Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012664/bm1359sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012664/bm1359Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012664/bm1359IIsup3.hkl |
CCDC references: 142720; 142721
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%.
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.
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.
[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) Å3 | 0.45 × 0.25 × 0.10 mm |
Z = 2 |
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 on F2 | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.040 | w = 1/[σ2(Fo2) + (0.0591P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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 |
[Mn(C7H4NO3S)(C12H8N2)2(H2O)](C7H4NO3S) | γ = 91.54 (3)° |
Mr = 797.71 | V = 1726.3 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.943 (2) Å | Mo Kα radiation |
b = 14.448 (3) Å | µ = 0.57 mm−1 |
c = 15.336 (3) Å | T = 150 K |
α = 99.01 (3)° | 0.45 × 0.25 × 0.10 mm |
β = 96.19 (3)° |
Siemens SMART CCD diffractometer | 8956 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 6420 reflections with I > 2σ(I) |
Tmin = 0.773, Tmax = 0.945 | Rint = 0.023 |
13847 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.095 | All H-atom parameters refined |
S = 1.01 | Δρmax = 0.39 e Å−3 |
8956 reflections | Δρmin = −0.36 e Å−3 |
591 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
[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) Å3 | Block, orange |
Z = 4 | 0.4 × 0.3 × 0.3 mm |
F(000) = 1548 |
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 on F2 | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0214P)2 + 2.8879P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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 |
[Co(C7H4NO3S)(C10H8N2)2(H2O)](C7H4NO3S) | V = 3183.36 (8) Å3 |
Mr = 753.66 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6982 (1) Å | µ = 0.73 mm−1 |
b = 31.3359 (5) Å | T = 150 K |
c = 13.2179 (2) Å | 0.4 × 0.3 × 0.3 mm |
β = 93.272 (1)° |
Siemens SMART CCD area-detector diffractometer | 7238 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 6294 reflections with I > 2σ(I) |
Tmin = 0.651, Tmax = 0.803 | Rint = 0.030 |
22343 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.079 | All H-atom parameters refined |
S = 1.15 | Δρmax = 0.37 e Å−3 |
7238 reflections | Δρmin = −0.43 e Å−3 |
555 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Mn(C7H4NO3S)(C12H8N2)2(H2O)](C7H4NO3S) | [Co(C7H4NO3S)(C10H8N2)2(H2O)](C7H4NO3S) |
Mr | 797.71 | 753.66 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 7.943 (2), 14.448 (3), 15.336 (3) | 7.6982 (1), 31.3359 (5), 13.2179 (2) |
α, β, γ (°) | 99.01 (3), 96.19 (3), 91.54 (3) | 90, 93.272 (1), 90 |
V (Å3) | 1726.3 (6) | 3183.36 (8) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.57 | 0.73 |
Crystal size (mm) | 0.45 × 0.25 × 0.10 | 0.4 × 0.3 × 0.3 |
Data collection | ||
Diffractometer | Siemens SMART CCD diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.773, 0.945 | 0.651, 0.803 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13847, 8956, 6420 | 22343, 7238, 6294 |
Rint | 0.023 | 0.030 |
(sin θ/λ)max (Å−1) | 0.711 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.095, 1.01 | 0.033, 0.079, 1.15 |
No. of reflections | 8956 | 7238 |
No. of parameters | 591 | 555 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.39, −0.36 | 0.37, −0.43 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1991), SHELXL97.
Mn1—N1 | 2.2253 (18) | N1—C1 | 1.354 (3) |
Mn1—N2 | 2.2382 (17) | N1—S1 | 1.6461 (17) |
Mn1—N3 | 2.2542 (18) | N6—C32 | 1.370 (3) |
Mn1—N4 | 2.2678 (19) | N6—S2 | 1.598 (2) |
Mn1—N5 | 2.2678 (17) | O4—H4A | 0.89 (3) |
Mn1—O4 | 2.1897 (17) | O4—H4B | 0.83 (3) |
N1—Mn1—N2 | 90.86 (6) | N3—Mn1—N5 | 101.68 (6) |
N1—Mn1—N3 | 100.84 (6) | N3—Mn1—O4 | 159.10 (6) |
N1—Mn1—N4 | 163.53 (6) | N4—Mn1—N5 | 73.82 (7) |
N1—Mn1—N5 | 89.81 (7) | N4—Mn1—O4 | 89.51 (7) |
N1—Mn1—O4 | 90.41 (7) | O4—Mn1—N5 | 95.86 (7) |
N2—Mn1—N3 | 74.42 (7) | C1—N1—S1 | 111.76 (14) |
N2—Mn1—N4 | 105.59 (7) | C32—N6—S2 | 111.59 (15) |
N2—Mn1—N5 | 176.09 (6) | Mn1—O4—H4A | 107 (2) |
N2—Mn1—O4 | 87.98 (7) | Mn1—O4—H4B | 124 (2) |
N3—Mn1—N4 | 84.61 (6) |
Co1—N1 | 2.1688 (17) | N1—C1 | 1.366 (2) |
Co1—N2 | 2.1339 (16) | N1—S1 | 1.6465 (16) |
Co1—N3 | 2.1482 (16) | N6—C28 | 1.364 (3) |
Co1—N4 | 2.1516 (16) | N6—S2 | 1.6180 (18) |
Co1—N5 | 2.1403 (17) | O4—H4A | 0.81 (3) |
Co1—O4 | 2.0565 (15) | O4—H4B | 0.95 (3) |
N1—Co1—N2 | 95.21 (6) | N3—Co1—N4 | 174.59 (6) |
N1—Co1—N3 | 91.02 (6) | N3—Co1—N5 | 98.11 (6) |
N1—Co1—N4 | 94.10 (6) | N3—Co1—O4 | 90.14 (6) |
N1—Co1—N5 | 170.83 (6) | N4—Co1—N5 | 76.75 (6) |
N1—Co1—O4 | 90.50 (6) | N4—Co1—O4 | 91.54 (6) |
N2—Co1—N3 | 76.58 (6) | N5—Co1—O4 | 90.30 (6) |
N2—Co1—N4 | 101.19 (6) | C1—N1—S1 | 111.40 (13) |
N2—Co1—N5 | 86.17 (6) | C28—N6—S2 | 112.20 (13) |
N2—Co1—O4 | 165.61 (6) |
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—Nphen 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—Nsac 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—Oaqua 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—Oaqua 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—Nbipy bond length is 2.144 (4) Å, though the ligand asymmetry seen in compound (I) is not displayed. The Co—Nsac 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—Oaqua distance of 2.057 (2) Å in (II) is similar to the shorter of the two independent Co—Oaqua 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].