Two novel mixed-ligand complexes containing organosulfonate ligands

The structures reported herein, viz. bis­(4-amino­naphthalene-1-sulfonato-κO)bis­(4,5-diaza­fluoren-9-one-κ²N,N′)copper(II), [Cu(C₁₀H₈NO₃S)₂(C₁₁H₆N₂O)₂], (I), and poly[[[diaqua­cadmium(II)]-bis­(μ-4-aminona­phthalene-1-sulfonato)-κ²O:N;κ²N:O] dihydrate], {[Cd(C₁₀H₈NO₃S)₂(H₂O)₂]·2H₂O}_n, (II), are rare examples of sulfonate-containing complexes where the anion does not fulfill a passive charge-balancing role, but takes an active part in coordination as a monodentate and/or bridging ligand. Monomeric complex (I) possesses a crystallographic inversion center at the Cu^II atom, and the asymmetric unit contains one-half of a Cu atom, one complete 4-amino­naphthalene-1-sulfonate (ans) ligand and one 4,5-diaza­fluoren-9-one (DAFO) ligand. The Cu^II atom has an elongated distorted octa­hedral coordination geometry formed by two O atoms from two monodentate ans ligands and by four N atoms from two DAFO mol­ecules. Complex (II) is polymeric and its crystal structure is built up by one-dimensional chains and solvent water mol­ecules. Here also the cation (a Cd^II atom) lies on a crystallographic inversion center and adopts a slightly distorted octa­hedral geometry. Each ans anion serves as a bridging ligand linking two Cd^II atoms into one-dimensional infinite chains along the [010] direction, with each Cd^II center coordinated by four ans ligands via O and N atoms and by two aqua ligands. In both structures, there are significant π–π stacking inter­actions between adjacent ligands and hydrogen bonds contribute to the formation of two- and three-dimensional networks.

S1. Comment

Owing to their weak coordination abilities to transition metal atoms, most of the reported complexes containing organosulfonate ligands are aqua–metal salts and the sulfonate species only acts as a counter-anion to balance the charge within the complex (Kosnic et al., 1992; Shubnell et al., 1994; Gunderman et al., 1997). In some rare cases, however, the sulfonate ligand can also bind to the metal centers in the presence of ancillary ligands (Cai, Chen, Liao, Feng & Chen, 2001; Cai, Chen, Liao, Yao et al., 2001; Chen et al., 2002). It is well known that the coordination behavior of one ligand can be influenced by the others within a mixed-ligand complex.

In this respect, 4-aminonaphthalene-1-sulfonate could be a potential bridging ligand, since it contains sulfonate and NH₂ groups located at opposite sides of a benzene ring, and could exhibit versatile coordination modes in the presence of adequate ancillary ligands. This behavior would be similar to that of p-aminobenzene sulfonate (Endres, 1984; Brodersen & Beck, 1987; Starynowicz, 1992; Shakri & Haussuhl, 1992a,b; Gunderman et al., 1996; Zhou et al., 2004). For p-aminobenzene sulfonate, it is common that the two functional groups simultaneously bind to metal ions; however, to our knowledge, no example of such behavior has been reported for 4-aminonaphthalene-1-sulfonate. As part of an investigation of the coordination behavior of sulfonates, a series of mixed-ligand complexes have been synthesized so far; in our previous work, the sulfonate group behaved only as a charge balance counter-anion (Li et al., 2005a,b, 2006, 2007). In order to obtain complexes in which the sulfonate group directly binds to the metal, ligands with a large conjugate plane, such as 2,2'-bipyridine, 1,10-phenanthroline and dipyridophenazine, were used as ancillary ligands. We present here two novel complexes in which the sulfonate group exhibits such behaviour, viz. [Cu(DAFO)₂(ans)₂], (I), and {[Cd(ans)₂(H₂O)₂].2H₂O}_n, (II) [where ans is 4-aminonaphthalene-1-sulfonate and DAFO is 4,5-diazafluorene-9-one).

The asymmetric unit of (I) consists of half a Cu atom, one complete ans ion and one neutral DAFO ligand (Fig. 1). The Cu^II atom lies on a crystallographic inversion centre and has an elongated distorted octahedral coordination geometry, formed by two O atoms from two monodentate ans ligands and by four N atoms from two DAFO molecules; the manner of coordination is unusual in that the elongated Jahn–Teller (J–T) axis of the molecule lies along one of the N—Cu—N vectors [Cu1—N2 = 2.6231 (18) Å] and not on the O—Cu—O axis [Cu1—O2 = 1.9890</span><span style=" font-weight:600;">(14) Å and O2—Cu1—O2 = 180°], which is occupied by ans counter-ions. As far as we know, this is one of the few examples of N₂O₂N₂' coordination to a Cu^II center with two anions bound trans in the equatorial plane and N atoms of the chelate directed along the J–T axis (Menon & Rajasekharan, 1998). This N₂X₂N₂' geometry has been observed in other Cu^II complexes with the 4,5-diazafluorene template and simple anions such as Cl^- or Br^- (Menon & Rajasekharan, 1998), while complexes with transition metals other than Cu^II, such as Re^I (Yam et al., 1998) and Ni^II (Xiong et al., 1996), typically exhibit a more symmetrical coordination.

Both ligands are planar within an r.m.s. deviation of 0.002 Å, with largest departures from the least-squares plane of 0.055 (2) Å for atom C9 in DAFO and 0.038 (2) Å for atom C13 in ans. Owing to the characteristic conjugated structures of both ligands there are not only intramolecular but also intermolecular π–π stacking interactions between adjacent planes. To describe the latter let us define Cg1 as the centroid of the C12–C17 benzene ring in ans and Cg2ⁱ as the centroid of the C4–C7/C11 ring in a symmetry related DAFO molecule [symmetry code (i): x + 2, -y + 1, -z], with α the dihedral angle between the two rings and β the angle between the intercentroid vector and the Cg1 plane. The values Cg1···Cg2ⁱ = 3.3570 (12) Å, α = 4.44° and β = 19.52° indicate that there is a significant intramolecular π–π aromatic stacking interaction (Evans & Boeyens, 1989). At the same time, there is a significant intermolecular π–π stacking interaction involving Cg1 and a neighbouring pyridine ring (Cg1···Cg3ⁱⁱⁱ = 3.5232 (11) Å; Cg3 is the centroid of the C7—C11/N2 ring; symmetry code: (iii) x - 1/2, -y + 1/2, -z).

Hydrogen-bond interactions play a key role in the formation of two-dimensional sheets and three-dimensional networks and in the stabilization of the crystal structure of (I). As shown in Fig. 2, one neutral complex links four neighbouring ones via N—H···O(S) bonds, forming two-dimensional layers extending in the (100) plane. Nonclassical C—H···O and C—H···N hydrogen bonds as well as the previously discussed π–π stacking interactions take part in the formation of a three-dimensional network.

Complex (II) (Fig. 3) also possesses a crystallographic inversion centre, this time located at the Cd^II atom, which displays a distorted octahedral geometry. The Cd atom is coordinated by four O atoms from two ans ligands and two water molecules, and by two N atoms belonging to another two ans anions, a situation similar to that in complexes of p-aminobenzene sulfonate with Zn^II, Co^II and Cd^II (Shakeri & Haussuhl, 1992a,b; Zhou et al., 2004). The Cd—O_water distances (Table 2) are in agreement with that within the complex of [Cd(µ₂-N,O-p-NH₂C₆H₄SO₃)₂(H₂O)₂]_n [2.303 (2) Å; Zhou et al., 2004], and the Cd—O(S) length (Table 2) is slightly longer than its counterpart in [Cd(µ₂-N,O-p-NH₂C₆H₄SO₃)₂(H₂O)₂]_n (2.294 Å). The Cd—N distance is close to that in [Cd(µ₂-N,O-p-NH₂C₆H₄SO₃)₂(H₂O)₂]_n [2.373 (3) Å] and longer than the equivalent Cd—N distances in [Cd(en)₂(H₂O)₂](ans)₂.2H₂O [2.240 (2) and 2.280 (2) Å; Li et al., 2006].

Each ans ligand links two cadmium(II) cations though O and N atoms; there are two such centrosymmetric bridges per Cd pair, defining a dimeric unit with a Cd···Cd distance of 9.2553 (6) Å (Fig. 3). Concatenation of these dimers leads to a doubly bridged, one-dimensional polymeric chain extending along [010]. The centroid–centroid distance, Cg1···Cg2^v, between phenyl rings in two symmetry related ans ligands is 3.5676 (9) Å [Cg1 and Cg2 are the centroids of the C1—C6 and C5—C10 rings, resepctively; symmetry code: (v) -x+1, -y + 2, -z+1), while α and β are 1.93 and 17.48°, respectively, indicating a significant π–π stacking interaction.

Hydrogen bonding plays a key role in the formation of a three-dimensional network through the linkage of chains and solvent water molecules. Fig. 4 shows the way in which this is achieved, with neighboring chains (pointing out of the projection plane in the [100] direction) linked through an extensive hydrogen-bond network involving all water molecules in a series of O—H···O_water, O—H···O(S) and N—H···O interactions (Table 4).

Related literature

For related literature, see: Brodersen & Beck (1987); Cai et al. (2001a, 2001b); Chen et al. (2002); Endres (1984); Evans & Boeyens (1989); Gunderman et al. (1996, 1997); Kosnic et al. (1992); Li et al. (2005a, 2005b, 2006, 2007); Menon & Rajasekharan (1998); Shakeri & Haussuhl (1992a, 1992b); Shubnell et al. (1994); Starynowicz (1992); Xiong et al. (1996); Yam et al. (1998); Zhou et al. (2004).

S2. Experimental

For the preparation of complex (I), an acetonitrile solution (10 ml) of 4,5-diazafluorene-9-one (0.183 g, 1 mmol) was added to an aqueous solution (20 ml) of Cu(OAc)₂.H₂O (0.100 g, 0.5 mmol) under constant stirring. After the mixture had been stirred for 2 h at 298 K, the solution was treated with 4-aminonaphthalene-1-sulfonic acid sodium salt tetrahydrate (0.32 g, 1 mmol) in 10 ml of methanol. After filtration, the red solution was allowed to stand at room temperature. Well shaped red block-shaped crystals were obtained by slow evaporation of the solvent over a period of about one week. Complex (II) was obtained as a by-product of the reaction of dipyridophenazine (0.283 g, 1 mmol), Cd(OAc)₂.2H₂O (0.133 g, 0.5 mmol) and 4-aminonaphthalene-1-sulfonic acid sodium salt tetrahydrate (0.32 g, 1 mmol) within mixed a solvent of water and acetonitrile (quantity?).

S3. Refinement

H atoms of water molecules and amine groups were located in a difference Fourier map and refined with the restraints O—H = 0.77 (3)–0.82 (2) Å and N—H = 0.79 (2)–0.83 (2) Å for (II), and N—H = 0.86 (3)–0.87 (3) Å for (I) [please give the values of the actual restraints used rather than the final distances obtained]; their U_iso(H) values were refined freely. C-bound H atoms were placed in geometrically idealized positions and treated as riding [C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)].

Computing details

For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level. [Symmetry code: (i) -x + 2, -y + 1, -z.]
	Fig. 2. Hydrogen-bonded two-dimensional sheets in (I). Some atoms have been omitted for clarity; hydrogen bonds are shown as dashed lines.
	Fig. 3. The molecular structure of (II), showing displacement ellipsoids at the 30% probability level. [Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+2, -z+2; (iii) -x+2, -y+2, -z+ ; (vii) x-1, y, z
	Fig. 4. The molecular packing of (II), with hydrogen bonds shown as dashed lines; some atoms have been omitted for clarity.

(I) Bis(4-aminonaphthalene-1-sulfonato-κO)bis(4,5-diazafluorene-9- one-κ²N,N')copper(II)

Crystal data

[Cu(C10H8NO3S)2(C11H6N2O)2]	F(000) = 1788
Mr = 872.36	Dx = 1.617 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5691 reflections
a = 14.8903 (13) Å	θ = 2.3–28.2°
b = 13.9907 (12) Å	µ = 0.80 mm^−1
c = 17.1961 (15) Å	T = 273 K
V = 3582.4 (5) Å^3	Block, red
Z = 4	0.48 × 0.14 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4319 independent reflections
Radiation source: fine-focus sealed tube	3396 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
phi and ω scans	θmax = 28.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −19→19
Tmin = 0.701, Tmax = 0.925	k = −18→9
22653 measured reflections	l = −22→22

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.049P)^2 + 1.8415P] where P = (Fo^2 + 2Fc^2)/3
4319 reflections	(Δ/σ)max = 0.001
276 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.34 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
Cu1	1.0000	0.5000	0.0000	0.02860 (10)
O1	0.68925 (11)	0.59330 (15)	0.23206 (10)	0.0629 (5)
N1	0.96807 (10)	0.54735 (10)	0.10539 (8)	0.0276 (3)
O2	0.99739 (9)	0.36895 (10)	0.04478 (8)	0.0406 (3)
S1	1.06197 (4)	0.29337 (4)	0.06827 (3)	0.03833 (14)
O4	1.01341 (12)	0.21419 (12)	0.10155 (9)	0.0542 (4)
O3	1.13417 (12)	0.33040 (13)	0.11557 (8)	0.0579 (4)
C1	1.02248 (13)	0.57913 (14)	0.16263 (11)	0.0326 (4)
H1	1.0842	0.5790	0.1542	0.039*
N2	0.82428 (12)	0.48805 (12)	−0.00475 (9)	0.0349 (4)
C2	0.99023 (13)	0.61194 (15)	0.23350 (11)	0.0353 (4)
H2	1.0302	0.6335	0.2712	0.042*
C3	0.89890 (14)	0.61275 (14)	0.24836 (11)	0.0360 (4)
H3	0.8760	0.6350	0.2953	0.043*
C4	0.84334 (12)	0.57898 (14)	0.19026 (11)	0.0322 (4)
C5	0.88092 (12)	0.54789 (12)	0.12104 (10)	0.0271 (4)
C6	0.74341 (14)	0.57185 (15)	0.18272 (12)	0.0395 (5)
C7	0.72671 (13)	0.53500 (15)	0.10224 (12)	0.0366 (4)
C8	0.65022 (15)	0.51719 (17)	0.05963 (15)	0.0479 (5)
H8	0.5932	0.5273	0.0801	0.057*
C9	0.66251 (17)	0.48351 (17)	−0.01527 (15)	0.0511 (6)
H9	0.6128	0.4696	−0.0460	0.061*
C10	0.74833 (16)	0.47031 (16)	−0.04506 (13)	0.0460 (5)
H10	0.7538	0.4479	−0.0958	0.055*
C11	0.80964 (13)	0.51960 (13)	0.06691 (11)	0.0307 (4)
C12	1.11201 (13)	0.25238 (14)	−0.01876 (10)	0.0322 (4)
C13	1.20308 (14)	0.25618 (15)	−0.02659 (12)	0.0377 (4)
H13	1.2375	0.2784	0.0147	0.045*
C14	1.24610 (14)	0.22754 (15)	−0.09498 (13)	0.0411 (5)
H14	1.3083	0.2314	−0.0986	0.049*
C15	1.19700 (14)	0.19366 (15)	−0.15707 (11)	0.0385 (4)
C16	1.10140 (13)	0.18284 (13)	−0.14930 (10)	0.0332 (4)
C17	1.05776 (13)	0.21383 (13)	−0.07998 (10)	0.0310 (4)
C18	0.96347 (15)	0.20465 (15)	−0.07562 (12)	0.0398 (4)
H18	0.9336	0.2253	−0.0312	0.048*
C19	0.91535 (15)	0.16587 (17)	−0.13558 (13)	0.0471 (5)
H19	0.8533	0.1606	−0.1314	0.057*
C21	1.04882 (16)	0.14207 (15)	−0.20935 (12)	0.0435 (5)
H21	1.0769	0.1202	−0.2543	0.052*
C20	0.95817 (16)	0.13426 (16)	−0.20272 (13)	0.0477 (5)
H20	0.9248	0.1078	−0.2430	0.057*
N3	1.23830 (17)	0.16708 (19)	−0.22550 (13)	0.0567 (6)
H3A	1.291 (2)	0.191 (2)	−0.2297 (17)	0.072 (10)*
H3B	1.203 (2)	0.162 (3)	−0.266 (2)	0.101 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03120 (18)	0.03328 (18)	0.02132 (16)	0.00381 (12)	0.00276 (12)	−0.00374 (12)
O1	0.0393 (9)	0.0925 (14)	0.0568 (10)	0.0050 (9)	0.0213 (8)	−0.0047 (9)
N1	0.0274 (7)	0.0307 (8)	0.0246 (7)	0.0032 (6)	0.0004 (6)	−0.0014 (6)
O2	0.0520 (9)	0.0354 (7)	0.0343 (7)	0.0071 (6)	0.0098 (6)	−0.0002 (6)
S1	0.0532 (3)	0.0400 (3)	0.0218 (2)	0.0030 (2)	0.0010 (2)	0.00122 (19)
O4	0.0783 (12)	0.0497 (9)	0.0345 (8)	−0.0012 (8)	0.0085 (8)	0.0149 (7)
O3	0.0688 (11)	0.0770 (12)	0.0278 (7)	−0.0027 (9)	−0.0082 (7)	−0.0097 (7)
C1	0.0282 (9)	0.0397 (10)	0.0298 (9)	0.0032 (8)	−0.0020 (7)	−0.0013 (8)
N2	0.0361 (9)	0.0372 (9)	0.0314 (8)	−0.0017 (7)	−0.0045 (6)	−0.0005 (6)
C2	0.0388 (11)	0.0406 (11)	0.0264 (9)	0.0023 (8)	−0.0061 (7)	−0.0026 (8)
C3	0.0429 (11)	0.0416 (11)	0.0235 (8)	0.0045 (9)	0.0042 (8)	−0.0015 (8)
C4	0.0315 (9)	0.0347 (10)	0.0304 (9)	0.0031 (8)	0.0054 (7)	0.0011 (7)
C5	0.0270 (9)	0.0276 (9)	0.0268 (8)	0.0007 (7)	0.0016 (7)	0.0000 (7)
C6	0.0331 (10)	0.0452 (12)	0.0402 (10)	0.0021 (8)	0.0088 (8)	0.0040 (9)
C7	0.0290 (10)	0.0371 (10)	0.0435 (11)	−0.0027 (8)	0.0021 (8)	0.0056 (9)
C8	0.0305 (10)	0.0500 (13)	0.0630 (15)	−0.0049 (9)	−0.0030 (10)	0.0104 (11)
C9	0.0420 (13)	0.0527 (14)	0.0586 (14)	−0.0100 (10)	−0.0197 (11)	0.0084 (11)
C10	0.0506 (13)	0.0471 (12)	0.0403 (11)	−0.0055 (10)	−0.0139 (10)	0.0002 (10)
C11	0.0299 (9)	0.0295 (9)	0.0326 (9)	−0.0022 (7)	−0.0005 (7)	0.0026 (7)
C12	0.0391 (10)	0.0312 (9)	0.0261 (8)	0.0055 (8)	−0.0016 (7)	0.0008 (7)
C13	0.0416 (11)	0.0363 (10)	0.0352 (10)	0.0040 (9)	−0.0085 (8)	0.0015 (8)
C14	0.0341 (10)	0.0431 (11)	0.0460 (12)	0.0052 (8)	0.0019 (9)	0.0039 (9)
C15	0.0421 (11)	0.0371 (10)	0.0362 (10)	0.0097 (9)	0.0051 (8)	0.0014 (8)
C16	0.0411 (10)	0.0302 (9)	0.0282 (9)	0.0050 (8)	0.0008 (8)	0.0011 (7)
C17	0.0381 (10)	0.0287 (9)	0.0262 (9)	0.0034 (7)	−0.0009 (7)	0.0034 (7)
C18	0.0399 (11)	0.0446 (11)	0.0348 (10)	−0.0002 (9)	0.0019 (9)	0.0014 (9)
C19	0.0408 (12)	0.0518 (13)	0.0487 (12)	−0.0074 (10)	−0.0045 (10)	0.0029 (10)
C21	0.0577 (14)	0.0401 (11)	0.0328 (10)	0.0049 (10)	−0.0024 (9)	−0.0069 (8)
C20	0.0523 (13)	0.0469 (12)	0.0440 (12)	−0.0036 (10)	−0.0123 (10)	−0.0081 (10)
N3	0.0491 (13)	0.0760 (15)	0.0451 (12)	0.0077 (12)	0.0129 (10)	−0.0122 (11)

Geometric parameters (Å, º)

Cu1—N1^i	1.9872 (14)	C7—C11	1.393 (3)
Cu1—N1	1.9872 (14)	C8—C9	1.384 (4)
Cu1—O2^i	1.9890 (14)	C8—H8	0.9300
Cu1—O2	1.9890 (14)	C9—C10	1.389 (4)
Cu1—N2	2.6231 (18)	C9—H9	0.9300
Cu1—N2^i	2.6231 (18)	C10—H10	0.9300
O1—C6	1.209 (2)	C12—C13	1.364 (3)
N1—C5	1.325 (2)	C12—C17	1.432 (3)
N1—C1	1.350 (2)	C13—C14	1.398 (3)
O2—S1	1.4853 (15)	C13—H13	0.9300
S1—O4	1.4413 (16)	C14—C15	1.378 (3)
S1—O3	1.4442 (17)	C14—H14	0.9300
S1—C12	1.7674 (19)	C15—N3	1.379 (3)
C1—C2	1.388 (3)	C15—C16	1.438 (3)
C1—H1	0.9300	C16—C21	1.416 (3)
N2—C11	1.327 (2)	C16—C17	1.425 (2)
N2—C10	1.349 (3)	C17—C18	1.412 (3)
C2—C3	1.384 (3)	C18—C19	1.368 (3)
C2—H2	0.9300	C18—H18	0.9300
C3—C4	1.380 (3)	C19—C20	1.391 (3)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.385 (2)	C21—C20	1.359 (3)
C4—C6	1.497 (3)	C21—H21	0.9300
C5—C11	1.466 (2)	C20—H20	0.9300
C6—C7	1.498 (3)	N3—H3A	0.86 (3)
C7—C8	1.377 (3)	N3—H3B	0.87 (4)
N1^i—Cu1—N1	180.00 (8)	C8—C9—C10	120.7 (2)
N1^i—Cu1—O2^i	87.11 (6)	C8—C9—H9	119.7
N1—Cu1—O2^i	92.89 (6)	C10—C9—H9	119.7
N1^i—Cu1—O2	92.89 (6)	N2—C10—C9	123.9 (2)
N1—Cu1—O2	87.11 (6)	N2—C10—H10	118.1
O2^i—Cu1—O2	180.00 (8)	C9—C10—H10	118.1
N2^i—Cu1—O2	93.80 (8)	N2—C11—C7	127.03 (18)
N1^i—Cu1—N1	180.00 (8)	N2—C11—C5	124.08 (17)
C5—N1—C1	115.95 (15)	C7—C11—C5	108.84 (17)
C5—N1—Cu1	114.92 (12)	C13—C12—C17	120.19 (18)
C1—N1—Cu1	129.13 (13)	C13—C12—S1	119.35 (15)
S1—O2—Cu1	138.50 (9)	C17—C12—S1	120.45 (15)
O4—S1—O3	115.18 (10)	C12—C13—C14	121.84 (19)
O4—S1—O2	109.29 (10)	C12—C13—H13	119.1
O3—S1—O2	112.32 (10)	C14—C13—H13	119.1
O4—S1—C12	107.36 (10)	C15—C14—C13	120.49 (19)
O3—S1—C12	106.23 (10)	C15—C14—H14	119.8
O2—S1—C12	105.88 (8)	C13—C14—H14	119.8
N1—C1—C2	122.78 (18)	C14—C15—N3	121.2 (2)
N1—C1—H1	118.6	C14—C15—C16	119.29 (18)
C2—C1—H1	118.6	N3—C15—C16	119.5 (2)
C11—N2—C10	113.61 (18)	C21—C16—C17	118.71 (18)
C3—C2—C1	120.32 (18)	C21—C16—C15	121.47 (18)
C3—C2—H2	119.8	C17—C16—C15	119.82 (17)
C1—C2—H2	119.8	C18—C17—C16	118.04 (17)
C4—C3—C2	116.90 (17)	C18—C17—C12	123.79 (17)
C4—C3—H3	121.6	C16—C17—C12	118.17 (17)
C2—C3—H3	121.6	C19—C18—C17	121.13 (19)
C3—C4—C5	119.17 (17)	C19—C18—H18	119.4
C3—C4—C6	132.93 (18)	C17—C18—H18	119.4
C5—C4—C6	107.82 (17)	C18—C19—C20	120.8 (2)
N1—C5—C4	124.87 (17)	C18—C19—H19	119.6
N1—C5—C11	125.33 (16)	C20—C19—H19	119.6
C4—C5—C11	109.75 (16)	C20—C21—C16	121.36 (19)
O1—C6—C4	125.9 (2)	C20—C21—H21	119.3
O1—C6—C7	128.6 (2)	C16—C21—H21	119.3
C4—C6—C7	105.55 (16)	C21—C20—C19	120.0 (2)
C8—C7—C11	118.2 (2)	C21—C20—H20	120.0
C8—C7—C6	133.7 (2)	C19—C20—H20	120.0
C11—C7—C6	108.00 (17)	C15—N3—H3A	112 (2)
C7—C8—C9	116.6 (2)	C15—N3—H3B	116 (2)
C7—C8—H8	121.7	H3A—N3—H3B	121 (3)
C9—C8—H8	121.7
O2^i—Cu1—N1—C5	94.52 (13)	C8—C7—C11—N2	−0.7 (3)
O2—Cu1—N1—C5	−85.48 (13)	C6—C7—C11—N2	−179.29 (18)
O2^i—Cu1—N1—C1	−85.21 (16)	C8—C7—C11—C5	176.97 (18)
O2—Cu1—N1—C1	94.79 (16)	C6—C7—C11—C5	−1.6 (2)
N1^i—Cu1—O2—S1	74.04 (14)	N1—C5—C11—N2	1.3 (3)
N1—Cu1—O2—S1	−105.96 (14)	C4—C5—C11—N2	178.91 (17)
Cu1—O2—S1—O4	176.95 (13)	N1—C5—C11—C7	−176.49 (17)
Cu1—O2—S1—O3	47.83 (16)	C4—C5—C11—C7	1.2 (2)
Cu1—O2—S1—C12	−67.70 (15)	O4—S1—C12—C13	−120.46 (17)
C5—N1—C1—C2	−0.9 (3)	O3—S1—C12—C13	3.27 (19)
Cu1—N1—C1—C2	178.80 (14)	O2—S1—C12—C13	122.88 (17)
N1—C1—C2—C3	0.3 (3)	O4—S1—C12—C17	58.35 (17)
C1—C2—C3—C4	0.6 (3)	O3—S1—C12—C17	−177.92 (15)
C2—C3—C4—C5	−0.9 (3)	O2—S1—C12—C17	−58.31 (17)
C2—C3—C4—C6	−177.2 (2)	C17—C12—C13—C14	3.2 (3)
C1—N1—C5—C4	0.6 (3)	S1—C12—C13—C14	−177.99 (16)
Cu1—N1—C5—C4	−179.15 (14)	C12—C13—C14—C15	−0.4 (3)
C1—N1—C5—C11	177.92 (17)	C13—C14—C15—N3	178.6 (2)
Cu1—N1—C5—C11	−1.8 (2)	C13—C14—C15—C16	−3.5 (3)
C3—C4—C5—N1	0.3 (3)	C14—C15—C16—C21	−175.49 (19)
C6—C4—C5—N1	177.48 (17)	N3—C15—C16—C21	2.4 (3)
C3—C4—C5—C11	−177.38 (16)	C14—C15—C16—C17	4.7 (3)
C6—C4—C5—C11	−0.2 (2)	N3—C15—C16—C17	−177.40 (19)
C3—C4—C6—O1	−3.2 (4)	C21—C16—C17—C18	−1.7 (3)
C5—C4—C6—O1	−179.8 (2)	C15—C16—C17—C18	178.08 (18)
C3—C4—C6—C7	175.9 (2)	C21—C16—C17—C12	178.21 (17)
C5—C4—C6—C7	−0.8 (2)	C15—C16—C17—C12	−2.0 (3)
O1—C6—C7—C8	2.2 (4)	C13—C12—C17—C18	178.02 (19)
C4—C6—C7—C8	−176.8 (2)	S1—C12—C17—C18	−0.8 (3)
O1—C6—C7—C11	−179.5 (2)	C13—C12—C17—C16	−1.9 (3)
C4—C6—C7—C11	1.5 (2)	S1—C12—C17—C16	179.28 (13)
C11—C7—C8—C9	1.1 (3)	C16—C17—C18—C19	1.0 (3)
C6—C7—C8—C9	179.2 (2)	C12—C17—C18—C19	−179.0 (2)
C7—C8—C9—C10	−1.0 (3)	C17—C18—C19—C20	0.0 (3)
C11—N2—C10—C9	0.0 (3)	C17—C16—C21—C20	1.6 (3)
C8—C9—C10—N2	0.4 (4)	C15—C16—C21—C20	−178.2 (2)
C10—N2—C11—C7	0.1 (3)	C16—C21—C20—C19	−0.6 (3)
C10—N2—C11—C5	−177.22 (18)	C18—C19—C20—C21	−0.2 (4)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O3^ii	0.87 (4)	2.28 (4)	3.142 (3)	168 (3)

Symmetry code: (ii) x, −y+1/2, z−1/2.

(II) Poly[[[Diaquacadmium(II)]-bis(µ-4-aminonaphthalene-1-sulfonato)- κ²O:N;κ²N:O] dihydrate]

Crystal data

[Cd(C10H8NO3S)2(H2O)2]·2H2O	F(000) = 636
Mr = 628.93	Dx = 1.840 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5932 reflections
a = 9.2553 (6) Å	θ = 2.3–29.7°
b = 15.6133 (9) Å	µ = 1.21 mm^−1
c = 8.1857 (5) Å	T = 273 K
β = 106.305 (1)°	Block, colorless
V = 1135.31 (12) Å^3	0.40 × 0.37 × 0.32 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	2729 independent reflections
Radiation source: fine-focus sealed tube	2613 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
phi and ω scans	θmax = 28.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→12
Tmin = 0.62, Tmax = 0.68	k = −20→18
7462 measured reflections	l = −7→10

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)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.052	w = 1/[σ^2(Fo^2) + (0.0267P)^2 + 0.5509P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
2729 reflections	Δρmax = 0.56 e Å^−3
185 parameters	Δρmin = −0.37 e Å^−3
2 restraints	Extinction correction: SHELXS97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0486 (13)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cd1	1.0000	1.0000	1.0000	0.02207 (7)
O1	0.11768 (15)	0.97584 (11)	0.79668 (18)	0.0415 (3)
O4	1.10339 (17)	1.13444 (9)	1.0009 (2)	0.0379 (3)
H4A	1.090 (3)	1.1596 (17)	0.910 (4)	0.055 (7)*
H4B	1.103 (3)	1.1670 (19)	1.068 (4)	0.057 (8)*
N1	0.80030 (15)	1.05294 (10)	0.7766 (2)	0.0286 (3)
H1A	0.824 (3)	1.0477 (16)	0.694 (3)	0.041 (6)*
H1B	0.802 (3)	1.1043 (16)	0.798 (3)	0.044 (6)*
S1	0.18805 (4)	0.91024 (3)	0.71746 (5)	0.02595 (10)
O2	0.10855 (13)	0.90148 (9)	0.53857 (16)	0.0351 (3)
O3	0.20730 (16)	0.83016 (10)	0.8099 (2)	0.0522 (4)
C1	0.36979 (16)	0.94930 (10)	0.72907 (19)	0.0222 (3)
C2	0.41026 (18)	1.02687 (11)	0.8044 (2)	0.0271 (3)
H2	0.3426	1.0572	0.8474	0.032*
C3	0.55322 (18)	1.06131 (10)	0.8177 (2)	0.0273 (3)
H3	0.5797	1.1141	0.8702	0.033*
C4	0.65332 (17)	1.01814 (10)	0.7545 (2)	0.0234 (3)
C5	0.61484 (16)	0.93781 (10)	0.67093 (19)	0.0221 (3)
C6	0.47031 (16)	0.90182 (9)	0.65861 (18)	0.0217 (3)
C7	0.43389 (19)	0.82177 (10)	0.5757 (2)	0.0290 (3)
H7	0.3411	0.7967	0.5683	0.035*
C8	0.5334 (2)	0.78091 (12)	0.5063 (2)	0.0359 (4)
H8	0.5075	0.7285	0.4520	0.043*
C9	0.6739 (2)	0.81719 (12)	0.5162 (2)	0.0364 (4)
H9	0.7399	0.7892	0.4670	0.044*
C10	0.71453 (18)	0.89329 (11)	0.5975 (2)	0.0305 (3)
H10	0.8088	0.9163	0.6049	0.037*
O5	−0.02582 (17)	0.72167 (9)	0.80732 (19)	0.0409 (3)
H5A	0.011 (3)	0.6882 (17)	0.883 (3)	0.056 (8)*
H5B	0.049 (3)	0.7475 (18)	0.800 (4)	0.064 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01691 (10)	0.02913 (11)	0.02169 (10)	−0.00119 (5)	0.00793 (6)	−0.00074 (5)
O1	0.0283 (6)	0.0642 (9)	0.0390 (7)	−0.0027 (6)	0.0210 (6)	−0.0131 (7)
O4	0.0495 (8)	0.0310 (7)	0.0333 (7)	−0.0112 (6)	0.0119 (6)	−0.0024 (6)
N1	0.0214 (6)	0.0365 (8)	0.0276 (7)	−0.0054 (5)	0.0061 (5)	0.0043 (6)
S1	0.01784 (17)	0.0376 (2)	0.02425 (19)	−0.00268 (14)	0.00888 (14)	0.00240 (15)
O2	0.0251 (6)	0.0503 (7)	0.0292 (6)	−0.0060 (5)	0.0063 (5)	−0.0076 (5)
O3	0.0342 (7)	0.0552 (9)	0.0673 (10)	−0.0061 (6)	0.0147 (7)	0.0302 (8)
C1	0.0161 (6)	0.0307 (7)	0.0208 (7)	−0.0009 (5)	0.0067 (5)	0.0022 (6)
C2	0.0242 (7)	0.0329 (8)	0.0255 (7)	0.0030 (6)	0.0093 (6)	−0.0024 (6)
C3	0.0266 (7)	0.0282 (7)	0.0263 (8)	−0.0023 (6)	0.0061 (6)	−0.0025 (6)
C4	0.0185 (7)	0.0295 (7)	0.0205 (7)	−0.0023 (6)	0.0025 (5)	0.0048 (6)
C5	0.0174 (6)	0.0286 (7)	0.0203 (7)	0.0025 (5)	0.0052 (5)	0.0046 (5)
C6	0.0201 (6)	0.0253 (7)	0.0200 (7)	0.0016 (5)	0.0060 (5)	0.0034 (5)
C7	0.0294 (8)	0.0269 (7)	0.0318 (8)	−0.0019 (6)	0.0103 (7)	0.0000 (6)
C8	0.0449 (9)	0.0267 (8)	0.0377 (10)	0.0048 (7)	0.0141 (8)	−0.0018 (6)
C9	0.0361 (9)	0.0392 (9)	0.0382 (9)	0.0153 (7)	0.0175 (8)	0.0008 (7)
C10	0.0206 (7)	0.0406 (9)	0.0323 (8)	0.0067 (6)	0.0104 (6)	0.0047 (7)
O5	0.0427 (8)	0.0370 (7)	0.0400 (8)	−0.0030 (6)	0.0067 (6)	0.0081 (6)

Geometric parameters (Å, º)

Cd1—O1^i	2.2620 (13)	C2—C3	1.404 (2)
Cd1—O1^ii	2.2620 (13)	C2—H2	0.9300
Cd1—O4	2.3060 (13)	C3—C4	1.360 (2)
Cd1—O4^iii	2.3060 (13)	C3—H3	0.9300
Cd1—N1	2.3549 (14)	C4—C5	1.425 (2)
Cd1—N1^iii	2.3549 (14)	C5—C10	1.417 (2)
O1—S1	1.4597 (14)	C5—C6	1.428 (2)
O1—Cd1^iv	2.2620 (12)	C6—C7	1.417 (2)
O4—H4A	0.82 (3)	C7—C8	1.368 (2)
O4—H4B	0.75 (3)	C7—H7	0.9300
N1—C4	1.428 (2)	C8—C9	1.400 (3)
N1—H1A	0.77 (3)	C8—H8	0.9300
N1—H1B	0.82 (3)	C9—C10	1.362 (3)
S1—O3	1.4465 (14)	C9—H9	0.9300
S1—O2	1.4490 (13)	C10—H10	0.9300
S1—C1	1.7664 (15)	O5—H5A	0.81 (3)
C1—C2	1.363 (2)	O5—H5B	0.81 (3)
C1—C6	1.431 (2)
O1^i—Cd1—O1^ii	180.000 (1)	C2—C1—C6	121.02 (13)
O1^i—Cd1—O4	82.48 (6)	C2—C1—S1	117.89 (11)
O1^ii—Cd1—O4	97.52 (6)	C6—C1—S1	121.09 (12)
O1^i—Cd1—O4^iii	97.52 (6)	C1—C2—C3	120.58 (14)
O1^ii—Cd1—O4^iii	82.48 (6)	C1—C2—H2	119.7
O4—Cd1—O4^iii	180.0	C3—C2—H2	119.7
O1^i—Cd1—N1	85.54 (6)	C4—C3—C2	120.57 (15)
O1^ii—Cd1—N1	94.46 (6)	C4—C3—H3	119.7
O4—Cd1—N1	85.27 (5)	C2—C3—H3	119.7
O4^iii—Cd1—N1	94.73 (5)	C3—C4—C5	120.91 (14)
O1^i—Cd1—N1^iii	94.46 (6)	C3—C4—N1	119.31 (15)
O1^ii—Cd1—N1^iii	85.54 (6)	C5—C4—N1	119.76 (15)
O4—Cd1—N1^iii	94.73 (5)	C10—C5—C4	122.06 (14)
O4^iii—Cd1—N1^iii	85.27 (5)	C10—C5—C6	119.05 (14)
N1—Cd1—N1^iii	180.0	C4—C5—C6	118.89 (13)
S1—O1—Cd1^iv	144.19 (10)	C7—C6—C5	118.23 (13)
Cd1—O4—H4A	118.5 (18)	C7—C6—C1	123.75 (14)
Cd1—O4—H4B	122 (2)	C5—C6—C1	118.01 (13)
H4A—O4—H4B	108 (3)	C8—C7—C6	120.85 (16)
C4—N1—Cd1	118.48 (10)	C8—C7—H7	119.6
C4—N1—H1A	110.2 (18)	C6—C7—H7	119.6
Cd1—N1—H1A	106.7 (18)	C7—C8—C9	120.67 (17)
C4—N1—H1B	110.9 (17)	C7—C8—H8	119.7
Cd1—N1—H1B	102.2 (17)	C9—C8—H8	119.7
H1A—N1—H1B	108 (2)	C10—C9—C8	120.40 (16)
O3—S1—O2	113.59 (9)	C10—C9—H9	119.8
O3—S1—O1	112.26 (10)	C8—C9—H9	119.8
O2—S1—O1	110.60 (8)	C9—C10—C5	120.79 (15)
O3—S1—C1	107.14 (8)	C9—C10—H10	119.6
O2—S1—C1	107.02 (7)	C5—C10—H10	119.6
O1—S1—C1	105.71 (8)	H5A—O5—H5B	101 (3)
O1^i—Cd1—N1—C4	126.28 (14)	C3—C4—C5—C10	177.22 (15)
O1^ii—Cd1—N1—C4	−53.72 (14)	N1—C4—C5—C10	−4.5 (2)
O4—Cd1—N1—C4	−150.92 (14)	C3—C4—C5—C6	−1.8 (2)
O4^iii—Cd1—N1—C4	29.08 (14)	N1—C4—C5—C6	176.50 (13)
Cd1^iv—O1—S1—O3	−9.53 (18)	C10—C5—C6—C7	1.2 (2)
Cd1^iv—O1—S1—O2	118.49 (15)	C4—C5—C6—C7	−179.78 (14)
Cd1^iv—O1—S1—C1	−126.01 (14)	C10—C5—C6—C1	−178.06 (14)
O3—S1—C1—C2	−119.48 (15)	C4—C5—C6—C1	1.0 (2)
O2—S1—C1—C2	118.35 (14)	C2—C1—C6—C7	−178.67 (15)
O1—S1—C1—C2	0.42 (16)	S1—C1—C6—C7	0.1 (2)
O3—S1—C1—C6	61.74 (15)	C2—C1—C6—C5	0.5 (2)
O2—S1—C1—C6	−60.43 (14)	S1—C1—C6—C5	179.28 (11)
O1—S1—C1—C6	−178.35 (13)	C5—C6—C7—C8	−1.3 (2)
C6—C1—C2—C3	−1.3 (2)	C1—C6—C7—C8	177.93 (16)
S1—C1—C2—C3	179.93 (12)	C6—C7—C8—C9	0.2 (3)
C1—C2—C3—C4	0.5 (3)	C7—C8—C9—C10	1.0 (3)
C2—C3—C4—C5	1.1 (2)	C8—C9—C10—C5	−1.0 (3)
C2—C3—C4—N1	−177.21 (15)	C4—C5—C10—C9	−179.04 (16)
Cd1—N1—C4—C3	98.64 (16)	C6—C5—C10—C9	−0.1 (2)
Cd1—N1—C4—C5	−79.66 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O5^v	0.82 (3)	1.96 (3)	2.778 (2)	171 (3)
O4—H4B···O5^ii	0.75 (3)	2.23 (3)	2.943 (2)	159 (3)
N1—H1A···O2^vi	0.77 (3)	2.31 (3)	3.016 (2)	154 (2)
O5—H5A···O2^vii	0.81 (3)	1.94 (3)	2.7394 (19)	171 (3)
O5—H5B···O3	0.81 (3)	1.94 (3)	2.738 (2)	167 (3)

Symmetry codes: (ii) −x+1, −y+2, −z+2; (v) −x+1, y+1/2, −z+3/2; (vi) −x+1, −y+2, −z+1; (vii) x, −y+3/2, z+1/2.