Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100019867/bm1435sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100019867/bm1435Isup2.hkl |
CCDC reference: 162556
Previously prepared [Cu(sac)2(H2O)4]·2H2O (1.07 g, 2.0 mmol) was dissolved with stirring in ethanol (50 ml) at 343 K and the solution was cooled to room temperature. Ethanolamine (0.25 g, 4.0 mmol) was then added to the solution dropwise. The resulting dark blue solution was left at room temperature until evaporation resulted in the formation of blue crystals of (I) suitable for X-ray diffraction analysis.
The hydroxyl-group H atom was located from a difference map and freely refined, with Uiso(H) = 1.5Ueq(O). The other H atoms were geometrically positioned at distances of 0.90, 0.93 and 0.97 Å for amino N—H, methylene and methyl C—H, and aromatic C—H, respectively, and refined riding on their parent atoms.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Cu(C7H4NO3S)2(C2H7NO)2] | F(000) = 566 |
Mr = 550.06 | Dx = 1.680 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.0346 (5) Å | Cell parameters from 4688 reflections |
b = 8.8957 (4) Å | θ = 2.9–30.0° |
c = 11.4161 (5) Å | µ = 1.25 mm−1 |
β = 103.946 (1)° | T = 298 K |
V = 1087.58 (8) Å3 | Block, blue |
Z = 2 | 0.32 × 0.24 × 0.17 mm |
Bruker SMART1000 CCD area-detector diffractometer | 3165 independent reflections |
Radiation source: fine-focus sealed tube | 2524 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 30.0°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −15→15 |
Tmin = 0.667, Tmax = 0.808 | k = −11→12 |
9396 measured reflections | l = −16→13 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0634P)2 + 0.0557P] where P = (Fo2 + 2Fc2)/3 |
3165 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.82 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[Cu(C7H4NO3S)2(C2H7NO)2] | V = 1087.58 (8) Å3 |
Mr = 550.06 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.0346 (5) Å | µ = 1.25 mm−1 |
b = 8.8957 (4) Å | T = 298 K |
c = 11.4161 (5) Å | 0.32 × 0.24 × 0.17 mm |
β = 103.946 (1)° |
Bruker SMART1000 CCD area-detector diffractometer | 3165 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2524 reflections with I > 2σ(I) |
Tmin = 0.667, Tmax = 0.808 | Rint = 0.022 |
9396 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.82 e Å−3 |
3165 reflections | Δρmin = −0.40 e Å−3 |
154 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 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 > σ(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 | ||
Cu | 0 | 0 | 1/2 | 0.02747 (10) | |
S1 | −0.19411 (4) | 0.25565 (5) | 0.33495 (4) | 0.03308 (12) | |
O1 | −0.28468 (15) | 0.02092 (15) | 0.56514 (14) | 0.0403 (3) | |
O2 | −0.19720 (16) | 0.17922 (17) | 0.22247 (14) | 0.0474 (4) | |
O3 | −0.10999 (15) | 0.38007 (16) | 0.36242 (16) | 0.0472 (4) | |
O4 | 0.12257 (15) | 0.19256 (19) | 0.45247 (14) | 0.0426 (3) | |
H4O | 0.174 (3) | 0.145 (3) | 0.437 (3) | 0.064* | |
N1 | −0.17082 (15) | 0.13121 (17) | 0.44424 (15) | 0.0318 (3) | |
N2 | 0.03883 (16) | 0.10842 (18) | 0.65734 (15) | 0.0358 (3) | |
H2A | −0.0297 | 0.1112 | 0.6870 | 0.043* | |
H2B | 0.0991 | 0.0590 | 0.7105 | 0.043* | |
C1 | −0.27366 (18) | 0.11583 (19) | 0.48943 (17) | 0.0313 (4) | |
C2 | −0.37596 (17) | 0.2233 (2) | 0.43427 (17) | 0.0318 (4) | |
C3 | −0.4905 (2) | 0.2415 (2) | 0.4620 (2) | 0.0414 (5) | |
H3 | −0.5131 | 0.1823 | 0.5204 | 0.050* | |
C4 | −0.5704 (2) | 0.3508 (3) | 0.4000 (2) | 0.0495 (5) | |
H4 | −0.6478 | 0.3650 | 0.4172 | 0.059* | |
C5 | −0.5371 (2) | 0.4392 (3) | 0.3131 (2) | 0.0483 (5) | |
H5 | −0.5922 | 0.5123 | 0.2736 | 0.058* | |
C6 | −0.4226 (2) | 0.4208 (2) | 0.28358 (19) | 0.0409 (4) | |
H6 | −0.3999 | 0.4796 | 0.2250 | 0.049* | |
C7 | −0.34472 (17) | 0.3109 (2) | 0.34576 (17) | 0.0319 (4) | |
C8 | 0.1717 (3) | 0.2681 (3) | 0.5644 (3) | 0.0563 (6) | |
H8A | 0.1897 | 0.3720 | 0.5488 | 0.068* | |
H8B | 0.2492 | 0.2206 | 0.6062 | 0.068* | |
C9 | 0.0806 (3) | 0.2630 (3) | 0.6418 (2) | 0.0505 (6) | |
H9A | 0.1191 | 0.3051 | 0.7204 | 0.061* | |
H9B | 0.0087 | 0.3244 | 0.6056 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.02934 (16) | 0.02610 (15) | 0.03108 (17) | −0.00061 (11) | 0.01530 (12) | −0.00205 (11) |
S1 | 0.0354 (2) | 0.0288 (2) | 0.0422 (3) | 0.00157 (16) | 0.02328 (19) | 0.00524 (18) |
O1 | 0.0463 (8) | 0.0366 (7) | 0.0474 (8) | 0.0043 (6) | 0.0298 (7) | 0.0086 (6) |
O2 | 0.0622 (10) | 0.0477 (8) | 0.0419 (8) | 0.0083 (7) | 0.0314 (7) | 0.0036 (7) |
O3 | 0.0402 (8) | 0.0340 (7) | 0.0737 (11) | −0.0043 (6) | 0.0263 (8) | 0.0095 (7) |
O4 | 0.0431 (8) | 0.0490 (8) | 0.0413 (8) | 0.0062 (7) | 0.0208 (6) | −0.0002 (7) |
N1 | 0.0344 (8) | 0.0290 (7) | 0.0382 (8) | 0.0012 (6) | 0.0207 (6) | 0.0039 (6) |
N2 | 0.0403 (9) | 0.0365 (8) | 0.0357 (8) | 0.0026 (7) | 0.0188 (7) | −0.0028 (7) |
C1 | 0.0355 (9) | 0.0284 (8) | 0.0359 (9) | −0.0022 (7) | 0.0198 (7) | −0.0031 (7) |
C2 | 0.0318 (9) | 0.0312 (8) | 0.0366 (9) | −0.0018 (7) | 0.0164 (7) | −0.0020 (7) |
C3 | 0.0374 (10) | 0.0478 (11) | 0.0464 (11) | 0.0011 (8) | 0.0245 (9) | 0.0044 (9) |
C4 | 0.0348 (10) | 0.0635 (14) | 0.0561 (13) | 0.0084 (10) | 0.0227 (10) | 0.0050 (11) |
C5 | 0.0428 (12) | 0.0538 (13) | 0.0502 (12) | 0.0135 (10) | 0.0151 (10) | 0.0097 (11) |
C6 | 0.0443 (11) | 0.0415 (10) | 0.0418 (10) | 0.0041 (8) | 0.0199 (9) | 0.0054 (9) |
C7 | 0.0330 (9) | 0.0315 (8) | 0.0355 (9) | −0.0010 (7) | 0.0162 (7) | −0.0013 (7) |
C8 | 0.0656 (16) | 0.0457 (12) | 0.0679 (16) | −0.0202 (11) | 0.0362 (13) | −0.0177 (11) |
C9 | 0.0649 (15) | 0.0439 (12) | 0.0486 (12) | −0.0119 (10) | 0.0254 (11) | −0.0134 (10) |
Cu—N1 | 2.1776 (16) | N2—C9 | 1.475 (3) |
Cu—N2 | 1.9923 (16) | C1—C2 | 1.498 (3) |
Cu—O4 | 2.3263 (16) | C2—C7 | 1.384 (2) |
S1—N1 | 1.6412 (16) | C2—C3 | 1.384 (2) |
S1—O2 | 1.4461 (15) | C3—C4 | 1.387 (3) |
S1—O3 | 1.4299 (15) | C4—C5 | 1.383 (3) |
S1—C7 | 1.7657 (18) | C5—C6 | 1.393 (3) |
O1—C1 | 1.235 (2) | C6—C7 | 1.380 (3) |
O4—C8 | 1.430 (3) | C8—C9 | 1.490 (3) |
N1—C1 | 1.362 (2) | O4—H4O | 0.76 (3) |
N1—Cu—N2 | 89.26 (7) | C1—N1—S1 | 111.32 (13) |
N1—Cu—O4 | 92.76 (5) | C1—N1—Cu | 125.24 (12) |
N2—Cu—O4 | 80.97 (6) | S1—N1—Cu | 123.34 (8) |
N2—Cu—N2i | 180 | C9—N2—Cu | 110.41 (13) |
N2i—Cu—N1 | 90.74 (7) | O1—C1—N1 | 124.43 (18) |
N2—Cu—N1i | 90.74 (7) | O1—C1—C2 | 122.64 (16) |
N2i—Cu—N1i | 89.26 (7) | N1—C1—C2 | 112.89 (15) |
N1—Cu—N1i | 180 | C7—C2—C3 | 120.21 (18) |
N2i—Cu—O4 | 99.03 (6) | C7—C2—C1 | 111.80 (15) |
N1i—Cu—O4 | 87.24 (5) | C3—C2—C1 | 127.99 (17) |
N2—Cu—O4i | 99.03 (6) | C2—C3—C4 | 117.91 (19) |
N2i—Cu—O4i | 80.97 (6) | C5—C4—C3 | 121.2 (2) |
N1—Cu—O4i | 87.24 (5) | C4—C5—C6 | 121.3 (2) |
N1i—Cu—O4i | 92.76 (5) | C7—C6—C5 | 116.56 (19) |
O4—Cu—O4i | 180 | C6—C7—C2 | 122.72 (17) |
O3—S1—O2 | 115.71 (9) | C6—C7—S1 | 129.90 (14) |
O3—S1—N1 | 112.39 (10) | C2—C7—S1 | 107.37 (14) |
O2—S1—N1 | 108.89 (9) | O4—C8—C9 | 110.6 (2) |
O3—S1—C7 | 109.96 (9) | N2—C9—C8 | 112.03 (18) |
O2—S1—C7 | 111.83 (9) | C8—O4—H4O | 109 (2) |
N1—S1—C7 | 96.45 (8) | Cu1—O4—H4O | 99 (2) |
C8—O4—Cu | 104.73 (12) | ||
N2—Cu—O4—C8 | 7.85 (15) | Cu—N1—C1—C2 | 179.28 (12) |
N2i—Cu—O4—C8 | −172.15 (15) | O1—C1—C2—C7 | −175.58 (18) |
N1—Cu—O4—C8 | 96.66 (15) | N1—C1—C2—C7 | 2.3 (2) |
N1i—Cu—O4—C8 | −83.34 (15) | O1—C1—C2—C3 | 4.5 (3) |
O3—S1—N1—C1 | 118.60 (14) | N1—C1—C2—C3 | −177.61 (19) |
O2—S1—N1—C1 | −111.85 (14) | C7—C2—C3—C4 | −1.0 (3) |
C7—S1—N1—C1 | 3.88 (15) | C1—C2—C3—C4 | 179.0 (2) |
O3—S1—N1—Cu | −64.78 (12) | C2—C3—C4—C5 | 0.0 (4) |
O2—S1—N1—Cu | 64.77 (12) | C3—C4—C5—C6 | 0.7 (4) |
C7—S1—N1—Cu | −179.50 (10) | C4—C5—C6—C7 | −0.3 (4) |
N2—Cu—N1—C1 | −70.87 (16) | C5—C6—C7—C2 | −0.8 (3) |
N2i—Cu—N1—C1 | 109.13 (16) | C5—C6—C7—S1 | −179.47 (18) |
O4—Cu—N1—C1 | −151.79 (15) | C3—C2—C7—C6 | 1.5 (3) |
O4i—Cu—N1—C1 | 28.21 (15) | C1—C2—C7—C6 | −178.51 (18) |
N2—Cu—N1—S1 | 112.99 (11) | C3—C2—C7—S1 | −179.59 (16) |
N2i—Cu—N1—S1 | −67.01 (11) | C1—C2—C7—S1 | 0.44 (19) |
O4—Cu—N1—S1 | 32.07 (11) | O3—S1—C7—C6 | 59.7 (2) |
O4i—Cu—N1—S1 | −147.93 (11) | O2—S1—C7—C6 | −70.2 (2) |
N1—Cu—N2—C9 | −74.11 (15) | N1—S1—C7—C6 | 176.4 (2) |
N1i—Cu—N2—C9 | 105.89 (15) | O3—S1—C7—C2 | −119.12 (14) |
O4—Cu—N2—C9 | 18.80 (15) | O2—S1—C7—C2 | 110.90 (14) |
O4i—Cu—N2—C9 | −161.20 (15) | N1—S1—C7—C2 | −2.44 (15) |
S1—N1—C1—O1 | 173.70 (16) | Cu—O4—C8—C9 | −32.6 (2) |
Cu—N1—C1—O1 | −2.8 (3) | Cu—N2—C9—C8 | −44.3 (3) |
S1—N1—C1—C2 | −4.2 (2) | O4—C8—C9—N2 | 52.8 (3) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4O···O1i | 0.76 (3) | 1.92 (3) | 2.650 (2) | 160 (3) |
N2—H2B···O2i | 0.90 | 2.42 | 3.214 (2) | 148 |
N2—H2A···O3ii | 0.90 | 2.38 | 3.169 (2) | 147 |
C6—H6···O1iii | 0.93 | 2.46 | 3.261 (2) | 144 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C7H4NO3S)2(C2H7NO)2] |
Mr | 550.06 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 11.0346 (5), 8.8957 (4), 11.4161 (5) |
β (°) | 103.946 (1) |
V (Å3) | 1087.58 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.32 × 0.24 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.667, 0.808 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9396, 3165, 2524 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.099, 1.04 |
No. of reflections | 3165 |
No. of parameters | 154 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.82, −0.40 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
Cu—N1 | 2.1776 (16) | Cu—O4 | 2.3263 (16) |
Cu—N2 | 1.9923 (16) | ||
N1—Cu—N2 | 89.26 (7) | N2—Cu—O4 | 80.97 (6) |
N1—Cu—O4 | 92.76 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4O···O1i | 0.76 (3) | 1.92 (3) | 2.650 (2) | 160 (3) |
N2—H2B···O2i | 0.90 | 2.42 | 3.214 (2) | 148 |
N2—H2A···O3ii | 0.90 | 2.38 | 3.169 (2) | 147 |
C6—H6···O1iii | 0.93 | 2.46 | 3.261 (2) | 144 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x, −y+1/2, z−1/2. |
Saccharin (o-sulfobenzimide) is widely used as a non-calorific artificial sweetener. The chemistry of its mixed-ligand metal complexes is of interest owing to their potential effectiveness in biological systems, due to the coordination ability of saccharin towards most metals present in body fluid (Haider et al., 1985). It has also been suggested that the importance of saccharin lies in its potential use as an antidote for metal poisoning (Ainscough et al., 1990). In the light of this interest, we have prepared the title compound, (I), and present its crystal structure here. \sch
In compound (I), the complex lies on an inversion centre and is octahedrally coordinated to two saccharinate (sac) ions and two ethanolamine (Hea) molecules. The Hea act as bidentate ligands and form two five-membered trans chelate rings which constitute the plane of the coordination octahedron, while each sac behaves as a monodentate ligand occupying an axial position (Fig. 1).
The Cu—O and Cu—NHea distances of 2.3263 (16) and 1.9923 (16) Å, respectively, are typical for Cu-Hea complexes (Hursthouse et al., 1990; Bombicz et al., 1997). The sac ligand is essentially planar and intramolecular bond lengths are virtually identical to those found in the free saccharin molecule (Okaya, 1969). The Cu—Nsac distance of 2.1776 (16) Å is significantly longer than in related CuII complexes: 2.030 (5) Å in [Cu(sac)2(bpy)2]sac·2H2O (Hergold-Brundić et al., 1991) and 2.032 (2) Å in [Cu(H2O)(py)2(sac)2] (Jovanovski et al., 1998).
The H atoms of the hydroxyl and nitrogen groups of the Hea molecules participate in both intra- and intermolecular hydrogen bonding with the carbonyl and sulfonyl O atoms of the sac ligand (Table 2). The phenyl H6 atom of the sac ligand appears to be involved in an intermolecular hydrogen bond with the carbonyl atom O1 of a sac ligand in a neighbouring molecule related by a screw axis operation.