Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112049748/fa3287sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112049748/fa3287Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112049748/fa3287IIsup3.hkl |
CCDC references: 925252; 925253
For related literature, see: Abrahams et al. (2006); Beagley et al. (1989); Falvello (1997); Kozlevcǎr et al. (2003); Li et al. (1998); Sheldrick (2008).
The title compounds were prepared using aqueous solutions of 2,2'-dipyridyl ketone, sodium bisulfite and transition metal nitrate in 2:2:1 molar ratios.
For the current work, the solutions were diluted tenfold relative to those used by Abrahams et al. (2006), i.e. 0.025 M di-2-pyridyl ketone (2 ml), 0.025 M sodium sulphite (2 ml) and 0.025 M copper or cobalt nitrate (1 ml). These were mixed together and left to stand in open containers at room temperature for a week in order to produce good-quality crystals.
H atoms were refined isotropically in both structures. Additionally, for the CuII complex, DFIX restraints (SHELXL97; Sheldrick, 2008) were applied to the water H atoms, whereby the O—H distances were restrained to 0.958 (10) Å and H···H distances to 1.516 (10) Å. [Values added by Co-Editor - please confirm]
For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).
Fig. 1. (a) The molecular structure of (I), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level
[Added by Co-Editor - please confirm]. The solvent water molecules have
been omitted for clarity. (b) The molecular structure of (II), showing
the atom-labelling scheme. Displacement ellipsoids are drawn at the 50%
probability level [Symmetry codes: (v) -x + 1, -y + 1, -z + 1; (vi) -x + 2, -y
+ 1, -z + 1.] [Added by Co-Editor - please confirm] Fig. 2. Bond lengths to the transition metal in the bis[hydroxybis(pyridin-2-yl)methanesulfonato-N,O,N']MII series, where M = Mn to Zn. Fig. 3. S—O bond lengths in the bis[hydroxybis(pyridin-2-yl)methanesulfonato-N,O,N']MII series, where M = Mn to Zn. Fig. 4. Water–sulfate hydrogen bonding in (I) (dashed lines). [Symmetry code: (vii) x + 1, y, z.] [As advised by Co-Editor, the O7···O4 hydrogen bond should be drawn from the relevant H atom, to match the other two.] Fig. 5. Hydroxy–sulfate hydrogen bonding in (II) (dashed lines). [Symmetry code: (viii) -x + 1, y + 1/2, -z + 1/2.] [Symop changed to match Table 4 - please confirm. Is this figure complete? It looks like it may be clipped on the right] |
[Cu(C11H9N2O4S)2]·6H2O | Z = 1 |
Mr = 702.16 | F(000) = 363 |
Triclinic, P1 | Dx = 1.684 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5892 (3) Å | Cell parameters from 3309 reflections |
b = 10.1399 (4) Å | θ = 2–27° |
c = 10.7325 (5) Å | µ = 1.02 mm−1 |
α = 108.675 (2)° | T = 100 K |
β = 109.920 (2)° | Block, blue |
γ = 101.025 (4)° | 0.24 × 0.1 × 0.08 mm |
V = 692.53 (5) Å3 |
Nonius KappaCCD area-detector diffractometer | 2715 independent reflections |
Radiation source: Enraf–Nonius FR590 | 2315 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.083 |
Detector resolution: 9 pixels mm-1 | θmax = 26°, θmin = 3.0° |
CCD rotation images, thick slices scans | h = 0→9 |
Absorption correction: multi-scan (Blessing, 1995) | k = −12→12 |
Tmin = 0.792, Tmax = 0.923 | l = −13→11 |
10846 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.064 | All H-atom parameters refined |
wR(F2) = 0.172 | w = 1/[σ2(Fo2) + (0.1015P)2 + 1.5123P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2715 reflections | Δρmax = 0.73 e Å−3 |
257 parameters | Δρmin = −0.83 e Å−3 |
9 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.033 (8) |
[Cu(C11H9N2O4S)2]·6H2O | γ = 101.025 (4)° |
Mr = 702.16 | V = 692.53 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.5892 (3) Å | Mo Kα radiation |
b = 10.1399 (4) Å | µ = 1.02 mm−1 |
c = 10.7325 (5) Å | T = 100 K |
α = 108.675 (2)° | 0.24 × 0.1 × 0.08 mm |
β = 109.920 (2)° |
Nonius KappaCCD area-detector diffractometer | 2715 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2315 reflections with I > 2σ(I) |
Tmin = 0.792, Tmax = 0.923 | Rint = 0.083 |
10846 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 9 restraints |
wR(F2) = 0.172 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.73 e Å−3 |
2715 reflections | Δρmin = −0.83 e Å−3 |
257 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6150 (6) | 0.3012 (5) | 0.2046 (4) | 0.0266 (9) | |
C2 | 0.6810 (6) | 0.2127 (5) | 0.2925 (5) | 0.0262 (9) | |
C3 | 0.5819 (6) | 0.0621 (5) | 0.2357 (5) | 0.0281 (9) | |
C4 | 0.6342 (7) | −0.0134 (5) | 0.3220 (5) | 0.0314 (10) | |
C5 | 0.7849 (7) | 0.0627 (5) | 0.4613 (5) | 0.0319 (10) | |
C6 | 0.8834 (7) | 0.2107 (5) | 0.5095 (5) | 0.0285 (9) | |
C7 | 0.5903 (6) | 0.4428 (4) | 0.2915 (4) | 0.0254 (9) | |
C8 | 0.4216 (6) | 0.4778 (5) | 0.2341 (5) | 0.0282 (9) | |
C9 | 0.4013 (7) | 0.6061 (5) | 0.3169 (5) | 0.0326 (10) | |
C10 | 0.5499 (7) | 0.6934 (5) | 0.4568 (5) | 0.0309 (10) | |
C11 | 0.7135 (7) | 0.6543 (5) | 0.5065 (5) | 0.0291 (9) | |
N1 | 0.8352 (5) | 0.2863 (4) | 0.4270 (4) | 0.0258 (7) | |
N2 | 0.7388 (5) | 0.5336 (4) | 0.4257 (4) | 0.0259 (7) | |
O1 | 0.4390 (5) | 0.2109 (3) | 0.0764 (3) | 0.0299 (7) | |
O2 | 0.9784 (4) | 0.4490 (3) | 0.2649 (3) | 0.0314 (7) | |
O3 | 0.7117 (5) | 0.4123 (4) | 0.0373 (4) | 0.0373 (8) | |
O4 | 0.8184 (5) | 0.2070 (3) | 0.0609 (4) | 0.0347 (7) | |
O5 | 0.7610 (5) | 0.7115 (4) | 0.1590 (4) | 0.0393 (8) | |
O6 | 0.1634 (5) | 0.1313 (4) | 0.1628 (4) | 0.0409 (8) | |
O7 | 0.8760 (6) | 0.1270 (4) | −0.1964 (4) | 0.0483 (9) | |
S1 | 0.79797 (16) | 0.34699 (12) | 0.13544 (11) | 0.0296 (3) | |
Cu1 | 1 | 0.5 | 0.5 | 0.0257 (3) | |
H5A | 0.739 (8) | 0.6078 (17) | 0.119 (6) | 0.050 (16)* | |
H5B | 0.641 (6) | 0.721 (6) | 0.100 (7) | 0.09 (3)* | |
H6A | 0.047 (5) | 0.158 (5) | 0.127 (6) | 0.053 (17)* | |
H6B | 0.110 (7) | 0.037 (4) | 0.163 (7) | 0.061 (19)* | |
H7A | 0.855 (7) | 0.177 (5) | −0.113 (4) | 0.047 (16)* | |
H7B | 1.011 (4) | 0.182 (6) | −0.171 (6) | 0.07 (2)* | |
H1 | 0.342 (9) | 0.191 (6) | 0.095 (6) | 0.038 (15)* | |
H3 | 0.501 (9) | 0.014 (6) | 0.143 (7) | 0.042 (15)* | |
H4 | 0.564 (8) | −0.114 (6) | 0.279 (6) | 0.039 (14)* | |
H5 | 0.812 (7) | 0.017 (5) | 0.525 (5) | 0.026 (12)* | |
H6 | 0.994 (8) | 0.269 (6) | 0.604 (6) | 0.036 (13)* | |
H8 | 0.323 (12) | 0.406 (9) | 0.144 (8) | 0.08 (2)* | |
H9 | 0.274 (8) | 0.634 (6) | 0.279 (6) | 0.035 (13)* | |
H10 | 0.537 (8) | 0.772 (6) | 0.512 (6) | 0.033 (13)* | |
H11 | 0.809 (7) | 0.708 (5) | 0.593 (6) | 0.025 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.028 (2) | 0.024 (2) | 0.022 (2) | 0.0071 (17) | 0.0063 (17) | 0.0084 (17) |
C2 | 0.028 (2) | 0.024 (2) | 0.026 (2) | 0.0111 (17) | 0.0107 (17) | 0.0105 (17) |
C3 | 0.025 (2) | 0.027 (2) | 0.027 (2) | 0.0077 (17) | 0.0080 (18) | 0.0100 (18) |
C4 | 0.031 (2) | 0.025 (2) | 0.035 (2) | 0.0078 (18) | 0.0121 (19) | 0.0128 (19) |
C5 | 0.036 (2) | 0.030 (2) | 0.033 (2) | 0.0120 (19) | 0.0137 (19) | 0.0176 (19) |
C6 | 0.027 (2) | 0.029 (2) | 0.026 (2) | 0.0092 (18) | 0.0087 (18) | 0.0110 (18) |
C7 | 0.030 (2) | 0.0206 (19) | 0.026 (2) | 0.0045 (16) | 0.0130 (17) | 0.0123 (17) |
C8 | 0.024 (2) | 0.026 (2) | 0.031 (2) | 0.0041 (17) | 0.0079 (18) | 0.0144 (18) |
C9 | 0.029 (2) | 0.031 (2) | 0.040 (3) | 0.0097 (19) | 0.014 (2) | 0.019 (2) |
C10 | 0.035 (2) | 0.025 (2) | 0.034 (2) | 0.0101 (19) | 0.017 (2) | 0.0120 (19) |
C11 | 0.027 (2) | 0.028 (2) | 0.027 (2) | 0.0070 (18) | 0.0099 (19) | 0.0103 (18) |
N1 | 0.0239 (17) | 0.0257 (17) | 0.0228 (17) | 0.0082 (14) | 0.0055 (14) | 0.0092 (14) |
N2 | 0.0269 (18) | 0.0238 (17) | 0.0229 (17) | 0.0070 (14) | 0.0076 (14) | 0.0093 (14) |
O1 | 0.0270 (16) | 0.0281 (16) | 0.0259 (16) | 0.0056 (13) | 0.0056 (13) | 0.0093 (13) |
O2 | 0.0287 (16) | 0.0317 (16) | 0.0247 (15) | 0.0036 (13) | 0.0084 (13) | 0.0082 (13) |
O3 | 0.0396 (18) | 0.0412 (18) | 0.0329 (17) | 0.0145 (15) | 0.0134 (15) | 0.0197 (15) |
O4 | 0.0326 (17) | 0.0299 (16) | 0.0346 (17) | 0.0083 (13) | 0.0136 (14) | 0.0074 (14) |
O5 | 0.0401 (19) | 0.0416 (19) | 0.0326 (17) | 0.0131 (15) | 0.0103 (15) | 0.0172 (15) |
O6 | 0.0369 (18) | 0.0395 (19) | 0.040 (2) | 0.0130 (15) | 0.0125 (16) | 0.0131 (16) |
O7 | 0.052 (2) | 0.050 (2) | 0.039 (2) | 0.0091 (18) | 0.0209 (18) | 0.0162 (17) |
S1 | 0.0300 (6) | 0.0286 (6) | 0.0258 (6) | 0.0084 (4) | 0.0091 (4) | 0.0102 (4) |
Cu1 | 0.0248 (4) | 0.0230 (4) | 0.0228 (4) | 0.0064 (3) | 0.0053 (3) | 0.0083 (3) |
C1—O1 | 1.410 (5) | C10—C11 | 1.362 (7) |
C1—C2 | 1.530 (6) | C10—H10 | 0.87 (6) |
C1—C7 | 1.527 (6) | C11—N2 | 1.345 (6) |
C1—S1 | 1.836 (5) | C11—H11 | 0.87 (5) |
C2—N1 | 1.354 (5) | N1—Cu1 | 2.020 (3) |
C2—C3 | 1.386 (6) | N2—Cu1 | 2.009 (4) |
C3—C4 | 1.385 (6) | O1—H1 | 0.83 (6) |
C3—H3 | 0.87 (6) | O2—S1 | 1.455 (3) |
C4—C5 | 1.378 (7) | O2—Cu1 | 2.347 (3) |
C4—H4 | 0.93 (6) | O3—S1 | 1.455 (3) |
C5—C6 | 1.375 (6) | O4—S1 | 1.456 (3) |
C5—H5 | 0.93 (5) | O5—H5A | 0.956 (10) |
C6—N1 | 1.352 (6) | O5—H5B | 0.957 (10) |
C6—H6 | 0.96 (5) | O6—H6A | 0.963 (10) |
C7—N2 | 1.357 (5) | O6—H6B | 0.966 (10) |
C7—C8 | 1.386 (6) | O7—H7A | 0.963 (10) |
C8—C9 | 1.392 (7) | O7—H7B | 0.962 (10) |
C8—H8 | 0.93 (8) | Cu1—N2i | 2.009 (4) |
C9—C10 | 1.387 (7) | Cu1—N1i | 2.020 (4) |
C9—H9 | 1.04 (5) | Cu1—O2i | 2.347 (3) |
O1—C1—C2 | 110.1 (3) | N2—C11—H11 | 116 (3) |
O1—C1—C7 | 111.0 (3) | C10—C11—H11 | 121 (3) |
C2—C1—C7 | 113.6 (3) | C6—N1—C2 | 118.1 (4) |
O1—C1—S1 | 103.3 (3) | C6—N1—Cu1 | 120.2 (3) |
C2—C1—S1 | 108.7 (3) | C2—N1—Cu1 | 121.6 (3) |
C7—C1—S1 | 109.5 (3) | C11—N2—C7 | 118.5 (4) |
N1—C2—C3 | 121.7 (4) | C11—N2—Cu1 | 119.6 (3) |
N1—C2—C1 | 118.0 (4) | C7—N2—Cu1 | 121.8 (3) |
C3—C2—C1 | 120.2 (4) | C1—O1—H1 | 111 (4) |
C4—C3—C2 | 119.1 (4) | S1—O2—Cu1 | 121.35 (17) |
C4—C3—H3 | 121 (4) | H5A—O5—H5B | 104.4 (15) |
C2—C3—H3 | 120 (4) | H6A—O6—H6B | 103.4 (14) |
C5—C4—C3 | 119.3 (4) | H7A—O7—H7B | 103.4 (14) |
C5—C4—H4 | 125 (3) | O2—S1—O3 | 114.08 (19) |
C3—C4—H4 | 116 (3) | O2—S1—O4 | 113.06 (19) |
C4—C5—C6 | 119.0 (4) | O3—S1—O4 | 113.0 (2) |
C4—C5—H5 | 121 (3) | O2—S1—C1 | 104.81 (18) |
C6—C5—H5 | 120 (3) | O3—S1—C1 | 105.4 (2) |
N1—C6—C5 | 122.7 (4) | O4—S1—C1 | 105.45 (19) |
N1—C6—H6 | 114 (3) | N2i—Cu1—N2 | 180.0000 (10) |
C5—C6—H6 | 123 (3) | N2i—Cu1—N1 | 94.09 (14) |
N2—C7—C8 | 121.1 (4) | N2—Cu1—N1 | 85.91 (14) |
N2—C7—C1 | 118.1 (4) | N2i—Cu1—N1i | 85.91 (14) |
C8—C7—C1 | 120.8 (4) | N2—Cu1—N1i | 94.09 (14) |
C7—C8—C9 | 119.6 (4) | N1—Cu1—N1i | 180.0 (2) |
C7—C8—H8 | 115 (5) | N2i—Cu1—O2i | 85.52 (13) |
C9—C8—H8 | 125 (5) | N2—Cu1—O2i | 94.48 (13) |
C10—C9—C8 | 118.4 (4) | N1—Cu1—O2i | 91.37 (12) |
C10—C9—H9 | 120 (3) | N1i—Cu1—O2i | 88.63 (12) |
C8—C9—H9 | 122 (3) | N2i—Cu1—O2 | 94.48 (13) |
C11—C10—C9 | 119.3 (4) | N2—Cu1—O2 | 85.52 (13) |
C11—C10—H10 | 121 (4) | N1—Cu1—O2 | 88.63 (12) |
C9—C10—H10 | 120 (4) | N1i—Cu1—O2 | 91.37 (12) |
N2—C11—C10 | 123.0 (4) | O2i—Cu1—O2 | 180 |
O1—C1—C2—N1 | −172.8 (4) | C1—C7—N2—Cu1 | 8.0 (5) |
C7—C1—C2—N1 | −47.6 (5) | Cu1—O2—S1—O3 | 121.5 (2) |
S1—C1—C2—N1 | 74.6 (4) | Cu1—O2—S1—O4 | −107.6 (2) |
O1—C1—C2—C3 | 6.1 (6) | Cu1—O2—S1—C1 | 6.7 (3) |
C7—C1—C2—C3 | 131.3 (4) | O1—C1—S1—O2 | 176.1 (3) |
S1—C1—C2—C3 | −106.5 (4) | C2—C1—S1—O2 | −67.0 (3) |
N1—C2—C3—C4 | 4.0 (7) | C7—C1—S1—O2 | 57.7 (3) |
C1—C2—C3—C4 | −174.9 (4) | O1—C1—S1—O3 | 55.4 (3) |
C2—C3—C4—C5 | −0.8 (7) | C2—C1—S1—O3 | 172.3 (3) |
C3—C4—C5—C6 | −1.9 (7) | C7—C1—S1—O3 | −63.0 (3) |
C4—C5—C6—N1 | 1.7 (7) | O1—C1—S1—O4 | −64.4 (3) |
O1—C1—C7—N2 | 172.8 (3) | C2—C1—S1—O4 | 52.6 (3) |
C2—C1—C7—N2 | 48.0 (5) | C7—C1—S1—O4 | 177.3 (3) |
S1—C1—C7—N2 | −73.8 (4) | C11—N2—Cu1—N1 | 137.9 (3) |
O1—C1—C7—C8 | −7.8 (5) | C7—N2—Cu1—N1 | −46.5 (3) |
C2—C1—C7—C8 | −132.5 (4) | C11—N2—Cu1—N1i | −42.1 (3) |
S1—C1—C7—C8 | 105.7 (4) | C7—N2—Cu1—N1i | 133.5 (3) |
N2—C7—C8—C9 | −1.9 (6) | C11—N2—Cu1—O2i | 46.8 (3) |
C1—C7—C8—C9 | 178.7 (4) | C7—N2—Cu1—O2i | −137.6 (3) |
C7—C8—C9—C10 | −1.6 (6) | C11—N2—Cu1—O2 | −133.2 (3) |
C8—C9—C10—C11 | 2.5 (6) | C7—N2—Cu1—O2 | 42.4 (3) |
C9—C10—C11—N2 | −0.1 (7) | C6—N1—Cu1—N2i | 43.5 (3) |
C5—C6—N1—C2 | 1.3 (7) | C2—N1—Cu1—N2i | −133.2 (3) |
C5—C6—N1—Cu1 | −175.5 (3) | C6—N1—Cu1—N2 | −136.5 (3) |
C3—C2—N1—C6 | −4.1 (6) | C2—N1—Cu1—N2 | 46.8 (3) |
C1—C2—N1—C6 | 174.7 (4) | C6—N1—Cu1—O2i | −42.1 (3) |
C3—C2—N1—Cu1 | 172.6 (3) | C2—N1—Cu1—O2i | 141.2 (3) |
C1—C2—N1—Cu1 | −8.5 (5) | C6—N1—Cu1—O2 | 137.9 (3) |
C10—C11—N2—C7 | −3.3 (6) | C2—N1—Cu1—O2 | −38.8 (3) |
C10—C11—N2—Cu1 | 172.4 (3) | S1—O2—Cu1—N2i | 130.8 (2) |
C8—C7—N2—C11 | 4.3 (6) | S1—O2—Cu1—N2 | −49.2 (2) |
C1—C7—N2—C11 | −176.3 (4) | S1—O2—Cu1—N1 | 36.8 (2) |
C8—C7—N2—Cu1 | −171.4 (3) | S1—O2—Cu1—N1i | −143.2 (2) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O6 | 0.83 (6) | 1.84 (6) | 2.653 (5) | 167 (6) |
O5—H5A···O3 | 0.96 (1) | 1.83 (1) | 2.783 (5) | 176 (6) |
O5—H5B···O1ii | 0.96 (1) | 2.15 (6) | 2.902 (5) | 134 (7) |
O5—H5B···O3ii | 0.96 (1) | 2.41 (4) | 3.212 (5) | 141 (5) |
O6—H6A···O4iii | 0.96 (1) | 1.87 (1) | 2.828 (5) | 178 (5) |
O6—H6B···O7iv | 0.97 (1) | 1.82 (2) | 2.731 (6) | 155 (4) |
O7—H7A···O4 | 0.96 (1) | 1.91 (2) | 2.828 (5) | 157 (5) |
O7—H7B···O5v | 0.96 (1) | 1.80 (2) | 2.745 (5) | 168 (6) |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) −x+1, −y, −z; (v) −x+2, −y+1, −z. |
[Co(C11H9N2O4S)2] | F(000) = 602 |
Mr = 589.45 | Dx = 1.75 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3777 reflections |
a = 7.7300 (3) Å | θ = 2–26° |
b = 9.3475 (4) Å | µ = 1.01 mm−1 |
c = 15.6518 (6) Å | T = 100 K |
β = 98.499 (2)° | Block, purple |
V = 1118.52 (8) Å3 | 0.25 × 0.12 × 0.09 mm |
Z = 2 |
Nonius KappaCCD area-detector diffractometer | 2558 independent reflections |
Radiation source: Enraf–Nonius FR590 | 2025 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
CCD rotation images, thick slices scans | h = −10→10 |
Absorption correction: multi-scan (Blessing, 1995) | k = −12→12 |
Tmin = 0.785, Tmax = 0.914 | l = −20→20 |
4704 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | All H-atom parameters refined |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0508P)2 + 1.8352P] where P = (Fo2 + 2Fc2)/3 |
2558 reflections | (Δ/σ)max < 0.001 |
203 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −0.60 e Å−3 |
[Co(C11H9N2O4S)2] | V = 1118.52 (8) Å3 |
Mr = 589.45 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.7300 (3) Å | µ = 1.01 mm−1 |
b = 9.3475 (4) Å | T = 100 K |
c = 15.6518 (6) Å | 0.25 × 0.12 × 0.09 mm |
β = 98.499 (2)° |
Nonius KappaCCD area-detector diffractometer | 2558 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2025 reflections with I > 2σ(I) |
Tmin = 0.785, Tmax = 0.914 | Rint = 0.048 |
4704 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.124 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.65 e Å−3 |
2558 reflections | Δρmin = −0.60 e Å−3 |
203 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6394 (4) | 0.7026 (3) | 0.36031 (18) | 0.0208 (6) | |
C2 | 0.7537 (4) | 0.5692 (3) | 0.37170 (18) | 0.0207 (6) | |
C3 | 0.8902 (4) | 0.5491 (4) | 0.3251 (2) | 0.0240 (7) | |
C4 | 0.9892 (4) | 0.4256 (4) | 0.3378 (2) | 0.0264 (7) | |
C5 | 0.9525 (5) | 0.3291 (4) | 0.3995 (2) | 0.0302 (7) | |
C6 | 0.8169 (4) | 0.3575 (4) | 0.4449 (2) | 0.0273 (7) | |
C7 | 0.6495 (4) | 0.7833 (3) | 0.44617 (18) | 0.0197 (6) | |
C8 | 0.7270 (4) | 0.9176 (3) | 0.4563 (2) | 0.0247 (7) | |
C9 | 0.7390 (4) | 0.9841 (3) | 0.5362 (2) | 0.0255 (7) | |
C10 | 0.6715 (4) | 0.9175 (4) | 0.6026 (2) | 0.0259 (7) | |
C11 | 0.5973 (4) | 0.7838 (4) | 0.5879 (2) | 0.0233 (6) | |
N1 | 0.7157 (3) | 0.4741 (3) | 0.43127 (17) | 0.0227 (5) | |
N2 | 0.5872 (3) | 0.7160 (3) | 0.51142 (16) | 0.0217 (5) | |
O1 | 0.6959 (3) | 0.7873 (3) | 0.29600 (14) | 0.0253 (5) | |
O2 | 0.3490 (3) | 0.5621 (3) | 0.38620 (14) | 0.0284 (5) | |
O3 | 0.3168 (3) | 0.7823 (2) | 0.30360 (15) | 0.0309 (5) | |
O4 | 0.4215 (3) | 0.5657 (3) | 0.24139 (14) | 0.0291 (5) | |
S1 | 0.41039 (10) | 0.64977 (8) | 0.31844 (5) | 0.0217 (2) | |
Co1 | 0.5 | 0.5 | 0.5 | 0.01982 (18) | |
H9 | 0.789 (5) | 1.074 (4) | 0.547 (2) | 0.024* | |
H11 | 0.553 (5) | 0.737 (4) | 0.628 (2) | 0.024* | |
H1 | 0.640 (6) | 0.858 (6) | 0.289 (3) | 0.058 (16)* | |
H3 | 0.916 (4) | 0.621 (4) | 0.288 (2) | 0.021 (8)* | |
H4 | 1.081 (5) | 0.410 (4) | 0.306 (2) | 0.023 (9)* | |
H5 | 1.009 (5) | 0.247 (4) | 0.408 (2) | 0.021 (9)* | |
H6 | 0.789 (5) | 0.303 (4) | 0.489 (2) | 0.024 (9)* | |
H8 | 0.780 (5) | 0.962 (4) | 0.406 (2) | 0.034 (10)* | |
H10 | 0.679 (5) | 0.959 (4) | 0.655 (3) | 0.031 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0289 (16) | 0.0180 (15) | 0.0165 (13) | −0.0008 (12) | 0.0065 (11) | 0.0019 (11) |
C2 | 0.0238 (15) | 0.0202 (15) | 0.0176 (14) | −0.0027 (12) | 0.0018 (11) | −0.0019 (12) |
C3 | 0.0245 (16) | 0.0261 (17) | 0.0217 (15) | −0.0041 (13) | 0.0041 (12) | 0.0022 (13) |
C4 | 0.0220 (15) | 0.0309 (18) | 0.0264 (16) | −0.0013 (14) | 0.0044 (12) | −0.0086 (14) |
C5 | 0.0298 (17) | 0.0252 (18) | 0.0346 (19) | 0.0058 (14) | 0.0014 (14) | −0.0007 (14) |
C6 | 0.0260 (16) | 0.0270 (18) | 0.0298 (17) | 0.0036 (13) | 0.0071 (13) | 0.0059 (14) |
C7 | 0.0207 (14) | 0.0203 (15) | 0.0181 (14) | 0.0022 (12) | 0.0030 (11) | 0.0019 (12) |
C8 | 0.0284 (16) | 0.0216 (16) | 0.0234 (15) | −0.0003 (13) | 0.0014 (12) | 0.0002 (12) |
C9 | 0.0287 (17) | 0.0190 (16) | 0.0271 (16) | 0.0011 (13) | −0.0014 (12) | −0.0016 (13) |
C10 | 0.0300 (17) | 0.0252 (17) | 0.0218 (16) | 0.0049 (13) | 0.0012 (12) | −0.0036 (13) |
C11 | 0.0272 (16) | 0.0243 (16) | 0.0192 (14) | 0.0035 (13) | 0.0060 (12) | 0.0019 (12) |
N1 | 0.0250 (13) | 0.0215 (13) | 0.0221 (12) | 0.0005 (11) | 0.0052 (10) | 0.0015 (10) |
N2 | 0.0249 (13) | 0.0213 (13) | 0.0193 (12) | 0.0016 (11) | 0.0047 (9) | 0.0001 (10) |
O1 | 0.0330 (13) | 0.0220 (12) | 0.0213 (11) | −0.0001 (10) | 0.0059 (9) | 0.0024 (9) |
O2 | 0.0267 (12) | 0.0350 (13) | 0.0230 (11) | −0.0045 (10) | 0.0016 (9) | 0.0087 (10) |
O3 | 0.0308 (12) | 0.0229 (12) | 0.0365 (13) | 0.0039 (10) | −0.0034 (10) | −0.0016 (10) |
O4 | 0.0385 (13) | 0.0265 (12) | 0.0232 (11) | −0.0029 (10) | 0.0073 (9) | −0.0081 (10) |
S1 | 0.0260 (4) | 0.0199 (4) | 0.0188 (4) | 0.0004 (3) | 0.0023 (3) | 0.0000 (3) |
Co1 | 0.0232 (3) | 0.0187 (3) | 0.0178 (3) | 0.0002 (2) | 0.0038 (2) | 0.0023 (2) |
C1—O1 | 1.401 (4) | C8—H8 | 1.03 (4) |
C1—C2 | 1.523 (4) | C9—C10 | 1.379 (5) |
C1—C7 | 1.533 (4) | C9—H9 | 0.94 (4) |
C1—S1 | 1.861 (3) | C10—C11 | 1.380 (5) |
C2—N1 | 1.351 (4) | C10—H10 | 0.90 (4) |
C2—C3 | 1.382 (4) | C11—N2 | 1.347 (4) |
C3—C4 | 1.382 (5) | C11—H11 | 0.88 (4) |
C3—H3 | 0.93 (3) | N1—Co1 | 2.127 (3) |
C4—C5 | 1.381 (5) | N2—Co1 | 2.128 (3) |
C4—H4 | 0.93 (4) | O1—H1 | 0.79 (5) |
C5—C6 | 1.376 (5) | O2—S1 | 1.473 (2) |
C5—H5 | 0.88 (4) | O2—Co1 | 2.064 (2) |
C6—N1 | 1.340 (4) | O3—S1 | 1.436 (2) |
C6—H6 | 0.91 (4) | O4—S1 | 1.453 (2) |
C7—N2 | 1.347 (4) | Co1—O2i | 2.064 (2) |
C7—C8 | 1.390 (4) | Co1—N1i | 2.127 (3) |
C8—C9 | 1.387 (4) | Co1—N2i | 2.128 (3) |
O1—C1—C2 | 108.1 (2) | N2—C11—C10 | 122.8 (3) |
O1—C1—C7 | 111.8 (2) | N2—C11—H11 | 115 (2) |
C2—C1—C7 | 110.3 (2) | C10—C11—H11 | 122 (2) |
O1—C1—S1 | 106.16 (19) | C6—N1—C2 | 117.6 (3) |
C2—C1—S1 | 109.2 (2) | C6—N1—Co1 | 119.6 (2) |
C7—C1—S1 | 111.2 (2) | C2—N1—Co1 | 122.7 (2) |
N1—C2—C3 | 122.4 (3) | C11—N2—C7 | 118.3 (3) |
N1—C2—C1 | 116.0 (3) | C11—N2—Co1 | 119.8 (2) |
C3—C2—C1 | 121.6 (3) | C7—N2—Co1 | 121.6 (2) |
C2—C3—C4 | 119.1 (3) | C1—O1—H1 | 111 (4) |
C2—C3—H3 | 119 (2) | S1—O2—Co1 | 125.20 (13) |
C4—C3—H3 | 122 (2) | O3—S1—O4 | 115.00 (14) |
C5—C4—C3 | 118.7 (3) | O3—S1—O2 | 112.84 (15) |
C5—C4—H4 | 121 (2) | O4—S1—O2 | 111.19 (14) |
C3—C4—H4 | 120 (2) | O3—S1—C1 | 104.95 (14) |
C6—C5—C4 | 119.0 (3) | O4—S1—C1 | 105.44 (14) |
C6—C5—H5 | 119 (2) | O2—S1—C1 | 106.56 (13) |
C4—C5—H5 | 122 (2) | O2—Co1—O2i | 180 |
N1—C6—C5 | 123.1 (3) | O2—Co1—N1i | 91.08 (9) |
N1—C6—H6 | 112 (2) | O2i—Co1—N1i | 88.92 (9) |
C5—C6—H6 | 124 (2) | O2—Co1—N1 | 88.92 (9) |
N2—C7—C8 | 122.1 (3) | O2i—Co1—N1 | 91.08 (9) |
N2—C7—C1 | 117.2 (3) | N1i—Co1—N1 | 180 |
C8—C7—C1 | 120.7 (3) | O2—Co1—N2i | 93.60 (10) |
C9—C8—C7 | 118.5 (3) | O2i—Co1—N2i | 86.40 (10) |
C9—C8—H8 | 122 (2) | N1i—Co1—N2i | 83.57 (10) |
C7—C8—H8 | 119 (2) | N1—Co1—N2i | 96.43 (10) |
C10—C9—C8 | 119.7 (3) | O2—Co1—N2 | 86.40 (10) |
C10—C9—H9 | 118 (2) | O2i—Co1—N2 | 93.60 (10) |
C8—C9—H9 | 123 (2) | N1i—Co1—N2 | 96.43 (10) |
C9—C10—C11 | 118.5 (3) | N1—Co1—N2 | 83.57 (10) |
C9—C10—H10 | 121 (3) | N2i—Co1—N2 | 180.00 (13) |
C11—C10—H10 | 121 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4ii | 0.79 (5) | 2.04 (5) | 2.789 (3) | 159 (5) |
Symmetry code: (ii) −x+1, y+1/2, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cu(C11H9N2O4S)2]·6H2O | [Co(C11H9N2O4S)2] |
Mr | 702.16 | 589.45 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 7.5892 (3), 10.1399 (4), 10.7325 (5) | 7.7300 (3), 9.3475 (4), 15.6518 (6) |
α, β, γ (°) | 108.675 (2), 109.920 (2), 101.025 (4) | 90, 98.499 (2), 90 |
V (Å3) | 692.53 (5) | 1118.52 (8) |
Z | 1 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.02 | 1.01 |
Crystal size (mm) | 0.24 × 0.1 × 0.08 | 0.25 × 0.12 × 0.09 |
Data collection | ||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.792, 0.923 | 0.785, 0.914 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10846, 2715, 2315 | 4704, 2558, 2025 |
Rint | 0.083 | 0.048 |
(sin θ/λ)max (Å−1) | 0.617 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.172, 1.07 | 0.048, 0.124, 1.05 |
No. of reflections | 2715 | 2558 |
No. of parameters | 257 | 203 |
No. of restraints | 9 | 0 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.73, −0.83 | 0.65, −0.60 |
Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).
N1—Cu1 | 2.020 (3) | O2—Cu1 | 2.347 (3) |
N2—Cu1 | 2.009 (4) | O3—S1 | 1.455 (3) |
O2—S1 | 1.455 (3) | O4—S1 | 1.456 (3) |
N2—Cu1—N1 | 85.91 (14) | N1—Cu1—O2 | 88.63 (12) |
N2—Cu1—O2 | 85.52 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O6 | 0.83 (6) | 1.84 (6) | 2.653 (5) | 167 (6) |
O5—H5A···O3 | 0.956 (10) | 1.828 (12) | 2.783 (5) | 176 (6) |
O5—H5B···O1i | 0.957 (10) | 2.15 (6) | 2.902 (5) | 134 (7) |
O5—H5B···O3i | 0.957 (10) | 2.41 (4) | 3.212 (5) | 141 (5) |
O6—H6A···O4ii | 0.963 (10) | 1.865 (12) | 2.828 (5) | 178 (5) |
O6—H6B···O7iii | 0.966 (10) | 1.82 (2) | 2.731 (6) | 155 (4) |
O7—H7A···O4 | 0.963 (10) | 1.91 (2) | 2.828 (5) | 157 (5) |
O7—H7B···O5iv | 0.962 (10) | 1.798 (17) | 2.745 (5) | 168 (6) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y, z; (iii) −x+1, −y, −z; (iv) −x+2, −y+1, −z. |
N1—Co1 | 2.127 (3) | O2—Co1 | 2.064 (2) |
N2—Co1 | 2.128 (3) | O3—S1 | 1.436 (2) |
O2—S1 | 1.473 (2) | O4—S1 | 1.453 (2) |
O2—Co1—N1 | 88.92 (9) | N1—Co1—N2 | 83.57 (10) |
O2—Co1—N2 | 86.40 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4i | 0.79 (5) | 2.04 (5) | 2.789 (3) | 159 (5) |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
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The distinction between bonding and supramolecular interactions is blurred in Jahn–Teller-distorted systems, where the weakening of some coordination bonds puts them on a par with hydrogen bonds. The interplay between the two types of bonding is of particular interest in copper complexes because of its occurrence in enzymes, e.g. the active site in copper amine oxidase from Hansenula polymorpha (Li et al., 1998).
Because of their complexity and, often, low resolution, protein structures are not the ideal platform for studying the subtler details of the relationship between these two interactions. Small inorganic complexes and salts provide a higher resolution and a more systematic means of investigation.
Beagley et al. (1989) established that, for the hexaaqua divalent metal cations in Tutton's salts, Cs2[M(H2O)6](SO4)2, Jahn–Teller distortion weakens the hydrogen bonds from the coordinated water with elongated Cu—O bonds. This is because the partial positive charge on their H atoms is reduced relative to the water H atoms which are more fully coordinated to the metal.
The current study is based on work carried out by Abrahams et al. (2006), who previously reported the structures of the bis[hydroxybis(pyridin-2-yl)methanesulfonato-κ3N,O,N']M(II) complexes for Mn, Fe, Ni and Zn. The structures of the Co and Cu complexes reported herein, namely bis[hydroxybis(pyridin-2-yl)methanesulfonato-κ3N,O,N']copper(II) hexahydrate, (I), and bis[hydroxybis(pyridin-2-yl)methanesulfonato-κ3N,O,N']cobalt(II), (II), complete the series from Mn to Zn
Each divalent metal in (I) and (II) is coordinated by two hydroxybis(pyridin-2-yl)methanesulfonate ligands in a centrosymmetric arrangement (Figs. 1a and 1b), with distinct Jahn–Teller tetragonal elongation in the Cu case. The Jahn–Teller radius, RJT, calculated using R2JT = Σ6i=1Δdi2, where di represents the deviation of the ith M—L bond distance from the mean of the six (Falvello, 1997), has a value of 0.385 Å, which is appropriate for the static Jahn–Teller tetragonal distortion seen in this case. It is interesting that, despite all the complexes being crystallized from aqueous solutions, it is only the copper complex that forms a hydrate; all the other complexes in this series so far form isostructural anhydrous crystals.
The extent of the M—O Jahn–Teller distortion can be seen when the M—O and M—N bond lengths from Abrahams et al. (2006) and the current work are plotted against d electron configuration (Fig. 2), while a similar plot of the three S—O bond lengths against d electron configuration (Fig. 3) shows the combined effect of hydrogen bonding and coordination on the sulfite group. The S—O bond for the coordinated O atom is significantly longer than the two noncoordinating S—O bonds in all but the copper complex. The nearly identical S—O bond lengths in the copper complex suggest that the strength of the Cu···O interaction is on a par with the SO···.HOH hydrogen bonds (Fig. 4). This contrasts with the situation in all the other complexes, where the S—O bonds involving the coordinated O atom remain significantly longer than the other S—O bonds, despite the involvement of one of the other O atoms in a strong hydrogen bond with the alcohol H atom (Fig. 5).
A useful comparison may be made between the current structure of (I) and bis[bis(3,5-dimethylpyrazol-1-yl)acetato]copper(II) and its hydrate (Kozlevcǎr et al., 2003). In both these structures, the Cu atom sits on an inversion centre. In the anhydrous compound, typical Jahn–Teller elongation of the Cu—O bonds is observed. On dehydration, the Cu—O bond length shrinks and a pair of Cu—N bonds lengthen to maintain the Jahn–Teller distortion. This is an extremely unusual situation, as only 3% of crystal structures studied to date in the well studied CuN4O2 system adopt Cu—N elongation rather than Cu—O [References?]. In the anhydrous compound, a significantly longer C—O distance [1.262 (3) Å] is observed for the coordinated carboxylate O atom compared with the noncoordinated carboxylate O atom [1.214 (3) Å]. For the hydrated compound, the two C—O distances are indistinguishable [1.245 (4) and 1.241 (4) Å]. The authors attributed the similar carboxylate C—O bonds in the hydrate to the binding of both O atoms to a Lewis acid, i.e. to the Cu and to a water molecule. In Cu structure (I), the overall effect is to make all three S—O bonds identical within experimental error, suggesting that a similar process to that seen in the above carboxylate is in operation.