Diaqua­tris(nicotinato-κO)bis­(1,10-phenanthroline-κ²N,N′)lanthanum(III) trihydrate

The title compound, [La(C₆H₄NO₂)₃(C₁₂H₈N₂)₂(H₂O)₂]·3H₂O, consists of a mononuclear complex and three non-coordinated water mol­ecules. The La atom is coordinated by five O atoms of three nicotinate groups and two coordinated water mol­ecules, and four N atoms of two bidentate phenanthroline mol­ecules, in a tricapped trigonal–prismatic coordination geometry. The complex mol­ecule and water mol­ecules are linked into layers through O—H...O and O—H...N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.020
• wR factor = 0.054
• Data-to-parameter ratio = 22.5

checkCIF/PLATON results

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S1. Comment

The title compound, (I), is isostructural with its [M(C₆H₄NO₂)₃(C₁₂H₈N₂)₂(H₂O)₂]·3H₂O [M = Pr (Yue et al., 2004), Nd (Liu & Wang, 2004) and Ce (Liu et al., 2004)] analogues. It consists of a mononuclear [La(C₆H₄NO₂)₃(C₁₂H₈N₂)₂(H₂O)₂] neutral molecule and three uncoordinated water molecules (Fig. 1). The La atom possesses trigonal prismatic coordination geometry (Table 1), in which the La—O bond distances range from 2.4199 (10) to 2.5416 (10) Å and the La—N bond distances range from 2.7565 (12) to 2.7757 (11) Å, which is similar to the previously reported isostructural complexes. In (I), the uncoordinated water molecules participate in the extensive hydrogen-bonding interactions formed between the water molecules and the N and O atoms of the nicotinate groups (Table 2), resulting in a layered structure.

S2. Experimental

1,10-Phenanthroline monohydrate (0.0198 g, 0.10 mmol) and nicotinic acid (0.0123 g, 0.10 mmol) were completely dissolved in CH₃OH/H₂O (30 ml, 1:1 v/v); La(CH₃COO)₃·3H₂O (0.0158 g) was added andthe mixture was stirred for 40 min. The resulting white slurry was filtered and the filtrate was left to stand at room temperature. Crystals of (I) suitable for X-ray analysis were obtained after two weeks (yield ca 35%).

S3. Refinement

H atoms attached to C atoms were included at calculated positions and treated as riding atoms [C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)]. The water H atoms were found in a diffrence map, relocated in idealized posiitons (O—H = 0.85 Å) and refined as riding with U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; 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.

Figures

Fig. 1. The asymmetric unit of (I), showing 35% probability displacement ellipsoids (arbitrary spheres for H atoms).

Diaquatris(nicotinato-kO)bis(1,10-phenanthroline-k²N,N')lanthanum(III) trihydrate

Crystal data

[La(C6H4NO2)3(C12H8N2)2(H2O)2]·3H2O	Z = 2
Mr = 955.70	F(000) = 968
Triclinic, P1	Dx = 1.537 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0676 (1) Å	Cell parameters from 985 reflections
b = 12.9618 (2) Å	θ = 3.3–26.7°
c = 17.9351 (3) Å	µ = 1.10 mm^−1
α = 84.998 (1)°	T = 290 K
β = 80.800 (1)°	Block, colorless
γ = 84.190 (1)°	0.20 × 0.20 × 0.18 mm
V = 2064.73 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	12414 independent reflections
Radiation source: fine-focus sealed tube	11284 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ϕ and ω scans	θmax = 30.7°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.791, Tmax = 0.811	k = −18→17
45880 measured reflections	l = −25→23

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap (O-H) and geom (others)
R[F^2 > 2σ(F^2)] = 0.020	H-atom parameters constrained
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0318P)^2 + 0.2509P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.005
12414 reflections	Δρmax = 0.50 e Å^−3
552 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0010 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
La	0.583247 (7)	0.741098 (5)	0.735662 (4)	0.02918 (3)
N1	0.68513 (13)	0.90575 (8)	0.63803 (7)	0.0370 (2)
N2	0.50559 (14)	0.77384 (10)	0.59248 (7)	0.0416 (3)
C1	0.76622 (17)	0.97387 (11)	0.65973 (9)	0.0433 (3)
H1A	0.7733	0.9728	0.7110	0.052*
C2	0.84199 (19)	1.04749 (12)	0.61017 (10)	0.0504 (4)
H2A	0.8970	1.0939	0.6284	0.060*
C3	0.83383 (19)	1.04989 (12)	0.53496 (10)	0.0494 (4)
H3A	0.8839	1.0978	0.5010	0.059*
C4	0.74891 (17)	0.97928 (11)	0.50904 (8)	0.0422 (3)
C5	0.7338 (2)	0.97814 (14)	0.43089 (9)	0.0523 (4)
H5A	0.7842	1.0239	0.3952	0.063*
C6	0.6482 (2)	0.91222 (14)	0.40835 (9)	0.0537 (4)
H6A	0.6412	0.9124	0.3572	0.064*
C7	0.56706 (18)	0.84125 (12)	0.46156 (8)	0.0449 (3)
C8	0.4698 (2)	0.77548 (15)	0.44079 (10)	0.0578 (4)
H8C	0.4593	0.7739	0.3902	0.069*
C9	0.3904 (2)	0.71375 (16)	0.49480 (11)	0.0632 (5)
H9C	0.3224	0.6719	0.4818	0.076*
C10	0.4126 (2)	0.71430 (14)	0.56997 (10)	0.0536 (4)
H10C	0.3596	0.6707	0.6062	0.064*
C11	0.58103 (15)	0.83852 (11)	0.53909 (8)	0.0372 (3)
C12	0.67429 (15)	0.90862 (10)	0.56325 (8)	0.0354 (3)
N3	0.49510 (14)	0.70097 (10)	0.88894 (7)	0.0421 (3)
N4	0.74812 (13)	0.59505 (9)	0.81828 (7)	0.0393 (2)
C13	0.37536 (19)	0.75361 (14)	0.92443 (10)	0.0543 (4)
H13A	0.3123	0.7950	0.8957	0.065*
C14	0.3396 (2)	0.74943 (17)	1.00397 (12)	0.0676 (5)
H14A	0.2561	0.7891	1.0269	0.081*
C15	0.4271 (3)	0.68774 (18)	1.04654 (11)	0.0682 (5)
H15A	0.4039	0.6844	1.0991	0.082*
C16	0.5522 (2)	0.62890 (15)	1.01191 (9)	0.0546 (4)
C17	0.6469 (3)	0.55723 (18)	1.05357 (10)	0.0678 (6)
H17A	0.6260	0.5510	1.1062	0.081*
C18	0.7631 (3)	0.49989 (16)	1.01882 (11)	0.0642 (5)
H18A	0.8201	0.4529	1.0473	0.077*
C19	0.80165 (19)	0.50957 (13)	0.93811 (10)	0.0501 (4)
C20	0.9241 (2)	0.45098 (15)	0.89952 (13)	0.0644 (5)
H20A	0.9821	0.4021	0.9261	0.077*
C21	0.9572 (2)	0.46590 (16)	0.82352 (12)	0.0669 (5)
H21A	1.0386	0.4280	0.7972	0.080*
C22	0.86718 (19)	0.53947 (14)	0.78475 (10)	0.0540 (4)
H22A	0.8925	0.5498	0.7325	0.065*
C24	0.58411 (17)	0.63903 (11)	0.93208 (8)	0.0404 (3)
O1	0.59043 (16)	0.96134 (10)	0.86802 (8)	0.0646 (3)
O2	0.73590 (11)	0.83138 (8)	0.81291 (6)	0.0416 (2)
N7	0.9590 (2)	0.77728 (19)	1.00024 (12)	0.0895 (6)
C23	0.71386 (16)	0.58049 (11)	0.89471 (8)	0.0391 (3)
C25	0.69444 (17)	0.89200 (11)	0.86703 (8)	0.0409 (3)
C26	0.77693 (18)	0.87694 (12)	0.93379 (8)	0.0440 (3)
C27	0.7390 (2)	0.94261 (17)	0.99230 (11)	0.0635 (5)
H27A	0.6639	0.9968	0.9904	0.076*
C28	0.8161 (3)	0.9252 (2)	1.05367 (12)	0.0743 (7)
H28A	0.7957	0.9692	1.0930	0.089*
C29	0.9213 (3)	0.8436 (3)	1.05567 (14)	0.0748 (9)
H29A	0.9705	0.8324	1.0977	0.090*
C30	0.8868 (2)	0.79661 (16)	0.94004 (11)	0.0615 (5)
H30A	0.9125	0.7534	0.9004	0.074*
O3	1.02074 (13)	0.75971 (11)	0.59165 (7)	0.0583 (3)
O4	0.81618 (11)	0.69314 (8)	0.65496 (6)	0.0418 (2)
C34	0.7637 (3)	0.54783 (18)	0.46312 (13)	0.0783 (6)
H34A	0.6972	0.4975	0.4638	0.094*
C31	0.91118 (15)	0.70821 (11)	0.59570 (8)	0.0385 (3)
C32	0.88553 (16)	0.66012 (11)	0.52625 (8)	0.0406 (3)
C33	0.9566 (2)	0.69361 (16)	0.45572 (10)	0.0592 (4)
H33A	1.0238	0.7439	0.4532	0.071*
N5	0.9350 (2)	0.65827 (16)	0.39077 (9)	0.0778 (5)
C35	0.8422 (3)	0.58503 (19)	0.39578 (12)	0.0769 (6)
H35A	0.8291	0.5571	0.3515	0.092*
C36	0.7848 (2)	0.58590 (14)	0.52952 (11)	0.0585 (4)
H36A	0.7324	0.5622	0.5757	0.070*
O5	0.30850 (13)	0.51845 (10)	0.73377 (10)	0.0674 (4)
O6	0.54465 (11)	0.55922 (7)	0.70809 (6)	0.0429 (2)
N6	0.7016 (2)	0.25106 (12)	0.74967 (10)	0.0669 (4)
C37	0.44594 (16)	0.49545 (11)	0.72525 (8)	0.0402 (3)
C38	0.49871 (17)	0.38246 (11)	0.73889 (8)	0.0410 (3)
C39	0.64924 (19)	0.34868 (12)	0.73132 (10)	0.0502 (4)
H39A	0.7183	0.3965	0.7124	0.060*
C40	0.5987 (3)	0.18318 (14)	0.77480 (12)	0.0736 (6)
H40A	0.6326	0.1148	0.7878	0.088*
C41	0.4488 (3)	0.20853 (14)	0.78231 (13)	0.0729 (6)
H41A	0.3823	0.1584	0.7994	0.087*
C42	0.3964 (2)	0.30960 (13)	0.76430 (11)	0.0572 (4)
H42A	0.2939	0.3288	0.7691	0.069*
O7	0.43149 (12)	0.91033 (9)	0.76985 (7)	0.0503 (3)
O8	0.30437 (11)	0.71789 (8)	0.75547 (7)	0.0514 (3)
O9	0.14993 (15)	0.00103 (11)	0.76982 (9)	0.0662 (3)
O10	0.03720 (12)	0.82433 (10)	0.73077 (7)	0.0555 (3)
O11	1.01842 (18)	0.19971 (12)	0.74285 (9)	0.0777 (4)
H7B	0.3434	0.9391	0.7685	0.050*
H8B	0.2195	0.7493	0.7498	0.050*
H9B	0.1056	0.0600	0.7587	0.050*
H9A	0.1032	−0.0446	0.7545	0.050*
H8A	0.2865	0.6562	0.7499	0.050*
H7A	0.4808	0.9332	0.8004	0.050*
H10B	−0.0480	0.8184	0.7576	0.050*
H11B	1.0374	0.2380	0.7022	0.050*
H11A	0.9241	0.2129	0.7539	0.050*
H10A	0.0380	0.8082	0.6858	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La	0.03010 (4)	0.02807 (4)	0.02927 (4)	−0.00298 (2)	−0.00568 (2)	0.00103 (2)
N1	0.0434 (6)	0.0318 (5)	0.0354 (6)	−0.0034 (4)	−0.0068 (4)	0.0023 (4)
N2	0.0459 (6)	0.0418 (6)	0.0393 (6)	−0.0085 (5)	−0.0144 (5)	0.0051 (5)
C1	0.0535 (8)	0.0357 (7)	0.0415 (7)	−0.0067 (6)	−0.0095 (6)	0.0001 (6)
C2	0.0582 (9)	0.0384 (7)	0.0549 (9)	−0.0136 (6)	−0.0054 (7)	0.0000 (7)
C3	0.0557 (9)	0.0380 (7)	0.0508 (9)	−0.0096 (6)	0.0026 (7)	0.0052 (6)
C4	0.0462 (7)	0.0359 (7)	0.0404 (7)	−0.0004 (5)	−0.0004 (6)	0.0053 (5)
C5	0.0623 (10)	0.0521 (9)	0.0369 (8)	−0.0027 (7)	0.0009 (7)	0.0093 (7)
C6	0.0645 (10)	0.0615 (10)	0.0324 (7)	0.0009 (8)	−0.0073 (7)	0.0051 (7)
C7	0.0524 (8)	0.0465 (8)	0.0353 (7)	0.0042 (6)	−0.0127 (6)	0.0008 (6)
C8	0.0706 (11)	0.0640 (11)	0.0432 (9)	−0.0019 (8)	−0.0249 (8)	−0.0031 (8)
C9	0.0736 (12)	0.0646 (11)	0.0613 (11)	−0.0185 (9)	−0.0359 (9)	0.0011 (9)
C10	0.0605 (9)	0.0544 (9)	0.0510 (9)	−0.0172 (7)	−0.0217 (7)	0.0062 (7)
C11	0.0403 (6)	0.0361 (6)	0.0342 (6)	0.0028 (5)	−0.0090 (5)	0.0016 (5)
C12	0.0385 (6)	0.0306 (6)	0.0347 (6)	0.0020 (5)	−0.0044 (5)	0.0026 (5)
N3	0.0437 (6)	0.0427 (6)	0.0373 (6)	−0.0056 (5)	0.0012 (5)	0.0002 (5)
N4	0.0414 (6)	0.0392 (6)	0.0357 (6)	0.0007 (4)	−0.0074 (5)	0.0038 (5)
C13	0.0512 (9)	0.0546 (9)	0.0513 (9)	−0.0022 (7)	0.0077 (7)	−0.0040 (7)
C14	0.0693 (12)	0.0719 (12)	0.0552 (11)	−0.0089 (9)	0.0186 (9)	−0.0176 (9)
C15	0.0866 (14)	0.0781 (13)	0.0385 (9)	−0.0214 (11)	0.0060 (9)	−0.0088 (9)
C16	0.0724 (11)	0.0608 (10)	0.0328 (7)	−0.0234 (8)	−0.0051 (7)	−0.0019 (7)
C17	0.0978 (15)	0.0773 (13)	0.0344 (8)	−0.0281 (12)	−0.0240 (9)	0.0109 (8)
C18	0.0809 (13)	0.0677 (12)	0.0498 (10)	−0.0376 (10)	−0.0315 (9)	0.0156 (9)
C19	0.0571 (9)	0.0479 (8)	0.0497 (9)	−0.0139 (7)	−0.0243 (7)	0.0132 (7)
C20	0.0574 (10)	0.0575 (10)	0.0784 (13)	0.0034 (8)	−0.0282 (9)	0.0179 (9)
C21	0.0525 (9)	0.0650 (11)	0.0759 (13)	0.0187 (8)	−0.0107 (9)	0.0099 (10)
C22	0.0510 (8)	0.0530 (9)	0.0514 (9)	0.0115 (7)	−0.0039 (7)	0.0076 (7)
C24	0.0497 (7)	0.0411 (7)	0.0320 (6)	−0.0156 (6)	−0.0062 (5)	0.0018 (5)
O1	0.0824 (9)	0.0480 (7)	0.0695 (8)	0.0144 (6)	−0.0361 (7)	−0.0160 (6)
O2	0.0454 (5)	0.0434 (5)	0.0389 (5)	−0.0078 (4)	−0.0132 (4)	−0.0030 (4)
N7	0.0940 (14)	0.1076 (16)	0.0698 (12)	0.0225 (12)	−0.0435 (11)	−0.0022 (11)
C23	0.0461 (7)	0.0374 (6)	0.0360 (7)	−0.0109 (5)	−0.0127 (5)	0.0055 (5)
C25	0.0525 (8)	0.0349 (6)	0.0389 (7)	−0.0112 (5)	−0.0166 (6)	0.0030 (5)
C26	0.0518 (8)	0.0445 (8)	0.0379 (7)	−0.0078 (6)	−0.0126 (6)	0.0002 (6)
C27	0.0716 (12)	0.0707 (12)	0.0520 (10)	0.0014 (9)	−0.0196 (9)	−0.0159 (9)
C28	0.0733 (17)	0.116 (2)	0.0490 (11)	−0.0024 (14)	−0.0207 (11)	−0.0267 (12)
C29	0.0733 (17)	0.142 (3)	0.0545 (13)	0.0086 (17)	−0.0398 (12)	−0.0077 (14)
C30	0.0656 (11)	0.0661 (11)	0.0558 (10)	0.0074 (9)	−0.0247 (9)	−0.0071 (9)
O3	0.0508 (6)	0.0791 (9)	0.0470 (6)	−0.0275 (6)	0.0008 (5)	−0.0062 (6)
O4	0.0410 (5)	0.0433 (5)	0.0370 (5)	−0.0032 (4)	0.0031 (4)	0.0025 (4)
C34	0.1066 (17)	0.0650 (12)	0.0710 (14)	−0.0374 (12)	−0.0148 (12)	−0.0117 (10)
C31	0.0380 (6)	0.0386 (7)	0.0366 (7)	−0.0023 (5)	−0.0018 (5)	0.0025 (5)
C32	0.0430 (7)	0.0384 (7)	0.0383 (7)	−0.0032 (5)	−0.0021 (5)	0.0003 (5)
C33	0.0686 (11)	0.0689 (11)	0.0410 (8)	−0.0267 (9)	−0.0002 (8)	0.0002 (8)
N5	0.1009 (14)	0.0941 (14)	0.0404 (8)	−0.0313 (11)	−0.0031 (8)	−0.0050 (8)
C35	0.1045 (17)	0.0810 (15)	0.0514 (11)	−0.0241 (13)	−0.0157 (11)	−0.0139 (10)
C36	0.0755 (11)	0.0491 (9)	0.0513 (9)	−0.0223 (8)	−0.0018 (8)	0.0001 (7)
O5	0.0428 (6)	0.0450 (6)	0.1154 (12)	−0.0083 (5)	−0.0113 (7)	−0.0082 (7)
O6	0.0428 (5)	0.0329 (5)	0.0531 (6)	−0.0080 (4)	−0.0059 (4)	−0.0004 (4)
N6	0.0772 (11)	0.0470 (8)	0.0698 (11)	0.0134 (7)	−0.0034 (8)	−0.0028 (7)
C37	0.0448 (7)	0.0341 (6)	0.0425 (7)	−0.0068 (5)	−0.0070 (6)	−0.0027 (5)
C38	0.0525 (8)	0.0329 (6)	0.0368 (7)	−0.0084 (5)	−0.0004 (6)	−0.0050 (5)
C39	0.0562 (9)	0.0395 (7)	0.0523 (9)	−0.0025 (6)	−0.0027 (7)	−0.0011 (6)
C40	0.1142 (18)	0.0333 (8)	0.0647 (12)	0.0023 (9)	0.0038 (12)	0.0019 (8)
C41	0.1016 (17)	0.0368 (9)	0.0731 (13)	−0.0197 (9)	0.0151 (12)	−0.0010 (8)
C42	0.0667 (10)	0.0407 (8)	0.0610 (11)	−0.0157 (7)	0.0082 (8)	−0.0066 (7)
O7	0.0448 (5)	0.0431 (6)	0.0644 (7)	0.0063 (4)	−0.0147 (5)	−0.0125 (5)
O8	0.0345 (5)	0.0436 (6)	0.0783 (8)	−0.0020 (4)	−0.0127 (5)	−0.0097 (5)
O9	0.0579 (7)	0.0618 (8)	0.0851 (10)	0.0084 (6)	−0.0316 (7)	−0.0183 (7)
O10	0.0405 (5)	0.0649 (7)	0.0644 (7)	−0.0026 (5)	−0.0147 (5)	−0.0141 (6)
O11	0.0789 (9)	0.0736 (9)	0.0728 (10)	0.0107 (7)	−0.0076 (7)	0.0114 (7)

Geometric parameters (Å, º)

La—O4	2.4199 (10)	C21—C22	1.403 (2)
La—O6	2.5200 (10)	C21—H21A	0.9300
La—O2	2.5355 (10)	C22—H22A	0.9300
La—O7	2.5367 (10)	C24—C23	1.437 (2)
La—O8	2.5416 (10)	O1—C25	1.2342 (19)
La—N2	2.7565 (12)	O2—C25	1.2873 (18)
La—N3	2.7566 (12)	N7—C30	1.343 (2)
La—N4	2.7678 (11)	N7—C29	1.351 (3)
La—N1	2.7757 (11)	C25—C26	1.499 (2)
N1—C1	1.3247 (18)	C26—C30	1.377 (2)
N1—C12	1.3574 (18)	C26—C27	1.387 (2)
N2—C10	1.328 (2)	C27—C28	1.386 (3)
N2—C11	1.3617 (18)	C27—H27A	0.9300
C1—C2	1.401 (2)	C28—C29	1.354 (4)
C1—H1A	0.9300	C28—H28A	0.9300
C2—C3	1.360 (2)	C29—H29A	0.9300
C2—H2A	0.9300	C30—H30A	0.9300
C3—C4	1.406 (2)	O3—C31	1.2412 (18)
C3—H3A	0.9300	O4—C31	1.2708 (16)
C4—C12	1.4149 (18)	C34—C35	1.375 (3)
C4—C5	1.431 (2)	C34—C36	1.376 (3)
C5—C6	1.338 (3)	C34—H34A	0.9300
C5—H5A	0.9300	C31—C32	1.501 (2)
C6—C7	1.434 (2)	C32—C33	1.380 (2)
C6—H6A	0.9300	C32—C36	1.383 (2)
C7—C8	1.399 (2)	C33—N5	1.338 (2)
C7—C11	1.413 (2)	C33—H33A	0.9300
C8—C9	1.362 (3)	N5—C35	1.320 (3)
C8—H8C	0.9300	C35—H35A	0.9300
C9—C10	1.395 (2)	C36—H36A	0.9300
C9—H9C	0.9300	O5—C37	1.2399 (18)
C10—H10C	0.9300	O6—C37	1.2634 (16)
C11—C12	1.439 (2)	N6—C39	1.338 (2)
N3—C13	1.325 (2)	N6—C40	1.345 (3)
N3—C24	1.3619 (19)	C37—C38	1.506 (2)
N4—C22	1.325 (2)	C38—C39	1.380 (2)
N4—C23	1.3571 (18)	C38—C42	1.388 (2)
C13—C14	1.409 (3)	C39—H39A	0.9300
C13—H13A	0.9300	C40—C41	1.354 (3)
C14—C15	1.345 (3)	C40—H40A	0.9300
C14—H14A	0.9300	C41—C42	1.377 (3)
C15—C16	1.392 (3)	C41—H41A	0.9300
C15—H15A	0.9300	C42—H42A	0.9300
C16—C24	1.412 (2)	O7—H7B	0.8498
C16—C17	1.443 (3)	O7—H7A	0.8497
C17—C18	1.328 (3)	O8—H8B	0.8497
C17—H17A	0.9300	O8—H8A	0.8495
C18—C19	1.431 (3)	O9—H9B	0.8498
C18—H18A	0.9300	O9—H9A	0.8494
C19—C20	1.401 (3)	O10—H10B	0.8496
C19—C23	1.418 (2)	O10—H10A	0.8498
C20—C21	1.349 (3)	O11—H11B	0.8495
C20—H20A	0.9300	O11—H11A	0.8498
O4—La—O6	78.67 (3)	C24—C16—C17	119.30 (18)
O4—La—O2	87.40 (4)	C18—C17—C16	121.76 (17)
O6—La—O2	139.00 (3)	C18—C17—H17A	119.1
O4—La—O7	135.61 (4)	C16—C17—H17A	119.1
O6—La—O7	139.88 (3)	C17—C18—C19	120.78 (17)
O2—La—O7	73.61 (3)	C17—C18—H18A	119.6
O4—La—O8	142.05 (4)	C19—C18—H18A	119.6
O6—La—O8	70.36 (3)	C20—C19—C23	118.00 (15)
O2—La—O8	130.48 (4)	C20—C19—C18	122.39 (16)
O7—La—O8	69.63 (4)	C23—C19—C18	119.60 (17)
O4—La—N2	77.16 (4)	C21—C20—C19	119.55 (15)
O6—La—N2	78.56 (4)	C21—C20—H20A	120.2
O2—La—N2	135.62 (3)	C19—C20—H20A	120.2
O7—La—N2	88.87 (4)	C20—C21—C22	119.05 (17)
O8—La—N2	75.68 (4)	C20—C21—H21A	120.5
O4—La—N3	130.98 (4)	C22—C21—H21A	120.5
O6—La—N3	92.29 (4)	N4—C22—C21	123.81 (17)
O2—La—N3	68.38 (4)	N4—C22—H22A	118.1
O7—La—N3	78.83 (4)	C21—C22—H22A	118.1
O8—La—N3	72.84 (4)	N3—C24—C16	122.48 (15)
N2—La—N3	148.49 (4)	N3—C24—C23	118.62 (12)
O4—La—N4	72.59 (3)	C16—C24—C23	118.89 (14)
O6—La—N4	69.06 (4)	C25—O2—La	130.85 (9)
O2—La—N4	70.00 (3)	C30—N7—C29	116.3 (2)
O7—La—N4	132.05 (4)	N4—C23—C19	122.02 (14)
O8—La—N4	113.97 (4)	N4—C23—C24	118.41 (12)
N2—La—N4	139.07 (4)	C19—C23—C24	119.57 (14)
N3—La—N4	59.39 (4)	O1—C25—O2	124.44 (13)
O4—La—N1	67.43 (3)	O1—C25—C26	117.61 (14)
O6—La—N1	129.96 (3)	O2—C25—C26	117.94 (13)
O2—La—N1	76.40 (3)	C30—C26—C27	118.63 (16)
O7—La—N1	69.21 (4)	C30—C26—C25	121.48 (15)
O8—La—N1	117.91 (4)	C27—C26—C25	119.84 (15)
N2—La—N1	59.23 (3)	C28—C27—C26	118.2 (2)
N3—La—N1	137.74 (4)	C28—C27—H27A	120.9
N4—La—N1	128.12 (3)	C26—C27—H27A	120.9
C1—N1—C12	117.60 (12)	C29—C28—C27	119.3 (2)
C1—N1—La	121.35 (9)	C29—C28—H28A	120.4
C12—N1—La	120.17 (8)	C27—C28—H28A	120.4
C10—N2—C11	117.76 (13)	N7—C29—C28	123.9 (2)
C10—N2—La	120.73 (10)	N7—C29—H29A	118.0
C11—N2—La	120.52 (9)	C28—C29—H29A	118.0
N1—C1—C2	123.96 (15)	N7—C30—C26	123.62 (19)
N1—C1—H1A	118.0	N7—C30—H30A	118.2
C2—C1—H1A	118.0	C26—C30—H30A	118.2
C3—C2—C1	118.89 (15)	C31—O4—La	151.35 (9)
C3—C2—H2A	120.6	C35—C34—C36	119.22 (19)
C1—C2—H2A	120.6	C35—C34—H34A	120.4
C2—C3—C4	119.37 (14)	C36—C34—H34A	120.4
C2—C3—H3A	120.3	O3—C31—O4	124.76 (14)
C4—C3—H3A	120.3	O3—C31—C32	118.85 (13)
C3—C4—C12	117.91 (14)	O4—C31—C32	116.38 (12)
C3—C4—C5	122.44 (14)	C33—C32—C36	117.60 (16)
C12—C4—C5	119.65 (15)	C33—C32—C31	120.28 (14)
C6—C5—C4	120.99 (15)	C36—C32—C31	122.01 (14)
C6—C5—H5A	119.5	N5—C33—C32	124.12 (17)
C4—C5—H5A	119.5	N5—C33—H33A	117.9
C5—C6—C7	121.32 (15)	C32—C33—H33A	117.9
C5—C6—H6A	119.3	C35—N5—C33	116.95 (17)
C7—C6—H6A	119.3	N5—C35—C34	123.37 (19)
C8—C7—C11	117.51 (15)	N5—C35—H35A	118.3
C8—C7—C6	122.97 (15)	C34—C35—H35A	118.3
C11—C7—C6	119.50 (15)	C34—C36—C32	118.67 (17)
C9—C8—C7	119.92 (16)	C34—C36—H36A	120.7
C9—C8—H8C	120.0	C32—C36—H36A	120.7
C7—C8—H8C	120.0	C37—O6—La	138.33 (9)
C8—C9—C10	118.98 (16)	C39—N6—C40	116.62 (18)
C8—C9—H9C	120.5	O5—C37—O6	125.39 (14)
C10—C9—H9C	120.5	O5—C37—C38	116.97 (13)
N2—C10—C9	123.46 (16)	O6—C37—C38	117.62 (13)
N2—C10—H10C	118.3	C39—C38—C42	117.71 (15)
C9—C10—H10C	118.3	C39—C38—C37	121.61 (13)
N2—C11—C7	122.31 (14)	C42—C38—C37	120.56 (15)
N2—C11—C12	118.47 (12)	N6—C39—C38	123.73 (16)
C7—C11—C12	119.19 (13)	N6—C39—H39A	118.1
N1—C12—C4	122.26 (13)	C38—C39—H39A	118.1
N1—C12—C11	118.41 (12)	N6—C40—C41	123.83 (18)
C4—C12—C11	119.32 (13)	N6—C40—H40A	118.1
C13—N3—C24	117.69 (14)	C41—C40—H40A	118.1
C13—N3—La	120.28 (11)	C40—C41—C42	118.98 (19)
C24—N3—La	121.30 (9)	C40—C41—H41A	120.5
C22—N4—C23	117.53 (13)	C42—C41—H41A	120.5
C22—N4—La	120.99 (10)	C41—C42—C38	119.1 (2)
C23—N4—La	121.43 (9)	C41—C42—H42A	120.5
N3—C13—C14	122.70 (18)	C38—C42—H42A	120.5
N3—C13—H13A	118.7	La—O7—H7B	138.5
C14—C13—H13A	118.7	La—O7—H7A	102.7
C15—C14—C13	119.56 (18)	H7B—O7—H7A	116.5
C15—C14—H14A	120.2	La—O8—H8B	142.8
C13—C14—H14A	120.2	La—O8—H8A	112.7
C14—C15—C16	119.96 (17)	H8B—O8—H8A	99.3
C14—C15—H15A	120.0	H9B—O9—H9A	107.0
C16—C15—H15A	120.0	H10B—O10—H10A	111.5
C15—C16—C24	117.56 (17)	H11B—O11—H11A	101.5
C15—C16—C17	123.12 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O1	0.85	1.77	2.612 (2)	172
O7—H7B···O9^i	0.85	1.85	2.701 (2)	178
O8—H8A···O5	0.85	1.82	2.643 (2)	163
O8—H8B···O10	0.85	1.90	2.744 (2)	176
O9—H9A···O10^ii	0.85	1.96	2.786 (2)	164
O9—H9B···O11^iii	0.85	1.92	2.763 (2)	173
O10—H10A···O3^iii	0.85	1.89	2.731 (2)	172
O10—H10B···O2^iii	0.85	2.05	2.886 (2)	169
O11—H11A···N6	0.85	2.04	2.868 (2)	165
O11—H11B···N5^iv	0.85	2.05	2.894 (2)	174

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) x−1, y, z; (iv) −x+2, −y+1, −z+1.