Hydrogen-bonded layers directed by the [3-O₃S–C₆H₄–PO₃H]²⁻ dianion: catena-poly[[silver(I)-μ-4,4′-bipyridine-κ²N:N′] 3-[hydroxy(oxido)phos­phinoyl]benzene­sulfonate trihydrate] and catena-poly[[[tetra­aqua­cobalt(II)]-μ-4,4′-bipyridine-κ²N:N′] 3-[hydroxy(oxido)phosphinoyl]­benzene­sulfonate]

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 Ag^I 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 Co^II; 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.

S1. Comment

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 π–π 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 Ag^I ions in the asymmetric unit of (I) (Fig. 1). Both Ag^I ions are two-coordinated by two N atoms from two 4,4'-bipy ligands in a linear geometry (Table 1). The interconnection of the Ag^I 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 π–π 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—O3W^iv 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 Co^II 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 Co^II 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

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).

S2. Experimental

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).

S3. Refinement

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 U_iso(H) = 1.2U_eq(C). Water H atoms and H atoms of protonated PO₃ were located in a difference map and refined with U_iso(H) = 1.5U_eq(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

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

	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.]
	Fig. 2. A view of the two-dimensional supramolecular layered architecture of {[Ag(C10H8N2)]2^2+}n in (I), down the b axis, showing the weak π–π interactions. Ag, N and C atoms are drawn as white, octant and black spheres, respectively.
	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.]
	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.]
	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.]
	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.]
	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]

Crystal data

[Ag2(C10H8N2)2](C6H5O6PS)·3H2O	Dx = 1.892 Mg m^−3
Mr = 818.29	Melting point: not measured K
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 7948 reflections
a = 14.539 (3) Å	θ = 2.0–27.5°
b = 17.472 (4) Å	µ = 1.55 mm^−1
c = 22.623 (4) Å	T = 293 K
V = 5747 (2) Å^3	Column, colourless
Z = 8	0.50 × 0.12 × 0.12 mm
F(000) = 3264

Data collection

Rigaku Mercury70 diffractometer	6577 independent reflections
Radiation source: fine-focus sealed tube	6186 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (CrystalClear; Molecular Structure Corporation & Rigaku, 2000)	h = −18→18
Tmin = 0.796, Tmax = 0.834	k = −22→22
42765 measured reflections	l = −28→29

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.027P)^2 + 8.9577P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
6577 reflections	Δρmax = 0.55 e Å^−3
434 parameters	Δρmin = −0.44 e Å^−3
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00031 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ag1	0.11592 (2)	0.52605 (2)	0.263230 (10)	0.06095 (10)
Ag2	0.111672 (17)	0.004184 (14)	0.494212 (9)	0.04443 (8)
S1	−0.01092 (4)	0.21176 (4)	0.48855 (3)	0.03244 (14)
P1	0.13992 (5)	0.28290 (4)	0.27070 (3)	0.03245 (15)
N1	0.11647 (18)	0.52311 (15)	0.35801 (10)	0.0421 (6)
N2	0.12518 (18)	0.48507 (15)	0.66924 (10)	0.0441 (6)
N3	0.12372 (16)	−0.00461 (13)	0.40033 (9)	0.0356 (5)
N4	0.12292 (17)	−0.01041 (13)	0.08803 (9)	0.0372 (5)
C1	0.08605 (17)	0.23371 (13)	0.44416 (10)	0.0275 (5)
C2	0.07593 (17)	0.24737 (14)	0.38402 (10)	0.0283 (5)
H2A	0.0178	0.2460	0.3670	0.034*
C3	0.15287 (17)	0.26311 (14)	0.34914 (10)	0.0287 (5)
C4	0.23881 (18)	0.26421 (17)	0.37578 (11)	0.0381 (6)
H4A	0.2907	0.2742	0.3530	0.046*
C5	0.24829 (19)	0.25064 (18)	0.43591 (13)	0.0427 (7)
H5A	0.3064	0.2518	0.4531	0.051*
C6	0.17227 (19)	0.23539 (16)	0.47053 (11)	0.0366 (6)
H6A	0.1787	0.2264	0.5108	0.044*
C7A	0.1496 (11)	0.4583 (4)	0.3829 (3)	0.043 (2)	0.58 (3)
H7A	0.1692	0.4187	0.3585	0.051*	0.58 (3)
C8A	0.1554 (10)	0.4490 (5)	0.4432 (4)	0.0392 (19)	0.58 (3)
H8A	0.1781	0.4036	0.4589	0.047*	0.58 (3)
C7B	0.1045 (14)	0.4563 (7)	0.3862 (5)	0.045 (3)	0.42 (3)
H7B	0.0904	0.4137	0.3633	0.053*	0.42 (3)
C8B	0.1113 (15)	0.4460 (7)	0.4459 (5)	0.041 (3)	0.42 (3)
H8B	0.1057	0.3974	0.4624	0.049*	0.42 (3)
C9	0.12655 (18)	0.50898 (14)	0.48123 (11)	0.0314 (5)
C10	0.12840 (18)	0.50078 (15)	0.54629 (11)	0.0316 (5)
C11	0.1402 (3)	0.43129 (18)	0.57361 (13)	0.0534 (8)
H11A	0.1492	0.3875	0.5509	0.064*
C12	0.1389 (3)	0.4258 (2)	0.63420 (14)	0.0649 (8)
H12A	0.1480	0.3781	0.6513	0.078*
C13	0.1154 (3)	0.5524 (2)	0.64329 (14)	0.0649 (8)
H13A	0.1075	0.5953	0.6672	0.078*
C14	0.1162 (3)	0.56266 (19)	0.58311 (13)	0.0689 (12)
H14A	0.1086	0.6114	0.5673	0.083*
C15A	0.0996 (8)	0.5748 (7)	0.4534 (6)	0.037 (2)	0.58 (3)
H15A	0.0842	0.6176	0.4758	0.044*	0.58 (3)
C16A	0.0951 (9)	0.5783 (8)	0.3922 (6)	0.039 (2)	0.58 (3)
H16A	0.0753	0.6238	0.3750	0.047*	0.58 (3)
C15B	0.1295 (14)	0.5809 (11)	0.4549 (9)	0.040 (3)	0.42 (3)
H15B	0.1362	0.6245	0.4781	0.048*	0.42 (3)
C16B	0.1226 (14)	0.5878 (11)	0.3946 (8)	0.040 (3)	0.42 (3)
H16B	0.1219	0.6363	0.3777	0.048*	0.42 (3)
C17	0.1516 (2)	0.05572 (16)	0.36856 (11)	0.0392 (6)
H17A	0.1684	0.1002	0.3884	0.047*
C18	0.1564 (2)	0.05479 (15)	0.30776 (11)	0.0380 (6)
H18A	0.1760	0.0981	0.2875	0.046*
C19	0.13214 (18)	−0.01066 (14)	0.27667 (11)	0.0308 (5)
C20	0.13086 (18)	−0.01127 (14)	0.21143 (11)	0.0304 (5)
C21	0.1141 (2)	0.05544 (16)	0.18024 (12)	0.0426 (7)
H21A	0.1052	0.1013	0.2003	0.051*
C22	0.1106 (2)	0.05355 (16)	0.11946 (12)	0.0458 (7)
H22A	0.0992	0.0989	0.0993	0.055*
C23	0.1400 (2)	−0.07456 (17)	0.11810 (12)	0.0467 (7)
H23A	0.1492	−0.1196	0.0970	0.056*
C24	0.1446 (2)	−0.07733 (16)	0.17894 (12)	0.0433 (7)
H24A	0.1569	−0.1234	0.1980	0.052*
C25	0.1046 (2)	−0.07358 (15)	0.31007 (11)	0.0392 (6)
H25A	0.0887	−0.1191	0.2914	0.047*
C26	0.1008 (2)	−0.06836 (16)	0.37082 (12)	0.0416 (7)
H26A	0.0815	−0.1109	0.3922	0.050*
O1	−0.00692 (16)	0.13015 (12)	0.49898 (10)	0.0531 (6)
O1W	−0.2535 (2)	0.2516 (2)	0.38081 (12)	0.0703 (8)
H11	−0.202 (4)	0.242 (3)	0.398 (2)	0.105*
H12	−0.241 (4)	0.256 (3)	0.349 (2)	0.105*
O2	−0.00010 (16)	0.25587 (15)	0.54226 (9)	0.0568 (6)
O2W	−0.0040 (2)	0.24892 (17)	0.66573 (12)	0.0663 (7)
H21	0.011 (3)	0.250 (3)	0.631 (2)	0.099*
H22	0.044 (4)	0.262 (3)	0.678 (2)	0.099*
O3	−0.09055 (14)	0.23458 (15)	0.45456 (9)	0.0552 (6)
O3W	0.3752 (2)	0.18899 (18)	0.25093 (13)	0.0672 (8)
H31	0.401 (4)	0.206 (3)	0.274 (2)	0.101*
H32	0.326 (4)	0.219 (3)	0.250 (2)	0.101*
O4	0.08479 (15)	0.21668 (11)	0.24432 (8)	0.0398 (4)
H4	0.0000	0.223 (3)	0.2500	0.060*
O5	0.08278 (14)	0.35699 (10)	0.26710 (8)	0.0385 (4)
H5	0.0000	0.348 (3)	0.2500	0.058*
O6	0.23315 (15)	0.28959 (14)	0.24400 (9)	0.0525 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.07049 (18)	0.0959 (2)	0.01643 (12)	0.00276 (15)	−0.00092 (10)	−0.00254 (11)
Ag2	0.06214 (15)	0.05730 (15)	0.01386 (10)	−0.00112 (11)	0.00122 (9)	−0.00027 (8)
S1	0.0391 (3)	0.0384 (3)	0.0198 (3)	0.0014 (3)	0.0049 (2)	0.0009 (2)
P1	0.0406 (4)	0.0379 (3)	0.0188 (3)	−0.0024 (3)	0.0021 (3)	0.0030 (2)
N1	0.0589 (15)	0.0484 (14)	0.0190 (11)	−0.0034 (12)	−0.0009 (10)	−0.0028 (9)
N2	0.0577 (15)	0.0571 (15)	0.0177 (11)	−0.0049 (12)	−0.0015 (10)	0.0028 (10)
N3	0.0527 (14)	0.0390 (12)	0.0152 (10)	0.0045 (10)	0.0000 (9)	0.0015 (8)
N4	0.0548 (14)	0.0416 (12)	0.0152 (10)	0.0038 (10)	0.0005 (9)	−0.0017 (8)
C1	0.0356 (12)	0.0263 (11)	0.0204 (11)	−0.0003 (9)	0.0002 (9)	0.0002 (9)
C2	0.0307 (12)	0.0332 (12)	0.0210 (11)	0.0008 (10)	−0.0028 (9)	0.0015 (9)
C3	0.0349 (12)	0.0308 (12)	0.0205 (11)	−0.0010 (10)	0.0000 (10)	0.0024 (9)
C4	0.0338 (13)	0.0492 (16)	0.0313 (14)	−0.0076 (11)	0.0014 (11)	0.0018 (11)
C5	0.0336 (13)	0.0601 (18)	0.0345 (14)	−0.0048 (13)	−0.0108 (11)	0.0011 (13)
C6	0.0457 (15)	0.0426 (14)	0.0216 (12)	0.0019 (12)	−0.0058 (11)	0.0020 (10)
C7A	0.068 (6)	0.040 (3)	0.019 (2)	0.005 (4)	0.006 (4)	−0.008 (2)
C8A	0.061 (6)	0.030 (3)	0.026 (3)	0.005 (4)	0.003 (4)	−0.0013 (19)
C7B	0.059 (8)	0.044 (5)	0.030 (4)	0.007 (5)	0.003 (5)	−0.013 (3)
C8B	0.072 (9)	0.032 (4)	0.019 (3)	0.003 (5)	−0.001 (5)	−0.006 (3)
C9	0.0436 (14)	0.0338 (13)	0.0168 (11)	−0.0007 (11)	−0.0010 (10)	−0.0033 (9)
C10	0.0394 (13)	0.0364 (13)	0.0188 (12)	−0.0027 (11)	0.0000 (10)	−0.0028 (9)
C11	0.096 (3)	0.0379 (15)	0.0266 (14)	0.0043 (16)	0.0037 (15)	−0.0017 (12)
C12	0.122 (2)	0.0468 (13)	0.0257 (11)	0.0051 (14)	0.0015 (13)	−0.0007 (9)
C13	0.122 (2)	0.0468 (13)	0.0257 (11)	0.0051 (14)	0.0015 (13)	−0.0007 (9)
C14	0.148 (4)	0.0364 (16)	0.0221 (14)	0.007 (2)	−0.0016 (18)	−0.0048 (12)
C15A	0.053 (5)	0.032 (4)	0.025 (3)	0.003 (4)	0.003 (4)	−0.002 (2)
C16A	0.056 (5)	0.033 (5)	0.029 (3)	−0.004 (3)	−0.003 (4)	0.003 (3)
C15B	0.067 (8)	0.033 (3)	0.021 (3)	−0.015 (5)	−0.001 (5)	−0.002 (2)
C16B	0.067 (8)	0.033 (3)	0.021 (3)	−0.015 (5)	−0.001 (5)	−0.002 (2)
C17	0.0614 (18)	0.0336 (13)	0.0225 (12)	0.0006 (12)	−0.0023 (12)	−0.0016 (10)
C18	0.0607 (17)	0.0331 (13)	0.0200 (12)	−0.0037 (12)	−0.0013 (12)	0.0023 (10)
C19	0.0447 (14)	0.0317 (13)	0.0160 (11)	0.0042 (10)	0.0004 (10)	0.0012 (9)
C20	0.0418 (14)	0.0343 (13)	0.0153 (11)	0.0024 (10)	0.0013 (9)	0.0004 (9)
C21	0.077 (2)	0.0306 (13)	0.0202 (12)	0.0047 (13)	−0.0021 (13)	−0.0026 (10)
C22	0.081 (2)	0.0345 (14)	0.0221 (13)	0.0045 (14)	−0.0052 (13)	0.0029 (10)
C23	0.078 (2)	0.0396 (15)	0.0227 (13)	0.0151 (15)	0.0002 (13)	−0.0063 (11)
C24	0.075 (2)	0.0333 (14)	0.0216 (12)	0.0140 (14)	−0.0029 (13)	−0.0009 (10)
C25	0.0664 (19)	0.0314 (13)	0.0198 (12)	−0.0029 (13)	0.0006 (12)	−0.0003 (10)
C26	0.0645 (19)	0.0374 (14)	0.0229 (13)	−0.0027 (13)	0.0031 (12)	0.0051 (10)
O1	0.0661 (14)	0.0409 (12)	0.0523 (13)	−0.0069 (10)	0.0152 (11)	0.0120 (10)
O1W	0.0633 (16)	0.103 (2)	0.0443 (15)	0.0079 (15)	0.0049 (13)	0.0088 (15)
O2	0.0685 (15)	0.0720 (16)	0.0299 (11)	−0.0028 (12)	0.0116 (10)	−0.0186 (10)
O2W	0.089 (2)	0.0716 (17)	0.0388 (13)	−0.0074 (15)	0.0056 (13)	−0.0009 (12)
O3	0.0370 (11)	0.0911 (18)	0.0375 (12)	0.0118 (11)	0.0049 (9)	0.0142 (11)
O3W	0.0784 (19)	0.0725 (18)	0.0507 (15)	0.0123 (15)	−0.0045 (13)	−0.0157 (13)
O4	0.0538 (12)	0.0331 (10)	0.0326 (10)	0.0054 (9)	−0.0071 (9)	−0.0077 (8)
O5	0.0569 (11)	0.0286 (9)	0.0301 (10)	−0.0037 (8)	−0.0063 (9)	0.0021 (7)
O6	0.0484 (12)	0.0772 (16)	0.0319 (10)	−0.0050 (11)	0.0109 (9)	0.0102 (10)

Geometric parameters (Å, º)

Ag1—N2^i	2.139 (2)	C9—C15A	1.369 (13)
Ag1—N1	2.145 (2)	C9—C15B	1.392 (19)
Ag2—N4^ii	2.131 (2)	C9—C10	1.479 (4)
Ag2—N3	2.137 (2)	C10—C11	1.373 (4)
Ag2—Ag2^iii	3.2610 (8)	C10—C14	1.376 (4)
S1—O3	1.446 (2)	C11—C12	1.374 (4)
S1—O1	1.446 (2)	C11—H11A	0.9300
S1—O2	1.447 (2)	C12—H12A	0.9300
S1—C1	1.773 (3)	C13—C14	1.373 (4)
P1—O6	1.488 (2)	C13—H13A	0.9300
P1—O4	1.529 (2)	C14—H14A	0.9300
P1—O5	1.540 (2)	C15A—C16A	1.389 (10)
P1—C3	1.818 (2)	C15A—H15A	0.9300
N1—C16A	1.274 (14)	C16A—H16A	0.9300
N1—C7B	1.342 (14)	C15B—C16B	1.372 (16)
N1—C7A	1.353 (10)	C15B—H15B	0.9300
N1—C16B	1.404 (18)	C16B—H16B	0.9300
N2—C12	1.319 (4)	C17—C18	1.377 (3)
N2—C13	1.323 (4)	C17—H17A	0.9300
N2—Ag1^iv	2.139 (2)	C18—C19	1.388 (4)
N3—C17	1.339 (3)	C18—H18A	0.9300
N3—C26	1.341 (4)	C19—C25	1.393 (4)
N4—C23	1.334 (4)	C19—C20	1.476 (3)
N4—C22	1.337 (4)	C20—C24	1.383 (4)
N4—Ag2^v	2.131 (2)	C20—C21	1.384 (4)
C1—C6	1.389 (4)	C21—C22	1.376 (4)
C1—C2	1.389 (3)	C21—H21A	0.9300
C2—C3	1.396 (3)	C22—H22A	0.9300
C2—H2A	0.9300	C23—C24	1.379 (4)
C3—C4	1.387 (4)	C23—H23A	0.9300
C4—C5	1.388 (4)	C24—H24A	0.9300
C4—H4A	0.9300	C25—C26	1.378 (4)
C5—C6	1.380 (4)	C25—H25A	0.9300
C5—H5A	0.9300	C26—H26A	0.9300
C6—H6A	0.9300	O1W—H11	0.87 (5)
C7A—C8A	1.375 (11)	O1W—H12	0.74 (5)
C7A—H7A	0.9300	O2W—H21	0.82 (5)
C8A—C9	1.419 (9)	O2W—H22	0.78 (5)
C8A—H8A	0.9300	O3W—H31	0.71 (5)
C7B—C8B	1.366 (16)	O3W—H32	0.88 (5)
C7B—H7B	0.9300	O4—H4	1.245 (5)
C8B—C9	1.378 (11)	O5—H5	1.273 (6)
C8B—H8B	0.9300
N2^i—Ag1—N1	172.38 (10)	C15A—C9—C10	123.0 (6)
N4^ii—Ag2—N3	170.82 (9)	C8B—C9—C10	120.1 (6)
N4^ii—Ag2—Ag2^iii	89.93 (7)	C15B—C9—C10	120.9 (8)
N3—Ag2—Ag2^iii	99.10 (6)	C8A—C9—C10	121.8 (4)
O3—S1—O1	113.00 (15)	C11—C10—C14	116.0 (3)
O3—S1—O2	112.75 (15)	C11—C10—C9	122.4 (2)
O1—S1—O2	112.55 (14)	C14—C10—C9	121.6 (3)
O3—S1—C1	106.02 (12)	C10—C11—C12	120.6 (3)
O1—S1—C1	105.88 (12)	C10—C11—H11A	119.7
O2—S1—C1	105.90 (13)	C12—C11—H11A	119.7
O6—P1—O4	112.24 (13)	N2—C12—C11	123.2 (3)
O6—P1—O5	113.81 (13)	N2—C12—H12A	118.4
O4—P1—O5	109.43 (11)	C11—C12—H12A	118.4
O6—P1—C3	108.46 (12)	N2—C13—C14	123.7 (3)
O4—P1—C3	106.94 (11)	N2—C13—H13A	118.1
O5—P1—C3	105.51 (11)	C14—C13—H13A	118.1
C16A—N1—C7B	109.8 (8)	C13—C14—C10	119.9 (3)
C16A—N1—C7A	117.9 (7)	C13—C14—H14A	120.0
C7B—N1—C16B	115.3 (9)	C10—C14—H14A	120.0
C7A—N1—C16B	113.9 (9)	C9—C15A—C16A	120.6 (8)
C16A—N1—Ag1	126.0 (6)	C9—C15A—H15A	119.7
C7B—N1—Ag1	119.7 (5)	C16A—C15A—H15A	119.7
C7A—N1—Ag1	116.0 (4)	N1—C16A—C15A	124.1 (8)
C16B—N1—Ag1	124.8 (8)	N1—C16A—H16A	118.0
C12—N2—C13	116.6 (3)	C15A—C16A—H16A	118.0
C12—N2—Ag1^iv	122.4 (2)	C16B—C15B—C9	120.1 (12)
C13—N2—Ag1^iv	121.0 (2)	C16B—C15B—H15B	119.9
C17—N3—C26	117.5 (2)	C9—C15B—H15B	119.9
C17—N3—Ag2	120.13 (18)	C15B—C16B—N1	121.4 (13)
C26—N3—Ag2	122.30 (18)	C15B—C16B—H16B	119.3
C23—N4—C22	117.1 (2)	N1—C16B—H16B	119.3
C23—N4—Ag2^v	124.39 (18)	N3—C17—C18	122.8 (3)
C22—N4—Ag2^v	118.48 (18)	N3—C17—H17A	118.6
C6—C1—C2	120.8 (2)	C18—C17—H17A	118.6
C6—C1—S1	118.63 (19)	C17—C18—C19	120.2 (2)
C2—C1—S1	120.51 (19)	C17—C18—H18A	119.9
C1—C2—C3	120.2 (2)	C19—C18—H18A	119.9
C1—C2—H2A	119.9	C18—C19—C25	116.7 (2)
C3—C2—H2A	119.9	C18—C19—C20	121.0 (2)
C4—C3—C2	118.6 (2)	C25—C19—C20	122.2 (2)
C4—C3—P1	120.98 (19)	C24—C20—C21	117.2 (2)
C2—C3—P1	120.41 (19)	C24—C20—C19	122.4 (2)
C3—C4—C5	120.9 (2)	C21—C20—C19	120.4 (2)
C3—C4—H4A	119.6	C22—C21—C20	119.7 (3)
C5—C4—H4A	119.6	C22—C21—H21A	120.1
C6—C5—C4	120.6 (3)	C20—C21—H21A	120.1
C6—C5—H5A	119.7	N4—C22—C21	123.1 (3)
C4—C5—H5A	119.7	N4—C22—H22A	118.4
C5—C6—C1	118.9 (2)	C21—C22—H22A	118.4
C5—C6—H6A	120.6	N4—C23—C24	123.2 (3)
C1—C6—H6A	120.6	N4—C23—H23A	118.4
N1—C7A—C8A	122.2 (7)	C24—C23—H23A	118.4
N1—C7A—H7A	118.9	C23—C24—C20	119.6 (3)
C8A—C7A—H7A	118.9	C23—C24—H24A	120.2
C7A—C8A—C9	119.7 (7)	C20—C24—H24A	120.2
C7A—C8A—H8A	120.1	C26—C25—C19	120.0 (3)
C9—C8A—H8A	120.1	C26—C25—H25A	120.0
N1—C7B—C8B	125.2 (10)	C19—C25—H25A	120.0
N1—C7B—H7B	117.4	N3—C26—C25	122.8 (3)
C8B—C7B—H7B	117.4	N3—C26—H26A	118.6
C7B—C8B—C9	118.6 (10)	C25—C26—H26A	118.6
C7B—C8B—H8B	120.7	H11—O1W—H12	104 (5)
C9—C8B—H8B	120.7	H21—O2W—H22	96 (5)
C15A—C9—C8B	111.1 (7)	H31—O3W—H32	101 (5)
C8B—C9—C15B	118.6 (9)	P1—O4—H4	114 (2)
C15A—C9—C8A	115.2 (7)	P1—O5—H5	115 (2)
C15B—C9—C8A	113.4 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O3	0.87 (5)	2.06 (5)	2.913 (4)	167 (5)
O1W—H12···O6^vi	0.74 (5)	2.19 (5)	2.916 (3)	166 (6)
O2W—H22···O3W^vii	0.78 (5)	2.20 (5)	2.898 (4)	149 (5)
O2W—H21···O2	0.82 (5)	2.01 (5)	2.796 (3)	161 (5)
O3W—H32···O6	0.88 (5)	1.84 (5)	2.717 (4)	174 (5)
O3W—H31···O2W^viii	0.71 (5)	2.09 (5)	2.795 (4)	171 (6)
O5—H5···O5^vi	1.27 (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]

Crystal data

[Co(C10H8N2)2(H2O)4](C6H5O6PS)	Dx = 1.693 Mg m^−3
Mr = 523.31	Melting point: not measured K
Orthorhombic, Cmca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2	Cell parameters from 4587 reflections
a = 14.9569 (8) Å	θ = 3.0–27.5°
b = 22.5625 (11) Å	µ = 1.07 mm^−1
c = 12.1697 (7) Å	T = 293 K
V = 4106.8 (4) Å^3	Brick, orange
Z = 8	0.43 × 0.20 × 0.20 mm
F(000) = 2152

Data collection

Rigaku Mercury70 diffractometer	2446 independent reflections
Radiation source: fine-focus sealed tube	2337 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan CrystalClear (Molecular Structure Corporation & Rigaku, 2000)	h = −19→16
Tmin = 0.771, Tmax = 0.811	k = −29→29
15395 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0409P)^2 + 9.3696P] where P = (Fo^2 + 2Fc^2)/3
2446 reflections	(Δ/σ)max = 0.001
171 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.2500	0.128788 (15)	0.2500	0.02164 (13)
S1	0.0000	0.27459 (3)	0.04910 (7)	0.02563 (18)
P1	0.0000	0.51061 (3)	0.16795 (7)	0.02425 (19)
N1	0.2500	0.22178 (10)	0.2500	0.0234 (5)
N2	0.2500	0.53483 (10)	0.2500	0.0232 (5)
C1	0.0000	0.32943 (13)	0.1546 (3)	0.0270 (6)
C2	0.0000	0.31315 (16)	0.2636 (3)	0.0394 (8)
H2A	0.0000	0.2733	0.2831	0.047*
C3	0.0000	0.35676 (18)	0.3442 (3)	0.0448 (9)
H3A	0.0000	0.3460	0.4179	0.054*
C4	0.0000	0.41636 (15)	0.3155 (3)	0.0350 (7)
H4A	0.0000	0.4452	0.3701	0.042*
C5	0.0000	0.43303 (13)	0.2062 (3)	0.0253 (6)
C6	0.0000	0.38905 (13)	0.1249 (3)	0.0264 (6)
H6A	0.0000	0.3997	0.0511	0.032*
C7	0.23873 (16)	0.25250 (10)	0.15735 (19)	0.0301 (5)
H7A	0.2301	0.2317	0.0922	0.036*
C8	0.23925 (17)	0.31367 (9)	0.15357 (19)	0.0301 (5)
H8A	0.2324	0.3333	0.0869	0.036*
C9	0.2500	0.34546 (12)	0.2500	0.0233 (6)
C10	0.2500	0.41125 (12)	0.2500	0.0228 (6)
C11	0.27934 (16)	0.44286 (9)	0.15931 (18)	0.0279 (5)
H11A	0.2994	0.4232	0.0968	0.033*
C12	0.27836 (15)	0.50412 (9)	0.16307 (19)	0.0276 (5)
H12A	0.2985	0.5249	0.1019	0.033*
O1	0.08066 (12)	0.28361 (7)	−0.01479 (15)	0.0407 (4)
O2	0.0000	0.21758 (9)	0.1056 (2)	0.0348 (5)
O3	−0.08390 (10)	0.52101 (6)	0.09627 (14)	0.0300 (4)
H3	−0.084 (3)	0.5000	0.0000	0.045*
O4	0.0000	0.54849 (10)	0.2688 (2)	0.0330 (5)
O1W	0.12786 (12)	0.12656 (7)	0.15875 (16)	0.0341 (4)
H11	0.101 (2)	0.1545 (15)	0.146 (3)	0.051*
H12	0.091 (2)	0.1036 (14)	0.184 (3)	0.051*
O2W	0.32333 (12)	0.12520 (7)	0.10323 (15)	0.0307 (4)
H21	0.356 (2)	0.1501 (13)	0.082 (3)	0.046*
H22	0.351 (2)	0.0959 (13)	0.097 (3)	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0267 (2)	0.01170 (19)	0.0265 (2)	0.000	0.00236 (16)	0.000
S1	0.0298 (4)	0.0163 (3)	0.0309 (4)	0.000	0.000	0.0021 (3)
P1	0.0241 (4)	0.0171 (4)	0.0316 (4)	0.000	0.000	−0.0045 (3)
N1	0.0314 (13)	0.0124 (11)	0.0263 (13)	0.000	0.0000 (10)	0.000
N2	0.0291 (13)	0.0121 (10)	0.0285 (13)	0.000	−0.0041 (10)	0.000
C1	0.0260 (15)	0.0219 (14)	0.0330 (17)	0.000	0.000	0.0002 (12)
C2	0.057 (2)	0.0239 (15)	0.038 (2)	0.000	0.000	0.0073 (14)
C3	0.068 (3)	0.040 (2)	0.0263 (18)	0.000	0.000	0.0051 (15)
C4	0.0432 (19)	0.0292 (16)	0.0327 (18)	0.000	0.000	−0.0030 (14)
C5	0.0232 (14)	0.0216 (13)	0.0310 (16)	0.000	0.000	0.0004 (12)
C6	0.0318 (16)	0.0201 (13)	0.0274 (16)	0.000	0.000	0.0011 (12)
C7	0.0486 (14)	0.0161 (9)	0.0257 (11)	0.0008 (9)	−0.0023 (10)	−0.0023 (8)
C8	0.0473 (14)	0.0165 (10)	0.0266 (11)	0.0006 (9)	−0.0041 (10)	0.0028 (8)
C9	0.0269 (14)	0.0147 (13)	0.0284 (15)	0.000	−0.0013 (12)	0.000
C10	0.0252 (14)	0.0161 (12)	0.0273 (15)	0.000	−0.0047 (12)	0.000
C11	0.0371 (12)	0.0176 (10)	0.0289 (11)	0.0017 (8)	0.0017 (10)	−0.0008 (8)
C12	0.0364 (11)	0.0190 (10)	0.0276 (11)	−0.0003 (9)	0.0008 (10)	0.0029 (8)
O1	0.0442 (10)	0.0322 (9)	0.0458 (11)	−0.0081 (7)	0.0137 (8)	−0.0035 (8)
O2	0.0446 (14)	0.0183 (10)	0.0414 (14)	0.000	0.000	0.0044 (9)
O3	0.0265 (8)	0.0248 (7)	0.0388 (9)	0.0052 (6)	−0.0029 (7)	−0.0042 (7)
O4	0.0337 (12)	0.0254 (11)	0.0400 (14)	0.000	0.000	−0.0114 (10)
O1W	0.0286 (9)	0.0224 (8)	0.0514 (11)	0.0006 (6)	−0.0036 (8)	0.0081 (7)
O2W	0.0337 (9)	0.0210 (7)	0.0374 (9)	0.0015 (6)	0.0110 (7)	0.0041 (7)

Geometric parameters (Å, º)

Co1—N1	2.098 (2)	C3—C4	1.389 (5)
Co1—O2W	2.0976 (17)	C3—H3A	0.9300
Co1—O2W^i	2.0976 (17)	C4—C5	1.382 (5)
Co1—N2^ii	2.120 (2)	C4—H4A	0.9300
Co1—O1W^i	2.1384 (18)	C5—C6	1.401 (4)
Co1—O1W	2.1384 (18)	C6—H6A	0.9300
S1—O1	1.4497 (18)	C7—C8	1.381 (3)
S1—O1^iii	1.4498 (18)	C7—H7A	0.9300
S1—O2	1.458 (2)	C8—C9	1.385 (3)
S1—C1	1.783 (3)	C8—H8A	0.9300
P1—O4	1.496 (2)	C9—C8^i	1.385 (3)
P1—O3	1.5462 (16)	C9—C10	1.484 (4)
P1—O3^iii	1.5462 (16)	C10—C11^i	1.385 (3)
P1—C5	1.811 (3)	C10—C11	1.385 (3)
N1—C7^i	1.334 (3)	C11—C12	1.383 (3)
N1—C7	1.334 (3)	C11—H11A	0.9300
N2—C12	1.334 (3)	C12—H12A	0.9300
N2—C12^i	1.334 (3)	O3—H3	1.2638 (16)
N2—Co1^iv	2.120 (2)	O1W—H11	0.76 (3)
C1—C2	1.376 (5)	O1W—H12	0.82 (3)
C1—C6	1.393 (4)	O2W—H21	0.79 (3)
C2—C3	1.389 (5)	O2W—H22	0.78 (3)
C2—H2A	0.9300
N1—Co1—O2W	92.21 (4)	C3—C2—H2A	120.3
N1—Co1—O2W^i	92.21 (4)	C2—C3—C4	120.5 (3)
O2W—Co1—O2W^i	175.58 (9)	C2—C3—H3A	119.7
N1—Co1—N2^ii	180.0	C4—C3—H3A	119.7
O2W—Co1—N2^ii	87.79 (4)	C5—C4—C3	120.4 (3)
O2W^i—Co1—N2^ii	87.79 (4)	C5—C4—H4A	119.8
N1—Co1—O1W^i	91.35 (4)	C3—C4—H4A	119.8
O2W—Co1—O1W^i	89.69 (7)	C4—C5—C6	119.1 (3)
O2W^i—Co1—O1W^i	90.21 (7)	C4—C5—P1	120.7 (2)
N2^ii—Co1—O1W^i	88.65 (4)	C6—C5—P1	120.2 (2)
N1—Co1—O1W	91.35 (4)	C1—C6—C5	120.1 (3)
O2W—Co1—O1W	90.21 (7)	C1—C6—H6A	120.0
O2W^i—Co1—O1W	89.69 (7)	C5—C6—H6A	120.0
N2^ii—Co1—O1W	88.65 (4)	N1—C7—C8	123.1 (2)
O1W^i—Co1—O1W	177.30 (9)	N1—C7—H7A	118.4
O1—S1—O1^iii	112.65 (16)	C8—C7—H7A	118.4
O1—S1—O2	112.13 (9)	C7—C8—C9	119.3 (2)
O1^iii—S1—O2	112.13 (9)	C7—C8—H8A	120.3
O1—S1—C1	106.78 (9)	C9—C8—H8A	120.3
O1^iii—S1—C1	106.78 (9)	C8^i—C9—C8	117.6 (3)
O2—S1—C1	105.82 (15)	C8^i—C9—C10	121.20 (13)
O4—P1—O3	112.11 (8)	C8—C9—C10	121.20 (13)
O4—P1—O3^iii	112.11 (8)	C11^i—C10—C11	118.0 (3)
O3—P1—O3^iii	108.50 (13)	C11^i—C10—C9	120.98 (13)
O4—P1—C5	109.96 (15)	C11—C10—C9	120.98 (13)
O3—P1—C5	106.95 (8)	C12—C11—C10	119.0 (2)
O3^iii—P1—C5	106.95 (8)	C12—C11—H11A	120.5
C7^i—N1—C7	117.4 (3)	C10—C11—H11A	120.5
C7^i—N1—Co1	121.30 (13)	N2—C12—C11	123.3 (2)
C7—N1—Co1	121.30 (13)	N2—C12—H12A	118.4
C12—N2—C12^i	117.4 (2)	C11—C12—H12A	118.4
C12—N2—Co1^iv	121.30 (12)	P1—O3—H3	117.8 (17)
C12^i—N2—Co1^iv	121.30 (12)	Co1—O1W—H11	122 (2)
C2—C1—C6	120.5 (3)	Co1—O1W—H12	113 (2)
C2—C1—S1	120.6 (2)	H11—O1W—H12	104 (3)
C6—C1—S1	118.9 (3)	Co1—O2W—H21	125 (2)
C1—C2—C3	119.4 (3)	Co1—O2W—H22	113 (2)
C1—C2—H2A	120.3	H21—O2W—H22	104 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O2	0.76 (3)	2.13 (3)	2.880 (2)	166 (3)
O1W—H12···O4^ii	0.82 (3)	1.93 (3)	2.745 (2)	175 (3)
O2W—H21···O1^v	0.79 (3)	1.95 (3)	2.730 (2)	170 (3)
O2W—H22···O3^vi	0.78 (3)	1.95 (3)	2.731 (2)	174 (3)
O3—H3···O3^vii	1.26 (1)	1.26 (1)	2.528 (3)	180 (4)

Symmetry codes: (ii) x, y−1/2, −z+1/2; (v) −x+1/2, −y+1/2, −z; (vi) x+1/2, y−1/2, z; (vii) x, −y+1, −z.