Download citation
Download citation
link to html
Both title compounds, {[Ag2(C10H8N2)2](C6H5O6PS)·3H2O}n, (I), and {[Co(C10H8N2)2(H2O)4](C6H5O6PS)}n, (II), respectively, contain similar novel symmetric dimeric [O3S–C6H4–PO3H]2− anions formed via two shared (O...H...O) H atoms on twofold positions between two –PO3H groups. The two-coordinate AgI structure features one-dimensional polymeric chains of {[Ag(4,4′-bipy)]22+}n (4,4′-bipy is 4,4′-bipyridine), weakly linked by π–π inter­actions, separated by the anionic dimers which are stabilized into layers by hydrogen bonding to three water mol­ecules. In (II), a twofold crystallographic axis runs through the one-dimensional {[Co(4,4′-bipy)(H2O)4]2+}n chains containing six-coordinate CoII; three-dimensional packing is provided by hydrogen bonding using all sulfonate and –PO3H O atoms as acceptors and the Co-bound water H atoms as donors. In this latter case, the benzenesulfonate aromatic rings are also constrained to a mirror plane. This report illustrates how a previously unreported dianion can affect the crystallization of polymeric metal complex cations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108028072/ga3106sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108028072/ga3106Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108028072/ga3106IIsup3.hkl
Contains datablock II

CCDC references: 687109; 687110

Comment top

During the past few years, interest in the design, synthesis, characterization and functions of hybrid inorganic–organic supramolecular compounds has been growing (Lehn, 1995). Usually, hydrogen bonding and ππ stacking interactions are important in solid-state assembly. In the case of ionic supramolecular compounds, the counterions play an important role in the stabilization of their structures through electrostatic interaction (Min & Suh, 2000; Noro et al., 2002). In general, small anions, such as NO3-, BF4-, ClO4-, PF6- etc., are used as counterions for cationic metal components. Reports on the use of phosphonic acids as a building block for supramolecular complexes are rare, although they have been shown to form extremely strong hydrogen bonds in their solid-state structures (Clearfield et al., 2001; Sharma & Clearfield, 2001). 3-Sulfophenylphosphonic acid, HO3S-C6H4-PO3H2, the first sulfonate–phosphonate ligand to be investigated, has recently been employed as a metal–organic coordination fragment due to its diverse coordination modes (Du et al., 2006a,b; Du, Li et al., 2007; Du, Prosvirin & Mao, 2007; Du, Xie & Wen, 2007; Du, Xu et al., 2007). When the deprotonated 3-sulfophenylphosphonic acid is not coordinated, it can also be employed as an organic counterion for constructing hybrid inorganic–organic supramolecular arrays. Here, we report the two title compounds, (I) and (II), which are the first examples illustrating two novel lattice architectures resulting from the association of metal–organic units with the [O3S-C6H4-PO3H]2- anion and water molecules.

The structure of compound (I) features one-dimensional chains of {[Ag(4,4'-bipy)]22+}n (4,4'-bipy is 4,4'-bipyridine) with [O3S-C6H4-PO3H]2- anions as counterions. There are two independent AgI ions in the asymmetric unit of (I) (Fig. 1). Both AgI ions are two-coordinated by two N atoms from two 4,4'-bipy ligands in a linear geometry (Table 1). The interconnection of the AgI ions by the bidentate bridging 4,4'-bipy ligands results in the formation of one-dimensional chains along the c axis. These chains are further assembled into a two-dimensional supramolecular layered architecture via weak ππ packing interactions (Fig. 2). One aryl ring in the 4,4'-bipy ligand is disordered, displaying two ring orientations (C7A/C8A/C9/C15A/C16A/N1 and C7B/C8B/C9/C15B/C16B/N1) (Fig. 1).

The [O3S-C6H4-PO3H]2- anion in (I) forms a dimer through two short hydrogen bonds between two pairs of twofold symmetry-related phosphonate O atoms, with the bonded H atoms (H4 and H5) located on a twofold axis (Fig. 3a and Table 2). This is a unique arrangement, with the most similar example being seen in diprotonated phosphonate groups (see, for example, Clarke et al., 2005). It is noted that symmetrical hydrogen bonds and hydrogen-bonded dimers with similar dimensions of other phosphonic acids have also been reported previously (Sharma & Clearfield, 2000a,b; Bowes et al., 2003; Man et al., 2006; Courtney et al., 2006; Latham et al., 2007). The dimer is further stabilized by extensive hydrogen bonding with solvent water molecules, using one phosphonate and two sulfonate O atoms as acceptors (Table 2). Coupled with this is a cyclic water tetramer formed by hydrogen-bonding associations between two O2W atoms and two O3W atoms (Fig. 4 and Table 1); the four O atoms are not coplanar, with the torsion angle O2Wii—O3W—O2Wiii—O3Wiv being ca 42.6° [symmetry codes: (ii) 1/2 - x, 1/2 - y, -1/2 + z; (iii) 1/2 + x, 1/2 - y, 1 - z; (iv) 1 - x, y, 1/2 - z Please check added text]. All water molecules act as a hydrogen-bond acceptor and two hydrogen-bond donors.

The hydrogen-bond interactions of these [O3S-C6H4-PO3H]2- dimers and water tetramers in (I) lead to the formation of a novel two-dimensional supramolecular layer aggregate (Fig. 4). The layer features two kinds of rings, dicussed according to graph-set analysis nomenclature (Bernstein et al., 1995). One ring, including one solvent water molecule, one [O3S-C6H4-PO3H]2- anion and one phosphonate group from another [O3S-C6H4-PO3H]2- anion, can be specified as having an R34(14) pattern, whereas the other ring, including five solvent water molecules, one [O3S-C6H4-PO3H]2- anion, and one phosphonate group and one sulfonate group from two other [O3S-C6H4-PO3H]2- anions, can be specified as having an R85(24) pattern. The whole packing scheme of (I) thus presents a layer structure following the alternating array pattern of ···ABAB···, where A is an [Ag(4,4'-bipy)]2 layer and B is an [(O3S-C6H4-PO3H).3(H2O)] layer.

The structure of compound (II) features one-dimensional cationic chains of {[Co(4,4'-bipy)(H2O)4]2+}n with similar dimer [O3S-C6H4-PO3H]2- anions as in (I). The cationic unit possesses twofold crystallographic symmetry, while the [O3S-C6H4-PO3H]2- anion is constrained to a mirror plane. The CoII ion is octahedrally coordinated by two N atoms from two symmetry-related 4,4'-bipy ligands and by two pairs of symmetry-related water molecules (Fig. 5 and Table 3). Although cationic {[Co(4,4'-bipy)(H2O)4]2+}n chains are commonly observed (see, for example, Wang et al., 2006), their supramolecular arrays are diverse and strongly affected by the different counterions being employed.

The dimer anions in (II) are similar to those in (I) through the common twofold symmetry relationship between each hydrogen-bonded [O3S-C6H4-PO3H]2- dimer centred on the bonded H atom (H3) (Table 4; Fig. 3b). In addition, the phenyl rings are all ordered and constrained to have mirror plane symmetry, so the dihedral angle bwteen the two phenyl rings in the dimer anion is 0°, whereas that in (I) is 24.5 (1)° for the ordered molecule. The dimer is stabilized by hydrogen bonding to two pairs of O2W water molecules, utilizing two pairs of sulfonate and two pairs of phosphonate O atoms as receptors. This dimer further utilizes its remaining one pair of sulfonate and one pair of phosphonate O atoms as receptors and is connected to four neighbouring dimers via the hydrogen-bonding associations of four pairs of O1W water molecules, leading to the formation of a novel two-dimensional supramolecular layer aggregate (Table 4; Fig. 6). This layer contains graph-set rings such as R24(8) and R44(12) etc., which are completely different to the supramolecular layer structure in (I). It is noted that all aqua molecules here act as hydrogen-bond donors and each is hydrogen-bonded to one phosphonate and one sulfonate O atom.

The interconnection of the CoII ions of (II) by the bidentate bridging 4,4'-bipy ligands results in the formation of one-dimensional chains along the b axis, which are further assembled into an extensive three-dimensional supramolecular architecture via the hydrogen-bond interactions described above (Fig. 7; Table 4).

In summary, two novel hydrogen-bonded layers directed by [O3S-C6H4-PO3H]2- anions have been observed in compounds (I) and (II). The [O3S-C6H4-PO3H]2- anions in both compounds form unique dimers via two short hydrogen bonds between two pairs of phosphonate O atoms, and are further hydrogen-bonded to solvent water or aqua molecules.

Related literature top

For related literature, see: Bernstein et al. (1995); Bowes et al. (2003); Clarke et al. (2005); Clearfield et al. (2001); Courtney et al. (2006); Du et al. (2006a, 2006b); Du, Li, Liu & Mao (2007); Du, Prosvirin & Mao (2007); Du, Xie & Wen (2007); Du, Xu, Li & Mao (2007); Latham et al. (2007); Lehn (1995); Man et al. (2006); Min & Suh (2000); Noro et al. (2002); Sharma & Clearfield (2000a, 2000b, 2001); Wang et al. (2006).

Experimental top

To prepare compound (I), a mixture of AgNO3 (56 mg, 0.33 mmol), 3-sulfophenylphosphonic acid (67 mg, 0.28 mmol) and 4,4'-bipy (52 mg, 0.33 mmol) in distilled water (10 ml) was placed in a Parr Teflon-lined autoclave (23 ml) and heated at 423 K for 4 d. Colourless column-shaped crystals of (I) were collected in a ca 72% yield based on Ag. Analysis, calculated for C26H27N4O9P1S1Ag2: C 38.16, H 3.33, N 6.85%; found: C 38.10, H 3.40, N 6.82%. IR data (KBr, ν, cm-1): 3429 (s), 3039 (m), 1599 (s), 1528 (m), 1486 (m), 1406 (m), 1217 (vs), 1190 (vs), 1107 (s), 1071 (m), 1037 (s), 995 (m), 904 (m), 851 (m), 803 (s), 732 (m), 689 (m), 618 (m), 564 (m), 531 (m).

To prepare compound (II), a mixture of CoCO3 (36 mg, 0.30 mmol), 3-sulfophenylphosphonic acid (83 mg, 0.35 mmol) and 4,4'-bipy (47 mg, 0.30 mmol) in distilled water (10 ml) was placed in a Parr Teflon-lined autoclave (23 ml) and heated at 413 K for 4 d. Orange brick-shaped crystals of (II) were collected in a ca 55% yield based on Co. Analysis, calculated for C16H21N2O10P1S1Co1: C 36.72, H 4.04, N 5.35%; found: C 36.68, H 4.11, N 5.31%. IR data (KBr, ν, cm-1): 3401 (s), 3071 (m), 1607 (s), 1534 (m), 1490 (m), 1414 (m), 1219 (m), 1171 (s), 1100 (vs), 1067 (s), 1030 (vs), 997 (s), 862 (m), 810 (m), 732 (m), 688 (m), 618 (m), 559 (m).

Refinement top

H atoms bonded to C atoms were positioned geometrically (C—H = 0.93 Å) and included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C). Water H atoms and H atoms of protonated PO3 were located in a difference map and refined with Uiso(H) = 1.5Ueq(O). Atoms C7, C8, C15 and C16 of the same benzene ring in (I) were found to be disordered and were modelled over two sets of positions (A and B), giving refined occupancies of 0.531 (6) and 0.469 (4)%, respectively. The anisotropic displacement parameters of atoms C15B and C16B were restrained due to their larger thermal parameter.

Computing details top

For both compounds, data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2000); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2000); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of compound (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. For the sake of clarity, only one orientation is shown for the disordered aryl ring (see text). Hydrogen bonds are represented by dashed lines. [Symmetry codes: (i) x, 1 - y, -1/2 + z; (ii) x, -y, 1/2 + z; (iii) x, 1 - y, 1/2 + z; (iv) x, -y, -1/2 + z.]
[Figure 2] Fig. 2. A view of the two-dimensional supramolecular layered architecture of {[Ag(C10H8N2)]22+}n in (I), down the b axis, showing the weak ππ interactions. Ag, N and C atoms are drawn as white, octant and black spheres, respectively.
[Figure 3] Fig. 3. The dimer of [O3S-C6H4-PO3H]2- anions in (a) compound (I) and (b) compound (II). H atoms attached to aryl C atoms have been omitted for clarity. The CPO3 and CSO3 groups are shaded in medium and light grey, respectively. O, C and H atoms are drawn as crossed, black and white spheres, respectively. Hydrogen bonds between [O3S-C6H4-PO3H]2- anions and water molecules are represented by dashed lines. [Symmetry code: (i) -x, 1 - y, -z.]
[Figure 4] Fig. 4. A view of the two-dimensional supramolecular layered architecture of {[(O3S-C6H4-PO3H)2-.3H2O])}n in (I), down the b axis. For display details, see the caption to Fig. 3. [Symmetry codes: (i) -x, y, 1/2 - z; (ii) 1/2 - x, 1/2 - y, -1/2 + z; (iii) 1/2 + x, 1/2 - y, 1 - z; (iv) 1 - x, y, 1/2 - z.]
[Figure 5] Fig. 5. The structure of compound (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Symmetry codes: (i) x, -1/2 + y, 1/2 - z; (ii) 1/2 - x, y, 1/2 - z; (iii)x, 1/2 + y, 1/2 - z; (iv) -x, y, z.]
[Figure 6] Fig. 6. Hydrogen-bond interactions between the [O3S-C6H4-PO3H]2- anions and aqua molecules in compound (II). For display details, see the caption to Fig. 3. [Symmetry codes: (i) 1/2 - x, y, 1/2 - z; (ii) 1/2 + x, -1/2 + y, z; (iii) 1/2 - x, 1/2 - y, -z.]
[Figure 7] Fig. 7. View of the structure of compound (II) down the c axis. H atoms have been omitted for clarity. Co atoms are drawn as white spheres; for other display details, see the caption to Fig. 3.
(I) catena-Poly[(µ-4,4'-bipyridine-κ2N:N')silver(I)] hydrogen 3-phosphonatobenzenesulfonate trihydrate] top
Crystal data top
[Ag2(C10H8N2)2](C6H5O6PS)·3H2ODx = 1.892 Mg m3
Mr = 818.29Melting point: not measured K
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 7948 reflections
a = 14.539 (3) Åθ = 2.0–27.5°
b = 17.472 (4) ŵ = 1.55 mm1
c = 22.623 (4) ÅT = 293 K
V = 5747 (2) Å3Column, colourless
Z = 80.50 × 0.12 × 0.12 mm
F(000) = 3264
Data collection top
Rigaku Mercury70
diffractometer
6577 independent reflections
Radiation source: fine-focus sealed tube6186 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan
(CrystalClear; Molecular Structure Corporation & Rigaku, 2000)
h = 1818
Tmin = 0.796, Tmax = 0.834k = 2222
42765 measured reflectionsl = 2829
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.027P)2 + 8.9577P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
6577 reflectionsΔρmax = 0.55 e Å3
434 parametersΔρmin = 0.44 e Å3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00031 (4)
Crystal data top
[Ag2(C10H8N2)2](C6H5O6PS)·3H2OV = 5747 (2) Å3
Mr = 818.29Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 14.539 (3) ŵ = 1.55 mm1
b = 17.472 (4) ÅT = 293 K
c = 22.623 (4) Å0.50 × 0.12 × 0.12 mm
Data collection top
Rigaku Mercury70
diffractometer
6577 independent reflections
Absorption correction: multi-scan
(CrystalClear; Molecular Structure Corporation & Rigaku, 2000)
6186 reflections with I > 2σ(I)
Tmin = 0.796, Tmax = 0.834Rint = 0.023
42765 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0363 restraints
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.55 e Å3
6577 reflectionsΔρmin = 0.44 e Å3
434 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*/UeqOcc. (<1)
Ag10.11592 (2)0.52605 (2)0.263230 (10)0.06095 (10)
Ag20.111672 (17)0.004184 (14)0.494212 (9)0.04443 (8)
S10.01092 (4)0.21176 (4)0.48855 (3)0.03244 (14)
P10.13992 (5)0.28290 (4)0.27070 (3)0.03245 (15)
N10.11647 (18)0.52311 (15)0.35801 (10)0.0421 (6)
N20.12518 (18)0.48507 (15)0.66924 (10)0.0441 (6)
N30.12372 (16)0.00461 (13)0.40033 (9)0.0356 (5)
N40.12292 (17)0.01041 (13)0.08803 (9)0.0372 (5)
C10.08605 (17)0.23371 (13)0.44416 (10)0.0275 (5)
C20.07593 (17)0.24737 (14)0.38402 (10)0.0283 (5)
H2A0.01780.24600.36700.034*
C30.15287 (17)0.26311 (14)0.34914 (10)0.0287 (5)
C40.23881 (18)0.26421 (17)0.37578 (11)0.0381 (6)
H4A0.29070.27420.35300.046*
C50.24829 (19)0.25064 (18)0.43591 (13)0.0427 (7)
H5A0.30640.25180.45310.051*
C60.17227 (19)0.23539 (16)0.47053 (11)0.0366 (6)
H6A0.17870.22640.51080.044*
C7A0.1496 (11)0.4583 (4)0.3829 (3)0.043 (2)0.58 (3)
H7A0.16920.41870.35850.051*0.58 (3)
C8A0.1554 (10)0.4490 (5)0.4432 (4)0.0392 (19)0.58 (3)
H8A0.17810.40360.45890.047*0.58 (3)
C7B0.1045 (14)0.4563 (7)0.3862 (5)0.045 (3)0.42 (3)
H7B0.09040.41370.36330.053*0.42 (3)
C8B0.1113 (15)0.4460 (7)0.4459 (5)0.041 (3)0.42 (3)
H8B0.10570.39740.46240.049*0.42 (3)
C90.12655 (18)0.50898 (14)0.48123 (11)0.0314 (5)
C100.12840 (18)0.50078 (15)0.54629 (11)0.0316 (5)
C110.1402 (3)0.43129 (18)0.57361 (13)0.0534 (8)
H11A0.14920.38750.55090.064*
C120.1389 (3)0.4258 (2)0.63420 (14)0.0649 (8)
H12A0.14800.37810.65130.078*
C130.1154 (3)0.5524 (2)0.64329 (14)0.0649 (8)
H13A0.10750.59530.66720.078*
C140.1162 (3)0.56266 (19)0.58311 (13)0.0689 (12)
H14A0.10860.61140.56730.083*
C15A0.0996 (8)0.5748 (7)0.4534 (6)0.037 (2)0.58 (3)
H15A0.08420.61760.47580.044*0.58 (3)
C16A0.0951 (9)0.5783 (8)0.3922 (6)0.039 (2)0.58 (3)
H16A0.07530.62380.37500.047*0.58 (3)
C15B0.1295 (14)0.5809 (11)0.4549 (9)0.040 (3)0.42 (3)
H15B0.13620.62450.47810.048*0.42 (3)
C16B0.1226 (14)0.5878 (11)0.3946 (8)0.040 (3)0.42 (3)
H16B0.12190.63630.37770.048*0.42 (3)
C170.1516 (2)0.05572 (16)0.36856 (11)0.0392 (6)
H17A0.16840.10020.38840.047*
C180.1564 (2)0.05479 (15)0.30776 (11)0.0380 (6)
H18A0.17600.09810.28750.046*
C190.13214 (18)0.01066 (14)0.27667 (11)0.0308 (5)
C200.13086 (18)0.01127 (14)0.21143 (11)0.0304 (5)
C210.1141 (2)0.05544 (16)0.18024 (12)0.0426 (7)
H21A0.10520.10130.20030.051*
C220.1106 (2)0.05355 (16)0.11946 (12)0.0458 (7)
H22A0.09920.09890.09930.055*
C230.1400 (2)0.07456 (17)0.11810 (12)0.0467 (7)
H23A0.14920.11960.09700.056*
C240.1446 (2)0.07733 (16)0.17894 (12)0.0433 (7)
H24A0.15690.12340.19800.052*
C250.1046 (2)0.07358 (15)0.31007 (11)0.0392 (6)
H25A0.08870.11910.29140.047*
C260.1008 (2)0.06836 (16)0.37082 (12)0.0416 (7)
H26A0.08150.11090.39220.050*
O10.00692 (16)0.13015 (12)0.49898 (10)0.0531 (6)
O1W0.2535 (2)0.2516 (2)0.38081 (12)0.0703 (8)
H110.202 (4)0.242 (3)0.398 (2)0.105*
H120.241 (4)0.256 (3)0.349 (2)0.105*
O20.00010 (16)0.25587 (15)0.54226 (9)0.0568 (6)
O2W0.0040 (2)0.24892 (17)0.66573 (12)0.0663 (7)
H210.011 (3)0.250 (3)0.631 (2)0.099*
H220.044 (4)0.262 (3)0.678 (2)0.099*
O30.09055 (14)0.23458 (15)0.45456 (9)0.0552 (6)
O3W0.3752 (2)0.18899 (18)0.25093 (13)0.0672 (8)
H310.401 (4)0.206 (3)0.274 (2)0.101*
H320.326 (4)0.219 (3)0.250 (2)0.101*
O40.08479 (15)0.21668 (11)0.24432 (8)0.0398 (4)
H40.00000.223 (3)0.25000.060*
O50.08278 (14)0.35699 (10)0.26710 (8)0.0385 (4)
H50.00000.348 (3)0.25000.058*
O60.23315 (15)0.28959 (14)0.24400 (9)0.0525 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.07049 (18)0.0959 (2)0.01643 (12)0.00276 (15)0.00092 (10)0.00254 (11)
Ag20.06214 (15)0.05730 (15)0.01386 (10)0.00112 (11)0.00122 (9)0.00027 (8)
S10.0391 (3)0.0384 (3)0.0198 (3)0.0014 (3)0.0049 (2)0.0009 (2)
P10.0406 (4)0.0379 (3)0.0188 (3)0.0024 (3)0.0021 (3)0.0030 (2)
N10.0589 (15)0.0484 (14)0.0190 (11)0.0034 (12)0.0009 (10)0.0028 (9)
N20.0577 (15)0.0571 (15)0.0177 (11)0.0049 (12)0.0015 (10)0.0028 (10)
N30.0527 (14)0.0390 (12)0.0152 (10)0.0045 (10)0.0000 (9)0.0015 (8)
N40.0548 (14)0.0416 (12)0.0152 (10)0.0038 (10)0.0005 (9)0.0017 (8)
C10.0356 (12)0.0263 (11)0.0204 (11)0.0003 (9)0.0002 (9)0.0002 (9)
C20.0307 (12)0.0332 (12)0.0210 (11)0.0008 (10)0.0028 (9)0.0015 (9)
C30.0349 (12)0.0308 (12)0.0205 (11)0.0010 (10)0.0000 (10)0.0024 (9)
C40.0338 (13)0.0492 (16)0.0313 (14)0.0076 (11)0.0014 (11)0.0018 (11)
C50.0336 (13)0.0601 (18)0.0345 (14)0.0048 (13)0.0108 (11)0.0011 (13)
C60.0457 (15)0.0426 (14)0.0216 (12)0.0019 (12)0.0058 (11)0.0020 (10)
C7A0.068 (6)0.040 (3)0.019 (2)0.005 (4)0.006 (4)0.008 (2)
C8A0.061 (6)0.030 (3)0.026 (3)0.005 (4)0.003 (4)0.0013 (19)
C7B0.059 (8)0.044 (5)0.030 (4)0.007 (5)0.003 (5)0.013 (3)
C8B0.072 (9)0.032 (4)0.019 (3)0.003 (5)0.001 (5)0.006 (3)
C90.0436 (14)0.0338 (13)0.0168 (11)0.0007 (11)0.0010 (10)0.0033 (9)
C100.0394 (13)0.0364 (13)0.0188 (12)0.0027 (11)0.0000 (10)0.0028 (9)
C110.096 (3)0.0379 (15)0.0266 (14)0.0043 (16)0.0037 (15)0.0017 (12)
C120.122 (2)0.0468 (13)0.0257 (11)0.0051 (14)0.0015 (13)0.0007 (9)
C130.122 (2)0.0468 (13)0.0257 (11)0.0051 (14)0.0015 (13)0.0007 (9)
C140.148 (4)0.0364 (16)0.0221 (14)0.007 (2)0.0016 (18)0.0048 (12)
C15A0.053 (5)0.032 (4)0.025 (3)0.003 (4)0.003 (4)0.002 (2)
C16A0.056 (5)0.033 (5)0.029 (3)0.004 (3)0.003 (4)0.003 (3)
C15B0.067 (8)0.033 (3)0.021 (3)0.015 (5)0.001 (5)0.002 (2)
C16B0.067 (8)0.033 (3)0.021 (3)0.015 (5)0.001 (5)0.002 (2)
C170.0614 (18)0.0336 (13)0.0225 (12)0.0006 (12)0.0023 (12)0.0016 (10)
C180.0607 (17)0.0331 (13)0.0200 (12)0.0037 (12)0.0013 (12)0.0023 (10)
C190.0447 (14)0.0317 (13)0.0160 (11)0.0042 (10)0.0004 (10)0.0012 (9)
C200.0418 (14)0.0343 (13)0.0153 (11)0.0024 (10)0.0013 (9)0.0004 (9)
C210.077 (2)0.0306 (13)0.0202 (12)0.0047 (13)0.0021 (13)0.0026 (10)
C220.081 (2)0.0345 (14)0.0221 (13)0.0045 (14)0.0052 (13)0.0029 (10)
C230.078 (2)0.0396 (15)0.0227 (13)0.0151 (15)0.0002 (13)0.0063 (11)
C240.075 (2)0.0333 (14)0.0216 (12)0.0140 (14)0.0029 (13)0.0009 (10)
C250.0664 (19)0.0314 (13)0.0198 (12)0.0029 (13)0.0006 (12)0.0003 (10)
C260.0645 (19)0.0374 (14)0.0229 (13)0.0027 (13)0.0031 (12)0.0051 (10)
O10.0661 (14)0.0409 (12)0.0523 (13)0.0069 (10)0.0152 (11)0.0120 (10)
O1W0.0633 (16)0.103 (2)0.0443 (15)0.0079 (15)0.0049 (13)0.0088 (15)
O20.0685 (15)0.0720 (16)0.0299 (11)0.0028 (12)0.0116 (10)0.0186 (10)
O2W0.089 (2)0.0716 (17)0.0388 (13)0.0074 (15)0.0056 (13)0.0009 (12)
O30.0370 (11)0.0911 (18)0.0375 (12)0.0118 (11)0.0049 (9)0.0142 (11)
O3W0.0784 (19)0.0725 (18)0.0507 (15)0.0123 (15)0.0045 (13)0.0157 (13)
O40.0538 (12)0.0331 (10)0.0326 (10)0.0054 (9)0.0071 (9)0.0077 (8)
O50.0569 (11)0.0286 (9)0.0301 (10)0.0037 (8)0.0063 (9)0.0021 (7)
O60.0484 (12)0.0772 (16)0.0319 (10)0.0050 (11)0.0109 (9)0.0102 (10)
Geometric parameters (Å, º) top
Ag1—N2i2.139 (2)C9—C15A1.369 (13)
Ag1—N12.145 (2)C9—C15B1.392 (19)
Ag2—N4ii2.131 (2)C9—C101.479 (4)
Ag2—N32.137 (2)C10—C111.373 (4)
Ag2—Ag2iii3.2610 (8)C10—C141.376 (4)
S1—O31.446 (2)C11—C121.374 (4)
S1—O11.446 (2)C11—H11A0.9300
S1—O21.447 (2)C12—H12A0.9300
S1—C11.773 (3)C13—C141.373 (4)
P1—O61.488 (2)C13—H13A0.9300
P1—O41.529 (2)C14—H14A0.9300
P1—O51.540 (2)C15A—C16A1.389 (10)
P1—C31.818 (2)C15A—H15A0.9300
N1—C16A1.274 (14)C16A—H16A0.9300
N1—C7B1.342 (14)C15B—C16B1.372 (16)
N1—C7A1.353 (10)C15B—H15B0.9300
N1—C16B1.404 (18)C16B—H16B0.9300
N2—C121.319 (4)C17—C181.377 (3)
N2—C131.323 (4)C17—H17A0.9300
N2—Ag1iv2.139 (2)C18—C191.388 (4)
N3—C171.339 (3)C18—H18A0.9300
N3—C261.341 (4)C19—C251.393 (4)
N4—C231.334 (4)C19—C201.476 (3)
N4—C221.337 (4)C20—C241.383 (4)
N4—Ag2v2.131 (2)C20—C211.384 (4)
C1—C61.389 (4)C21—C221.376 (4)
C1—C21.389 (3)C21—H21A0.9300
C2—C31.396 (3)C22—H22A0.9300
C2—H2A0.9300C23—C241.379 (4)
C3—C41.387 (4)C23—H23A0.9300
C4—C51.388 (4)C24—H24A0.9300
C4—H4A0.9300C25—C261.378 (4)
C5—C61.380 (4)C25—H25A0.9300
C5—H5A0.9300C26—H26A0.9300
C6—H6A0.9300O1W—H110.87 (5)
C7A—C8A1.375 (11)O1W—H120.74 (5)
C7A—H7A0.9300O2W—H210.82 (5)
C8A—C91.419 (9)O2W—H220.78 (5)
C8A—H8A0.9300O3W—H310.71 (5)
C7B—C8B1.366 (16)O3W—H320.88 (5)
C7B—H7B0.9300O4—H41.245 (5)
C8B—C91.378 (11)O5—H51.273 (6)
C8B—H8B0.9300
N2i—Ag1—N1172.38 (10)C15A—C9—C10123.0 (6)
N4ii—Ag2—N3170.82 (9)C8B—C9—C10120.1 (6)
N4ii—Ag2—Ag2iii89.93 (7)C15B—C9—C10120.9 (8)
N3—Ag2—Ag2iii99.10 (6)C8A—C9—C10121.8 (4)
O3—S1—O1113.00 (15)C11—C10—C14116.0 (3)
O3—S1—O2112.75 (15)C11—C10—C9122.4 (2)
O1—S1—O2112.55 (14)C14—C10—C9121.6 (3)
O3—S1—C1106.02 (12)C10—C11—C12120.6 (3)
O1—S1—C1105.88 (12)C10—C11—H11A119.7
O2—S1—C1105.90 (13)C12—C11—H11A119.7
O6—P1—O4112.24 (13)N2—C12—C11123.2 (3)
O6—P1—O5113.81 (13)N2—C12—H12A118.4
O4—P1—O5109.43 (11)C11—C12—H12A118.4
O6—P1—C3108.46 (12)N2—C13—C14123.7 (3)
O4—P1—C3106.94 (11)N2—C13—H13A118.1
O5—P1—C3105.51 (11)C14—C13—H13A118.1
C16A—N1—C7B109.8 (8)C13—C14—C10119.9 (3)
C16A—N1—C7A117.9 (7)C13—C14—H14A120.0
C7B—N1—C16B115.3 (9)C10—C14—H14A120.0
C7A—N1—C16B113.9 (9)C9—C15A—C16A120.6 (8)
C16A—N1—Ag1126.0 (6)C9—C15A—H15A119.7
C7B—N1—Ag1119.7 (5)C16A—C15A—H15A119.7
C7A—N1—Ag1116.0 (4)N1—C16A—C15A124.1 (8)
C16B—N1—Ag1124.8 (8)N1—C16A—H16A118.0
C12—N2—C13116.6 (3)C15A—C16A—H16A118.0
C12—N2—Ag1iv122.4 (2)C16B—C15B—C9120.1 (12)
C13—N2—Ag1iv121.0 (2)C16B—C15B—H15B119.9
C17—N3—C26117.5 (2)C9—C15B—H15B119.9
C17—N3—Ag2120.13 (18)C15B—C16B—N1121.4 (13)
C26—N3—Ag2122.30 (18)C15B—C16B—H16B119.3
C23—N4—C22117.1 (2)N1—C16B—H16B119.3
C23—N4—Ag2v124.39 (18)N3—C17—C18122.8 (3)
C22—N4—Ag2v118.48 (18)N3—C17—H17A118.6
C6—C1—C2120.8 (2)C18—C17—H17A118.6
C6—C1—S1118.63 (19)C17—C18—C19120.2 (2)
C2—C1—S1120.51 (19)C17—C18—H18A119.9
C1—C2—C3120.2 (2)C19—C18—H18A119.9
C1—C2—H2A119.9C18—C19—C25116.7 (2)
C3—C2—H2A119.9C18—C19—C20121.0 (2)
C4—C3—C2118.6 (2)C25—C19—C20122.2 (2)
C4—C3—P1120.98 (19)C24—C20—C21117.2 (2)
C2—C3—P1120.41 (19)C24—C20—C19122.4 (2)
C3—C4—C5120.9 (2)C21—C20—C19120.4 (2)
C3—C4—H4A119.6C22—C21—C20119.7 (3)
C5—C4—H4A119.6C22—C21—H21A120.1
C6—C5—C4120.6 (3)C20—C21—H21A120.1
C6—C5—H5A119.7N4—C22—C21123.1 (3)
C4—C5—H5A119.7N4—C22—H22A118.4
C5—C6—C1118.9 (2)C21—C22—H22A118.4
C5—C6—H6A120.6N4—C23—C24123.2 (3)
C1—C6—H6A120.6N4—C23—H23A118.4
N1—C7A—C8A122.2 (7)C24—C23—H23A118.4
N1—C7A—H7A118.9C23—C24—C20119.6 (3)
C8A—C7A—H7A118.9C23—C24—H24A120.2
C7A—C8A—C9119.7 (7)C20—C24—H24A120.2
C7A—C8A—H8A120.1C26—C25—C19120.0 (3)
C9—C8A—H8A120.1C26—C25—H25A120.0
N1—C7B—C8B125.2 (10)C19—C25—H25A120.0
N1—C7B—H7B117.4N3—C26—C25122.8 (3)
C8B—C7B—H7B117.4N3—C26—H26A118.6
C7B—C8B—C9118.6 (10)C25—C26—H26A118.6
C7B—C8B—H8B120.7H11—O1W—H12104 (5)
C9—C8B—H8B120.7H21—O2W—H2296 (5)
C15A—C9—C8B111.1 (7)H31—O3W—H32101 (5)
C8B—C9—C15B118.6 (9)P1—O4—H4114 (2)
C15A—C9—C8A115.2 (7)P1—O5—H5115 (2)
C15B—C9—C8A113.4 (9)
Symmetry codes: (i) x, y+1, z1/2; (ii) x, y, z+1/2; (iii) x, y, z+1; (iv) x, y+1, z+1/2; (v) x, y, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H11···O30.87 (5)2.06 (5)2.913 (4)167 (5)
O1W—H12···O6vi0.74 (5)2.19 (5)2.916 (3)166 (6)
O2W—H22···O3Wvii0.78 (5)2.20 (5)2.898 (4)149 (5)
O2W—H21···O20.82 (5)2.01 (5)2.796 (3)161 (5)
O3W—H32···O60.88 (5)1.84 (5)2.717 (4)174 (5)
O3W—H31···O2Wviii0.71 (5)2.09 (5)2.795 (4)171 (6)
O5—H5···O5vi1.27 (1)1.27 (1)2.528 (4)166 (5)
Symmetry codes: (vi) x, y, z+1/2; (vii) x+1/2, y+1/2, z+1/2; (viii) x+1/2, y+1/2, z+1.
(II) catena-Poly[µ-4,4'-bipyridine-κ2N:N'-tetraaquacobalt(II)] hydrogen 3-phosphonatobenzenesulfonate] top
Crystal data top
[Co(C10H8N2)2(H2O)4](C6H5O6PS)Dx = 1.693 Mg m3
Mr = 523.31Melting point: not measured K
Orthorhombic, CmcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2Cell parameters from 4587 reflections
a = 14.9569 (8) Åθ = 3.0–27.5°
b = 22.5625 (11) ŵ = 1.07 mm1
c = 12.1697 (7) ÅT = 293 K
V = 4106.8 (4) Å3Brick, orange
Z = 80.43 × 0.20 × 0.20 mm
F(000) = 2152
Data collection top
Rigaku Mercury70
diffractometer
2446 independent reflections
Radiation source: fine-focus sealed tube2337 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ω scansθmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan
CrystalClear (Molecular Structure Corporation & Rigaku, 2000)
h = 1916
Tmin = 0.771, Tmax = 0.811k = 2929
15395 measured reflectionsl = 1515
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0409P)2 + 9.3696P]
where P = (Fo2 + 2Fc2)/3
2446 reflections(Δ/σ)max = 0.001
171 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
[Co(C10H8N2)2(H2O)4](C6H5O6PS)V = 4106.8 (4) Å3
Mr = 523.31Z = 8
Orthorhombic, CmcaMo Kα radiation
a = 14.9569 (8) ŵ = 1.07 mm1
b = 22.5625 (11) ÅT = 293 K
c = 12.1697 (7) Å0.43 × 0.20 × 0.20 mm
Data collection top
Rigaku Mercury70
diffractometer
2446 independent reflections
Absorption correction: multi-scan
CrystalClear (Molecular Structure Corporation & Rigaku, 2000)
2337 reflections with I > 2σ(I)
Tmin = 0.771, Tmax = 0.811Rint = 0.030
15395 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.51 e Å3
2446 reflectionsΔρmin = 0.42 e Å3
171 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
Co10.25000.128788 (15)0.25000.02164 (13)
S10.00000.27459 (3)0.04910 (7)0.02563 (18)
P10.00000.51061 (3)0.16795 (7)0.02425 (19)
N10.25000.22178 (10)0.25000.0234 (5)
N20.25000.53483 (10)0.25000.0232 (5)
C10.00000.32943 (13)0.1546 (3)0.0270 (6)
C20.00000.31315 (16)0.2636 (3)0.0394 (8)
H2A0.00000.27330.28310.047*
C30.00000.35676 (18)0.3442 (3)0.0448 (9)
H3A0.00000.34600.41790.054*
C40.00000.41636 (15)0.3155 (3)0.0350 (7)
H4A0.00000.44520.37010.042*
C50.00000.43303 (13)0.2062 (3)0.0253 (6)
C60.00000.38905 (13)0.1249 (3)0.0264 (6)
H6A0.00000.39970.05110.032*
C70.23873 (16)0.25250 (10)0.15735 (19)0.0301 (5)
H7A0.23010.23170.09220.036*
C80.23925 (17)0.31367 (9)0.15357 (19)0.0301 (5)
H8A0.23240.33330.08690.036*
C90.25000.34546 (12)0.25000.0233 (6)
C100.25000.41125 (12)0.25000.0228 (6)
C110.27934 (16)0.44286 (9)0.15931 (18)0.0279 (5)
H11A0.29940.42320.09680.033*
C120.27836 (15)0.50412 (9)0.16307 (19)0.0276 (5)
H12A0.29850.52490.10190.033*
O10.08066 (12)0.28361 (7)0.01479 (15)0.0407 (4)
O20.00000.21758 (9)0.1056 (2)0.0348 (5)
O30.08390 (10)0.52101 (6)0.09627 (14)0.0300 (4)
H30.084 (3)0.50000.00000.045*
O40.00000.54849 (10)0.2688 (2)0.0330 (5)
O1W0.12786 (12)0.12656 (7)0.15875 (16)0.0341 (4)
H110.101 (2)0.1545 (15)0.146 (3)0.051*
H120.091 (2)0.1036 (14)0.184 (3)0.051*
O2W0.32333 (12)0.12520 (7)0.10323 (15)0.0307 (4)
H210.356 (2)0.1501 (13)0.082 (3)0.046*
H220.351 (2)0.0959 (13)0.097 (3)0.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0267 (2)0.01170 (19)0.0265 (2)0.0000.00236 (16)0.000
S10.0298 (4)0.0163 (3)0.0309 (4)0.0000.0000.0021 (3)
P10.0241 (4)0.0171 (4)0.0316 (4)0.0000.0000.0045 (3)
N10.0314 (13)0.0124 (11)0.0263 (13)0.0000.0000 (10)0.000
N20.0291 (13)0.0121 (10)0.0285 (13)0.0000.0041 (10)0.000
C10.0260 (15)0.0219 (14)0.0330 (17)0.0000.0000.0002 (12)
C20.057 (2)0.0239 (15)0.038 (2)0.0000.0000.0073 (14)
C30.068 (3)0.040 (2)0.0263 (18)0.0000.0000.0051 (15)
C40.0432 (19)0.0292 (16)0.0327 (18)0.0000.0000.0030 (14)
C50.0232 (14)0.0216 (13)0.0310 (16)0.0000.0000.0004 (12)
C60.0318 (16)0.0201 (13)0.0274 (16)0.0000.0000.0011 (12)
C70.0486 (14)0.0161 (9)0.0257 (11)0.0008 (9)0.0023 (10)0.0023 (8)
C80.0473 (14)0.0165 (10)0.0266 (11)0.0006 (9)0.0041 (10)0.0028 (8)
C90.0269 (14)0.0147 (13)0.0284 (15)0.0000.0013 (12)0.000
C100.0252 (14)0.0161 (12)0.0273 (15)0.0000.0047 (12)0.000
C110.0371 (12)0.0176 (10)0.0289 (11)0.0017 (8)0.0017 (10)0.0008 (8)
C120.0364 (11)0.0190 (10)0.0276 (11)0.0003 (9)0.0008 (10)0.0029 (8)
O10.0442 (10)0.0322 (9)0.0458 (11)0.0081 (7)0.0137 (8)0.0035 (8)
O20.0446 (14)0.0183 (10)0.0414 (14)0.0000.0000.0044 (9)
O30.0265 (8)0.0248 (7)0.0388 (9)0.0052 (6)0.0029 (7)0.0042 (7)
O40.0337 (12)0.0254 (11)0.0400 (14)0.0000.0000.0114 (10)
O1W0.0286 (9)0.0224 (8)0.0514 (11)0.0006 (6)0.0036 (8)0.0081 (7)
O2W0.0337 (9)0.0210 (7)0.0374 (9)0.0015 (6)0.0110 (7)0.0041 (7)
Geometric parameters (Å, º) top
Co1—N12.098 (2)C3—C41.389 (5)
Co1—O2W2.0976 (17)C3—H3A0.9300
Co1—O2Wi2.0976 (17)C4—C51.382 (5)
Co1—N2ii2.120 (2)C4—H4A0.9300
Co1—O1Wi2.1384 (18)C5—C61.401 (4)
Co1—O1W2.1384 (18)C6—H6A0.9300
S1—O11.4497 (18)C7—C81.381 (3)
S1—O1iii1.4498 (18)C7—H7A0.9300
S1—O21.458 (2)C8—C91.385 (3)
S1—C11.783 (3)C8—H8A0.9300
P1—O41.496 (2)C9—C8i1.385 (3)
P1—O31.5462 (16)C9—C101.484 (4)
P1—O3iii1.5462 (16)C10—C11i1.385 (3)
P1—C51.811 (3)C10—C111.385 (3)
N1—C7i1.334 (3)C11—C121.383 (3)
N1—C71.334 (3)C11—H11A0.9300
N2—C121.334 (3)C12—H12A0.9300
N2—C12i1.334 (3)O3—H31.2638 (16)
N2—Co1iv2.120 (2)O1W—H110.76 (3)
C1—C21.376 (5)O1W—H120.82 (3)
C1—C61.393 (4)O2W—H210.79 (3)
C2—C31.389 (5)O2W—H220.78 (3)
C2—H2A0.9300
N1—Co1—O2W92.21 (4)C3—C2—H2A120.3
N1—Co1—O2Wi92.21 (4)C2—C3—C4120.5 (3)
O2W—Co1—O2Wi175.58 (9)C2—C3—H3A119.7
N1—Co1—N2ii180.0C4—C3—H3A119.7
O2W—Co1—N2ii87.79 (4)C5—C4—C3120.4 (3)
O2Wi—Co1—N2ii87.79 (4)C5—C4—H4A119.8
N1—Co1—O1Wi91.35 (4)C3—C4—H4A119.8
O2W—Co1—O1Wi89.69 (7)C4—C5—C6119.1 (3)
O2Wi—Co1—O1Wi90.21 (7)C4—C5—P1120.7 (2)
N2ii—Co1—O1Wi88.65 (4)C6—C5—P1120.2 (2)
N1—Co1—O1W91.35 (4)C1—C6—C5120.1 (3)
O2W—Co1—O1W90.21 (7)C1—C6—H6A120.0
O2Wi—Co1—O1W89.69 (7)C5—C6—H6A120.0
N2ii—Co1—O1W88.65 (4)N1—C7—C8123.1 (2)
O1Wi—Co1—O1W177.30 (9)N1—C7—H7A118.4
O1—S1—O1iii112.65 (16)C8—C7—H7A118.4
O1—S1—O2112.13 (9)C7—C8—C9119.3 (2)
O1iii—S1—O2112.13 (9)C7—C8—H8A120.3
O1—S1—C1106.78 (9)C9—C8—H8A120.3
O1iii—S1—C1106.78 (9)C8i—C9—C8117.6 (3)
O2—S1—C1105.82 (15)C8i—C9—C10121.20 (13)
O4—P1—O3112.11 (8)C8—C9—C10121.20 (13)
O4—P1—O3iii112.11 (8)C11i—C10—C11118.0 (3)
O3—P1—O3iii108.50 (13)C11i—C10—C9120.98 (13)
O4—P1—C5109.96 (15)C11—C10—C9120.98 (13)
O3—P1—C5106.95 (8)C12—C11—C10119.0 (2)
O3iii—P1—C5106.95 (8)C12—C11—H11A120.5
C7i—N1—C7117.4 (3)C10—C11—H11A120.5
C7i—N1—Co1121.30 (13)N2—C12—C11123.3 (2)
C7—N1—Co1121.30 (13)N2—C12—H12A118.4
C12—N2—C12i117.4 (2)C11—C12—H12A118.4
C12—N2—Co1iv121.30 (12)P1—O3—H3117.8 (17)
C12i—N2—Co1iv121.30 (12)Co1—O1W—H11122 (2)
C2—C1—C6120.5 (3)Co1—O1W—H12113 (2)
C2—C1—S1120.6 (2)H11—O1W—H12104 (3)
C6—C1—S1118.9 (3)Co1—O2W—H21125 (2)
C1—C2—C3119.4 (3)Co1—O2W—H22113 (2)
C1—C2—H2A120.3H21—O2W—H22104 (3)
Symmetry codes: (i) x+1/2, y, z+1/2; (ii) x, y1/2, z+1/2; (iii) x, y, z; (iv) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H11···O20.76 (3)2.13 (3)2.880 (2)166 (3)
O1W—H12···O4ii0.82 (3)1.93 (3)2.745 (2)175 (3)
O2W—H21···O1v0.79 (3)1.95 (3)2.730 (2)170 (3)
O2W—H22···O3vi0.78 (3)1.95 (3)2.731 (2)174 (3)
O3—H3···O3vii1.26 (1)1.26 (1)2.528 (3)180 (4)
Symmetry codes: (ii) x, y1/2, z+1/2; (v) x+1/2, y+1/2, z; (vi) x+1/2, y1/2, z; (vii) x, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formula[Ag2(C10H8N2)2](C6H5O6PS)·3H2O[Co(C10H8N2)2(H2O)4](C6H5O6PS)
Mr818.29523.31
Crystal system, space groupOrthorhombic, PbcnOrthorhombic, Cmca
Temperature (K)293293
a, b, c (Å)14.539 (3), 17.472 (4), 22.623 (4)14.9569 (8), 22.5625 (11), 12.1697 (7)
V3)5747 (2)4106.8 (4)
Z88
Radiation typeMo KαMo Kα
µ (mm1)1.551.07
Crystal size (mm)0.50 × 0.12 × 0.120.43 × 0.20 × 0.20
Data collection
DiffractometerRigaku Mercury70
diffractometer
Rigaku Mercury70
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Molecular Structure Corporation & Rigaku, 2000)
Multi-scan
CrystalClear (Molecular Structure Corporation & Rigaku, 2000)
Tmin, Tmax0.796, 0.8340.771, 0.811
No. of measured, independent and
observed [I > 2σ(I)] reflections
42765, 6577, 6186 15395, 2446, 2337
Rint0.0230.030
(sin θ/λ)max1)0.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.078, 1.04 0.040, 0.092, 1.06
No. of reflections65772446
No. of parameters434171
No. of restraints30
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.55, 0.440.51, 0.42

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) for (I) top
Ag1—N2i2.139 (2)Ag2—N32.137 (2)
Ag1—N12.145 (2)Ag2—Ag2iii3.2610 (8)
Ag2—N4ii2.131 (2)
N2i—Ag1—N1172.38 (10)N4ii—Ag2—N3170.82 (9)
Symmetry codes: (i) x, y+1, z1/2; (ii) x, y, z+1/2; (iii) x, y, z+1.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1W—H11···O30.87 (5)2.06 (5)2.913 (4)167 (5)
O1W—H12···O6iv0.74 (5)2.19 (5)2.916 (3)166 (6)
O2W—H22···O3Wv0.78 (5)2.20 (5)2.898 (4)149 (5)
O2W—H21···O20.82 (5)2.01 (5)2.796 (3)161 (5)
O3W—H32···O60.88 (5)1.84 (5)2.717 (4)174 (5)
O3W—H31···O2Wvi0.71 (5)2.09 (5)2.795 (4)171 (6)
O5—H5···O5iv1.273 (6)1.273 (6)2.528 (4)166 (5)
Symmetry codes: (iv) x, y, z+1/2; (v) x+1/2, y+1/2, z+1/2; (vi) x+1/2, y+1/2, z+1.
Selected bond lengths (Å) for (II) top
Co1—N12.098 (2)Co1—N2i2.120 (2)
Co1—O2W2.0976 (17)Co1—O1W2.1384 (18)
Symmetry code: (i) x, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1W—H11···O20.76 (3)2.13 (3)2.880 (2)166 (3)
O1W—H12···O4i0.82 (3)1.93 (3)2.745 (2)175 (3)
O2W—H21···O1ii0.79 (3)1.95 (3)2.730 (2)170 (3)
O2W—H22···O3iii0.78 (3)1.95 (3)2.731 (2)174 (3)
O3—H3···O3iv1.2638 (16)1.2638 (16)2.528 (3)180 (4)
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x+1/2, y+1/2, z; (iii) x+1/2, y1/2, z; (iv) x, y+1, z.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds