Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033405/bt2431sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033405/bt2431Isup2.hkl |
CCDC reference: 657748
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- R factor = 0.035
- wR factor = 0.088
- Data-to-parameter ratio = 15.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT034_ALERT_1_C No Flack Parameter Given. Z .GT. Si, NonCentro . ?
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.87 From the CIF: _reflns_number_total 4209 Count of symmetry unique reflns 2655 Completeness (_total/calc) 158.53% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1554 Fraction of Friedel pairs measured 0.585 Are heavy atom types Z>Si present yes PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Allen et al. (1987); Gomes de Mesquita (1967); Harmjanz (1997); Herres et al. (2005); Kaitner & Pavlovic (1997); Lee & Bryant (1970); Neuba et al. (2007); Pohl et al. (2000); Schneider (2000); Waden (1999); Wittmann et al. (2001).
A solution of dimethylethylenechloroformamidinium chloride (5.07 g, 30 mmol) in dry MeCN was added dropwise to an ice-cooled solution of 2,2'-dithiodianiline (3.73 g, 15 mmol) and triethylamine (4.18 ml, 3.03 g, 30 mmol) in dry MeCN. After 3 h under reflux, a solution of NaOH (1.2 g, 30 mmol) in water was added. The solvents and NEt3 were then evaporated under vacuum. In order to deprotonate the bis-hydrochloride, 50 wt% KOH (aqueous, 15 ml) was added and the free base was extracted into the THF phase (3 x 80 ml). The organic phase was dried with Na2SO4. After filtration, the solvent was evaporated under reduced pressure. Colourless crystals suitable for X-ray diffraction were obtained by diffusion of Et2O into a cold saturated MeCN solution.
1H NMR (500 MHz, CDCl3): δ 2.65 (s, 12H, Me), 3.3 (s, 8H, CH2), 6.79 (m, 4H, CHarom), 6.95 (m, 2H, CHarom), 7.45 (m, 2H, CHarom); 13C NMR (125 MHz, CDCl3): δ 43.8 (Me), 48.4 (CH2), 121.1 (CHarom), 122.0 (CHarom), 125.2 (CHarom), 125.8 (CHarom), 128.9 (Cquart), 147.2 (Cquart), 155.5 (Cgua); IR (KBr, \v, cm-1): 3035 (w), 2946 (m), 2858 (m), 1636 (versus, C═ N), 1613 (versus, C═N), 1568 (versus), 1441 (s), 1283 (s), 1034 (s), 966 (m), 740 (m). EI—MS: m/z (%) 440 (40) [M+], 344 (70), 248 (85), 220 (90), 165 (80), 124 (90), 80 (75), 44 (80), 28 (30); Elemental analysis (M = 440.63 g mol-1): calcd. for C22H28N6S2: C: 59.97; H: 6.41; N: 19.07; found C: 60.05, H: 6.62, N: 19.00.
Hydrogen atoms located from difference Fourier maps were refined at idealized positions riding on the carbon atoms with isotropic displacement parameters Uiso(H) = 1.2U(Ceq) or 1.5U(CH3). All CH3 hydrogen atoms were allowed to rotate but not to tip. The crystal was refined as an inversion twin with the ratio of the two domains of 0.34 (6)/0.66 (6).
The synthesis and characterization of molecules containing nitrogen and sulfur as donor functions is important for biomimetic coordination chemistry. The use of this molecules as ligands in the synthesis of copper-complexes as mimics for active centres like the CuA in cytochrome-c-oxidase and N2O-reductase is currently of considerable interest in bioinorganic chemistry. In search of multifunctional ligands we have extended our studies to guanidyl-type systems with N-donor functions. The first derivative, the ligand bis(tetramethyl-guanidino)propylene and its complexes with Cu, Fe, Ni and Mn have recently been investigated (Harmjanz, 1997; Waden, 1999; Pohl et al., 2000; Schneider, 2000; Wittmann et al., 2001; Herres et al., 2005, Neuba et al., 2007). We have now developed the title compound with disulfide group as novel ligand with redoxactivity for use in biomimetic copper-sulfur chemistry.
The most interesting feature are the torsion angles τ C–S1–S2–C' and C–C'–S1–S2 which indicate pπ-dπ interactions between the fully occupied pz orbital on the carbon C atom (part of the aromatic π system) with an empty d orbital on the S atom as reported for 2,2'-diaminodiphenyl disulfide (Lee & Bryant, 1970). The S–S bond length in disulfide compounds is correlated with the C–S–S–C torsion angles, being around 2.031 Å (τ = 75–105°) or 2.070 Å (t = 0–20°) (Allen et al., 1987). For (I) τ is 84.65 (10)° and the S1–S2 bond length 2.0435 (7) Å matching these ranges. As may be seen from the geometric bonding parameters (Table 1), the guanidyl double bonds C1═ N1 and C18═N14 are clearly localized.
The packing pattern shows intermolecular C–H···N hydrogen interactions (Table 2) with molecules stacked in [010] direction.
For related literature, see: Allen et al. (1987); Gomes de Mesquita (1967); Harmjanz (1997); Herres et al. (2005); Kaitner & Pavlovic (1997); Lee & Bryant (1970); Neuba et al. (2007); Pohl et al. (2000); Schneider (2000); Waden (1999); Wittmann et al. (2001).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C22H28N6S2 | F(000) = 468 |
Mr = 440.62 | Dx = 1.317 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yc | Cell parameters from 913 reflections |
a = 8.2794 (12) Å | θ = 2.5–28.2° |
b = 10.1065 (14) Å | µ = 0.26 mm−1 |
c = 13.7018 (19) Å | T = 120 K |
β = 104.333 (3)° | Prism, colourless |
V = 1110.8 (3) Å3 | 0.42 × 0.39 × 0.36 mm |
Z = 2 |
Bruker SMART APEX diffractometer | 4209 independent reflections |
Radiation source: sealed tube | 4074 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
φ and ω scans | θmax = 27.9°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −10→9 |
Tmin = 0.898, Tmax = 0.912 | k = −13→13 |
8801 measured reflections | l = −15→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.051P)2 + 0.0758P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
4209 reflections | Δρmax = 0.35 e Å−3 |
276 parameters | Δρmin = −0.23 e Å−3 |
2 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.34 (6) |
C22H28N6S2 | V = 1110.8 (3) Å3 |
Mr = 440.62 | Z = 2 |
Monoclinic, Pc | Mo Kα radiation |
a = 8.2794 (12) Å | µ = 0.26 mm−1 |
b = 10.1065 (14) Å | T = 120 K |
c = 13.7018 (19) Å | 0.42 × 0.39 × 0.36 mm |
β = 104.333 (3)° |
Bruker SMART APEX diffractometer | 4209 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 4074 reflections with I > 2σ(I) |
Tmin = 0.898, Tmax = 0.912 | Rint = 0.033 |
8801 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.088 | Δρmax = 0.35 e Å−3 |
S = 1.06 | Δρmin = −0.23 e Å−3 |
4209 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
276 parameters | Absolute structure parameter: 0.34 (6) |
2 restraints |
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 | ||
S1 | 0.55549 (6) | 0.30126 (4) | 0.67932 (4) | 0.02459 (12) | |
S2 | 0.65522 (6) | 0.12261 (4) | 0.73258 (4) | 0.02580 (12) | |
N1 | 0.4194 (2) | 0.50987 (16) | 0.54669 (13) | 0.0256 (4) | |
N2 | 0.3726 (2) | 0.72951 (16) | 0.57965 (14) | 0.0254 (4) | |
N3 | 0.5600 (2) | 0.69499 (14) | 0.49018 (14) | 0.0263 (4) | |
N4 | 0.8884 (2) | −0.09539 (16) | 0.77503 (14) | 0.0272 (4) | |
N5 | 1.0402 (2) | −0.1713 (2) | 0.94000 (15) | 0.0329 (4) | |
N6 | 0.9051 (2) | −0.31590 (17) | 0.82600 (16) | 0.0338 (5) | |
C1 | 0.4521 (2) | 0.63399 (19) | 0.53619 (15) | 0.0232 (4) | |
C2 | 0.2088 (3) | 0.7044 (2) | 0.5944 (2) | 0.0382 (6) | |
H2A | 0.2052 | 0.6150 | 0.6215 | 0.057* | |
H2B | 0.1258 | 0.7120 | 0.5298 | 0.057* | |
H2C | 0.1842 | 0.7692 | 0.6420 | 0.057* | |
C3 | 0.4088 (3) | 0.86078 (19) | 0.54545 (18) | 0.0309 (5) | |
H3A | 0.4261 | 0.9263 | 0.6008 | 0.037* | |
H3B | 0.3179 | 0.8918 | 0.4886 | 0.037* | |
C4 | 0.5678 (3) | 0.8371 (2) | 0.51246 (18) | 0.0310 (5) | |
H4A | 0.5699 | 0.8899 | 0.4519 | 0.037* | |
H4B | 0.6673 | 0.8591 | 0.5669 | 0.037* | |
C5 | 0.7065 (3) | 0.6331 (2) | 0.46938 (19) | 0.0320 (5) | |
H5A | 0.6830 | 0.6092 | 0.3979 | 0.048* | |
H5B | 0.7348 | 0.5533 | 0.5106 | 0.048* | |
H5C | 0.8003 | 0.6952 | 0.4855 | 0.048* | |
C6 | 0.4730 (2) | 0.40803 (19) | 0.49286 (16) | 0.0243 (4) | |
C7 | 0.4507 (3) | 0.4075 (2) | 0.38863 (18) | 0.0312 (5) | |
H7A | 0.4041 | 0.4829 | 0.3506 | 0.037* | |
C8 | 0.4953 (3) | 0.2983 (2) | 0.33941 (18) | 0.0343 (5) | |
H8A | 0.4807 | 0.3001 | 0.2684 | 0.041* | |
C9 | 0.5613 (3) | 0.1865 (2) | 0.39408 (19) | 0.0330 (5) | |
H9A | 0.5916 | 0.1117 | 0.3606 | 0.040* | |
C10 | 0.5827 (3) | 0.18485 (18) | 0.49752 (18) | 0.0282 (4) | |
H10A | 0.6288 | 0.1088 | 0.5350 | 0.034* | |
C11 | 0.5374 (2) | 0.29307 (17) | 0.54681 (16) | 0.0224 (4) | |
C12 | 0.8746 (3) | 0.14206 (19) | 0.75131 (15) | 0.0246 (4) | |
C13 | 0.9518 (3) | 0.2624 (2) | 0.74463 (18) | 0.0313 (5) | |
H13A | 0.8864 | 0.3404 | 0.7290 | 0.038* | |
C14 | 1.1245 (3) | 0.2698 (2) | 0.76067 (19) | 0.0378 (5) | |
H14A | 1.1769 | 0.3522 | 0.7556 | 0.045* | |
C15 | 1.2188 (3) | 0.1562 (3) | 0.78401 (19) | 0.0370 (5) | |
H15A | 1.3365 | 0.1608 | 0.7949 | 0.044* | |
C16 | 1.1434 (3) | 0.0360 (2) | 0.79161 (17) | 0.0317 (5) | |
H16A | 1.2101 | −0.0412 | 0.8077 | 0.038* | |
C17 | 0.9701 (3) | 0.02614 (19) | 0.77599 (15) | 0.0249 (4) | |
C18 | 0.9436 (3) | −0.1845 (2) | 0.84325 (17) | 0.0268 (4) | |
C19 | 1.0216 (4) | −0.0560 (3) | 1.0000 (2) | 0.0419 (6) | |
H19A | 0.9221 | −0.0665 | 1.0259 | 0.063* | |
H19B | 1.0099 | 0.0236 | 0.9580 | 0.063* | |
H19C | 1.1201 | −0.0473 | 1.0566 | 0.063* | |
C20 | 1.0484 (3) | −0.2999 (2) | 0.9920 (2) | 0.0411 (6) | |
H20A | 0.9661 | −0.3045 | 1.0335 | 0.049* | |
H20B | 1.1613 | −0.3165 | 1.0354 | 0.049* | |
C21 | 1.0063 (3) | −0.3963 (2) | 0.9055 (2) | 0.0383 (6) | |
H21A | 1.1080 | −0.4284 | 0.8873 | 0.046* | |
H21B | 0.9428 | −0.4729 | 0.9214 | 0.046* | |
C22 | 0.8467 (4) | −0.3676 (2) | 0.7259 (2) | 0.0429 (6) | |
H22A | 0.9403 | −0.4068 | 0.7041 | 0.064* | |
H22B | 0.7980 | −0.2959 | 0.6798 | 0.064* | |
H22C | 0.7620 | −0.4355 | 0.7253 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0266 (3) | 0.0221 (2) | 0.0259 (2) | 0.00218 (18) | 0.00804 (19) | 0.00260 (18) |
S2 | 0.0213 (2) | 0.0223 (2) | 0.0330 (3) | −0.00125 (17) | 0.00521 (19) | 0.00647 (19) |
N1 | 0.0261 (9) | 0.0233 (7) | 0.0274 (9) | 0.0044 (6) | 0.0064 (7) | 0.0029 (6) |
N2 | 0.0258 (9) | 0.0230 (7) | 0.0263 (9) | 0.0023 (6) | 0.0047 (7) | −0.0028 (6) |
N3 | 0.0282 (10) | 0.0219 (7) | 0.0296 (10) | 0.0016 (6) | 0.0088 (7) | 0.0014 (6) |
N4 | 0.0230 (9) | 0.0245 (7) | 0.0306 (9) | 0.0001 (6) | −0.0001 (7) | 0.0027 (7) |
N5 | 0.0265 (10) | 0.0428 (10) | 0.0273 (10) | −0.0012 (8) | 0.0025 (8) | 0.0063 (8) |
N6 | 0.0294 (10) | 0.0259 (8) | 0.0419 (12) | 0.0045 (7) | 0.0008 (9) | 0.0063 (7) |
C1 | 0.0196 (10) | 0.0277 (9) | 0.0197 (10) | 0.0042 (7) | 0.0000 (8) | 0.0017 (7) |
C2 | 0.0278 (12) | 0.0357 (11) | 0.0533 (17) | 0.0040 (9) | 0.0143 (11) | −0.0082 (10) |
C3 | 0.0346 (12) | 0.0245 (9) | 0.0316 (12) | 0.0037 (8) | 0.0045 (9) | 0.0000 (8) |
C4 | 0.0332 (12) | 0.0229 (9) | 0.0346 (12) | −0.0009 (8) | 0.0043 (9) | −0.0012 (8) |
C5 | 0.0273 (11) | 0.0335 (11) | 0.0375 (12) | 0.0011 (8) | 0.0121 (9) | 0.0009 (8) |
C6 | 0.0199 (10) | 0.0250 (8) | 0.0275 (11) | 0.0011 (7) | 0.0049 (8) | 0.0009 (7) |
C7 | 0.0262 (11) | 0.0344 (10) | 0.0296 (11) | 0.0053 (8) | 0.0006 (9) | 0.0037 (9) |
C8 | 0.0327 (13) | 0.0448 (12) | 0.0244 (11) | −0.0012 (9) | 0.0054 (9) | −0.0046 (9) |
C9 | 0.0332 (13) | 0.0322 (10) | 0.0352 (13) | −0.0012 (8) | 0.0117 (10) | −0.0105 (9) |
C10 | 0.0259 (11) | 0.0225 (8) | 0.0365 (12) | 0.0008 (7) | 0.0085 (9) | −0.0012 (8) |
C11 | 0.0172 (9) | 0.0244 (8) | 0.0255 (10) | −0.0021 (7) | 0.0048 (7) | −0.0001 (7) |
C12 | 0.0214 (10) | 0.0276 (9) | 0.0235 (10) | −0.0028 (7) | 0.0029 (8) | 0.0006 (7) |
C13 | 0.0316 (12) | 0.0257 (9) | 0.0352 (12) | −0.0040 (8) | 0.0055 (9) | 0.0040 (8) |
C14 | 0.0332 (13) | 0.0407 (11) | 0.0368 (13) | −0.0137 (9) | 0.0038 (10) | 0.0074 (9) |
C15 | 0.0224 (11) | 0.0543 (13) | 0.0326 (12) | −0.0061 (10) | 0.0036 (9) | 0.0097 (10) |
C16 | 0.0234 (11) | 0.0409 (11) | 0.0292 (11) | 0.0032 (8) | 0.0039 (8) | 0.0061 (9) |
C17 | 0.0250 (10) | 0.0285 (9) | 0.0198 (9) | −0.0021 (7) | 0.0032 (7) | 0.0014 (7) |
C18 | 0.0182 (10) | 0.0292 (9) | 0.0311 (11) | 0.0012 (7) | 0.0025 (8) | 0.0017 (7) |
C19 | 0.0423 (14) | 0.0529 (13) | 0.0310 (13) | −0.0202 (11) | 0.0100 (10) | −0.0038 (10) |
C20 | 0.0300 (13) | 0.0553 (14) | 0.0368 (14) | 0.0031 (10) | 0.0060 (10) | 0.0198 (11) |
C21 | 0.0261 (12) | 0.0350 (11) | 0.0524 (16) | 0.0036 (8) | 0.0071 (10) | 0.0190 (10) |
C22 | 0.0491 (16) | 0.0256 (10) | 0.0465 (15) | −0.0001 (9) | −0.0020 (12) | −0.0008 (9) |
S1—C11 | 1.786 (2) | C6—C11 | 1.409 (3) |
S1—S2 | 2.0435 (7) | C7—C8 | 1.390 (3) |
S2—C12 | 1.781 (2) | C7—H7A | 0.9500 |
N1—C1 | 1.299 (3) | C8—C9 | 1.391 (3) |
N1—C6 | 1.401 (3) | C8—H8A | 0.9500 |
N2—C1 | 1.383 (3) | C9—C10 | 1.384 (3) |
N2—C2 | 1.442 (3) | C9—H9A | 0.9500 |
N2—C3 | 1.463 (3) | C10—C11 | 1.385 (3) |
N3—C1 | 1.362 (3) | C10—H10A | 0.9500 |
N3—C5 | 1.454 (3) | C12—C13 | 1.388 (3) |
N3—C4 | 1.466 (2) | C12—C17 | 1.407 (3) |
N4—C18 | 1.297 (3) | C13—C14 | 1.394 (3) |
N4—C17 | 1.401 (3) | C13—H13A | 0.9500 |
N5—C18 | 1.375 (3) | C14—C15 | 1.380 (4) |
N5—C19 | 1.457 (3) | C14—H14A | 0.9500 |
N5—C20 | 1.475 (3) | C15—C16 | 1.382 (3) |
N6—C18 | 1.373 (3) | C15—H15A | 0.9500 |
N6—C22 | 1.435 (3) | C16—C17 | 1.401 (3) |
N6—C21 | 1.448 (3) | C16—H16A | 0.9500 |
C2—H2A | 0.9800 | C19—H19A | 0.9800 |
C2—H2B | 0.9800 | C19—H19B | 0.9800 |
C2—H2C | 0.9800 | C19—H19C | 0.9800 |
C3—C4 | 1.513 (3) | C20—C21 | 1.507 (4) |
C3—H3A | 0.9900 | C20—H20A | 0.9900 |
C3—H3B | 0.9900 | C20—H20B | 0.9900 |
C4—H4A | 0.9900 | C21—H21A | 0.9900 |
C4—H4B | 0.9900 | C21—H21B | 0.9900 |
C5—H5A | 0.9800 | C22—H22A | 0.9800 |
C5—H5B | 0.9800 | C22—H22B | 0.9800 |
C5—H5C | 0.9800 | C22—H22C | 0.9800 |
C6—C7 | 1.394 (3) | ||
C11—S1—S2 | 104.29 (6) | C10—C9—H9A | 120.2 |
C12—S2—S1 | 105.15 (7) | C8—C9—H9A | 120.2 |
C1—N1—C6 | 123.32 (19) | C9—C10—C11 | 120.54 (19) |
C1—N2—C2 | 120.12 (17) | C9—C10—H10A | 119.7 |
C1—N2—C3 | 109.76 (19) | C11—C10—H10A | 119.7 |
C2—N2—C3 | 118.61 (18) | C10—C11—C6 | 120.6 (2) |
C1—N3—C5 | 124.81 (16) | C10—C11—S1 | 124.58 (16) |
C1—N3—C4 | 110.31 (18) | C6—C11—S1 | 114.86 (15) |
C5—N3—C4 | 117.79 (18) | C13—C12—C17 | 120.3 (2) |
C18—N4—C17 | 121.27 (18) | C13—C12—S2 | 123.86 (17) |
C18—N5—C19 | 120.3 (2) | C17—C12—S2 | 115.80 (15) |
C18—N5—C20 | 109.09 (19) | C12—C13—C14 | 120.5 (2) |
C19—N5—C20 | 115.5 (2) | C12—C13—H13A | 119.8 |
C18—N6—C22 | 121.73 (19) | C14—C13—H13A | 119.8 |
C18—N6—C21 | 110.3 (2) | C15—C14—C13 | 119.5 (2) |
C22—N6—C21 | 120.65 (19) | C15—C14—H14A | 120.3 |
N1—C1—N3 | 131.85 (19) | C13—C14—H14A | 120.3 |
N1—C1—N2 | 119.5 (2) | C14—C15—C16 | 120.6 (2) |
N3—C1—N2 | 108.66 (17) | C14—C15—H15A | 119.7 |
N2—C2—H2A | 109.5 | C16—C15—H15A | 119.7 |
N2—C2—H2B | 109.5 | C15—C16—C17 | 121.0 (2) |
H2A—C2—H2B | 109.5 | C15—C16—H16A | 119.5 |
N2—C2—H2C | 109.5 | C17—C16—H16A | 119.5 |
H2A—C2—H2C | 109.5 | N4—C17—C16 | 122.52 (19) |
H2B—C2—H2C | 109.5 | N4—C17—C12 | 119.12 (19) |
N2—C3—C4 | 102.41 (16) | C16—C17—C12 | 118.11 (18) |
N2—C3—H3A | 111.3 | N4—C18—N6 | 121.5 (2) |
C4—C3—H3A | 111.3 | N4—C18—N5 | 130.2 (2) |
N2—C3—H3B | 111.3 | N6—C18—N5 | 108.33 (18) |
C4—C3—H3B | 111.3 | N5—C19—H19A | 109.5 |
H3A—C3—H3B | 109.2 | N5—C19—H19B | 109.5 |
N3—C4—C3 | 102.73 (17) | H19A—C19—H19B | 109.5 |
N3—C4—H4A | 111.2 | N5—C19—H19C | 109.5 |
C3—C4—H4A | 111.2 | H19A—C19—H19C | 109.5 |
N3—C4—H4B | 111.2 | H19B—C19—H19C | 109.5 |
C3—C4—H4B | 111.2 | N5—C20—C21 | 102.4 (2) |
H4A—C4—H4B | 109.1 | N5—C20—H20A | 111.3 |
N3—C5—H5A | 109.5 | C21—C20—H20A | 111.3 |
N3—C5—H5B | 109.5 | N5—C20—H20B | 111.3 |
H5A—C5—H5B | 109.5 | C21—C20—H20B | 111.3 |
N3—C5—H5C | 109.5 | H20A—C20—H20B | 109.2 |
H5A—C5—H5C | 109.5 | N6—C21—C20 | 101.97 (19) |
H5B—C5—H5C | 109.5 | N6—C21—H21A | 111.4 |
C7—C6—N1 | 124.29 (18) | C20—C21—H21A | 111.4 |
C7—C6—C11 | 118.10 (18) | N6—C21—H21B | 111.4 |
N1—C6—C11 | 117.25 (19) | C20—C21—H21B | 111.4 |
C8—C7—C6 | 121.1 (2) | H21A—C21—H21B | 109.2 |
C8—C7—H7A | 119.4 | N6—C22—H22A | 109.5 |
C6—C7—H7A | 119.4 | N6—C22—H22B | 109.5 |
C7—C8—C9 | 120.0 (2) | H22A—C22—H22B | 109.5 |
C7—C8—H8A | 120.0 | N6—C22—H22C | 109.5 |
C9—C8—H8A | 120.0 | H22A—C22—H22C | 109.5 |
C10—C9—C8 | 119.7 (2) | H22B—C22—H22C | 109.5 |
C11—S1—S2—C12 | 84.65 (10) | S1—S2—C12—C13 | 9.0 (2) |
C6—N1—C1—N3 | −12.6 (3) | S1—S2—C12—C17 | −172.24 (15) |
C6—N1—C1—N2 | 169.64 (18) | C17—C12—C13—C14 | 1.0 (4) |
C5—N3—C1—N1 | −21.9 (4) | S2—C12—C13—C14 | 179.77 (19) |
C4—N3—C1—N1 | −171.5 (2) | C12—C13—C14—C15 | −0.4 (4) |
C5—N3—C1—N2 | 156.0 (2) | C13—C14—C15—C16 | 0.0 (4) |
C4—N3—C1—N2 | 6.4 (2) | C14—C15—C16—C17 | −0.1 (4) |
C2—N2—C1—N1 | −28.6 (3) | C18—N4—C17—C16 | 45.6 (3) |
C3—N2—C1—N1 | −171.40 (18) | C18—N4—C17—C12 | −140.4 (2) |
C2—N2—C1—N3 | 153.2 (2) | C15—C16—C17—N4 | 174.7 (2) |
C3—N2—C1—N3 | 10.4 (2) | C15—C16—C17—C12 | 0.6 (3) |
C1—N2—C3—C4 | −21.8 (2) | C13—C12—C17—N4 | −175.4 (2) |
C2—N2—C3—C4 | −165.25 (19) | S2—C12—C17—N4 | 5.8 (3) |
C1—N3—C4—C3 | −19.5 (2) | C13—C12—C17—C16 | −1.1 (3) |
C5—N3—C4—C3 | −171.50 (19) | S2—C12—C17—C16 | −179.95 (17) |
N2—C3—C4—N3 | 23.9 (2) | C17—N4—C18—N6 | −156.8 (2) |
C1—N1—C6—C7 | −50.4 (3) | C17—N4—C18—N5 | 24.8 (4) |
C1—N1—C6—C11 | 136.7 (2) | C22—N6—C18—N4 | 19.0 (4) |
N1—C6—C7—C8 | −174.8 (2) | C21—N6—C18—N4 | 169.2 (2) |
C11—C6—C7—C8 | −2.0 (3) | C22—N6—C18—N5 | −162.3 (2) |
C6—C7—C8—C9 | 0.9 (4) | C21—N6—C18—N5 | −12.1 (3) |
C7—C8—C9—C10 | −0.2 (4) | C19—N5—C18—N4 | 34.9 (4) |
C8—C9—C10—C11 | 0.6 (3) | C20—N5—C18—N4 | 171.7 (2) |
C9—C10—C11—C6 | −1.7 (3) | C19—N5—C18—N6 | −143.7 (2) |
C9—C10—C11—S1 | 178.80 (17) | C20—N5—C18—N6 | −6.8 (3) |
C7—C6—C11—C10 | 2.3 (3) | C18—N5—C20—C21 | 21.7 (3) |
N1—C6—C11—C10 | 175.74 (19) | C19—N5—C20—C21 | 160.8 (2) |
C7—C6—C11—S1 | −178.12 (16) | C18—N6—C21—C20 | 25.1 (3) |
N1—C6—C11—S1 | −4.7 (2) | C22—N6—C21—C20 | 175.6 (2) |
S2—S1—C11—C10 | 0.55 (19) | N5—C20—C21—N6 | −27.1 (2) |
S2—S1—C11—C6 | −178.97 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···N2i | 0.95 | 2.54 | 3.463 (3) | 165 |
Symmetry code: (i) x, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C22H28N6S2 |
Mr | 440.62 |
Crystal system, space group | Monoclinic, Pc |
Temperature (K) | 120 |
a, b, c (Å) | 8.2794 (12), 10.1065 (14), 13.7018 (19) |
β (°) | 104.333 (3) |
V (Å3) | 1110.8 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.42 × 0.39 × 0.36 |
Data collection | |
Diffractometer | Bruker SMART APEX |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.898, 0.912 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8801, 4209, 4074 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.088, 1.06 |
No. of reflections | 4209 |
No. of parameters | 276 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.23 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | 0.34 (6) |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXTL (Bruker, 2002), SHELXTL.
S1—C11 | 1.786 (2) | N3—C1 | 1.362 (3) |
S1—S2 | 2.0435 (7) | N4—C18 | 1.297 (3) |
S2—C12 | 1.781 (2) | N4—C17 | 1.401 (3) |
N1—C1 | 1.299 (3) | N5—C18 | 1.375 (3) |
N1—C6 | 1.401 (3) | N6—C18 | 1.373 (3) |
N2—C1 | 1.383 (3) | ||
C11—S1—S2 | 104.29 (6) | C1—N1—C6 | 123.32 (19) |
C12—S2—S1 | 105.15 (7) | C18—N4—C17 | 121.27 (18) |
C11—S1—S2—C12 | 84.65 (10) | S1—S2—C12—C13 | 9.0 (2) |
S2—S1—C11—C10 | 0.55 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···N2i | 0.95 | 2.54 | 3.463 (3) | 164.8 |
Symmetry code: (i) x, −y+1, z−1/2. |
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The synthesis and characterization of molecules containing nitrogen and sulfur as donor functions is important for biomimetic coordination chemistry. The use of this molecules as ligands in the synthesis of copper-complexes as mimics for active centres like the CuA in cytochrome-c-oxidase and N2O-reductase is currently of considerable interest in bioinorganic chemistry. In search of multifunctional ligands we have extended our studies to guanidyl-type systems with N-donor functions. The first derivative, the ligand bis(tetramethyl-guanidino)propylene and its complexes with Cu, Fe, Ni and Mn have recently been investigated (Harmjanz, 1997; Waden, 1999; Pohl et al., 2000; Schneider, 2000; Wittmann et al., 2001; Herres et al., 2005, Neuba et al., 2007). We have now developed the title compound with disulfide group as novel ligand with redoxactivity for use in biomimetic copper-sulfur chemistry.
The most interesting feature are the torsion angles τ C–S1–S2–C' and C–C'–S1–S2 which indicate pπ-dπ interactions between the fully occupied pz orbital on the carbon C atom (part of the aromatic π system) with an empty d orbital on the S atom as reported for 2,2'-diaminodiphenyl disulfide (Lee & Bryant, 1970). The S–S bond length in disulfide compounds is correlated with the C–S–S–C torsion angles, being around 2.031 Å (τ = 75–105°) or 2.070 Å (t = 0–20°) (Allen et al., 1987). For (I) τ is 84.65 (10)° and the S1–S2 bond length 2.0435 (7) Å matching these ranges. As may be seen from the geometric bonding parameters (Table 1), the guanidyl double bonds C1═ N1 and C18═N14 are clearly localized.
The packing pattern shows intermolecular C–H···N hydrogen interactions (Table 2) with molecules stacked in [010] direction.