Bis{2,2′-[ethane-1,2-diylbis(iminomethylene)]diphenolato-κ2O,N,N′,O′}cerium(IV) chloroform solvate
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705101X/at2424sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680705101X/at2424Isup2.hkl |
CCDC reference: 656518
To a solution containing N,N-bis(2-hydroxybenzyl)ethane-1,2-diamine (1.52 g, 5 mmol) and ethanol (20 ml), a solution of cerium nitrate (1.09 g, 5 mmol) and methanol (10 ml) was added with stirring for 3 h at 333–343 K; the solid obtained was filtered off, washed successively with ethanol, and dried at room temperature. Dark red crystals of (I) suitable for X-ray structure analysis were obtained by slow evaporation of a chloroform–ethanol (1:2) solution containing the product over a period of one week.
All H atoms were located in difference Fourier maps and then treated as riding atoms, with C—H distances of 0.93 Å (aryl), 0.97 Å (methylene), 0.98 Å (methine), N—H distances of 0.91 Å (amine), and with Uiso(H) = 1.2Ueq(C,N) (aryl, methylene, methine, amine).
Some CeIVcomplexs has been shown to hydrolyze DNA effectively at a reasonable rate (Franklin, 2001; Williams et al.,1999; Takasaki & Chin, 1994; Branum et al., 2001; Komiyama et al., 1999). We have reported recently the crystyl structure of a CeIV complex (Liu et al., 2007). As part of our study of the CeIVcomplexes with the diamine derives, We report here the crystal structure of a new CeIVcomplex, bis[N,N'-bis(2-oxidobenzyl)ethane-1,2-diamine-κ2N,N',O,O'] cerium(IV) chloroform disolvate, (I).
Compound (I) crystallizes in the space group P21/n, and the asymmetric unit contains a title complex and one chloroform molecule, which are linked by one N—H···Cl and one C—H···O hydrogen bonds into a dimeric structure (Table 2 and Fig. 1). The CeIV atom is coordinated by four O atoms and four N atoms from two tetradentate ligand, N,N'-(2-oxidobenzyl)ethane-1,2-diamine, forming a complex eight-coordinated stereochemistry geometry (Fig. 1). Two least-squares planes are defined by the atoms Ce1/O1/O2/N1/N2 and Ce1/O3/O4/N3/N4, and which are approximately planar, the maximum deviation are -0.079 (3) Å for N2 and -0.118 (3) Å for N3, respectively. The dihedral angle between the two least-squares planes are 89.23 (9)°. The average Ce—O and Ce—N distance are 2.192 (4) Å and 2.620 (4) Å, these values are approximately similar to the CeIV complexes reported [2.199 (4)Å and 2.624 (4) Å; Liu et al., 2007], and the bond angles ranges around CeIV atom are O—Ce—O of 95.1 (2)° - 149.1 (1)°, N—Ce—N of 66.5 (1)° - 135.3 (1)° (see in Table 1). The crystal structure of (I) is stabilized by two C—H···π, one N—H···Cl and one C—H···Cl interactions (Table. 2).
For related literature, see: Branum et al. (2001); Franklin (2001); Komiyama et al. (1999); Liu et al. (2007); Takasaki & Chin (1994); Williams et al. (1999).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. For clarity, H atoms have been omitted. |
[Ce(C16H18N2O2)2]·CHCl3 | F(000) = 1616 |
Mr = 800.14 | Dx = 1.526 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5182 reflections |
a = 12.493 (1) Å | θ = 2.3–25.4° |
b = 14.199 (2) Å | µ = 1.58 mm−1 |
c = 20.253 (2) Å | T = 298 K |
β = 104.263 (2)° | Block, dark red |
V = 3481.8 (7) Å3 | 0.57 × 0.51 × 0.39 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 6130 independent reflections |
Radiation source: fine-focus sealed tube | 3810 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
φ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→14 |
Tmin = 0.466, Tmax = 0.578 | k = −16→16 |
17037 measured reflections | l = −18→24 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0568P)2] where P = (Fo2 + 2Fc2)/3 |
6130 reflections | (Δ/σ)max < 0.001 |
406 parameters | Δρmax = 1.50 e Å−3 |
0 restraints | Δρmin = −0.77 e Å−3 |
[Ce(C16H18N2O2)2]·CHCl3 | V = 3481.8 (7) Å3 |
Mr = 800.14 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.493 (1) Å | µ = 1.58 mm−1 |
b = 14.199 (2) Å | T = 298 K |
c = 20.253 (2) Å | 0.57 × 0.51 × 0.39 mm |
β = 104.263 (2)° |
Bruker SMART CCD area-detector diffractometer | 6130 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3810 reflections with I > 2σ(I) |
Tmin = 0.466, Tmax = 0.578 | Rint = 0.064 |
17037 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.06 | Δρmax = 1.50 e Å−3 |
6130 reflections | Δρmin = −0.77 e Å−3 |
406 parameters |
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 | ||
Ce1 | 0.49514 (2) | 0.39970 (2) | 0.249313 (17) | 0.03636 (13) | |
N1 | 0.6295 (3) | 0.3382 (3) | 0.1791 (2) | 0.0420 (12) | |
H1 | 0.6932 | 0.3713 | 0.1942 | 0.050* | |
N2 | 0.5780 (3) | 0.2327 (3) | 0.2880 (2) | 0.0403 (12) | |
H2 | 0.5283 | 0.1900 | 0.2649 | 0.048* | |
N3 | 0.4776 (3) | 0.5594 (3) | 0.3112 (3) | 0.0437 (12) | |
H3 | 0.4642 | 0.5447 | 0.3522 | 0.052* | |
N4 | 0.2960 (3) | 0.4716 (3) | 0.2136 (3) | 0.0425 (12) | |
H4 | 0.2902 | 0.4974 | 0.1718 | 0.051* | |
O1 | 0.4930 (3) | 0.4995 (3) | 0.1663 (2) | 0.0506 (11) | |
O2 | 0.4336 (3) | 0.3579 (3) | 0.3389 (2) | 0.0499 (11) | |
O3 | 0.6658 (3) | 0.4371 (3) | 0.3088 (2) | 0.0518 (11) | |
O4 | 0.3878 (3) | 0.2954 (3) | 0.1861 (2) | 0.0473 (11) | |
C1 | 0.5930 (5) | 0.3567 (4) | 0.1052 (3) | 0.0505 (16) | |
H1A | 0.5171 | 0.3361 | 0.0885 | 0.061* | |
H1B | 0.6384 | 0.3206 | 0.0817 | 0.061* | |
C2 | 0.6012 (4) | 0.4591 (4) | 0.0896 (3) | 0.0451 (16) | |
C3 | 0.5489 (4) | 0.5277 (4) | 0.1208 (3) | 0.0434 (15) | |
C4 | 0.5554 (5) | 0.6209 (5) | 0.1045 (3) | 0.0536 (17) | |
H4A | 0.5212 | 0.6665 | 0.1251 | 0.064* | |
C5 | 0.6131 (6) | 0.6465 (6) | 0.0573 (4) | 0.066 (2) | |
H5 | 0.6156 | 0.7099 | 0.0461 | 0.079* | |
C6 | 0.6669 (6) | 0.5825 (6) | 0.0260 (4) | 0.069 (2) | |
H6 | 0.7063 | 0.6017 | −0.0051 | 0.083* | |
C7 | 0.6602 (5) | 0.4894 (5) | 0.0424 (3) | 0.0632 (19) | |
H7 | 0.6957 | 0.4447 | 0.0217 | 0.076* | |
C8 | 0.5915 (5) | 0.2124 (5) | 0.3613 (3) | 0.0563 (18) | |
H8A | 0.6323 | 0.2633 | 0.3881 | 0.068* | |
H8B | 0.6340 | 0.1550 | 0.3731 | 0.068* | |
C9 | 0.4812 (5) | 0.2014 (4) | 0.3783 (3) | 0.0480 (15) | |
C10 | 0.4068 (5) | 0.2771 (5) | 0.3661 (3) | 0.0470 (16) | |
C11 | 0.3065 (5) | 0.2667 (5) | 0.3833 (3) | 0.0584 (18) | |
H11 | 0.2557 | 0.3158 | 0.3757 | 0.070* | |
C12 | 0.2818 (6) | 0.1829 (6) | 0.4119 (4) | 0.070 (2) | |
H12 | 0.2142 | 0.1768 | 0.4230 | 0.084* | |
C13 | 0.3541 (7) | 0.1099 (5) | 0.4239 (4) | 0.070 (2) | |
H13 | 0.3363 | 0.0542 | 0.4429 | 0.084* | |
C14 | 0.4530 (6) | 0.1194 (5) | 0.4076 (3) | 0.0605 (18) | |
H14 | 0.5030 | 0.0697 | 0.4162 | 0.073* | |
C15 | 0.6596 (5) | 0.2388 (4) | 0.1918 (4) | 0.0574 (19) | |
H15A | 0.7254 | 0.2253 | 0.1762 | 0.069* | |
H15B | 0.6003 | 0.1992 | 0.1665 | 0.069* | |
C16 | 0.6807 (5) | 0.2169 (4) | 0.2665 (3) | 0.0523 (17) | |
H16A | 0.7042 | 0.1520 | 0.2748 | 0.063* | |
H16B | 0.7388 | 0.2574 | 0.2922 | 0.063* | |
C17 | 0.5802 (4) | 0.6174 (4) | 0.3255 (3) | 0.0530 (17) | |
H17A | 0.5643 | 0.6796 | 0.3405 | 0.064* | |
H17B | 0.6046 | 0.6247 | 0.2839 | 0.064* | |
C18 | 0.6705 (5) | 0.5735 (5) | 0.3788 (3) | 0.0476 (16) | |
C19 | 0.7083 (5) | 0.4835 (5) | 0.3672 (3) | 0.0513 (17) | |
C20 | 0.7945 (5) | 0.4448 (5) | 0.4167 (4) | 0.0617 (19) | |
H20 | 0.8211 | 0.3853 | 0.4100 | 0.074* | |
C21 | 0.8406 (6) | 0.4933 (7) | 0.4752 (4) | 0.079 (3) | |
H21 | 0.8982 | 0.4659 | 0.5074 | 0.095* | |
C22 | 0.8046 (6) | 0.5810 (6) | 0.4876 (4) | 0.080 (2) | |
H22 | 0.8368 | 0.6133 | 0.5275 | 0.096* | |
C23 | 0.7188 (6) | 0.6199 (6) | 0.4389 (4) | 0.072 (2) | |
H23 | 0.6927 | 0.6791 | 0.4467 | 0.086* | |
C24 | 0.2056 (4) | 0.4024 (4) | 0.2043 (3) | 0.0451 (16) | |
H24A | 0.1363 | 0.4363 | 0.1972 | 0.054* | |
H24B | 0.2149 | 0.3663 | 0.2460 | 0.054* | |
C25 | 0.1980 (4) | 0.3355 (4) | 0.1465 (3) | 0.0422 (15) | |
C26 | 0.2905 (4) | 0.2832 (4) | 0.1421 (3) | 0.0403 (14) | |
C27 | 0.2786 (5) | 0.2156 (4) | 0.0908 (3) | 0.0548 (17) | |
H27 | 0.3396 | 0.1804 | 0.0871 | 0.066* | |
C28 | 0.1775 (6) | 0.2002 (5) | 0.0456 (4) | 0.067 (2) | |
H28 | 0.1712 | 0.1545 | 0.0119 | 0.081* | |
C29 | 0.0880 (6) | 0.2507 (5) | 0.0496 (4) | 0.065 (2) | |
H29 | 0.0201 | 0.2398 | 0.0192 | 0.078* | |
C30 | 0.0981 (5) | 0.3193 (5) | 0.0998 (3) | 0.0573 (18) | |
H30 | 0.0367 | 0.3550 | 0.1021 | 0.069* | |
C31 | 0.3810 (5) | 0.6138 (4) | 0.2725 (4) | 0.0549 (18) | |
H31A | 0.3950 | 0.6367 | 0.2303 | 0.066* | |
H31B | 0.3681 | 0.6676 | 0.2990 | 0.066* | |
C32 | 0.2805 (4) | 0.5497 (4) | 0.2573 (4) | 0.0539 (18) | |
H32A | 0.2686 | 0.5253 | 0.2996 | 0.065* | |
H32B | 0.2156 | 0.5856 | 0.2348 | 0.065* | |
Cl1 | 0.88566 (18) | 0.46389 (19) | 0.19706 (14) | 0.1116 (8) | |
Cl2 | 1.02770 (19) | 0.52366 (17) | 0.32317 (13) | 0.1072 (8) | |
Cl3 | 0.9785 (2) | 0.32984 (16) | 0.29798 (18) | 0.1389 (12) | |
C33 | 0.9284 (6) | 0.4425 (5) | 0.2845 (4) | 0.069 (2) | |
H33 | 0.8645 | 0.4487 | 0.3042 | 0.083* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ce1 | 0.03244 (18) | 0.0353 (2) | 0.0427 (2) | 0.00136 (14) | 0.01173 (14) | −0.00221 (19) |
N1 | 0.040 (3) | 0.042 (3) | 0.045 (3) | 0.004 (2) | 0.012 (2) | 0.001 (3) |
N2 | 0.037 (2) | 0.044 (3) | 0.040 (3) | 0.003 (2) | 0.010 (2) | 0.000 (3) |
N3 | 0.039 (3) | 0.047 (3) | 0.047 (3) | 0.000 (2) | 0.016 (2) | 0.003 (3) |
N4 | 0.036 (2) | 0.039 (3) | 0.054 (3) | 0.000 (2) | 0.014 (2) | 0.005 (3) |
O1 | 0.055 (2) | 0.051 (3) | 0.052 (3) | 0.0118 (19) | 0.025 (2) | 0.007 (2) |
O2 | 0.056 (2) | 0.051 (3) | 0.046 (3) | 0.005 (2) | 0.018 (2) | 0.007 (2) |
O3 | 0.041 (2) | 0.054 (3) | 0.057 (3) | −0.0004 (19) | 0.005 (2) | −0.006 (3) |
O4 | 0.035 (2) | 0.045 (3) | 0.058 (3) | 0.0046 (18) | 0.0031 (19) | −0.015 (2) |
C1 | 0.064 (4) | 0.048 (4) | 0.041 (4) | 0.008 (3) | 0.016 (3) | −0.003 (3) |
C2 | 0.043 (3) | 0.055 (4) | 0.035 (4) | −0.004 (3) | 0.004 (3) | 0.001 (3) |
C3 | 0.042 (3) | 0.051 (4) | 0.036 (4) | −0.003 (3) | 0.006 (3) | −0.003 (3) |
C4 | 0.066 (4) | 0.048 (4) | 0.044 (4) | −0.009 (3) | 0.007 (3) | −0.006 (4) |
C5 | 0.076 (5) | 0.061 (5) | 0.050 (5) | −0.025 (4) | −0.005 (4) | 0.008 (4) |
C6 | 0.069 (5) | 0.091 (6) | 0.049 (5) | −0.024 (4) | 0.016 (4) | 0.000 (5) |
C7 | 0.058 (4) | 0.083 (6) | 0.054 (5) | −0.004 (4) | 0.022 (4) | −0.008 (4) |
C8 | 0.050 (4) | 0.055 (4) | 0.059 (5) | 0.007 (3) | 0.005 (3) | 0.009 (4) |
C9 | 0.058 (4) | 0.046 (4) | 0.039 (4) | −0.007 (3) | 0.009 (3) | −0.005 (3) |
C10 | 0.054 (4) | 0.053 (4) | 0.034 (4) | −0.004 (3) | 0.010 (3) | −0.005 (3) |
C11 | 0.057 (4) | 0.073 (5) | 0.051 (4) | −0.002 (3) | 0.025 (3) | 0.002 (4) |
C12 | 0.062 (4) | 0.094 (6) | 0.060 (5) | −0.025 (4) | 0.028 (4) | −0.002 (5) |
C13 | 0.095 (6) | 0.064 (5) | 0.055 (5) | −0.025 (4) | 0.028 (5) | −0.009 (4) |
C14 | 0.078 (5) | 0.049 (4) | 0.055 (5) | 0.004 (3) | 0.019 (4) | −0.002 (4) |
C15 | 0.058 (4) | 0.053 (4) | 0.069 (5) | 0.016 (3) | 0.030 (4) | 0.005 (4) |
C16 | 0.049 (3) | 0.048 (4) | 0.065 (5) | 0.018 (3) | 0.023 (3) | 0.014 (4) |
C17 | 0.050 (4) | 0.044 (4) | 0.069 (5) | −0.013 (3) | 0.022 (3) | −0.017 (4) |
C18 | 0.040 (3) | 0.051 (4) | 0.053 (4) | −0.012 (3) | 0.015 (3) | −0.008 (4) |
C19 | 0.038 (3) | 0.072 (5) | 0.046 (4) | −0.016 (3) | 0.016 (3) | 0.001 (4) |
C20 | 0.049 (4) | 0.073 (5) | 0.063 (5) | −0.008 (4) | 0.014 (4) | 0.006 (4) |
C21 | 0.053 (4) | 0.126 (8) | 0.050 (5) | −0.021 (5) | −0.004 (4) | 0.014 (6) |
C22 | 0.078 (5) | 0.094 (7) | 0.065 (6) | −0.019 (5) | 0.008 (5) | −0.026 (5) |
C23 | 0.069 (5) | 0.075 (5) | 0.075 (6) | −0.020 (4) | 0.025 (4) | −0.017 (5) |
C24 | 0.030 (3) | 0.051 (4) | 0.056 (4) | 0.001 (3) | 0.014 (3) | −0.004 (3) |
C25 | 0.040 (3) | 0.039 (4) | 0.049 (4) | −0.008 (3) | 0.013 (3) | 0.006 (3) |
C26 | 0.041 (3) | 0.039 (4) | 0.041 (4) | −0.006 (3) | 0.011 (3) | 0.001 (3) |
C27 | 0.059 (4) | 0.049 (4) | 0.058 (5) | 0.000 (3) | 0.015 (4) | 0.005 (4) |
C28 | 0.068 (5) | 0.075 (5) | 0.054 (5) | −0.008 (4) | 0.005 (4) | −0.015 (4) |
C29 | 0.064 (5) | 0.074 (5) | 0.048 (5) | −0.010 (4) | −0.003 (4) | 0.002 (4) |
C30 | 0.046 (4) | 0.063 (5) | 0.057 (5) | 0.000 (3) | 0.001 (3) | 0.011 (4) |
C31 | 0.054 (4) | 0.041 (4) | 0.070 (5) | 0.007 (3) | 0.016 (3) | −0.015 (4) |
C32 | 0.040 (3) | 0.053 (4) | 0.072 (5) | 0.014 (3) | 0.019 (3) | −0.009 (4) |
Cl1 | 0.0901 (15) | 0.132 (2) | 0.109 (2) | −0.0049 (14) | 0.0177 (14) | 0.0137 (18) |
Cl2 | 0.1048 (16) | 0.0996 (18) | 0.113 (2) | −0.0105 (13) | 0.0196 (15) | −0.0147 (16) |
Cl3 | 0.133 (2) | 0.0693 (16) | 0.218 (4) | 0.0123 (14) | 0.049 (2) | 0.036 (2) |
C33 | 0.078 (5) | 0.062 (5) | 0.075 (6) | 0.007 (4) | 0.035 (4) | 0.018 (5) |
Ce1—O1 | 2.193 (4) | C12—C13 | 1.357 (9) |
Ce1—O2 | 2.218 (4) | C12—H12 | 0.9300 |
Ce1—O3 | 2.239 (4) | C13—C14 | 1.362 (9) |
Ce1—O4 | 2.188 (4) | C13—H13 | 0.9300 |
Ce1—N1 | 2.603 (4) | C14—H14 | 0.9300 |
Ce1—N2 | 2.628 (4) | C15—C16 | 1.501 (8) |
Ce1—N4 | 2.621 (4) | C15—H15A | 0.9700 |
Ce1—N3 | 2.626 (5) | C15—H15B | 0.9700 |
N1—C15 | 1.467 (7) | C16—H16A | 0.9700 |
N1—C1 | 1.478 (7) | C16—H16B | 0.9700 |
N1—H1 | 0.9100 | C17—C18 | 1.492 (8) |
N2—C16 | 1.471 (6) | C17—H17A | 0.9700 |
N2—C8 | 1.481 (7) | C17—H17B | 0.9700 |
N2—H2 | 0.9100 | C18—C23 | 1.385 (9) |
N3—C31 | 1.484 (7) | C18—C19 | 1.402 (8) |
N3—C17 | 1.491 (6) | C19—C20 | 1.391 (9) |
N3—H3 | 0.9100 | C20—C21 | 1.369 (9) |
N4—C32 | 1.460 (7) | C20—H20 | 0.9300 |
N4—C24 | 1.473 (6) | C21—C22 | 1.37 (1) |
N4—H4 | 0.9100 | C21—H21 | 0.9300 |
O1—C3 | 1.347 (6) | C22—C23 | 1.38 (1) |
O2—C10 | 1.350 (7) | C22—H22 | 0.9300 |
O3—C19 | 1.343 (7) | C23—H23 | 0.9300 |
O4—C26 | 1.330 (6) | C24—C25 | 1.491 (8) |
C1—C2 | 1.497 (8) | C24—H24A | 0.9700 |
C1—H1A | 0.9700 | C24—H24B | 0.9700 |
C1—H1B | 0.9700 | C25—C30 | 1.387 (8) |
C2—C3 | 1.407 (8) | C25—C26 | 1.396 (7) |
C2—C7 | 1.410 (8) | C26—C27 | 1.394 (8) |
C3—C4 | 1.372 (8) | C27—C28 | 1.383 (8) |
C4—C5 | 1.380 (9) | C27—H27 | 0.9300 |
C4—H4A | 0.9300 | C28—C29 | 1.348 (9) |
C5—C6 | 1.38 (1) | C28—H28 | 0.9300 |
C5—H5 | 0.9300 | C29—C30 | 1.391 (9) |
C6—C7 | 1.372 (9) | C29—H29 | 0.9300 |
C6—H6 | 0.9300 | C30—H30 | 0.9300 |
C7—H7 | 0.9300 | C31—C32 | 1.519 (8) |
C8—C9 | 1.510 (8) | C31—H31A | 0.9700 |
C8—H8A | 0.9700 | C31—H31B | 0.9700 |
C8—H8B | 0.9700 | C32—H32A | 0.9700 |
C9—C14 | 1.391 (8) | C32—H32B | 0.9700 |
C9—C10 | 1.402 (8) | Cl1—C33 | 1.745 (7) |
C10—C11 | 1.389 (8) | Cl2—C33 | 1.733 (8) |
C11—C12 | 1.390 (9) | Cl3—C33 | 1.715 (7) |
C11—H11 | 0.9300 | C33—H33 | 0.9800 |
O4—Ce1—O1 | 95.7 (2) | C11—C10—C9 | 118.3 (6) |
O4—Ce1—O2 | 90.7 (2) | C10—C11—C12 | 120.1 (7) |
O1—Ce1—O2 | 149.1 (1) | C10—C11—H11 | 119.9 |
O4—Ce1—O3 | 147.2 (1) | C12—C11—H11 | 119.9 |
O1—Ce1—O3 | 95.1 (2) | C13—C12—C11 | 121.5 (7) |
O2—Ce1—O3 | 95.7 (2) | C13—C12—H12 | 119.3 |
O4—Ce1—N1 | 80.7 (1) | C11—C12—H12 | 119.3 |
O1—Ce1—N1 | 71.7 (1) | C12—C13—C14 | 119.0 (7) |
O2—Ce1—N1 | 139.2 (2) | C12—C13—H13 | 120.5 |
O3—Ce1—N1 | 73.6 (2) | C14—C13—H13 | 120.5 |
O4—Ce1—N4 | 72.5 (2) | C13—C14—C9 | 121.7 (7) |
O1—Ce1—N4 | 72.9 (1) | C13—C14—H14 | 119.1 |
O2—Ce1—N4 | 80.4 (1) | C9—C14—H14 | 119.1 |
O3—Ce1—N4 | 140.3 (2) | N1—C15—C16 | 110.4 (5) |
N1—Ce1—N4 | 132.6 (2) | N1—C15—H15A | 109.6 |
O4—Ce1—N3 | 138.8 (1) | C16—C15—H15A | 109.6 |
O1—Ce1—N3 | 79.7 (2) | N1—C15—H15B | 109.6 |
O2—Ce1—N3 | 75.8 (2) | C16—C15—H15B | 109.6 |
O3—Ce1—N3 | 73.7 (1) | H15A—C15—H15B | 108.1 |
N1—Ce1—N3 | 133.7 (1) | N2—C16—C15 | 108.5 (5) |
N4—Ce1—N3 | 67.1 (1) | N2—C16—H16A | 110.0 |
O4—Ce1—N2 | 72.7 (1) | C15—C16—H16A | 110.0 |
O1—Ce1—N2 | 137.8 (1) | N2—C16—H16B | 110.0 |
O2—Ce1—N2 | 72.8 (1) | C15—C16—H16B | 110.0 |
O3—Ce1—N2 | 78.5 (2) | H16A—C16—H16B | 108.4 |
N1—Ce1—N2 | 66.5 (1) | N3—C17—C18 | 111.7 (5) |
N4—Ce1—N2 | 135.3 (1) | N3—C17—H17A | 109.3 |
N3—Ce1—N2 | 135.2 (2) | C18—C17—H17A | 109.3 |
C15—N1—C1 | 110.5 (5) | N3—C17—H17B | 109.3 |
C15—N1—Ce1 | 113.5 (3) | C18—C17—H17B | 109.3 |
C1—N1—Ce1 | 114.5 (3) | H17A—C17—H17B | 107.9 |
C15—N1—H1 | 105.8 | C23—C18—C19 | 119.3 (7) |
C1—N1—H1 | 105.8 | C23—C18—C17 | 121.7 (6) |
Ce1—N1—H1 | 105.8 | C19—C18—C17 | 119.0 (6) |
C16—N2—C8 | 112.0 (4) | O3—C19—C20 | 120.6 (7) |
C16—N2—Ce1 | 110.9 (3) | O3—C19—C18 | 121.3 (6) |
C8—N2—Ce1 | 114.4 (3) | C20—C19—C18 | 118.1 (7) |
C16—N2—H2 | 106.3 | C21—C20—C19 | 120.8 (7) |
C8—N2—H2 | 106.3 | C21—C20—H20 | 119.6 |
Ce1—N2—H2 | 106.3 | C19—C20—H20 | 119.6 |
C31—N3—C17 | 111.2 (5) | C22—C21—C20 | 122.0 (8) |
C31—N3—Ce1 | 110.5 (3) | C22—C21—H21 | 119.0 |
C17—N3—Ce1 | 113.6 (3) | C20—C21—H21 | 119.0 |
C31—N3—H3 | 107.1 | C21—C22—C23 | 117.7 (8) |
C17—N3—H3 | 107.1 | C21—C22—H22 | 121.2 |
Ce1—N3—H3 | 107.1 | C23—C22—H22 | 121.2 |
C32—N4—C24 | 111.9 (4) | C22—C23—C18 | 122.1 (7) |
C32—N4—Ce1 | 112.8 (3) | C22—C23—H23 | 118.9 |
C24—N4—Ce1 | 114.9 (3) | C18—C23—H23 | 118.9 |
C32—N4—H4 | 105.4 | N4—C24—C25 | 115.1 (4) |
C24—N4—H4 | 105.4 | N4—C24—H24A | 108.5 |
Ce1—N4—H4 | 105.4 | C25—C24—H24A | 108.5 |
C3—O1—Ce1 | 143.7 (4) | N4—C24—H24B | 108.5 |
C10—O2—Ce1 | 137.1 (4) | C25—C24—H24B | 108.5 |
C19—O3—Ce1 | 135.0 (3) | H24A—C24—H24B | 107.5 |
C26—O4—Ce1 | 143.9 (3) | C30—C25—C26 | 119.2 (6) |
N1—C1—C2 | 111.5 (5) | C30—C25—C24 | 120.9 (5) |
N1—C1—H1A | 109.3 | C26—C25—C24 | 119.7 (5) |
C2—C1—H1A | 109.3 | O4—C26—C27 | 120.0 (5) |
N1—C1—H1B | 109.3 | O4—C26—C25 | 121.5 (5) |
C2—C1—H1B | 109.3 | C27—C26—C25 | 118.5 (5) |
H1A—C1—H1B | 108.0 | C28—C27—C26 | 121.0 (6) |
C3—C2—C7 | 118.2 (6) | C28—C27—H27 | 119.5 |
C3—C2—C1 | 120.9 (5) | C26—C27—H27 | 119.5 |
C7—C2—C1 | 120.9 (6) | C29—C28—C27 | 120.7 (7) |
O1—C3—C4 | 121.5 (6) | C29—C28—H28 | 119.6 |
O1—C3—C2 | 118.6 (5) | C27—C28—H28 | 119.6 |
C4—C3—C2 | 119.8 (6) | C28—C29—C30 | 119.3 (6) |
C3—C4—C5 | 119.6 (7) | C28—C29—H29 | 120.3 |
C3—C4—H4A | 120.2 | C30—C29—H29 | 120.3 |
C5—C4—H4A | 120.2 | C25—C30—C29 | 121.3 (6) |
C6—C5—C4 | 122.9 (7) | C25—C30—H30 | 119.3 |
C6—C5—H5 | 118.6 | C29—C30—H30 | 119.3 |
C4—C5—H5 | 118.6 | N3—C31—C32 | 108.6 (5) |
C7—C6—C5 | 117.4 (7) | N3—C31—H31A | 110.0 |
C7—C6—H6 | 121.3 | C32—C31—H31A | 110.0 |
C5—C6—H6 | 121.3 | N3—C31—H31B | 110.0 |
C6—C7—C2 | 122.1 (6) | C32—C31—H31B | 110.0 |
C6—C7—H7 | 118.9 | H31A—C31—H31B | 108.3 |
C2—C7—H7 | 118.9 | N4—C32—C31 | 110.6 (4) |
N2—C8—C9 | 111.3 (5) | N4—C32—H32A | 109.5 |
N2—C8—H8A | 109.4 | C31—C32—H32A | 109.5 |
C9—C8—H8A | 109.4 | N4—C32—H32B | 109.5 |
N2—C8—H8B | 109.4 | C31—C32—H32B | 109.5 |
C9—C8—H8B | 109.4 | H32A—C32—H32B | 108.1 |
H8A—C8—H8B | 108.0 | Cl3—C33—Cl2 | 110.8 (4) |
C14—C9—C10 | 119.4 (6) | Cl3—C33—Cl1 | 109.4 (4) |
C14—C9—C8 | 121.7 (6) | Cl2—C33—Cl1 | 110.4 (4) |
C10—C9—C8 | 118.9 (6) | Cl3—C33—H33 | 108.7 |
O2—C10—C11 | 121.6 (6) | Cl2—C33—H33 | 108.7 |
O2—C10—C9 | 120.2 (5) | Cl1—C33—H33 | 108.7 |
O4—Ce1—N1—C15 | −64.5 (4) | N4—Ce1—O4—C26 | 16.1 (6) |
O1—Ce1—N1—C15 | −163.7 (4) | N3—Ce1—O4—C26 | 27.0 (7) |
O2—Ce1—N1—C15 | 15.6 (5) | N2—Ce1—O4—C26 | 167.6 (6) |
O3—Ce1—N1—C15 | 95.0 (4) | C15—N1—C1—C2 | −159.3 (5) |
N4—Ce1—N1—C15 | −120.1 (4) | Ce1—N1—C1—C2 | 71.0 (5) |
N3—Ce1—N1—C15 | 141.5 (4) | N1—C1—C2—C3 | −54.8 (7) |
N2—Ce1—N1—C15 | 10.7 (4) | N1—C1—C2—C7 | 126.2 (6) |
O4—Ce1—N1—C1 | 63.7 (4) | Ce1—O1—C3—C4 | −141.8 (5) |
O1—Ce1—N1—C1 | −35.5 (4) | Ce1—O1—C3—C2 | 38.4 (9) |
O2—Ce1—N1—C1 | 143.8 (4) | C7—C2—C3—O1 | −179.6 (5) |
O3—Ce1—N1—C1 | −136.8 (4) | C1—C2—C3—O1 | 1.4 (8) |
N4—Ce1—N1—C1 | 8.1 (5) | C7—C2—C3—C4 | 0.6 (8) |
N3—Ce1—N1—C1 | −90.3 (4) | C1—C2—C3—C4 | −178.4 (5) |
N2—Ce1—N1—C1 | 138.9 (4) | O1—C3—C4—C5 | −179.6 (5) |
O4—Ce1—N2—C16 | 108.5 (4) | C2—C3—C4—C5 | 0.2 (9) |
O1—Ce1—N2—C16 | 29.4 (5) | C3—C4—C5—C6 | −1 (1) |
O2—Ce1—N2—C16 | −155.2 (4) | C4—C5—C6—C7 | 1 (1) |
O3—Ce1—N2—C16 | −55.5 (4) | C5—C6—C7—C2 | 0 (1) |
N1—Ce1—N2—C16 | 21.4 (4) | C3—C2—C7—C6 | −0.6 (9) |
N4—Ce1—N2—C16 | 148.9 (4) | C1—C2—C7—C6 | 178.5 (6) |
N3—Ce1—N2—C16 | −107.8 (4) | C16—N2—C8—C9 | −163.6 (5) |
O4—Ce1—N2—C8 | −123.6 (4) | Ce1—N2—C8—C9 | 69.0 (6) |
O1—Ce1—N2—C8 | 157.3 (3) | N2—C8—C9—C14 | 122.0 (6) |
O2—Ce1—N2—C8 | −27.3 (3) | N2—C8—C9—C10 | −59.9 (7) |
O3—Ce1—N2—C8 | 72.4 (4) | Ce1—O2—C10—C11 | −129.1 (5) |
N1—Ce1—N2—C8 | 149.3 (4) | Ce1—O2—C10—C9 | 51.5 (8) |
N4—Ce1—N2—C8 | −83.2 (4) | C14—C9—C10—O2 | 178.8 (5) |
N3—Ce1—N2—C8 | 20.1 (4) | C8—C9—C10—O2 | 0.7 (9) |
O4—Ce1—N3—C31 | −32.3 (5) | C14—C9—C10—C11 | −0.6 (9) |
O1—Ce1—N3—C31 | 54.6 (4) | C8—C9—C10—C11 | −178.7 (6) |
O2—Ce1—N3—C31 | −106.5 (4) | O2—C10—C11—C12 | −179.4 (6) |
O3—Ce1—N3—C31 | 153.1 (4) | C9—C10—C11—C12 | 0.0 (9) |
N1—Ce1—N3—C31 | 106.6 (4) | C10—C11—C12—C13 | 0 (1) |
N4—Ce1—N3—C31 | −21.1 (3) | C11—C12—C13—C14 | 0 (1) |
N2—Ce1—N3—C31 | −153.1 (3) | C12—C13—C14—C9 | 0 (1) |
O4—Ce1—N3—C17 | −158.1 (4) | C10—C9—C14—C13 | 1 (1) |
O1—Ce1—N3—C17 | −71.2 (4) | C8—C9—C14—C13 | 179.0 (6) |
O2—Ce1—N3—C17 | 127.7 (4) | C1—N1—C15—C16 | −171.8 (5) |
O3—Ce1—N3—C17 | 27.3 (4) | Ce1—N1—C15—C16 | −41.6 (6) |
N1—Ce1—N3—C17 | −19.2 (5) | C8—N2—C16—C15 | 179.8 (5) |
N4—Ce1—N3—C17 | −146.9 (4) | Ce1—N2—C16—C15 | −50.9 (6) |
N2—Ce1—N3—C17 | 81.1 (4) | N1—C15—C16—N2 | 62.5 (6) |
O4—Ce1—N4—C32 | 161.1 (4) | C31—N3—C17—C18 | 165.2 (5) |
O1—Ce1—N4—C32 | −97.0 (4) | Ce1—N3—C17—C18 | −69.4 (6) |
O2—Ce1—N4—C32 | 67.3 (4) | N3—C17—C18—C23 | −121.0 (6) |
O3—Ce1—N4—C32 | −20.0 (5) | N3—C17—C18—C19 | 60.0 (7) |
N1—Ce1—N4—C32 | −140.3 (4) | Ce1—O3—C19—C20 | 131.1 (5) |
N3—Ce1—N4—C32 | −11.2 (4) | Ce1—O3—C19—C18 | −51.5 (8) |
N2—Ce1—N4—C32 | 120.7 (4) | C23—C18—C19—O3 | −178.2 (5) |
O4—Ce1—N4—C24 | 31.2 (4) | C17—C18—C19—O3 | 0.8 (8) |
O1—Ce1—N4—C24 | 133.1 (4) | C23—C18—C19—C20 | −0.7 (9) |
O2—Ce1—N4—C24 | −62.6 (4) | C17—C18—C19—C20 | 178.3 (5) |
O3—Ce1—N4—C24 | −149.9 (4) | O3—C19—C20—C21 | 177.7 (6) |
N1—Ce1—N4—C24 | 89.8 (4) | C18—C19—C20—C21 | 0.2 (9) |
N3—Ce1—N4—C24 | −141.1 (4) | C19—C20—C21—C22 | 0 (1) |
N2—Ce1—N4—C24 | −9.2 (5) | C20—C21—C22—C23 | 0 (1) |
O4—Ce1—O1—C3 | −96.5 (6) | C21—C22—C23—C18 | 0 (1) |
O2—Ce1—O1—C3 | 162.6 (5) | C19—C18—C23—C22 | 1 (1) |
O3—Ce1—O1—C3 | 52.5 (6) | C17—C18—C23—C22 | −178.0 (6) |
N1—Ce1—O1—C3 | −18.3 (6) | C32—N4—C24—C25 | 163.9 (5) |
N4—Ce1—O1—C3 | −166.2 (7) | Ce1—N4—C24—C25 | −65.7 (6) |
N3—Ce1—O1—C3 | 124.8 (6) | N4—C24—C25—C30 | −131.3 (5) |
N2—Ce1—O1—C3 | −26.1 (7) | N4—C24—C25—C26 | 53.5 (7) |
O4—Ce1—O2—C10 | 39.8 (5) | Ce1—O4—C26—C27 | 148.5 (5) |
O1—Ce1—O2—C10 | 142.1 (5) | Ce1—O4—C26—C25 | −32.8 (9) |
O3—Ce1—O2—C10 | −107.9 (5) | C30—C25—C26—O4 | −179.3 (5) |
N1—Ce1—O2—C10 | −36.6 (6) | C24—C25—C26—O4 | −4.0 (8) |
N4—Ce1—O2—C10 | 111.9 (5) | C30—C25—C26—C27 | −0.5 (8) |
N3—Ce1—O2—C10 | −179.5 (5) | C24—C25—C26—C27 | 174.7 (5) |
N2—Ce1—O2—C10 | −31.8 (5) | O4—C26—C27—C28 | 178.4 (6) |
O4—Ce1—O3—C19 | −142.9 (5) | C25—C26—C27—C28 | −0.3 (9) |
O1—Ce1—O3—C19 | 108.3 (6) | C26—C27—C28—C29 | 0 (1) |
O2—Ce1—O3—C19 | −42.8 (6) | C27—C28—C29—C30 | 0 (1) |
N1—Ce1—O3—C19 | 177.5 (6) | C26—C25—C30—C29 | 1.3 (9) |
N4—Ce1—O3—C19 | 39.0 (7) | C24—C25—C30—C29 | −173.9 (6) |
N3—Ce1—O3—C19 | 30.6 (6) | C28—C29—C30—C25 | −1 (1) |
N2—Ce1—O3—C19 | −113.9 (6) | C17—N3—C31—C32 | 177.8 (5) |
O1—Ce1—O4—C26 | −53.9 (6) | Ce1—N3—C31—C32 | 50.6 (6) |
O2—Ce1—O4—C26 | 95.9 (6) | C24—N4—C32—C31 | 173.5 (5) |
O3—Ce1—O4—C26 | −162.6 (5) | Ce1—N4—C32—C31 | 42.1 (6) |
N1—Ce1—O4—C26 | −124.3 (6) | N3—C31—C32—N4 | −63.2 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.91 | 2.73 | 3.604 (5) | 162 |
C33—H33···O3 | 0.98 | 2.51 | 3.437 (7) | 157 |
N2—H2···Cl2i | 0.91 | 2.94 | 3.762 (5) | 151 |
C4—H4A···Cl3ii | 0.93 | 2.79 | 3.646 (7) | 153 |
C29—H29···Cg1iii | 0.93 | 2.85 | 3.626 (7) | 142 |
C31—H31B···Cg2iv | 0.97 | 2.79 | 3.712 (6) | 158 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−3/2, −y−1/2, z−3/2; (iv) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ce(C16H18N2O2)2]·CHCl3 |
Mr | 800.14 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 12.493 (1), 14.199 (2), 20.253 (2) |
β (°) | 104.263 (2) |
V (Å3) | 3481.8 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.58 |
Crystal size (mm) | 0.57 × 0.51 × 0.39 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.466, 0.578 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17037, 6130, 3810 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.129, 1.06 |
No. of reflections | 6130 |
No. of parameters | 406 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.50, −0.77 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
Ce1—O1 | 2.193 (4) | Ce1—N1 | 2.603 (4) |
Ce1—O2 | 2.218 (4) | Ce1—N2 | 2.628 (4) |
Ce1—O3 | 2.239 (4) | Ce1—N4 | 2.621 (4) |
Ce1—O4 | 2.188 (4) | Ce1—N3 | 2.626 (5) |
O4—Ce1—O1 | 95.7 (2) | N1—Ce1—N4 | 132.6 (2) |
O4—Ce1—O2 | 90.7 (2) | N1—Ce1—N3 | 133.7 (1) |
O1—Ce1—O2 | 149.1 (1) | N4—Ce1—N3 | 67.1 (1) |
O4—Ce1—O3 | 147.2 (1) | N1—Ce1—N2 | 66.5 (1) |
O1—Ce1—O3 | 95.1 (2) | N4—Ce1—N2 | 135.3 (1) |
O2—Ce1—O3 | 95.7 (2) | N3—Ce1—N2 | 135.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.91 | 2.73 | 3.604 (5) | 161.8 |
C33—H33···O3 | 0.98 | 2.51 | 3.437 (7) | 157.0 |
N2—H2···Cl2i | 0.91 | 2.94 | 3.762 (5) | 151.4 |
C4—H4A···Cl3ii | 0.93 | 2.79 | 3.646 (7) | 153.0 |
C29—H29···Cg1iii | 0.93 | 2.85 | 3.626 (7) | 142 |
C31—H31B···Cg2iv | 0.97 | 2.79 | 3.712 (6) | 158 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−3/2, −y−1/2, z−3/2; (iv) −x+1/2, y+1/2, −z+1/2. |
Some CeIVcomplexs has been shown to hydrolyze DNA effectively at a reasonable rate (Franklin, 2001; Williams et al.,1999; Takasaki & Chin, 1994; Branum et al., 2001; Komiyama et al., 1999). We have reported recently the crystyl structure of a CeIV complex (Liu et al., 2007). As part of our study of the CeIVcomplexes with the diamine derives, We report here the crystal structure of a new CeIVcomplex, bis[N,N'-bis(2-oxidobenzyl)ethane-1,2-diamine-κ2N,N',O,O'] cerium(IV) chloroform disolvate, (I).
Compound (I) crystallizes in the space group P21/n, and the asymmetric unit contains a title complex and one chloroform molecule, which are linked by one N—H···Cl and one C—H···O hydrogen bonds into a dimeric structure (Table 2 and Fig. 1). The CeIV atom is coordinated by four O atoms and four N atoms from two tetradentate ligand, N,N'-(2-oxidobenzyl)ethane-1,2-diamine, forming a complex eight-coordinated stereochemistry geometry (Fig. 1). Two least-squares planes are defined by the atoms Ce1/O1/O2/N1/N2 and Ce1/O3/O4/N3/N4, and which are approximately planar, the maximum deviation are -0.079 (3) Å for N2 and -0.118 (3) Å for N3, respectively. The dihedral angle between the two least-squares planes are 89.23 (9)°. The average Ce—O and Ce—N distance are 2.192 (4) Å and 2.620 (4) Å, these values are approximately similar to the CeIV complexes reported [2.199 (4)Å and 2.624 (4) Å; Liu et al., 2007], and the bond angles ranges around CeIV atom are O—Ce—O of 95.1 (2)° - 149.1 (1)°, N—Ce—N of 66.5 (1)° - 135.3 (1)° (see in Table 1). The crystal structure of (I) is stabilized by two C—H···π, one N—H···Cl and one C—H···Cl interactions (Table. 2).