metal-organic compounds
Bis(2-{[bis(dimethylamino)methylidene]amino-κN}benzenesulfonato-κN)copper(II)
aUniversität Paderborn, Fakultät für Naturwissenschaften, Department Chemie, Warburger Strasse 100, 33098 Paderborn, Germany
*Correspondence e-mail: ulrich.floerke@upb.de
The molecular structure of the title compound, [Cu(C11H16N3O3S)2], shows the CuII atom with a distorted square-planar coordination geometry from the N2O2 donor set of the two chelating 2-{[bis(dimethylamino)methylidene]amino}benzenesulfonate ligands. The CuII atom lies 0.065 (1) Å above the N2O2 plane and the Cu—O [2 × 1.945 (2) Å] and Cu—N bond lengths [1.968 (3) and 1.962 (3) Å] lie in expected ranges. The two aromatic ring planes make a dihedral angle of 85.48 (1)°.
Related literature
For bifunctional peralkylated guanidine ligands, see: Bienemann et al. (2011); Börner et al. (2009); Herres-Pawlis et al. (2005, 2009); Neuba et al. (2008, 2010); Pohl et al. (2000); Raab et al. (2003); Wittmann et al. (2001). For guanidine–sulfur hybrids to mimic the structural and physical as well as functional characteristics of the CuII atom in cytochrome c oxidase and N2O reductase, see: Neuba et al. (2011, 2012). For related structures with Cu(N2O2) motifs, see: Robinson et al. (2004).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
Supporting information
10.1107/S1600536812046387/aa2076sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046387/aa2076Isup2.hkl
In a first step the mixed-valent copper thiolate complex [Cu6(NGuaS)6](PF6)2 [NGuaS = 2-(1,1,3,3-tetramethylguanidino)benzenethiolate, C11H16N3S] was synthesized (Neuba et al., 2011): reaction of 1,1,3,3-tetramethyl-2-(2-(tritylthio)phenyl)guanidine (510 mg, 1.1 mmol) with [Cu(MeCN)4]PF6 (186.2 mg, 0.5 mmol) dissolved in 5 ml of ABS. MeCN led to a deep blue/green solution. The reaction mixture was stirred for a period of 30 min. at room temperature followed by heating under reflux for 30 min. After cooling the solution was filtered. Second step: slow diffusion of air at -20°C to the filtrate leads after several weeks to dark red crystals of [Cu(C11H16N3O3S)2] suitable for X-ray diffraction. We suppose a copper mediated oxidation of the o-tetramethylguanidinobenzenethiolate ligand to the corresponding benzenesulfonate.
H atoms were clearly identified in difference syntheses, refined at idealized positions riding on the carbon atoms with isotropic displacement parameters Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). All CH3 hydrogen atoms were allowed to rotate but not to tip.
Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.Fig. 1. Molecular structure of the title compound. Anistropic displacement parameters are shown at the 50% probability level. |
[Cu(C11H16N3O3S)2] | F(000) = 1260 |
Mr = 604.20 | Dx = 1.495 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 1013 reflections |
a = 19.940 (3) Å | θ = 2.5–23.8° |
b = 12.2947 (14) Å | µ = 1.02 mm−1 |
c = 10.9508 (14) Å | T = 120 K |
V = 2684.7 (6) Å3 | Block, red |
Z = 4 | 0.29 × 0.23 × 0.20 mm |
Bruker SMART APEX diffractometer | 6315 independent reflections |
Radiation source: sealed tube | 4939 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
ϕ and ω scans | θmax = 27.9°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −26→25 |
Tmin = 0.757, Tmax = 0.822 | k = −16→14 |
22901 measured reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0383P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
6315 reflections | Δρmax = 0.63 e Å−3 |
342 parameters | Δρmin = −0.29 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 2953 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.021 (12) |
[Cu(C11H16N3O3S)2] | V = 2684.7 (6) Å3 |
Mr = 604.20 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 19.940 (3) Å | µ = 1.02 mm−1 |
b = 12.2947 (14) Å | T = 120 K |
c = 10.9508 (14) Å | 0.29 × 0.23 × 0.20 mm |
Bruker SMART APEX diffractometer | 6315 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 4939 reflections with I > 2σ(I) |
Tmin = 0.757, Tmax = 0.822 | Rint = 0.063 |
22901 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.093 | Δρmax = 0.63 e Å−3 |
S = 1.02 | Δρmin = −0.29 e Å−3 |
6315 reflections | Absolute structure: Flack (1983), 2953 Friedel pairs |
342 parameters | Absolute structure parameter: 0.021 (12) |
1 restraint |
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 > 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 | ||
Cu1 | 0.375129 (18) | 0.12574 (3) | 0.29666 (4) | 0.01655 (10) | |
S1 | 0.25801 (4) | 0.02454 (7) | 0.41807 (8) | 0.01986 (19) | |
S2 | 0.49473 (4) | 0.22745 (7) | 0.40833 (8) | 0.01868 (18) | |
O1 | 0.28279 (12) | 0.12436 (19) | 0.3539 (2) | 0.0220 (6) | |
O2 | 0.18969 (13) | 0.0382 (2) | 0.4554 (3) | 0.0313 (7) | |
O3 | 0.30433 (13) | −0.0077 (2) | 0.5122 (2) | 0.0267 (6) | |
O4 | 0.46904 (11) | 0.12775 (18) | 0.3447 (2) | 0.0211 (6) | |
O5 | 0.45077 (14) | 0.2585 (2) | 0.5066 (2) | 0.0254 (6) | |
O6 | 0.56389 (12) | 0.2136 (2) | 0.4400 (3) | 0.0321 (7) | |
N1 | 0.37774 (14) | −0.0306 (2) | 0.2583 (2) | 0.0173 (6) | |
N2 | 0.44573 (14) | −0.1771 (2) | 0.3195 (3) | 0.0219 (7) | |
N3 | 0.48764 (15) | −0.0454 (2) | 0.1876 (3) | 0.0235 (7) | |
N4 | 0.37182 (14) | 0.2806 (2) | 0.2535 (3) | 0.0165 (6) | |
N5 | 0.26055 (14) | 0.2943 (3) | 0.1932 (3) | 0.0226 (7) | |
N6 | 0.30479 (14) | 0.4264 (2) | 0.3212 (3) | 0.0230 (7) | |
C1 | 0.43704 (18) | −0.0852 (3) | 0.2543 (3) | 0.0195 (8) | |
C2 | 0.40296 (18) | −0.2039 (3) | 0.4219 (4) | 0.0270 (8) | |
H2A | 0.3828 | −0.1373 | 0.4545 | 0.040* | |
H2B | 0.4297 | −0.2392 | 0.4858 | 0.040* | |
H2C | 0.3674 | −0.2535 | 0.3949 | 0.040* | |
C3 | 0.4881 (2) | −0.2670 (3) | 0.2783 (4) | 0.0370 (10) | |
H3A | 0.5061 | −0.2504 | 0.1972 | 0.055* | |
H3B | 0.4613 | −0.3338 | 0.2742 | 0.055* | |
H3C | 0.5252 | −0.2772 | 0.3359 | 0.055* | |
C4 | 0.55762 (19) | −0.0533 (3) | 0.2252 (4) | 0.0357 (11) | |
H4A | 0.5607 | −0.0962 | 0.3004 | 0.054* | |
H4B | 0.5755 | 0.0198 | 0.2397 | 0.054* | |
H4C | 0.5837 | −0.0888 | 0.1606 | 0.054* | |
C5 | 0.4752 (2) | 0.0283 (3) | 0.0868 (4) | 0.0321 (10) | |
H5A | 0.4288 | 0.0199 | 0.0589 | 0.048* | |
H5B | 0.5059 | 0.0115 | 0.0195 | 0.048* | |
H5C | 0.4824 | 0.1034 | 0.1138 | 0.048* | |
C6 | 0.31920 (17) | −0.0947 (3) | 0.2379 (3) | 0.0196 (8) | |
C7 | 0.3188 (2) | −0.1734 (3) | 0.1472 (4) | 0.0278 (9) | |
H7A | 0.3586 | −0.1886 | 0.1028 | 0.033* | |
C8 | 0.2598 (2) | −0.2305 (3) | 0.1211 (4) | 0.0330 (10) | |
H8A | 0.2597 | −0.2837 | 0.0582 | 0.040* | |
C9 | 0.2016 (2) | −0.2100 (3) | 0.1860 (4) | 0.0335 (10) | |
H9A | 0.1618 | −0.2493 | 0.1676 | 0.040* | |
C10 | 0.20118 (18) | −0.1333 (3) | 0.2766 (4) | 0.0265 (9) | |
H10A | 0.1613 | −0.1195 | 0.3214 | 0.032* | |
C11 | 0.25995 (15) | −0.0753 (3) | 0.3028 (4) | 0.0198 (7) | |
C12 | 0.31265 (18) | 0.3351 (3) | 0.2543 (3) | 0.0204 (8) | |
C13 | 0.19238 (19) | 0.3016 (4) | 0.2378 (5) | 0.0399 (12) | |
H13A | 0.1925 | 0.3323 | 0.3204 | 0.060* | |
H13B | 0.1724 | 0.2288 | 0.2397 | 0.060* | |
H13C | 0.1661 | 0.3486 | 0.1835 | 0.060* | |
C14 | 0.2704 (2) | 0.2234 (4) | 0.0906 (4) | 0.0324 (10) | |
H14A | 0.3151 | 0.2359 | 0.0558 | 0.049* | |
H14B | 0.2362 | 0.2383 | 0.0286 | 0.049* | |
H14C | 0.2668 | 0.1475 | 0.1174 | 0.049* | |
C15 | 0.34810 (19) | 0.4524 (3) | 0.4234 (4) | 0.0292 (9) | |
H15A | 0.3693 | 0.3858 | 0.4536 | 0.044* | |
H15B | 0.3215 | 0.4854 | 0.4889 | 0.044* | |
H15C | 0.3828 | 0.5037 | 0.3968 | 0.044* | |
C16 | 0.2584 (2) | 0.5139 (3) | 0.2842 (4) | 0.0388 (11) | |
H16A | 0.2398 | 0.4973 | 0.2035 | 0.058* | |
H16B | 0.2827 | 0.5831 | 0.2809 | 0.058* | |
H16C | 0.2218 | 0.5193 | 0.3438 | 0.058* | |
C17 | 0.42974 (17) | 0.3458 (3) | 0.2312 (3) | 0.0166 (7) | |
C18 | 0.42834 (19) | 0.4263 (3) | 0.1423 (3) | 0.0231 (8) | |
H18A | 0.3881 | 0.4391 | 0.0981 | 0.028* | |
C19 | 0.4846 (2) | 0.4882 (3) | 0.1173 (4) | 0.0279 (10) | |
H19A | 0.4830 | 0.5418 | 0.0549 | 0.033* | |
C20 | 0.5430 (2) | 0.4726 (3) | 0.1823 (4) | 0.0300 (9) | |
H20A | 0.5810 | 0.5169 | 0.1664 | 0.036* | |
C21 | 0.54617 (16) | 0.3927 (3) | 0.2703 (3) | 0.0223 (9) | |
H21A | 0.5866 | 0.3811 | 0.3142 | 0.027* | |
C22 | 0.49011 (15) | 0.3290 (2) | 0.2949 (4) | 0.0178 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01765 (18) | 0.01225 (17) | 0.0197 (2) | −0.00136 (15) | 0.0002 (2) | −0.0011 (2) |
S1 | 0.0212 (4) | 0.0173 (4) | 0.0211 (5) | −0.0007 (3) | 0.0063 (4) | −0.0007 (4) |
S2 | 0.0192 (4) | 0.0167 (4) | 0.0201 (4) | 0.0001 (3) | −0.0057 (4) | 0.0007 (4) |
O1 | 0.0205 (13) | 0.0171 (13) | 0.0285 (14) | −0.0015 (10) | 0.0076 (11) | −0.0011 (11) |
O2 | 0.0256 (14) | 0.0276 (15) | 0.0408 (18) | −0.0018 (12) | 0.0135 (12) | 0.0006 (13) |
O3 | 0.0312 (15) | 0.0294 (15) | 0.0196 (15) | 0.0041 (11) | 0.0017 (12) | −0.0027 (11) |
O4 | 0.0197 (12) | 0.0135 (12) | 0.0302 (15) | 0.0007 (10) | −0.0074 (10) | 0.0005 (10) |
O5 | 0.0356 (16) | 0.0233 (14) | 0.0172 (14) | 0.0032 (12) | −0.0013 (12) | 0.0026 (11) |
O6 | 0.0263 (14) | 0.0326 (15) | 0.0375 (18) | −0.0030 (12) | −0.0152 (13) | 0.0035 (14) |
N1 | 0.0208 (15) | 0.0131 (14) | 0.0179 (16) | −0.0041 (12) | 0.0043 (11) | −0.0022 (11) |
N2 | 0.0244 (15) | 0.0207 (16) | 0.0207 (18) | 0.0054 (12) | 0.0022 (13) | −0.0001 (13) |
N3 | 0.0235 (16) | 0.0179 (16) | 0.0291 (18) | −0.0016 (13) | 0.0101 (14) | −0.0048 (14) |
N4 | 0.0173 (14) | 0.0135 (14) | 0.0186 (15) | −0.0018 (13) | −0.0016 (11) | 0.0028 (11) |
N5 | 0.0164 (15) | 0.0264 (18) | 0.0248 (18) | 0.0016 (13) | −0.0050 (13) | 0.0017 (14) |
N6 | 0.0247 (15) | 0.0230 (16) | 0.0212 (19) | 0.0083 (13) | −0.0048 (13) | −0.0012 (13) |
C1 | 0.0224 (18) | 0.0156 (17) | 0.0204 (19) | −0.0027 (15) | 0.0026 (14) | −0.0069 (14) |
C2 | 0.0304 (19) | 0.025 (2) | 0.026 (2) | 0.0015 (16) | 0.0050 (18) | 0.0047 (18) |
C3 | 0.050 (3) | 0.027 (2) | 0.034 (3) | 0.0107 (18) | 0.015 (2) | 0.002 (2) |
C4 | 0.023 (2) | 0.032 (2) | 0.052 (3) | −0.0043 (18) | 0.0107 (19) | −0.009 (2) |
C5 | 0.045 (3) | 0.023 (2) | 0.029 (2) | −0.004 (2) | 0.0171 (19) | 0.0026 (19) |
C6 | 0.0225 (18) | 0.0146 (17) | 0.0217 (19) | 0.0022 (14) | −0.0016 (15) | −0.0006 (15) |
C7 | 0.031 (2) | 0.025 (2) | 0.028 (2) | −0.0015 (17) | 0.0000 (17) | −0.0042 (17) |
C8 | 0.045 (3) | 0.0205 (19) | 0.033 (2) | −0.004 (2) | −0.008 (2) | −0.0078 (19) |
C9 | 0.034 (2) | 0.023 (2) | 0.044 (3) | −0.0131 (18) | −0.010 (2) | −0.001 (2) |
C10 | 0.0195 (17) | 0.0264 (19) | 0.034 (3) | −0.0017 (15) | −0.0020 (16) | 0.0059 (18) |
C11 | 0.0229 (16) | 0.0155 (15) | 0.0210 (18) | −0.0027 (13) | 0.0007 (18) | 0.0012 (17) |
C12 | 0.0229 (19) | 0.0182 (18) | 0.0200 (19) | −0.0030 (15) | −0.0038 (14) | 0.0055 (14) |
C13 | 0.019 (2) | 0.042 (3) | 0.058 (3) | −0.004 (2) | −0.0020 (19) | 0.010 (2) |
C14 | 0.030 (2) | 0.031 (2) | 0.036 (3) | −0.005 (2) | −0.0153 (18) | 0.004 (2) |
C15 | 0.041 (2) | 0.0206 (19) | 0.026 (2) | 0.0099 (16) | −0.0083 (19) | −0.0069 (18) |
C16 | 0.054 (3) | 0.030 (2) | 0.032 (2) | 0.0243 (19) | −0.010 (2) | −0.004 (2) |
C17 | 0.0178 (17) | 0.0164 (17) | 0.0156 (18) | 0.0010 (14) | −0.0017 (14) | −0.0009 (14) |
C18 | 0.0263 (19) | 0.0196 (19) | 0.023 (2) | 0.0016 (16) | −0.0028 (16) | 0.0005 (15) |
C19 | 0.040 (2) | 0.0171 (19) | 0.027 (2) | −0.0073 (17) | 0.0046 (18) | 0.0057 (16) |
C20 | 0.030 (2) | 0.028 (2) | 0.032 (2) | −0.0157 (18) | 0.0079 (18) | −0.0024 (18) |
C21 | 0.0128 (15) | 0.0208 (18) | 0.033 (3) | −0.0030 (14) | 0.0020 (14) | −0.0012 (16) |
C22 | 0.0192 (15) | 0.0154 (15) | 0.0190 (16) | −0.0009 (12) | 0.0014 (17) | −0.0023 (17) |
Cu1—O4 | 1.945 (2) | C4—H4C | 0.9800 |
Cu1—O1 | 1.945 (2) | C5—H5A | 0.9800 |
Cu1—N4 | 1.962 (3) | C5—H5B | 0.9800 |
Cu1—N1 | 1.968 (3) | C5—H5C | 0.9800 |
S1—O2 | 1.432 (3) | C6—C7 | 1.386 (5) |
S1—O3 | 1.440 (3) | C6—C11 | 1.400 (5) |
S1—O1 | 1.498 (2) | C7—C8 | 1.399 (6) |
S1—C11 | 1.761 (4) | C7—H7A | 0.9500 |
S2—O6 | 1.432 (3) | C8—C9 | 1.385 (6) |
S2—O5 | 1.439 (3) | C8—H8A | 0.9500 |
S2—O4 | 1.500 (2) | C9—C10 | 1.369 (6) |
S2—C22 | 1.764 (4) | C9—H9A | 0.9500 |
N1—C1 | 1.361 (4) | C10—C11 | 1.402 (5) |
N1—C6 | 1.426 (4) | C10—H10A | 0.9500 |
N2—C1 | 1.348 (4) | C13—H13A | 0.9800 |
N2—C2 | 1.447 (5) | C13—H13B | 0.9800 |
N2—C3 | 1.463 (4) | C13—H13C | 0.9800 |
N3—C1 | 1.338 (4) | C14—H14A | 0.9800 |
N3—C5 | 1.450 (5) | C14—H14B | 0.9800 |
N3—C4 | 1.458 (5) | C14—H14C | 0.9800 |
N4—C12 | 1.357 (4) | C15—H15A | 0.9800 |
N4—C17 | 1.427 (4) | C15—H15B | 0.9800 |
N5—C12 | 1.333 (5) | C15—H15C | 0.9800 |
N5—C14 | 1.436 (5) | C16—H16A | 0.9800 |
N5—C13 | 1.447 (5) | C16—H16B | 0.9800 |
N6—C12 | 1.350 (4) | C16—H16C | 0.9800 |
N6—C15 | 1.449 (5) | C17—C18 | 1.389 (5) |
N6—C16 | 1.475 (4) | C17—C22 | 1.407 (5) |
C2—H2A | 0.9800 | C18—C19 | 1.383 (5) |
C2—H2B | 0.9800 | C18—H18A | 0.9500 |
C2—H2C | 0.9800 | C19—C20 | 1.377 (6) |
C3—H3A | 0.9800 | C19—H19A | 0.9500 |
C3—H3B | 0.9800 | C20—C21 | 1.378 (5) |
C3—H3C | 0.9800 | C20—H20A | 0.9500 |
C4—H4A | 0.9800 | C21—C22 | 1.391 (4) |
C4—H4B | 0.9800 | C21—H21A | 0.9500 |
O4—Cu1—O1 | 145.52 (11) | H5B—C5—H5C | 109.5 |
O4—Cu1—N4 | 94.88 (10) | C7—C6—C11 | 118.6 (3) |
O1—Cu1—N4 | 93.10 (11) | C7—C6—N1 | 120.2 (3) |
O4—Cu1—N1 | 92.56 (11) | C11—C6—N1 | 121.1 (3) |
O1—Cu1—N1 | 94.89 (11) | C6—C7—C8 | 120.1 (4) |
N4—Cu1—N1 | 153.75 (11) | C6—C7—H7A | 120.0 |
O2—S1—O3 | 115.99 (17) | C8—C7—H7A | 120.0 |
O2—S1—O1 | 110.59 (15) | C9—C8—C7 | 120.6 (4) |
O3—S1—O1 | 110.46 (15) | C9—C8—H8A | 119.7 |
O2—S1—C11 | 107.89 (16) | C7—C8—H8A | 119.7 |
O3—S1—C11 | 107.88 (16) | C10—C9—C8 | 120.1 (4) |
O1—S1—C11 | 103.18 (15) | C10—C9—H9A | 119.9 |
O6—S2—O5 | 115.89 (17) | C8—C9—H9A | 119.9 |
O6—S2—O4 | 110.14 (15) | C9—C10—C11 | 119.6 (4) |
O5—S2—O4 | 110.87 (15) | C9—C10—H10A | 120.2 |
O6—S2—C22 | 107.76 (15) | C11—C10—H10A | 120.2 |
O5—S2—C22 | 107.88 (15) | C6—C11—C10 | 121.0 (3) |
O4—S2—C22 | 103.47 (15) | C6—C11—S1 | 120.1 (3) |
S1—O1—Cu1 | 118.07 (14) | C10—C11—S1 | 118.9 (3) |
S2—O4—Cu1 | 117.69 (14) | N5—C12—N6 | 119.6 (3) |
C1—N1—C6 | 115.7 (3) | N5—C12—N4 | 119.3 (3) |
C1—N1—Cu1 | 120.8 (2) | N6—C12—N4 | 121.0 (3) |
C6—N1—Cu1 | 123.5 (2) | N5—C13—H13A | 109.5 |
C1—N2—C2 | 121.7 (3) | N5—C13—H13B | 109.5 |
C1—N2—C3 | 123.0 (3) | H13A—C13—H13B | 109.5 |
C2—N2—C3 | 114.0 (3) | N5—C13—H13C | 109.5 |
C1—N3—C5 | 121.0 (3) | H13A—C13—H13C | 109.5 |
C1—N3—C4 | 122.9 (3) | H13B—C13—H13C | 109.5 |
C5—N3—C4 | 114.9 (3) | N5—C14—H14A | 109.5 |
C12—N4—C17 | 115.3 (3) | N5—C14—H14B | 109.5 |
C12—N4—Cu1 | 120.5 (2) | H14A—C14—H14B | 109.5 |
C17—N4—Cu1 | 124.0 (2) | N5—C14—H14C | 109.5 |
C12—N5—C14 | 120.9 (3) | H14A—C14—H14C | 109.5 |
C12—N5—C13 | 122.6 (4) | H14B—C14—H14C | 109.5 |
C14—N5—C13 | 115.5 (3) | N6—C15—H15A | 109.5 |
C12—N6—C15 | 122.2 (3) | N6—C15—H15B | 109.5 |
C12—N6—C16 | 122.0 (3) | H15A—C15—H15B | 109.5 |
C15—N6—C16 | 115.1 (3) | N6—C15—H15C | 109.5 |
N3—C1—N2 | 119.9 (3) | H15A—C15—H15C | 109.5 |
N3—C1—N1 | 119.5 (3) | H15B—C15—H15C | 109.5 |
N2—C1—N1 | 120.5 (3) | N6—C16—H16A | 109.5 |
N2—C2—H2A | 109.5 | N6—C16—H16B | 109.5 |
N2—C2—H2B | 109.5 | H16A—C16—H16B | 109.5 |
H2A—C2—H2B | 109.5 | N6—C16—H16C | 109.5 |
N2—C2—H2C | 109.5 | H16A—C16—H16C | 109.5 |
H2A—C2—H2C | 109.5 | H16B—C16—H16C | 109.5 |
H2B—C2—H2C | 109.5 | C18—C17—C22 | 118.0 (3) |
N2—C3—H3A | 109.5 | C18—C17—N4 | 120.3 (3) |
N2—C3—H3B | 109.5 | C22—C17—N4 | 121.7 (3) |
H3A—C3—H3B | 109.5 | C19—C18—C17 | 121.0 (4) |
N2—C3—H3C | 109.5 | C19—C18—H18A | 119.5 |
H3A—C3—H3C | 109.5 | C17—C18—H18A | 119.5 |
H3B—C3—H3C | 109.5 | C20—C19—C18 | 120.4 (4) |
N3—C4—H4A | 109.5 | C20—C19—H19A | 119.8 |
N3—C4—H4B | 109.5 | C18—C19—H19A | 119.8 |
H4A—C4—H4B | 109.5 | C19—C20—C21 | 120.0 (3) |
N3—C4—H4C | 109.5 | C19—C20—H20A | 120.0 |
H4A—C4—H4C | 109.5 | C21—C20—H20A | 120.0 |
H4B—C4—H4C | 109.5 | C20—C21—C22 | 120.0 (3) |
N3—C5—H5A | 109.5 | C20—C21—H21A | 120.0 |
N3—C5—H5B | 109.5 | C22—C21—H21A | 120.0 |
H5A—C5—H5B | 109.5 | C21—C22—C17 | 120.6 (3) |
N3—C5—H5C | 109.5 | C21—C22—S2 | 119.5 (3) |
H5A—C5—H5C | 109.5 | C17—C22—S2 | 119.9 (2) |
O2—S1—O1—Cu1 | 179.11 (16) | C7—C6—C11—C10 | −0.5 (6) |
O3—S1—O1—Cu1 | 49.3 (2) | N1—C6—C11—C10 | 175.5 (3) |
C11—S1—O1—Cu1 | −65.74 (18) | C7—C6—C11—S1 | −179.6 (3) |
O4—Cu1—O1—S1 | −68.1 (3) | N1—C6—C11—S1 | −3.5 (5) |
N4—Cu1—O1—S1 | −171.33 (17) | C9—C10—C11—C6 | −0.1 (6) |
N1—Cu1—O1—S1 | 33.69 (18) | C9—C10—C11—S1 | 179.0 (3) |
O6—S2—O4—Cu1 | 178.28 (16) | O2—S1—C11—C6 | 171.3 (3) |
O5—S2—O4—Cu1 | 48.7 (2) | O3—S1—C11—C6 | −62.6 (3) |
C22—S2—O4—Cu1 | −66.76 (18) | O1—S1—C11—C6 | 54.3 (3) |
O1—Cu1—O4—S2 | −66.2 (2) | O2—S1—C11—C10 | −7.7 (4) |
N4—Cu1—O4—S2 | 36.56 (18) | O3—S1—C11—C10 | 118.3 (3) |
N1—Cu1—O4—S2 | −168.63 (17) | O1—S1—C11—C10 | −124.8 (3) |
O4—Cu1—N1—C1 | −10.2 (3) | C14—N5—C12—N6 | 158.1 (3) |
O1—Cu1—N1—C1 | −156.5 (3) | C13—N5—C12—N6 | −33.5 (5) |
N4—Cu1—N1—C1 | 96.2 (4) | C14—N5—C12—N4 | −25.5 (5) |
O4—Cu1—N1—C6 | 167.3 (3) | C13—N5—C12—N4 | 142.9 (4) |
O1—Cu1—N1—C6 | 21.0 (3) | C15—N6—C12—N5 | 155.9 (3) |
N4—Cu1—N1—C6 | −86.3 (4) | C16—N6—C12—N5 | −33.5 (5) |
O4—Cu1—N4—C12 | −156.2 (3) | C15—N6—C12—N4 | −20.5 (5) |
O1—Cu1—N4—C12 | −9.8 (3) | C16—N6—C12—N4 | 150.2 (4) |
N1—Cu1—N4—C12 | 97.8 (3) | C17—N4—C12—N5 | 133.9 (3) |
O4—Cu1—N4—C17 | 17.6 (3) | Cu1—N4—C12—N5 | −51.8 (4) |
O1—Cu1—N4—C17 | 164.0 (3) | C17—N4—C12—N6 | −49.8 (4) |
N1—Cu1—N4—C17 | −88.3 (4) | Cu1—N4—C12—N6 | 124.6 (3) |
C5—N3—C1—N2 | 158.8 (3) | C12—N4—C17—C18 | −41.9 (4) |
C4—N3—C1—N2 | −34.6 (5) | Cu1—N4—C17—C18 | 144.0 (3) |
C5—N3—C1—N1 | −23.0 (5) | C12—N4—C17—C22 | 140.0 (3) |
C4—N3—C1—N1 | 143.6 (3) | Cu1—N4—C17—C22 | −34.1 (4) |
C2—N2—C1—N3 | 159.1 (3) | C22—C17—C18—C19 | −0.1 (5) |
C3—N2—C1—N3 | −34.5 (5) | N4—C17—C18—C19 | −178.2 (3) |
C2—N2—C1—N1 | −19.1 (5) | C17—C18—C19—C20 | −1.4 (6) |
C3—N2—C1—N1 | 147.3 (4) | C18—C19—C20—C21 | 2.0 (6) |
C6—N1—C1—N3 | 131.5 (3) | C19—C20—C21—C22 | −1.0 (6) |
Cu1—N1—C1—N3 | −50.8 (4) | C20—C21—C22—C17 | −0.5 (5) |
C6—N1—C1—N2 | −50.3 (4) | C20—C21—C22—S2 | −179.7 (3) |
Cu1—N1—C1—N2 | 127.4 (3) | C18—C17—C22—C21 | 1.0 (5) |
C1—N1—C6—C7 | −41.8 (5) | N4—C17—C22—C21 | 179.1 (3) |
Cu1—N1—C6—C7 | 140.6 (3) | C18—C17—C22—S2 | −179.8 (3) |
C1—N1—C6—C11 | 142.3 (3) | N4—C17—C22—S2 | −1.7 (5) |
Cu1—N1—C6—C11 | −35.4 (4) | O6—S2—C22—C21 | −12.1 (3) |
C11—C6—C7—C8 | 0.9 (6) | O5—S2—C22—C21 | 113.7 (3) |
N1—C6—C7—C8 | −175.1 (4) | O4—S2—C22—C21 | −128.8 (3) |
C6—C7—C8—C9 | −0.7 (6) | O6—S2—C22—C17 | 168.7 (3) |
C7—C8—C9—C10 | 0.1 (7) | O5—S2—C22—C17 | −65.5 (3) |
C8—C9—C10—C11 | 0.3 (6) | O4—S2—C22—C17 | 52.1 (3) |
Experimental details
Crystal data | |
Chemical formula | [Cu(C11H16N3O3S)2] |
Mr | 604.20 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 120 |
a, b, c (Å) | 19.940 (3), 12.2947 (14), 10.9508 (14) |
V (Å3) | 2684.7 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.02 |
Crystal size (mm) | 0.29 × 0.23 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.757, 0.822 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22901, 6315, 4939 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.093, 1.02 |
No. of reflections | 6315 |
No. of parameters | 342 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.63, −0.29 |
Absolute structure | Flack (1983), 2953 Friedel pairs |
Absolute structure parameter | 0.021 (12) |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008) and local programs.
Acknowledgements
We thank the German Research Council (DFG) and the Federal Ministry of Education and Research (BMBF) for continuous support of our work.
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