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Crystallization of the title compound, di-μ-pyridazine-1κ2N:2κ2N′-bis­[(2,3-dihydro-3-oxobenzisosulfonazolato-κN)silver(I)], [Ag2(C7H4NO3S)2(C4H4N2)2], from acetonitrile yields both monoclinic, (I), and triclinic, (II), polymorphs. In both forms, the silver(I) ions have a slightly distorted trigonal AgN3 coordination geometry and are doubly bridged by two neutral pyridazine (pydz) ligands, generating a centrosymmetric dimeric structure. The saccharinate (sac) ligands are N-coordinated. The dihedral angles between the sac and pydz rings are 8.43 (7) and 7.94 (8)° in (I) and (II), respectively, suggesting that the dimeric mol­ecule is nearly flat. The bond geometry is similar in both polymorphs. In (I), the dimers inter­act with each other via aromatic πsac–πpydz stacking inter­actions, forming two-dimensional layers, which are further crosslinked by weak C—H...O inter­actions. Compound (II) exhibits similar C—H...O and π–π inter­actions, but additional C—H...π and π...Ag inter­actions help to stabilize the packing of the dimers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105036334/gd1419sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105036334/gd1419Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105036334/gd1419IIsup3.hkl
Contains datablock II

CCDC references: 296322; 296323

Comment top

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 (ππ and C—H···O interactions) stabilize the structure. There are two aromatic ππ 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 ππ 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.

Experimental top

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(CO) 1651; νas(SO) 1286, 1257; νs(SO) 1151.

Refinement top

All H atoms were refined with a riding model, with C—H distances of 0.93 Å and Uiso(H) = 1.2 Ueq(C).

Structure description top

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 (ππ and C—H···O interactions) stabilize the structure. There are two aromatic ππ 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 ππ 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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecule of (I), showing the atom-labelling scheme (50% probability displacement ellipsoids). Hydrogen bonds are shown as dashed lines. [Symmetry code as in Table 1.]
[Figure 2] Fig. 2. The packing of (I), viewed along the a axis. Hydrogen bonds are shown as dashed lines and benzene H atoms have been omitted.
[Figure 3] Fig. 3. The packing of (II), viewed along the a axis. Hydrogen bonds are shown as dashed lines and benzene H atoms not involved in hydrogen bonding have been omitted.
(I) di-µ-pyridazine-1κ2N:2κN'-bis[(2,3-dihydro-3- oxobenzisosulfonazolato)silver(I)] top
Crystal data top
[Ag2(C7H4NO3S)2(C4H4N2)2]F(000) = 728
Mr = 740.27Dx = 2.070 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 15455 reflections
a = 7.2388 (5) Åθ = 1.8–27.3°
b = 22.3068 (11) ŵ = 1.88 mm1
c = 7.7746 (5) ÅT = 100 K
β = 108.884 (5)°Prismatic plate, colourless
V = 1187.83 (13) Å30.42 × 0.28 × 0.17 mm
Z = 2
Data collection top
STOE IPDS-2
diffractometer
2602 independent reflections
Radiation source: fine-focus sealed tube2458 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.086
Detector resolution: 6.67 pixels mm-1θmax = 27.1°, θmin = 1.8°
ω scansh = 99
Absorption correction: integration
(X-RED; Stoe & Cie, 2002)
k = 2828
Tmin = 0.552, Tmax = 0.741l = 99
15455 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.063H-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 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.85 e Å3
Crystal data top
[Ag2(C7H4NO3S)2(C4H4N2)2]V = 1187.83 (13) Å3
Mr = 740.27Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.2388 (5) ŵ = 1.88 mm1
b = 22.3068 (11) ÅT = 100 K
c = 7.7746 (5) Å0.42 × 0.28 × 0.17 mm
β = 108.884 (5)°
Data collection top
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 = 0.741Rint = 0.086
15455 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.063H-atom parameters constrained
S = 1.10Δρmax = 0.50 e Å3
2602 reflectionsΔρmin = 0.85 e Å3
172 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
xyzUiso*/Ueq
C10.7094 (3)0.65178 (10)0.7564 (3)0.0176 (4)
C20.7278 (4)0.69917 (10)0.8754 (3)0.0207 (4)
H20.68630.73760.83440.025*
C30.8116 (4)0.68651 (11)1.0601 (3)0.0224 (5)
H30.82520.71701.14480.027*
C40.8751 (4)0.62883 (12)1.1196 (3)0.0224 (5)
H40.93060.62161.24350.027*
C50.8571 (3)0.58186 (11)0.9971 (3)0.0200 (4)
H50.90010.54341.03700.024*
C60.7728 (3)0.59448 (10)0.8138 (3)0.0177 (4)
C70.7424 (3)0.55245 (11)0.6561 (3)0.0189 (4)
C80.7745 (4)0.41229 (11)0.3371 (3)0.0211 (4)
H80.80140.43030.45040.025*
C90.8392 (4)0.35369 (11)0.3293 (3)0.0213 (5)
H90.90630.33280.43450.026*
C100.8003 (4)0.32821 (10)0.1613 (3)0.0212 (5)
H100.84070.28940.14750.025*
C110.6975 (4)0.36278 (10)0.0118 (3)0.0206 (4)
H110.67000.34610.10350.025*
N10.6654 (3)0.58094 (9)0.4932 (2)0.0194 (4)
N20.6768 (3)0.44337 (9)0.1910 (3)0.0194 (4)
N30.6367 (3)0.41804 (9)0.0249 (2)0.0192 (4)
O10.4175 (3)0.66446 (8)0.4442 (2)0.0242 (4)
O20.7448 (3)0.68941 (7)0.4478 (2)0.0232 (3)
O30.7824 (3)0.49898 (7)0.6746 (2)0.0248 (4)
S10.62333 (8)0.65133 (2)0.51645 (7)0.01779 (12)
Ag10.55623 (3)0.535018 (7)0.22747 (2)0.02210 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0198 (11)0.0203 (11)0.0127 (9)0.0007 (8)0.0052 (8)0.0006 (8)
C20.0237 (11)0.0193 (10)0.0196 (10)0.0010 (9)0.0077 (9)0.0024 (8)
C30.0249 (12)0.0261 (12)0.0166 (10)0.0031 (9)0.0072 (9)0.0074 (9)
C40.0235 (12)0.0297 (12)0.0138 (10)0.0017 (9)0.0056 (9)0.0013 (9)
C50.0237 (12)0.0205 (11)0.0154 (10)0.0005 (9)0.0056 (9)0.0020 (8)
C60.0206 (11)0.0169 (10)0.0158 (10)0.0021 (8)0.0064 (8)0.0014 (8)
C70.0211 (11)0.0204 (11)0.0138 (10)0.0023 (9)0.0040 (8)0.0007 (8)
C80.0232 (11)0.0225 (11)0.0162 (10)0.0003 (9)0.0044 (9)0.0007 (8)
C90.0212 (11)0.0233 (11)0.0183 (10)0.0012 (9)0.0049 (9)0.0021 (9)
C100.0222 (11)0.0176 (10)0.0246 (11)0.0006 (8)0.0086 (9)0.0010 (8)
C110.0240 (11)0.0208 (11)0.0177 (10)0.0006 (9)0.0077 (9)0.0039 (8)
N10.0286 (10)0.0167 (9)0.0115 (8)0.0013 (7)0.0046 (7)0.0013 (7)
N20.0232 (10)0.0201 (9)0.0144 (8)0.0003 (8)0.0052 (7)0.0020 (7)
N30.0220 (10)0.0214 (9)0.0139 (8)0.0003 (7)0.0051 (7)0.0015 (7)
O10.0255 (9)0.0275 (9)0.0177 (8)0.0053 (7)0.0044 (7)0.0009 (6)
O20.0324 (9)0.0199 (8)0.0199 (8)0.0016 (7)0.0119 (7)0.0042 (6)
O30.0375 (10)0.0163 (8)0.0191 (8)0.0032 (7)0.0073 (7)0.0002 (6)
S10.0240 (3)0.0167 (3)0.0124 (2)0.0021 (2)0.0055 (2)0.00056 (18)
Ag10.03251 (13)0.01815 (11)0.01322 (11)0.00155 (6)0.00402 (8)0.00151 (6)
Geometric parameters (Å, º) top
C1—C61.382 (3)C8—C91.396 (3)
C1—C21.383 (3)C8—H80.9300
C1—S11.765 (2)C9—C101.367 (3)
C2—C31.395 (3)C9—H90.9300
C2—H20.9300C10—C111.393 (3)
C3—C41.394 (4)C10—H100.9300
C3—H30.9300C11—N31.324 (3)
C4—C51.393 (3)C11—H110.9300
C4—H40.9300N1—S11.621 (2)
C5—C61.386 (3)N2—N31.352 (3)
C5—H50.9300O1—S11.4420 (18)
C6—C71.502 (3)O2—S11.4435 (17)
C7—O31.225 (3)N1—Ag12.2099 (18)
C7—N11.364 (3)N2—Ag12.276 (2)
C8—N21.324 (3)N3—Ag1i2.2632 (19)
C6—C1—C2122.7 (2)C10—C9—H9121.2
C6—C1—S1107.60 (16)C8—C9—H9121.2
C2—C1—S1129.52 (18)C9—C10—H10121.4
C1—C2—C3116.7 (2)C11—C10—H10121.4
C1—C2—H2121.6N3—C11—C10123.5 (2)
C3—C2—H2121.6N3—C11—H11118.2
C4—C3—C2121.0 (2)C10—C11—H11118.2
C4—C3—H3119.5C7—N1—S1112.49 (15)
C2—C3—H3119.5C7—N1—Ag1124.53 (15)
C5—C4—C3121.3 (2)S1—N1—Ag1122.02 (10)
C5—C4—H4119.4C8—N2—N3119.4 (2)
C3—C4—H4119.4C8—N2—Ag1118.90 (15)
C6—C5—C4117.6 (2)N3—N2—Ag1121.46 (15)
C6—C5—H5121.2C11—N3—N2119.25 (19)
C4—C5—H5121.2C11—N3—Ag1i119.43 (15)
C1—C6—C5120.6 (2)N2—N3—Ag1i121.06 (15)
C1—C6—C7111.59 (19)O1—S1—O2114.37 (10)
C5—C6—C7127.7 (2)O1—S1—N1111.16 (11)
O3—C7—N1125.0 (2)O2—S1—N1111.71 (10)
O3—C7—C6123.0 (2)O1—S1—C1112.16 (10)
N1—C7—C6112.0 (2)O2—S1—C1109.79 (11)
N2—C8—C9123.1 (2)N1—S1—C196.25 (10)
N2—C8—H8118.4N1—Ag1—N2119.82 (7)
C9—C8—H8118.4N1—Ag1—N3i121.97 (7)
C10—C9—C8117.5 (2)N3i—Ag1—N2117.48 (7)
C9—C10—C11117.2 (2)
C6—C1—C2—C31.1 (4)C10—C11—N3—Ag1i173.50 (18)
S1—C1—C2—C3176.42 (19)C8—N2—N3—C110.5 (3)
C1—C2—C3—C40.7 (4)Ag1—N2—N3—C11174.80 (17)
C2—C3—C4—C50.1 (4)C8—N2—N3—Ag1i173.57 (17)
C3—C4—C5—C60.3 (4)Ag1—N2—N3—Ag1i0.7 (2)
C2—C1—C6—C50.8 (4)C7—N1—S1—O1116.04 (17)
S1—C1—C6—C5176.99 (18)Ag1—N1—S1—O153.24 (15)
C2—C1—C6—C7177.7 (2)C7—N1—S1—O2114.88 (18)
S1—C1—C6—C71.5 (2)Ag1—N1—S1—O275.84 (15)
C4—C5—C6—C10.1 (3)C7—N1—S1—C10.66 (19)
C4—C5—C6—C7178.1 (2)Ag1—N1—S1—C1169.94 (13)
C1—C6—C7—O3177.8 (2)C6—C1—S1—O1116.43 (17)
C5—C6—C7—O33.9 (4)C2—C1—S1—O167.7 (3)
C1—C6—C7—N12.0 (3)C6—C1—S1—O2115.24 (17)
C5—C6—C7—N1176.3 (2)C2—C1—S1—O260.6 (2)
N2—C8—C9—C100.7 (4)C6—C1—S1—N10.54 (18)
C8—C9—C10—C110.6 (3)C2—C1—S1—N1176.4 (2)
C9—C10—C11—N30.1 (4)C7—N1—Ag1—N3i164.08 (17)
O3—C7—N1—S1178.2 (2)S1—N1—Ag1—N3i3.88 (17)
C6—C7—N1—S11.6 (3)C7—N1—Ag1—N226.0 (2)
O3—C7—N1—Ag19.2 (3)S1—N1—Ag1—N2166.01 (11)
C6—C7—N1—Ag1170.56 (15)C8—N2—Ag1—N116.0 (2)
C9—C8—N2—N30.2 (4)N3—N2—Ag1—N1169.68 (15)
C9—C8—N2—Ag1174.23 (18)C8—N2—Ag1—N3i173.63 (17)
C10—C11—N3—N20.7 (4)N3—N2—Ag1—N3i0.7 (2)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···O30.932.363.245 (3)160
C9—H9···O2ii0.932.443.101 (3)128
C10—H10···O2iii0.932.373.199 (3)148
C11—H11···O1i0.932.533.423 (3)162
Symmetry codes: (i) x+1, y+1, z; (ii) x+2, y+1, z+1; (iii) x+3/2, y1/2, z+1/2.
(II) di-µ-pyridazine-1κ2N:2κN'-bis[(saccharinato)silver(I)] top
Crystal data top
[Ag2(C7H4NO3S)2(C4H4N2)2]Z = 1
Mr = 740.27F(000) = 364
Triclinic, P1Dx = 2.074 Mg m3
Hall symbol: -P 1nMo Kα radiation, λ = 0.71073 Å
a = 7.3231 (8) ÅCell parameters from 10253 reflections
b = 7.7516 (9) Åθ = 2.9–28.0°
c = 11.5389 (14) ŵ = 1.88 mm1
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
Data collection top
STOE IPDS-2
diffractometer
2737 independent reflections
Radiation source: fine-focus sealed tube2650 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.099
Detector resolution: 6.67 pixels mm-1θmax = 27.6°, θmin = 2.9°
ω scansh = 99
Absorption correction: integration
(X-RED; Stoe & Cie, 2002)
k = 1010
Tmin = 0.368, Tmax = 0.579l = 1415
10253 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-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 parametersΔρmax = 0.74 e Å3
0 restraintsΔρmin = 1.19 e Å3
Crystal data top
[Ag2(C7H4NO3S)2(C4H4N2)2]γ = 71.148 (9)°
Mr = 740.27V = 592.82 (12) Å3
Triclinic, P1Z = 1
a = 7.3231 (8) ÅMo Kα radiation
b = 7.7516 (9) ŵ = 1.88 mm1
c = 11.5389 (14) ÅT = 100 K
α = 73.090 (9)°0.60 × 0.51 × 0.33 mm
β = 83.087 (10)°
Data collection top
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 = 0.579Rint = 0.099
10253 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.066H-atom parameters constrained
S = 1.08Δρmax = 0.74 e Å3
2320 reflectionsΔρmin = 1.19 e Å3
172 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
xyzUiso*/Ueq
C10.2961 (4)0.6328 (3)0.8038 (3)0.0184 (5)
C20.2856 (4)0.7137 (4)0.8978 (3)0.0206 (5)
H20.33180.64100.97390.025*
C30.2027 (4)0.9086 (4)0.8727 (3)0.0236 (6)
H30.19490.96860.93300.028*
C40.1310 (4)1.0157 (4)0.7585 (3)0.0241 (6)
H40.07431.14580.74440.029*
C50.1428 (4)0.9318 (4)0.6657 (3)0.0212 (5)
H50.09491.00360.58970.025*
C60.2285 (4)0.7371 (4)0.6895 (2)0.0187 (5)
C70.2542 (4)0.6145 (3)0.6054 (3)0.0192 (5)
C80.2204 (4)0.4099 (4)0.3283 (3)0.0205 (5)
H80.19230.50830.36480.025*
C90.1538 (4)0.4492 (4)0.2127 (3)0.0216 (5)
H90.08470.57150.17190.026*
C100.1926 (4)0.3040 (4)0.1612 (3)0.0223 (5)
H100.14970.32290.08460.027*
C110.2997 (4)0.1248 (4)0.2281 (3)0.0214 (5)
H110.32740.02370.19420.026*
N10.3338 (3)0.4268 (3)0.6626 (2)0.0201 (4)
N20.3230 (3)0.2371 (3)0.3892 (2)0.0198 (4)
N30.3635 (3)0.0922 (3)0.3375 (2)0.0205 (5)
O10.2573 (3)0.2919 (2)0.88383 (18)0.0223 (4)
O20.5813 (3)0.3087 (3)0.82572 (19)0.0241 (4)
O30.2102 (3)0.6773 (3)0.49987 (18)0.0252 (4)
S10.37842 (9)0.39200 (8)0.80332 (6)0.01781 (14)
Ag10.44028 (3)0.19733 (2)0.571644 (17)0.02225 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0176 (11)0.0136 (11)0.0254 (14)0.0065 (9)0.0016 (10)0.0048 (9)
C20.0233 (12)0.0199 (12)0.0209 (14)0.0086 (10)0.0017 (10)0.0061 (10)
C30.0256 (13)0.0241 (13)0.0277 (15)0.0108 (11)0.0013 (11)0.0140 (11)
C40.0244 (13)0.0160 (11)0.0322 (16)0.0063 (10)0.0003 (11)0.0074 (11)
C50.0218 (12)0.0171 (12)0.0241 (14)0.0082 (10)0.0006 (10)0.0020 (10)
C60.0199 (11)0.0202 (12)0.0189 (13)0.0102 (10)0.0012 (10)0.0057 (10)
C70.0183 (11)0.0160 (11)0.0235 (15)0.0069 (9)0.0020 (10)0.0049 (10)
C80.0212 (12)0.0161 (11)0.0241 (14)0.0046 (9)0.0021 (10)0.0058 (10)
C90.0197 (12)0.0205 (12)0.0234 (14)0.0060 (10)0.0021 (10)0.0034 (10)
C100.0206 (12)0.0266 (13)0.0205 (14)0.0089 (10)0.0018 (10)0.0051 (10)
C110.0208 (12)0.0207 (12)0.0238 (14)0.0058 (10)0.0015 (10)0.0077 (10)
N10.0258 (11)0.0151 (10)0.0198 (12)0.0051 (8)0.0028 (9)0.0060 (8)
N20.0231 (10)0.0164 (10)0.0205 (12)0.0059 (8)0.0006 (9)0.0064 (8)
N30.0233 (11)0.0152 (10)0.0237 (12)0.0054 (8)0.0001 (9)0.0070 (8)
O10.0291 (10)0.0178 (8)0.0217 (10)0.0102 (7)0.0022 (8)0.0036 (7)
O20.0241 (9)0.0188 (9)0.0287 (11)0.0030 (7)0.0067 (8)0.0067 (8)
O30.0358 (10)0.0206 (9)0.0192 (11)0.0080 (8)0.0023 (8)0.0053 (8)
S10.0212 (3)0.0140 (3)0.0195 (3)0.0055 (2)0.0030 (2)0.0053 (2)
Ag10.03078 (13)0.01544 (12)0.01939 (14)0.00346 (8)0.00270 (9)0.00617 (8)
Geometric parameters (Å, º) top
C1—C21.385 (4)C8—C91.391 (4)
C1—C61.384 (4)C8—H80.9300
C1—S11.768 (2)C9—C101.357 (4)
C2—C31.390 (4)C9—H90.9300
C2—H20.9300C10—C111.400 (4)
C3—C41.397 (4)C10—H100.9300
C3—H30.9300C11—N31.324 (4)
C4—C51.387 (4)C11—H110.9300
C4—H40.9300N1—S11.623 (2)
C5—C61.391 (4)N2—N31.356 (3)
C5—H50.9300O2—S11.438 (2)
C6—C71.503 (4)O1—S11.4418 (19)
C7—O31.213 (4)N1—Ag12.206 (2)
C7—N11.371 (3)N2—Ag12.270 (2)
C8—N21.334 (3)N3—Ag1i2.261 (2)
C2—C1—C6123.0 (2)C8—C9—H9120.9
C2—C1—S1129.7 (2)C9—C10—C11117.3 (3)
C6—C1—S1107.2 (2)C9—C10—H10121.3
C1—C2—C3116.8 (3)C11—C10—H10121.3
C1—C2—H2121.6N3—C11—C10123.1 (2)
C3—C2—H2121.6N3—C11—H11118.4
C2—C3—C4121.0 (3)C10—C11—H11118.4
C2—C3—H3119.5C7—N1—S1112.50 (19)
C4—C3—H3119.5C7—N1—Ag1125.13 (19)
C5—C4—C3121.2 (2)S1—N1—Ag1121.53 (11)
C5—C4—H4119.4C8—N2—N3119.1 (2)
C3—C4—H4119.4C8—N2—Ag1119.04 (18)
C4—C5—C6118.1 (3)N3—N2—Ag1121.71 (16)
C4—C5—H5121.0C11—N3—N2119.4 (2)
C6—C5—H5121.0C11—N3—Ag1i119.65 (17)
C1—C6—C5119.9 (3)N2—N3—Ag1i120.72 (17)
C1—C6—C7112.2 (2)O2—S1—O1114.46 (11)
C5—C6—C7127.9 (3)O2—S1—N1111.56 (12)
O3—C7—N1125.2 (3)O1—S1—N1111.23 (12)
O3—C7—C6123.2 (2)O2—S1—C1112.10 (12)
N1—C7—C6111.6 (2)O1—S1—C1109.65 (12)
N2—C8—C9122.8 (2)N1—S1—C196.45 (12)
N2—C8—H8118.6N1—Ag1—N2119.53 (8)
C9—C8—H8118.6N1—Ag1—N3i122.52 (9)
C10—C9—C8118.1 (2)N3i—Ag1—N2117.54 (8)
C10—C9—H9120.9
C6—C1—C2—C30.1 (4)C10—C11—N3—Ag1i174.0 (2)
S1—C1—C2—C3176.2 (2)C8—N2—N3—C110.4 (4)
C1—C2—C3—C41.1 (4)Ag1—N2—N3—C11176.60 (18)
C2—C3—C4—C51.0 (4)C8—N2—N3—Ag1i174.24 (18)
C3—C4—C5—C60.0 (4)Ag1—N2—N3—Ag1i2.0 (3)
C2—C1—C6—C51.0 (4)C7—N1—S1—O2117.49 (19)
S1—C1—C6—C5175.9 (2)Ag1—N1—S1—O252.53 (16)
C2—C1—C6—C7179.0 (2)C7—N1—S1—O1113.38 (19)
S1—C1—C6—C72.1 (3)Ag1—N1—S1—O176.60 (16)
C4—C5—C6—C11.0 (4)C7—N1—S1—C10.6 (2)
C4—C5—C6—C7178.6 (2)Ag1—N1—S1—C1169.38 (13)
C1—C6—C7—O3177.7 (2)C2—C1—S1—O265.3 (3)
C5—C6—C7—O34.5 (4)C6—C1—S1—O2118.06 (19)
C1—C6—C7—N11.8 (3)C2—C1—S1—O162.9 (3)
C5—C6—C7—N1176.0 (2)C6—C1—S1—O1113.66 (19)
N2—C8—C9—C101.2 (4)C2—C1—S1—N1178.2 (2)
C8—C9—C10—C110.8 (4)C6—C1—S1—N11.6 (2)
C9—C10—C11—N30.1 (4)C7—N1—Ag1—N3i163.75 (19)
O3—C7—N1—S1179.0 (2)S1—N1—Ag1—N3i4.96 (18)
C6—C7—N1—S10.5 (3)C7—N1—Ag1—N223.8 (2)
O3—C7—N1—Ag19.4 (4)S1—N1—Ag1—N2167.46 (12)
C6—C7—N1—Ag1170.09 (16)C8—N2—Ag1—N112.9 (2)
C9—C8—N2—N30.6 (4)N3—N2—Ag1—N1170.85 (17)
C9—C8—N2—Ag1175.75 (19)C8—N2—Ag1—N3i174.31 (18)
C10—C11—N3—N20.7 (4)N3—N2—Ag1—N3i1.9 (2)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1ii0.932.583.163 (3)121
C8—H8···O30.932.353.236 (3)160
C9—H9···O1iii0.932.473.152 (3)131
C10—H10···O1iv0.932.413.203 (4)143
C11—H11···O2i0.932.523.410 (3)161
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1, z; (iii) x, y+1, z+1; (iv) x, y, z1.

Experimental details

(I)(II)
Crystal data
Chemical formula[Ag2(C7H4NO3S)2(C4H4N2)2][Ag2(C7H4NO3S)2(C4H4N2)2]
Mr740.27740.27
Crystal system, space groupMonoclinic, P21/nTriclinic, P1
Temperature (K)100100
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), 9073.090 (9), 83.087 (10), 71.148 (9)
V3)1187.83 (13)592.82 (12)
Z21
Radiation typeMo KαMo Kα
µ (mm1)1.881.88
Crystal size (mm)0.42 × 0.28 × 0.170.60 × 0.51 × 0.33
Data collection
DiffractometerSTOE IPDS2STOE IPDS2
Absorption correctionIntegration
(X-RED; Stoe & Cie, 2002)
Integration
(X-RED; Stoe & Cie, 2002)
Tmin, Tmax0.552, 0.7410.368, 0.579
No. of measured, independent and
observed [I > 2σ(I)] reflections
15455, 2602, 2458 10253, 2737, 2650
Rint0.0860.099
(sin θ/λ)max1)0.6410.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.063, 1.10 0.025, 0.066, 1.08
No. of reflections26022320
No. of parameters172172
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.850.74, 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).

Selected geometric parameters (Å, º) for (I) top
N1—Ag12.2099 (18)N3—Ag1i2.2632 (19)
N2—Ag12.276 (2)
N1—Ag1—N2119.82 (7)N3i—Ag1—N2117.48 (7)
N1—Ag1—N3i121.97 (7)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C8—H8···O30.932.363.245 (3)160
C9—H9···O2ii0.932.443.101 (3)128
C10—H10···O2iii0.932.373.199 (3)148
C11—H11···O1i0.932.533.423 (3)162
Symmetry codes: (i) x+1, y+1, z; (ii) x+2, y+1, z+1; (iii) x+3/2, y1/2, z+1/2.
Selected geometric parameters (Å, º) for (II) top
N1—Ag12.206 (2)N3—Ag1i2.261 (2)
N2—Ag12.270 (2)
N1—Ag1—N2119.53 (8)N3i—Ag1—N2117.54 (8)
N1—Ag1—N3i122.52 (9)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1ii0.932.583.163 (3)121
C8—H8···O30.932.353.236 (3)160
C9—H9···O1iii0.932.473.152 (3)131
C10—H10···O1iv0.932.413.203 (4)143
C11—H11···O2i0.932.523.410 (3)161
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1, z; (iii) x, y+1, z+1; (iv) x, y, z1.
 

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