The Cu
II complex bis[hydroxybis(pyridin-2-yl)methanesulfonato-κ
3N,
O,
N′]copper(II) hexahydrate, [Cu(C
11H
9N
2O
4S)
2]·6H
2O, (I), crystallizes in the space group
P, compared with
P2
1/
c for the anhydrous Co
II analogue bis[hydroxybis(pyridin-2-yl)methanesulfonato-κ
3N,
O,
N′]cobalt(II), [Co(C
11H
9N
2O
4S)
2], (II). However, both molecules sit on a crystallographic inversion centre and are thus very similar in appearance. Jahn–Teller elongation of the Cu—O bonds [2.347 (3) Å in (I) and 2.064 (2) Å in (II)] influences the S—O bond lengths, which are all around 1.455 (3) Å in (I) and 1.436 (2)–1.473 (2) Å in (II).
Supporting information
CCDC references: 925252; 925253
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).
(I) bis[hydroxybis(pyridin-2-yl)methanesulfonato-
κ3N,
O,
N']copper(II) hexahydrate
top
Crystal data top
[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 | |
Data collection top
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 top
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) |
Crystal data top
[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)° | |
Data collection top
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 | |
Refinement top
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 | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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)* | |
Atomic displacement parameters (Å2) top | 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) |
Geometric parameters (Å, º) top
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. |
Hydrogen-bond geometry (Å, º) top
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. |
(II) bis[hydroxybis(pyridin-2-yl)methanesulfonato-
κ3N,
O,
N']cobalt(II)
top
Crystal data top
[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 | |
Data collection top
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 top
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 |
Crystal data top
[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)° | |
Data collection top
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 | |
Refinement top
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 | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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)* | |
Atomic displacement parameters (Å2) top | 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) |
Geometric parameters (Å, º) top
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. |
Hydrogen-bond geometry (Å, º) top
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 |
Selected geometric parameters (Å, º) for (I) topN1—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) | | |
Hydrogen-bond geometry (Å, º) for (I) top
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. |
Selected geometric parameters (Å, º) for (II) topN1—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) | | |
Hydrogen-bond geometry (Å, º) for (II) top
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. |
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.