Two saccharinate complexes: [Mn(phen)₂(sac)(H₂O)]⁺·sac^- and [Co(bipy)₂(sac)(H₂O)]⁺·sac^-

The title saccharinate complexes, aqua[1,2-benzisothiazol-3(2H)-onato 1,1-dioxide-N]bis(1,10-phenanthroline-N,N')man­ganese(II) 1,2-benz­isothia­zol-3(2H)-onate 1,1-dioxide,[Mn(C₇H₄NO₃S)(C₁₂H₈N₂)₂(H₂O)](C₇H₄NO₃S), and aqua[1,2-benz­iso­thiazol-3(2H)-onato 1,1-dioxide-N]­bis­(2,2'-bi­pyri­dine-N,N')­cobalt(II) 1,2-benz­iso­thia­zol-3(2H)-onate 1,1-di­oxide, [Co­(C₇H₄NO₃S)­(C₁₀H₈N₂)₂­(H₂O)]­(C₇H₄NO₃S), have been prepared and their crystal structures determined at 150 K. The structure of the manganese complex consists of repeated alternating [Mn(phen)₂(sac)(H₂O)]⁺ cations and non-coordinated saccharinate anions. The water molecule, bound to manganese as part of a slightly distorted octahedral arrangement, is hydrogen bonded to an O atom of the SO₂ group in the saccharinate counter-ion. In contrast, the cobalt complex has one pseudo-octahedral [Co(bipy)₂(sac)(H₂O)]⁺ cation, with the cobalt-bound water molecule hydrogen bonded to the N atom of the accompanying free saccharinate anion.

S1. Comment

In an earlier paper (Dillon et al., 1999), we summarized previous work on the crystal structures of transition metal–1,2-benzisothiazol-3(2H)-onate 1,1-dioxide (saccharinate) complexes, particularly those with the bidentate ligands 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen) present. These included examples with all the saccharinate ligands attached to the metal (Hergold-Brundic et al., 1989), ones where saccharinate is present merely as the counter-ion (Ainscough et al., 1990; Li, Chen et al., 1993; Li, Wei et al., 1993), and, for some copper complexes only, where it occurs in both the cation and the anion (Li et al., 1991; Hergold-Brundic et al., 1991; Zhang et al., 1994). We described previously the first structure of a manganese(II) complex with saccharinate present in both the cation and anion (Dillon et al., 1999).

The synthesis and crystal structures are now reported of two further saccharinate complexes with saccharinate (sac) present both in the cation and as the counter-ion, namely [Mn(phen)₂(sac)(H₂O)]^+.sac⁻, (I), and [Co(bipy)₂(sac)(H₂O)]^+.sac⁻, (II), the latter representing the first cobalt(II) example of this kind of structure.

The structures of (I) (Fig. 1) and (II) (Fig. 2) both consist of polymeric cation chains composed of [Mn(phen)₂(sac)(H₂O)]⁺ and [Co(bipy)₂(sac)(H₂O)]⁺ units, respectively, and saccharinate counter-ions. Within the cation of (I), the mean Mn—N_phen bond length is 2.257 (6) Å, with one of the phen ligands (N2/N3) bound more asymmetrically than the other, as was also found in the structure of [Mn(bipy)₂(sac)(H₂O)]⁺ (Dillon et al., 1999). The Mn—N_sac bond length of 2.225 (2) Å is close to that in the bipy complex and may be compared with the corresponding distance of 2.281 (1) Å in [Mn(sac)₂(H₂O)₄]^.2H₂O (Kamenar & Jovanovski, 1982). The Mn—O_aqua separation of 2.189 (2) Å is rather longer than in the bipy complex [2.127 (3) Å], possibly reflecting the greater steric requirements of the phen ligand, and is intermediate between the two independent Mn—O_aqua distances of 2.162 (1) and 2.219 (2) Å in [Mn(sac)₂(H₂O)₄]^.2H₂O (Kamenar & Jovanovski, 1982). Bond angles about manganese show even greater distortion from idealized octahedral geometry than in the bipy complex (Dillon et al., 1999), with N2—Mn—N5 = 176.09 (6)°, O4—Mn—N3 = 159.10 (6)° and N1—Mn—N4 = 163.53 (6)°. This result is again not unexpected for the more sterically demanding phen ligand. An interesting difference from the structure of the bipy complex is that the water molecule attached to manganese is hydrogen bonded to an O atom of the SO₂ group in the free saccharinate anion (Fig. 1), with an H···O7 distance of 1.91 (3) Å; in the former, the water is hydrogen bonded to the N atom in the counter-ion.

As expected, the corresponding bond lengths in the cobalt complex, (II), are shorter than those in (I), just as in the saccharinate species [M(sac)₂(H₂O)₄]^.2H₂O [M = Mn (Kamenar & Jovanovski, 1982) and Co (Haider et al., 1983)]. The average Co—N_bipy bond length is 2.144 (4) Å, though the ligand asymmetry seen in compound (I) is not displayed. The Co—N_sac distance of 2.169 (2) Å compares well with the distance of 2.200 (1) Å in [Co(sac)₂(H₂O)₄]^.2H₂O (Haider et al., 1983), while the Co—O_aqua distance of 2.057 (2) Å in (II) is similar to the shorter of the two independent Co—O_aqua bond lengths of 2.060 (1) and 2.124 (2) Å in [Co(sac)₂(H₂O)₄]^.2H₂O. Some distortion of regular geometry is apparent in the cation [O4—Co1—N2 = 165.61 (6)°, N3–Co1—N4 = 174.59 (6)° and N5—Co1—N1 = 170.83 (6)°], though this is less pronounced than in the manganese compound (I), again showing the sterically less demanding nature of the bipy ligand compared with phen. The water molecule in (II) is hydrogen bonded to the N6 atom in the adjacent free saccharinate ion, at an H···O distance of 1.78 (3) Å, as in the structure of [Mn(sac)(bipy)₂(H₂O)](sac) (Dillon et al., 1999). The structural parameters for the free anions in both (I) and (II) are again very similar to those in K₂Na(sac)₃^.H₂O (Malik et al., 1984).

The packing of compound (I) involves parallel stacking of pairs of phen ligands, as shown in Fig. 3. The structure demonstrates two significant intermolecular contacts. In addition to the hydrogen bond between O7 in the SO₂ group and the bound water molecule mentioned above, a phenyl H atom from the phenanthroline ligand (H20), which stacks in a pairwise fashion, also forms a close contact with O6ⁱ at a distance of 2.50 (2) Å [symmetry code: (i) −x, 1 − y, 1 − z]. The three-dimensional arrangement of compound (II) is very similar to that of the manganese analogue reported previously (Dillon et al., 1999). The free and bound saccharinate groups alternate in a staggered conformation, as shown in Fig. 4. The pairs of sac ligands are linked by close intermolecular contacts of 2.50 (3) Å for C6—H6···O7═S2 and 2.56 (2) Å for C33—H33···O3═S1. There is also a close contact of 2.49 (3) Å between C20—H20 and O1ⁱⁱ═C1ⁱⁱ, as well as a linear hydrogen bond of 1.78 (3) Å between H4B and N6ⁱⁱⁱ with an O—H···N angle of 174.0 (3)° [symmetry codes: (ii) 2 − x, −y, 1 − z; (iii) x, y, z − 1].

S2. Experimental

Compound (I) was prepared by adding with stirring a warm solution of 1,10-phenanthroline (0.1546 g, 0.78 mmol) in water (50 ml) to a warm clear solution of [Mn(sac)₂(H₂O)₄]^.2H₂O (0.2100 g, 0.39 mmol) in water (50 ml). The resultant yellow solution was warmed on a hot-plate with stirring and the volume reduced to 25 ml. The bright-yellow solution was allowed to stand overnight and yellow crystals were deposited. These were collected by filtration, washed with three 5 ml portions of cold water and dried over silica gel [yield 0.1213 g (75.8%), m.p. 485 K]. Elemental analyses, including Mn and Co by atomic absorption, were performed by the microanalytical services of the Department of Chemistry, University of Durham; found: C 57.29, H 3.18, N 10.38, Mn 6.22%; C₃₈H₂₆MnN₆O₇S₂ requires: C 57.22, H 3.29, N 10.54, Mn 6.89%. Compound (II) was prepared by adding with stirring a warm solution of 2,2'-bipyridine (0.1176 g, 0.75 mmol) in water (25 ml) to a warm solution of [Co(sac)₂(H₂O)₄]^.2H₂O (0.2002 g, 0.38 mmol) in water (25 ml). The resultant intense yellow solution was warmed on a hot-plate with stirring until the volume was reduced to 20 ml·The brown solution was allowed to stand overnight and bright orange crystals of the compound were then isolated [yield 0.2110 g (75.9%), m.p. 455 K]. Found: C 53.71, H 3.36, N 10.97, Co 7.90%; C₃₄H₂₆CoN₆O₇S₂ requires: C 54.18, H 3.48, N 11.15, Co 7.82%.

S3. Refinement

All H atoms were refined and the C—H distances are in the ranges 0.83 (3)–1.03 (3) and 0.90 (3)–0.99 (3) Å for (I) and (II), respectively.

Computing details

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (1) showing 50% probability displacement ellipsoids.
	Fig. 2. The molecular structure of (2) showing 50% probability displacement ellipsoids.
	Fig. 3. Packing diagram of (1) with intermolecular contacts indicated by dotted lines.
	Fig. 4. Packing diagram of (2); note the free and bound saccharinate groups alternating in a staggered conformation.

(I) (1,2-benzisothiazol-3(2H)-one-1,1-dioxide)aquabis(1,10-phenanthroline) manganese(II)1,2-benzisothiazol-3(2H)-one-1,1-dioxide

Crystal data

[Mn(C7H4NO3S)(C12H8N2)2(H2O)](C7H4NO3S)	F(000) = 818
Mr = 797.71	Dx = 1.535 Mg m^−3
Triclinic, P1	Melting point: 485 K
a = 7.943 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.448 (3) Å	Cell parameters from 998 reflections
c = 15.336 (3) Å	θ = 10.3–27.3°
α = 99.01 (3)°	µ = 0.57 mm^−1
β = 96.19 (3)°	T = 150 K
γ = 91.54 (3)°	Block, yellow
V = 1726.3 (6) Å^3	0.45 × 0.25 × 0.10 mm
Z = 2

Data collection

Siemens SMART CCD diffractometer	8956 independent reflections
Radiation source: fine-focus sealed tube	6420 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 30.4°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→10
Tmin = 0.773, Tmax = 0.945	k = −20→17
13847 measured reflections	l = −21→19

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0591P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.095	(Δ/σ)max = 0.001
S = 1.01	Δρmax = 0.39 e Å^−3
8956 reflections	Δρmin = −0.36 e Å^−3
591 parameters

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 on F² for ALL reflections except for 62 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R-factor-obs 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
Mn1	0.03678 (4)	0.23451 (2)	0.336526 (19)	0.02073 (8)
N1	0.1821 (2)	0.13097 (12)	0.25497 (11)	0.0225 (3)
C1	0.3291 (2)	0.09288 (14)	0.28130 (13)	0.0219 (4)
O1	0.40911 (19)	0.11296 (11)	0.35673 (9)	0.0288 (3)
C2	0.3890 (2)	0.02297 (14)	0.20984 (13)	0.0221 (4)
C3	0.5340 (3)	−0.02699 (16)	0.21403 (16)	0.0313 (5)
H3	0.608 (3)	−0.0210 (17)	0.2668 (17)	0.036 (7)*
C4	0.5678 (3)	−0.08664 (17)	0.13816 (18)	0.0393 (6)
H4	0.670 (4)	−0.123 (2)	0.1384 (19)	0.059 (9)*
C5	0.4567 (3)	−0.09589 (17)	0.06051 (18)	0.0403 (6)
H5	0.487 (4)	−0.140 (2)	0.006 (2)	0.060 (9)*
C6	0.3094 (3)	−0.04587 (17)	0.05528 (15)	0.0334 (5)
H6	0.236 (3)	−0.0485 (17)	0.0052 (17)	0.035 (7)*
C7	0.2797 (3)	0.01332 (14)	0.13164 (13)	0.0242 (4)
S1	0.11444 (7)	0.09117 (4)	0.15017 (3)	0.02468 (12)
O2	−0.04753 (19)	0.04203 (12)	0.14378 (11)	0.0371 (4)
O3	0.1246 (2)	0.16505 (11)	0.09770 (10)	0.0369 (4)
N2	0.1484 (2)	0.35208 (11)	0.27892 (11)	0.0239 (4)
C8	0.3068 (3)	0.38839 (15)	0.29802 (15)	0.0283 (5)
H8	0.381 (3)	0.3626 (16)	0.3435 (16)	0.032 (6)*
C9	0.3707 (3)	0.45808 (16)	0.25463 (16)	0.0332 (5)
H9	0.482 (3)	0.4778 (17)	0.2673 (16)	0.038 (7)*
C10	0.2663 (3)	0.49298 (15)	0.19226 (16)	0.0335 (5)
H10	0.304 (3)	0.5400 (16)	0.1609 (16)	0.032 (6)*
C11	0.0981 (3)	0.45624 (14)	0.16991 (14)	0.0280 (5)
C12	−0.0215 (3)	0.48844 (16)	0.10555 (14)	0.0329 (5)
H12	0.017 (3)	0.5384 (18)	0.0802 (18)	0.045 (7)*
C13	−0.1790 (3)	0.44955 (16)	0.08460 (15)	0.0341 (5)
H13	−0.263 (3)	0.4709 (18)	0.0445 (18)	0.043 (7)*
C14	−0.2354 (3)	0.37307 (15)	0.12617 (13)	0.0272 (4)
C15	−0.3982 (3)	0.32869 (17)	0.10620 (15)	0.0322 (5)
H15	−0.478 (3)	0.3487 (18)	0.0608 (18)	0.045 (7)*
C16	−0.4413 (3)	0.25778 (17)	0.14999 (15)	0.0319 (5)
H16	−0.548 (3)	0.2315 (17)	0.1361 (16)	0.033 (7)*
C17	−0.3209 (3)	0.22828 (15)	0.21227 (14)	0.0278 (4)
H17	−0.345 (3)	0.1736 (18)	0.2443 (17)	0.040 (7)*
N3	−0.1651 (2)	0.26757 (11)	0.23232 (11)	0.0229 (3)
C18	−0.1226 (3)	0.34026 (13)	0.19046 (13)	0.0224 (4)
C19	0.0459 (3)	0.38350 (13)	0.21417 (13)	0.0237 (4)
N4	−0.1353 (2)	0.30262 (12)	0.43442 (11)	0.0259 (4)
C20	−0.1656 (3)	0.39353 (16)	0.45211 (16)	0.0335 (5)
H20	−0.108 (3)	0.4382 (16)	0.4227 (15)	0.025 (6)*
C21	−0.2760 (3)	0.42872 (19)	0.51364 (18)	0.0427 (6)
H21	−0.290 (4)	0.496 (2)	0.521 (2)	0.057 (9)*
C22	−0.3533 (3)	0.36870 (19)	0.55958 (17)	0.0398 (6)
H22	−0.439 (3)	0.3923 (17)	0.5983 (17)	0.040 (7)*
C23	−0.3239 (3)	0.27214 (17)	0.54273 (14)	0.0308 (5)
C24	−0.3979 (3)	0.2046 (2)	0.58870 (16)	0.0391 (6)
H24	−0.459 (3)	0.2247 (18)	0.6275 (18)	0.039 (7)*
C25	−0.3665 (3)	0.1127 (2)	0.57008 (15)	0.0367 (6)
H25	−0.412 (4)	0.0703 (19)	0.6030 (18)	0.048 (8)*
C26	−0.2638 (3)	0.07888 (16)	0.50194 (14)	0.0297 (5)
C27	−0.2367 (3)	−0.01712 (17)	0.47549 (16)	0.0348 (6)
H27	−0.284 (3)	−0.0594 (16)	0.5043 (15)	0.029 (6)*
C28	−0.1441 (3)	−0.04490 (16)	0.40712 (16)	0.0327 (5)
H28	−0.128 (3)	−0.1098 (17)	0.3892 (15)	0.029 (6)*
C29	−0.0733 (3)	0.02389 (15)	0.36513 (15)	0.0278 (5)
H29	−0.014 (3)	0.0073 (16)	0.3195 (17)	0.030 (6)*
N5	−0.0924 (2)	0.11560 (11)	0.38831 (11)	0.0228 (3)
C30	−0.1881 (2)	0.14330 (15)	0.45552 (13)	0.0240 (4)
C31	−0.2149 (2)	0.24198 (15)	0.47812 (13)	0.0245 (4)
O4	0.2498 (2)	0.25742 (12)	0.44185 (11)	0.0285 (3)
H4A	0.319 (4)	0.211 (2)	0.430 (2)	0.061 (9)*
H4B	0.239 (4)	0.262 (2)	0.495 (2)	0.057 (9)*
N6	0.3809 (2)	0.35949 (13)	0.74971 (12)	0.0320 (4)
C32	0.3739 (3)	0.34008 (14)	0.83388 (15)	0.0270 (4)
O5	0.4934 (2)	0.34951 (13)	0.89285 (11)	0.0412 (4)
C33	0.1985 (2)	0.30597 (13)	0.84816 (13)	0.0216 (4)
C34	0.1454 (3)	0.27714 (15)	0.92365 (14)	0.0261 (4)
H34	0.225 (3)	0.2750 (15)	0.9743 (15)	0.025 (6)*
C35	−0.0245 (3)	0.25014 (16)	0.92192 (15)	0.0308 (5)
H35	−0.063 (3)	0.2313 (18)	0.9720 (18)	0.043 (7)*
C36	−0.1392 (3)	0.25325 (18)	0.84767 (17)	0.0364 (5)
H36	−0.254 (3)	0.2396 (17)	0.8482 (16)	0.038 (7)*
C37	−0.0863 (3)	0.28172 (17)	0.77117 (16)	0.0320 (5)
H37	−0.162 (3)	0.2853 (16)	0.7226 (16)	0.031 (6)*
C38	0.0834 (3)	0.30704 (14)	0.77394 (13)	0.0233 (4)
S2	0.19823 (7)	0.34714 (4)	0.69318 (3)	0.02619 (12)
O6	0.1379 (2)	0.43468 (11)	0.67060 (11)	0.0409 (4)
O7	0.1951 (2)	0.27284 (11)	0.61649 (10)	0.0362 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02215 (16)	0.02157 (16)	0.01955 (15)	−0.00155 (11)	0.00339 (11)	0.00641 (12)
N1	0.0229 (8)	0.0274 (9)	0.0166 (8)	0.0010 (7)	0.0000 (6)	0.0031 (7)
C1	0.0211 (9)	0.0252 (10)	0.0200 (9)	−0.0015 (8)	0.0010 (7)	0.0065 (8)
O1	0.0287 (8)	0.0379 (8)	0.0181 (7)	0.0025 (6)	−0.0038 (6)	0.0035 (6)
C2	0.0233 (10)	0.0230 (10)	0.0201 (9)	−0.0021 (8)	0.0025 (8)	0.0040 (8)
C3	0.0291 (11)	0.0297 (12)	0.0351 (12)	0.0032 (9)	0.0018 (10)	0.0064 (10)
C4	0.0351 (13)	0.0337 (13)	0.0483 (15)	0.0089 (10)	0.0090 (11)	0.0000 (11)
C5	0.0468 (15)	0.0337 (13)	0.0382 (14)	0.0011 (11)	0.0136 (12)	−0.0063 (11)
C6	0.0386 (13)	0.0362 (13)	0.0230 (11)	−0.0055 (10)	0.0036 (10)	−0.0019 (10)
C7	0.0256 (10)	0.0237 (10)	0.0237 (10)	−0.0022 (8)	0.0038 (8)	0.0046 (8)
S1	0.0245 (3)	0.0311 (3)	0.0175 (2)	0.0023 (2)	−0.00214 (19)	0.0040 (2)
O2	0.0241 (8)	0.0488 (10)	0.0339 (9)	−0.0036 (7)	−0.0032 (7)	−0.0014 (8)
O3	0.0480 (10)	0.0400 (9)	0.0245 (8)	0.0085 (8)	−0.0017 (7)	0.0133 (7)
N2	0.0278 (9)	0.0207 (8)	0.0239 (9)	−0.0021 (7)	0.0068 (7)	0.0041 (7)
C8	0.0280 (11)	0.0257 (11)	0.0310 (11)	−0.0038 (9)	0.0075 (9)	0.0016 (9)
C9	0.0328 (12)	0.0275 (11)	0.0398 (13)	−0.0078 (10)	0.0157 (10)	0.0009 (10)
C10	0.0477 (14)	0.0205 (11)	0.0363 (13)	−0.0053 (10)	0.0223 (11)	0.0055 (9)
C11	0.0431 (13)	0.0198 (10)	0.0238 (10)	0.0008 (9)	0.0152 (9)	0.0043 (8)
C12	0.0561 (16)	0.0245 (11)	0.0220 (11)	0.0041 (10)	0.0137 (10)	0.0095 (9)
C13	0.0518 (15)	0.0306 (12)	0.0228 (11)	0.0101 (11)	0.0060 (10)	0.0106 (9)
C14	0.0365 (12)	0.0267 (11)	0.0195 (10)	0.0069 (9)	0.0052 (9)	0.0043 (8)
C15	0.0351 (12)	0.0379 (13)	0.0220 (11)	0.0090 (10)	−0.0022 (9)	0.0020 (9)
C16	0.0274 (12)	0.0362 (12)	0.0298 (12)	−0.0013 (10)	−0.0010 (9)	0.0016 (10)
C17	0.0280 (11)	0.0291 (11)	0.0265 (11)	−0.0016 (9)	0.0039 (9)	0.0048 (9)
N3	0.0259 (9)	0.0215 (8)	0.0223 (8)	−0.0014 (7)	0.0049 (7)	0.0054 (7)
C18	0.0295 (10)	0.0200 (9)	0.0185 (9)	0.0031 (8)	0.0066 (8)	0.0030 (8)
C19	0.0321 (11)	0.0183 (9)	0.0222 (10)	0.0013 (8)	0.0102 (8)	0.0029 (8)
N4	0.0286 (9)	0.0260 (9)	0.0237 (9)	0.0006 (7)	0.0038 (7)	0.0060 (7)
C20	0.0394 (13)	0.0282 (11)	0.0329 (12)	0.0033 (10)	0.0048 (10)	0.0040 (10)
C21	0.0439 (15)	0.0371 (14)	0.0435 (15)	0.0097 (11)	0.0054 (12)	−0.0065 (12)
C22	0.0279 (12)	0.0535 (16)	0.0354 (13)	0.0028 (11)	0.0079 (10)	−0.0045 (12)
C23	0.0189 (10)	0.0474 (14)	0.0247 (11)	−0.0013 (9)	0.0002 (8)	0.0037 (10)
C24	0.0202 (11)	0.0731 (19)	0.0245 (12)	−0.0066 (11)	0.0045 (9)	0.0091 (12)
C25	0.0217 (11)	0.0637 (17)	0.0273 (12)	−0.0127 (11)	−0.0016 (9)	0.0213 (12)
C26	0.0186 (10)	0.0445 (13)	0.0276 (11)	−0.0087 (9)	−0.0066 (8)	0.0186 (10)
C27	0.0278 (12)	0.0401 (13)	0.0383 (13)	−0.0150 (10)	−0.0089 (10)	0.0238 (11)
C28	0.0316 (12)	0.0231 (11)	0.0427 (14)	−0.0091 (9)	−0.0112 (10)	0.0153 (10)
C29	0.0276 (11)	0.0256 (11)	0.0297 (12)	−0.0024 (9)	−0.0035 (9)	0.0081 (9)
N5	0.0219 (8)	0.0229 (8)	0.0242 (9)	−0.0013 (7)	−0.0005 (7)	0.0076 (7)
C30	0.0181 (9)	0.0339 (11)	0.0210 (10)	−0.0049 (8)	−0.0021 (7)	0.0118 (8)
C31	0.0198 (9)	0.0337 (11)	0.0202 (10)	−0.0012 (8)	−0.0003 (8)	0.0069 (8)
O4	0.0302 (8)	0.0365 (9)	0.0182 (8)	0.0007 (7)	0.0018 (6)	0.0033 (7)
N6	0.0321 (10)	0.0345 (10)	0.0305 (10)	−0.0078 (8)	0.0108 (8)	0.0055 (8)
C32	0.0246 (10)	0.0257 (11)	0.0318 (11)	−0.0009 (8)	0.0074 (9)	0.0052 (9)
O5	0.0239 (8)	0.0573 (11)	0.0430 (10)	−0.0048 (8)	−0.0006 (7)	0.0137 (9)
C33	0.0216 (9)	0.0209 (9)	0.0232 (10)	0.0011 (7)	0.0046 (8)	0.0049 (8)
C34	0.0272 (11)	0.0301 (11)	0.0232 (10)	0.0045 (9)	0.0029 (8)	0.0105 (9)
C35	0.0316 (12)	0.0356 (12)	0.0304 (12)	0.0001 (9)	0.0122 (9)	0.0152 (10)
C36	0.0234 (11)	0.0443 (14)	0.0445 (14)	−0.0047 (10)	0.0069 (10)	0.0155 (11)
C37	0.0277 (11)	0.0389 (13)	0.0302 (12)	−0.0035 (10)	−0.0011 (9)	0.0117 (10)
C38	0.0289 (10)	0.0217 (10)	0.0202 (9)	−0.0011 (8)	0.0046 (8)	0.0054 (8)
S2	0.0377 (3)	0.0226 (2)	0.0198 (2)	−0.0031 (2)	0.0086 (2)	0.0052 (2)
O6	0.0636 (12)	0.0311 (9)	0.0330 (9)	0.0037 (8)	0.0119 (8)	0.0156 (7)
O7	0.0579 (11)	0.0300 (8)	0.0205 (8)	−0.0040 (7)	0.0104 (7)	0.0004 (6)

Geometric parameters (Å, º)

Mn1—N1	2.2253 (18)	N3—C18	1.367 (2)
Mn1—N2	2.2382 (17)	C18—C19	1.446 (3)
Mn1—N3	2.2542 (18)	N4—C20	1.333 (3)
Mn1—N4	2.2678 (19)	N4—C31	1.365 (3)
Mn1—N5	2.2678 (17)	C20—C21	1.403 (4)
Mn1—O4	2.1897 (17)	C20—H20	0.97 (2)
N1—C1	1.354 (3)	C21—C22	1.372 (4)
N1—S1	1.6461 (17)	C21—H21	0.97 (3)
C1—O1	1.246 (2)	C22—C23	1.409 (4)
C1—C2	1.496 (3)	C22—H22	0.98 (3)
C2—C3	1.377 (3)	C23—C31	1.411 (3)
C2—C7	1.388 (3)	C23—C24	1.438 (3)
C3—C4	1.391 (3)	C24—C25	1.349 (4)
C3—H3	0.94 (3)	C24—H24	0.83 (3)
C4—C5	1.390 (4)	C25—C26	1.429 (3)
C4—H4	0.98 (3)	C25—H25	0.94 (3)
C5—C6	1.394 (4)	C26—C27	1.412 (3)
C5—H5	1.03 (3)	C26—C30	1.416 (3)
C6—C7	1.384 (3)	C27—C28	1.361 (4)
C6—H6	0.91 (2)	C27—H27	0.91 (2)
C7—S1	1.769 (2)	C28—C29	1.403 (3)
S1—O2	1.4389 (17)	C28—H28	0.95 (2)
S1—O3	1.4395 (16)	C29—N5	1.334 (3)
N2—C8	1.335 (3)	C29—H29	0.89 (3)
N2—C19	1.357 (3)	N5—C30	1.363 (3)
C8—C9	1.403 (3)	C30—C31	1.441 (3)
C8—H8	0.99 (2)	N6—C32	1.370 (3)
C9—C10	1.364 (4)	N6—S2	1.598 (2)
C9—H9	0.91 (3)	C32—O5	1.228 (3)
C10—C11	1.411 (3)	C32—C33	1.514 (3)
C10—H10	0.95 (2)	C33—C38	1.384 (3)
C11—C19	1.413 (3)	C33—C34	1.392 (3)
C11—C12	1.435 (3)	C34—C35	1.391 (3)
C12—C13	1.343 (4)	C34—H34	0.95 (2)
C12—H12	0.93 (3)	C35—C36	1.387 (3)
C13—C14	1.443 (3)	C35—H35	0.93 (3)
C13—H13	0.95 (3)	C36—C37	1.404 (3)
C14—C18	1.407 (3)	C36—H36	0.93 (3)
C14—C15	1.409 (3)	C37—C38	1.381 (3)
C15—C16	1.365 (3)	C37—H37	0.91 (2)
C15—H15	0.97 (3)	C38—S2	1.773 (2)
C16—C17	1.401 (3)	S2—O6	1.4434 (17)
C16—H16	0.91 (3)	S2—O7	1.4604 (16)
C17—N3	1.331 (3)	O4—H4A	0.89 (3)
C17—H17	1.02 (3)	O4—H4B	0.83 (3)
N1—Mn1—N2	90.86 (6)	C18—N3—Mn1	114.65 (13)
N1—Mn1—N3	100.84 (6)	N3—C18—C14	122.49 (19)
N1—Mn1—N4	163.53 (6)	N3—C18—C19	117.53 (18)
N1—Mn1—N5	89.81 (7)	C14—C18—C19	119.98 (18)
N1—Mn1—O4	90.41 (7)	N2—C19—C11	122.43 (19)
N2—Mn1—N3	74.42 (7)	N2—C19—C18	118.04 (17)
N2—Mn1—N4	105.59 (7)	C11—C19—C18	119.53 (19)
N2—Mn1—N5	176.09 (6)	C20—N4—C31	118.39 (19)
N2—Mn1—O4	87.98 (7)	C20—N4—Mn1	126.84 (15)
N3—Mn1—N4	84.61 (6)	C31—N4—Mn1	114.77 (14)
N3—Mn1—N5	101.68 (6)	N4—C20—C21	122.5 (2)
N3—Mn1—O4	159.10 (6)	N4—C20—H20	119.7 (13)
N4—Mn1—N5	73.82 (7)	C21—C20—H20	117.8 (13)
N4—Mn1—O4	89.51 (7)	C22—C21—C20	119.6 (2)
O4—Mn1—N5	95.86 (7)	C22—C21—H21	124.9 (18)
C1—N1—S1	111.76 (14)	C20—C21—H21	115.5 (18)
C1—N1—Mn1	127.27 (13)	C21—C22—C23	119.5 (2)
S1—N1—Mn1	120.98 (9)	C21—C22—H22	119.5 (15)
O1—C1—N1	124.61 (19)	C23—C22—H22	120.6 (15)
O1—C1—C2	122.29 (18)	C22—C23—C31	117.4 (2)
N1—C1—C2	113.09 (17)	C22—C23—C24	123.1 (2)
C3—C2—C7	120.4 (2)	C31—C23—C24	119.5 (2)
C3—C2—C1	127.93 (19)	C25—C24—C23	121.0 (2)
C7—C2—C1	111.63 (18)	C25—C24—H24	121.8 (18)
C2—C3—C4	118.3 (2)	C23—C24—H24	117.2 (18)
C2—C3—H3	120.7 (16)	C24—C25—C26	121.2 (2)
C4—C3—H3	121.0 (16)	C24—C25—H25	119.4 (17)
C5—C4—C3	120.6 (2)	C26—C25—H25	119.4 (17)
C5—C4—H4	118.7 (17)	C27—C26—C30	117.0 (2)
C3—C4—H4	120.7 (17)	C27—C26—C25	123.5 (2)
C4—C5—C6	121.8 (2)	C30—C26—C25	119.4 (2)
C4—C5—H5	118.0 (17)	C28—C27—C26	120.4 (2)
C6—C5—H5	120.3 (17)	C28—C27—H27	121.2 (15)
C7—C6—C5	116.3 (2)	C26—C27—H27	118.3 (15)
C7—C6—H6	119.4 (16)	C27—C28—C29	118.6 (2)
C5—C6—H6	124.3 (16)	C27—C28—H28	119.7 (14)
C6—C7—C2	122.6 (2)	C29—C28—H28	121.7 (14)
C6—C7—S1	129.90 (18)	N5—C29—C28	123.5 (2)
C2—C7—S1	107.47 (15)	N5—C29—H29	116.3 (15)
O2—S1—O3	116.62 (10)	C28—C29—H29	120.2 (15)
O2—S1—N1	110.01 (10)	C29—N5—C30	117.91 (18)
O3—S1—N1	110.15 (10)	C29—N5—Mn1	127.10 (15)
O2—S1—C7	111.93 (10)	C30—N5—Mn1	114.75 (13)
O3—S1—C7	110.20 (10)	N5—C30—C26	122.5 (2)
N1—S1—C7	96.01 (10)	N5—C30—C31	117.99 (17)
C8—N2—C19	118.33 (18)	C26—C30—C31	119.5 (2)
C8—N2—Mn1	126.20 (15)	N4—C31—C23	122.6 (2)
C19—N2—Mn1	115.30 (13)	N4—C31—C30	118.11 (18)
N2—C8—C9	122.8 (2)	C23—C31—C30	119.29 (19)
N2—C8—H8	117.1 (14)	H4A—O4—H4B	107 (3)
C9—C8—H8	120.1 (14)	C32—N6—S2	111.59 (15)
C10—C9—C8	119.2 (2)	O5—C32—N6	125.2 (2)
C10—C9—H9	121.3 (16)	O5—C32—C33	122.35 (19)
C8—C9—H9	119.5 (16)	N6—C32—C33	112.43 (18)
C9—C10—C11	119.7 (2)	C38—C33—C34	119.99 (19)
C9—C10—H10	122.2 (15)	C38—C33—C32	111.49 (17)
C11—C10—H10	118.0 (15)	C34—C33—C32	128.51 (19)
C10—C11—C19	117.4 (2)	C35—C34—C33	118.3 (2)
C10—C11—C12	123.9 (2)	C35—C34—H34	121.5 (14)
C19—C11—C12	118.7 (2)	C33—C34—H34	120.2 (14)
C13—C12—C11	121.8 (2)	C36—C35—C34	121.1 (2)
C13—C12—H12	122.7 (17)	C36—C35—H35	119.2 (17)
C11—C12—H12	115.5 (17)	C34—C35—H35	119.7 (16)
C12—C13—C14	121.2 (2)	C35—C36—C37	120.9 (2)
C12—C13—H13	124.1 (16)	C35—C36—H36	120.9 (16)
C14—C13—H13	114.7 (16)	C37—C36—H36	118.1 (16)
C18—C14—C15	117.48 (19)	C38—C37—C36	117.0 (2)
C18—C14—C13	118.7 (2)	C38—C37—H37	121.8 (15)
C15—C14—C13	123.8 (2)	C36—C37—H37	121.2 (15)
C16—C15—C14	119.7 (2)	C37—C38—C33	122.69 (19)
C16—C15—H15	121.1 (15)	C37—C38—S2	130.85 (17)
C14—C15—H15	119.2 (15)	C33—C38—S2	106.45 (15)
C15—C16—C17	119.3 (2)	O6—S2—O7	113.44 (10)
C15—C16—H16	117.3 (16)	O6—S2—N6	112.42 (11)
C17—C16—H16	123.3 (16)	O7—S2—N6	111.12 (11)
N3—C17—C16	122.8 (2)	O6—S2—C38	111.75 (10)
N3—C17—H17	115.1 (15)	O7—S2—C38	109.15 (10)
C16—C17—H17	122.1 (15)	N6—S2—C38	97.92 (10)
C17—N3—C18	118.12 (18)	Mn1—O4—H4A	107 (2)
C17—N3—Mn1	127.08 (14)	Mn1—O4—H4B	124 (2)

(II) (1,2-benzisothiazol-3(2H)-one-1,1-dioxide)aquabis(2,2'-bipyridine) cobalt(II)1,2-benzisothiazol-3(2H)-one-1,1-dioxide

Crystal data

[Co(C7H4NO3S)(C10H8N2)2(H2O)](C7H4NO3S)	Dx = 1.573 Mg m^−3
Mr = 753.66	Melting point: 455 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.6982 (1) Å	Cell parameters from 501 reflections
b = 31.3359 (5) Å	θ = 14.9–20.0°
c = 13.2179 (2) Å	µ = 0.73 mm^−1
β = 93.272 (1)°	T = 150 K
V = 3183.36 (8) Å^3	Block, orange
Z = 4	0.4 × 0.3 × 0.3 mm
F(000) = 1548

Data collection

Siemens SMART CCD area-detector diffractometer	7238 independent reflections
Radiation source: fine-focus sealed tube	6294 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 27.5°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.651, Tmax = 0.803	k = −40→40
22343 measured reflections	l = −17→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0214P)^2 + 2.8879P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.079	(Δ/σ)max = 0.001
S = 1.15	Δρmax = 0.37 e Å^−3
7238 reflections	Δρmin = −0.43 e Å^−3
555 parameters

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 on F² for ALL reflections except for 191 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.98479 (3)	0.149168 (8)	0.444220 (18)	0.01770 (7)
N1	1.1660 (2)	0.13975 (5)	0.57402 (11)	0.0183 (3)
C1	1.3089 (2)	0.11384 (6)	0.57894 (14)	0.0195 (4)
O1	1.36922 (19)	0.09556 (5)	0.50532 (10)	0.0277 (3)
C2	1.3876 (2)	0.10876 (6)	0.68433 (14)	0.0196 (4)
C3	1.5276 (3)	0.08295 (7)	0.71654 (17)	0.0278 (4)
H3	1.584 (3)	0.0671 (7)	0.6685 (17)	0.024 (6)*
C4	1.5749 (3)	0.08196 (7)	0.81968 (17)	0.0314 (5)
H4	1.676 (4)	0.0642 (9)	0.843 (2)	0.043 (7)*
C5	1.4847 (3)	0.10561 (7)	0.88906 (17)	0.0301 (5)
H5	1.519 (3)	0.1031 (8)	0.9599 (19)	0.034 (7)*
C6	1.3428 (3)	0.13112 (7)	0.85692 (15)	0.0259 (4)
H6	1.274 (3)	0.1470 (8)	0.9041 (19)	0.034 (7)*
C7	1.2990 (2)	0.13205 (6)	0.75375 (14)	0.0195 (4)
S1	1.12605 (6)	0.158874 (14)	0.68637 (3)	0.01833 (10)
O2	1.15131 (19)	0.20465 (4)	0.68975 (11)	0.0267 (3)
O3	0.96057 (17)	0.14355 (5)	0.71762 (10)	0.0256 (3)
N2	0.8260 (2)	0.19417 (5)	0.51738 (12)	0.0196 (3)
C8	0.6807 (3)	0.18422 (6)	0.56372 (16)	0.0252 (4)
H8	0.663 (3)	0.1544 (8)	0.5727 (17)	0.025 (6)*
C9	0.5672 (3)	0.21471 (7)	0.59817 (17)	0.0295 (4)
H9	0.468 (3)	0.2052 (8)	0.632 (2)	0.040 (7)*
C10	0.6061 (3)	0.25743 (7)	0.58349 (17)	0.0290 (4)
H10	0.534 (3)	0.2793 (8)	0.6048 (19)	0.038 (7)*
C11	0.7561 (3)	0.26803 (6)	0.53591 (16)	0.0252 (4)
H11	0.782 (3)	0.2968 (8)	0.5255 (17)	0.029 (6)*
C12	0.8642 (2)	0.23576 (6)	0.50377 (14)	0.0189 (4)
C13	1.0275 (2)	0.24417 (6)	0.45145 (14)	0.0200 (4)
C14	1.0989 (3)	0.28492 (7)	0.44179 (17)	0.0282 (4)
H14	1.049 (3)	0.3085 (8)	0.4704 (18)	0.032 (6)*
C15	1.2492 (3)	0.29005 (7)	0.38897 (18)	0.0336 (5)
H15	1.304 (3)	0.3176 (9)	0.3827 (19)	0.039 (7)*
C16	1.3236 (3)	0.25440 (7)	0.34774 (18)	0.0330 (5)
H16	1.425 (4)	0.2567 (9)	0.313 (2)	0.046 (8)*
C17	1.2481 (3)	0.21469 (7)	0.36177 (16)	0.0274 (4)
H17	1.297 (3)	0.1883 (8)	0.3357 (18)	0.030 (6)*
N3	1.1024 (2)	0.20945 (5)	0.41186 (12)	0.0205 (3)
N4	0.8460 (2)	0.09075 (5)	0.46791 (12)	0.0217 (3)
C18	0.8849 (3)	0.06192 (7)	0.54072 (16)	0.0271 (4)
H18	0.963 (3)	0.0704 (8)	0.5962 (18)	0.029 (6)*
C19	0.8134 (3)	0.02110 (7)	0.54113 (18)	0.0296 (4)
H19	0.841 (3)	0.0020 (8)	0.5982 (18)	0.029 (6)*
C20	0.6990 (3)	0.00947 (7)	0.46058 (18)	0.0295 (4)
H20	0.652 (3)	−0.0182 (8)	0.4557 (18)	0.030 (6)*
C21	0.6543 (3)	0.03911 (7)	0.38513 (17)	0.0271 (4)
H21	0.570 (3)	0.0337 (7)	0.3289 (17)	0.023 (6)*
C22	0.7288 (2)	0.07973 (6)	0.39147 (15)	0.0219 (4)
C23	0.6831 (2)	0.11441 (6)	0.31739 (14)	0.0213 (4)
C24	0.5377 (3)	0.11237 (7)	0.24996 (16)	0.0265 (4)
H24	0.470 (3)	0.0882 (8)	0.2489 (17)	0.024 (6)*
C25	0.4945 (3)	0.14743 (7)	0.18933 (16)	0.0293 (4)
H25	0.397 (3)	0.1466 (7)	0.1424 (17)	0.025 (6)*
C26	0.6007 (3)	0.18343 (7)	0.19652 (16)	0.0288 (4)
H26	0.580 (3)	0.2090 (9)	0.161 (2)	0.037 (7)*
C27	0.7455 (3)	0.18272 (7)	0.26366 (16)	0.0263 (4)
H27	0.817 (3)	0.2071 (8)	0.2714 (17)	0.028 (6)*
N5	0.7866 (2)	0.14928 (5)	0.32386 (12)	0.0221 (3)
O4	1.1524 (2)	0.11886 (5)	0.35208 (11)	0.0269 (3)
H4A	1.228 (4)	0.1065 (9)	0.385 (2)	0.048 (9)*
H4B	1.125 (4)	0.1041 (10)	0.291 (2)	0.056 (9)*
N6	1.0912 (2)	0.07970 (5)	1.16974 (12)	0.0262 (4)
C28	1.1902 (3)	0.04510 (6)	1.14836 (14)	0.0229 (4)
O5	1.2777 (2)	0.02422 (5)	1.21230 (11)	0.0330 (3)
C29	1.1843 (2)	0.03518 (6)	1.03642 (14)	0.0193 (4)
C30	1.2679 (3)	0.00285 (6)	0.98692 (16)	0.0255 (4)
H30	1.339 (3)	−0.0171 (8)	1.0217 (18)	0.030 (6)*
C31	1.2410 (3)	−0.00047 (7)	0.88190 (17)	0.0293 (4)
H31	1.294 (3)	−0.0213 (8)	0.8491 (19)	0.035 (7)*
C32	1.1325 (3)	0.02799 (7)	0.82807 (15)	0.0279 (4)
H32	1.118 (3)	0.0258 (8)	0.7539 (19)	0.032 (6)*
C33	1.0491 (3)	0.06112 (6)	0.87699 (15)	0.0238 (4)
H33	0.978 (3)	0.0807 (8)	0.8412 (18)	0.028 (6)*
C34	1.0781 (2)	0.06363 (6)	0.98142 (14)	0.0191 (4)
S2	1.00275 (6)	0.101487 (14)	1.06847 (4)	0.02171 (10)
O6	0.81530 (19)	0.10186 (5)	1.06813 (12)	0.0312 (3)
O7	1.0814 (2)	0.14267 (5)	1.05018 (12)	0.0316 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01781 (13)	0.01648 (12)	0.01891 (13)	−0.00050 (9)	0.00190 (9)	−0.00071 (9)
N1	0.0186 (7)	0.0186 (7)	0.0178 (7)	0.0019 (6)	0.0021 (6)	−0.0018 (6)
C1	0.0203 (9)	0.0164 (8)	0.0221 (9)	−0.0006 (7)	0.0028 (7)	0.0010 (7)
O1	0.0296 (8)	0.0300 (8)	0.0240 (7)	0.0101 (6)	0.0056 (6)	−0.0034 (6)
C2	0.0173 (8)	0.0188 (9)	0.0229 (9)	−0.0018 (7)	0.0018 (7)	0.0029 (7)
C3	0.0224 (10)	0.0288 (10)	0.0326 (11)	0.0046 (8)	0.0044 (8)	0.0052 (9)
C4	0.0214 (10)	0.0354 (12)	0.0371 (12)	0.0006 (9)	−0.0025 (8)	0.0134 (9)
C5	0.0266 (11)	0.0367 (12)	0.0260 (10)	−0.0076 (9)	−0.0063 (8)	0.0069 (9)
C6	0.0254 (10)	0.0294 (10)	0.0228 (10)	−0.0044 (8)	0.0002 (8)	−0.0017 (8)
C7	0.0171 (9)	0.0188 (8)	0.0223 (9)	−0.0012 (7)	−0.0006 (7)	0.0007 (7)
S1	0.0184 (2)	0.0187 (2)	0.0181 (2)	0.00214 (16)	0.00276 (16)	−0.00135 (16)
O2	0.0317 (8)	0.0201 (7)	0.0286 (7)	0.0036 (6)	0.0044 (6)	−0.0026 (6)
O3	0.0192 (7)	0.0334 (8)	0.0244 (7)	0.0029 (6)	0.0047 (5)	0.0045 (6)
N2	0.0188 (8)	0.0177 (7)	0.0224 (8)	−0.0004 (6)	0.0021 (6)	0.0005 (6)
C8	0.0216 (9)	0.0209 (9)	0.0336 (11)	−0.0008 (7)	0.0060 (8)	0.0021 (8)
C9	0.0210 (10)	0.0290 (11)	0.0394 (12)	0.0000 (8)	0.0103 (9)	0.0016 (9)
C10	0.0263 (11)	0.0247 (10)	0.0368 (12)	0.0063 (8)	0.0071 (9)	−0.0015 (9)
C11	0.0286 (10)	0.0162 (9)	0.0310 (10)	0.0015 (8)	0.0044 (8)	0.0009 (8)
C12	0.0193 (9)	0.0179 (8)	0.0194 (9)	−0.0010 (7)	0.0000 (7)	0.0006 (7)
C13	0.0212 (9)	0.0206 (9)	0.0182 (9)	0.0005 (7)	0.0009 (7)	0.0017 (7)
C14	0.0313 (11)	0.0198 (10)	0.0341 (11)	−0.0024 (8)	0.0067 (9)	0.0026 (8)
C15	0.0340 (12)	0.0262 (11)	0.0413 (13)	−0.0084 (9)	0.0097 (10)	0.0051 (9)
C16	0.0295 (11)	0.0348 (12)	0.0358 (12)	−0.0069 (9)	0.0125 (9)	0.0033 (9)
C17	0.0272 (10)	0.0275 (10)	0.0284 (10)	−0.0024 (8)	0.0094 (8)	−0.0007 (8)
N3	0.0205 (8)	0.0207 (8)	0.0206 (8)	−0.0011 (6)	0.0036 (6)	0.0010 (6)
N4	0.0210 (8)	0.0178 (7)	0.0267 (8)	0.0007 (6)	0.0039 (6)	−0.0002 (6)
C18	0.0278 (10)	0.0239 (10)	0.0296 (10)	0.0003 (8)	0.0024 (8)	0.0022 (8)
C19	0.0304 (11)	0.0217 (10)	0.0375 (12)	0.0034 (8)	0.0069 (9)	0.0045 (9)
C20	0.0306 (11)	0.0170 (9)	0.0420 (12)	−0.0028 (8)	0.0116 (9)	−0.0036 (8)
C21	0.0238 (10)	0.0251 (10)	0.0330 (11)	−0.0028 (8)	0.0066 (8)	−0.0063 (8)
C22	0.0193 (9)	0.0211 (9)	0.0260 (10)	0.0004 (7)	0.0065 (7)	−0.0041 (7)
C23	0.0192 (9)	0.0235 (9)	0.0216 (9)	0.0003 (7)	0.0039 (7)	−0.0044 (7)
C24	0.0207 (10)	0.0299 (11)	0.0291 (10)	−0.0031 (8)	0.0022 (8)	−0.0063 (8)
C25	0.0231 (10)	0.0378 (12)	0.0266 (10)	0.0029 (9)	−0.0015 (8)	−0.0031 (9)
C26	0.0300 (11)	0.0312 (11)	0.0248 (10)	0.0044 (9)	−0.0006 (8)	0.0018 (8)
C27	0.0279 (10)	0.0241 (10)	0.0268 (10)	−0.0023 (8)	0.0001 (8)	0.0005 (8)
N5	0.0218 (8)	0.0220 (8)	0.0225 (8)	−0.0012 (6)	0.0004 (6)	−0.0003 (6)
O4	0.0267 (8)	0.0328 (8)	0.0212 (7)	0.0045 (6)	0.0016 (6)	−0.0082 (6)
N6	0.0346 (10)	0.0237 (8)	0.0199 (8)	−0.0002 (7)	−0.0014 (7)	−0.0036 (6)
C28	0.0256 (10)	0.0199 (9)	0.0227 (9)	−0.0059 (7)	−0.0035 (7)	−0.0016 (7)
O5	0.0387 (9)	0.0315 (8)	0.0273 (8)	−0.0008 (7)	−0.0102 (6)	0.0036 (6)
C29	0.0196 (9)	0.0185 (9)	0.0201 (9)	−0.0046 (7)	0.0023 (7)	0.0003 (7)
C30	0.0254 (10)	0.0196 (9)	0.0320 (11)	0.0001 (8)	0.0061 (8)	0.0032 (8)
C31	0.0352 (11)	0.0222 (10)	0.0321 (11)	−0.0016 (8)	0.0150 (9)	−0.0049 (8)
C32	0.0363 (11)	0.0282 (10)	0.0197 (10)	−0.0098 (9)	0.0068 (8)	−0.0037 (8)
C33	0.0245 (10)	0.0240 (9)	0.0228 (9)	−0.0061 (8)	0.0004 (8)	0.0034 (8)
C34	0.0188 (9)	0.0170 (8)	0.0216 (9)	−0.0039 (7)	0.0021 (7)	−0.0014 (7)
S2	0.0241 (2)	0.0179 (2)	0.0233 (2)	0.00010 (18)	0.00228 (18)	−0.00254 (17)
O6	0.0257 (8)	0.0311 (8)	0.0372 (8)	0.0043 (6)	0.0056 (6)	−0.0033 (6)
O7	0.0384 (9)	0.0191 (7)	0.0376 (8)	−0.0026 (6)	0.0058 (7)	−0.0026 (6)

Geometric parameters (Å, º)

Co1—N1	2.1688 (17)	C17—N3	1.345 (3)
Co1—N2	2.1339 (16)	C17—H17	0.98 (2)
Co1—N3	2.1482 (16)	N4—C18	1.341 (3)
Co1—N4	2.1516 (16)	N4—C22	1.360 (3)
Co1—N5	2.1403 (17)	C18—C19	1.393 (3)
Co1—O4	2.0565 (15)	C18—H18	0.96 (2)
N1—C1	1.366 (2)	C19—C20	1.391 (3)
N1—S1	1.6465 (16)	C19—H19	0.98 (2)
C1—O1	1.242 (2)	C20—C21	1.392 (3)
C1—C2	1.496 (3)	C20—H20	0.94 (2)
C2—C7	1.382 (3)	C21—C22	1.396 (3)
C2—C3	1.394 (3)	C21—H21	0.97 (2)
C3—C4	1.391 (3)	C22—C23	1.491 (3)
C3—H3	0.93 (2)	C23—N5	1.353 (2)
C4—C5	1.395 (3)	C23—C24	1.392 (3)
C4—H4	0.99 (3)	C24—C25	1.389 (3)
C5—C6	1.400 (3)	C24—H24	0.92 (2)
C5—H5	0.96 (3)	C25—C26	1.393 (3)
C6—C7	1.386 (3)	C25—H25	0.95 (2)
C6—H6	0.98 (3)	C26—C27	1.385 (3)
C7—S1	1.7712 (19)	C26—H26	0.94 (3)
S1—O3	1.4436 (14)	C27—N5	1.343 (3)
S1—O2	1.4480 (15)	C27—H27	0.94 (2)
N2—C8	1.342 (2)	N6—C28	1.364 (3)
N2—C12	1.350 (2)	N6—S2	1.6180 (18)
C8—C9	1.389 (3)	C28—O5	1.238 (2)
C8—H8	0.95 (2)	C28—C29	1.510 (3)
C9—C10	1.388 (3)	C29—C30	1.385 (3)
C9—H9	0.95 (3)	C29—C34	1.387 (3)
C10—C11	1.386 (3)	C30—C31	1.396 (3)
C10—H10	0.94 (3)	C30—H30	0.94 (2)
C11—C12	1.392 (3)	C31—C32	1.390 (3)
C11—H11	0.93 (2)	C31—H31	0.90 (3)
C12—C13	1.492 (3)	C32—C33	1.398 (3)
C13—N3	1.351 (2)	C32—H32	0.98 (2)
C13—C14	1.399 (3)	C33—C34	1.388 (3)
C14—C15	1.394 (3)	C33—H33	0.93 (2)
C14—H14	0.92 (3)	C34—S2	1.7730 (19)
C15—C16	1.381 (3)	S2—O6	1.4428 (16)
C15—H15	0.97 (3)	S2—O7	1.4515 (15)
C16—C17	1.390 (3)	O4—H4A	0.81 (3)
C16—H16	0.93 (3)	O4—H4B	0.95 (3)
N1—Co1—N2	95.21 (6)	C17—C16—H16	120.3 (17)
N1—Co1—N3	91.02 (6)	N3—C17—C16	122.8 (2)
N1—Co1—N4	94.10 (6)	N3—C17—H17	114.8 (14)
N1—Co1—N5	170.83 (6)	C16—C17—H17	122.4 (14)
N1—Co1—O4	90.50 (6)	C17—N3—C13	118.61 (17)
N2—Co1—N3	76.58 (6)	C17—N3—Co1	125.33 (13)
N2—Co1—N4	101.19 (6)	C13—N3—Co1	115.93 (12)
N2—Co1—N5	86.17 (6)	C18—N4—C22	118.25 (17)
N2—Co1—O4	165.61 (6)	C18—N4—Co1	125.81 (14)
N3—Co1—N4	174.59 (6)	C22—N4—Co1	114.95 (13)
N3—Co1—N5	98.11 (6)	N4—C18—C19	123.3 (2)
N3—Co1—O4	90.14 (6)	N4—C18—H18	117.8 (14)
N4—Co1—N5	76.75 (6)	C19—C18—H18	118.8 (14)
N4—Co1—O4	91.54 (6)	C20—C19—C18	118.1 (2)
N5—Co1—O4	90.30 (6)	C20—C19—H19	122.0 (14)
C1—N1—S1	111.40 (13)	C18—C19—H19	119.9 (14)
C1—N1—Co1	126.76 (12)	C19—C20—C21	119.58 (19)
S1—N1—Co1	121.27 (8)	C19—C20—H20	121.2 (15)
O1—C1—N1	124.98 (17)	C21—C20—H20	119.3 (15)
O1—C1—C2	122.06 (17)	C20—C21—C22	118.8 (2)
N1—C1—C2	112.95 (16)	C20—C21—H21	124.0 (13)
C7—C2—C3	120.36 (18)	C22—C21—H21	117.2 (13)
C7—C2—C1	111.91 (16)	N4—C22—C21	121.92 (18)
C3—C2—C1	127.67 (18)	N4—C22—C23	115.10 (16)
C4—C3—C2	117.8 (2)	C21—C22—C23	122.96 (18)
C4—C3—H3	123.3 (14)	N5—C23—C24	121.81 (18)
C2—C3—H3	118.9 (14)	N5—C23—C22	115.55 (16)
C3—C4—C5	121.3 (2)	C24—C23—C22	122.54 (18)
C3—C4—H4	118.0 (16)	C25—C24—C23	119.34 (19)
C5—C4—H4	120.7 (16)	C25—C24—H24	121.9 (14)
C4—C5—C6	120.9 (2)	C23—C24—H24	118.7 (14)
C4—C5—H5	118.5 (15)	C24—C25—C26	118.76 (19)
C6—C5—H5	120.5 (15)	C24—C25—H25	120.7 (14)
C7—C6—C5	116.9 (2)	C26—C25—H25	120.5 (14)
C7—C6—H6	120.4 (15)	C27—C26—C25	118.6 (2)
C5—C6—H6	122.7 (15)	C27—C26—H26	116.3 (16)
C2—C7—C6	122.72 (18)	C25—C26—H26	125.1 (16)
C2—C7—S1	107.57 (14)	N5—C27—C26	123.1 (2)
C6—C7—S1	129.65 (16)	N5—C27—H27	116.8 (14)
O3—S1—O2	116.09 (9)	C26—C27—H27	120.0 (14)
O3—S1—N1	110.51 (9)	C27—N5—C23	118.35 (17)
O2—S1—N1	110.90 (8)	C27—N5—Co1	125.16 (14)
O3—S1—C7	110.39 (9)	C23—N5—Co1	115.98 (13)
O2—S1—C7	111.03 (9)	Co1—O4—H4A	111 (2)
N1—S1—C7	96.14 (9)	Co1—O4—H4B	128.1 (18)
C8—N2—C12	118.61 (16)	H4A—O4—H4B	110 (3)
C8—N2—Co1	124.55 (13)	C28—N6—S2	112.20 (13)
C12—N2—Co1	116.26 (12)	O5—C28—N6	124.58 (18)
N2—C8—C9	123.08 (19)	O5—C28—C29	123.05 (18)
N2—C8—H8	114.3 (14)	N6—C28—C29	112.37 (16)
C9—C8—H8	122.6 (14)	C30—C29—C34	119.92 (18)
C10—C9—C8	118.23 (19)	C30—C29—C28	128.65 (18)
C10—C9—H9	123.5 (16)	C34—C29—C28	111.43 (16)
C8—C9—H9	118.2 (16)	C29—C30—C31	118.54 (19)
C11—C10—C9	119.11 (19)	C29—C30—H30	122.2 (15)
C11—C10—H10	119.0 (16)	C31—C30—H30	119.2 (15)
C9—C10—H10	121.9 (16)	C32—C31—C30	120.81 (19)
C10—C11—C12	119.51 (18)	C32—C31—H31	119.9 (16)
C10—C11—H11	119.1 (15)	C30—C31—H31	119.3 (16)
C12—C11—H11	121.4 (15)	C31—C32—C33	121.21 (19)
N2—C12—C11	121.45 (17)	C31—C32—H32	119.8 (14)
N2—C12—C13	115.34 (16)	C33—C32—H32	119.0 (14)
C11—C12—C13	123.21 (17)	C34—C33—C32	116.73 (19)
N3—C13—C14	121.41 (18)	C34—C33—H33	121.6 (14)
N3—C13—C12	115.26 (16)	C32—C33—H33	121.7 (14)
C14—C13—C12	123.32 (17)	C29—C34—C33	122.79 (18)
C15—C14—C13	119.5 (2)	C29—C34—S2	107.14 (14)
C15—C14—H14	119.4 (15)	C33—C34—S2	130.04 (15)
C13—C14—H14	121.1 (15)	O6—S2—O7	114.77 (9)
C16—C15—C14	118.6 (2)	O6—S2—N6	112.31 (10)
C16—C15—H15	119.9 (16)	O7—S2—N6	110.67 (9)
C14—C15—H15	121.4 (16)	O6—S2—C34	111.56 (9)
C15—C16—C17	119.0 (2)	O7—S2—C34	109.38 (9)
C15—C16—H16	120.7 (17)	N6—S2—C34	96.70 (9)