Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040407/ob6598sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040407/ob6598Isup2.hkl |
CCDC reference: 296624
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.002 Å
- R factor = 0.025
- wR factor = 0.052
- Data-to-parameter ratio = 16.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.62 Ratio
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 27.48 From the CIF: _reflns_number_total 3626 Count of symmetry unique reflns 2127 Completeness (_total/calc) 170.47% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1499 Fraction of Friedel pairs measured 0.705 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion
The tripodal ligand N,N-bis(carboxymethyl)-L-leucine (H3bcmle) was synthesized from L-leucine according to the literature method of Uehara et al. (1970). K2[Co(bcmle)(CO3)] was obtained from the reaction of K3[Co(CO3)3] and H3bcmle. To a 0.2 M aqueous solution (10 ml) of K2[Co(bcmle)(CO3)] was added an equimolar amount of ethylenediamine, neutralized with HCl, and the resulting mixture was stirred at 323 K for 12 h under conditions of pH 6–7 in the presence of active charcoal. After filtration, the reaction mixture was purified using a QAE Sephadex A-25 column (Cl− form) [Solvent?], eluting a non-absorbed reddish-violet solution of the product. Evaporation of the reddish-violet solution and recrystallization of the precipitated product in water gave the red crystals of (I) suitable for X-ray analysis (yield 4.2%).
All H atoms were located in difference Fourier maps. The positions of the water H atoms were refined freely, with Uiso(H) = 1.2Ueq(O). All other H atoms were constrained to ride on their parent atoms, with N—H = 0.92 Å and C—H = 0.98–1.00 Å, and with Uiso(H) = 1.2Ueq(C,N). Each methyl group was allowed to rotate freely about the C—C bond. The absolute structure determination based on the Flack (1983) parameter is consistent with the known absolute configuration of L-leucine (Voet & Voet, 2004).
Data collection: Crystal Clear (Rigaku, 1999); cell refinement: Crystal Clear; data reduction: Crystal Structure (Rigaku/MSC, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: RASTER3D (Merritt & Bacon, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: CrystalStructure.
[Co(C10H14NO6)(C2H8N2)]·H2O | F(000) = 800.00 |
Mr = 381.27 | Dx = 1.597 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5217 reflections |
a = 7.4740 (4) Å | θ = 3.1–27.5° |
b = 7.3532 (4) Å | µ = 1.12 mm−1 |
c = 28.8604 (16) Å | T = 173 K |
V = 1586.10 (15) Å3 | Prism, red |
Z = 4 | 0.19 × 0.16 × 0.16 mm |
Rigaku Mercury CCD area-detector diffractometer | 3626 independent reflections |
Radiation source: Rigaku rotating anode generator | 3261 reflections with F2 > 2σ(F2) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 14.63 pixels mm-1 | θmax = 27.5° |
ω scans | h = −9→9 |
Absorption correction: numerical (ABSCOR; Higashi, 1999) | k = −9→9 |
Tmin = 0.761, Tmax = 0.799 | l = −37→27 |
12559 measured reflections |
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0037P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.025 | (Δ/σ)max = 0.002 |
wR(F2) = 0.052 | Δρmax = 0.40 e Å−3 |
S = 1.02 | Δρmin = −0.27 e Å−3 |
3626 reflections | Absolute structure: Flack (1983), with 1510 Friedel pairs |
215 parameters | Absolute structure parameter: 0.001 (11) |
H atoms treated by a mixture of independent and constrained refinement |
[Co(C10H14NO6)(C2H8N2)]·H2O | V = 1586.10 (15) Å3 |
Mr = 381.27 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.4740 (4) Å | µ = 1.12 mm−1 |
b = 7.3532 (4) Å | T = 173 K |
c = 28.8604 (16) Å | 0.19 × 0.16 × 0.16 mm |
Rigaku Mercury CCD area-detector diffractometer | 3626 independent reflections |
Absorption correction: numerical (ABSCOR; Higashi, 1999) | 3261 reflections with F2 > 2σ(F2) |
Tmin = 0.761, Tmax = 0.799 | Rint = 0.030 |
12559 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.052 | Δρmax = 0.40 e Å−3 |
S = 1.02 | Δρmin = −0.27 e Å−3 |
3626 reflections | Absolute structure: Flack (1983), with 1510 Friedel pairs |
215 parameters | Absolute structure parameter: 0.001 (11) |
Experimental. Spectroscopic analysis: UV-vis (H2O, σmax, cm−1): 19.3 (logε = 2.23), 27.2 (logε = 2.25); CD (H20, σmax, cm−1): 17.3 (Δε = 2.24), 21.5 (Δε = −1.60), 27.0 (Δε = 0.81); 1H NMR (D2O, δ, p.p.m.): 4.54 (d, 1H, J = 16.5 Hz), 4.32 (d, 1H, J = 16.7 Hz), 4.26 (d, 1H, J = 18.1 Hz), 4.07 (dd, 1H, J = 4.2, 7.7 Hz), 3.92 (d, 1H, J = 18.2 Hz); 3.05 (m, 1H), 2.94 (m, 1H), 2.60 (m, 1H), 2.56 (m, 1H), 2.10(m, 1H), 1.90 (m, 1H), 1.90 (m, 2H), 1.06 (d, 3H, J = 3.7 Hz), 1.05 (d, 3H, J = 3.6 Hz). |
Refinement. Refinement using reflections with F2 > 2.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.88858 (3) | 0.74722 (3) | 0.806470 (10) | 0.01208 (6) | |
O2 | 1.13040 (16) | 0.82404 (17) | 0.80247 (4) | 0.0161 (2) | |
O3 | 0.80288 (16) | 0.98894 (17) | 0.80351 (5) | 0.0158 (2) | |
O4 | 1.36625 (18) | 0.8791 (2) | 0.84747 (5) | 0.0224 (3) | |
O5 | 0.67538 (19) | 1.20206 (18) | 0.84717 (5) | 0.0222 (3) | |
O6 | 0.97386 (18) | 0.50862 (17) | 0.81836 (4) | 0.0178 (3) | |
O7 | 1.06173 (19) | 0.33578 (19) | 0.87781 (5) | 0.0241 (3) | |
O8 | 0.4509 (2) | 0.4480 (2) | 0.88876 (8) | 0.0437 (5) | |
N1 | 0.9011 (2) | 0.78846 (19) | 0.87301 (5) | 0.0123 (3) | |
N2 | 0.6416 (2) | 0.6564 (2) | 0.80334 (6) | 0.0174 (3) | |
N3 | 0.89026 (19) | 0.7194 (2) | 0.74004 (5) | 0.0135 (3) | |
C1 | 0.7508 (2) | 0.9157 (2) | 0.88375 (6) | 0.0144 (4) | |
C2 | 0.7404 (2) | 1.0500 (2) | 0.84267 (6) | 0.0157 (4) | |
C3 | 0.7600 (2) | 1.0067 (2) | 0.93135 (6) | 0.0183 (4) | |
C4 | 0.5762 (2) | 1.0316 (2) | 0.95412 (6) | 0.0214 (4) | |
C5 | 0.5930 (3) | 1.1629 (3) | 0.99487 (8) | 0.0377 (6) | |
C6 | 0.4981 (3) | 0.8507 (3) | 0.96989 (8) | 0.0326 (5) | |
C7 | 0.8896 (2) | 0.6045 (2) | 0.89412 (6) | 0.0159 (4) | |
C8 | 0.9846 (2) | 0.4694 (2) | 0.86218 (6) | 0.0170 (4) | |
C9 | 1.0796 (2) | 0.8740 (2) | 0.88241 (6) | 0.0155 (4) | |
C10 | 1.2057 (2) | 0.8549 (2) | 0.84193 (6) | 0.0148 (4) | |
C11 | 0.5992 (2) | 0.6038 (2) | 0.75476 (6) | 0.0194 (4) | |
C12 | 0.7044 (2) | 0.7248 (2) | 0.72288 (6) | 0.0175 (4) | |
H1 | 0.6382 | 0.8422 | 0.8831 | 0.017* | |
H2 | 0.8175 | 1.1272 | 0.9280 | 0.022* | |
H3 | 0.8362 | 0.9321 | 0.9520 | 0.022* | |
H4 | 0.4932 | 1.0863 | 0.9308 | 0.026* | |
H5 | 0.4742 | 1.1866 | 1.0079 | 0.045* | |
H6 | 0.6458 | 1.2774 | 0.9841 | 0.045* | |
H7 | 0.6699 | 1.1090 | 1.0187 | 0.045* | |
H8 | 0.3785 | 0.8707 | 0.9828 | 0.039* | |
H9 | 0.5756 | 0.7972 | 0.9936 | 0.039* | |
H10 | 0.4899 | 0.7679 | 0.9434 | 0.039* | |
H11 | 0.7628 | 0.5690 | 0.8980 | 0.019* | |
H12 | 0.9473 | 0.6049 | 0.9250 | 0.019* | |
H13 | 1.1337 | 0.8160 | 0.9100 | 0.019* | |
H14 | 1.0624 | 1.0046 | 0.8894 | 0.019* | |
H15 | 0.6289 | 0.5574 | 0.8225 | 0.021* | |
H16 | 0.5637 | 0.7454 | 0.8131 | 0.021* | |
H17 | 0.4695 | 0.6182 | 0.7488 | 0.023* | |
H18 | 0.6316 | 0.4749 | 0.7494 | 0.023* | |
H19 | 0.6981 | 0.6795 | 0.6906 | 0.021* | |
H20 | 0.6573 | 0.8506 | 0.7238 | 0.021* | |
H21 | 0.9557 | 0.8116 | 0.7267 | 0.016* | |
H22 | 0.9425 | 0.6104 | 0.7322 | 0.016* | |
H23 | 0.349 (2) | 0.414 (2) | 0.8906 (7) | 0.0210* | |
H24 | 0.493 (2) | 0.353 (2) | 0.8843 (8) | 0.0210* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01029 (11) | 0.01487 (12) | 0.01108 (11) | −0.00110 (12) | 0.00064 (10) | −0.00027 (12) |
O2 | 0.0115 (6) | 0.0229 (6) | 0.0139 (6) | −0.0027 (5) | −0.0001 (6) | 0.0010 (5) |
O3 | 0.0166 (6) | 0.0168 (6) | 0.0141 (6) | 0.0006 (5) | 0.0015 (6) | 0.0018 (6) |
O4 | 0.0100 (7) | 0.0341 (8) | 0.0231 (7) | −0.0019 (6) | −0.0001 (6) | 0.0018 (6) |
O5 | 0.0207 (7) | 0.0216 (8) | 0.0244 (7) | 0.0067 (6) | 0.0007 (6) | 0.0000 (6) |
O6 | 0.0211 (7) | 0.0158 (6) | 0.0166 (7) | 0.0019 (6) | 0.0024 (5) | −0.0006 (5) |
O7 | 0.0279 (8) | 0.0197 (7) | 0.0249 (8) | 0.0059 (6) | −0.0021 (6) | 0.0040 (6) |
O8 | 0.0350 (10) | 0.0273 (10) | 0.0689 (13) | 0.0064 (8) | 0.0028 (10) | −0.0097 (10) |
N1 | 0.0088 (7) | 0.0158 (8) | 0.0124 (7) | −0.0005 (7) | −0.0001 (6) | 0.0006 (6) |
N2 | 0.0146 (8) | 0.0227 (8) | 0.0148 (8) | −0.0040 (6) | −0.0001 (7) | −0.0001 (7) |
N3 | 0.0137 (7) | 0.0143 (8) | 0.0126 (7) | −0.0004 (7) | 0.0011 (6) | −0.0001 (6) |
C1 | 0.0090 (9) | 0.0194 (10) | 0.0148 (10) | 0.0013 (8) | 0.0014 (7) | −0.0021 (8) |
C2 | 0.0086 (9) | 0.0214 (11) | 0.0172 (10) | −0.0022 (8) | −0.0002 (8) | −0.0009 (8) |
C3 | 0.0170 (10) | 0.0211 (10) | 0.0170 (10) | 0.0016 (9) | 0.0012 (8) | −0.0032 (9) |
C4 | 0.0203 (11) | 0.0283 (11) | 0.0157 (10) | 0.0056 (10) | 0.0022 (8) | −0.0004 (9) |
C5 | 0.0364 (14) | 0.0437 (15) | 0.0331 (13) | 0.0033 (12) | 0.0127 (12) | −0.0149 (11) |
C6 | 0.0277 (13) | 0.0465 (15) | 0.0237 (12) | −0.0038 (11) | 0.0095 (10) | 0.0000 (11) |
C7 | 0.0191 (10) | 0.0156 (9) | 0.0130 (9) | −0.0021 (9) | −0.0019 (9) | 0.0009 (7) |
C8 | 0.0147 (10) | 0.0178 (10) | 0.0185 (10) | −0.0037 (8) | −0.0008 (8) | −0.0001 (8) |
C9 | 0.0095 (10) | 0.0208 (10) | 0.0162 (9) | −0.0020 (8) | −0.0018 (8) | −0.0020 (8) |
C10 | 0.0138 (10) | 0.0122 (9) | 0.0184 (10) | 0.0007 (8) | 0.0007 (8) | 0.0017 (8) |
C11 | 0.0170 (10) | 0.0234 (10) | 0.0177 (10) | −0.0044 (9) | −0.0032 (9) | −0.0042 (8) |
C12 | 0.0148 (8) | 0.0221 (11) | 0.0156 (9) | 0.0005 (9) | −0.0034 (7) | −0.0016 (9) |
Co1—O2 | 1.8971 (12) | O8—H23 | 0.80 (2) |
Co1—O3 | 1.8912 (12) | O8—H24 | 0.77 (2) |
Co1—O6 | 1.8979 (12) | N2—H15 | 0.920 |
Co1—N1 | 1.9464 (14) | N2—H16 | 0.920 |
Co1—N2 | 1.9648 (15) | N3—H21 | 0.920 |
Co1—N3 | 1.9281 (14) | N3—H22 | 0.920 |
O2—C10 | 1.290 (2) | C1—H1 | 1.000 |
O3—C2 | 1.303 (2) | C3—H2 | 0.990 |
O4—C10 | 1.224 (2) | C3—H3 | 0.990 |
O5—C2 | 1.226 (2) | C4—H4 | 1.000 |
O6—C8 | 1.300 (2) | C5—H5 | 0.980 |
O7—C8 | 1.226 (2) | C5—H6 | 0.980 |
N1—C1 | 1.494 (2) | C5—H7 | 0.980 |
N1—C7 | 1.486 (2) | C6—H8 | 0.980 |
N1—C9 | 1.500 (2) | C6—H9 | 0.980 |
N2—C11 | 1.489 (2) | C6—H10 | 0.980 |
N3—C12 | 1.475 (2) | C7—H11 | 0.990 |
C1—C2 | 1.545 (2) | C7—H12 | 0.990 |
C1—C3 | 1.530 (2) | C9—H13 | 0.990 |
C3—C4 | 1.534 (2) | C9—H14 | 0.990 |
C4—C5 | 1.527 (3) | C11—H17 | 0.990 |
C4—C6 | 1.522 (3) | C11—H18 | 0.990 |
C7—C8 | 1.530 (2) | C12—H19 | 0.990 |
C9—C10 | 1.507 (2) | C12—H20 | 0.990 |
C11—C12 | 1.503 (2) | ||
O2—Co1—O3 | 92.30 (5) | C11—N2—H16 | 109.8 |
O2—Co1—O6 | 88.07 (5) | H15—N2—H16 | 108.2 |
O2—Co1—N1 | 88.17 (5) | Co1—N3—H21 | 109.9 |
O2—Co1—N2 | 173.37 (6) | Co1—N3—H22 | 109.9 |
O2—Co1—N3 | 87.99 (5) | C12—N3—H21 | 109.9 |
O3—Co1—O6 | 172.17 (5) | C12—N3—H22 | 109.9 |
O3—Co1—N1 | 85.09 (6) | H21—N3—H22 | 108.3 |
O3—Co1—N2 | 89.95 (5) | N1—C1—H1 | 106.9 |
O3—Co1—N3 | 93.26 (6) | C2—C1—H1 | 106.9 |
O6—Co1—N1 | 87.11 (5) | C3—C1—H1 | 106.9 |
O6—Co1—N2 | 90.56 (6) | C1—C3—H2 | 108.9 |
O6—Co1—N3 | 94.56 (5) | C1—C3—H3 | 108.9 |
N1—Co1—N2 | 98.24 (6) | C4—C3—H2 | 108.9 |
N1—Co1—N3 | 175.75 (6) | C4—C3—H3 | 108.9 |
N2—Co1—N3 | 85.66 (6) | H2—C3—H3 | 107.7 |
Co1—O2—C10 | 114.46 (11) | C3—C4—H4 | 108.4 |
Co1—O3—C2 | 113.95 (12) | C5—C4—H4 | 108.4 |
Co1—O6—C8 | 113.67 (11) | C6—C4—H4 | 108.4 |
Co1—N1—C1 | 105.44 (11) | C4—C5—H5 | 109.5 |
Co1—N1—C7 | 105.07 (10) | C4—C5—H6 | 109.5 |
Co1—N1—C9 | 106.64 (11) | C4—C5—H7 | 109.5 |
C1—N1—C7 | 116.21 (14) | H5—C5—H6 | 109.5 |
C1—N1—C9 | 111.64 (13) | H5—C5—H7 | 109.5 |
C7—N1—C9 | 111.01 (14) | H6—C5—H7 | 109.5 |
Co1—N2—C11 | 109.39 (11) | C4—C6—H8 | 109.5 |
Co1—N3—C12 | 108.96 (10) | C4—C6—H9 | 109.5 |
N1—C1—C2 | 106.18 (14) | C4—C6—H10 | 109.5 |
N1—C1—C3 | 115.24 (15) | H8—C6—H9 | 109.5 |
C2—C1—C3 | 114.33 (16) | H8—C6—H10 | 109.5 |
O3—C2—O5 | 123.24 (18) | H9—C6—H10 | 109.5 |
O3—C2—C1 | 115.32 (16) | N1—C7—H11 | 110.0 |
O5—C2—C1 | 121.43 (17) | N1—C7—H12 | 110.0 |
C1—C3—C4 | 113.38 (16) | C8—C7—H11 | 110.0 |
C3—C4—C5 | 109.38 (17) | C8—C7—H12 | 110.0 |
C3—C4—C6 | 111.55 (17) | H11—C7—H12 | 108.4 |
C5—C4—C6 | 110.73 (17) | N1—C9—H13 | 109.2 |
N1—C7—C8 | 108.50 (14) | N1—C9—H14 | 109.2 |
O6—C8—O7 | 124.39 (18) | C10—C9—H13 | 109.2 |
O6—C8—C7 | 114.46 (16) | C10—C9—H14 | 109.2 |
O7—C8—C7 | 121.15 (17) | H13—C9—H14 | 107.9 |
N1—C9—C10 | 112.14 (15) | N2—C11—H17 | 110.1 |
O2—C10—O4 | 124.64 (18) | N2—C11—H18 | 110.1 |
O2—C10—C9 | 115.33 (16) | C12—C11—H17 | 110.1 |
O4—C10—C9 | 119.88 (17) | C12—C11—H18 | 110.1 |
N2—C11—C12 | 108.11 (15) | H17—C11—H18 | 108.4 |
N3—C12—C11 | 105.75 (14) | N3—C12—H19 | 110.6 |
H23—O8—H24 | 97 (2) | N3—C12—H20 | 110.6 |
Co1—N2—H15 | 109.8 | C11—C12—H19 | 110.6 |
Co1—N2—H16 | 109.8 | C11—C12—H20 | 110.6 |
C11—N2—H15 | 109.8 | H19—C12—H20 | 108.7 |
O2—Co1—O3—C2 | −107.54 (12) | Co1—O2—C10—C9 | −15.69 (19) |
O3—Co1—O2—C10 | 90.36 (12) | Co1—O3—C2—O5 | −178.24 (14) |
O2—Co1—O6—C8 | 95.02 (12) | Co1—O3—C2—C1 | 0.85 (19) |
O6—Co1—O2—C10 | −81.81 (12) | Co1—O6—C8—O7 | −167.95 (15) |
O2—Co1—N1—C1 | 124.87 (10) | Co1—O6—C8—C7 | 12.7 (2) |
O2—Co1—N1—C7 | −111.84 (11) | Co1—N1—C1—C2 | −37.53 (15) |
O2—Co1—N1—C9 | 6.07 (11) | Co1—N1—C1—C3 | −165.19 (13) |
N1—Co1—O2—C10 | 5.35 (12) | Co1—N1—C7—C8 | 34.35 (16) |
O2—Co1—N3—C12 | −158.59 (12) | Co1—N1—C9—C10 | −15.02 (17) |
N3—Co1—O2—C10 | −176.45 (12) | C1—N1—C7—C8 | 150.44 (15) |
O3—Co1—N1—C1 | 32.41 (10) | C7—N1—C1—C2 | −153.42 (14) |
O3—Co1—N1—C7 | 155.70 (12) | C7—N1—C1—C3 | 78.92 (19) |
O3—Co1—N1—C9 | −86.40 (11) | C1—N1—C9—C10 | −129.69 (16) |
N1—Co1—O3—C2 | −19.58 (12) | C9—N1—C1—C2 | 77.88 (17) |
O3—Co1—N2—C11 | 97.92 (12) | C9—N1—C1—C3 | −49.8 (2) |
N2—Co1—O3—C2 | 78.69 (12) | C7—N1—C9—C10 | 98.90 (17) |
O3—Co1—N3—C12 | −66.41 (11) | C9—N1—C7—C8 | −80.56 (17) |
N3—Co1—O3—C2 | 164.34 (12) | Co1—N2—C11—C12 | −31.04 (17) |
O6—Co1—N1—C1 | −146.97 (11) | Co1—N3—C12—C11 | −45.54 (16) |
O6—Co1—N1—C7 | −23.68 (11) | N1—C1—C2—O3 | 25.4 (2) |
O6—Co1—N1—C9 | 94.22 (11) | N1—C1—C2—O5 | −155.49 (17) |
N1—Co1—O6—C8 | 6.76 (13) | N1—C1—C3—C4 | −143.53 (16) |
O6—Co1—N2—C11 | −89.89 (11) | C2—C1—C3—C4 | 93.03 (19) |
N2—Co1—O6—C8 | −91.46 (13) | C3—C1—C2—O3 | 153.60 (16) |
O6—Co1—N3—C12 | 113.51 (11) | C3—C1—C2—O5 | −27.3 (2) |
N3—Co1—O6—C8 | −177.15 (12) | C1—C3—C4—C5 | −166.06 (17) |
N1—Co1—N2—C11 | −177.05 (11) | C1—C3—C4—C6 | 71.1 (2) |
N2—Co1—N1—C1 | −56.83 (11) | N1—C7—C8—O6 | −32.4 (2) |
N2—Co1—N1—C7 | 66.46 (12) | N1—C7—C8—O7 | 148.19 (17) |
N2—Co1—N1—C9 | −175.63 (11) | N1—C9—C10—O2 | 20.8 (2) |
N2—Co1—N3—C12 | 23.30 (12) | N1—C9—C10—O4 | −163.34 (16) |
N3—Co1—N2—C11 | 4.64 (11) | N2—C11—C12—N3 | 49.49 (18) |
Co1—O2—C10—O4 | 168.70 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H23···O7i | 0.80 (2) | 2.25 (2) | 3.040 (2) | 166 |
O8—H24···O5ii | 0.77 (2) | 2.06 (2) | 2.744 (2) | 147 |
N2—H16···O4i | 0.92 | 2.03 | 2.922 (2) | 162 |
N3—H21···O6iii | 0.92 | 2.02 | 2.8973 (19) | 160 |
Symmetry codes: (i) x−1, y, z; (ii) x, y−1, z; (iii) −x+2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C10H14NO6)(C2H8N2)]·H2O |
Mr | 381.27 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 173 |
a, b, c (Å) | 7.4740 (4), 7.3532 (4), 28.8604 (16) |
V (Å3) | 1586.10 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.12 |
Crystal size (mm) | 0.19 × 0.16 × 0.16 |
Data collection | |
Diffractometer | Rigaku Mercury CCD area-detector diffractometer |
Absorption correction | Numerical (ABSCOR; Higashi, 1999) |
Tmin, Tmax | 0.761, 0.799 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 12559, 3626, 3261 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.052, 1.02 |
No. of reflections | 3626 |
No. of parameters | 215 |
No. of restraints | ? |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.27 |
Absolute structure | Flack (1983), with 1510 Friedel pairs |
Absolute structure parameter | 0.001 (11) |
Computer programs: Crystal Clear (Rigaku, 1999), Crystal Clear, Crystal Structure (Rigaku/MSC, 2005), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), RASTER3D (Merritt & Bacon, 1997) and Mercury (Bruno et al., 2002), CrystalStructure.
Co1—O2 | 1.8971 (12) | Co1—N1 | 1.9464 (14) |
Co1—O3 | 1.8912 (12) | Co1—N2 | 1.9648 (15) |
Co1—O6 | 1.8979 (12) | Co1—N3 | 1.9281 (14) |
O2—Co1—O3 | 92.30 (5) | O3—Co1—N3 | 93.26 (6) |
O2—Co1—O6 | 88.07 (5) | O6—Co1—N1 | 87.11 (5) |
O2—Co1—N1 | 88.17 (5) | O6—Co1—N2 | 90.56 (6) |
O2—Co1—N2 | 173.37 (6) | O6—Co1—N3 | 94.56 (5) |
O2—Co1—N3 | 87.99 (5) | N1—Co1—N2 | 98.24 (6) |
O3—Co1—O6 | 172.17 (5) | N1—Co1—N3 | 175.75 (6) |
O3—Co1—N1 | 85.09 (6) | N2—Co1—N3 | 85.66 (6) |
O3—Co1—N2 | 89.95 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H23···O7i | 0.80 (2) | 2.25 (2) | 3.040 (2) | 166 |
O8—H24···O5ii | 0.77 (2) | 2.06 (2) | 2.744 (2) | 147 |
N2—H16···O4i | 0.920 | 2.032 | 2.922 (2) | 162 |
N3—H21···O6iii | 0.920 | 2.017 | 2.8973 (19) | 160 |
Symmetry codes: (i) x−1, y, z; (ii) x, y−1, z; (iii) −x+2, y+1/2, −z+3/2. |
High efficiency and specificity of biological reactions are achieved by molecular recognition utilizing steric repulsion and weak non-covalent interactions, such as hydrogen bonding, electrostatic, hydrophobic and aromatic ring-stacking interactions (Rebek, 1990). In order to understand such non-covalent interactions of the molecular recognition sites of proteins, we have studied inorganic complexes containing amino acid derivatives as model compounds (Jitsukawa et al., 1994; Kumita et al., 2001). In this paper, we report the crystal structure of the title compound, [CoII(L-bcmle)(en)]·H2O, (I). The L-bcmle ligand was derived from the natural amino acid L-leucine (L-Leu).
For complex (I), there are three possible types of stereoisomers, depending on the position of the Cα site and the orientation of the isobutyl group of the L-Leu unit in L-bcmle. Our preparation method facilely gave the red single crystalline product, (I) (Fig. 1). 1H NMR spectroscopic analysis also suggested that (I) was dominantly formed in the synthetic solution through the procedure. The coordination mode of L-bcmle in (I) is the same as those observed in the crystals of analogous CoIII (Jitsukawa et al., 1994, Kumita et al. 1998, 2001) and CrIII complexes (Borcarsly et al., 1990). Their CD [Please define] spectra in aqueous solution exhibited characteristically large positive and negative bands in the d–d region, which are induced by the coordination geometry and the absolute configuration around the asymmetric centres.
In (I), the CoIII centre has a distorted octahedral geometry, with Co—O = 1.8912 (12)–1.8979 (12) Å and Co—N = 1.9281 (14)–1.9648 (15) Å (Table 1). These values are slightly shorter than the generally reported values of Co—O(carboxylate) = 1.894–1.918 Å and Co—N(amine) = 1.938–1.977 Å (Orpen et al., 1989), and are in the range of the reported values of Co—O(carboxylate) = 1.854 (9)–1.947 (3) Å and Co—N(amine) = 1.907 (4)–1.962 (3) Å for the corresponding CoIII complexes with nitrilotriacetic acid analogues (Jitsukawa et al., 1994; Kumita et al., 1998, 2001; Swanminathan et al. 1989).
Intermolecular hydrogen bonds (Table 2) between the [CoIII(L-bcmle)(en)] and H2O molecules form hydrophilic layers parallel to the (001) plane (Fig. 2). The isobutyl groups of the L-bcmle ligands are located outside the hydrophilic layers, and interdigitation of the alkyl chains forms a bilayer structure.