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The title complexes, [Co(C3H6NO)(C4H7N2O2)2(C8H11N)] and [Co(C4H8NO)(C4H7N2O2)2(C8H11N)]·H2O, were resolved from [(RS)-1-carbamoylethyl]bis(dimethylglyoximato)[(S)-1-phenylethylamine]cobalt(III) and bis(dimethylglyoximato)[(RS)-1-(N-methylcarbamoyl)ethyl][(R)-1-phenylethylamine]cobalt(III), respectively, and their crystal structures were determined in order to reveal the absolute configuration of the major enantiomer produced in the photoisomerization of each series of 2-carbamoylethyl and 2-(N-methylcarbamoyl)ethyl cobaloxime complexes.
Supporting information
CCDC references: 269016; 269017
Complexes (I) and (II) were prepared according to the literature method of Ohgo et al. (1996). [(RS)-1-carbamoylethyl] bis(dimethylglyoximato-N,N')[(S)-1-phenylethylamine]cobalt(III) was recrystallized five times from dichloromethane–hexane to afford yellow crystals Red below of complex (I), with maximum optical rotation [α]589 = +27.6, [α]578 = +41.4, [α]546 = +100.5 (c = 0.102, CHCl3). Analysis found: C 47.1, H 6.4, N 17.2%; calculated for C19H31CoN6O5: C 47.3, H 6.5, N 17.4%. Bis(dimethylglyoximato-N,N')[(RS)-1-(N-methylcarbamoyl)ethyl] [(R)-1-phenylethylamine]cobalt(III) was recrystallized six times from benzene–hexane and finally from benzene [including 1% (R)-phenylethylamine]–hexane to afford dark-red crystals of complex (II) with maximum optical rotation [α]589 = −60.4, [α]578 = −82.5, [α]546 = −158.2 (c = 0.104, CHCl3). Analysis found: C 46.9, H 6.8, N 16.3%; calculated for C20H35CoN6O6: C 46.7, H 6.9, N 16.3%. Please give ratios of solvents used for both crystals.
Water H atoms were located in difference maps; O—H distances were constrained at 0.95 Å and Uiso(H) were set at 1.2Ueq(O). All other H atoms were refined using a riding model, with C—H distances of 0.96 for primary, 0.97 for secondary and 0.93 Å for aromatic, and with Uiso(H) = 1.2Ueq(C) (1.5 for methyl groups). The absolute structures were set by reference to the known chirality of the enantiopure amine coordinated in each complex and the Flack parameter is in agreement with each expected configuration.
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992). Program(s) used to solve structure: MULTAN88 (Debaerdemaeker, 1988) for (I); SIR92 (Altomare et al., 1993) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SV (Nemoto & Ohashi, 1993) and ORTEP (Johnson, 1965); software used to prepare material for publication: SHELXL97.
(I) [(
S)-1-Carbamoylethyl]bis(dimethylglyoximato-
κ2N,
N')[(S)-1- phenylethylamine]cobalt(III)
top
Crystal data top
[Co(C3H6NO)(C4H7N2O2)2(C8H11N)] | F(000) = 508 |
Mr = 482.43 | Dx = 1.458 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P2yb | Cell parameters from 25 reflections |
a = 8.743 (2) Å | θ = 12.6–14.9° |
b = 14.696 (3) Å | µ = 0.82 mm−1 |
c = 8.565 (3) Å | T = 223 K |
β = 93.29 (2)° | Needle, red |
V = 1098.7 (5) Å3 | 0.23 × 0.18 × 0.17 mm |
Z = 2 | |
Data collection top
Rigaku AFC-7R diffractometer | 2404 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.027 |
Graphite monochromator | θmax = 27.5°, θmin = 2.7° |
ω/2θ scans | h = −6→11 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→19 |
Tmin = 0.789, Tmax = 0.869 | l = −11→11 |
3200 measured reflections | 3 standard reflections every 100 reflections |
2624 independent reflections | intensity decay: 0.7% |
Refinement top
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)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0308P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.21 | (Δ/σ)max < 0.001 |
2624 reflections | Δρmax = 0.22 e Å−3 |
299 parameters | Δρmin = −0.23 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with how many Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.004 (14) |
Crystal data top
[Co(C3H6NO)(C4H7N2O2)2(C8H11N)] | V = 1098.7 (5) Å3 |
Mr = 482.43 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.743 (2) Å | µ = 0.82 mm−1 |
b = 14.696 (3) Å | T = 223 K |
c = 8.565 (3) Å | 0.23 × 0.18 × 0.17 mm |
β = 93.29 (2)° | |
Data collection top
Rigaku AFC-7R diffractometer | 2404 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.027 |
Tmin = 0.789, Tmax = 0.869 | 3 standard reflections every 100 reflections |
3200 measured reflections | intensity decay: 0.7% |
2624 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | Δρmax = 0.22 e Å−3 |
S = 1.21 | Δρmin = −0.23 e Å−3 |
2624 reflections | Absolute structure: Flack (1983), with how many Friedel pairs |
299 parameters | Absolute structure parameter: −0.004 (14) |
1 restraint | |
Special details top
Experimental. 1H NMR (CDCl3, p.p.m.): 0.32 (3H, d), 1.23 (3H, d), 1.46 (1H, dd), 1.89 (1H, q), 2.20 (12H, d), 2.33 (1H, dd), 3.62 (1H, m), 7.04–7.33 (m). |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.61819 (4) | 0.86456 (2) | 0.12322 (4) | 0.01723 (9) | |
O1 | 0.3405 (2) | 0.95407 (15) | 0.0257 (2) | 0.0271 (4) | |
O2 | 0.7967 (2) | 0.74302 (16) | −0.0571 (3) | 0.0341 (5) | |
H2 | 0.8510 | 0.7507 | 0.0245 | 0.051* | |
O3 | 0.8951 (2) | 0.77424 (15) | 0.2194 (3) | 0.0319 (5) | |
O4 | 0.4512 (2) | 0.99594 (15) | 0.2924 (3) | 0.0305 (5) | |
H4 | 0.4026 | 0.9929 | 0.2064 | 0.046* | |
O5 | 0.4061 (3) | 0.64932 (15) | 0.0388 (3) | 0.0341 (5) | |
N1 | 0.4449 (3) | 0.89254 (15) | −0.0103 (3) | 0.0210 (5) | |
N2 | 0.6636 (3) | 0.79086 (15) | −0.0487 (3) | 0.0224 (5) | |
N3 | 0.7875 (3) | 0.83271 (17) | 0.2599 (3) | 0.0231 (5) | |
N4 | 0.5724 (3) | 0.93830 (16) | 0.2935 (3) | 0.0219 (5) | |
N5 | 0.7316 (3) | 0.97004 (16) | 0.0171 (3) | 0.0204 (4) | |
H5A | 0.7149 | 0.9620 | −0.0878 | 0.024* | |
H5B | 0.6820 | 1.0221 | 0.0414 | 0.024* | |
N6 | 0.6284 (3) | 0.62084 (19) | 0.1761 (4) | 0.0336 (6) | |
H6D | 0.693 (5) | 0.651 (3) | 0.228 (5) | 0.051 (13)* | |
H6E | 0.643 (5) | 0.570 (4) | 0.115 (5) | 0.067 (15)* | |
C1 | 0.4327 (3) | 0.84861 (19) | −0.1424 (3) | 0.0252 (7) | |
C2 | 0.5623 (3) | 0.7880 (2) | −0.1649 (3) | 0.0253 (6) | |
C3 | 0.7924 (3) | 0.8704 (3) | 0.3982 (3) | 0.0259 (5) | |
C4 | 0.6636 (3) | 0.9328 (2) | 0.4177 (3) | 0.0243 (5) | |
C5 | 0.2974 (4) | 0.8593 (3) | −0.2565 (4) | 0.0419 (8) | |
H5C | 0.2223 | 0.8988 | −0.2120 | 0.063* | |
H5D | 0.2518 | 0.8002 | −0.2786 | 0.063* | |
H5E | 0.3303 | 0.8859 | −0.3526 | 0.063* | |
C6 | 0.5761 (4) | 0.7291 (2) | −0.3049 (4) | 0.0398 (8) | |
H6A | 0.6804 | 0.7068 | −0.3075 | 0.060* | |
H6B | 0.5504 | 0.7641 | −0.3988 | 0.060* | |
H6C | 0.5065 | 0.6779 | −0.2997 | 0.060* | |
C7 | 0.9182 (4) | 0.8545 (3) | 0.5213 (4) | 0.0370 (8) | |
H7A | 1.0093 | 0.8337 | 0.4725 | 0.056* | |
H7B | 0.8861 | 0.8087 | 0.5941 | 0.056* | |
H7C | 0.9407 | 0.9108 | 0.5771 | 0.056* | |
C8 | 0.6414 (4) | 0.9862 (2) | 0.5636 (3) | 0.0380 (8) | |
H8A | 0.5498 | 1.0232 | 0.5492 | 0.057* | |
H8B | 0.7294 | 1.0252 | 0.5858 | 0.057* | |
H8C | 0.6304 | 0.9447 | 0.6504 | 0.057* | |
C9 | 0.4943 (3) | 0.76118 (19) | 0.2266 (3) | 0.0224 (5) | |
H9 | 0.5448 | 0.7505 | 0.3314 | 0.027* | |
C10 | 0.5059 (3) | 0.67391 (19) | 0.1379 (3) | 0.0234 (5) | |
C11 | 0.3274 (3) | 0.7848 (2) | 0.2526 (4) | 0.0335 (7) | |
H11A | 0.3234 | 0.8405 | 0.3132 | 0.050* | |
H11B | 0.2809 | 0.7357 | 0.3088 | 0.050* | |
H11C | 0.2719 | 0.7934 | 0.1524 | 0.050* | |
C12 | 0.8995 (3) | 0.98892 (19) | 0.0453 (3) | 0.0233 (5) | |
H12 | 0.9545 | 0.9301 | 0.0439 | 0.028* | |
C13 | 0.9367 (3) | 1.03343 (19) | 0.2019 (3) | 0.0225 (5) | |
C14 | 0.8454 (3) | 1.1009 (2) | 0.2623 (3) | 0.0293 (6) | |
H14 | 0.7545 | 1.1188 | 0.2068 | 0.035* | |
C15 | 0.8879 (4) | 1.1416 (2) | 0.4038 (4) | 0.0352 (7) | |
H15 | 0.8237 | 1.1858 | 0.4452 | 0.042* | |
C16 | 1.0243 (4) | 1.1182 (3) | 0.4855 (4) | 0.0349 (8) | |
H16 | 1.0524 | 1.1463 | 0.5816 | 0.042* | |
C17 | 1.1172 (4) | 1.0538 (2) | 0.4245 (4) | 0.0367 (7) | |
H17 | 1.2106 | 1.0383 | 0.4776 | 0.044* | |
C18 | 1.0728 (3) | 1.0111 (2) | 0.2829 (3) | 0.0290 (6) | |
H18 | 1.1366 | 0.9665 | 0.2423 | 0.035* | |
C19 | 0.9574 (4) | 1.0485 (3) | −0.0862 (3) | 0.0363 (7) | |
H19A | 0.9412 | 1.0171 | −0.1854 | 0.054* | |
H19B | 1.0658 | 1.0605 | −0.0661 | 0.054* | |
H19C | 0.9016 | 1.1056 | −0.0902 | 0.054* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.02021 (15) | 0.01547 (14) | 0.01575 (14) | 0.00054 (15) | −0.00113 (10) | −0.00037 (13) |
O1 | 0.0223 (9) | 0.0268 (11) | 0.0318 (10) | 0.0049 (8) | −0.0024 (8) | 0.0025 (8) |
O2 | 0.0336 (11) | 0.0317 (12) | 0.0378 (12) | 0.0095 (10) | 0.0078 (9) | −0.0055 (10) |
O3 | 0.0268 (10) | 0.0277 (11) | 0.0404 (12) | 0.0101 (9) | −0.0049 (9) | 0.0021 (9) |
O4 | 0.0279 (10) | 0.0310 (12) | 0.0325 (11) | 0.0093 (9) | 0.0004 (9) | −0.0061 (9) |
O5 | 0.0360 (12) | 0.0285 (11) | 0.0365 (12) | −0.0066 (9) | −0.0090 (9) | −0.0054 (9) |
N1 | 0.0241 (10) | 0.0178 (11) | 0.0210 (10) | −0.0022 (8) | 0.0000 (8) | 0.0028 (8) |
N2 | 0.0293 (12) | 0.0172 (11) | 0.0210 (11) | 0.0006 (9) | 0.0056 (9) | −0.0005 (9) |
N3 | 0.0221 (11) | 0.0186 (10) | 0.0280 (12) | 0.0014 (9) | −0.0020 (9) | 0.0024 (9) |
N4 | 0.0240 (11) | 0.0203 (11) | 0.0215 (11) | −0.0004 (9) | 0.0008 (8) | −0.0016 (9) |
N5 | 0.0220 (10) | 0.0176 (10) | 0.0212 (11) | −0.0025 (9) | −0.0019 (9) | 0.0005 (9) |
N6 | 0.0376 (14) | 0.0234 (13) | 0.0391 (15) | 0.0028 (11) | −0.0037 (12) | −0.0011 (11) |
C1 | 0.0321 (13) | 0.0232 (19) | 0.0196 (12) | −0.0071 (11) | −0.0054 (10) | 0.0026 (10) |
C2 | 0.0362 (15) | 0.0210 (14) | 0.0188 (12) | −0.0080 (12) | 0.0029 (11) | −0.0013 (10) |
C3 | 0.0318 (12) | 0.0229 (13) | 0.0223 (11) | −0.0043 (15) | −0.0058 (9) | 0.0035 (14) |
C4 | 0.0327 (14) | 0.0235 (13) | 0.0166 (11) | −0.0066 (12) | −0.0005 (10) | −0.0005 (10) |
C5 | 0.0457 (17) | 0.045 (2) | 0.0327 (15) | −0.001 (2) | −0.0192 (12) | 0.0008 (19) |
C6 | 0.060 (2) | 0.0346 (18) | 0.0248 (15) | −0.0071 (16) | 0.0065 (14) | −0.0118 (13) |
C7 | 0.0427 (16) | 0.0307 (19) | 0.0356 (15) | −0.0060 (16) | −0.0160 (12) | 0.0048 (15) |
C8 | 0.053 (2) | 0.041 (2) | 0.0201 (14) | −0.0085 (16) | 0.0027 (13) | −0.0089 (13) |
C9 | 0.0276 (13) | 0.0198 (13) | 0.0197 (12) | −0.0033 (11) | 0.0000 (10) | 0.0012 (10) |
C10 | 0.0270 (13) | 0.0186 (12) | 0.0248 (12) | −0.0041 (11) | 0.0022 (10) | 0.0045 (10) |
C11 | 0.0314 (15) | 0.0307 (16) | 0.0396 (16) | −0.0023 (13) | 0.0133 (13) | 0.0040 (13) |
C12 | 0.0220 (12) | 0.0229 (14) | 0.0252 (13) | 0.0014 (10) | 0.0022 (10) | −0.0016 (10) |
C13 | 0.0208 (12) | 0.0218 (13) | 0.0248 (13) | −0.0033 (10) | 0.0010 (10) | 0.0005 (10) |
C14 | 0.0286 (14) | 0.0258 (15) | 0.0327 (15) | 0.0041 (12) | −0.0048 (12) | −0.0050 (12) |
C15 | 0.0414 (17) | 0.0274 (15) | 0.0365 (16) | 0.0024 (13) | −0.0015 (13) | −0.0071 (13) |
C16 | 0.046 (2) | 0.0319 (15) | 0.0254 (15) | −0.0088 (15) | −0.0075 (14) | 0.0002 (12) |
C17 | 0.0321 (15) | 0.0403 (18) | 0.0358 (16) | −0.0049 (14) | −0.0134 (12) | 0.0049 (14) |
C18 | 0.0231 (13) | 0.0315 (15) | 0.0319 (14) | −0.0002 (12) | −0.0024 (11) | 0.0003 (12) |
C19 | 0.0323 (15) | 0.0474 (19) | 0.0293 (14) | −0.0093 (14) | 0.0039 (12) | 0.0002 (14) |
Geometric parameters (Å, º) top
Co1—N4 | 1.879 (2) | C6—H6A | 0.9700 |
Co1—N2 | 1.888 (2) | C6—H6B | 0.9700 |
Co1—N1 | 1.890 (2) | C6—H6C | 0.9700 |
Co1—N3 | 1.892 (2) | C7—H7A | 0.9700 |
Co1—N5 | 2.077 (2) | C7—H7B | 0.9700 |
Co1—C9 | 2.092 (3) | C7—H7C | 0.9700 |
O1—N1 | 1.334 (3) | C8—H8A | 0.9700 |
O2—N2 | 1.365 (3) | C8—H8B | 0.9700 |
O2—H2 | 0.8300 | C8—H8C | 0.9700 |
O3—N3 | 1.334 (3) | C9—C10 | 1.497 (4) |
O4—N4 | 1.356 (3) | C9—C11 | 1.529 (4) |
O4—H4 | 0.8300 | C9—H9 | 0.9900 |
O5—C10 | 1.236 (3) | C11—H11A | 0.9700 |
N1—C1 | 1.301 (4) | C11—H11B | 0.9700 |
N2—C2 | 1.294 (4) | C11—H11C | 0.9700 |
N3—C3 | 1.306 (4) | C12—C13 | 1.511 (4) |
N4—C4 | 1.294 (3) | C12—C19 | 1.535 (4) |
N5—C12 | 1.500 (3) | C12—H12 | 0.9900 |
N5—H5A | 0.9100 | C13—C18 | 1.382 (4) |
N5—H5B | 0.9100 | C13—C14 | 1.391 (4) |
N6—C10 | 1.350 (4) | C14—C15 | 1.383 (4) |
N6—H6D | 0.83 (5) | C14—H14 | 0.9400 |
N6—H6E | 0.92 (5) | C15—C16 | 1.391 (5) |
C1—C2 | 1.463 (4) | C15—H15 | 0.9400 |
C1—C5 | 1.499 (4) | C16—C17 | 1.371 (5) |
C2—C6 | 1.490 (4) | C16—H16 | 0.9400 |
C3—C4 | 1.469 (5) | C17—C18 | 1.400 (4) |
C3—C7 | 1.498 (4) | C17—H17 | 0.9400 |
C4—C8 | 1.498 (4) | C18—H18 | 0.9400 |
C5—H5C | 0.9700 | C19—H19A | 0.9700 |
C5—H5D | 0.9700 | C19—H19B | 0.9700 |
C5—H5E | 0.9700 | C19—H19C | 0.9700 |
| | | |
N4—Co1—N2 | 179.7 (1) | H6A—C6—H6C | 109.5 |
N4—Co1—N1 | 98.4 (1) | H6B—C6—H6C | 109.5 |
N2—Co1—N1 | 81.4 (1) | C3—C7—H7A | 109.5 |
N4—Co1—N3 | 81.7 (1) | C3—C7—H7B | 109.5 |
N2—Co1—N3 | 98.6 (1) | H7A—C7—H7B | 109.5 |
N1—Co1—N3 | 177.8 (1) | C3—C7—H7C | 109.5 |
N4—Co1—N5 | 92.2 (1) | H7A—C7—H7C | 109.5 |
N2—Co1—N5 | 87.7 (1) | H7B—C7—H7C | 109.5 |
N1—Co1—N5 | 87.64 (9) | C4—C8—H8A | 109.5 |
N3—Co1—N5 | 94.5 (1) | C4—C8—H8B | 109.5 |
N4—Co1—C9 | 87.2 (1) | H8A—C8—H8B | 109.5 |
N2—Co1—C9 | 92.9 (1) | C4—C8—H8C | 109.5 |
N1—Co1—C9 | 89.9 (1) | H8A—C8—H8C | 109.5 |
N3—Co1—C9 | 88.0 (1) | H8B—C8—H8C | 109.5 |
N5—Co1—C9 | 177.3 (1) | C10—C9—C11 | 111.2 (2) |
N2—O2—H2 | 109.5 | C10—C9—Co1 | 110.8 (2) |
N4—O4—H4 | 109.5 | C11—C9—Co1 | 114.7 (2) |
C1—N1—O1 | 121.0 (2) | C10—C9—H9 | 106.5 |
C1—N1—Co1 | 116.2 (2) | C11—C9—H9 | 106.5 |
O1—N1—Co1 | 122.9 (2) | Co1—C9—H9 | 106.5 |
C2—N2—O2 | 119.3 (2) | O5—C10—N6 | 121.1 (3) |
C2—N2—Co1 | 117.0 (2) | O5—C10—C9 | 122.2 (3) |
O2—N2—Co1 | 123.7 (2) | N6—C10—C9 | 116.6 (3) |
C3—N3—O3 | 121.4 (2) | C9—C11—H11A | 109.5 |
C3—N3—Co1 | 116.1 (2) | C9—C11—H11B | 109.5 |
O3—N3—Co1 | 122.4 (2) | H11A—C11—H11B | 109.5 |
C4—N4—O4 | 119.3 (2) | C9—C11—H11C | 109.5 |
C4—N4—Co1 | 116.9 (2) | H11A—C11—H11C | 109.5 |
O4—N4—Co1 | 123.8 (2) | H11B—C11—H11C | 109.5 |
C12—N5—Co1 | 123.7 (2) | N5—C12—C13 | 112.4 (2) |
C12—N5—H5A | 106.4 | N5—C12—C19 | 110.4 (2) |
Co1—N5—H5A | 106.4 | C13—C12—C19 | 109.9 (2) |
C12—N5—H5B | 106.4 | N5—C12—H12 | 108.0 |
Co1—N5—H5B | 106.4 | C13—C12—H12 | 108.0 |
H5A—N5—H5B | 106.5 | C19—C12—H12 | 108.0 |
C10—N6—H6D | 109 (3) | C18—C13—C14 | 118.6 (3) |
C10—N6—H6E | 118 (3) | C18—C13—C12 | 118.6 (3) |
H6D—N6—H6E | 128 (4) | C14—C13—C12 | 122.7 (2) |
N1—C1—C2 | 113.0 (2) | C15—C14—C13 | 120.2 (3) |
N1—C1—C5 | 122.4 (3) | C15—C14—H14 | 119.9 |
C2—C1—C5 | 124.5 (3) | C13—C14—H14 | 119.9 |
N2—C2—C1 | 112.3 (2) | C14—C15—C16 | 120.9 (3) |
N2—C2—C6 | 123.7 (3) | C14—C15—H15 | 119.6 |
C1—C2—C6 | 124.0 (3) | C16—C15—H15 | 119.6 |
N3—C3—C4 | 112.5 (2) | C17—C16—C15 | 119.2 (3) |
N3—C3—C7 | 123.8 (3) | C17—C16—H16 | 120.4 |
C4—C3—C7 | 123.7 (3) | C15—C16—H16 | 120.4 |
N4—C4—C3 | 112.7 (2) | C16—C17—C18 | 120.0 (3) |
N4—C4—C8 | 123.3 (3) | C16—C17—H17 | 120.0 |
C3—C4—C8 | 124.0 (2) | C18—C17—H17 | 120.0 |
C1—C5—H5C | 109.5 | C13—C18—C17 | 121.1 (3) |
C1—C5—H5D | 109.5 | C13—C18—H18 | 119.5 |
H5C—C5—H5D | 109.5 | C17—C18—H18 | 119.5 |
C1—C5—H5E | 109.5 | C12—C19—H19A | 109.5 |
H5C—C5—H5E | 109.5 | C12—C19—H19B | 109.5 |
H5D—C5—H5E | 109.5 | H19A—C19—H19B | 109.5 |
C2—C6—H6A | 109.5 | C12—C19—H19C | 109.5 |
C2—C6—H6B | 109.5 | H19A—C19—H19C | 109.5 |
H6A—C6—H6B | 109.5 | H19B—C19—H19C | 109.5 |
C2—C6—H6C | 109.5 | | |
| | | |
N4—Co1—N1—C1 | −176.5 (2) | Co1—N2—C2—C6 | −176.2 (2) |
N2—Co1—N1—C1 | 3.6 (2) | N1—C1—C2—N2 | −0.4 (4) |
N5—Co1—N1—C1 | 91.6 (2) | C5—C1—C2—N2 | −179.5 (3) |
C9—Co1—N1—C1 | −89.4 (2) | N1—C1—C2—C6 | 179.2 (3) |
N4—Co1—N1—O1 | 4.0 (2) | C5—C1—C2—C6 | 0.1 (5) |
N2—Co1—N1—O1 | −175.8 (2) | O3—N3—C3—C4 | 179.6 (2) |
N5—Co1—N1—O1 | −87.8 (2) | Co1—N3—C3—C4 | −1.3 (4) |
C9—Co1—N1—O1 | 91.2 (2) | O3—N3—C3—C7 | 1.7 (5) |
N1—Co1—N2—C2 | −3.9 (2) | Co1—N3—C3—C7 | −179.2 (3) |
N3—Co1—N2—C2 | 173.9 (2) | O4—N4—C4—C3 | −177.6 (2) |
N5—Co1—N2—C2 | −91.8 (2) | Co1—N4—C4—C3 | 2.2 (3) |
C9—Co1—N2—C2 | 85.5 (2) | O4—N4—C4—C8 | 1.0 (4) |
N1—Co1—N2—O2 | 174.8 (2) | Co1—N4—C4—C8 | −179.2 (2) |
N3—Co1—N2—O2 | −7.5 (2) | N3—C3—C4—N4 | −0.6 (4) |
N5—Co1—N2—O2 | 86.8 (2) | C7—C3—C4—N4 | 177.4 (3) |
C9—Co1—N2—O2 | −95.8 (2) | N3—C3—C4—C8 | −179.2 (3) |
N4—Co1—N3—C3 | 1.9 (2) | C7—C3—C4—C8 | −1.3 (5) |
N2—Co1—N3—C3 | −178.2 (2) | N4—Co1—C9—C10 | −174.4 (2) |
N5—Co1—N3—C3 | 93.4 (2) | N2—Co1—C9—C10 | 5.9 (2) |
C9—Co1—N3—C3 | −85.6 (2) | N1—Co1—C9—C10 | 87.3 (2) |
N4—Co1—N3—O3 | −179.0 (2) | N3—Co1—C9—C10 | −92.5 (2) |
N2—Co1—N3—O3 | 0.9 (2) | N4—Co1—C9—C11 | 58.7 (2) |
N5—Co1—N3—O3 | −87.5 (2) | N2—Co1—C9—C11 | −121.1 (2) |
C9—Co1—N3—O3 | 93.5 (2) | N1—Co1—C9—C11 | −39.7 (2) |
N1—Co1—N4—C4 | 175.5 (2) | N3—Co1—C9—C11 | 140.5 (2) |
N3—Co1—N4—C4 | −2.3 (2) | C11—C9—C10—O5 | 32.0 (4) |
N5—Co1—N4—C4 | −96.6 (2) | Co1—C9—C10—O5 | −96.9 (3) |
C9—Co1—N4—C4 | 86.0 (2) | C11—C9—C10—N6 | −145.2 (3) |
N1—Co1—N4—O4 | −4.7 (2) | Co1—C9—C10—N6 | 85.9 (3) |
N3—Co1—N4—O4 | 177.5 (2) | Co1—N5—C12—C13 | −75.4 (3) |
N5—Co1—N4—O4 | 83.2 (2) | Co1—N5—C12—C19 | 161.4 (2) |
C9—Co1—N4—O4 | −94.1 (2) | N5—C12—C13—C18 | 144.5 (3) |
N4—Co1—N5—C12 | 89.8 (2) | C19—C12—C13—C18 | −92.1 (3) |
N2—Co1—N5—C12 | −90.4 (2) | N5—C12—C13—C14 | −40.5 (4) |
N1—Co1—N5—C12 | −171.9 (2) | C19—C12—C13—C14 | 82.9 (3) |
N3—Co1—N5—C12 | 8.0 (2) | C18—C13—C14—C15 | −2.6 (5) |
O1—N1—C1—C2 | 176.7 (2) | C12—C13—C14—C15 | −177.6 (3) |
Co1—N1—C1—C2 | −2.7 (3) | C13—C14—C15—C16 | 2.1 (5) |
O1—N1—C1—C5 | −4.2 (4) | C14—C15—C16—C17 | −0.1 (5) |
Co1—N1—C1—C5 | 176.4 (3) | C15—C16—C17—C18 | −1.3 (5) |
O2—N2—C2—C1 | −175.3 (2) | C14—C13—C18—C17 | 1.3 (4) |
Co1—N2—C2—C1 | 3.4 (3) | C12—C13—C18—C17 | 176.5 (3) |
O2—N2—C2—C6 | 5.1 (4) | C16—C17—C18—C13 | 0.6 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3 | 0.83 | 1.73 | 2.515 (3) | 158 |
O4—H4···O1 | 0.83 | 1.71 | 2.506 (3) | 160 |
N5—H5B···O5i | 0.91 | 2.12 | 2.925 (3) | 147 |
N6—H6D···O3 | 0.83 (5) | 2.53 (5) | 3.249 (4) | 145 (4) |
N6—H6E···O1ii | 0.92 (5) | 2.10 (5) | 3.021 (4) | 176 (4) |
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) −x+1, y−1/2, −z. |
(II) bis(dimethylglyoximato-
κ2N,
N')[(
R)-1-(
N-methylcarbamoyl)ethyl][(
R)- 1-phenylethylamine]cobalt(III) monohydrate
top
Crystal data top
[Co(C4H8NO)(C4H7N2O2)2(C8H11N)]·H2O | F(000) = 1088 |
Mr = 514.47 | Dx = 1.380 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P2ac2ab | Cell parameters from 25 reflections |
a = 14.1206 (19) Å | θ = 12.8–14.7° |
b = 14.169 (2) Å | µ = 0.74 mm−1 |
c = 12.372 (2) Å | T = 293 K |
V = 2475.3 (6) Å3 | Needle, red |
Z = 4 | 0.25 × 0.15 × 0.12 mm |
Data collection top
Rigaku AFC-7R diffractometer | 1749 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.039 |
Graphite monochromator | θmax = 27.5°, θmin = 2.6° |
ω/2θ scans | h = −10→18 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→18 |
Tmin = 0.838, Tmax = 0.917 | l = −9→16 |
4662 measured reflections | 3 standard reflections every 100 reflections |
3581 independent reflections | intensity decay: −0.8% |
Refinement top
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)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.029P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max < 0.001 |
3581 reflections | Δρmax = 0.43 e Å−3 |
317 parameters | Δρmin = −0.80 e Å−3 |
2 restraints | Absolute structure: Flack (1983), with how many Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (3) |
Crystal data top
[Co(C4H8NO)(C4H7N2O2)2(C8H11N)]·H2O | V = 2475.3 (6) Å3 |
Mr = 514.47 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 14.1206 (19) Å | µ = 0.74 mm−1 |
b = 14.169 (2) Å | T = 293 K |
c = 12.372 (2) Å | 0.25 × 0.15 × 0.12 mm |
Data collection top
Rigaku AFC-7R diffractometer | 1749 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.039 |
Tmin = 0.838, Tmax = 0.917 | 3 standard reflections every 100 reflections |
4662 measured reflections | intensity decay: −0.8% |
3581 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.105 | Δρmax = 0.43 e Å−3 |
S = 0.98 | Δρmin = −0.80 e Å−3 |
3581 reflections | Absolute structure: Flack (1983), with how many Friedel pairs |
317 parameters | Absolute structure parameter: 0.02 (3) |
2 restraints | |
Special details top
Experimental. 1H NMR (CDCl3, p.p.m.): 0.33 (3H, d), 1.23 (3H, d), 1.44 (1H, dd), 1.85 (1H, q), 2.17 (12H, d), 2.25 (1H, dd), 2.52 (3H, d), 3.62 (1H, m), 5.32 (1H, q), 7.05–7.37 (m). |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.42129 (6) | 0.26852 (6) | 0.32901 (7) | 0.0319 (2) | |
O1 | 0.4301 (4) | 0.0758 (3) | 0.4031 (3) | 0.0452 (12) | |
H1 | 0.4232 | 0.0704 | 0.3376 | 0.068* | |
O2 | 0.4526 (3) | 0.4341 (3) | 0.4552 (4) | 0.0550 (15) | |
O3 | 0.4225 (4) | 0.4594 (3) | 0.2582 (4) | 0.0550 (13) | |
H3 | 0.4349 | 0.4633 | 0.3228 | 0.082* | |
O4 | 0.4000 (3) | 0.1035 (3) | 0.2035 (3) | 0.0431 (13) | |
O5 | 0.2098 (3) | 0.1949 (3) | 0.4989 (4) | 0.0516 (14) | |
O6 | 0.2008 (4) | 0.0629 (3) | 0.6684 (5) | 0.0693 (15) | |
H6F | 0.156 (4) | 0.014 (4) | 0.650 (6) | 0.083* | |
H6G | 0.201 (5) | 0.096 (5) | 0.601 (4) | 0.083* | |
N1 | 0.4319 (4) | 0.1690 (4) | 0.4298 (4) | 0.0372 (14) | |
N2 | 0.4416 (4) | 0.3403 (4) | 0.4557 (4) | 0.0397 (16) | |
N3 | 0.4104 (4) | 0.3685 (4) | 0.2313 (4) | 0.0362 (15) | |
N4 | 0.3993 (3) | 0.1970 (4) | 0.2021 (4) | 0.0315 (14) | |
N5 | 0.2240 (4) | 0.1159 (4) | 0.3431 (5) | 0.0411 (13) | |
H5 | 0.2360 | 0.1189 | 0.2750 | 0.049* | |
N6 | 0.5669 (3) | 0.2641 (3) | 0.3100 (3) | 0.0360 (12) | |
H6D | 0.5851 | 0.3226 | 0.2910 | 0.043* | |
H6E | 0.5915 | 0.2532 | 0.3760 | 0.043* | |
C1 | 0.4424 (5) | 0.1925 (5) | 0.5307 (6) | 0.0374 (17) | |
C2 | 0.4483 (5) | 0.2935 (5) | 0.5466 (5) | 0.0405 (19) | |
C3 | 0.3893 (5) | 0.3468 (5) | 0.1328 (5) | 0.0375 (18) | |
C4 | 0.3844 (4) | 0.2456 (4) | 0.1147 (5) | 0.0316 (16) | |
C5 | 0.4486 (5) | 0.1210 (5) | 0.6200 (5) | 0.059 (2) | |
H5A | 0.4794 | 0.0652 | 0.5938 | 0.089* | |
H5B | 0.3860 | 0.1053 | 0.6443 | 0.089* | |
H5C | 0.4843 | 0.1469 | 0.6791 | 0.089* | |
C6 | 0.4635 (5) | 0.3421 (5) | 0.6533 (5) | 0.058 (2) | |
H6A | 0.4367 | 0.4043 | 0.6505 | 0.087* | |
H6B | 0.5301 | 0.3465 | 0.6678 | 0.087* | |
H6C | 0.4333 | 0.3065 | 0.7096 | 0.087* | |
C7 | 0.3748 (5) | 0.4193 (5) | 0.0462 (5) | 0.057 (2) | |
H7A | 0.4120 | 0.4742 | 0.0623 | 0.085* | |
H7B | 0.3091 | 0.4362 | 0.0429 | 0.085* | |
H7C | 0.3942 | 0.3937 | −0.0222 | 0.085* | |
C8 | 0.3672 (5) | 0.2002 (5) | 0.0070 (5) | 0.055 (2) | |
H8A | 0.3379 | 0.1398 | 0.0174 | 0.082* | |
H8B | 0.4265 | 0.1921 | −0.0299 | 0.082* | |
H8C | 0.3263 | 0.2397 | −0.0354 | 0.082* | |
C9 | 0.2752 (4) | 0.2786 (4) | 0.3471 (5) | 0.0377 (16) | |
H9 | 0.2489 | 0.2781 | 0.2738 | 0.045* | |
C10 | 0.2342 (5) | 0.1939 (5) | 0.4035 (6) | 0.0358 (17) | |
C11 | 0.1930 (5) | 0.0255 (5) | 0.3894 (5) | 0.056 (2) | |
H11A | 0.1710 | −0.0151 | 0.3325 | 0.084* | |
H11B | 0.1426 | 0.0365 | 0.4399 | 0.084* | |
H11C | 0.2452 | −0.0039 | 0.4259 | 0.084* | |
C12 | 0.2403 (5) | 0.3703 (5) | 0.3996 (6) | 0.058 (2) | |
H12A | 0.2723 | 0.4231 | 0.3676 | 0.087* | |
H12B | 0.2533 | 0.3687 | 0.4757 | 0.087* | |
H12C | 0.1733 | 0.3766 | 0.3884 | 0.087* | |
C13 | 0.6150 (4) | 0.1976 (5) | 0.2341 (5) | 0.0374 (18) | |
H13 | 0.5831 | 0.1362 | 0.2384 | 0.045* | |
C14 | 0.6111 (4) | 0.2314 (5) | 0.1186 (5) | 0.0352 (16) | |
C15 | 0.6140 (5) | 0.3244 (5) | 0.0864 (6) | 0.0416 (19) | |
H15 | 0.6153 | 0.3717 | 0.1386 | 0.050* | |
C16 | 0.6151 (5) | 0.3490 (6) | −0.0212 (7) | 0.060 (2) | |
H16 | 0.6152 | 0.4123 | −0.0412 | 0.073* | |
C17 | 0.6160 (5) | 0.2807 (8) | −0.0981 (6) | 0.069 (3) | |
H17 | 0.6166 | 0.2977 | −0.1708 | 0.082* | |
C18 | 0.6161 (6) | 0.1875 (7) | −0.0704 (7) | 0.067 (3) | |
H18 | 0.6183 | 0.1411 | −0.1235 | 0.081* | |
C19 | 0.6129 (5) | 0.1629 (5) | 0.0371 (6) | 0.054 (2) | |
H19 | 0.6120 | 0.0994 | 0.0560 | 0.065* | |
C20 | 0.7181 (5) | 0.1843 (6) | 0.2658 (6) | 0.069 (3) | |
H20A | 0.7214 | 0.1567 | 0.3365 | 0.103* | |
H20B | 0.7494 | 0.2444 | 0.2662 | 0.103* | |
H20C | 0.7485 | 0.1433 | 0.2146 | 0.103* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0353 (4) | 0.0307 (4) | 0.0296 (4) | −0.0015 (4) | −0.0001 (5) | 0.0016 (4) |
O1 | 0.055 (3) | 0.031 (2) | 0.050 (3) | 0.003 (3) | 0.003 (3) | −0.001 (2) |
O2 | 0.067 (4) | 0.038 (3) | 0.060 (3) | −0.011 (3) | −0.006 (3) | −0.008 (2) |
O3 | 0.080 (4) | 0.030 (3) | 0.055 (3) | −0.007 (3) | −0.002 (3) | 0.005 (2) |
O4 | 0.056 (3) | 0.031 (3) | 0.042 (3) | 0.001 (2) | 0.007 (2) | −0.006 (2) |
O5 | 0.068 (4) | 0.052 (3) | 0.036 (3) | −0.006 (3) | 0.017 (3) | 0.000 (3) |
O6 | 0.093 (4) | 0.062 (4) | 0.053 (3) | −0.017 (3) | −0.006 (4) | 0.014 (3) |
N1 | 0.032 (4) | 0.035 (3) | 0.044 (3) | 0.000 (3) | −0.008 (3) | 0.003 (3) |
N2 | 0.042 (4) | 0.045 (4) | 0.032 (3) | −0.004 (3) | 0.004 (3) | −0.002 (3) |
N3 | 0.041 (4) | 0.030 (3) | 0.038 (4) | −0.003 (3) | −0.001 (3) | 0.007 (3) |
N4 | 0.026 (3) | 0.028 (3) | 0.041 (3) | −0.002 (2) | 0.000 (2) | −0.007 (2) |
N5 | 0.041 (3) | 0.047 (3) | 0.035 (3) | 0.000 (3) | 0.005 (3) | 0.006 (3) |
N6 | 0.037 (3) | 0.040 (3) | 0.031 (3) | 0.000 (3) | −0.002 (3) | 0.005 (3) |
C1 | 0.024 (4) | 0.048 (4) | 0.041 (4) | −0.002 (3) | 0.003 (3) | 0.010 (3) |
C2 | 0.037 (5) | 0.059 (5) | 0.026 (4) | −0.010 (4) | 0.002 (3) | 0.001 (4) |
C3 | 0.033 (4) | 0.049 (5) | 0.030 (4) | −0.001 (4) | −0.003 (3) | 0.010 (3) |
C4 | 0.028 (3) | 0.042 (5) | 0.024 (3) | −0.004 (3) | −0.002 (3) | 0.000 (3) |
C5 | 0.072 (6) | 0.060 (5) | 0.046 (5) | −0.005 (4) | −0.010 (4) | 0.019 (4) |
C6 | 0.052 (5) | 0.095 (6) | 0.026 (4) | −0.015 (4) | −0.008 (4) | −0.007 (4) |
C7 | 0.058 (5) | 0.058 (5) | 0.053 (5) | −0.008 (4) | −0.011 (4) | 0.021 (4) |
C8 | 0.045 (4) | 0.082 (6) | 0.038 (4) | −0.013 (4) | −0.005 (3) | −0.019 (4) |
C9 | 0.027 (3) | 0.040 (4) | 0.046 (4) | 0.004 (3) | 0.006 (3) | 0.004 (4) |
C10 | 0.028 (4) | 0.044 (4) | 0.035 (4) | −0.004 (3) | −0.004 (3) | 0.002 (4) |
C11 | 0.059 (5) | 0.046 (5) | 0.063 (5) | −0.005 (4) | 0.009 (4) | 0.007 (4) |
C12 | 0.045 (5) | 0.047 (5) | 0.082 (6) | 0.016 (4) | 0.016 (5) | 0.005 (4) |
C13 | 0.033 (4) | 0.036 (4) | 0.044 (4) | 0.007 (3) | −0.002 (3) | −0.003 (3) |
C14 | 0.027 (3) | 0.046 (4) | 0.032 (3) | −0.004 (4) | 0.005 (3) | −0.007 (4) |
C15 | 0.044 (5) | 0.042 (5) | 0.039 (4) | −0.002 (4) | 0.002 (3) | 0.003 (3) |
C16 | 0.045 (5) | 0.072 (6) | 0.064 (6) | 0.001 (4) | 0.010 (4) | 0.023 (5) |
C17 | 0.053 (5) | 0.119 (8) | 0.033 (4) | −0.009 (6) | 0.000 (4) | 0.012 (6) |
C18 | 0.053 (6) | 0.101 (7) | 0.047 (5) | −0.013 (5) | 0.007 (4) | −0.015 (5) |
C19 | 0.062 (6) | 0.050 (5) | 0.052 (5) | 0.000 (4) | −0.001 (4) | −0.004 (4) |
C20 | 0.053 (5) | 0.104 (7) | 0.049 (5) | 0.026 (5) | −0.002 (4) | −0.002 (5) |
Geometric parameters (Å, º) top
Co1—N3 | 1.868 (5) | C6—H6B | 0.9600 |
Co1—N1 | 1.889 (5) | C6—H6C | 0.9600 |
Co1—N2 | 1.890 (5) | C7—H7A | 0.9600 |
Co1—N4 | 1.894 (5) | C7—H7B | 0.9600 |
Co1—N6 | 2.070 (4) | C7—H7C | 0.9600 |
Co1—C9 | 2.080 (5) | C8—H8A | 0.9600 |
O1—N1 | 1.362 (6) | C8—H8B | 0.9600 |
O1—H1 | 0.8200 | C8—H8C | 0.9600 |
O2—N2 | 1.339 (6) | C9—C10 | 1.504 (8) |
O3—N3 | 1.342 (6) | C9—C12 | 1.534 (8) |
O3—H3 | 0.8200 | C9—H9 | 0.9800 |
O4—N4 | 1.326 (6) | C11—H11A | 0.9600 |
O5—C10 | 1.229 (7) | C11—H11B | 0.9600 |
O6—H6F | 0.97 (3) | C11—H11C | 0.9600 |
O6—H6G | 0.96 (3) | C12—H12A | 0.9600 |
N1—C1 | 1.300 (8) | C12—H12B | 0.9600 |
N2—C2 | 1.310 (8) | C12—H12C | 0.9600 |
N3—C3 | 1.292 (7) | C13—C14 | 1.508 (8) |
N4—C4 | 1.298 (7) | C13—C20 | 1.519 (8) |
N5—C10 | 1.342 (8) | C13—H13 | 0.9800 |
N5—C11 | 1.470 (8) | C14—C15 | 1.377 (9) |
N5—H5 | 0.8600 | C14—C19 | 1.400 (8) |
N6—C13 | 1.494 (7) | C15—C16 | 1.376 (9) |
N6—H6D | 0.9000 | C15—H15 | 0.9300 |
N6—H6E | 0.9000 | C16—C17 | 1.357 (10) |
C1—C2 | 1.447 (9) | C16—H16 | 0.9300 |
C1—C5 | 1.501 (8) | C17—C18 | 1.365 (11) |
C2—C6 | 1.504 (8) | C17—H17 | 0.9300 |
C3—C4 | 1.453 (9) | C18—C19 | 1.375 (10) |
C3—C7 | 1.498 (8) | C18—H18 | 0.9300 |
C4—C8 | 1.500 (8) | C19—H19 | 0.9300 |
C5—H5A | 0.9600 | C20—H20A | 0.9600 |
C5—H5B | 0.9600 | C20—H20B | 0.9600 |
C5—H5C | 0.9600 | C20—H20C | 0.9600 |
C6—H6A | 0.9600 | | |
| | | |
N3—Co1—N1 | 179.0 (3) | C3—C7—H7A | 109.5 |
N3—Co1—N2 | 98.1 (2) | C3—C7—H7B | 109.5 |
N1—Co1—N2 | 80.9 (2) | H7A—C7—H7B | 109.5 |
N3—Co1—N4 | 81.7 (2) | C3—C7—H7C | 109.5 |
N1—Co1—N4 | 99.3 (2) | H7A—C7—H7C | 109.5 |
N2—Co1—N4 | 179.3 (2) | H7B—C7—H7C | 109.5 |
N3—Co1—N6 | 91.8 (2) | C4—C8—H8A | 109.5 |
N1—Co1—N6 | 88.5 (2) | C4—C8—H8B | 109.5 |
N2—Co1—N6 | 87.7 (2) | H8A—C8—H8B | 109.5 |
N4—Co1—N6 | 93.0 (2) | C4—C8—H8C | 109.5 |
N3—Co1—C9 | 86.3 (3) | H8A—C8—H8C | 109.5 |
N1—Co1—C9 | 93.4 (3) | H8B—C8—H8C | 109.5 |
N2—Co1—C9 | 91.4 (3) | C10—C9—C12 | 110.8 (5) |
N4—Co1—C9 | 87.9 (2) | C10—C9—Co1 | 112.1 (4) |
N6—Co1—C9 | 177.8 (2) | C12—C9—Co1 | 115.0 (4) |
N1—O1—H1 | 109.5 | C10—C9—H9 | 106.0 |
N3—O3—H3 | 109.5 | C12—C9—H9 | 106.0 |
H6F—O6—H6G | 99 (6) | Co1—C9—H9 | 106.0 |
C1—N1—O1 | 118.9 (5) | O5—C10—N5 | 120.9 (6) |
C1—N1—Co1 | 116.9 (5) | O5—C10—C9 | 123.0 (7) |
O1—N1—Co1 | 124.2 (4) | N5—C10—C9 | 116.1 (6) |
C2—N2—O2 | 119.9 (6) | N5—C11—H11A | 109.5 |
C2—N2—Co1 | 116.8 (5) | N5—C11—H11B | 109.5 |
O2—N2—Co1 | 123.2 (4) | H11A—C11—H11B | 109.5 |
C3—N3—O3 | 119.5 (6) | N5—C11—H11C | 109.5 |
C3—N3—Co1 | 116.7 (5) | H11A—C11—H11C | 109.5 |
O3—N3—Co1 | 123.8 (4) | H11B—C11—H11C | 109.5 |
C4—N4—O4 | 122.8 (5) | C9—C12—H12A | 109.5 |
C4—N4—Co1 | 115.7 (4) | C9—C12—H12B | 109.5 |
O4—N4—Co1 | 121.5 (4) | H12A—C12—H12B | 109.5 |
C10—N5—C11 | 122.2 (5) | C9—C12—H12C | 109.5 |
C10—N5—H5 | 118.9 | H12A—C12—H12C | 109.5 |
C11—N5—H5 | 118.9 | H12B—C12—H12C | 109.5 |
C13—N6—Co1 | 122.8 (4) | N6—C13—C14 | 112.2 (5) |
C13—N6—H6D | 106.6 | N6—C13—C20 | 110.6 (5) |
Co1—N6—H6D | 106.6 | C14—C13—C20 | 108.6 (5) |
C13—N6—H6E | 106.6 | N6—C13—H13 | 108.4 |
Co1—N6—H6E | 106.6 | C14—C13—H13 | 108.4 |
H6D—N6—H6E | 106.6 | C20—C13—H13 | 108.4 |
N1—C1—C2 | 112.9 (6) | C15—C14—C19 | 117.1 (6) |
N1—C1—C5 | 122.7 (7) | C15—C14—C13 | 125.3 (6) |
C2—C1—C5 | 124.3 (7) | C19—C14—C13 | 117.4 (7) |
N2—C2—C1 | 112.3 (6) | C16—C15—C14 | 121.5 (7) |
N2—C2—C6 | 122.1 (6) | C16—C15—H15 | 119.3 |
C1—C2—C6 | 125.5 (7) | C14—C15—H15 | 119.3 |
N3—C3—C4 | 113.0 (6) | C17—C16—C15 | 119.9 (8) |
N3—C3—C7 | 122.9 (7) | C17—C16—H16 | 120.1 |
C4—C3—C7 | 124.1 (6) | C15—C16—H16 | 120.1 |
N4—C4—C3 | 112.8 (6) | C16—C17—C18 | 120.9 (8) |
N4—C4—C8 | 122.6 (6) | C16—C17—H17 | 119.6 |
C3—C4—C8 | 124.6 (6) | C18—C17—H17 | 119.6 |
C1—C5—H5A | 109.5 | C17—C18—C19 | 119.2 (8) |
C1—C5—H5B | 109.5 | C17—C18—H18 | 120.4 |
H5A—C5—H5B | 109.5 | C19—C18—H18 | 120.4 |
C1—C5—H5C | 109.5 | C18—C19—C14 | 121.4 (7) |
H5A—C5—H5C | 109.5 | C18—C19—H19 | 119.3 |
H5B—C5—H5C | 109.5 | C14—C19—H19 | 119.3 |
C2—C6—H6A | 109.5 | C13—C20—H20A | 109.5 |
C2—C6—H6B | 109.5 | C13—C20—H20B | 109.5 |
H6A—C6—H6B | 109.5 | H20A—C20—H20B | 109.5 |
C2—C6—H6C | 109.5 | C13—C20—H20C | 109.5 |
H6A—C6—H6C | 109.5 | H20A—C20—H20C | 109.5 |
H6B—C6—H6C | 109.5 | H20B—C20—H20C | 109.5 |
| | | |
N2—Co1—N1—C1 | 3.1 (5) | N1—C1—C2—N2 | 0.1 (10) |
N4—Co1—N1—C1 | −176.2 (5) | C5—C1—C2—N2 | 179.6 (6) |
N6—Co1—N1—C1 | 91.0 (5) | N1—C1—C2—C6 | −178.0 (6) |
C9—Co1—N1—C1 | −87.8 (6) | C5—C1—C2—C6 | 1.5 (12) |
N2—Co1—N1—O1 | −176.2 (6) | O3—N3—C3—C4 | 176.4 (6) |
N4—Co1—N1—O1 | 4.5 (6) | Co1—N3—C3—C4 | −4.1 (8) |
N6—Co1—N1—O1 | −88.3 (6) | O3—N3—C3—C7 | −1.7 (11) |
C9—Co1—N1—O1 | 92.9 (6) | Co1—N3—C3—C7 | 177.8 (5) |
N3—Co1—N2—C2 | 176.7 (5) | O4—N4—C4—C3 | −178.6 (5) |
N1—Co1—N2—C2 | −3.0 (5) | Co1—N4—C4—C3 | 1.0 (7) |
N6—Co1—N2—C2 | −91.8 (5) | O4—N4—C4—C8 | −0.5 (9) |
C9—Co1—N2—C2 | 90.2 (5) | Co1—N4—C4—C8 | 179.1 (4) |
N3—Co1—N2—O2 | −5.8 (5) | N3—C3—C4—N4 | 2.0 (9) |
N1—Co1—N2—O2 | 174.5 (6) | C7—C3—C4—N4 | −180.0 (6) |
N6—Co1—N2—O2 | 85.6 (5) | N3—C3—C4—C8 | −176.0 (6) |
C9—Co1—N2—O2 | −92.3 (5) | C7—C3—C4—C8 | 2.0 (10) |
N2—Co1—N3—C3 | −175.6 (6) | N3—Co1—C9—C10 | 166.1 (5) |
N4—Co1—N3—C3 | 3.7 (5) | N1—Co1—C9—C10 | −14.8 (5) |
N6—Co1—N3—C3 | 96.5 (6) | N2—Co1—C9—C10 | −95.8 (5) |
C9—Co1—N3—C3 | −84.7 (6) | N4—Co1—C9—C10 | 84.3 (5) |
N2—Co1—N3—O3 | 3.9 (6) | N3—Co1—C9—C12 | −66.0 (5) |
N4—Co1—N3—O3 | −176.8 (6) | N1—Co1—C9—C12 | 113.0 (5) |
N6—Co1—N3—O3 | −84.1 (6) | N2—Co1—C9—C12 | 32.0 (5) |
C9—Co1—N3—O3 | 94.7 (6) | N4—Co1—C9—C12 | −147.8 (5) |
N3—Co1—N4—C4 | −2.5 (4) | C11—N5—C10—O5 | −6.5 (10) |
N1—Co1—N4—C4 | 177.2 (5) | C11—N5—C10—C9 | 174.4 (5) |
N6—Co1—N4—C4 | −93.9 (5) | C12—C9—C10—O5 | −26.9 (8) |
C9—Co1—N4—C4 | 84.1 (5) | Co1—C9—C10—O5 | 103.2 (7) |
N3—Co1—N4—O4 | 177.1 (5) | C12—C9—C10—N5 | 152.2 (6) |
N1—Co1—N4—O4 | −3.2 (5) | Co1—C9—C10—N5 | −77.8 (6) |
N6—Co1—N4—O4 | 85.7 (4) | Co1—N6—C13—C14 | 79.4 (6) |
C9—Co1—N4—O4 | −96.3 (4) | Co1—N6—C13—C20 | −159.2 (4) |
N3—Co1—N6—C13 | −96.2 (4) | N6—C13—C14—C15 | 34.0 (9) |
N1—Co1—N6—C13 | 84.7 (5) | C20—C13—C14—C15 | −88.5 (8) |
N2—Co1—N6—C13 | 165.7 (5) | N6—C13—C14—C19 | −151.9 (6) |
N4—Co1—N6—C13 | −14.5 (5) | C20—C13—C14—C19 | 85.5 (8) |
O1—N1—C1—C2 | 176.8 (6) | C19—C14—C15—C16 | 2.4 (10) |
Co1—N1—C1—C2 | −2.6 (8) | C13—C14—C15—C16 | 176.5 (6) |
O1—N1—C1—C5 | −2.7 (11) | C14—C15—C16—C17 | −1.9 (11) |
Co1—N1—C1—C5 | 177.9 (5) | C15—C16—C17—C18 | −0.2 (12) |
O2—N2—C2—C1 | −175.1 (6) | C16—C17—C18—C19 | 1.6 (13) |
Co1—N2—C2—C1 | 2.5 (8) | C17—C18—C19—C14 | −1.0 (13) |
O2—N2—C2—C6 | 3.0 (10) | C15—C14—C19—C18 | −1.0 (11) |
Co1—N2—C2—C6 | −179.4 (5) | C13—C14—C19—C18 | −175.5 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4 | 0.82 | 1.75 | 2.536 (6) | 159 |
O3—H3···O2 | 0.82 | 1.71 | 2.499 (6) | 162 |
O6—H6F···O4i | 0.97 (3) | 1.96 (5) | 2.787 (6) | 143 (6) |
O6—H6G···O5 | 0.96 (3) | 1.89 (4) | 2.813 (7) | 162 (7) |
N5—H5···O4 | 0.86 | 2.49 | 3.030 (7) | 122 |
N6—H6D···O6ii | 0.90 | 2.36 | 3.108 (7) | 141 |
N6—H6E···O5ii | 0.90 | 2.39 | 3.163 (6) | 143 |
Symmetry codes: (i) −x+1/2, −y, z+1/2; (ii) x+1/2, −y+1/2, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Co(C3H6NO)(C4H7N2O2)2(C8H11N)] | [Co(C4H8NO)(C4H7N2O2)2(C8H11N)]·H2O |
Mr | 482.43 | 514.47 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 223 | 293 |
a, b, c (Å) | 8.743 (2), 14.696 (3), 8.565 (3) | 14.1206 (19), 14.169 (2), 12.372 (2) |
α, β, γ (°) | 90, 93.29 (2), 90 | 90, 90, 90 |
V (Å3) | 1098.7 (5) | 2475.3 (6) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.82 | 0.74 |
Crystal size (mm) | 0.23 × 0.18 × 0.17 | 0.25 × 0.15 × 0.12 |
|
Data collection |
Diffractometer | Rigaku AFC-7R diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.789, 0.869 | 0.838, 0.917 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3200, 2624, 2404 | 4662, 3581, 1749 |
Rint | 0.027 | 0.039 |
(sin θ/λ)max (Å−1) | 0.649 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.066, 1.21 | 0.038, 0.105, 0.98 |
No. of reflections | 2624 | 3581 |
No. of parameters | 299 | 317 |
No. of restraints | 1 | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.23 | 0.43, −0.80 |
Absolute structure | Flack (1983), with how many Friedel pairs | Flack (1983), with how many Friedel pairs |
Absolute structure parameter | −0.004 (14) | 0.02 (3) |
Selected geometric parameters (Å, º) for (I) topCo1—N4 | 1.879 (2) | Co1—C9 | 2.092 (3) |
Co1—N2 | 1.888 (2) | O5—C10 | 1.236 (3) |
Co1—N1 | 1.890 (2) | N6—C10 | 1.350 (4) |
Co1—N3 | 1.892 (2) | C9—C10 | 1.497 (4) |
Co1—N5 | 2.077 (2) | C9—C11 | 1.529 (4) |
| | | |
N5—Co1—C9 | 177.3 (1) | O5—C10—N6 | 121.1 (3) |
C10—C9—C11 | 111.2 (2) | O5—C10—C9 | 122.2 (3) |
C10—C9—Co1 | 110.8 (2) | N6—C10—C9 | 116.6 (3) |
C11—C9—Co1 | 114.7 (2) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3 | 0.83 | 1.73 | 2.515 (3) | 158 |
O4—H4···O1 | 0.83 | 1.71 | 2.506 (3) | 160 |
N5—H5B···O5i | 0.91 | 2.12 | 2.925 (3) | 147 |
N6—H6D···O3 | 0.83 (5) | 2.53 (5) | 3.249 (4) | 145 (4) |
N6—H6E···O1ii | 0.92 (5) | 2.10 (5) | 3.021 (4) | 176 (4) |
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) −x+1, y−1/2, −z. |
Selected geometric parameters (Å, º) for (II) topCo1—N3 | 1.868 (5) | O5—C10 | 1.229 (7) |
Co1—N1 | 1.889 (5) | N5—C10 | 1.342 (8) |
Co1—N2 | 1.890 (5) | N5—C11 | 1.470 (8) |
Co1—N4 | 1.894 (5) | C9—C10 | 1.504 (8) |
Co1—N6 | 2.070 (4) | C9—C12 | 1.534 (8) |
Co1—C9 | 2.080 (5) | | |
| | | |
N6—Co1—C9 | 177.8 (2) | C12—C9—Co1 | 115.0 (4) |
C10—N5—C11 | 122.2 (5) | O5—C10—N5 | 120.9 (6) |
C10—C9—C12 | 110.8 (5) | O5—C10—C9 | 123.0 (7) |
C10—C9—Co1 | 112.1 (4) | N5—C10—C9 | 116.1 (6) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4 | 0.82 | 1.75 | 2.536 (6) | 159 |
O3—H3···O2 | 0.82 | 1.71 | 2.499 (6) | 162 |
O6—H6F···O4i | 0.97 (3) | 1.96 (5) | 2.787 (6) | 143 (6) |
O6—H6G···O5 | 0.96 (3) | 1.89 (4) | 2.813 (7) | 162 (7) |
N5—H5···O4 | 0.86 | 2.49 | 3.030 (7) | 122 |
N6—H6D···O6ii | 0.90 | 2.36 | 3.108 (7) | 141 |
N6—H6E···O5ii | 0.90 | 2.39 | 3.163 (6) | 143 |
Symmetry codes: (i) −x+1/2, −y, z+1/2; (ii) x+1/2, −y+1/2, −z+1. |
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Solid-state specific and unidirectional photoisomerization of 2-cyanoethyl, 2-methoxycarbonylethyl, 2-carbamoylethyl, 2-(N-methylcarbamoyl)ethyl and 3-substituted propyl cobaloximes have been reported previously (Ohgo & Takeuchi, 1985; Kurashima et al., 1995; Ohgo et al., 1994, 1996, 2000, 2001). Moreover, asymmetric induction was found to occur in the (β → α) photoisomerization of various 2-substututed ethyl cobaloximes having chiral axial ligands as the chiral handle for forming the chiral lattice (Ohgo et al., 1994, 1996, 2000). However, the absolute configuration of the alkyl moiety of each chiral product has not yet been determined in the cases of the series of 2-carbamoylethyl and 2-(N-methylcarbamoyl)ethyl cobaloximes. The crystal structure analyses of the title complexes were undertaken to reveal the configurational correlation of asymmetric photoisomerization.
The crystal structure of the title 1-carbamoylethyl complex, (I), viewed along the c axis, and a stereoview of the crystal structure of the 1-(N-methylcarbamoyl)ethyl complex, (II), are shown in Figs. 1 and 2, respectively. The molecular structures of (I) and (II) are shown in Figs. 3 and 4, respectively. The absolute configuration (S) of the 1-carbamoylethyl group in (I) was set by reference to the known chirality of the axial base, (S)-1-phenylethylamine. Similarly, the absolute configuration (R) of the 1-(N-methylcarbamoyl)ethyl group in (II) was set by reference to that of the coordinated (R)-1-phenylethylamine. Selected bond distances and angles are given in Tables 1 and 3, respectively. The hydrogen bonds in (I) and (II) are given in Tables 2 and 4, respectively.
The molecular structures of (I) and (II) essentially maintain similar structural features except for their configurations. Each Calkyl—Co—Namine moiety is almost linear: the C9—Co—N5 and C9—Co—N6 angles in (I) and (II) are 177.3 (1) and 177.8 (2)°, respectively. Both the carbamoyl group and the phenylethyl group of the axial base of each complex are located on the same side, namely the O2—O3 side in (I) and the O1—O4 side in (II); the C12—N5—C9—C10 and C13—N6—C9—C10 torsion angles in (I) and (II) are −85.3 (2) and 70.7 (6)°, respectively. The N—H bond of each carbamoyl group is directed to one of the O atoms on the planar ligands to form an intramolecular hydrogen bond [N6—H6D···O3 in (I) and N5—H5···O4 in (II)]. The aromatic ring lies parallel with the Co–glyoxime plane, and the dihedral angles between the Co–glyoxime plane, Co/C3/C4/N3/N4, and the aromatic rings, C13–C18 in (I) and C14–C19 in (II), are 8.8 (2) and 12.7 (1)°, respectively.
Adjacent molecules in the structure of (I) are connected by intermolecular N5—H5B···O5i and N6—H6E···O1ii hydrogen bonds [symmetry codes: (i) 1/2 − x, 1/2 + y, − z; (ii) 1 − x, y − 1/2, − z], forming chains along the b axis. In the structure of (II), adjacent molecules are linked into a three-dimensional network by intermolecular hydrogen bonds involving the solvent water molecule, the coordinated amine group and the amide group in the 1-(N-methylcarbamoyl)ethyl moiety. Thus, the molecules are interconnected, forming chains along the a axis through intermolecular N6—H6E···O5ii hydrogen bonds [symmetry code: (ii) 1/2 + x, 1/2 − y, 1 − z]. Each chain so formed is connected to four neighbouring chains by bridging water molecules via three intermolecular hydrogen bonds, N6—H6D···O6ii, O6—H6G···O5 and O6—H6F···O4i [symmetry code: (i) 1/2 − x, − y, 1/2 + z], to form a three-dimensional hydrogen-bond network.
The axial base of (II) was displaced by methyldiphenylphosphine to afford bis(dimethylglyoximato-N,N')[(R)-1-(N-methylcarbamoyl)ethyl] (methyldiphenylphosphine)cobalt(III) {optical rotation [α]589 = +28.6, [α]578 = +23.7, [α]546 = +2.0 (c = 0.101, CHCl3)}, which was analyzed by high-performance liquid chromatography (HPLC) using a chiral column. The powdered sample of bis(dimethylglyoximato)[2-(N-methylcarbamoyl)ethyl] [methyl (S)-phenylalaninate-N]cobalt(III), complex (III) (Ohgo et al., 1996, 2000), was irradiated with a solar simulator (flux density 100 mW cm−2) to give a diastereomeric mixture of bis(dimethylglyoximato)[1-(N-methylcarbamoyl)ethyl] [methyl (S)-phenylalaninate-N]cobalt(III), which was also analyzed by HPLC after displacement of the axial ligand with methyldiphenylphosphine. From a comparison of the results of the HPLC analysis of these samples, the absolute configuration of the major enantiomer produced by photoisomerization of complex (III) was determined to be (S). On the other hand, the axial base of (I) was displaced by dimethylphenylphosphine to afford [(S)-1-carbamoylethyl]bis(dimethylglyoximato-N,N') (dimethylphenylphosphine)cobalt(III), complex (IV) {optical rotation [α]589 = −47.9, [α]578 = −47.9, [α]546 = −46.2 (CHCl3)}. The configuration of the major enantiomer produced by irradiation of the powdered crystals of a series of 2-carbamoylethyl cobaloximes was also revealed from a comparison of the optical rotation of complex (IV) with that of the photoisomerization products treated with dimethylphenylphosphine.