Tris(thio­cyanato-κN)tris­(triphenyl­phosphine oxide-κO)terbium(III)

Pham, L.N.; Thames, A.T.; White, F.D.; Xiang, K.R.; Sykora, R.E.

doi:10.1107/S1600536812047289

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page m1531

doi:10.1107/S1600536812047289

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Tris(thiocyanato-κN)tris(triphenylphosphine oxide-κO)terbium(III)

Lam N. Pham,^a Anthony T. Thames,^a Frankie D. White,^a Kang Rui Xiang ^a and Richard E. Sykora ^a ^*

^aDepartment of Chemistry, University of South Alabama, Mobile, AL 36688, USA
^*Correspondence e-mail: rsykora@southalabama.edu

(Received 8 November 2012; accepted 16 November 2012; online 24 November 2012)

The title compound, [Tb(NCS)₃(C₁₈H₁₅OP)₃], contains a six-coordinate Tb^II cation surrounded by three O-bound triphenylphosphine oxide ligands and three N-bound thiocyanate ligands, each in a fac arrangement. There are two crystallographically unique Tb^III atoms in the asymmetric unit. One Tb^III atom resides on a threefold rotation axis, while the other has no imposed crystallographic symmetry. The thiocyanate ligands are bound through N atoms, illustrating the hard–hard bonding principles of metal complex chemistry.

Related literature

For information on structures of related lanthanide phosphine oxide complexes, see: Bowden et al. (2012 ); Feazell et al. (2004 ). For the synthesis and characterization of lanthanide triphenylphosphine oxides with nitrate and thiocyanate anions, see: Cousins & Hart (1967 , 1968 ). For more information on the sizes of lanthanide ions, see: Brown & Altermatt (1985 ).

Experimental

Crystal data

[Tb(NCS)₃(C₁₈H₁₅OP)₃]
M_r = 1168.01
Trigonal, R 3
a = 38.6774 (5) Å
c = 12.3956 (2) Å
V = 16058.8 (4) Å³
Z = 12
Mo Kα radiation
μ = 1.57 mm⁻¹
T = 180 K
0.17 × 0.12 × 0.05 mm

Data collection

Agilent Xcalibur Eos CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.913, T_max = 1.000
79947 measured reflections
13045 independent reflections
11605 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.056
S = 1.06
13045 reflections
841 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.51 e Å⁻³
Absolute structure: Flack (1983 ), 6522 Friedel pairs
Flack parameter: −0.028 (4)

Table 1
Selected bond lengths (Å)

Tb1—O1	2.265 (3)
Tb1—O2	2.246 (3)
Tb1—O3	2.243 (3)
Tb1—N1	2.350 (4)
Tb1—N2	2.359 (4)
Tb1—N3	2.356 (4)
Tb2—N4	2.355 (4)
Tb2—O4	2.267 (3)

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablock global. DOI: 10.1107/S1600536812047289/hy2605sup1.cif

checkCIF report

Comment top

Lanthanide complexes containing triphenylphosphine oxides have been studied previously (Bowden et al., 2012; Cousins & Hart, 1967, 1968; Feazell et al., 2004) and are particularly interesting due to their tendency to simultaneously present a large number of these bulky ligands. In complexes of the larger lanthanides, such as [Nd(NCS)₃{OP(C₆H₅)₃}₄], four triphenylphosphine oxide ligands are able to coordinate the metal center (Feazell et al., 2004). With smallar lanthanide ions, such as Tb(III) in the title compound, [Tb(NCS)₃{OP(C₆H₅)₃}₃], only three phosphine ligands are observed to coordinate. Even with a 1:4 mol ratio of terbium(III) nitrate to triphenylphosphine oxide in the synthetic strategy, there are only three triphenylphosphine oxide ligands that bind to the terbium center in the resultant products. In related lanthanide complexes containing triethylphosphine oxide ligands, the larger, lighter lanthanide ions contain three phosphine ligands and the smaller, heavier lanthanide ions contain only two ligands (Bowden et al., 2012), which is also consistent with the trend observed in structural reports in the triphenylphosphine oxide complexes reported earlier and reported here. Interestingly, it seems apparent that the anhydrous nature of the lanthanide triphenylphosphine oxide systems are dominant as the title compound and past structural reports alike show this behaviour.

Related literature top

For information on structures of related lanthanide phosphine oxide complexes, see: Bowden et al. (2012); Feazell et al. (2004). For the synthesis and characterization of lanthanide triphenylphosphine oxides with nitrate and thiocyanate anions, see: Cousins & Hart (1967, 1968). For more information on the sizes of lanthanide ions, see: Brown & Altermatt (1985).

Experimental top

An ethanol solution of terbium(III) nitrate hydrate (1 mmol) and potassium thiocyanate (5 mmol) were combined. The precipitated KNO₃ was removed by filtration from the reaction mixture and was discarded. After filtration, the resulting mixture was combined with an ethanol solution of triphenylphosphine oxide (4 mmol). The solution volume was reduced and the title compound crystallized as colourless single Tris(thiocyanato-κN)tris(triphenylphosphine oxide-κO)terbium(III)crystals from the solution after approximately one hour. No recrystallization was needed.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) 1-y, 1+x-y, z; (ii) -x+y, 1-x, z.]

Tris(thiocyanato-κN)tris(triphenylphosphine oxide-κO)terbium(III) top

Crystal data top

[Tb(NCS)₃(C₁₈H₁₅OP)₃]	D_x = 1.449 Mg m⁻³
M_r = 1168.01	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 21753 reflections
Hall symbol: R 3	θ = 3.1–25.3°
a = 38.6774 (5) Å	µ = 1.57 mm⁻¹
c = 12.3956 (2) Å	T = 180 K
V = 16058.8 (4) Å³	Prism, colourless
Z = 12	0.17 × 0.12 × 0.05 mm
F(000) = 7080

Data collection top

Agilent Xcalibur Eos CCD diffractometer	13045 independent reflections
Radiation source: Enhance (Mo) X-ray Source	11605 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 16.0514 pixels mm^-1	θ_max = 25.4°, θ_min = 3.1°
ω scans	h = −46→46
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −46→46
T_min = 0.913, T_max = 1.000	l = −14→14
79947 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0195P)² + 17.3876P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
13045 reflections	Δρ_max = 0.46 e Å⁻³
841 parameters	Δρ_min = −0.51 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 6522 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.028 (4)

Crystal data top

[Tb(NCS)₃(C₁₈H₁₅OP)₃]	Z = 12
M_r = 1168.01	Mo Kα radiation
Trigonal, R3	µ = 1.57 mm⁻¹
a = 38.6774 (5) Å	T = 180 K
c = 12.3956 (2) Å	0.17 × 0.12 × 0.05 mm
V = 16058.8 (4) Å³

Data collection top

Agilent Xcalibur Eos CCD diffractometer	13045 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	11605 reflections with I > 2σ(I)
T_min = 0.913, T_max = 1.000	R_int = 0.034
79947 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0195P)² + 17.3876P] where P = (F_o² + 2F_c²)/3
S = 1.06	Δρ_max = 0.46 e Å⁻³
13045 reflections	Δρ_min = −0.51 e Å⁻³
841 parameters	Absolute structure: Flack (1983), 6522 Friedel pairs
1 restraint	Absolute structure parameter: −0.028 (4)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Tb1	0.497674 (4)	0.499999 (4)	0.446699 (13)	0.02628 (5)
Tb2	0.3333	0.6667	0.13775 (2)	0.02520 (11)
P3	0.58595 (3)	0.57069 (3)	0.60883 (7)	0.0274 (2)
P1	0.42911 (3)	0.52091 (3)	0.61339 (8)	0.0291 (2)
P4	0.31745 (3)	0.57934 (3)	0.30108 (8)	0.0298 (2)
S3	0.53514 (4)	0.61380 (4)	0.17730 (10)	0.0639 (3)
S2	0.57413 (4)	0.46737 (4)	0.16746 (10)	0.0593 (3)
S4	0.41608 (4)	0.63107 (4)	−0.11001 (11)	0.0747 (4)
C4	0.39288 (12)	0.64579 (12)	−0.0310 (3)	0.0373 (11)
C51	0.65967 (13)	0.69068 (12)	0.5925 (3)	0.0546 (11)
H51	0.6854	0.7092	0.6147	0.066*
O1	0.45464 (8)	0.50789 (8)	0.5536 (2)	0.0358 (7)
O3	0.54690 (7)	0.54550 (8)	0.5507 (2)	0.0361 (7)
N4	0.37642 (12)	0.65641 (12)	0.0250 (3)	0.0459 (10)
O4	0.33202 (8)	0.61932 (7)	0.2483 (2)	0.0363 (7)
P2	0.47985 (3)	0.41103 (3)	0.60768 (8)	0.0300 (2)
O2	0.49021 (9)	0.44989 (8)	0.5539 (2)	0.0402 (8)
C65	0.31722 (10)	0.58382 (10)	0.4444 (3)	0.0333 (8)
S1	0.38132 (6)	0.41797 (5)	0.19602 (16)	0.1286 (8)
C71	0.26838 (11)	0.54414 (10)	0.2577 (3)	0.0389 (9)
C22	0.36604 (11)	0.45058 (11)	0.5413 (3)	0.0436 (9)
H22	0.3854	0.4445	0.5200	0.052*
C17	0.37722 (10)	0.48661 (11)	0.5903 (3)	0.0347 (8)
C18	0.34790 (10)	0.49577 (12)	0.6215 (3)	0.0433 (9)
H18	0.3553	0.5204	0.6527	0.052*
C41	0.62123 (9)	0.55611 (9)	0.5662 (3)	0.0288 (7)
C47	0.60574 (10)	0.62262 (10)	0.5790 (3)	0.0332 (8)
C5	0.43799 (10)	0.52439 (10)	0.7551 (3)	0.0320 (8)
C11	0.44195 (10)	0.57042 (10)	0.5705 (3)	0.0347 (8)
C53	0.57978 (9)	0.56384 (10)	0.7520 (3)	0.0319 (8)
C29	0.47584 (10)	0.41461 (10)	0.7501 (3)	0.0311 (8)
C36	0.42050 (13)	0.37379 (12)	0.4573 (3)	0.0546 (11)
H36	0.4380	0.3937	0.4105	0.065*
C35	0.43226 (10)	0.37226 (10)	0.5611 (3)	0.0349 (8)
C23	0.51747 (10)	0.39792 (10)	0.5858 (3)	0.0340 (8)
C12	0.46025 (13)	0.58369 (13)	0.4722 (4)	0.0579 (12)
H12	0.4643	0.5666	0.4280	0.069*
C42	0.62219 (11)	0.54830 (12)	0.4578 (3)	0.0432 (9)
H42	0.6061	0.5522	0.4093	0.052*
C43	0.64722 (12)	0.53453 (13)	0.4213 (3)	0.0517 (11)
H43	0.6479	0.5293	0.3484	0.062*
C48	0.58323 (12)	0.63523 (11)	0.5240 (3)	0.0456 (10)
H48	0.5577	0.6168	0.5004	0.055*
N3	0.51559 (12)	0.55353 (11)	0.3266 (3)	0.0503 (10)
C59	0.34993 (11)	0.55985 (10)	0.2705 (3)	0.0347 (8)
C44	0.67081 (12)	0.52877 (13)	0.4930 (4)	0.0538 (11)
H44	0.6872	0.5191	0.4689	0.065*
C58	0.56276 (13)	0.52526 (11)	0.7911 (3)	0.0547 (11)
H58	0.5549	0.5041	0.7434	0.066*
C66	0.34695 (12)	0.61711 (11)	0.4941 (3)	0.0504 (10)
H66	0.3661	0.6380	0.4528	0.060*
C70	0.28860 (11)	0.55285 (11)	0.5085 (3)	0.0398 (9)
H70	0.2682	0.5301	0.4762	0.048*
C46	0.64555 (11)	0.55085 (11)	0.6375 (3)	0.0427 (9)
H46	0.6453	0.5565	0.7104	0.051*
C20	0.29724 (12)	0.43215 (14)	0.5569 (3)	0.0583 (12)
H20	0.2704	0.4136	0.5461	0.070*
C16	0.43541 (12)	0.59601 (11)	0.6347 (3)	0.0482 (10)
H16	0.4227	0.5872	0.7009	0.058*
C50	0.63667 (15)	0.70303 (12)	0.5393 (3)	0.0610 (12)
H50	0.6467	0.7301	0.5270	0.073*
C6	0.47519 (11)	0.55264 (11)	0.7945 (3)	0.0450 (9)
H6	0.4951	0.5693	0.7464	0.054*
C19	0.30802 (11)	0.46814 (14)	0.6059 (3)	0.0527 (11)
H19	0.2885	0.4738	0.6285	0.063*
C52	0.64440 (11)	0.65055 (10)	0.6127 (3)	0.0449 (9)
H52	0.6598	0.6420	0.6489	0.054*
C67	0.34860 (14)	0.61969 (14)	0.6052 (4)	0.0649 (13)
H67	0.3691	0.6423	0.6379	0.078*
C21	0.32615 (12)	0.42350 (13)	0.5238 (4)	0.0609 (12)
H21	0.3188	0.3994	0.4895	0.073*
C37	0.38306 (15)	0.34607 (15)	0.4226 (4)	0.0675 (14)
H37	0.3754	0.3474	0.3523	0.081*
C9	0.41732 (12)	0.50365 (12)	0.9381 (3)	0.0462 (10)
H9	0.3979	0.4871	0.9872	0.055*
C3	0.52387 (12)	0.57841 (12)	0.2642 (3)	0.0400 (10)
C72	0.24116 (11)	0.55670 (12)	0.2374 (3)	0.0540 (11)
H72	0.2487	0.5834	0.2470	0.065*
C8	0.45469 (12)	0.53253 (12)	0.9747 (3)	0.0453 (10)
H8	0.4603	0.5355	1.0482	0.054*
C61	0.37610 (14)	0.51666 (13)	0.3076 (3)	0.0597 (12)
H61	0.3769	0.4975	0.3511	0.072*
C45	0.67034 (12)	0.53714 (13)	0.6000 (3)	0.0540 (11)
H45	0.6868	0.5336	0.6481	0.065*
C40	0.40580 (11)	0.34186 (11)	0.6291 (3)	0.0492 (10)
H40	0.4134	0.3404	0.6994	0.059*
N1	0.44182 (12)	0.46278 (12)	0.3357 (3)	0.0567 (11)
C10	0.40893 (11)	0.49949 (11)	0.8300 (3)	0.0411 (9)
H10	0.3838	0.4801	0.8061	0.049*
C38	0.35679 (14)	0.31654 (16)	0.4891 (4)	0.0701 (14)
H38	0.3313	0.2983	0.4650	0.084*
C60	0.35217 (12)	0.53192 (12)	0.3363 (3)	0.0501 (10)
H60	0.3374	0.5236	0.3998	0.060*
C39	0.36843 (13)	0.31391 (14)	0.5927 (4)	0.0704 (14)
H39	0.3511	0.2933	0.6379	0.085*
C24	0.50903 (11)	0.35862 (11)	0.5887 (3)	0.0421 (9)
H24	0.4827	0.3379	0.5915	0.050*
C14	0.46665 (15)	0.64753 (14)	0.5032 (5)	0.0735 (15)
H14	0.4754	0.6736	0.4812	0.088*
C68	0.32109 (15)	0.59001 (14)	0.6672 (3)	0.0607 (12)
H68	0.3226	0.5924	0.7419	0.073*
C32	0.46498 (13)	0.41878 (14)	0.9697 (3)	0.0567 (11)
H32	0.4614	0.4205	1.0433	0.068*
C30	0.48218 (13)	0.39124 (13)	0.8237 (3)	0.0570 (12)
H30	0.4904	0.3739	0.7987	0.068*
C25	0.53996 (14)	0.35029 (13)	0.5874 (3)	0.0562 (11)
H25	0.5342	0.3239	0.5902	0.067*
C69	0.29066 (13)	0.55606 (13)	0.6193 (3)	0.0532 (11)
H69	0.2717	0.5355	0.6617	0.064*
C31	0.47658 (13)	0.39319 (14)	0.9316 (3)	0.0608 (12)
H31	0.4807	0.3770	0.9792	0.073*
C34	0.46363 (14)	0.43976 (13)	0.7911 (3)	0.0587 (12)
H34	0.4587	0.4556	0.7445	0.070*
C7	0.48309 (12)	0.55644 (12)	0.9024 (3)	0.0515 (10)
H7	0.5082	0.5756	0.9269	0.062*
C26	0.57884 (13)	0.38046 (15)	0.5822 (3)	0.0613 (12)
H26	0.5994	0.3746	0.5818	0.074*
C15	0.44761 (15)	0.63415 (13)	0.6011 (4)	0.0639 (13)
H15	0.4430	0.6511	0.6445	0.077*
C63	0.39710 (16)	0.55732 (14)	0.1507 (4)	0.0704 (15)
H63	0.4125	0.5661	0.0884	0.084*
C1	0.41704 (15)	0.44470 (13)	0.2774 (4)	0.0501 (13)
C62	0.39892 (15)	0.52932 (13)	0.2156 (3)	0.0629 (13)
H62	0.4154	0.5191	0.1974	0.075*
C2	0.55123 (12)	0.47549 (11)	0.2650 (3)	0.0417 (10)
N2	0.53486 (12)	0.48160 (12)	0.3335 (3)	0.0502 (10)
C28	0.55682 (12)	0.42797 (12)	0.5777 (4)	0.0594 (12)
H28	0.5629	0.4544	0.5724	0.071*
C49	0.59883 (16)	0.67590 (13)	0.5037 (3)	0.0626 (13)
H49	0.5838	0.6846	0.4664	0.075*
C64	0.37262 (14)	0.57240 (13)	0.1772 (3)	0.0537 (12)
H64	0.3713	0.5910	0.1325	0.064*
C54	0.59052 (12)	0.59435 (11)	0.8253 (3)	0.0553 (11)
H54	0.6018	0.6205	0.8009	0.066*
C55	0.58479 (13)	0.58651 (13)	0.9335 (3)	0.0692 (14)
H55	0.5919	0.6074	0.9819	0.083*
C73	0.20311 (13)	0.52994 (15)	0.2033 (4)	0.0685 (13)
H73	0.1852	0.5388	0.1895	0.082*
C56	0.56874 (12)	0.54826 (14)	0.9710 (3)	0.0600 (12)
H56	0.5657	0.5431	1.0447	0.072*
C57	0.55741 (14)	0.51801 (14)	0.8996 (4)	0.0641 (13)
H57	0.5458	0.4919	0.9246	0.077*
C74	0.19151 (16)	0.49143 (18)	0.1899 (4)	0.0869 (18)
H74	0.1654	0.4734	0.1693	0.104*
C27	0.58739 (13)	0.41903 (16)	0.5775 (4)	0.0768 (16)
H27	0.6138	0.4395	0.5741	0.092*
C33	0.45873 (17)	0.44177 (15)	0.8990 (4)	0.0787 (16)
H33	0.4509	0.4594	0.9249	0.094*
C76	0.25688 (15)	0.50466 (13)	0.2384 (5)	0.0909 (19)
H76	0.2752	0.4959	0.2469	0.109*
C13	0.47266 (16)	0.62224 (15)	0.4385 (5)	0.0814 (17)
H13	0.4851	0.6310	0.3718	0.098*
C75	0.21866 (18)	0.47841 (15)	0.2070 (6)	0.126 (3)
H75	0.2108	0.4516	0.1969	0.151*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.02646 (11)	0.02665 (13)	0.02659 (10)	0.01392 (11)	0.00029 (10)	0.00162 (9)
Tb2	0.02401 (13)	0.02401 (13)	0.0276 (2)	0.01201 (6)	0.000	0.000
P3	0.0224 (5)	0.0253 (5)	0.0320 (5)	0.0101 (4)	−0.0032 (4)	0.0014 (4)
P1	0.0245 (5)	0.0304 (5)	0.0344 (5)	0.0153 (4)	0.0018 (4)	−0.0009 (4)
P4	0.0316 (5)	0.0243 (5)	0.0315 (5)	0.0124 (4)	−0.0007 (4)	0.0037 (4)
S3	0.0716 (8)	0.0649 (8)	0.0577 (7)	0.0359 (7)	0.0134 (6)	0.0363 (6)
S2	0.0656 (8)	0.0551 (7)	0.0596 (8)	0.0320 (6)	0.0266 (6)	−0.0029 (6)
S4	0.0617 (8)	0.0616 (8)	0.0860 (9)	0.0198 (6)	0.0362 (7)	−0.0226 (7)
C4	0.034 (2)	0.035 (2)	0.031 (2)	0.0081 (18)	0.0123 (18)	0.0039 (17)
C51	0.055 (3)	0.036 (2)	0.052 (3)	0.007 (2)	0.012 (2)	0.0042 (19)
O1	0.0308 (14)	0.0394 (16)	0.0413 (18)	0.0206 (13)	−0.0008 (12)	−0.0040 (13)
O3	0.0229 (13)	0.0362 (15)	0.0427 (17)	0.0099 (12)	−0.0065 (12)	0.0011 (12)
N4	0.048 (2)	0.061 (3)	0.038 (2)	0.034 (2)	0.0204 (18)	0.0076 (19)
O4	0.0411 (16)	0.0284 (14)	0.0406 (16)	0.0183 (12)	0.0045 (12)	0.0061 (12)
P2	0.0327 (5)	0.0246 (5)	0.0356 (6)	0.0165 (4)	0.0054 (4)	0.0063 (4)
O2	0.0499 (18)	0.0292 (15)	0.0436 (19)	0.0214 (13)	0.0081 (14)	0.0088 (13)
C65	0.0273 (18)	0.0238 (18)	0.050 (2)	0.0139 (16)	0.0000 (16)	0.0050 (16)
S1	0.1507 (17)	0.0882 (12)	0.1559 (17)	0.0665 (12)	−0.1274 (15)	−0.0623 (11)
C71	0.040 (2)	0.035 (2)	0.0317 (19)	0.0114 (17)	−0.0074 (16)	0.0038 (15)
C22	0.037 (2)	0.044 (2)	0.048 (2)	0.0186 (19)	0.0021 (18)	−0.0053 (18)
C17	0.0295 (19)	0.046 (2)	0.0294 (18)	0.0193 (17)	0.0009 (15)	0.0046 (16)
C18	0.038 (2)	0.050 (2)	0.043 (2)	0.0233 (19)	−0.0007 (17)	−0.0016 (18)
C41	0.0263 (17)	0.0248 (17)	0.0325 (18)	0.0106 (14)	−0.0010 (14)	−0.0012 (14)
C47	0.036 (2)	0.0309 (19)	0.0297 (18)	0.0148 (16)	0.0064 (15)	0.0048 (14)
C5	0.0260 (18)	0.0338 (19)	0.045 (2)	0.0218 (16)	−0.0007 (16)	−0.0080 (16)
C11	0.0281 (18)	0.036 (2)	0.042 (2)	0.0180 (16)	0.0007 (15)	0.0035 (16)
C53	0.0180 (17)	0.0313 (19)	0.043 (2)	0.0099 (15)	0.0009 (15)	0.0067 (16)
C29	0.0235 (18)	0.0271 (19)	0.043 (2)	0.0126 (16)	0.0039 (15)	0.0055 (16)
C36	0.062 (3)	0.048 (3)	0.047 (3)	0.022 (2)	−0.007 (2)	0.002 (2)
C35	0.038 (2)	0.0324 (19)	0.041 (2)	0.0218 (17)	0.0045 (16)	0.0015 (16)
C23	0.0342 (19)	0.036 (2)	0.0346 (19)	0.0199 (17)	0.0069 (15)	0.0036 (15)
C12	0.069 (3)	0.059 (3)	0.063 (3)	0.045 (3)	0.028 (2)	0.022 (2)
C42	0.043 (2)	0.055 (3)	0.036 (2)	0.028 (2)	−0.0060 (17)	−0.0014 (18)
C43	0.053 (3)	0.067 (3)	0.040 (2)	0.034 (2)	−0.002 (2)	−0.009 (2)
C48	0.057 (3)	0.042 (2)	0.044 (2)	0.028 (2)	−0.010 (2)	−0.0026 (18)
N3	0.070 (3)	0.047 (2)	0.034 (2)	0.029 (2)	0.0062 (19)	0.0161 (17)
C59	0.046 (2)	0.0294 (19)	0.0328 (19)	0.0219 (17)	0.0011 (16)	0.0016 (15)
C44	0.050 (3)	0.060 (3)	0.060 (3)	0.034 (2)	0.007 (2)	−0.003 (2)
C58	0.085 (3)	0.036 (2)	0.042 (2)	0.029 (2)	0.008 (2)	0.0042 (18)
C66	0.051 (2)	0.041 (2)	0.042 (2)	0.011 (2)	−0.0079 (19)	−0.0028 (18)
C70	0.039 (2)	0.044 (2)	0.036 (2)	0.0202 (18)	0.0063 (16)	0.0088 (16)
C46	0.043 (2)	0.059 (3)	0.034 (2)	0.032 (2)	−0.0090 (17)	−0.0064 (18)
C20	0.029 (2)	0.075 (3)	0.052 (3)	0.012 (2)	−0.0016 (19)	−0.001 (2)
C16	0.061 (3)	0.045 (2)	0.044 (2)	0.031 (2)	−0.0032 (19)	−0.0009 (18)
C50	0.093 (4)	0.032 (2)	0.048 (3)	0.024 (2)	0.011 (2)	0.0078 (19)
C6	0.036 (2)	0.043 (2)	0.046 (2)	0.0121 (18)	−0.0032 (17)	0.0041 (18)
C19	0.034 (2)	0.078 (3)	0.049 (2)	0.031 (2)	0.0008 (18)	0.003 (2)
C52	0.033 (2)	0.031 (2)	0.057 (2)	0.0065 (17)	0.0045 (18)	0.0075 (18)
C67	0.072 (3)	0.052 (3)	0.057 (3)	0.020 (3)	−0.019 (3)	−0.008 (2)
C21	0.044 (3)	0.055 (3)	0.066 (3)	0.011 (2)	−0.005 (2)	−0.015 (2)
C37	0.071 (4)	0.073 (4)	0.058 (3)	0.036 (3)	−0.024 (3)	−0.011 (3)
C9	0.047 (2)	0.054 (3)	0.038 (2)	0.026 (2)	0.0035 (18)	−0.0012 (18)
C3	0.038 (2)	0.044 (2)	0.037 (2)	0.020 (2)	0.0037 (17)	0.0036 (19)
C72	0.042 (2)	0.049 (3)	0.067 (3)	0.020 (2)	0.003 (2)	0.005 (2)
C8	0.054 (3)	0.056 (3)	0.037 (2)	0.036 (2)	−0.0105 (19)	−0.0101 (19)
C61	0.095 (4)	0.067 (3)	0.045 (2)	0.061 (3)	0.004 (2)	0.016 (2)
C45	0.048 (2)	0.076 (3)	0.054 (3)	0.043 (2)	−0.009 (2)	−0.005 (2)
C40	0.044 (2)	0.046 (2)	0.048 (2)	0.015 (2)	0.0056 (19)	0.0000 (19)
N1	0.052 (2)	0.059 (3)	0.049 (2)	0.020 (2)	−0.021 (2)	−0.009 (2)
C10	0.035 (2)	0.048 (2)	0.039 (2)	0.0201 (19)	0.0016 (16)	−0.0058 (17)
C38	0.046 (3)	0.088 (4)	0.075 (4)	0.032 (3)	−0.017 (2)	−0.032 (3)
C60	0.072 (3)	0.061 (3)	0.037 (2)	0.047 (2)	0.0126 (19)	0.0192 (19)
C39	0.045 (3)	0.060 (3)	0.075 (3)	0.002 (2)	0.016 (2)	−0.007 (3)
C24	0.043 (2)	0.034 (2)	0.056 (2)	0.0246 (18)	−0.0016 (18)	−0.0013 (17)
C14	0.076 (4)	0.050 (3)	0.101 (4)	0.036 (3)	−0.001 (3)	0.021 (3)
C68	0.095 (4)	0.077 (3)	0.031 (2)	0.058 (3)	−0.008 (2)	−0.003 (2)
C32	0.062 (3)	0.082 (3)	0.040 (2)	0.047 (3)	0.004 (2)	−0.004 (2)
C30	0.092 (3)	0.070 (3)	0.039 (2)	0.063 (3)	0.013 (2)	0.014 (2)
C25	0.073 (3)	0.056 (3)	0.062 (3)	0.049 (3)	−0.003 (2)	−0.006 (2)
C69	0.058 (3)	0.062 (3)	0.044 (2)	0.034 (2)	0.012 (2)	0.015 (2)
C31	0.081 (3)	0.084 (3)	0.043 (2)	0.061 (3)	0.015 (2)	0.020 (2)
C34	0.094 (4)	0.067 (3)	0.049 (3)	0.065 (3)	−0.005 (2)	−0.004 (2)
C7	0.041 (2)	0.050 (3)	0.055 (3)	0.016 (2)	−0.017 (2)	−0.006 (2)
C26	0.054 (3)	0.089 (4)	0.060 (3)	0.050 (3)	−0.001 (2)	−0.016 (3)
C15	0.090 (4)	0.053 (3)	0.065 (3)	0.048 (3)	−0.020 (3)	−0.012 (2)
C63	0.117 (4)	0.076 (3)	0.055 (3)	0.076 (3)	0.040 (3)	0.026 (2)
C1	0.068 (3)	0.055 (3)	0.047 (3)	0.045 (3)	−0.023 (2)	−0.018 (2)
C62	0.099 (4)	0.072 (3)	0.053 (3)	0.069 (3)	0.015 (2)	0.009 (2)
C2	0.046 (3)	0.032 (2)	0.049 (3)	0.020 (2)	0.000 (2)	−0.0019 (18)
N2	0.058 (2)	0.065 (3)	0.041 (2)	0.041 (2)	0.0095 (18)	−0.0047 (19)
C28	0.038 (2)	0.040 (2)	0.094 (3)	0.015 (2)	0.019 (2)	0.000 (2)
C49	0.101 (4)	0.052 (3)	0.052 (3)	0.051 (3)	−0.006 (3)	0.010 (2)
C64	0.089 (3)	0.053 (3)	0.040 (2)	0.052 (3)	0.019 (2)	0.014 (2)
C54	0.059 (3)	0.033 (2)	0.044 (2)	0.001 (2)	0.002 (2)	0.0010 (18)
C55	0.069 (3)	0.055 (3)	0.041 (2)	−0.001 (2)	0.005 (2)	−0.007 (2)
C73	0.039 (3)	0.074 (3)	0.077 (3)	0.017 (2)	−0.009 (2)	0.007 (3)
C56	0.046 (3)	0.077 (3)	0.035 (2)	0.014 (2)	−0.0027 (19)	0.008 (2)
C57	0.089 (4)	0.054 (3)	0.054 (3)	0.040 (3)	0.015 (3)	0.020 (2)
C74	0.057 (3)	0.080 (4)	0.081 (4)	0.003 (3)	−0.029 (3)	−0.004 (3)
C27	0.037 (2)	0.071 (3)	0.117 (5)	0.023 (2)	0.014 (3)	−0.014 (3)
C33	0.135 (5)	0.094 (4)	0.057 (3)	0.095 (4)	0.003 (3)	−0.009 (3)
C76	0.081 (4)	0.039 (3)	0.143 (5)	0.023 (3)	−0.056 (4)	−0.024 (3)
C13	0.094 (4)	0.074 (4)	0.097 (4)	0.057 (3)	0.048 (3)	0.047 (3)
C75	0.104 (5)	0.041 (3)	0.205 (8)	0.015 (3)	−0.093 (5)	−0.033 (4)

Geometric parameters (Å, º) top

Tb1—O1	2.265 (3)	C20—C19	1.379 (6)
Tb1—O2	2.246 (3)	C20—C21	1.380 (6)
Tb1—O3	2.243 (3)	C16—H16	0.9300
Tb1—N1	2.350 (4)	C16—C15	1.369 (5)
Tb1—N2	2.359 (4)	C50—H50	0.9300
Tb1—N3	2.356 (4)	C50—C49	1.379 (6)
Tb2—N4	2.355 (4)	C6—H6	0.9300
Tb2—O4	2.267 (3)	C6—C7	1.364 (5)
P3—O3	1.509 (3)	C19—H19	0.9300
P3—C41	1.797 (3)	C52—H52	0.9300
P3—C47	1.794 (3)	C67—H67	0.9300
P3—C53	1.793 (4)	C67—C68	1.349 (6)
P1—O1	1.508 (3)	C21—H21	0.9300
P1—C17	1.791 (3)	C37—H37	0.9300
P1—C5	1.782 (4)	C37—C38	1.362 (7)
P1—C11	1.801 (4)	C9—H9	0.9300
P4—O4	1.505 (3)	C9—C8	1.389 (5)
P4—C65	1.786 (4)	C9—C10	1.369 (5)
P4—C71	1.778 (4)	C72—H72	0.9300
P4—C59	1.799 (4)	C72—C73	1.376 (5)
S3—C3	1.621 (4)	C8—H8	0.9300
S2—C2	1.619 (4)	C8—C7	1.360 (5)
S4—C4	1.613 (4)	C61—H61	0.9300
C4—N4	1.148 (5)	C61—C60	1.370 (5)
C51—H51	0.9300	C61—C62	1.374 (6)
C51—C50	1.371 (6)	C45—H45	0.9300
C51—C52	1.380 (5)	C40—H40	0.9300
P2—O2	1.504 (3)	C40—C39	1.378 (6)
P2—C29	1.784 (4)	N1—C1	1.123 (5)
P2—C35	1.792 (4)	C10—H10	0.9300
P2—C23	1.784 (3)	C38—H38	0.9300
C65—C66	1.371 (5)	C38—C39	1.381 (6)
C65—C70	1.402 (5)	C60—H60	0.9300
S1—C1	1.602 (5)	C39—H39	0.9300
C71—C72	1.385 (5)	C24—H24	0.9300
C71—C76	1.381 (5)	C24—C25	1.386 (5)
C22—H22	0.9300	C14—H14	0.9300
C22—C17	1.377 (5)	C14—C15	1.379 (7)
C22—C21	1.382 (5)	C14—C13	1.372 (7)
C17—C18	1.401 (5)	C68—H68	0.9300
C18—H18	0.9300	C68—C69	1.384 (6)
C18—C19	1.382 (5)	C32—H32	0.9300
C41—C42	1.381 (5)	C32—C31	1.360 (5)
C41—C46	1.378 (5)	C32—C33	1.353 (6)
C47—C48	1.373 (5)	C30—H30	0.9300
C47—C52	1.401 (5)	C30—C31	1.363 (5)
C5—C6	1.389 (5)	C25—H25	0.9300
C5—C10	1.404 (5)	C25—C26	1.368 (6)
C11—C12	1.374 (5)	C69—H69	0.9300
C11—C16	1.388 (5)	C31—H31	0.9300
C53—C58	1.383 (5)	C34—H34	0.9300
C53—C54	1.378 (5)	C34—C33	1.359 (6)
C29—C30	1.389 (5)	C7—H7	0.9300
C29—C34	1.374 (5)	C26—H26	0.9300
C36—H36	0.9300	C26—C27	1.358 (6)
C36—C35	1.376 (5)	C15—H15	0.9300
C36—C37	1.371 (6)	C63—H63	0.9300
C35—C40	1.391 (5)	C63—C62	1.379 (5)
C23—C24	1.386 (5)	C63—C64	1.377 (6)
C23—C28	1.382 (5)	C62—H62	0.9300
C12—H12	0.9300	C2—N2	1.152 (5)
C12—C13	1.383 (6)	C28—H28	0.9300
C42—H42	0.9300	C28—C27	1.388 (6)
C42—C43	1.393 (5)	C49—H49	0.9300
C43—H43	0.9300	C64—H64	0.9300
C43—C44	1.370 (6)	C54—H54	0.9300
C48—H48	0.9300	C54—C55	1.368 (5)
C48—C49	1.397 (5)	C55—H55	0.9300
N3—C3	1.148 (5)	C55—C56	1.368 (6)
C59—C60	1.390 (5)	C73—H73	0.9300
C59—C64	1.384 (5)	C73—C74	1.334 (7)
C44—H44	0.9300	C56—H56	0.9300
C44—C45	1.368 (6)	C56—C57	1.353 (6)
C58—H58	0.9300	C57—H57	0.9300
C58—C57	1.367 (5)	C74—H74	0.9300
C66—H66	0.9300	C74—C75	1.389 (8)
C66—C67	1.379 (6)	C27—H27	0.9300
C70—H70	0.9300	C33—H33	0.9300
C70—C69	1.377 (5)	C76—H76	0.9300
C46—H46	0.9300	C76—C75	1.366 (6)
C46—C45	1.387 (5)	C13—H13	0.9300
C20—H20	0.9300	C75—H75	0.9300

O1—Tb1—N3	99.48 (12)	C15—C16—H16	119.8
O1—Tb1—N1	84.99 (12)	C51—C50—H50	119.5
O1—Tb1—N2	171.36 (12)	C51—C50—C49	121.0 (4)
O3—Tb1—O1	87.18 (10)	C49—C50—H50	119.5
O3—Tb1—O2	91.69 (10)	C5—C6—H6	119.4
O3—Tb1—N3	84.97 (11)	C7—C6—C5	121.2 (4)
O3—Tb1—N1	167.59 (12)	C7—C6—H6	119.4
O3—Tb1—N2	99.90 (11)	C18—C19—H19	120.0
O2—Tb1—O1	89.08 (10)	C20—C19—C18	120.0 (4)
O2—Tb1—N3	170.63 (13)	C20—C19—H19	120.0
O2—Tb1—N1	97.79 (12)	C51—C52—C47	120.3 (4)
O2—Tb1—N2	85.77 (11)	C51—C52—H52	119.8
N3—Tb1—N2	86.18 (13)	C47—C52—H52	119.8
N1—Tb1—N3	86.84 (14)	C66—C67—H67	119.4
N1—Tb1—N2	88.83 (14)	C68—C67—C66	121.3 (4)
N4ⁱ—Tb2—N4ⁱⁱ	88.40 (14)	C68—C67—H67	119.4
N4ⁱ—Tb2—N4	88.41 (14)	C22—C21—H21	119.9
N4ⁱⁱ—Tb2—N4	88.41 (14)	C20—C21—C22	120.1 (4)
O4—Tb2—N4ⁱⁱ	97.42 (12)	C20—C21—H21	119.9
O4ⁱ—Tb2—N4ⁱⁱ	172.71 (11)	C36—C37—H37	119.3
O4ⁱⁱ—Tb2—N4	172.71 (11)	C38—C37—C36	121.3 (5)
O4ⁱ—Tb2—N4	97.42 (12)	C38—C37—H37	119.3
O4—Tb2—N4	87.38 (11)	C8—C9—H9	119.8
O4ⁱⁱ—Tb2—N4ⁱ	97.41 (12)	C10—C9—H9	119.8
O4ⁱ—Tb2—N4ⁱ	87.38 (11)	C10—C9—C8	120.3 (4)
O4—Tb2—N4ⁱ	172.71 (12)	N3—C3—S3	179.0 (4)
O4ⁱⁱ—Tb2—N4ⁱⁱ	87.38 (11)	C71—C72—H72	119.8
O4ⁱⁱ—Tb2—O4ⁱ	87.27 (10)	C73—C72—C71	120.4 (4)
O4ⁱⁱ—Tb2—O4	87.27 (10)	C73—C72—H72	119.8
O4ⁱ—Tb2—O4	87.27 (10)	C9—C8—H8	120.2
O3—P3—C41	109.19 (15)	C7—C8—C9	119.6 (4)
O3—P3—C47	110.67 (16)	C7—C8—H8	120.2
O3—P3—C53	111.18 (16)	C60—C61—H61	119.5
C47—P3—C41	108.95 (15)	C60—C61—C62	120.9 (4)
C53—P3—C41	108.10 (16)	C62—C61—H61	119.5
C53—P3—C47	108.68 (16)	C44—C45—C46	120.6 (4)
O1—P1—C17	110.64 (16)	C44—C45—H45	119.7
O1—P1—C5	112.06 (16)	C46—C45—H45	119.7
O1—P1—C11	109.36 (16)	C35—C40—H40	119.9
C17—P1—C11	110.58 (16)	C39—C40—C35	120.3 (4)
C5—P1—C17	108.41 (16)	C39—C40—H40	119.9
C5—P1—C11	105.69 (16)	C1—N1—Tb1	174.7 (4)
O4—P4—C65	110.52 (16)	C5—C10—H10	119.8
O4—P4—C71	111.29 (16)	C9—C10—C5	120.4 (4)
O4—P4—C59	110.95 (16)	C9—C10—H10	119.8
C65—P4—C59	106.78 (16)	C37—C38—H38	120.3
C71—P4—C65	108.68 (17)	C37—C38—C39	119.3 (4)
C71—P4—C59	108.47 (17)	C39—C38—H38	120.3
N4—C4—S4	179.7 (4)	C59—C60—H60	120.0
C50—C51—H51	120.3	C61—C60—C59	120.0 (4)
C50—C51—C52	119.5 (4)	C61—C60—H60	120.0
C52—C51—H51	120.3	C40—C39—C38	120.0 (4)
P1—O1—Tb1	168.67 (18)	C40—C39—H39	120.0
P3—O3—Tb1	164.49 (17)	C38—C39—H39	120.0
C4—N4—Tb2	170.0 (4)	C23—C24—H24	120.1
P4—O4—Tb2	159.75 (17)	C25—C24—C23	119.8 (4)
O2—P2—C29	110.55 (16)	C25—C24—H24	120.1
O2—P2—C35	110.03 (17)	C15—C14—H14	120.1
O2—P2—C23	111.66 (16)	C13—C14—H14	120.1
C29—P2—C35	106.91 (16)	C13—C14—C15	119.8 (4)
C29—P2—C23	106.70 (16)	C67—C68—H68	120.1
C23—P2—C35	110.84 (16)	C67—C68—C69	119.8 (4)
P2—O2—Tb1	168.4 (2)	C69—C68—H68	120.1
C66—C65—P4	119.7 (3)	C31—C32—H32	120.5
C66—C65—C70	118.8 (4)	C33—C32—H32	120.5
C70—C65—P4	121.4 (3)	C33—C32—C31	119.0 (4)
C72—C71—P4	119.6 (3)	C29—C30—H30	119.2
C76—C71—P4	122.0 (3)	C31—C30—C29	121.6 (4)
C76—C71—C72	118.4 (4)	C31—C30—H30	119.2
C17—C22—H22	119.9	C24—C25—H25	119.6
C17—C22—C21	120.2 (4)	C26—C25—C24	120.7 (4)
C21—C22—H22	119.9	C26—C25—H25	119.6
C22—C17—P1	119.3 (3)	C70—C69—C68	119.8 (4)
C22—C17—C18	119.6 (3)	C70—C69—H69	120.1
C18—C17—P1	121.2 (3)	C68—C69—H69	120.1
C17—C18—H18	120.1	C32—C31—C30	120.0 (4)
C19—C18—C17	119.8 (4)	C32—C31—H31	120.0
C19—C18—H18	120.1	C30—C31—H31	120.0
C42—C41—P3	117.5 (3)	C29—C34—H34	119.6
C46—C41—P3	122.6 (3)	C33—C34—C29	120.8 (4)
C46—C41—C42	119.8 (3)	C33—C34—H34	119.6
C48—C47—P3	120.6 (3)	C6—C7—H7	119.6
C48—C47—C52	119.7 (3)	C8—C7—C6	120.8 (4)
C52—C47—P3	119.7 (3)	C8—C7—H7	119.6
C6—C5—P1	119.4 (3)	C25—C26—H26	120.0
C6—C5—C10	117.8 (3)	C27—C26—C25	119.9 (4)
C10—C5—P1	122.9 (3)	C27—C26—H26	120.0
C12—C11—P1	118.4 (3)	C16—C15—C14	120.2 (4)
C12—C11—C16	119.1 (4)	C16—C15—H15	119.9
C16—C11—P1	122.5 (3)	C14—C15—H15	119.9
C58—C53—P3	117.6 (3)	C62—C63—H63	119.7
C54—C53—P3	124.4 (3)	C64—C63—H63	119.7
C54—C53—C58	118.0 (3)	C64—C63—C62	120.6 (4)
C30—C29—P2	123.3 (3)	N1—C1—S1	178.6 (5)
C34—C29—P2	119.7 (3)	C61—C62—C63	119.2 (4)
C34—C29—C30	116.9 (4)	C61—C62—H62	120.4
C35—C36—H36	119.9	C63—C62—H62	120.4
C37—C36—H36	119.9	N2—C2—S2	179.1 (4)
C37—C36—C35	120.1 (4)	C2—N2—Tb1	168.7 (3)
C36—C35—P2	119.2 (3)	C23—C28—H28	119.7
C36—C35—C40	118.9 (4)	C23—C28—C27	120.5 (4)
C40—C35—P2	121.7 (3)	C27—C28—H28	119.7
C24—C23—P2	121.9 (3)	C48—C49—H49	120.1
C28—C23—P2	118.9 (3)	C50—C49—C48	119.7 (4)
C28—C23—C24	118.7 (3)	C50—C49—H49	120.1
C11—C12—H12	119.8	C59—C64—H64	120.0
C11—C12—C13	120.5 (4)	C63—C64—C59	120.0 (4)
C13—C12—H12	119.8	C63—C64—H64	120.0
C41—C42—H42	120.0	C53—C54—H54	119.7
C41—C42—C43	120.0 (3)	C55—C54—C53	120.7 (4)
C43—C42—H42	120.0	C55—C54—H54	119.7
C42—C43—H43	120.1	C54—C55—H55	119.7
C44—C43—C42	119.8 (4)	C56—C55—C54	120.5 (4)
C44—C43—H43	120.1	C56—C55—H55	119.7
C47—C48—H48	120.1	C72—C73—H73	119.5
C47—C48—C49	119.7 (4)	C74—C73—C72	121.0 (5)
C49—C48—H48	120.1	C74—C73—H73	119.5
C3—N3—Tb1	176.9 (3)	C55—C56—H56	120.4
C60—C59—P4	122.0 (3)	C57—C56—C55	119.2 (4)
C64—C59—P4	118.8 (3)	C57—C56—H56	120.4
C64—C59—C60	119.2 (3)	C58—C57—H57	119.5
C43—C44—H44	119.9	C56—C57—C58	121.0 (4)
C45—C44—C43	120.2 (4)	C56—C57—H57	119.5
C45—C44—H44	119.9	C73—C74—H74	120.2
C53—C58—H58	119.8	C73—C74—C75	119.5 (5)
C57—C58—C53	120.5 (4)	C75—C74—H74	120.2
C57—C58—H58	119.8	C26—C27—C28	120.2 (4)
C65—C66—H66	119.9	C26—C27—H27	119.9
C65—C66—C67	120.2 (4)	C28—C27—H27	119.9
C67—C66—H66	119.9	C32—C33—C34	121.6 (4)
C65—C70—H70	119.9	C32—C33—H33	119.2
C69—C70—C65	120.2 (4)	C34—C33—H33	119.2
C69—C70—H70	119.9	C71—C76—H76	119.9
C41—C46—H46	120.2	C75—C76—C71	120.1 (5)
C41—C46—C45	119.7 (3)	C75—C76—H76	119.9
C45—C46—H46	120.2	C12—C13—H13	120.0
C19—C20—H20	119.9	C14—C13—C12	120.0 (5)
C19—C20—C21	120.2 (4)	C14—C13—H13	120.0
C21—C20—H20	119.9	C74—C75—H75	119.8
C11—C16—H16	119.8	C76—C75—C74	120.5 (5)
C15—C16—C11	120.4 (4)	C76—C75—H75	119.8

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

Experimental details

Crystal data
Chemical formula	[Tb(NCS)₃(C₁₈H₁₅OP)₃]
M_r	1168.01
Crystal system, space group	Trigonal, R3
Temperature (K)	180
a, c (Å)	38.6774 (5), 12.3956 (2)
V (Å³)	16058.8 (4)
Z	12
Radiation type	Mo Kα
µ (mm⁻¹)	1.57
Crystal size (mm)	0.17 × 0.12 × 0.05

Data collection
Diffractometer	Agilent Xcalibur Eos CCD diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.913, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	79947, 13045, 11605
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.056, 1.06
No. of reflections	13045
No. of parameters	841
No. of restraints	1
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0195P)² + 17.3876P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.51
Absolute structure	Flack (1983), 6522 Friedel pairs
Absolute structure parameter	−0.028 (4)

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Tb1—O1	2.265 (3)	Tb1—N2	2.359 (4)
Tb1—O2	2.246 (3)	Tb1—N3	2.356 (4)
Tb1—O3	2.243 (3)	Tb2—N4	2.355 (4)
Tb1—N1	2.350 (4)	Tb2—O4	2.267 (3)

Acknowledgements

The authors acknowledge the National Science Foundation for its generous support (NSF Career grant to RES, No. CHE-0846680).

References

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