883 (12) | 1.1196 (3) | 0.0224 (5) | |
H4 | 0.9306 | 0.6216 | 1.2435 | 0.027* | |
C5 | 0.8571 (3) | 0.58186 (11) | 0.9971 (3) | 0.0200 (4) | |
H5 | 0.9001 | 0.5434 | 1.0370 | 0.024* | |
C6 | 0.7728 (3) | 0.59448 (10) | 0.8138 (3) | 0.0177 (4) | |
C7 | 0.7424 (3) | 0.55245 (11) | 0.6561 (3) | 0.0189 (4) | |
C8 | 0.7745 (4) | 0.41229 (11) | 0.3371 (3) | 0.0211 (4) | |
H8 | 0.8014 | 0.4303 | 0.4504 | 0.025* | |
C9 | 0.8392 (4) | 0.35369 (11) | 0.3293 (3) | 0.0213 (5) | |
H9 | 0.9063 | 0.3328 | 0.4345 | 0.026* | |
C10 | 0.8003 (4) | 0.32821 (10) | 0.1613 (3) | 0.0212 (5) | |
H10 | 0.8407 | 0.2894 | 0.1475 | 0.025* | |
C11 | 0.6975 (4) | 0.36278 (10) | 0.0118 (3) | 0.0206 (4) | |
H11 | 0.6700 | 0.3461 | −0.1035 | 0.025* | |
N1 | 0.6654 (3) | 0.58094 (9) | 0.4932 (2) | 0.0194 (4) | |
N2 | 0.6768 (3) | 0.44337 (9) | 0.1910 (3) | 0.0194 (4) | |
N3 | 0.6367 (3) | 0.41804 (9) | 0.0249 (2) | 0.0192 (4) | |
O1 | 0.4175 (3) | 0.66446 (8) | 0.4442 (2) | 0.0242 (4) | |
O2 | 0.7448 (3) | 0.68941 (7) | 0.4478 (2) | 0.0232 (3) | |
O3 | 0.7824 (3) | 0.49898 (7) | 0.6746 (2) | 0.0248 (4) | |
S1 | 0.62333 (8) | 0.65133 (2) | 0.51645 (7) | 0.01779 (12) | |
Ag1 | 0.55623 (3) | 0.535018 (7) | 0.22747 (2) | 0.02210 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0198 (11) | 0.0203 (11) | 0.0127 (9) | −0.0007 (8) | 0.0052 (8) | −0.0006 (8) |
C2 | 0.0237 (11) | 0.0193 (10) | 0.0196 (10) | 0.0010 (9) | 0.0077 (9) | −0.0024 (8) |
C3 | 0.0249 (12) | 0.0261 (12) | 0.0166 (10) | −0.0031 (9) | 0.0072 (9) | −0.0074 (9) |
C4 | 0.0235 (12) | 0.0297 (12) | 0.0138 (10) | −0.0017 (9) | 0.0056 (9) | −0.0013 (9) |
C5 | 0.0237 (12) | 0.0205 (11) | 0.0154 (10) | 0.0005 (9) | 0.0056 (9) | 0.0020 (8) |
C6 | 0.0206 (11) | 0.0169 (10) | 0.0158 (10) | −0.0021 (8) | 0.0064 (8) | −0.0014 (8) |
C7 | 0.0211 (11) | 0.0204 (11) | 0.0138 (10) | −0.0023 (9) | 0.0040 (8) | −0.0007 (8) |
C8 | 0.0232 (11) | 0.0225 (11) | 0.0162 (10) | −0.0003 (9) | 0.0044 (9) | −0.0007 (8) |
C9 | 0.0212 (11) | 0.0233 (11) | 0.0183 (10) | 0.0012 (9) | 0.0049 (9) | 0.0021 (9) |
C10 | 0.0222 (11) | 0.0176 (10) | 0.0246 (11) | 0.0006 (8) | 0.0086 (9) | −0.0010 (8) |
C11 | 0.0240 (11) | 0.0208 (11) | 0.0177 (10) | −0.0006 (9) | 0.0077 (9) | −0.0039 (8) |
N1 | 0.0286 (10) | 0.0167 (9) | 0.0115 (8) | 0.0013 (7) | 0.0046 (7) | −0.0013 (7) |
N2 | 0.0232 (10) | 0.0201 (9) | 0.0144 (8) | −0.0003 (8) | 0.0052 (7) | −0.0020 (7) |
N3 | 0.0220 (10) | 0.0214 (9) | 0.0139 (8) | −0.0003 (7) | 0.0051 (7) | −0.0015 (7) |
O1 | 0.0255 (9) | 0.0275 (9) | 0.0177 (8) | 0.0053 (7) | 0.0044 (7) | 0.0009 (6) |
O2 | 0.0324 (9) | 0.0199 (8) | 0.0199 (8) | 0.0016 (7) | 0.0119 (7) | 0.0042 (6) |
O3 | 0.0375 (10) | 0.0163 (8) | 0.0191 (8) | 0.0032 (7) | 0.0073 (7) | 0.0002 (6) |
S1 | 0.0240 (3) | 0.0167 (3) | 0.0124 (2) | 0.0021 (2) | 0.0055 (2) | 0.00056 (18) |
Ag1 | 0.03251 (13) | 0.01815 (11) | 0.01322 (11) | 0.00155 (6) | 0.00402 (8) | −0.00151 (6) |
C1—C6 | 1.382 (3) | C8—C9 | 1.396 (3) |
C1—C2 | 1.383 (3) | C8—H8 | 0.9300 |
C1—S1 | 1.765 (2) | C9—C10 | 1.367 (3) |
C2—C3 | 1.395 (3) | C9—H9 | 0.9300 |
C2—H2 | 0.9300 | C10—C11 | 1.393 (3) |
C3—C4 | 1.394 (4) | C10—H10 | 0.9300 |
C3—H3 | 0.9300 | C11—N3 | 1.324 (3) |
C4—C5 | 1.393 (3) | C11—H11 | 0.9300 |
C4—H4 | 0.9300 | N1—S1 | 1.621 (2) |
C5—C6 | 1.386 (3) | N2—N3 | 1.352 (3) |
C5—H5 | 0.9300 | O1—S1 | 1.4420 (18) |
C6—C7 | 1.502 (3) | O2—S1 | 1.4435 (17) |
C7—O3 | 1.225 (3) | N1—Ag1 | 2.2099 (18) |
C7—N1 | 1.364 (3) | N2—Ag1 | 2.276 (2) |
C8—N2 | 1.324 (3) | N3—Ag1i | 2.2632 (19) |
C6—C1—C2 | 122.7 (2) | C10—C9—H9 | 121.2 |
C6—C1—S1 | 107.60 (16) | C8—C9—H9 | 121.2 |
C2—C1—S1 | 129.52 (18) | C9—C10—H10 | 121.4 |
C1—C2—C3 | 116.7 (2) | C11—C10—H10 | 121.4 |
C1—C2—H2 | 121.6 | N3—C11—C10 | 123.5 (2) |
C3—C2—H2 | 121.6 | N3—C11—H11 | 118.2 |
C4—C3—C2 | 121.0 (2) | C10—C11—H11 | 118.2 |
C4—C3—H3 | 119.5 | C7—N1—S1 | 112.49 (15) |
C2—C3—H3 | 119.5 | C7—N1—Ag1 | 124.53 (15) |
C5—C4—C3 | 121.3 (2) | S1—N1—Ag1 | 122.02 (10) |
C5—C4—H4 | 119.4 | C8—N2—N3 | 119.4 (2) |
C3—C4—H4 | 119.4 | C8—N2—Ag1 | 118.90 (15) |
C6—C5—C4 | 117.6 (2) | N3—N2—Ag1 | 121.46 (15) |
C6—C5—H5 | 121.2 | C11—N3—N2 | 119.25 (19) |
C4—C5—H5 | 121.2 | C11—N3—Ag1i | 119.43 (15) |
C1—C6—C5 | 120.6 (2) | N2—N3—Ag1i | 121.06 (15) |
C1—C6—C7 | 111.59 (19) | O1—S1—O2 | 114.37 (10) |
C5—C6—C7 | 127.7 (2) | O1—S1—N1 | 111.16 (11) |
O3—C7—N1 | 125.0 (2) | O2—S1—N1 | 111.71 (10) |
O3—C7—C6 | 123.0 (2) | O1—S1—C1 | 112.16 (10) |
N1—C7—C6 | 112.0 (2) | O2—S1—C1 | 109.79 (11) |
N2—C8—C9 | 123.1 (2) | N1—S1—C1 | 96.25 (10) |
N2—C8—H8 | 118.4 | N1—Ag1—N2 | 119.82 (7) |
C9—C8—H8 | 118.4 | N1—Ag1—N3i | 121.97 (7) |
C10—C9—C8 | 117.5 (2) | N3i—Ag1—N2 | 117.48 (7) |
C9—C10—C11 | 117.2 (2) | ||
C6—C1—C2—C3 | −1.1 (4) | C10—C11—N3—Ag1i | −173.50 (18) |
S1—C1—C2—C3 | −176.42 (19) | C8—N2—N3—C11 | −0.5 (3) |
C1—C2—C3—C4 | 0.7 (4) | Ag1—N2—N3—C11 | −174.80 (17) |
C2—C3—C4—C5 | −0.1 (4) | C8—N2—N3—Ag1i | 173.57 (17) |
C3—C4—C5—C6 | −0.3 (4) | Ag1—N2—N3—Ag1i | −0.7 (2) |
C2—C1—C6—C5 | 0.8 (4) | C7—N1—S1—O1 | −116.04 (17) |
S1—C1—C6—C5 | 176.99 (18) | Ag1—N1—S1—O1 | 53.24 (15) |
C2—C1—C6—C7 | −177.7 (2) | C7—N1—S1—O2 | 114.88 (18) |
S1—C1—C6—C7 | −1.5 (2) | Ag1—N1—S1—O2 | −75.84 (15) |
C4—C5—C6—C1 | −0.1 (3) | C7—N1—S1—C1 | 0.66 (19) |
C4—C5—C6—C7 | 178.1 (2) | Ag1—N1—S1—C1 | 169.94 (13) |
C1—C6—C7—O3 | −177.8 (2) | C6—C1—S1—O1 | 116.43 (17) |
C5—C6—C7—O3 | 3.9 (4) | C2—C1—S1—O1 | −67.7 (3) |
C1—C6—C7—N1 | 2.0 (3) | C6—C1—S1—O2 | −115.24 (17) |
C5—C6—C7—N1 | −176.3 (2) | C2—C1—S1—O2 | 60.6 (2) |
N2—C8—C9—C10 | 0.7 (4) | C6—C1—S1—N1 | 0.54 (18) |
C8—C9—C10—C11 | −0.6 (3) | C2—C1—S1—N1 | 176.4 (2) |
C9—C10—C11—N3 | −0.1 (4) | C7—N1—Ag1—N3i | 164.08 (17) |
O3—C7—N1—S1 | 178.2 (2) | S1—N1—Ag1—N3i | −3.88 (17) |
C6—C7—N1—S1 | −1.6 (3) | C7—N1—Ag1—N2 | −26.0 (2) |
O3—C7—N1—Ag1 | 9.2 (3) | S1—N1—Ag1—N2 | 166.01 (11) |
C6—C7—N1—Ag1 | −170.56 (15) | C8—N2—Ag1—N1 | 16.0 (2) |
C9—C8—N2—N3 | −0.2 (4) | N3—N2—Ag1—N1 | −169.68 (15) |
C9—C8—N2—Ag1 | 174.23 (18) | C8—N2—Ag1—N3i | −173.63 (17) |
C10—C11—N3—N2 | 0.7 (4) | N3—N2—Ag1—N3i | 0.7 (2) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O3 | 0.93 | 2.36 | 3.245 (3) | 160 |
C9—H9···O2ii | 0.93 | 2.44 | 3.101 (3) | 128 |
C10—H10···O2iii | 0.93 | 2.37 | 3.199 (3) | 148 |
C11—H11···O1i | 0.93 | 2.53 | 3.423 (3) | 162 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y−1/2, −z+1/2. |
[Ag2(C7H4NO3S)2(C4H4N2)2] | Z = 1 |
Mr = 740.27 | F(000) = 364 |
Triclinic, P1 | Dx = 2.074 Mg m−3 |
Hall symbol: -P 1n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3231 (8) Å | Cell parameters from 10253 reflections |
b = 7.7516 (9) Å | θ = 2.9–28.0° |
c = 11.5389 (14) Å | µ = 1.88 mm−1 |
α = 73.090 (9)° | T = 100 K |
β = 83.087 (10)° | Prismatic stick, colourless |
γ = 71.148 (9)° | 0.60 × 0.51 × 0.33 mm |
V = 592.82 (12) Å3 |
STOE IPDS-2 diffractometer | 2737 independent reflections |
Radiation source: fine-focus sealed tube | 2650 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.6°, θmin = 2.9° |
ω scans | h = −9→9 |
Absorption correction: integration (X-RED; Stoe & Cie, 2002) | k = −10→10 |
Tmin = 0.368, Tmax = 0.579 | l = −14→15 |
10253 measured reflections |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.03P)2 + 0.5506P] where P = (Fo2 + 2Fc2)/3 |
2320 reflections | (Δ/σ)max = 0.001 |
172 parameters | Δρmax = 0.74 e Å−3 |
0 restraints | Δρmin = −1.19 e Å−3 |
[Ag2(C7H4NO3S)2(C4H4N2)2] | γ = 71.148 (9)° |
Mr = 740.27 | V = 592.82 (12) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.3231 (8) Å | Mo Kα radiation |
b = 7.7516 (9) Å | µ = 1.88 mm−1 |
c = 11.5389 (14) Å | T = 100 K |
α = 73.090 (9)° | 0.60 × 0.51 × 0.33 mm |
β = 83.087 (10)° |
STOE IPDS-2 diffractometer | 2737 independent reflections |
Absorption correction: integration (X-RED; Stoe & Cie, 2002) | 2650 reflections with I > 2σ(I) |
Tmin = 0.368, Tmax = 0.579 | Rint = 0.099 |
10253 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.74 e Å−3 |
2320 reflections | Δρmin = −1.19 e Å−3 |
172 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2961 (4) | 0.6328 (3) | 0.8038 (3) | 0.0184 (5) | |
C2 | 0.2856 (4) | 0.7137 (4) | 0.8978 (3) | 0.0206 (5) | |
H2 | 0.3318 | 0.6410 | 0.9739 | 0.025* | |
C3 | 0.2027 (4) | 0.9086 (4) | 0.8727 (3) | 0.0236 (6) | |
H3 | 0.1949 | 0.9686 | 0.9330 | 0.028* | |
C4 | 0.1310 (4) | 1.0157 (4) | 0.7585 (3) | 0.0241 (6) | |
H4 | 0.0743 | 1.1458 | 0.7444 | 0.029* | |
C5 | 0.1428 (4) | 0.9318 (4) | 0.6657 (3) | 0.0212 (5) | |
H5 | 0.0949 | 1.0036 | 0.5897 | 0.025* | |
C6 | 0.2285 (4) | 0.7371 (4) | 0.6895 (2) | 0.0187 (5) | |
C7 | 0.2542 (4) | 0.6145 (3) | 0.6054 (3) | 0.0192 (5) | |
C8 | 0.2204 (4) | 0.4099 (4) | 0.3283 (3) | 0.0205 (5) | |
H8 | 0.1923 | 0.5083 | 0.3648 | 0.025* | |
C9 | 0.1538 (4) | 0.4492 (4) | 0.2127 (3) | 0.0216 (5) | |
H9 | 0.0847 | 0.5715 | 0.1719 | 0.026* | |
C10 | 0.1926 (4) | 0.3040 (4) | 0.1612 (3) | 0.0223 (5) | |
H10 | 0.1497 | 0.3229 | 0.0846 | 0.027* | |
C11 | 0.2997 (4) | 0.1248 (4) | 0.2281 (3) | 0.0214 (5) | |
H11 | 0.3274 | 0.0237 | 0.1942 | 0.026* | |
N1 | 0.3338 (3) | 0.4268 (3) | 0.6626 (2) | 0.0201 (4) | |
N2 | 0.3230 (3) | 0.2371 (3) | 0.3892 (2) | 0.0198 (4) | |
N3 | 0.3635 (3) | 0.0922 (3) | 0.3375 (2) | 0.0205 (5) | |
O1 | 0.2573 (3) | 0.2919 (2) | 0.88383 (18) | 0.0223 (4) | |
O2 | 0.5813 (3) | 0.3087 (3) | 0.82572 (19) | 0.0241 (4) | |
O3 | 0.2102 (3) | 0.6773 (3) | 0.49987 (18) | 0.0252 (4) | |
S1 | 0.37842 (9) | 0.39200 (8) | 0.80332 (6) | 0.01781 (14) | |
Ag1 | 0.44028 (3) | 0.19733 (2) | 0.571644 (17) | 0.02225 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0176 (11) | 0.0136 (11) | 0.0254 (14) | −0.0065 (9) | −0.0016 (10) | −0.0048 (9) |
C2 | 0.0233 (12) | 0.0199 (12) | 0.0209 (14) | −0.0086 (10) | −0.0017 (10) | −0.0061 (10) |
C3 | 0.0256 (13) | 0.0241 (13) | 0.0277 (15) | −0.0108 (11) | 0.0013 (11) | −0.0140 (11) |
C4 | 0.0244 (13) | 0.0160 (11) | 0.0322 (16) | −0.0063 (10) | 0.0003 (11) | −0.0074 (11) |
C5 | 0.0218 (12) | 0.0171 (12) | 0.0241 (14) | −0.0082 (10) | −0.0006 (10) | −0.0020 (10) |
C6 | 0.0199 (11) | 0.0202 (12) | 0.0189 (13) | −0.0102 (10) | 0.0012 (10) | −0.0057 (10) |
C7 | 0.0183 (11) | 0.0160 (11) | 0.0235 (15) | −0.0069 (9) | 0.0020 (10) | −0.0049 (10) |
C8 | 0.0212 (12) | 0.0161 (11) | 0.0241 (14) | −0.0046 (9) | −0.0021 (10) | −0.0058 (10) |
C9 | 0.0197 (12) | 0.0205 (12) | 0.0234 (14) | −0.0060 (10) | −0.0021 (10) | −0.0034 (10) |
C10 | 0.0206 (12) | 0.0266 (13) | 0.0205 (14) | −0.0089 (10) | −0.0018 (10) | −0.0051 (10) |
C11 | 0.0208 (12) | 0.0207 (12) | 0.0238 (14) | −0.0058 (10) | −0.0015 (10) | −0.0077 (10) |
N1 | 0.0258 (11) | 0.0151 (10) | 0.0198 (12) | −0.0051 (8) | −0.0028 (9) | −0.0060 (8) |
N2 | 0.0231 (10) | 0.0164 (10) | 0.0205 (12) | −0.0059 (8) | 0.0006 (9) | −0.0064 (8) |
N3 | 0.0233 (11) | 0.0152 (10) | 0.0237 (12) | −0.0054 (8) | −0.0001 (9) | −0.0070 (8) |
O1 | 0.0291 (10) | 0.0178 (8) | 0.0217 (10) | −0.0102 (7) | −0.0022 (8) | −0.0036 (7) |
O2 | 0.0241 (9) | 0.0188 (9) | 0.0287 (11) | −0.0030 (7) | −0.0067 (8) | −0.0067 (8) |
O3 | 0.0358 (10) | 0.0206 (9) | 0.0192 (11) | −0.0080 (8) | −0.0023 (8) | −0.0053 (8) |
S1 | 0.0212 (3) | 0.0140 (3) | 0.0195 (3) | −0.0055 (2) | −0.0030 (2) | −0.0053 (2) |
Ag1 | 0.03078 (13) | 0.01544 (12) | 0.01939 (14) | −0.00346 (8) | −0.00270 (9) | −0.00617 (8) |
C1—C2 | 1.385 (4) | C8—C9 | 1.391 (4) |
C1—C6 | 1.384 (4) | C8—H8 | 0.9300 |
C1—S1 | 1.768 (2) | C9—C10 | 1.357 (4) |
C2—C3 | 1.390 (4) | C9—H9 | 0.9300 |
C2—H2 | 0.9300 | C10—C11 | 1.400 (4) |
C3—C4 | 1.397 (4) | C10—H10 | 0.9300 |
C3—H3 | 0.9300 | C11—N3 | 1.324 (4) |
C4—C5 | 1.387 (4) | C11—H11 | 0.9300 |
C4—H4 | 0.9300 | N1—S1 | 1.623 (2) |
C5—C6 | 1.391 (4) | N2—N3 | 1.356 (3) |
C5—H5 | 0.9300 | O2—S1 | 1.438 (2) |
C6—C7 | 1.503 (4) | O1—S1 | 1.4418 (19) |
C7—O3 | 1.213 (4) | N1—Ag1 | 2.206 (2) |
C7—N1 | 1.371 (3) | N2—Ag1 | 2.270 (2) |
C8—N2 | 1.334 (3) | N3—Ag1i | 2.261 (2) |
C2—C1—C6 | 123.0 (2) | C8—C9—H9 | 120.9 |
C2—C1—S1 | 129.7 (2) | C9—C10—C11 | 117.3 (3) |
C6—C1—S1 | 107.2 (2) | C9—C10—H10 | 121.3 |
C1—C2—C3 | 116.8 (3) | C11—C10—H10 | 121.3 |
C1—C2—H2 | 121.6 | N3—C11—C10 | 123.1 (2) |
C3—C2—H2 | 121.6 | N3—C11—H11 | 118.4 |
C2—C3—C4 | 121.0 (3) | C10—C11—H11 | 118.4 |
C2—C3—H3 | 119.5 | C7—N1—S1 | 112.50 (19) |
C4—C3—H3 | 119.5 | C7—N1—Ag1 | 125.13 (19) |
C5—C4—C3 | 121.2 (2) | S1—N1—Ag1 | 121.53 (11) |
C5—C4—H4 | 119.4 | C8—N2—N3 | 119.1 (2) |
C3—C4—H4 | 119.4 | C8—N2—Ag1 | 119.04 (18) |
C4—C5—C6 | 118.1 (3) | N3—N2—Ag1 | 121.71 (16) |
C4—C5—H5 | 121.0 | C11—N3—N2 | 119.4 (2) |
C6—C5—H5 | 121.0 | C11—N3—Ag1i | 119.65 (17) |
C1—C6—C5 | 119.9 (3) | N2—N3—Ag1i | 120.72 (17) |
C1—C6—C7 | 112.2 (2) | O2—S1—O1 | 114.46 (11) |
C5—C6—C7 | 127.9 (3) | O2—S1—N1 | 111.56 (12) |
O3—C7—N1 | 125.2 (3) | O1—S1—N1 | 111.23 (12) |
O3—C7—C6 | 123.2 (2) | O2—S1—C1 | 112.10 (12) |
N1—C7—C6 | 111.6 (2) | O1—S1—C1 | 109.65 (12) |
N2—C8—C9 | 122.8 (2) | N1—S1—C1 | 96.45 (12) |
N2—C8—H8 | 118.6 | N1—Ag1—N2 | 119.53 (8) |
C9—C8—H8 | 118.6 | N1—Ag1—N3i | 122.52 (9) |
C10—C9—C8 | 118.1 (2) | N3i—Ag1—N2 | 117.54 (8) |
C10—C9—H9 | 120.9 | ||
C6—C1—C2—C3 | −0.1 (4) | C10—C11—N3—Ag1i | −174.0 (2) |
S1—C1—C2—C3 | −176.2 (2) | C8—N2—N3—C11 | −0.4 (4) |
C1—C2—C3—C4 | 1.1 (4) | Ag1—N2—N3—C11 | −176.60 (18) |
C2—C3—C4—C5 | −1.0 (4) | C8—N2—N3—Ag1i | 174.24 (18) |
C3—C4—C5—C6 | 0.0 (4) | Ag1—N2—N3—Ag1i | −2.0 (3) |
C2—C1—C6—C5 | −1.0 (4) | C7—N1—S1—O2 | −117.49 (19) |
S1—C1—C6—C5 | 175.9 (2) | Ag1—N1—S1—O2 | 52.53 (16) |
C2—C1—C6—C7 | −179.0 (2) | C7—N1—S1—O1 | 113.38 (19) |
S1—C1—C6—C7 | −2.1 (3) | Ag1—N1—S1—O1 | −76.60 (16) |
C4—C5—C6—C1 | 1.0 (4) | C7—N1—S1—C1 | −0.6 (2) |
C4—C5—C6—C7 | 178.6 (2) | Ag1—N1—S1—C1 | 169.38 (13) |
C1—C6—C7—O3 | −177.7 (2) | C2—C1—S1—O2 | −65.3 (3) |
C5—C6—C7—O3 | 4.5 (4) | C6—C1—S1—O2 | 118.06 (19) |
C1—C6—C7—N1 | 1.8 (3) | C2—C1—S1—O1 | 62.9 (3) |
C5—C6—C7—N1 | −176.0 (2) | C6—C1—S1—O1 | −113.66 (19) |
N2—C8—C9—C10 | 1.2 (4) | C2—C1—S1—N1 | 178.2 (2) |
C8—C9—C10—C11 | −0.8 (4) | C6—C1—S1—N1 | 1.6 (2) |
C9—C10—C11—N3 | −0.1 (4) | C7—N1—Ag1—N3i | 163.75 (19) |
O3—C7—N1—S1 | 179.0 (2) | S1—N1—Ag1—N3i | −4.96 (18) |
C6—C7—N1—S1 | −0.5 (3) | C7—N1—Ag1—N2 | −23.8 (2) |
O3—C7—N1—Ag1 | 9.4 (4) | S1—N1—Ag1—N2 | 167.46 (12) |
C6—C7—N1—Ag1 | −170.09 (16) | C8—N2—Ag1—N1 | 12.9 (2) |
C9—C8—N2—N3 | −0.6 (4) | N3—N2—Ag1—N1 | −170.85 (17) |
C9—C8—N2—Ag1 | 175.75 (19) | C8—N2—Ag1—N3i | −174.31 (18) |
C10—C11—N3—N2 | 0.7 (4) | N3—N2—Ag1—N3i | 1.9 (2) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1ii | 0.93 | 2.58 | 3.163 (3) | 121 |
C8—H8···O3 | 0.93 | 2.35 | 3.236 (3) | 160 |
C9—H9···O1iii | 0.93 | 2.47 | 3.152 (3) | 131 |
C10—H10···O1iv | 0.93 | 2.41 | 3.203 (4) | 143 |
C11—H11···O2i | 0.93 | 2.52 | 3.410 (3) | 161 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y+1, z; (iii) −x, −y+1, −z+1; (iv) x, y, z−1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Ag2(C7H4NO3S)2(C4H4N2)2] | [Ag2(C7H4NO3S)2(C4H4N2)2] |
Mr | 740.27 | 740.27 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 7.2388 (5), 22.3068 (11), 7.7746 (5) | 7.3231 (8), 7.7516 (9), 11.5389 (14) |
α, β, γ (°) | 90, 108.884 (5), 90 | 73.090 (9), 83.087 (10), 71.148 (9) |
V (Å3) | 1187.83 (13) | 592.82 (12) |
Z | 2 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.88 | 1.88 |
Crystal size (mm) | 0.42 × 0.28 × 0.17 | 0.60 × 0.51 × 0.33 |
Data collection | ||
Diffractometer | STOE IPDS2 | STOE IPDS2 |
Absorption correction | Integration (X-RED; Stoe & Cie, 2002) | Integration (X-RED; Stoe & Cie, 2002) |
Tmin, Tmax | 0.552, 0.741 | 0.368, 0.579 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15455, 2602, 2458 | 10253, 2737, 2650 |
Rint | 0.086 | 0.099 |
(sin θ/λ)max (Å−1) | 0.641 | 0.651 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.063, 1.10 | 0.025, 0.066, 1.08 |
No. of reflections | 2602 | 2320 |
No. of parameters | 172 | 172 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.85 | 0.74, −1.19 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
N1—Ag1 | 2.2099 (18) | N3—Ag1i | 2.2632 (19) |
N2—Ag1 | 2.276 (2) | ||
N1—Ag1—N2 | 119.82 (7) | N3i—Ag1—N2 | 117.48 (7) |
N1—Ag1—N3i | 121.97 (7) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O3 | 0.93 | 2.36 | 3.245 (3) | 160 |
C9—H9···O2ii | 0.93 | 2.44 | 3.101 (3) | 128 |
C10—H10···O2iii | 0.93 | 2.37 | 3.199 (3) | 148 |
C11—H11···O1i | 0.93 | 2.53 | 3.423 (3) | 162 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y−1/2, −z+1/2. |
N1—Ag1 | 2.206 (2) | N3—Ag1i | 2.261 (2) |
N2—Ag1 | 2.270 (2) | ||
N1—Ag1—N2 | 119.53 (8) | N3i—Ag1—N2 | 117.54 (8) |
N1—Ag1—N3i | 122.52 (9) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1ii | 0.93 | 2.58 | 3.163 (3) | 121 |
C8—H8···O3 | 0.93 | 2.35 | 3.236 (3) | 160 |
C9—H9···O1iii | 0.93 | 2.47 | 3.152 (3) | 131 |
C10—H10···O1iv | 0.93 | 2.41 | 3.203 (4) | 143 |
C11—H11···O2i | 0.93 | 2.52 | 3.410 (3) | 161 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y+1, z; (iii) −x, −y+1, −z+1; (iv) x, y, z−1. |
Saccharin, alternatively named 1,2-benzisothiazoline-3(2H)-one-1,1-dioxide, is one of the best known and most widely used non-caloric sweeteners and food additives. Owing to its potential harmfulness and especially its suspected carcinogenic nature (Cohen-Addad et al., 1986; Suzuki & Suzuki, 1995), saccharin is probably one of the most studied components of the food supply. Simultaneously, it was shown that the deprotonated form of saccharin, saccharinate (sac), acts as a polyfunctional ligand through four sites, viz. the negatively charged imine N atom, and one carbonyl and two sulfonyl O atoms. The sac ligand can behave as a mono-, bi- or tridentate ligand, and in some cases also as a bridging ligand between metal ions (Baran, 2005; Baran & Yilmaz, 2005). As a part of our study on the synthesis, spectral, thermal and crystallographic characterization of metal complexes of sac, an attempt to synthesize a silver(I) complex of sac with pyridazine (pydz) resulted in the concurrent crystallization, from acetonitrile, of monoclinic, (I), and triclinic, (II), forms of bis(pyridazine)bis(saccharinato)disilver(I) as concomitant polymorphs (Fig. 1, and Tables 1 and 3).
Visual examination of the crystals under a microscope indicated that most of the crystals (ca 90%) consisted of (I). Data collections performed at 293 K also produced the same outcome, indicating that the polymorphism observed in the title compound is not associated with a temperature phase transition. In both (I) and (II), the silver(I) ions have a slightly distorted trigonal AgN3 coordination geometry, and are doubly bridged by two neutral pyridazine (pydz) ligands, forming a centrosymmetric dimeric structure. The anionic sac ligands are N-coordinated. The sac (atoms C1–C7, N1 and S1) and pydz (atoms C8–C11, N2 and N3) ligands are both essentially planar, and the dihedral angles between the mean planes of these ligands are 8.43 (7) and 7.94 (8)° in (I) and (II), respectively, suggesting that the dimeric molecules is nearly flat. The bond geometry is similar in both polymorphs. The average intra-dimer Ag···Ag distance of 3.706 (2) Å in (I) and (II) is much longer than the upper limit of 3.30 Å, reported by Jansen (1987), for an Ag···Ag contact in silver(I) complexes. The Ag—Nsac bond distances in (I) and (II) are similar to those found in [Ag2(sac)2(hep)2]n [2.1718 (17) and 2.1819 (17) Å; hep is N-(2-hydroxyethyl)piperazine; Hamamci, et al., 2005a], [Ag2(sac)2(pyet)2] [2.1444 (12) Å; pyet is 2-pyridylethanol; Yilmaz et al., 2005] and [Ag(sac)(py)]n [2.084 (2) Å; py is pyridine; Hamamci et al., 2005b], but significantly shorter than those reported for [Ag2(sac)2(aepy)2] [2.449 (2) Å; aepy is 2-(2-aminoethyl)pyridine; Hamamci et al., 2005c)].
The molecular packing in (I) and (II) is shown in Figs. 2 and 3. The most obvious difference between the two polymorphs is clearly seen in their intermolecular interactions (Tables 2 and 4). In the monoclinic polymorph, (I), two types of interactions (π–π and C—H···O interactions) stabilize the structure. There are two aromatic π–π stacking interactions between the closely associated pairs of both sac and pydz aromatic rings [Cg1···Cg1i = 3.6955 Å and Cg1···Cg1ii = 3.8277 Å; symmetry codes: (i) 2 - x, -y, 2 - z; (ii) 1 - x, -y, -z], leading to two-dimensional layers, which are further cross-linked by two weak C—H···O interactions (Fig. 2). Although the C—H···O interactions in (II) are similar to (I), (II) also exhibits a π–π interaction between the aromatic rings of sac and pydz [Cg1···Cg1i = 3.7008 Å; symmetry code: (i) 1 - x, 1 - y, 1 - z] and a C—H···π interaction [C10—H10···Cgi = 3.2755 Å; symmetry code: (i) 2 - x,1 - y,1 - z], and a π···M interaction between the aromatic ring of sac and the silver(I) ion [Cg···Agi = 3.879 Å; symmetry code: (i) x, -1 + y, z]. In addition to other interactions, these extra weak intermolecular interactions stabilize the triclinic polymorphic structure.