Bis(2-{[bis­(dimethyl­amino)­methyl­idene]amino-κN}benzene­sulfonato-κN)copper(II)

Neuba, A.; Flörke, U.; Henkel, G.

doi:10.1107/S1600536812046387

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page m1482

doi:10.1107/S1600536812046387

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Bis(2-{[bis(dimethylamino)methylidene]amino-κN}benzenesulfonato-κN)copper(II)

Adam Neuba,^a Ulrich Flörke ^a ^* and Gerald Henkel ^a

^aUniversität Paderborn, Fakultät für Naturwissenschaften, Department Chemie, Warburger Strasse 100, 33098 Paderborn, Germany
^*Correspondence e-mail: ulrich.floerke@upb.de

(Received 31 October 2012; accepted 9 November 2012; online 14 November 2012)

The molecular structure of the title compound, [Cu(C₁₁H₁₆N₃O₃S)₂], shows the Cu^II 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 Cu^II 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 Cu^II 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

[Cu(C₁₁H₁₆N₃O₃S)₂]
M_r = 604.20
Orthorhombic, P n a 2₁
a = 19.940 (3) Å
b = 12.2947 (14) Å
c = 10.9508 (14) Å
V = 2684.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 120 K
0.29 × 0.23 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.757, T_max = 0.822
22901 measured reflections
6315 independent reflections
4939 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.093
S = 1.02
6315 reflections
342 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ), 2953 Friedel pairs
Flack parameter: 0.021 (12)

Data collection: SMART (Bruker, 2002 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812046387/aa2076sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046387/aa2076Isup2.hkl

checkCIF report

Related literature top

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 Cu center in cytochrome c oxidase and N₂O reductase, see: Neuba et al. (2011, 2012). For related structures with Cu(N₂O₂) core, see: Robinson et al. (2004).

Experimental top

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.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: 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.

Figures top

Fig. 1. Molecular structure of the title compound. Anistropic displacement parameters are shown at the 50% probability level.

Bis(2-{[bis(dimethylamino)methylidene]amino-κN}benzenesulfonato-κN)copper(II) top

Crystal data top

[Cu(C₁₁H₁₆N₃O₃S)₂]	F(000) = 1260
M_r = 604.20	D_x = 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

Data collection top

Bruker SMART APEX diffractometer	6315 independent reflections
Radiation source: sealed tube	4939 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ϕ and ω scans	θ_max = 27.9°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −26→25
T_min = 0.757, T_max = 0.822	k = −16→14
22901 measured reflections	l = −14→14

Refinement top

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(F_o²) + (0.0383P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
6315 reflections	Δρ_max = 0.63 e Å⁻³
342 parameters	Δρ_min = −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)

Crystal data top

[Cu(C₁₁H₁₆N₃O₃S)₂]	V = 2684.7 (6) Å³
M_r = 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

Data collection top

Bruker SMART APEX diffractometer	6315 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	4939 reflections with I > 2σ(I)
T_min = 0.757, T_max = 0.822	R_int = 0.063
22901 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.093	Δρ_max = 0.63 e Å⁻³
S = 1.02	Δρ_min = −0.29 e Å⁻³
6315 reflections	Absolute structure: Flack (1983), 2953 Friedel pairs
342 parameters	Absolute structure parameter: 0.021 (12)
1 restraint

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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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]
M_r	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)
T_min, T_max	0.757, 0.822
No. of measured, independent and observed [I > 2σ(I)] reflections	22901, 6315, 4939
R_int	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
Δρ_max, Δρ_min (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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