Bis{2,2′-[ethane-1,2-diylbis(iminomethyl­ene)]diphenolato-κ2O,N,N′,O′}cerium(IV) chloro­form solvate

Yang, S.-P.; Han, L.-J.; Wang, D.-Q.; Wang, B.

doi:10.1107/S160053680705101X

Bis{2,2′-[ethane-1,2-diylbis(iminomethylene)]diphenolato-κ²O,N,N′,O′}cerium(IV) chloroform solvate

S.-P. Yang, L.-J. Han, D.-Q. Wang and B. Wang

In the title compound, [Ce(C₁₆H₁₈N₂O₂)₂]·CHCl₃, the Ce^IV atom has an eight-coordinate geometry involving two tetradentate N,N′-(2-oxidobenzyl)ethane-1,2-diamine ligands. The asymmetric unit contains one molecule of the title complex and one chloroform molecule, linked by C—H

O and N—H

Cl hydrogen bonds. These neighbouring molecules are connected by two C—H

π interactions, and by N—H

Cl and C—H

Cl interactions, resulting in a three-dimensional network.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705101X/at2424sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680705101X/at2424Isup2.hkl Contains datablock I

CCDC reference: 656518

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.010 Å
R factor = 0.046
wR factor = 0.128
Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.94
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C21    -   C22     ..       5.48 su
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C33
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         10
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2     ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3     ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4     ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  CL2     ..       2.94 Ang.
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      56.00 A   3 

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.935
            Tmax scaled      0.540 Tmin scaled      0.436
PLAT793_ALERT_1_G Check the Absolute Configuration of N1     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of N2     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of N3     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of N4     = ...          S
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ce1         (3)       3.42

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Some Ce^IVcomplexs 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 Ce^IV complex (Liu et al., 2007). As part of our study of the Ce^IVcomplexes with the diamine derives, We report here the crystal structure of a new Ce^IVcomplex, 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 Ce^IV 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 Ce^IV complexes reported [2.199 (4)Å and 2.624 (4) Å; Liu et al., 2007], and the bond angles ranges around Ce^IV 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).

Related literature top

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).

Experimental top

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.

Structure description top

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).

Computing details top

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).

Figures top

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.

Bis{2,2'-[ethane-1,2-diylbis(iminomethylene)]diphenolato- κ⁴O,N,N',O'}cerium(IV) chloroform solvate top

Crystal data top

[Ce(C₁₆H₁₈N₂O₂)₂]·CHCl₃	F(000) = 1616
M_r = 800.14	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	6130 independent reflections
Radiation source: fine-focus sealed tube	3810 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→14
T_min = 0.466, T_max = 0.578	k = −16→16
17037 measured reflections	l = −18→24

Refinement top

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(F_o²) + (0.0568P)²] where P = (F_o² + 2F_c²)/3
6130 reflections	(Δ/σ)_max < 0.001
406 parameters	Δρ_max = 1.50 e Å⁻³
0 restraints	Δρ_min = −0.77 e Å⁻³

Crystal data top

[Ce(C₁₆H₁₈N₂O₂)₂]·CHCl₃	V = 3481.8 (7) Å³
M_r = 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)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6130 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3810 reflections with I > 2σ(I)
T_min = 0.466, T_max = 0.578	R_int = 0.064
17037 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.06	Δρ_max = 1.50 e Å⁻³
6130 reflections	Δρ_min = −0.77 e Å⁻³
406 parameters

Special details top

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	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Cg2^iv	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
M_r	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)
T_min, T_max	0.466, 0.578
No. of measured, independent and observed [I > 2σ(I)] reflections	17037, 6130, 3810
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	1.50, −0.77

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Selected geometric parameters (Å, º) top

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)