Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102006728/na1562sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006728/na1562Isup2.hkl |
CCDC reference: 188598
The investigated diastereomer was obtained by the action of the S-tyrosinate ligand on trans-dichlorobis(1,2-diaminoethane)cobalt(III) chloride according to Miodragović et al. (2001). Red crystals of (I) were recrystallized from water in a 62% yield.
All H atoms of the complex cation were placed at calculated positions (C—H = 0.93–0.98 Å and N—H = 0.90 Å) using a riding model and isotropic displacement parameters were set equal to 1.2 times the equivalent isotropic displacement parameter of the parent atoms. Water and hydroxyl H-atom positions were determined by the HYDROGEN program (Nardelli, 1999) and were refined using a riding model with a fixed O—H bond length of 0.85 Å; isotropic displacement parameters were set equal to 1.5 times the equivalent isotropic displacement parameter of the parent atoms. It should be noted that all calculated data for water and hydroxyl H atoms are on the basis of an approximate model. A Gaussian-type absorption correction based on the crystal morphology was applied (Spek, 1990, 1998).
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 EXPRESS (Enraf-Nonius, 1994); program(s) used to solve structure: SHELXS97 (Scheldrick, 1997); program(s) used to refine structure: SHELXL97 (Scheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97, PARST (Nardelli, 1995) and WinGX (Farrugia, 1999).
[Co(C9H10NO3)2(C2H8N2)]Cl·4H2O | F(000) = 616 |
Mr = 586.91 | Dx = 1.468 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.232 (3) Å | Cell parameters from 25 reflections |
b = 15.348 (5) Å | θ = 11.3–15.6° |
c = 10.539 (3) Å | µ = 0.81 mm−1 |
β = 94.50 (2)° | T = 293 K |
V = 1327.4 (8) Å3 | Prismatic, red |
Z = 2 | 0.29 × 0.14 × 0.11 mm |
Enraf-Nonius CAD-4 diffractometer | 4768 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.011 |
Graphite monochromator | θmax = 27.0°, θmin = 1.9° |
ω/2θ scans | h = 0→10 |
Absorption correction: gaussian (Spek, 1990, 1998) | k = −18→18 |
Tmin = 0.882, Tmax = 0.926 | l = −13→13 |
11424 measured reflections | 2 standard reflections every 60 min |
5323 independent reflections | intensity decay: none |
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)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.045P)2 + 0.7052P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
5323 reflections | Δρmax = 0.32 e Å−3 |
325 parameters | Δρmin = −0.30 e Å−3 |
1 restraint | Absolute structure: (Flack, 1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.008 (12) |
[Co(C9H10NO3)2(C2H8N2)]Cl·4H2O | V = 1327.4 (8) Å3 |
Mr = 586.91 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.232 (3) Å | µ = 0.81 mm−1 |
b = 15.348 (5) Å | T = 293 K |
c = 10.539 (3) Å | 0.29 × 0.14 × 0.11 mm |
β = 94.50 (2)° |
Enraf-Nonius CAD-4 diffractometer | 4768 reflections with I > 2σ(I) |
Absorption correction: gaussian (Spek, 1990, 1998) | Rint = 0.011 |
Tmin = 0.882, Tmax = 0.926 | 2 standard reflections every 60 min |
11424 measured reflections | intensity decay: none |
5323 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.088 | Δρmax = 0.32 e Å−3 |
S = 1.10 | Δρmin = −0.30 e Å−3 |
5323 reflections | Absolute structure: (Flack, 1983) |
325 parameters | Absolute structure parameter: −0.008 (12) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
Co | 0.36432 (4) | −0.184147 (19) | 0.56184 (3) | 0.02179 (8) | |
N3 | 0.2004 (2) | −0.1885 (2) | 0.41807 (19) | 0.0283 (4) | |
H1N3 | 0.1008 | −0.1957 | 0.4462 | 0.034* | |
H2N3 | 0.2007 | −0.1383 | 0.3741 | 0.034* | |
N4 | 0.4974 (3) | −0.25376 (16) | 0.4539 (2) | 0.0296 (5) | |
H1N4 | 0.5967 | −0.2295 | 0.4521 | 0.035* | |
H2N4 | 0.5099 | −0.3079 | 0.4861 | 0.035* | |
C19 | 0.2381 (4) | −0.2619 (2) | 0.3353 (3) | 0.0386 (7) | |
H19A | 0.1787 | −0.2562 | 0.2526 | 0.046* | |
H19B | 0.2085 | −0.3167 | 0.3730 | 0.046* | |
C20 | 0.4174 (4) | −0.2583 (2) | 0.3229 (3) | 0.0371 (7) | |
H20A | 0.4529 | −0.3098 | 0.2796 | 0.044* | |
H20B | 0.4447 | −0.2073 | 0.2745 | 0.044* | |
O1 | 0.4563 (2) | −0.08050 (13) | 0.50342 (19) | 0.0281 (4) | |
O2 | 0.4296 (3) | 0.06246 (14) | 0.4927 (2) | 0.0437 (6) | |
N1 | 0.2256 (3) | −0.10611 (15) | 0.6532 (2) | 0.0254 (5) | |
H1N1 | 0.1238 | −0.1276 | 0.6510 | 0.031* | |
H2N1 | 0.2646 | −0.1016 | 0.7352 | 0.031* | |
C1 | 0.3811 (4) | −0.00906 (18) | 0.5258 (3) | 0.0285 (6) | |
C2 | 0.2236 (3) | −0.01889 (18) | 0.5917 (3) | 0.0271 (6) | |
H2 | 0.1328 | −0.0179 | 0.5258 | 0.032* | |
C3 | 0.1990 (4) | 0.0564 (2) | 0.6832 (3) | 0.0356 (7) | |
H3A | 0.2950 | 0.0610 | 0.7424 | 0.043* | |
H3B | 0.1903 | 0.1102 | 0.6346 | 0.043* | |
C4 | 0.0507 (4) | 0.0483 (2) | 0.7588 (3) | 0.0334 (6) | |
C5 | −0.0999 (4) | 0.0209 (2) | 0.7060 (3) | 0.0362 (7) | |
H5 | −0.1103 | 0.0027 | 0.6216 | 0.043* | |
C6 | −0.2358 (4) | 0.0198 (2) | 0.7758 (3) | 0.0372 (7) | |
H6 | −0.3359 | 0.0012 | 0.7384 | 0.045* | |
C7 | −0.2214 (4) | 0.0465 (2) | 0.9014 (3) | 0.0378 (7) | |
O3 | −0.3595 (3) | 0.04689 (19) | 0.9668 (2) | 0.0509 (7) | |
H1O3 | −0.3548 | 0.0891 | 1.0193 | 0.076* | |
C8 | −0.0729 (5) | 0.0721 (2) | 0.9562 (3) | 0.0465 (8) | |
H8 | −0.0628 | 0.0895 | 1.0410 | 0.056* | |
C9 | 0.0628 (4) | 0.0724 (2) | 0.8858 (3) | 0.0438 (8) | |
H9 | 0.1634 | 0.0890 | 0.9246 | 0.053* | |
O4 | 0.2741 (2) | −0.28452 (13) | 0.6334 (2) | 0.0293 (4) | |
O5 | 0.3062 (3) | −0.38214 (15) | 0.7868 (2) | 0.0403 (5) | |
N2 | 0.5316 (3) | −0.19277 (19) | 0.7042 (2) | 0.0270 (5) | |
H1N2 | 0.6305 | −0.1827 | 0.6764 | 0.032* | |
H2N2 | 0.5132 | −0.1525 | 0.7635 | 0.032* | |
C10 | 0.3574 (4) | −0.31985 (18) | 0.7274 (3) | 0.0292 (6) | |
C11 | 0.5269 (3) | −0.28214 (19) | 0.7612 (3) | 0.0306 (6) | |
H11 | 0.6056 | −0.3184 | 0.7202 | 0.037* | |
C12 | 0.5732 (4) | −0.2835 (2) | 0.9042 (3) | 0.0404 (7) | |
H12A | 0.4867 | −0.2559 | 0.9470 | 0.048* | |
H12B | 0.5799 | −0.3437 | 0.9322 | 0.048* | |
C13 | 0.7325 (4) | −0.2387 (2) | 0.9457 (3) | 0.0354 (7) | |
C14 | 0.8717 (4) | −0.2525 (2) | 0.8825 (3) | 0.0420 (7) | |
H14 | 0.8661 | −0.2885 | 0.8113 | 0.050* | |
C15 | 1.0184 (4) | −0.2142 (2) | 0.9230 (3) | 0.0441 (8) | |
H15 | 1.1101 | −0.2243 | 0.8789 | 0.053* | |
C16 | 1.0291 (4) | −0.1612 (2) | 1.0282 (3) | 0.0407 (8) | |
O6 | 1.1780 (3) | −0.1256 (2) | 1.0665 (3) | 0.0553 (7) | |
H1O6 | 1.2108 | −0.1462 | 1.1389 | 0.083* | |
C17 | 0.8917 (5) | −0.1464 (3) | 1.0930 (3) | 0.0503 (9) | |
H17 | 0.8976 | −0.1107 | 1.1645 | 0.060* | |
C18 | 0.7455 (4) | −0.1852 (3) | 1.0508 (3) | 0.0454 (7) | |
H18 | 0.6536 | −0.1747 | 1.0946 | 0.055* | |
Cl | −0.13650 (9) | −0.19990 (7) | 0.54624 (9) | 0.0531 (3) | |
O1W | 0.4064 (3) | −0.0795 (2) | 0.9008 (2) | 0.0504 (6) | |
H11W | 0.4627 | −0.0351 | 0.9241 | 0.076* | |
H21W | 0.3531 | −0.0950 | 0.9629 | 0.076* | |
O2W | −0.0286 (4) | −0.3968 (2) | 0.6341 (3) | 0.0707 (9) | |
H12W | −0.0810 | −0.3493 | 0.6229 | 0.106* | |
H22W | 0.0546 | −0.3939 | 0.5914 | 0.106* | |
O3W | −0.2111 (4) | −0.5173 (2) | 0.7437 (3) | 0.0681 (8) | |
H13W | −0.1500 | −0.4794 | 0.7127 | 0.102* | |
H23W | −0.2230 | −0.5029 | 0.8203 | 0.102* | |
O4W | 0.4509 (5) | −0.5448 (2) | 0.7442 (3) | 0.0788 (10) | |
H14W | 0.4313 | −0.5735 | 0.6757 | 0.118* | |
H24W | 0.5242 | −0.5075 | 0.7315 | 0.118* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.02055 (14) | 0.01730 (15) | 0.02802 (15) | −0.00076 (16) | 0.00508 (11) | 0.00091 (16) |
N3 | 0.0253 (10) | 0.0263 (11) | 0.0336 (10) | −0.0029 (13) | 0.0043 (8) | 0.0013 (13) |
N4 | 0.0272 (11) | 0.0243 (12) | 0.0381 (13) | 0.0019 (10) | 0.0087 (10) | −0.0018 (10) |
C19 | 0.0436 (17) | 0.0340 (17) | 0.0374 (16) | −0.0019 (14) | −0.0019 (13) | −0.0082 (13) |
C20 | 0.0468 (18) | 0.0314 (16) | 0.0344 (15) | 0.0015 (14) | 0.0120 (13) | −0.0054 (12) |
O1 | 0.0272 (10) | 0.0209 (10) | 0.0374 (11) | −0.0014 (8) | 0.0104 (8) | 0.0028 (8) |
O2 | 0.0558 (14) | 0.0208 (10) | 0.0572 (14) | −0.0083 (11) | 0.0209 (12) | 0.0011 (9) |
N1 | 0.0234 (11) | 0.0244 (13) | 0.0291 (12) | 0.0009 (9) | 0.0062 (9) | 0.0009 (9) |
C1 | 0.0336 (14) | 0.0216 (14) | 0.0306 (13) | −0.0003 (12) | 0.0052 (11) | −0.0012 (11) |
C2 | 0.0282 (13) | 0.0204 (13) | 0.0331 (14) | 0.0044 (11) | 0.0057 (11) | 0.0016 (11) |
C3 | 0.0387 (16) | 0.0229 (14) | 0.0460 (17) | 0.0009 (13) | 0.0092 (13) | −0.0060 (12) |
C4 | 0.0376 (16) | 0.0228 (14) | 0.0405 (16) | 0.0071 (12) | 0.0080 (12) | −0.0026 (12) |
C5 | 0.0447 (17) | 0.0313 (15) | 0.0327 (15) | 0.0060 (14) | 0.0048 (13) | −0.0066 (12) |
C6 | 0.0356 (16) | 0.0367 (17) | 0.0391 (16) | −0.0006 (14) | 0.0023 (13) | −0.0083 (13) |
C7 | 0.0415 (17) | 0.0317 (16) | 0.0421 (17) | 0.0003 (14) | 0.0146 (13) | −0.0054 (13) |
O3 | 0.0470 (14) | 0.0568 (16) | 0.0515 (14) | −0.0098 (12) | 0.0206 (11) | −0.0214 (12) |
C8 | 0.052 (2) | 0.051 (2) | 0.0372 (17) | −0.0046 (17) | 0.0083 (15) | −0.0171 (15) |
C9 | 0.0414 (18) | 0.046 (2) | 0.0443 (18) | −0.0046 (16) | 0.0052 (14) | −0.0148 (15) |
O4 | 0.0275 (10) | 0.0232 (10) | 0.0375 (11) | −0.0042 (9) | 0.0052 (8) | 0.0052 (9) |
O5 | 0.0456 (13) | 0.0321 (11) | 0.0440 (12) | −0.0052 (10) | 0.0101 (10) | 0.0114 (10) |
N2 | 0.0241 (10) | 0.0257 (13) | 0.0312 (10) | −0.0018 (11) | 0.0028 (8) | 0.0025 (11) |
C10 | 0.0319 (14) | 0.0223 (13) | 0.0346 (14) | 0.0013 (12) | 0.0111 (11) | 0.0026 (11) |
C11 | 0.0291 (14) | 0.0252 (14) | 0.0376 (15) | 0.0030 (12) | 0.0026 (12) | 0.0057 (12) |
C12 | 0.0398 (17) | 0.0439 (19) | 0.0372 (16) | −0.0035 (15) | 0.0018 (13) | 0.0119 (14) |
C13 | 0.0359 (15) | 0.0379 (17) | 0.0317 (14) | 0.0040 (14) | −0.0017 (12) | 0.0093 (12) |
C14 | 0.0443 (18) | 0.0439 (19) | 0.0379 (16) | 0.0006 (16) | 0.0030 (13) | −0.0057 (14) |
C15 | 0.0389 (17) | 0.050 (2) | 0.0445 (18) | −0.0009 (15) | 0.0098 (14) | −0.0033 (14) |
C16 | 0.0381 (16) | 0.044 (2) | 0.0401 (16) | −0.0025 (13) | 0.0041 (13) | 0.0021 (13) |
O6 | 0.0459 (14) | 0.0674 (18) | 0.0528 (15) | −0.0146 (13) | 0.0043 (11) | −0.0086 (13) |
C17 | 0.052 (2) | 0.060 (2) | 0.0398 (18) | 0.0030 (18) | 0.0070 (16) | −0.0111 (16) |
C18 | 0.0411 (15) | 0.0567 (19) | 0.0395 (14) | 0.004 (2) | 0.0093 (11) | 0.000 (2) |
Cl | 0.0273 (3) | 0.0690 (9) | 0.0643 (5) | −0.0078 (4) | 0.0120 (3) | −0.0044 (5) |
O1W | 0.0471 (14) | 0.0614 (17) | 0.0433 (13) | −0.0054 (13) | 0.0080 (10) | −0.0125 (12) |
O2W | 0.0552 (17) | 0.062 (2) | 0.096 (2) | −0.0185 (15) | 0.0097 (17) | −0.0191 (17) |
O3W | 0.076 (2) | 0.071 (2) | 0.0554 (16) | 0.0012 (17) | −0.0073 (15) | 0.0161 (15) |
O4W | 0.109 (3) | 0.060 (2) | 0.073 (2) | 0.0163 (19) | 0.0432 (19) | 0.0090 (16) |
Co—O1 | 1.886 (2) | O3—H1O3 | 0.8500 |
Co—O4 | 1.892 (2) | C8—C9 | 1.388 (5) |
Co—N3 | 1.950 (2) | C8—H8 | 0.9300 |
Co—N4 | 1.957 (2) | C9—H9 | 0.9300 |
Co—N1 | 1.959 (2) | O4—C10 | 1.281 (4) |
Co—N2 | 1.960 (2) | O5—C10 | 1.235 (4) |
N3—C19 | 1.472 (4) | N2—C11 | 1.499 (4) |
N3—H1N3 | 0.9000 | N2—H1N2 | 0.9000 |
N3—H2N3 | 0.9000 | N2—H2N2 | 0.9000 |
N4—C20 | 1.484 (4) | C10—C11 | 1.527 (4) |
N4—H1N4 | 0.9000 | C11—C12 | 1.526 (4) |
N4—H2N4 | 0.9000 | C11—H11 | 0.9800 |
C19—C20 | 1.493 (5) | C12—C13 | 1.515 (5) |
C19—H19A | 0.9700 | C12—H12A | 0.9700 |
C19—H19B | 0.9700 | C12—H12B | 0.9700 |
C20—H20A | 0.9700 | C13—C18 | 1.376 (5) |
C20—H20B | 0.9700 | C13—C14 | 1.386 (5) |
O1—C1 | 1.290 (4) | C14—C15 | 1.381 (5) |
O2—C1 | 1.228 (4) | C14—H14 | 0.9300 |
N1—C2 | 1.487 (4) | C15—C16 | 1.372 (5) |
N1—H1N1 | 0.9000 | C15—H15 | 0.9300 |
N1—H2N1 | 0.9000 | C16—O6 | 1.373 (4) |
C1—C2 | 1.526 (4) | C16—C17 | 1.385 (5) |
C2—C3 | 1.529 (4) | O6—H1O6 | 0.8500 |
C2—H2 | 0.9800 | C17—C18 | 1.384 (5) |
C3—C4 | 1.514 (4) | C17—H17 | 0.9300 |
C3—H3A | 0.9700 | C18—H18 | 0.9300 |
C3—H3B | 0.9700 | O1W—H11W | 0.85 |
C4—C9 | 1.385 (4) | O1W—H21W | 0.85 |
C4—C5 | 1.384 (5) | O2W—H12W | 0.85 |
C5—C6 | 1.386 (5) | O2W—H22W | 0.85 |
C5—H5 | 0.9300 | O3W—H13W | 0.85 |
C6—C7 | 1.381 (4) | O3W—H23W | 0.85 |
C6—H6 | 0.9300 | O4W—H14W | 0.85 |
C7—C8 | 1.368 (5) | O4W—H24W | 0.85 |
C7—O3 | 1.376 (4) | ||
O1—Co—O4 | 175.55 (10) | C5—C4—C3 | 123.2 (3) |
O1—Co—N3 | 92.66 (11) | C4—C5—C6 | 121.7 (3) |
O4—Co—N3 | 90.71 (10) | C4—C5—H5 | 119.2 |
O1—Co—N4 | 90.77 (11) | C6—C5—H5 | 119.2 |
O4—Co—N4 | 92.41 (10) | C7—C6—C5 | 119.5 (3) |
N3—Co—N4 | 85.09 (11) | C7—C6—H6 | 120.2 |
O1—Co—N1 | 84.79 (9) | C5—C6—H6 | 120.2 |
O4—Co—N1 | 92.29 (10) | C8—C7—O3 | 122.2 (3) |
N3—Co—N1 | 90.49 (11) | C8—C7—C6 | 119.8 (3) |
N4—Co—N1 | 173.59 (11) | O3—C7—C6 | 118.0 (3) |
O1—Co—N2 | 91.77 (10) | C7—O3—H1O3 | 109.4 |
O4—Co—N2 | 85.07 (10) | C7—C8—C9 | 120.3 (3) |
N3—Co—N2 | 174.08 (14) | C7—C8—H8 | 119.8 |
N4—Co—N2 | 90.94 (11) | C9—C8—H8 | 119.8 |
N1—Co—N2 | 93.81 (11) | C4—C9—C8 | 121.0 (3) |
C19—N3—Co | 108.73 (19) | C4—C9—H9 | 119.5 |
C19—N3—H1N3 | 109.9 | C8—C9—H9 | 119.5 |
Co—N3—H1N3 | 109.9 | C10—O4—Co | 116.76 (19) |
C19—N3—H2N3 | 109.9 | C11—N2—Co | 109.27 (18) |
Co—N3—H2N3 | 109.9 | C11—N2—H1N2 | 109.8 |
H1N3—N3—H2N3 | 108.3 | Co—N2—H1N2 | 109.8 |
C20—N4—Co | 109.79 (18) | C11—N2—H2N2 | 109.8 |
C20—N4—H1N4 | 109.7 | Co—N2—H2N2 | 109.8 |
Co—N4—H1N4 | 109.7 | H1N2—N2—H2N2 | 108.3 |
C20—N4—H2N4 | 109.7 | O5—C10—O4 | 122.5 (3) |
Co—N4—H2N4 | 109.7 | O5—C10—C11 | 121.2 (3) |
H1N4—N4—H2N4 | 108.2 | O4—C10—C11 | 116.3 (2) |
N3—C19—C20 | 106.3 (2) | N2—C11—C10 | 107.8 (2) |
N3—C19—H19A | 110.5 | N2—C11—C12 | 113.4 (3) |
C20—C19—H19A | 110.5 | C10—C11—C12 | 112.2 (2) |
N3—C19—H19B | 110.5 | N2—C11—H11 | 107.8 |
C20—C19—H19B | 110.5 | C10—C11—H11 | 107.8 |
H19A—C19—H19B | 108.7 | C12—C11—H11 | 107.8 |
N4—C20—C19 | 106.8 (2) | C13—C12—C11 | 115.0 (3) |
N4—C20—H20A | 110.4 | C13—C12—H12A | 108.5 |
C19—C20—H20A | 110.4 | C11—C12—H12A | 108.5 |
N4—C20—H20B | 110.4 | C13—C12—H12B | 108.5 |
C19—C20—H20B | 110.4 | C11—C12—H12B | 108.5 |
H20A—C20—H20B | 108.6 | H12A—C12—H12B | 107.5 |
C1—O1—Co | 116.53 (18) | C18—C13—C14 | 117.6 (3) |
C2—N1—Co | 108.85 (17) | C18—C13—C12 | 121.0 (3) |
C2—N1—H1N1 | 109.9 | C14—C13—C12 | 121.4 (3) |
Co—N1—H1N1 | 109.9 | C15—C14—C13 | 121.5 (3) |
C2—N1—H2N1 | 109.9 | C15—C14—H14 | 119.3 |
Co—N1—H2N1 | 109.9 | C13—C14—H14 | 119.3 |
H1N1—N1—H2N1 | 108.3 | C16—C15—C14 | 120.1 (3) |
O2—C1—O1 | 122.5 (3) | C16—C15—H15 | 120.0 |
O2—C1—C2 | 121.6 (3) | C14—C15—H15 | 120.0 |
O1—C1—C2 | 115.9 (2) | O6—C16—C15 | 118.2 (3) |
N1—C2—C1 | 107.9 (2) | O6—C16—C17 | 122.3 (3) |
N1—C2—C3 | 113.8 (2) | C15—C16—C17 | 119.5 (3) |
C1—C2—C3 | 111.8 (2) | C16—O6—H1O6 | 109.2 |
N1—C2—H2 | 107.7 | C16—C17—C18 | 119.6 (3) |
C1—C2—H2 | 107.7 | C16—C17—H17 | 120.2 |
C3—C2—H2 | 107.7 | C18—C17—H17 | 120.2 |
C4—C3—C2 | 114.9 (3) | C13—C18—C17 | 121.7 (3) |
C4—C3—H3A | 108.5 | C13—C18—H18 | 119.1 |
C2—C3—H3A | 108.5 | C17—C18—H18 | 119.1 |
C4—C3—H3B | 108.5 | H11W—O1W—H21W | 107.7 |
C2—C3—H3B | 108.5 | H12W—O2W—H22W | 107.7 |
H3A—C3—H3B | 107.5 | H13W—O3W—H23W | 107.7 |
C9—C4—C5 | 117.6 (3) | H14W—O4W—H24W | 107.7 |
C9—C4—C3 | 119.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N3···Cl | 0.90 | 2.29 | 3.183 (2) | 170 |
N3—H2N3···O3Wi | 0.90 | 2.24 | 3.138 (5) | 176 |
N1—H1N1···Cl | 0.90 | 2.58 | 3.421 (3) | 155 |
N1—H2N1···O1W | 0.90 | 2.05 | 2.929 (4) | 165 |
N2—H2N2···O1W | 0.90 | 2.08 | 2.951 (4) | 163 |
N4—H1N4···Clii | 0.90 | 2.38 | 3.202 (3) | 152 |
N2—H1N2···Clii | 0.90 | 2.46 | 3.311 (2) | 158 |
N4—H2N4···O2iii | 0.90 | 2.06 | 2.929 (3) | 162 |
O3—H1O3···O5iv | 0.85 | 2.10 | 2.818 (3) | 142 |
O6—H1O6···O3Wv | 0.85 | 2.33 | 2.599 (4) | 98 |
O1W—H11W···O3ii | 0.85 | 1.96 | 2.784 (4) | 165 |
O1W—H21W···O6vi | 0.85 | 1.93 | 2.758 (4) | 163 |
O2W—H12W···Cl | 0.85 | 2.46 | 3.263 (4) | 157 |
O2W—H22W···O4 | 0.85 | 2.48 | 3.030 (4) | 123 |
O3W—H13W···O2W | 0.85 | 1.85 | 2.699 (5) | 176 |
O3W—H23W···O6vii | 0.85 | 2.24 | 2.599 (4) | 105 |
O4W—H14W···O1iii | 0.85 | 2.17 | 2.830 (4) | 134 |
O4W—H24W···O3Wii | 0.85 | 2.18 | 2.815 (5) | 132 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+1; (iv) −x, y+1/2, −z+2; (v) −x+1, y+1/2, −z+2; (vi) x−1, y, z; (vii) −x+1, y−1/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C9H10NO3)2(C2H8N2)]Cl·4H2O |
Mr | 586.91 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 8.232 (3), 15.348 (5), 10.539 (3) |
β (°) | 94.50 (2) |
V (Å3) | 1327.4 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.29 × 0.14 × 0.11 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Gaussian (Spek, 1990, 1998) |
Tmin, Tmax | 0.882, 0.926 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11424, 5323, 4768 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.638 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.088, 1.10 |
No. of reflections | 5323 |
No. of parameters | 325 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.30 |
Absolute structure | (Flack, 1983) |
Absolute structure parameter | −0.008 (12) |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, CAD-4 EXPRESS (Enraf-Nonius, 1994), SHELXS97 (Scheldrick, 1997), SHELXL97 (Scheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97, PARST (Nardelli, 1995) and WinGX (Farrugia, 1999).
Co—O1 | 1.886 (2) | O2—C1 | 1.228 (4) |
Co—O4 | 1.892 (2) | N1—C2 | 1.487 (4) |
Co—N3 | 1.950 (2) | C1—C2 | 1.526 (4) |
Co—N4 | 1.957 (2) | O4—C10 | 1.281 (4) |
Co—N1 | 1.959 (2) | O5—C10 | 1.235 (4) |
Co—N2 | 1.960 (2) | N2—C11 | 1.499 (4) |
O1—C1 | 1.290 (4) | C10—C11 | 1.527 (4) |
O1—Co—O4 | 175.55 (10) | N3—Co—N1 | 90.49 (11) |
O1—Co—N3 | 92.66 (11) | N4—Co—N1 | 173.59 (11) |
O4—Co—N3 | 90.71 (10) | O1—Co—N2 | 91.77 (10) |
O1—Co—N4 | 90.77 (11) | O4—Co—N2 | 85.07 (10) |
O4—Co—N4 | 92.41 (10) | N3—Co—N2 | 174.08 (14) |
N3—Co—N4 | 85.09 (11) | N4—Co—N2 | 90.94 (11) |
O1—Co—N1 | 84.79 (9) | N1—Co—N2 | 93.81 (11) |
O4—Co—N1 | 92.29 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N3···Cl | 0.90 | 2.29 | 3.183 (2) | 170 |
N3—H2N3···O3Wi | 0.90 | 2.24 | 3.138 (5) | 176 |
N1—H1N1···Cl | 0.90 | 2.58 | 3.421 (3) | 155 |
N1—H2N1···O1W | 0.90 | 2.05 | 2.929 (4) | 165 |
N2—H2N2···O1W | 0.90 | 2.08 | 2.951 (4) | 163 |
N4—H1N4···Clii | 0.90 | 2.38 | 3.202 (3) | 152 |
N2—H1N2···Clii | 0.90 | 2.46 | 3.311 (2) | 158 |
N4—H2N4···O2iii | 0.90 | 2.06 | 2.929 (3) | 162 |
O3—H1O3···O5iv | 0.85 | 2.10 | 2.818 (3) | 142 |
O6—H1O6···O3Wv | 0.85 | 2.33 | 2.599 (4) | 98 |
O1W—H11W···O3ii | 0.85 | 1.96 | 2.784 (4) | 165 |
O1W—H21W···O6vi | 0.85 | 1.93 | 2.758 (4) | 163 |
O2W—H12W···Cl | 0.85 | 2.46 | 3.263 (4) | 157 |
O2W—H22W···O4 | 0.85 | 2.48 | 3.030 (4) | 123 |
O3W—H13W···O2W | 0.85 | 1.85 | 2.699 (5) | 176 |
O3W—H23W···O6vii | 0.85 | 2.24 | 2.599 (4) | 105 |
O4W—H14W···O1iii | 0.85 | 2.17 | 2.830 (4) | 134 |
O4W—H24W···O3Wii | 0.85 | 2.18 | 2.815 (5) | 132 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+1; (iv) −x, y+1/2, −z+2; (v) −x+1, y+1/2, −z+2; (vi) x−1, y, z; (vii) −x+1, y−1/2, −z+2. |
The crystal structure of the title compound, (I), represents further work in our investigation the the structure and stereochemistry of cobalt(III) complexes with aromatic amino acids (Miodragović et al., 2001). Complexes of cobalt(III) with aromatic amino acids are interesting as a simple model system for the investigation of non-covalent interactions in which aromatic amino acids are involved (Jitsukawa et al., 1997; Kumita et al., 1998, 2001), because it is known that their side chains, through non-covalent interactions, play an important role in molecular recognition in vivo (Fontecave et al., 1996; Ma & Dougherty, 1997; Pomponi et al., 1998; Hofstädter et al., 1999). Mixed (1,2-diaminoethane)bis(S-aminocarboxylato)cobalt(III) complexescan occur in the form of three geometrical isomers, and each of them has an optical counterpart.
In our previous paper (Miodragović et al., 2001), we described the synthesis and characterization of five out of six theoretically possible diastereomers of the (1,2-diaminoethane)bis(S-tyrosinato)cobalt(III) complex and presented the X-ray crystal structure of the Δ—C1-cis(O) diastereomer, (II). By a subsequent recrystallization of the diastereomers, high quality monocrystals of the Λ-trans(O) diastereomer, (I), were obtained, whose crystal structure is presented in this paper (Fig. 1).
The greatest differences between complexes (I) and (II) are in different coordination of the O and N atoms of the S-tyrosinato ligands. Namely, complex (II) has a cis(O),cis(N) configuration, while complex (I) has a trans(O),trans(N) configuration, leading to different Co—O bond lengths. Hence, in complex (I), Co—O1 = 1.886 (2) Å and Co—O4 = 1.892 (2) Å, which are shorter than the in (II) [Co—O1 = 1.912 (6) Å and Co—O4 = 1.909 (5) Å]. There are also differences in the Co—N(S-tyrosinato) bond lengths, i.e. in (II), they are different [Co—N1 = 1.93 (7) Å and Co—N1 = 1.965 (6) Å], while in the title complex (I), they are almost the same, i.e. Co—N1 = 1.959 (2) Å and Co—N2 = 1.960 (2) Å.
In addition to the differences in coordination, the complexes also exhibit differences in the conformation of the amino acidic chelate rings. Namely, although these chelate rings exhibit the same conformation (envelope), in (I), the rings are less puckered. The puckering parameters for the Co—O1—C1—C2—N1 (q2) and Co—O4—C10—C11—N2 (q2') chelate rings for complex (I) are q2 = 0.267 (2) Å and q2' = 0.230 (3) Å, while for complex (II), the puckering parameters are q2 = 0.65 (8) Å and q2' = 0.323 (7) Å (Cremer & Pople, 1975). Such a difference in the planarity of the amino acidic chelate rings leads to somewhat smaller H—N1—C2—H and H—N2—C11—H torsion angles in complex (I), namely, the H atoms bonded to chelate-ring N and C atoms are closer to eclipsed positions in complex (I).
The puckering parameters of the diamine five-membered chelate ring (Co—N3—C19—C20—N4) are q2 = 0.446 (3) Å and ϕ = -99.0 (3)°. There are no remarkable differences between the conformations of the chelate rings of the 1,2-diaminoethane ligands in both complexes. In both cases, this chelate ring adopts a conformation which is intermediate between half-chair (with a local pseudo-twofold axis along Co and the midpoint of the C19—C20 bond) and envelope (with a local pseudo-mirror along C19 and the midpoint of the Co—N4 bond).
Due to the formation of three five-membered chelate rings, the coordinate angles deviate markedly from the ideal values of 90 and 180° (Table 1). The crystal structure is stabilized by a great number of hydrogen bonds (Table 2). In the crystal lattice of (I), the chloride anions are located approximately between two neighboring Co atoms [Co···Cl = 4.120 (2) Å and Cl···Coi = 4.132 (2) Å; symmetry code: (i) x - 1, y, z], forming hydrogen bonds with the NH2 groups coordinated to the Co atoms. However, in the crystal lattice of complex (II), the complex cations also form intermolecular hydrogen bonds, but these are directly through the COO and NH2 groups from the coordination sphere of the Co atom.
In the crystal lattice of complex (I), there is a weak intermolecular π···π interaction between the phenyl rings of the amino acidic ligands. The phenyl rings are oriented in such a way that the perpendicular distance from the C4–C9 ring to the C13i–C18i ring is 3.88 Å, with the closest distance being C8···C17i of 3.672 (6) Å. The distance between the ring centroids is 4.142 (3) Å. An unhomogeneous arrangement of π-electron density through the phenyl ring is probably responsible for mutual orientation of the phenyl rings (Fig. 2) and the PD (parallel-displaced) type of π···π interactions (Kamishima et al., 2001).
It was subsequently established (i.e. it had not been published earlier) that in (II), the phenyl rings of tyrosine are involved in the formation of intermolecular C—H···π interactions with the following geometrical parameters: (i) the distance between an H atom bonded to atom C14 and the centre of the C4–C9 aromatic ring is 2.67 Å; (ii) the distance between an H atom bonded to atom C14 and the plane of the C4–C9 aromatic ring is 2.66 Å; (iii) the angle between the line connecting an H atom and the centre of the ring, and the normal to the C4–C9 plane is 4.6°; (iv) the angle C14—H···M (M = ring center) is 172°.
From the results presented in this paper, it can be concluded that the phenyl rings of amino acids present in the same complex, but having different geometrical configurations, can form two kinds of interactions, that is, C—H···π and π···π interactions. It can also be concluded that in both complexes, the complex cations form intermolecular hydrogen bonds of different type. In complex (II), the hydrogen bonds are formed through coordinated COO and NH2 groups, while in complex (I), a chloride anion is positioned centrally between two complex cations and forms multiple hydrogen bonds with coordinated NH2 groups.