metal-organic compounds

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1 metal-organic compounds Acta Crystallographica Section C Crystal Structure Communications ISSN Two saccharinate complexes: [Mn(phen) 2 (sac)(h 2 O)] + sac ± and [Co(bipy) 2 (sac)(h 2 O)] + sac ± present both in the cation and as the counter-ion, namely [Mn(phen) 2 (sac)(h 2 O)] + sac, (I), and [Co(bipy) 2 (sac)- (H 2 O)] + sac, (II), the latter representing the rst 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)(h 2 O)] + Robert M. K. Deng, a Clair Bilton, b Keith B. Dillon b * and Judith A. K. Howard b a Chemistry Department, University of Botswana, Private Bag 0022, Gaborone, Botswana, and b Chemistry Department, University of Durham, South Road, Durham DH1 3LE, England Correspondence k.b.dillon@dur.ac.uk Received 6 July 1999 Accepted 5 October 1999 The title saccharinate complexes, aqua[1,2-benzisothiazol- 3(2H)-onato 1,1-dioxide-N]bis(1,10-phenanthroline-N,N 0 )- manganese(ii) 1,2-benzisothiazol-3(2H)-onate 1,1-dioxide, [Mn(C 7 H 4 NO 3 S)(C 12 H 8 N 2 ) 2 (H 2 O)](C 7 H 4 NO 3 S), and aqua- [1,2-benzisothiazol-3(2H)-onato 1,1-dioxide-N]bis(2,2 0 -bipyridine-n,n 0 )cobalt(ii) 1,2-benzisothiazol-3(2H)-onate 1,1-dioxide, [Co(C 7 H 4 NO 3 S)(C 10 H 8 N 2 ) 2 (H 2 O)](C 7 H 4 NO 3 S), 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)(h 2 O)] + 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 SO 2 group in the saccharinate counter-ion. In contrast, the cobalt complex has one pseudo-octahedral [Co(bipy) 2 (sac)(h 2 O)] + cation, with the cobalt-bound water molecule hydrogen bonded to the N atom of the accompanying free saccharinate anion. 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 0 - bipyridine (bipy) or 1,10-phenanthroline (phen) present. These included examples with all the saccharinate ligands attached to the metal (Hergol-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 rst 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) and [Co(bipy) 2 (sac)(h 2 O)] + units, respectively, and saccharinate counter-ions. Within the cation of (I), the mean MnÐ N phen bond length is (6) A Ê, 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)(h 2 O)] + (Dillon et al., 1999). The MnÐN sac bond length of (2) A Ê is close to that in the bipy complex and may be compared with the corresponding distance of (1) A Ê in [Mn(sac) 2 - (H 2 O) 4 ]2H 2 O (Kamenar & Jovanovski, 1982). The MnÐ O aqua separation of (2) A Ê is rather longer than in the bipy complex [2.127 (3) A Ê ], possibly re ecting the greater steric requirements of the phen ligand, and is intermediate between the two independent MnÐO aqua distances of (1) and (2) A Ê in [Mn(sac) 2 (H 2 O) 4 ]2H 2 O (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 N2ÐMnÐN5 = (6), O4ÐMnÐN3 = (6) and N1ÐMnÐN4 = (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 SO 2 group in the free saccharinate anion (Fig. 1), with an HO7 distance of 1.91 (3) A Ê ; 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 (H 2 O) 4 ]2H 2 O [M = Mn (Kamenar & Jovanovski, 1982) and Co (Haider et al., 1983)]. The average CoÐN bipy bond length is (4) A Ê, though the 142 Robert M. K. Deng et al. Mn± and Co±C 7 H 4 NO 3 S complexes Acta Cryst. (2000). C56, 142±145

2 metal-organic compounds ligand asymmetry seen in compound (I) is not displayed. The CoÐN sac distance of (2) A Ê compares well with the distance of (1) A Ê in [Co(sac) 2 (H 2 O) 4 ]2H 2 O (Haider et al., 1983), while the CoÐO aqua distance of (2) A Ê in (II) is similar to the shorter of the two independent CoÐO aqua bond lengths of (1) and (2) A Ê in [Co(sac) 2 - (H 2 O) 4 ]2H 2 O. Some distortion of regular geometry is apparent in the cation [O4ÐCo1ÐN2 = (6), N3Ð Co1ÐN4 = (6) and N5ÐCo1ÐN1 = (6) ], though this is less pronounced than in the manganese compound (I), again showing the sterically less demanding Figure 1 The molecular structure of (I) showing 50% probability displacement ellipsoids. Figure 2 The molecular structure of (II) showing 50% probability displacement ellipsoids. Figure 3 Packing diagram of (I) with intermolecular contacts indicated by dotted lines. Acta Cryst. (2000). C56, 142±145 Robert M. K. Deng et al. Mn± and Co±C 7 H 4 NO 3 S complexes 143

3 metal-organic compounds Experimental Compound (I) was prepared by adding with stirring a warm solution of 1,10-phenanthroline ( g, 0.78 mmol) in water (50 ml) to a warm clear solution of [Mn(sac) 2 (H 2 O) 4 ]2H 2 O ( g, 0.39 mmol) in water (50 ml). The resulting yellow solution was warmed on a hotplate 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 ltration, washed with three 5 ml portions of cold water and dried over silica gel [yield 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%; C 38 H 26 MnN 6 O 7 S 2 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 0 -bipyridine ( g, 0.75 mmol) in water (25 ml) to a warm solution of [Co(sac) 2 (H 2 O) 4 ]2H 2 O ( g, 0.38 mmol) in water (25 ml). The resulting intense yellow solution was warmed on a hot-plate with stirring and the volume reduced to 20 ml. The brown solution was allowed to stand overnight and bright orange crystals of the compound were then isolated [yield g (75.9%), m.p. 455 K]. Found: C 53.71, H 3.36, N 10.97, Co 7.90%; C 34 H 26 CoN 6 O 7 S 2 requires: C 54.18, H 3.48, N 11.15, Co 7.82%. Compound (I) Figure 4 Packing diagram of (II); note the free and bound saccharinate groups alternating in a staggered conformation. 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 HO distance of 1.78 (3) A Ê, as in the structure of [Mn(sac)(bipy) 2 (H 2 O)](sac) (Dillon et al., 1999). The structural parameters for the free anions in both (I) and (II) are again very similar to those in K 2 Na(sac) 3 H 2 O (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 signi cant intermolecular contacts. In addition to the hydrogen bond between O7 in the SO 2 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 O6 i at a distance of 2.50 (2) A Ê [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) A Ê for C6ÐH6O7 S2 and 2.56 (2) A Ê for C33Ð H33O3 S1. There is also a close contact of 2.49 (3) A Ê between C20ÐH20 and O1 ii C1 ii, as well as a linear hydrogen bond of 1.78 (3) A Ê between H4B and N6 iii with an OÐHN angle of (3) [symmetry codes: (ii) 2 x, y, 1 z; (iii) x, y, z 1]. Crystal data [Mn(C 7 H 4 NO 3 S)(C 12 H 8 N 2 ) 2 - (H 2 O)](C 7 H 4 NO 3 S) M r = Triclinic, P1 a = (2) A Ê b = (3) A Ê c = (3) A Ê = (3) = (3) = (3) V = (6) A Ê 3 Data collection Siemens SMART CCD diffractometer! scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.773, T max = measured re ections Table 1 Selected geometric parameters (A Ê, ) for (I). Mn1ÐN (18) Mn1ÐN (17) Mn1ÐN (18) Mn1ÐN (19) Mn1ÐN (17) Mn1ÐO (17) N1ÐMn1ÐN (6) N1ÐMn1ÐN (6) N1ÐMn1ÐN (6) N1ÐMn1ÐN (7) N1ÐMn1ÐO (7) N2ÐMn1ÐN (7) N2ÐMn1ÐN (7) N2ÐMn1ÐN (6) N2ÐMn1ÐO (7) N3ÐMn1ÐN (6) Z =2 D x = Mg m 3 Mo K radiation Cell parameters from 998 re ections = 10.25±27.34 = mm 1 T = 150 K Block, yellow mm 8956 independent re ections 6420 re ections with I > 2(I) R int = max = h = 11! 10 k = 20! 17 l = 21! 19 N1ÐC (3) N1ÐS (17) N6ÐC (3) N6ÐS (2) O4ÐH4A 0.89 (3) O4ÐH4B 0.83 (3) N3ÐMn1ÐN (6) N3ÐMn1ÐO (6) N4ÐMn1ÐN (7) N4ÐMn1ÐO (7) O4ÐMn1ÐN (7) C1ÐN1ÐS (14) C32ÐN6ÐS (15) Mn1ÐO4ÐH4A 107 (2) Mn1ÐO4ÐH4B 124 (2) 144 Robert M. K. Deng et al. Mn± and Co±C 7 H 4 NO 3 S complexes Acta Cryst. (2000). C56, 142±145

4 metal-organic compounds Re nement Re nement on F 2 R(F) = wr(f 2 ) = S = re ections 591 parameters Compound (II) Crystal data [Co(C 7 H 4 NO 3 S)(C 10 H 8 N 2 ) 2 - (H 2 O)](C 7 H 4 NO 3 S) M r = Monoclinic, P2 1 =n a = (1) A Ê b = (5) A Ê c = (2) A Ê = (1) V = (8) A Ê 3 Z =4 Data collection Siemens SMART CCD areadetector diffractometer! scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.651, T max = measured re ections Re nement Re nement on F 2 R(F) = wr(f 2 ) = S = re ections 555 parameters All H-atom parameters re ned w = 1/[ 2 (F o 2 ) + (0.0591P) 2 ] where P =(F o 2 +2F c 2 )/3 (/) max = max = 0.39 e A Ê 3 min = 0.36 e A Ê 3 D x = Mg m 3 Mo K radiation Cell parameters from 501 re ections = 14.87±19.99 = mm 1 T = 150 K Block, orange mm 7238 independent re ections 6294 re ections with I > 2(I) R int = max = h = 9! 9 k = 40! 40 l = 17! 12 All H-atom parameters re ned w = 1/[ 2 (F o 2 ) + (0.0214P) P] where P =(F o 2 +2F c 2 )/3 max = 0.37 e A Ê 3 min = 0.43 e A Ê 3 All H atoms were re ned and the CÐH distances are in the ranges 0.83 (3)±1.03 (3) and 0.90 (3)±0.99 (3) A Ê for (I) and (II), respectively. For both compounds, data collection: SMART (Siemens, 1995); cell re nement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1991); software used to prepare material for publication: SHELXL97. JAKH thanks the University of Durham for a Sir Derman Christopherson Foundation Fellowship and CB thanks the EPSRC for nancial support. Table 2 Selected geometric parameters (A Ê, ) for (II). Co1ÐN (17) Co1ÐN (16) Co1ÐN (16) Co1ÐN (16) Co1ÐN (17) Co1ÐO (15) N1ÐCo1ÐN (6) N1ÐCo1ÐN (6) N1ÐCo1ÐN (6) N1ÐCo1ÐN (6) N1ÐCo1ÐO (6) N2ÐCo1ÐN (6) N2ÐCo1ÐN (6) N2ÐCo1ÐN (6) N2ÐCo1ÐO (6) Supplementary data for this paper are available from the IUCr electronic archives (Reference: BM1359). Services for accessing these data are described at the back of the journal. References N1ÐC (2) N1ÐS (16) N6ÐC (3) N6ÐS (18) O4ÐH4A 0.81 (3) O4ÐH4B 0.95 (3) N3ÐCo1ÐN (6) N3ÐCo1ÐN (6) N3ÐCo1ÐO (6) N4ÐCo1ÐN (6) N4ÐCo1ÐO (6) N5ÐCo1ÐO (6) C1ÐN1ÐS (13) C28ÐN6ÐS (13) Ainscough, E. W., Baker, E. N., Brodie, A. M., Cresswell, R. J., Ranford, J. D. & Waters, J. M. (1990). Inorg. Chim. Acta, 172, 185±190. Dillon, K. B., Bilton, C., Howard, J. A. K., Hoy, V. J., Deng, R. M. K. & Sethatho, D. T. (1999). Acta Cryst. C55, 330±331. Haider, S. Z., Malik, K. M. A., Ahmed, K. J., Hess, H., Riffel, H. & Hursthouse, M. B. (1983). Inorg. Chim. Acta, 72, 21±27. Hergold-Brundic, A., Grupce, O. & Jovanovski, G. (1991). Acta Cryst. C47, 556±558. Hergold-Brundic, A., Kamenar, B. & Jovanovski, G. (1989). Acta Cryst. C45, 556±558. Kamenar, B. & Jovanovski, G. (1982). Cryst. Struct. Commun. 11, 251±261. Li, J., Chen, H., Wu, Q. & Wu, X. (1993). Cryst. Res. Technol. 28, 181±186. Li, J., Lin, W., Zhang, Y., Liu, S. & Huang, J. (1991). Polyhedron, 10, 403±407. Li, J., Wei, J., Wu, X., Zhu, N. & Zhang, Y. (1993). Cryst. Res. Technol. 28, 11±14. Malik, K. M. A., Haider, S. Z., Hossain, M. A. & Hursthouse, M. B. (1984). Acta Cryst. C40, 1696±1698. Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473. Sheldrick, G. M. (1991). SHELXTL. Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Sheldrick, G. M. (1996). SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997). SHELXL97. University of GoÈttingen, Germany. Siemens (1995). SMART and SAINT. Versions Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Zhang, Y., Li, J., We, J., Wu, X. & Du, S. (1994). Cryst. Res. Technol. 29, 975±980. Acta Cryst. (2000). C56, 142±145 Robert M. K. Deng et al. Mn± and Co±C 7 H 4 NO 3 S complexes 145

5 supporting information [doi: /s ] Two saccharinate complexes: [Mn(phen) 2 (sac)(h 2 O)] + sac and [Co(bipy) 2 (sac) (H 2 O)] + sac Robert M. K. Deng, Clair Bilton, Keith B. Dillon and Judith A. K. Howard 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. (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(C 7 H 4 NO 3 S)(C 12 H 8 N 2 ) 2 (H 2 O)](C 7 H 4 NO 3 S) M r = Triclinic, P1 a = (2) Å b = (3) Å c = (3) Å α = (3) β = (3) γ = (3) V = (6) Å 3 Z = 2 Data collection Siemens SMART CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.773, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 591 parameters F(000) = 818 D x = Mg m 3 Melting point: 485 K Mo Kα radiation, λ = Å Cell parameters from 998 reflections θ = µ = 0.57 mm 1 T = 150 K Block, yellow mm measured reflections 8956 independent reflections 6420 reflections with I > 2σ(I) R int = θ max = 30.4, θ min = 1.4 h = k = l = restraints All H-atom parameters refined w = 1/[σ 2 (F o2 ) + (0.0591P) 2 ] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.39 e Å 3 Δρ min = 0.36 e Å 3 sup-1

6 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 F 2 for ALL reflections except for 62 with very negative F 2 or flagged by the user for potential systematic errors. Weighted R-factors wr and all goodnesses of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The observed criterion of F 2 > σ(f 2 ) is used only for calculating R- factor-obs etc and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq Mn (4) (2) (19) (8) N (2) (12) (11) (3) C (2) (14) (13) (4) O (19) (11) (9) (3) C (2) (14) (13) (4) C (3) (16) (16) (5) H (3) (17) (17) (7)* C (3) (17) (18) (6) H (4) (2) (19) (9)* C (3) (17) (18) (6) H (4) (2) (2) (9)* C (3) (17) (15) (5) H (3) (17) (17) (7)* C (3) (14) (13) (4) S (7) (4) (3) (12) O (19) (12) (11) (4) O (2) (11) (10) (4) N (2) (11) (11) (4) C (3) (15) (15) (5) H (3) (16) (16) (6)* C (3) (16) (16) (5) H (3) (17) (16) (7)* C (3) (15) (16) (5) H (3) (16) (16) (6)* C (3) (14) (14) (5) C (3) (16) (14) (5) H (3) (18) (18) (7)* C (3) (16) (15) (5) H (3) (18) (18) (7)* C (3) (15) (13) (4) C (3) (17) (15) (5) H (3) (18) (18) (7)* C (3) (17) (15) (5) H (3) (17) (16) (7)* sup-2

7 C (3) (15) (14) (4) H (3) (18) (17) (7)* N (2) (11) (11) (3) C (3) (13) (13) (4) C (3) (13) (13) (4) N (2) (12) (11) (4) C (3) (16) (16) (5) H (3) (16) (15) (6)* C (3) (19) (18) (6) H (4) (2) (2) (9)* C (3) (19) (17) (6) H (3) (17) (17) (7)* C (3) (17) (14) (5) C (3) (2) (16) (6) H (3) (18) (18) (7)* C (3) (2) (15) (6) H (4) (19) (18) (8)* C (3) (16) (14) (5) C (3) (17) (16) (6) H (3) (16) (15) (6)* C (3) (16) (16) (5) H (3) (17) (15) (6)* C (3) (15) (15) (5) H (3) (16) (17) (6)* N (2) (11) (11) (3) C (2) (15) (13) (4) C (2) (15) (13) (4) O (2) (12) (11) (3) H4A (4) (2) (2) (9)* H4B (4) (2) (2) (9)* N (2) (13) (12) (4) C (3) (14) (15) (4) O (2) (13) (11) (4) C (2) (13) (13) (4) C (3) (15) (14) (4) H (3) (15) (15) (6)* C (3) (16) (15) (5) H (3) (18) (18) (7)* C (3) (18) (17) (5) H (3) (17) (16) (7)* C (3) (17) (16) (5) H (3) (16) (16) (6)* C (3) (14) (13) (4) S (7) (4) (3) (12) O (2) (11) (11) (4) O (2) (11) (10) (4) sup-3

8 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Mn (16) (16) (15) (11) (11) (12) N (8) (9) (8) (7) (6) (7) C (9) (10) (9) (8) (7) (8) O (8) (8) (7) (6) (6) (6) C (10) (10) (9) (8) (8) (8) C (11) (12) (12) (9) (10) (10) C (13) (13) (15) (10) (11) (11) C (15) (13) (14) (11) (12) (11) C (13) (13) (11) (10) (10) (10) C (10) (10) (10) (8) (8) (8) S (3) (3) (2) (2) (19) (2) O (8) (10) (9) (7) (7) (8) O (10) (9) (8) (8) (7) (7) N (9) (8) (9) (7) (7) (7) C (11) (11) (11) (9) (9) (9) C (12) (11) (13) (10) (10) (10) C (14) (11) (13) (10) (11) (9) C (13) (10) (10) (9) (9) (8) C (16) (11) (11) (10) (10) (9) C (15) (12) (11) (11) (10) (9) C (12) (11) (10) (9) (9) (8) C (12) (13) (11) (10) (9) (9) C (12) (12) (12) (10) (9) (10) C (11) (11) (11) (9) (9) (9) N (9) (8) (8) (7) (7) (7) C (10) (9) (9) (8) (8) (8) C (11) (9) (10) (8) (8) (8) N (9) (9) (9) (7) (7) (7) C (13) (11) (12) (10) (10) (10) C (15) (14) (15) (11) (12) (12) C (12) (16) (13) (11) (10) (12) C (10) (14) (11) (9) (8) (10) C (11) (19) (12) (11) (9) (12) C (11) (17) (12) (11) (9) (12) C (10) (13) (11) (9) (8) (10) C (12) (13) (13) (10) (10) (11) C (12) (11) (14) (9) (10) (10) C (11) (11) (12) (9) (9) (9) N (8) (8) (9) (7) (7) (7) C (9) (11) (10) (8) (7) (8) C (9) (11) (10) (8) (8) (8) O (8) (9) (8) (7) (6) (7) N (10) (10) (10) (8) (8) (8) C (10) (11) (11) (8) (9) (9) O (8) (11) (10) (8) (7) (9) sup-4

9 C (9) (9) (10) (7) (8) (8) C (11) (11) (10) (9) (8) (9) C (12) (12) (12) (9) (9) (10) C (11) (14) (14) (10) (10) (11) C (11) (13) (12) (10) (9) (10) C (10) (10) (9) (8) (8) (8) S (3) (2) (2) (2) (2) (2) O (12) (9) (9) (8) (8) (7) O (11) (8) (8) (7) (7) (6) Geometric parameters (Å, º) Mn1 N (18) N3 C (2) Mn1 N (17) C18 C (3) Mn1 N (18) N4 C (3) Mn1 N (19) N4 C (3) Mn1 N (17) C20 C (4) Mn1 O (17) C20 H (2) N1 C (3) C21 C (4) N1 S (17) C21 H (3) C1 O (2) C22 C (4) C1 C (3) C22 H (3) C2 C (3) C23 C (3) C2 C (3) C23 C (3) C3 C (3) C24 C (4) C3 H (3) C24 H (3) C4 C (4) C25 C (3) C4 H (3) C25 H (3) C5 C (4) C26 C (3) C5 H (3) C26 C (3) C6 C (3) C27 C (4) C6 H (2) C27 H (2) C7 S (2) C28 C (3) S1 O (17) C28 H (2) S1 O (16) C29 N (3) N2 C (3) C29 H (3) N2 C (3) N5 C (3) C8 C (3) C30 C (3) C8 H (2) N6 C (3) C9 C (4) N6 S (2) C9 H (3) C32 O (3) C10 C (3) C32 C (3) C10 H (2) C33 C (3) C11 C (3) C33 C (3) C11 C (3) C34 C (3) C12 C (4) C34 H (2) C12 H (3) C35 C (3) C13 C (3) C35 H (3) sup-5

10 C13 H (3) C36 C (3) C14 C (3) C36 H (3) C14 C (3) C37 C (3) C15 C (3) C37 H (2) C15 H (3) C38 S (2) C16 C (3) S2 O (17) C16 H (3) S2 O (16) C17 N (3) O4 H4A 0.89 (3) C17 H (3) O4 H4B 0.83 (3) N1 Mn1 N (6) C18 N3 Mn (13) N1 Mn1 N (6) N3 C18 C (19) N1 Mn1 N (6) N3 C18 C (18) N1 Mn1 N (7) C14 C18 C (18) N1 Mn1 O (7) N2 C19 C (19) N2 Mn1 N (7) N2 C19 C (17) N2 Mn1 N (7) C11 C19 C (19) N2 Mn1 N (6) C20 N4 C (19) N2 Mn1 O (7) C20 N4 Mn (15) N3 Mn1 N (6) C31 N4 Mn (14) N3 Mn1 N (6) N4 C20 C (2) N3 Mn1 O (6) N4 C20 H (13) N4 Mn1 N (7) C21 C20 H (13) N4 Mn1 O (7) C22 C21 C (2) O4 Mn1 N (7) C22 C21 H (18) C1 N1 S (14) C20 C21 H (18) C1 N1 Mn (13) C21 C22 C (2) S1 N1 Mn (9) C21 C22 H (15) O1 C1 N (19) C23 C22 H (15) O1 C1 C (18) C22 C23 C (2) N1 C1 C (17) C22 C23 C (2) C3 C2 C (2) C31 C23 C (2) C3 C2 C (19) C25 C24 C (2) C7 C2 C (18) C25 C24 H (18) C2 C3 C (2) C23 C24 H (18) C2 C3 H (16) C24 C25 C (2) C4 C3 H (16) C24 C25 H (17) C5 C4 C (2) C26 C25 H (17) C5 C4 H (17) C27 C26 C (2) C3 C4 H (17) C27 C26 C (2) C4 C5 C (2) C30 C26 C (2) C4 C5 H (17) C28 C27 C (2) C6 C5 H (17) C28 C27 H (15) C7 C6 C (2) C26 C27 H (15) C7 C6 H (16) C27 C28 C (2) C5 C6 H (16) C27 C28 H (14) C6 C7 C (2) C29 C28 H (14) C6 C7 S (18) N5 C29 C (2) sup-6

11 C2 C7 S (15) N5 C29 H (15) O2 S1 O (10) C28 C29 H (15) O2 S1 N (10) C29 N5 C (18) O3 S1 N (10) C29 N5 Mn (15) O2 S1 C (10) C30 N5 Mn (13) O3 S1 C (10) N5 C30 C (2) N1 S1 C (10) N5 C30 C (17) C8 N2 C (18) C26 C30 C (2) C8 N2 Mn (15) N4 C31 C (2) C19 N2 Mn (13) N4 C31 C (18) N2 C8 C (2) C23 C31 C (19) N2 C8 H (14) H4A O4 H4B 107 (3) C9 C8 H (14) C32 N6 S (15) C10 C9 C (2) O5 C32 N (2) C10 C9 H (16) O5 C32 C (19) C8 C9 H (16) N6 C32 C (18) C9 C10 C (2) C38 C33 C (19) C9 C10 H (15) C38 C33 C (17) C11 C10 H (15) C34 C33 C (19) C10 C11 C (2) C35 C34 C (2) C10 C11 C (2) C35 C34 H (14) C19 C11 C (2) C33 C34 H (14) C13 C12 C (2) C36 C35 C (2) C13 C12 H (17) C36 C35 H (17) C11 C12 H (17) C34 C35 H (16) C12 C13 C (2) C35 C36 C (2) C12 C13 H (16) C35 C36 H (16) C14 C13 H (16) C37 C36 H (16) C18 C14 C (19) C38 C37 C (2) C18 C14 C (2) C38 C37 H (15) C15 C14 C (2) C36 C37 H (15) C16 C15 C (2) C37 C38 C (19) C16 C15 H (15) C37 C38 S (17) C14 C15 H (15) C33 C38 S (15) C15 C16 C (2) O6 S2 O (10) C15 C16 H (16) O6 S2 N (11) C17 C16 H (16) O7 S2 N (11) N3 C17 C (2) O6 S2 C (10) N3 C17 H (15) O7 S2 C (10) C16 C17 H (15) N6 S2 C (10) C17 N3 C (18) Mn1 O4 H4A 107 (2) C17 N3 Mn (14) Mn1 O4 H4B 124 (2) sup-7

12 (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(C 7 H 4 NO 3 S)(C 10 H 8 N 2 ) 2 (H 2 O)](C 7 H 4 NO 3 S) M r = Monoclinic, P2 1 /n a = (1) Å b = (5) Å c = (2) Å β = (1) V = (8) Å 3 Z = 4 F(000) = 1548 Data collection Siemens SMART CCD area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.651, T max = D x = Mg m 3 Melting point: 455 K Mo Kα radiation, λ = Å Cell parameters from 501 reflections θ = µ = 0.73 mm 1 T = 150 K Block, orange mm measured reflections 7238 independent reflections 6294 reflections with I > 2σ(I) R int = θ max = 27.5, θ min = 1.3 h = 9 9 k = l = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 555 parameters 0 restraints All H-atom parameters refined w = 1/[σ 2 (F o2 ) + (0.0214P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.37 e Å 3 Δρ min = 0.43 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 on F 2 for ALL reflections except for 191 with very negative F 2 or flagged by the user for potential systematic errors. Weighted R-factors wr and all goodnesses of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The observed criterion of F 2 > σ(f 2 ) is used only for calculating -Rfactor-obs etc.and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq Co (3) (8) (18) (7) N (2) (5) (11) (3) C (2) (6) (14) (4) O (19) (5) (10) (3) C (2) (6) (14) (4) sup-8

13 C (3) (7) (17) (4) H (3) (7) (17) (6)* C (3) (7) (17) (5) H (4) (9) (2) (7)* C (3) (7) (17) (5) H (3) (8) (19) (7)* C (3) (7) (15) (4) H (3) (8) (19) (7)* C (2) (6) (14) (4) S (6) (14) (3) (10) O (19) (4) (11) (3) O (17) (5) (10) (3) N (2) (5) (12) (3) C (3) (6) (16) (4) H (3) (8) (17) (6)* C (3) (7) (17) (4) H (3) (8) (2) (7)* C (3) (7) (17) (4) H (3) (8) (19) (7)* C (3) (6) (16) (4) H (3) (8) (17) (6)* C (2) (6) (14) (4) C (2) (6) (14) (4) C (3) (7) (17) (4) H (3) (8) (18) (6)* C (3) (7) (18) (5) H (3) (9) (19) (7)* C (3) (7) (18) (5) H (4) (9) (2) (8)* C (3) (7) (16) (4) H (3) (8) (18) (6)* N (2) (5) (12) (3) N (2) (5) (12) (3) C (3) (7) (16) (4) H (3) (8) (18) (6)* C (3) (7) (18) (4) H (3) (8) (18) (6)* C (3) (7) (18) (4) H (3) (8) (18) (6)* C (3) (7) (17) (4) H (3) (7) (17) (6)* C (2) (6) (15) (4) C (2) (6) (14) (4) C (3) (7) (16) (4) H (3) (8) (17) (6)* C (3) (7) (16) (4) H (3) (7) (17) (6)* C (3) (7) (16) (4) sup-9

14 H (3) (9) (2) (7)* C (3) (7) (16) (4) H (3) (8) (17) (6)* N (2) (5) (12) (3) O (2) (5) (11) (3) H4A (4) (9) (2) (9)* H4B (4) (10) (2) (9)* N (2) (5) (12) (4) C (3) (6) (14) (4) O (2) (5) (11) (3) C (2) (6) (14) (4) C (3) (6) (16) (4) H (3) (8) (18) (6)* C (3) (7) (17) (4) H (3) (8) (19) (7)* C (3) (7) (15) (4) H (3) (8) (19) (6)* C (3) (6) (15) (4) H (3) (8) (18) (6)* C (2) (6) (14) (4) S (6) (14) (4) (10) O (19) (5) (12) (3) O (2) (5) (12) (3) Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Co (13) (12) (13) (9) (9) (9) N (7) (7) (7) (6) (6) (6) C (9) (8) (9) (7) (7) (7) O (8) (8) (7) (6) (6) (6) C (8) (9) (9) (7) (7) (7) C (10) (10) (11) (8) (8) (9) C (10) (12) (12) (9) (8) (9) C (11) (12) (10) (9) (8) (9) C (10) (10) (10) (8) (8) (8) C (9) (8) (9) (7) (7) (7) S (2) (2) (2) (16) (16) (16) O (8) (7) (7) (6) (6) (6) O (7) (8) (7) (6) (5) (6) N (8) (7) (8) (6) (6) (6) C (9) (9) (11) (7) (8) (8) C (10) (11) (12) (8) (9) (9) C (11) (10) (12) (8) (9) (9) C (10) (9) (10) (8) (8) (8) C (9) (8) (9) (7) (7) (7) C (9) (9) (9) (7) (7) (7) C (11) (10) (11) (8) (9) (8) sup-10

15 C (12) (11) (13) (9) (10) (9) C (11) (12) (12) (9) (9) (9) C (10) (10) (10) (8) (8) (8) N (8) (8) (8) (6) (6) (6) N (8) (7) (8) (6) (6) (6) C (10) (10) (10) (8) (8) (8) C (11) (10) (12) (8) (9) (9) C (11) (9) (12) (8) (9) (8) C (10) (10) (11) (8) (8) (8) C (9) (9) (10) (7) (7) (7) C (9) (9) (9) (7) (7) (7) C (10) (11) (10) (8) (8) (8) C (10) (12) (10) (9) (8) (9) C (11) (11) (10) (9) (8) (8) C (10) (10) (10) (8) (8) (8) N (8) (8) (8) (6) (6) (6) O (8) (8) (7) (6) (6) (6) N (10) (8) (8) (7) (7) (6) C (10) (9) (9) (7) (7) (7) O (9) (8) (8) (7) (6) (6) C (9) (9) (9) (7) (7) (7) C (10) (9) (11) (8) (8) (8) C (11) (10) (11) (8) (9) (8) C (11) (10) (10) (9) (8) (8) C (10) (9) (9) (8) (8) (8) C (9) (8) (9) (7) (7) (7) S (2) (2) (2) (18) (18) (17) O (8) (8) (8) (6) (6) (6) O (9) (7) (8) (6) (7) (6) Geometric parameters (Å, º) Co1 N (17) C17 N (3) Co1 N (16) C17 H (2) Co1 N (16) N4 C (3) Co1 N (16) N4 C (3) Co1 N (17) C18 C (3) Co1 O (15) C18 H (2) N1 C (2) C19 C (3) N1 S (16) C19 H (2) C1 O (2) C20 C (3) C1 C (3) C20 H (2) C2 C (3) C21 C (3) C2 C (3) C21 H (2) C3 C (3) C22 C (3) C3 H (2) C23 N (2) C4 C (3) C23 C (3) C4 H (3) C24 C (3) sup-11

16 C5 C (3) C24 H (2) C5 H (3) C25 C (3) C6 C (3) C25 H (2) C6 H (3) C26 C (3) C7 S (19) C26 H (3) S1 O (14) C27 N (3) S1 O (15) C27 H (2) N2 C (2) N6 C (3) N2 C (2) N6 S (18) C8 C (3) C28 O (2) C8 H (2) C28 C (3) C9 C (3) C29 C (3) C9 H (3) C29 C (3) C10 C (3) C30 C (3) C10 H (3) C30 H (2) C11 C (3) C31 C (3) C11 H (2) C31 H (3) C12 C (3) C32 C (3) C13 N (2) C32 H (2) C13 C (3) C33 C (3) C14 C (3) C33 H (2) C14 H (3) C34 S (19) C15 C (3) S2 O (16) C15 H (3) S2 O (15) C16 C (3) O4 H4A 0.81 (3) C16 H (3) O4 H4B 0.95 (3) N1 Co1 N (6) C17 C16 H (17) N1 Co1 N (6) N3 C17 C (2) N1 Co1 N (6) N3 C17 H (14) N1 Co1 N (6) C16 C17 H (14) N1 Co1 O (6) C17 N3 C (17) N2 Co1 N (6) C17 N3 Co (13) N2 Co1 N (6) C13 N3 Co (12) N2 Co1 N (6) C18 N4 C (17) N2 Co1 O (6) C18 N4 Co (14) N3 Co1 N (6) C22 N4 Co (13) N3 Co1 N (6) N4 C18 C (2) N3 Co1 O (6) N4 C18 H (14) N4 Co1 N (6) C19 C18 H (14) N4 Co1 O (6) C20 C19 C (2) N5 Co1 O (6) C20 C19 H (14) C1 N1 S (13) C18 C19 H (14) C1 N1 Co (12) C19 C20 C (19) S1 N1 Co (8) C19 C20 H (15) O1 C1 N (17) C21 C20 H (15) O1 C1 C (17) C20 C21 C (2) N1 C1 C (16) C20 C21 H (13) sup-12

17 C7 C2 C (18) C22 C21 H (13) C7 C2 C (16) N4 C22 C (18) C3 C2 C (18) N4 C22 C (16) C4 C3 C (2) C21 C22 C (18) C4 C3 H (14) N5 C23 C (18) C2 C3 H (14) N5 C23 C (16) C3 C4 C (2) C24 C23 C (18) C3 C4 H (16) C25 C24 C (19) C5 C4 H (16) C25 C24 H (14) C4 C5 C (2) C23 C24 H (14) C4 C5 H (15) C24 C25 C (19) C6 C5 H (15) C24 C25 H (14) C7 C6 C (2) C26 C25 H (14) C7 C6 H (15) C27 C26 C (2) C5 C6 H (15) C27 C26 H (16) C2 C7 C (18) C25 C26 H (16) C2 C7 S (14) N5 C27 C (2) C6 C7 S (16) N5 C27 H (14) O3 S1 O (9) C26 C27 H (14) O3 S1 N (9) C27 N5 C (17) O2 S1 N (8) C27 N5 Co (14) O3 S1 C (9) C23 N5 Co (13) O2 S1 C (9) Co1 O4 H4A 111 (2) N1 S1 C (9) Co1 O4 H4B (18) C8 N2 C (16) H4A O4 H4B 110 (3) C8 N2 Co (13) C28 N6 S (13) C12 N2 Co (12) O5 C28 N (18) N2 C8 C (19) O5 C28 C (18) N2 C8 H (14) N6 C28 C (16) C9 C8 H (14) C30 C29 C (18) C10 C9 C (19) C30 C29 C (18) C10 C9 H (16) C34 C29 C (16) C8 C9 H (16) C29 C30 C (19) C11 C10 C (19) C29 C30 H (15) C11 C10 H (16) C31 C30 H (15) C9 C10 H (16) C32 C31 C (19) C10 C11 C (18) C32 C31 H (16) C10 C11 H (15) C30 C31 H (16) C12 C11 H (15) C31 C32 C (19) N2 C12 C (17) C31 C32 H (14) N2 C12 C (16) C33 C32 H (14) C11 C12 C (17) C34 C33 C (19) N3 C13 C (18) C34 C33 H (14) N3 C13 C (16) C32 C33 H (14) C14 C13 C (17) C29 C34 C (18) C15 C14 C (2) C29 C34 S (14) C15 C14 H (15) C33 C34 S (15) C13 C14 H (15) O6 S2 O (9) sup-13

18 C16 C15 C (2) O6 S2 N (10) C16 C15 H (16) O7 S2 N (9) C14 C15 H (16) O6 S2 C (9) C15 C16 C (2) O7 S2 C (9) C15 C16 H (17) N6 S2 C (9) sup-14