Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046739/ci2472sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046739/ci2472Isup2.hkl |
CCDC reference: 667099
Compound (I) was synthesized according to the literature method of Shi et al. (2004). The reaction of LaCl3.7H2O (37 mg, 0.1 mmol) with 1,10-phenanthroline (20 mg, 0.1 mmol) in EtOH (25 ml) for a few minutes afforded a white powder solid, which was filtered, washed with acetone, and dried in air. Single crystals suitable for X-ray analysis were obtained by slow diffusion of Et2O into the DMF solution of the solid mentioned above after several days (yield: ~30%). Analysis calculated for C33H37Cl3LaN7O3: C 48.05, H 4.52, N 11.88%; found: C 48.26, H 4.48, N 11.96%.
H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 (aromatic) or 0.96 Å (methyl) and Uiso(H) = 1.2–1.5 Ueq(C). A rotating group model was used for the methyl groups.
In recent years, much attention has been focused on the synthetic approach and structural control of rare-earth (RE) complexes with various ligands, such as 2,2'-bipyridine and 1,10-phenanthroline (phen), not only because of their fascinating structural diversities but also their potential applications as optical materials, electronic materials, catalytic materials, molecular based magnets and so on (Bünzli, 2006; Suárez et al., 2004). Many novel functional complexes with 2,2'-bipyridine-like ligands have been reported (Edmonds et al., 2004; Molander & Romero, 2002; Wan et al., 2003; Ye et al., 2005). We report here the crystal structure of a LaIII complex with a chelating 1,10-phenanthroline ligand, [La(phen)2(DMF)Cl3](DMF)2, the title compound, (I) (DMF is N,N-dimethylformamide).
Compound (I) consists of mononuclear [La(phen)2(DMF)Cl3] units and free DMF molecules. The LaIII ion is eight-coordinated and surrounded by four N donors from two phen ligands, one O atom from one DMF molecule, and three Cl- anions (Fig. 1). The La—Cl distances range from 2.7905 (10) to 2.8212 (10) Å, and those of La—N range from 2.694 (3) to 2.758 (3) Å, which are in the normal range expected for such coordination complexes (Bünzli, 2006) (Table 1). The adjacent mononuclear [La(phen)2(DMF)Cl3] units are linked into a chain along the a axis by weak C—H···Cl hydrogen bonding interactions (Table 2) between the phen ligands and coordinated Cl- anions (Desiraju & Steiner,1999). The chains are cross-linked to generate a two-dimensional network parallel to the ab plane by intermolecular π-π stacking interactions between the phenanthroline ring systems, with centroid-centroid distances ranging from 3.589 (2) to 3.708 (2) Å (Fig. 2).
For synthesis, see: Shi et al. (2004). For hydrogen-bond details, see: Desiraju & Steiner (1999). For related literature, see: Bünzli (2006); Edmonds et al. (2004); Molander & Romero (2002); Suárez et al. (2004); Wan et al. (2003); Ye et al. (2005).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998) and PLATON (Spek, 2003).
[LaCl3(C12H8N2)2(C3H7NO)]·2C3H7NO | F(000) = 1664 |
Mr = 824.96 | Dx = 1.513 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5052 reflections |
a = 10.0344 (11) Å | θ = 2.3–22.9° |
b = 17.3861 (19) Å | µ = 1.44 mm−1 |
c = 20.768 (2) Å | T = 294 K |
β = 91.521 (1)° | Block, colourless |
V = 3621.9 (7) Å3 | 0.28 × 0.18 × 0.16 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 6738 independent reflections |
Radiation source: fine-focus sealed tube | 5246 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
φ and ω scans | θmax = 25.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −12→12 |
Tmin = 0.691, Tmax = 0.800 | k = −21→21 |
26591 measured reflections | l = −25→25 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0362P)2 + 2.0867P] where P = (Fo2 + 2Fc2)/3 |
6738 reflections | (Δ/σ)max = 0.001 |
430 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
[LaCl3(C12H8N2)2(C3H7NO)]·2C3H7NO | V = 3621.9 (7) Å3 |
Mr = 824.96 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.0344 (11) Å | µ = 1.44 mm−1 |
b = 17.3861 (19) Å | T = 294 K |
c = 20.768 (2) Å | 0.28 × 0.18 × 0.16 mm |
β = 91.521 (1)° |
Bruker SMART CCD area-detector diffractometer | 6738 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 5246 reflections with I > 2σ(I) |
Tmin = 0.691, Tmax = 0.800 | Rint = 0.043 |
26591 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.65 e Å−3 |
6738 reflections | Δρmin = −0.35 e Å−3 |
430 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 | ||
La1 | 0.26566 (2) | 0.257762 (11) | 0.006982 (10) | 0.03058 (8) | |
Cl1 | 0.42502 (11) | 0.22137 (6) | −0.09739 (5) | 0.0509 (3) | |
Cl2 | 0.09143 (12) | 0.32315 (6) | −0.08456 (5) | 0.0587 (3) | |
Cl3 | 0.03624 (10) | 0.23105 (6) | 0.07937 (5) | 0.0520 (3) | |
O1 | 0.3370 (3) | 0.27886 (15) | 0.12551 (12) | 0.0440 (6) | |
O2 | 0.6722 (5) | 0.1430 (3) | 0.2457 (2) | 0.1301 (19) | |
O3 | 0.7636 (5) | 0.4546 (3) | 0.2676 (3) | 0.144 (2) | |
N1 | 0.2527 (3) | 0.40798 (16) | 0.04116 (15) | 0.0373 (7) | |
N2 | 0.4970 (3) | 0.34111 (17) | 0.02658 (15) | 0.0400 (8) | |
N3 | 0.3672 (3) | 0.12430 (16) | 0.05227 (14) | 0.0356 (7) | |
N4 | 0.1654 (3) | 0.12260 (16) | −0.03921 (14) | 0.0352 (7) | |
N5 | 0.3434 (4) | 0.35285 (19) | 0.21560 (15) | 0.0496 (9) | |
N6 | 0.8099 (4) | 0.2435 (2) | 0.2642 (2) | 0.0698 (11) | |
N7 | 0.7912 (6) | 0.5802 (3) | 0.24929 (19) | 0.0836 (14) | |
C1 | 0.6158 (4) | 0.3090 (3) | 0.0201 (2) | 0.0585 (12) | |
H1 | 0.6203 | 0.2614 | 0.0000 | 0.070* | |
C2 | 0.7353 (4) | 0.3434 (3) | 0.0421 (3) | 0.0701 (14) | |
H2 | 0.8166 | 0.3187 | 0.0373 | 0.084* | |
C3 | 0.7290 (4) | 0.4140 (3) | 0.0707 (2) | 0.0641 (13) | |
H3 | 0.8067 | 0.4377 | 0.0859 | 0.077* | |
C4 | 0.6068 (4) | 0.4505 (2) | 0.07696 (19) | 0.0468 (10) | |
C5 | 0.5942 (5) | 0.5259 (3) | 0.1058 (2) | 0.0581 (12) | |
H5 | 0.6703 | 0.5528 | 0.1188 | 0.070* | |
C6 | 0.4740 (5) | 0.5572 (2) | 0.1138 (2) | 0.0598 (12) | |
H6 | 0.4683 | 0.6055 | 0.1328 | 0.072* | |
C7 | 0.3546 (4) | 0.5186 (2) | 0.09412 (19) | 0.0462 (10) | |
C8 | 0.2273 (5) | 0.5492 (2) | 0.1026 (2) | 0.0632 (13) | |
H8 | 0.2175 | 0.5962 | 0.1233 | 0.076* | |
C9 | 0.1166 (5) | 0.5098 (2) | 0.0802 (2) | 0.0602 (12) | |
H9 | 0.0315 | 0.5296 | 0.0854 | 0.072* | |
C10 | 0.1348 (4) | 0.4399 (2) | 0.04980 (19) | 0.0453 (10) | |
H10 | 0.0595 | 0.4137 | 0.0345 | 0.054* | |
C11 | 0.3634 (4) | 0.44669 (19) | 0.06299 (17) | 0.0357 (8) | |
C12 | 0.4919 (4) | 0.4117 (2) | 0.05481 (17) | 0.0375 (9) | |
C13 | 0.4663 (4) | 0.1231 (2) | 0.09572 (19) | 0.0428 (10) | |
H13 | 0.4993 | 0.1700 | 0.1107 | 0.051* | |
C14 | 0.5246 (4) | 0.0559 (2) | 0.1206 (2) | 0.0484 (10) | |
H14 | 0.5949 | 0.0584 | 0.1506 | 0.058* | |
C15 | 0.4764 (4) | −0.0129 (2) | 0.10010 (18) | 0.0433 (10) | |
H15 | 0.5136 | −0.0583 | 0.1160 | 0.052* | |
C16 | 0.3702 (4) | −0.0157 (2) | 0.05486 (17) | 0.0377 (9) | |
C17 | 0.3136 (4) | −0.0860 (2) | 0.0320 (2) | 0.0489 (10) | |
H17 | 0.3460 | −0.1323 | 0.0485 | 0.059* | |
C18 | 0.2146 (4) | −0.0872 (2) | −0.01270 (19) | 0.0474 (10) | |
H18 | 0.1801 | −0.1340 | −0.0269 | 0.057* | |
C19 | 0.1617 (4) | −0.0170 (2) | −0.03869 (18) | 0.0380 (9) | |
C20 | 0.0596 (4) | −0.0155 (2) | −0.08625 (19) | 0.0494 (11) | |
H20 | 0.0237 | −0.0613 | −0.1021 | 0.059* | |
C21 | 0.0136 (4) | 0.0529 (2) | −0.1090 (2) | 0.0509 (11) | |
H21 | −0.0535 | 0.0545 | −0.1407 | 0.061* | |
C22 | 0.0683 (4) | 0.1209 (2) | −0.08395 (18) | 0.0437 (10) | |
H22 | 0.0350 | 0.1675 | −0.0995 | 0.052* | |
C23 | 0.2118 (3) | 0.0541 (2) | −0.01683 (17) | 0.0330 (8) | |
C24 | 0.3191 (3) | 0.05489 (19) | 0.03160 (17) | 0.0325 (8) | |
C25 | 0.2831 (4) | 0.3200 (2) | 0.16585 (19) | 0.0435 (9) | |
H25 | 0.1920 | 0.3285 | 0.1605 | 0.052* | |
C26 | 0.4842 (5) | 0.3404 (3) | 0.2277 (2) | 0.0818 (17) | |
H26A | 0.5181 | 0.3064 | 0.1957 | 0.123* | |
H26B | 0.4978 | 0.3179 | 0.2696 | 0.123* | |
H26C | 0.5304 | 0.3887 | 0.2260 | 0.123* | |
C27 | 0.2728 (6) | 0.4020 (3) | 0.2598 (2) | 0.0888 (19) | |
H27A | 0.1803 | 0.4043 | 0.2470 | 0.133* | |
H27B | 0.3103 | 0.4528 | 0.2591 | 0.133* | |
H27C | 0.2812 | 0.3814 | 0.3026 | 0.133* | |
C28 | 0.7594 (6) | 0.1871 (4) | 0.2296 (3) | 0.0913 (18) | |
H28 | 0.7935 | 0.1800 | 0.1888 | 0.110* | |
C29 | 0.9215 (7) | 0.2898 (4) | 0.2434 (3) | 0.125 (3) | |
H29A | 0.9457 | 0.2742 | 0.2009 | 0.187* | |
H29B | 0.9961 | 0.2826 | 0.2727 | 0.187* | |
H29C | 0.8964 | 0.3430 | 0.2428 | 0.187* | |
C30 | 0.7630 (5) | 0.2612 (3) | 0.3266 (2) | 0.0706 (14) | |
H30A | 0.6812 | 0.2341 | 0.3334 | 0.106* | |
H30B | 0.7477 | 0.3155 | 0.3298 | 0.106* | |
H30C | 0.8285 | 0.2458 | 0.3586 | 0.106* | |
C31 | 0.7195 (7) | 0.5191 (4) | 0.2607 (3) | 0.0947 (19) | |
H31 | 0.6279 | 0.5257 | 0.2638 | 0.114* | |
C32 | 0.9289 (7) | 0.5736 (6) | 0.2425 (4) | 0.176 (5) | |
H32A | 0.9736 | 0.5875 | 0.2822 | 0.265* | |
H32B | 0.9570 | 0.6072 | 0.2088 | 0.265* | |
H32C | 0.9506 | 0.5214 | 0.2318 | 0.265* | |
C33 | 0.7247 (9) | 0.6535 (4) | 0.2441 (3) | 0.163 (4) | |
H33A | 0.7305 | 0.6725 | 0.2009 | 0.245* | |
H33B | 0.7666 | 0.6894 | 0.2734 | 0.245* | |
H33C | 0.6327 | 0.6476 | 0.2547 | 0.245* |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.03234 (12) | 0.02500 (11) | 0.03420 (12) | 0.00314 (9) | −0.00294 (8) | −0.00165 (9) |
Cl1 | 0.0566 (6) | 0.0495 (6) | 0.0471 (6) | 0.0077 (5) | 0.0107 (5) | −0.0044 (5) |
Cl2 | 0.0715 (8) | 0.0464 (6) | 0.0568 (7) | 0.0191 (5) | −0.0240 (6) | −0.0020 (5) |
Cl3 | 0.0413 (5) | 0.0584 (7) | 0.0565 (6) | −0.0077 (5) | 0.0072 (5) | −0.0122 (5) |
O1 | 0.0524 (17) | 0.0405 (15) | 0.0387 (15) | 0.0028 (12) | −0.0036 (13) | −0.0026 (12) |
O2 | 0.125 (4) | 0.137 (4) | 0.128 (4) | −0.054 (3) | −0.008 (3) | −0.042 (3) |
O3 | 0.154 (5) | 0.095 (4) | 0.182 (5) | −0.011 (3) | −0.047 (4) | 0.037 (3) |
N1 | 0.0376 (18) | 0.0280 (16) | 0.0460 (19) | 0.0024 (13) | −0.0009 (15) | 0.0007 (14) |
N2 | 0.0380 (18) | 0.0356 (18) | 0.046 (2) | 0.0034 (14) | −0.0009 (15) | −0.0005 (14) |
N3 | 0.0353 (17) | 0.0339 (17) | 0.0373 (18) | 0.0038 (13) | −0.0059 (14) | −0.0009 (13) |
N4 | 0.0363 (17) | 0.0318 (17) | 0.0372 (17) | 0.0019 (13) | −0.0058 (14) | −0.0023 (13) |
N5 | 0.061 (2) | 0.051 (2) | 0.036 (2) | −0.0058 (17) | −0.0053 (17) | −0.0072 (16) |
N6 | 0.069 (3) | 0.064 (3) | 0.077 (3) | −0.002 (2) | 0.013 (2) | −0.014 (2) |
N7 | 0.139 (5) | 0.056 (3) | 0.055 (3) | −0.011 (3) | −0.005 (3) | 0.005 (2) |
C1 | 0.040 (2) | 0.051 (3) | 0.085 (3) | 0.013 (2) | 0.001 (2) | −0.005 (2) |
C2 | 0.033 (3) | 0.079 (4) | 0.099 (4) | 0.007 (2) | 0.001 (3) | 0.004 (3) |
C3 | 0.039 (3) | 0.078 (4) | 0.075 (3) | −0.011 (2) | −0.010 (2) | 0.007 (3) |
C4 | 0.049 (3) | 0.051 (3) | 0.040 (2) | −0.013 (2) | −0.0027 (19) | 0.0043 (19) |
C5 | 0.066 (3) | 0.058 (3) | 0.050 (3) | −0.027 (2) | −0.010 (2) | −0.002 (2) |
C6 | 0.079 (4) | 0.039 (2) | 0.061 (3) | −0.016 (2) | −0.004 (3) | −0.009 (2) |
C7 | 0.063 (3) | 0.031 (2) | 0.044 (2) | −0.0052 (19) | −0.001 (2) | −0.0037 (17) |
C8 | 0.083 (4) | 0.035 (2) | 0.072 (3) | 0.007 (2) | 0.005 (3) | −0.014 (2) |
C9 | 0.060 (3) | 0.046 (3) | 0.075 (3) | 0.020 (2) | −0.002 (3) | −0.009 (2) |
C10 | 0.042 (2) | 0.037 (2) | 0.057 (3) | 0.0067 (18) | −0.004 (2) | −0.0037 (19) |
C11 | 0.046 (2) | 0.0257 (18) | 0.035 (2) | −0.0021 (16) | −0.0010 (18) | 0.0037 (15) |
C12 | 0.041 (2) | 0.036 (2) | 0.036 (2) | −0.0059 (17) | −0.0014 (17) | 0.0055 (16) |
C13 | 0.046 (2) | 0.033 (2) | 0.049 (2) | 0.0002 (17) | −0.010 (2) | −0.0032 (17) |
C14 | 0.046 (2) | 0.049 (3) | 0.050 (3) | 0.0069 (19) | −0.011 (2) | 0.002 (2) |
C15 | 0.050 (2) | 0.036 (2) | 0.044 (2) | 0.0122 (18) | −0.003 (2) | 0.0074 (17) |
C16 | 0.046 (2) | 0.031 (2) | 0.036 (2) | 0.0074 (17) | 0.0035 (18) | 0.0010 (16) |
C17 | 0.068 (3) | 0.026 (2) | 0.053 (3) | 0.0053 (19) | 0.005 (2) | 0.0012 (18) |
C18 | 0.058 (3) | 0.029 (2) | 0.055 (3) | −0.0016 (18) | 0.001 (2) | −0.0068 (18) |
C19 | 0.041 (2) | 0.033 (2) | 0.040 (2) | −0.0037 (16) | 0.0047 (18) | −0.0050 (16) |
C20 | 0.053 (3) | 0.046 (3) | 0.050 (3) | −0.010 (2) | −0.005 (2) | −0.012 (2) |
C21 | 0.048 (3) | 0.053 (3) | 0.051 (3) | −0.005 (2) | −0.015 (2) | −0.008 (2) |
C22 | 0.046 (2) | 0.038 (2) | 0.046 (2) | 0.0038 (18) | −0.013 (2) | −0.0015 (18) |
C23 | 0.0292 (19) | 0.035 (2) | 0.035 (2) | 0.0036 (15) | 0.0055 (16) | −0.0026 (16) |
C24 | 0.036 (2) | 0.0276 (18) | 0.034 (2) | 0.0024 (15) | 0.0035 (17) | −0.0016 (15) |
C25 | 0.045 (2) | 0.044 (2) | 0.041 (2) | 0.0005 (19) | −0.0059 (19) | 0.0025 (19) |
C26 | 0.063 (3) | 0.124 (5) | 0.057 (3) | −0.015 (3) | −0.015 (3) | −0.008 (3) |
C27 | 0.112 (5) | 0.093 (4) | 0.062 (4) | 0.009 (3) | −0.003 (3) | −0.030 (3) |
C28 | 0.090 (5) | 0.102 (5) | 0.082 (4) | 0.007 (4) | −0.007 (4) | −0.018 (4) |
C29 | 0.132 (6) | 0.112 (5) | 0.134 (6) | −0.038 (5) | 0.071 (5) | −0.032 (5) |
C30 | 0.070 (3) | 0.070 (3) | 0.072 (3) | 0.000 (3) | −0.004 (3) | −0.002 (3) |
C31 | 0.110 (5) | 0.089 (5) | 0.085 (4) | 0.009 (4) | −0.006 (4) | 0.023 (4) |
C32 | 0.092 (6) | 0.277 (12) | 0.158 (8) | −0.051 (6) | −0.041 (5) | 0.131 (8) |
C33 | 0.309 (12) | 0.073 (5) | 0.110 (6) | 0.048 (6) | 0.048 (7) | −0.017 (4) |
La1—O1 | 2.572 (3) | C9—H9 | 0.93 |
La1—N3 | 2.694 (3) | C10—H10 | 0.93 |
La1—N1 | 2.710 (3) | C11—C12 | 1.440 (5) |
La1—N4 | 2.721 (3) | C13—C14 | 1.400 (5) |
La1—N2 | 2.758 (3) | C13—H13 | 0.93 |
La1—Cl2 | 2.7905 (10) | C14—C15 | 1.355 (5) |
La1—Cl1 | 2.7999 (10) | C14—H14 | 0.93 |
La1—Cl3 | 2.8212 (10) | C15—C16 | 1.402 (5) |
O1—C25 | 1.237 (4) | C15—H15 | 0.93 |
O2—C28 | 1.217 (7) | C16—C24 | 1.411 (5) |
O3—C31 | 1.213 (7) | C16—C17 | 1.424 (5) |
N1—C10 | 1.323 (4) | C17—C18 | 1.342 (6) |
N1—C11 | 1.366 (4) | C17—H17 | 0.93 |
N2—C1 | 1.326 (5) | C18—C19 | 1.430 (5) |
N2—C12 | 1.361 (4) | C18—H18 | 0.93 |
N3—C13 | 1.325 (4) | C19—C20 | 1.404 (5) |
N3—C24 | 1.365 (4) | C19—C23 | 1.406 (5) |
N4—C22 | 1.329 (4) | C20—C21 | 1.355 (6) |
N4—C23 | 1.356 (4) | C20—H20 | 0.93 |
N5—C25 | 1.314 (5) | C21—C22 | 1.399 (5) |
N5—C26 | 1.445 (5) | C21—H21 | 0.93 |
N5—C27 | 1.453 (6) | C22—H22 | 0.93 |
N6—C28 | 1.310 (7) | C23—C24 | 1.454 (5) |
N6—C30 | 1.424 (6) | C25—H25 | 0.93 |
N6—C29 | 1.455 (7) | C26—H26A | 0.96 |
N7—C31 | 1.308 (7) | C26—H26B | 0.96 |
N7—C32 | 1.397 (8) | C26—H26C | 0.96 |
N7—C33 | 1.441 (8) | C27—H27A | 0.96 |
C1—C2 | 1.405 (6) | C27—H27B | 0.96 |
C1—H1 | 0.93 | C27—H27C | 0.96 |
C2—C3 | 1.365 (6) | C28—H28 | 0.93 |
C2—H2 | 0.93 | C29—H29A | 0.96 |
C3—C4 | 1.389 (6) | C29—H29B | 0.96 |
C3—H3 | 0.93 | C29—H29C | 0.96 |
C4—C12 | 1.403 (5) | C30—H30A | 0.96 |
C4—C5 | 1.448 (6) | C30—H30B | 0.96 |
C5—C6 | 1.337 (6) | C30—H30C | 0.96 |
C5—H5 | 0.93 | C31—H31 | 0.93 |
C6—C7 | 1.424 (6) | C32—H32A | 0.96 |
C6—H6 | 0.93 | C32—H32B | 0.96 |
C7—C8 | 1.398 (6) | C32—H32C | 0.96 |
C7—C11 | 1.412 (5) | C33—H33A | 0.96 |
C8—C9 | 1.375 (6) | C33—H33B | 0.96 |
C8—H8 | 0.93 | C33—H33C | 0.96 |
C9—C10 | 1.384 (5) | ||
O1—La1—N3 | 72.27 (8) | N2—C12—C11 | 118.4 (3) |
O1—La1—N1 | 68.04 (9) | C4—C12—C11 | 119.3 (3) |
N3—La1—N1 | 139.37 (9) | N3—C13—C14 | 124.3 (3) |
O1—La1—N4 | 123.48 (8) | N3—C13—H13 | 117.9 |
N3—La1—N4 | 60.79 (9) | C14—C13—H13 | 117.9 |
N1—La1—N4 | 154.78 (9) | C15—C14—C13 | 118.6 (4) |
O1—La1—N2 | 64.66 (9) | C15—C14—H14 | 120.7 |
N3—La1—N2 | 95.27 (9) | C13—C14—H14 | 120.7 |
N1—La1—N2 | 60.07 (9) | C14—C15—C16 | 120.0 (3) |
N4—La1—N2 | 143.87 (9) | C14—C15—H15 | 120.0 |
O1—La1—Cl2 | 138.37 (6) | C16—C15—H15 | 120.0 |
N3—La1—Cl2 | 144.41 (7) | C15—C16—C24 | 117.5 (3) |
N1—La1—Cl2 | 75.66 (7) | C15—C16—C17 | 122.8 (3) |
N4—La1—Cl2 | 83.83 (6) | C24—C16—C17 | 119.7 (3) |
N2—La1—Cl2 | 113.34 (7) | C18—C17—C16 | 121.6 (4) |
O1—La1—Cl1 | 128.55 (6) | C18—C17—H17 | 119.2 |
N3—La1—Cl1 | 81.78 (7) | C16—C17—H17 | 119.2 |
N1—La1—Cl1 | 116.93 (7) | C17—C18—C19 | 120.6 (3) |
N4—La1—Cl1 | 75.24 (7) | C17—C18—H18 | 119.7 |
N2—La1—Cl1 | 74.76 (7) | C19—C18—H18 | 119.7 |
Cl2—La1—Cl1 | 85.70 (3) | C20—C19—C23 | 117.3 (3) |
O1—La1—Cl3 | 73.96 (6) | C20—C19—C18 | 122.6 (3) |
N3—La1—Cl3 | 88.78 (7) | C23—C19—C18 | 120.1 (3) |
N1—La1—Cl3 | 88.48 (7) | C21—C20—C19 | 119.8 (4) |
N4—La1—Cl3 | 75.32 (7) | C21—C20—H20 | 120.1 |
N2—La1—Cl3 | 134.71 (7) | C19—C20—H20 | 120.1 |
Cl2—La1—Cl3 | 85.68 (4) | C20—C21—C22 | 119.1 (4) |
Cl1—La1—Cl3 | 150.02 (3) | C20—C21—H21 | 120.5 |
C25—O1—La1 | 128.0 (2) | C22—C21—H21 | 120.5 |
C10—N1—C11 | 118.1 (3) | N4—C22—C21 | 123.5 (4) |
C10—N1—La1 | 119.3 (2) | N4—C22—H22 | 118.3 |
C11—N1—La1 | 121.1 (2) | C21—C22—H22 | 118.3 |
C1—N2—C12 | 117.8 (3) | N4—C23—C19 | 123.1 (3) |
C1—N2—La1 | 121.3 (3) | N4—C23—C24 | 118.0 (3) |
C12—N2—La1 | 119.8 (2) | C19—C23—C24 | 118.9 (3) |
C13—N3—C24 | 117.0 (3) | N3—C24—C16 | 122.6 (3) |
C13—N3—La1 | 121.4 (2) | N3—C24—C23 | 118.4 (3) |
C24—N3—La1 | 121.6 (2) | C16—C24—C23 | 119.0 (3) |
C22—N4—C23 | 117.3 (3) | O1—C25—N5 | 125.7 (4) |
C22—N4—La1 | 121.5 (2) | O1—C25—H25 | 117.2 |
C23—N4—La1 | 121.2 (2) | N5—C25—H25 | 117.2 |
C25—N5—C26 | 120.0 (4) | N5—C26—H26A | 109.5 |
C25—N5—C27 | 122.0 (4) | N5—C26—H26B | 109.5 |
C26—N5—C27 | 118.0 (4) | H26A—C26—H26B | 109.5 |
C28—N6—C30 | 122.0 (5) | N5—C26—H26C | 109.5 |
C28—N6—C29 | 122.7 (5) | H26A—C26—H26C | 109.5 |
C30—N6—C29 | 115.3 (4) | H26B—C26—H26C | 109.5 |
C31—N7—C32 | 120.1 (6) | N5—C27—H27A | 109.5 |
C31—N7—C33 | 118.4 (7) | N5—C27—H27B | 109.5 |
C32—N7—C33 | 121.5 (6) | H27A—C27—H27B | 109.5 |
N2—C1—C2 | 123.4 (4) | N5—C27—H27C | 109.5 |
N2—C1—H1 | 118.3 | H27A—C27—H27C | 109.5 |
C2—C1—H1 | 118.3 | H27B—C27—H27C | 109.5 |
C3—C2—C1 | 118.4 (4) | O2—C28—N6 | 126.1 (6) |
C3—C2—H2 | 120.8 | O2—C28—H28 | 116.9 |
C1—C2—H2 | 120.8 | N6—C28—H28 | 116.9 |
C2—C3—C4 | 120.2 (4) | N6—C29—H29A | 109.5 |
C2—C3—H3 | 119.9 | N6—C29—H29B | 109.5 |
C4—C3—H3 | 119.9 | H29A—C29—H29B | 109.5 |
C3—C4—C12 | 118.0 (4) | N6—C29—H29C | 109.5 |
C3—C4—C5 | 122.7 (4) | H29A—C29—H29C | 109.5 |
C12—C4—C5 | 119.4 (4) | H29B—C29—H29C | 109.5 |
C6—C5—C4 | 120.6 (4) | N6—C30—H30A | 109.5 |
C6—C5—H5 | 119.7 | N6—C30—H30B | 109.5 |
C4—C5—H5 | 119.7 | H30A—C30—H30B | 109.5 |
C5—C6—C7 | 121.8 (4) | N6—C30—H30C | 109.5 |
C5—C6—H6 | 119.1 | H30A—C30—H30C | 109.5 |
C7—C6—H6 | 119.1 | H30B—C30—H30C | 109.5 |
C8—C7—C11 | 117.6 (4) | O3—C31—N7 | 124.9 (7) |
C8—C7—C6 | 123.4 (4) | O3—C31—H31 | 117.5 |
C11—C7—C6 | 119.1 (4) | N7—C31—H31 | 117.5 |
C9—C8—C7 | 120.1 (4) | N7—C32—H32A | 109.5 |
C9—C8—H8 | 120.0 | N7—C32—H32B | 109.5 |
C7—C8—H8 | 120.0 | H32A—C32—H32B | 109.5 |
C8—C9—C10 | 118.4 (4) | N7—C32—H32C | 109.5 |
C8—C9—H9 | 120.8 | H32A—C32—H32C | 109.5 |
C10—C9—H9 | 120.8 | H32B—C32—H32C | 109.5 |
N1—C10—C9 | 124.0 (4) | N7—C33—H33A | 109.5 |
N1—C10—H10 | 118.0 | N7—C33—H33B | 109.5 |
C9—C10—H10 | 118.0 | H33A—C33—H33B | 109.5 |
N1—C11—C7 | 121.8 (3) | N7—C33—H33C | 109.5 |
N1—C11—C12 | 118.4 (3) | H33A—C33—H33C | 109.5 |
C7—C11—C12 | 119.7 (3) | H33B—C33—H33C | 109.5 |
N2—C12—C4 | 122.3 (4) | ||
N3—La1—O1—C25 | −145.3 (3) | C5—C6—C7—C8 | 179.1 (4) |
N1—La1—O1—C25 | 43.6 (3) | C5—C6—C7—C11 | −2.5 (7) |
N4—La1—O1—C25 | −110.9 (3) | C11—C7—C8—C9 | −0.7 (6) |
N2—La1—O1—C25 | 109.8 (3) | C6—C7—C8—C9 | 177.7 (4) |
Cl2—La1—O1—C25 | 12.5 (4) | C7—C8—C9—C10 | 0.3 (7) |
Cl1—La1—O1—C25 | 151.2 (3) | C11—N1—C10—C9 | −0.7 (6) |
Cl3—La1—O1—C25 | −51.4 (3) | La1—N1—C10—C9 | 165.5 (3) |
O1—La1—N1—C10 | −105.8 (3) | C8—C9—C10—N1 | 0.5 (7) |
N3—La1—N1—C10 | −118.8 (3) | C10—N1—C11—C7 | 0.1 (5) |
N4—La1—N1—C10 | 16.9 (4) | La1—N1—C11—C7 | −165.8 (3) |
N2—La1—N1—C10 | −178.3 (3) | C10—N1—C11—C12 | 178.9 (3) |
Cl2—La1—N1—C10 | 53.4 (3) | La1—N1—C11—C12 | 13.0 (4) |
Cl1—La1—N1—C10 | 130.9 (3) | C8—C7—C11—N1 | 0.6 (6) |
Cl3—La1—N1—C10 | −32.5 (3) | C6—C7—C11—N1 | −177.9 (4) |
O1—La1—N1—C11 | 59.9 (3) | C8—C7—C11—C12 | −178.2 (4) |
N3—La1—N1—C11 | 46.9 (3) | C6—C7—C11—C12 | 3.3 (6) |
N4—La1—N1—C11 | −177.4 (2) | C1—N2—C12—C4 | −0.2 (6) |
N2—La1—N1—C11 | −12.6 (2) | La1—N2—C12—C4 | 167.8 (3) |
Cl2—La1—N1—C11 | −140.8 (3) | C1—N2—C12—C11 | −179.1 (4) |
Cl1—La1—N1—C11 | −63.4 (3) | La1—N2—C12—C11 | −11.1 (4) |
Cl3—La1—N1—C11 | 133.2 (3) | C3—C4—C12—N2 | −1.4 (6) |
O1—La1—N2—C1 | 101.3 (3) | C5—C4—C12—N2 | 179.2 (3) |
N3—La1—N2—C1 | 33.7 (3) | C3—C4—C12—C11 | 177.5 (4) |
N1—La1—N2—C1 | 179.5 (3) | C5—C4—C12—C11 | −1.9 (5) |
N4—La1—N2—C1 | −11.4 (4) | N1—C11—C12—N2 | −1.0 (5) |
Cl2—La1—N2—C1 | −124.6 (3) | C7—C11—C12—N2 | 177.8 (3) |
Cl1—La1—N2—C1 | −46.2 (3) | N1—C11—C12—C4 | −179.9 (3) |
Cl3—La1—N2—C1 | 127.3 (3) | C7—C11—C12—C4 | −1.2 (5) |
O1—La1—N2—C12 | −66.3 (3) | C24—N3—C13—C14 | 0.8 (6) |
N3—La1—N2—C12 | −133.8 (3) | La1—N3—C13—C14 | −179.2 (3) |
N1—La1—N2—C12 | 11.9 (2) | N3—C13—C14—C15 | −1.0 (6) |
N4—La1—N2—C12 | −179.0 (2) | C13—C14—C15—C16 | 0.0 (6) |
Cl2—La1—N2—C12 | 67.9 (3) | C14—C15—C16—C24 | 1.0 (6) |
Cl1—La1—N2—C12 | 146.2 (3) | C14—C15—C16—C17 | −179.0 (4) |
Cl3—La1—N2—C12 | −40.3 (3) | C15—C16—C17—C18 | −178.0 (4) |
O1—La1—N3—C13 | −33.8 (3) | C24—C16—C17—C18 | 1.9 (6) |
N1—La1—N3—C13 | −21.1 (3) | C16—C17—C18—C19 | −0.5 (6) |
N4—La1—N3—C13 | 178.9 (3) | C17—C18—C19—C20 | 179.0 (4) |
N2—La1—N3—C13 | 27.5 (3) | C17—C18—C19—C23 | −0.9 (6) |
Cl2—La1—N3—C13 | 171.8 (2) | C23—C19—C20—C21 | −0.1 (6) |
Cl1—La1—N3—C13 | 101.2 (3) | C18—C19—C20—C21 | 180.0 (4) |
Cl3—La1—N3—C13 | −107.3 (3) | C19—C20—C21—C22 | −0.5 (6) |
O1—La1—N3—C24 | 146.2 (3) | C23—N4—C22—C21 | −0.6 (6) |
N1—La1—N3—C24 | 158.9 (2) | La1—N4—C22—C21 | −179.8 (3) |
N4—La1—N3—C24 | −1.2 (2) | C20—C21—C22—N4 | 0.9 (6) |
N2—La1—N3—C24 | −152.5 (3) | C22—N4—C23—C19 | −0.1 (5) |
Cl2—La1—N3—C24 | −8.2 (3) | La1—N4—C23—C19 | 179.1 (3) |
Cl1—La1—N3—C24 | −78.8 (3) | C22—N4—C23—C24 | 179.3 (3) |
Cl3—La1—N3—C24 | 72.7 (3) | La1—N4—C23—C24 | −1.5 (4) |
O1—La1—N4—C22 | 142.5 (3) | C20—C19—C23—N4 | 0.5 (5) |
N3—La1—N4—C22 | −179.5 (3) | C18—C19—C23—N4 | −179.6 (3) |
N1—La1—N4—C22 | 31.9 (4) | C20—C19—C23—C24 | −179.0 (3) |
N2—La1—N4—C22 | −125.4 (3) | C18—C19—C23—C24 | 1.0 (5) |
Cl2—La1—N4—C22 | −3.6 (3) | C13—N3—C24—C16 | 0.3 (5) |
Cl1—La1—N4—C22 | −90.7 (3) | La1—N3—C24—C16 | −179.7 (3) |
Cl3—La1—N4—C22 | 83.6 (3) | C13—N3—C24—C23 | −179.0 (3) |
O1—La1—N4—C23 | −36.7 (3) | La1—N3—C24—C23 | 1.0 (4) |
N3—La1—N4—C23 | 1.3 (2) | C15—C16—C24—N3 | −1.2 (5) |
N1—La1—N4—C23 | −147.3 (2) | C17—C16—C24—N3 | 178.9 (3) |
N2—La1—N4—C23 | 55.4 (3) | C15—C16—C24—C23 | 178.1 (3) |
Cl2—La1—N4—C23 | 177.2 (3) | C17—C16—C24—C23 | −1.8 (5) |
Cl1—La1—N4—C23 | 90.1 (2) | N4—C23—C24—N3 | 0.3 (5) |
Cl3—La1—N4—C23 | −95.6 (3) | C19—C23—C24—N3 | 179.8 (3) |
C12—N2—C1—C2 | 1.4 (7) | N4—C23—C24—C16 | −179.0 (3) |
La1—N2—C1—C2 | −166.4 (4) | C19—C23—C24—C16 | 0.4 (5) |
N2—C1—C2—C3 | −1.1 (8) | La1—O1—C25—N5 | −152.2 (3) |
C1—C2—C3—C4 | −0.6 (8) | C26—N5—C25—O1 | −1.7 (6) |
C2—C3—C4—C12 | 1.7 (7) | C27—N5—C25—O1 | 178.4 (4) |
C2—C3—C4—C5 | −178.9 (4) | C30—N6—C28—O2 | −1.9 (10) |
C3—C4—C5—C6 | −176.6 (4) | C29—N6—C28—O2 | 175.0 (7) |
C12—C4—C5—C6 | 2.8 (6) | C32—N7—C31—O3 | 1.7 (10) |
C4—C5—C6—C7 | −0.6 (7) | C33—N7—C31—O3 | −178.2 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cl3i | 0.93 | 2.80 | 3.662 (5) | 155 |
C14—H14···O2 | 0.93 | 2.57 | 3.322 (6) | 139 |
C22—H22···Cl2 | 0.93 | 2.78 | 3.524 (4) | 138 |
C29—H29A···Cl3i | 0.96 | 2.81 | 3.766 (6) | 176 |
C29—H29C···O3 | 0.96 | 2.42 | 3.319 (9) | 157 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [LaCl3(C12H8N2)2(C3H7NO)]·2C3H7NO |
Mr | 824.96 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 10.0344 (11), 17.3861 (19), 20.768 (2) |
β (°) | 91.521 (1) |
V (Å3) | 3621.9 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.44 |
Crystal size (mm) | 0.28 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.691, 0.800 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26591, 6738, 5246 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.082, 1.01 |
No. of reflections | 6738 |
No. of parameters | 430 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.35 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998) and PLATON (Spek, 2003).
La1—O1 | 2.572 (3) | La1—N2 | 2.758 (3) |
La1—N3 | 2.694 (3) | La1—Cl2 | 2.7905 (10) |
La1—N1 | 2.710 (3) | La1—Cl1 | 2.7999 (10) |
La1—N4 | 2.721 (3) | La1—Cl3 | 2.8212 (10) |
O1—La1—N3 | 72.27 (8) | N2—La1—Cl2 | 113.34 (7) |
O1—La1—N1 | 68.04 (9) | O1—La1—Cl1 | 128.55 (6) |
N3—La1—N1 | 139.37 (9) | N3—La1—Cl1 | 81.78 (7) |
O1—La1—N4 | 123.48 (8) | N1—La1—Cl1 | 116.93 (7) |
N3—La1—N4 | 60.79 (9) | N4—La1—Cl1 | 75.24 (7) |
N1—La1—N4 | 154.78 (9) | N2—La1—Cl1 | 74.76 (7) |
O1—La1—N2 | 64.66 (9) | Cl2—La1—Cl1 | 85.70 (3) |
N3—La1—N2 | 95.27 (9) | O1—La1—Cl3 | 73.96 (6) |
N1—La1—N2 | 60.07 (9) | N3—La1—Cl3 | 88.78 (7) |
N4—La1—N2 | 143.87 (9) | N1—La1—Cl3 | 88.48 (7) |
O1—La1—Cl2 | 138.37 (6) | N4—La1—Cl3 | 75.32 (7) |
N3—La1—Cl2 | 144.41 (7) | N2—La1—Cl3 | 134.71 (7) |
N1—La1—Cl2 | 75.66 (7) | Cl2—La1—Cl3 | 85.68 (4) |
N4—La1—Cl2 | 83.83 (6) | Cl1—La1—Cl3 | 150.02 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cl3i | 0.93 | 2.80 | 3.662 (5) | 155 |
C14—H14···O2 | 0.93 | 2.57 | 3.322 (6) | 139 |
C22—H22···Cl2 | 0.93 | 2.78 | 3.524 (4) | 138 |
C29—H29A···Cl3i | 0.96 | 2.81 | 3.766 (6) | 176 |
C29—H29C···O3 | 0.96 | 2.42 | 3.319 (9) | 157 |
Symmetry code: (i) x+1, y, z. |
In recent years, much attention has been focused on the synthetic approach and structural control of rare-earth (RE) complexes with various ligands, such as 2,2'-bipyridine and 1,10-phenanthroline (phen), not only because of their fascinating structural diversities but also their potential applications as optical materials, electronic materials, catalytic materials, molecular based magnets and so on (Bünzli, 2006; Suárez et al., 2004). Many novel functional complexes with 2,2'-bipyridine-like ligands have been reported (Edmonds et al., 2004; Molander & Romero, 2002; Wan et al., 2003; Ye et al., 2005). We report here the crystal structure of a LaIII complex with a chelating 1,10-phenanthroline ligand, [La(phen)2(DMF)Cl3](DMF)2, the title compound, (I) (DMF is N,N-dimethylformamide).
Compound (I) consists of mononuclear [La(phen)2(DMF)Cl3] units and free DMF molecules. The LaIII ion is eight-coordinated and surrounded by four N donors from two phen ligands, one O atom from one DMF molecule, and three Cl- anions (Fig. 1). The La—Cl distances range from 2.7905 (10) to 2.8212 (10) Å, and those of La—N range from 2.694 (3) to 2.758 (3) Å, which are in the normal range expected for such coordination complexes (Bünzli, 2006) (Table 1). The adjacent mononuclear [La(phen)2(DMF)Cl3] units are linked into a chain along the a axis by weak C—H···Cl hydrogen bonding interactions (Table 2) between the phen ligands and coordinated Cl- anions (Desiraju & Steiner,1999). The chains are cross-linked to generate a two-dimensional network parallel to the ab plane by intermolecular π-π stacking interactions between the phenanthroline ring systems, with centroid-centroid distances ranging from 3.589 (2) to 3.708 (2) Å (Fig. 2).