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Acta Cryst. (2012). E68, m1531    [ doi:10.1107/S1600536812047289 ]

Tris(thiocyanato-[kappa]N)tris(triphenylphosphine oxide-[kappa]O)terbium(III)

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

Abstract top

The title compound, [Tb(NCS)3(C18H15OP)3], contains a six-coordinate TbII 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 TbIII atoms in the asymmetric unit. One TbIII 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.

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.

Refinement top

H atoms were placed in calculated positions and allowed to ride during subsequent refinement, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

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
[Figure 1] 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]Dx = 1.449 Mg m−3
Mr = 1168.01Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 21753 reflections
Hall symbol: R 3θ = 3.1–25.3°
a = 38.6774 (5) ŵ = 1.57 mm−1
c = 12.3956 (2) ÅT = 180 K
V = 16058.8 (4) Å3Prism, colourless
Z = 120.17 × 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 Source11605 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 16.0514 pixels mm-1θmax = 25.4°, θmin = 3.1°
ω scansh = −46→46
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		k = −46→46
Tmin = 0.913, Tmax = 1.000l = −14→14
79947 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.056 w = 1/[σ2(Fo2) + (0.0195P)2 + 17.3876P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
13045 reflectionsΔρmax = 0.46 e Å−3
841 parametersΔρmin = −0.51 e Å−3
1 restraintAbsolute structure: Flack (1983), 6522 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.028 (4)
Crystal data top
[Tb(NCS)3(C18H15OP)3]Z = 12
Mr = 1168.01Mo Kα radiation
Trigonal, R3µ = 1.57 mm−1
a = 38.6774 (5) ÅT = 180 K
c = 12.3956 (2) Å0.17 × 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)
Tmin = 0.913, Tmax = 1.000Rint = 0.034
79947 measured reflectionsθmax = 25.4°
Refinement top
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.056 w = 1/[σ2(Fo2) + (0.0195P)2 + 17.3876P]
where P = (Fo2 + 2Fc2)/3
S = 1.06Δρmax = 0.46 e Å−3
13045 reflectionsΔρmin = −0.51 e Å−3
841 parametersAbsolute structure: Flack (1983), 6522 Friedel pairs
1 restraintFlack 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
xyzUiso*/Ueq
Tb10.497674 (4)0.499999 (4)0.446699 (13)0.02628 (5)
Tb20.33330.66670.13775 (2)0.02520 (11)
P30.58595 (3)0.57069 (3)0.60883 (7)0.0274 (2)
P10.42911 (3)0.52091 (3)0.61339 (8)0.0291 (2)
P40.31745 (3)0.57934 (3)0.30108 (8)0.0298 (2)
S30.53514 (4)0.61380 (4)0.17730 (10)0.0639 (3)
S20.57413 (4)0.46737 (4)0.16746 (10)0.0593 (3)
S40.41608 (4)0.63107 (4)−0.11001 (11)0.0747 (4)
C40.39288 (12)0.64579 (12)−0.0310 (3)0.0373 (11)
C510.65967 (13)0.69068 (12)0.5925 (3)0.0546 (11)
H510.68540.70920.61470.066*
O10.45464 (8)0.50789 (8)0.5536 (2)0.0358 (7)
O30.54690 (7)0.54550 (8)0.5507 (2)0.0361 (7)
N40.37642 (12)0.65641 (12)0.0250 (3)0.0459 (10)
O40.33202 (8)0.61932 (7)0.2483 (2)0.0363 (7)
P20.47985 (3)0.41103 (3)0.60768 (8)0.0300 (2)
O20.49021 (9)0.44989 (8)0.5539 (2)0.0402 (8)
C650.31722 (10)0.58382 (10)0.4444 (3)0.0333 (8)
S10.38132 (6)0.41797 (5)0.19602 (16)0.1286 (8)
C710.26838 (11)0.54414 (10)0.2577 (3)0.0389 (9)
C220.36604 (11)0.45058 (11)0.5413 (3)0.0436 (9)
H220.38540.44450.52000.052*
C170.37722 (10)0.48661 (11)0.5903 (3)0.0347 (8)
C180.34790 (10)0.49577 (12)0.6215 (3)0.0433 (9)
H180.35530.52040.65270.052*
C410.62123 (9)0.55611 (9)0.5662 (3)0.0288 (7)
C470.60574 (10)0.62262 (10)0.5790 (3)0.0332 (8)
C50.43799 (10)0.52439 (10)0.7551 (3)0.0320 (8)
C110.44195 (10)0.57042 (10)0.5705 (3)0.0347 (8)
C530.57978 (9)0.56384 (10)0.7520 (3)0.0319 (8)
C290.47584 (10)0.41461 (10)0.7501 (3)0.0311 (8)
C360.42050 (13)0.37379 (12)0.4573 (3)0.0546 (11)
H360.43800.39370.41050.065*
C350.43226 (10)0.37226 (10)0.5611 (3)0.0349 (8)
C230.51747 (10)0.39792 (10)0.5858 (3)0.0340 (8)
C120.46025 (13)0.58369 (13)0.4722 (4)0.0579 (12)
H120.46430.56660.42800.069*
C420.62219 (11)0.54830 (12)0.4578 (3)0.0432 (9)
H420.60610.55220.40930.052*
C430.64722 (12)0.53453 (13)0.4213 (3)0.0517 (11)
H430.64790.52930.34840.062*
C480.58323 (12)0.63523 (11)0.5240 (3)0.0456 (10)
H480.55770.61680.50040.055*
N30.51559 (12)0.55353 (11)0.3266 (3)0.0503 (10)
C590.34993 (11)0.55985 (10)0.2705 (3)0.0347 (8)
C440.67081 (12)0.52877 (13)0.4930 (4)0.0538 (11)
H440.68720.51910.46890.065*
C580.56276 (13)0.52526 (11)0.7911 (3)0.0547 (11)
H580.55490.50410.74340.066*
C660.34695 (12)0.61711 (11)0.4941 (3)0.0504 (10)
H660.36610.63800.45280.060*
C700.28860 (11)0.55285 (11)0.5085 (3)0.0398 (9)
H700.26820.53010.47620.048*
C460.64555 (11)0.55085 (11)0.6375 (3)0.0427 (9)
H460.64530.55650.71040.051*
C200.29724 (12)0.43215 (14)0.5569 (3)0.0583 (12)
H200.27040.41360.54610.070*
C160.43541 (12)0.59601 (11)0.6347 (3)0.0482 (10)
H160.42270.58720.70090.058*
C500.63667 (15)0.70303 (12)0.5393 (3)0.0610 (12)
H500.64670.73010.52700.073*
C60.47519 (11)0.55264 (11)0.7945 (3)0.0450 (9)
H60.49510.56930.74640.054*
C190.30802 (11)0.46814 (14)0.6059 (3)0.0527 (11)
H190.28850.47380.62850.063*
C520.64440 (11)0.65055 (10)0.6127 (3)0.0449 (9)
H520.65980.64200.64890.054*
C670.34860 (14)0.61969 (14)0.6052 (4)0.0649 (13)
H670.36910.64230.63790.078*
C210.32615 (12)0.42350 (13)0.5238 (4)0.0609 (12)
H210.31880.39940.48950.073*
C370.38306 (15)0.34607 (15)0.4226 (4)0.0675 (14)
H370.37540.34740.35230.081*
C90.41732 (12)0.50365 (12)0.9381 (3)0.0462 (10)
H90.39790.48710.98720.055*
C30.52387 (12)0.57841 (12)0.2642 (3)0.0400 (10)
C720.24116 (11)0.55670 (12)0.2374 (3)0.0540 (11)
H720.24870.58340.24700.065*
C80.45469 (12)0.53253 (12)0.9747 (3)0.0453 (10)
H80.46030.53551.04820.054*
C610.37610 (14)0.51666 (13)0.3076 (3)0.0597 (12)
H610.37690.49750.35110.072*
C450.67034 (12)0.53714 (13)0.6000 (3)0.0540 (11)
H450.68680.53360.64810.065*
C400.40580 (11)0.34186 (11)0.6291 (3)0.0492 (10)
H400.41340.34040.69940.059*
N10.44182 (12)0.46278 (12)0.3357 (3)0.0567 (11)
C100.40893 (11)0.49949 (11)0.8300 (3)0.0411 (9)
H100.38380.48010.80610.049*
C380.35679 (14)0.31654 (16)0.4891 (4)0.0701 (14)
H380.33130.29830.46500.084*
C600.35217 (12)0.53192 (12)0.3363 (3)0.0501 (10)
H600.33740.52360.39980.060*
C390.36843 (13)0.31391 (14)0.5927 (4)0.0704 (14)
H390.35110.29330.63790.085*
C240.50903 (11)0.35862 (11)0.5887 (3)0.0421 (9)
H240.48270.33790.59150.050*
C140.46665 (15)0.64753 (14)0.5032 (5)0.0735 (15)
H140.47540.67360.48120.088*
C680.32109 (15)0.59001 (14)0.6672 (3)0.0607 (12)
H680.32260.59240.74190.073*
C320.46498 (13)0.41878 (14)0.9697 (3)0.0567 (11)
H320.46140.42051.04330.068*
C300.48218 (13)0.39124 (13)0.8237 (3)0.0570 (12)
H300.49040.37390.79870.068*
C250.53996 (14)0.35029 (13)0.5874 (3)0.0562 (11)
H250.53420.32390.59020.067*
C690.29066 (13)0.55606 (13)0.6193 (3)0.0532 (11)
H690.27170.53550.66170.064*
C310.47658 (13)0.39319 (14)0.9316 (3)0.0608 (12)
H310.48070.37700.97920.073*
C340.46363 (14)0.43976 (13)0.7911 (3)0.0587 (12)
H340.45870.45560.74450.070*
C70.48309 (12)0.55644 (12)0.9024 (3)0.0515 (10)
H70.50820.57560.92690.062*
C260.57884 (13)0.38046 (15)0.5822 (3)0.0613 (12)
H260.59940.37460.58180.074*
C150.44761 (15)0.63415 (13)0.6011 (4)0.0639 (13)
H150.44300.65110.64450.077*
C630.39710 (16)0.55732 (14)0.1507 (4)0.0704 (15)
H630.41250.56610.08840.084*
C10.41704 (15)0.44470 (13)0.2774 (4)0.0501 (13)
C620.39892 (15)0.52932 (13)0.2156 (3)0.0629 (13)
H620.41540.51910.19740.075*
C20.55123 (12)0.47549 (11)0.2650 (3)0.0417 (10)
N20.53486 (12)0.48160 (12)0.3335 (3)0.0502 (10)
C280.55682 (12)0.42797 (12)0.5777 (4)0.0594 (12)
H280.56290.45440.57240.071*
C490.59883 (16)0.67590 (13)0.5037 (3)0.0626 (13)
H490.58380.68460.46640.075*
C640.37262 (14)0.57240 (13)0.1772 (3)0.0537 (12)
H640.37130.59100.13250.064*
C540.59052 (12)0.59435 (11)0.8253 (3)0.0553 (11)
H540.60180.62050.80090.066*
C550.58479 (13)0.58651 (13)0.9335 (3)0.0692 (14)
H550.59190.60740.98190.083*
C730.20311 (13)0.52994 (15)0.2033 (4)0.0685 (13)
H730.18520.53880.18950.082*
C560.56874 (12)0.54826 (14)0.9710 (3)0.0600 (12)
H560.56570.54311.04470.072*
C570.55741 (14)0.51801 (14)0.8996 (4)0.0641 (13)
H570.54580.49190.92460.077*
C740.19151 (16)0.49143 (18)0.1899 (4)0.0869 (18)
H740.16540.47340.16930.104*
C270.58739 (13)0.41903 (16)0.5775 (4)0.0768 (16)
H270.61380.43950.57410.092*
C330.45873 (17)0.44177 (15)0.8990 (4)0.0787 (16)
H330.45090.45940.92490.094*
C760.25688 (15)0.50466 (13)0.2384 (5)0.0909 (19)
H760.27520.49590.24690.109*
C130.47266 (16)0.62224 (15)0.4385 (5)0.0814 (17)
H130.48510.63100.37180.098*
C750.21866 (18)0.47841 (15)0.2070 (6)0.126 (3)
H750.21080.45160.19690.151*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Tb10.02646 (11)0.02665 (13)0.02659 (10)0.01392 (11)0.00029 (10)0.00162 (9)
Tb20.02401 (13)0.02401 (13)0.0276 (2)0.01201 (6)0.0000.000
P30.0224 (5)0.0253 (5)0.0320 (5)0.0101 (4)−0.0032 (4)0.0014 (4)
P10.0245 (5)0.0304 (5)0.0344 (5)0.0153 (4)0.0018 (4)−0.0009 (4)
P40.0316 (5)0.0243 (5)0.0315 (5)0.0124 (4)−0.0007 (4)0.0037 (4)
S30.0716 (8)0.0649 (8)0.0577 (7)0.0359 (7)0.0134 (6)0.0363 (6)
S20.0656 (8)0.0551 (7)0.0596 (8)0.0320 (6)0.0266 (6)−0.0029 (6)
S40.0617 (8)0.0616 (8)0.0860 (9)0.0198 (6)0.0362 (7)−0.0226 (7)
C40.034 (2)0.035 (2)0.031 (2)0.0081 (18)0.0123 (18)0.0039 (17)
C510.055 (3)0.036 (2)0.052 (3)0.007 (2)0.012 (2)0.0042 (19)
O10.0308 (14)0.0394 (16)0.0413 (18)0.0206 (13)−0.0008 (12)−0.0040 (13)
O30.0229 (13)0.0362 (15)0.0427 (17)0.0099 (12)−0.0065 (12)0.0011 (12)
N40.048 (2)0.061 (3)0.038 (2)0.034 (2)0.0204 (18)0.0076 (19)
O40.0411 (16)0.0284 (14)0.0406 (16)0.0183 (12)0.0045 (12)0.0061 (12)
P20.0327 (5)0.0246 (5)0.0356 (6)0.0165 (4)0.0054 (4)0.0063 (4)
O20.0499 (18)0.0292 (15)0.0436 (19)0.0214 (13)0.0081 (14)0.0088 (13)
C650.0273 (18)0.0238 (18)0.050 (2)0.0139 (16)0.0000 (16)0.0050 (16)
S10.1507 (17)0.0882 (12)0.1559 (17)0.0665 (12)−0.1274 (15)−0.0623 (11)
C710.040 (2)0.035 (2)0.0317 (19)0.0114 (17)−0.0074 (16)0.0038 (15)
C220.037 (2)0.044 (2)0.048 (2)0.0186 (19)0.0021 (18)−0.0053 (18)
C170.0295 (19)0.046 (2)0.0294 (18)0.0193 (17)0.0009 (15)0.0046 (16)
C180.038 (2)0.050 (2)0.043 (2)0.0233 (19)−0.0007 (17)−0.0016 (18)
C410.0263 (17)0.0248 (17)0.0325 (18)0.0106 (14)−0.0010 (14)−0.0012 (14)
C470.036 (2)0.0309 (19)0.0297 (18)0.0148 (16)0.0064 (15)0.0048 (14)
C50.0260 (18)0.0338 (19)0.045 (2)0.0218 (16)−0.0007 (16)−0.0080 (16)
C110.0281 (18)0.036 (2)0.042 (2)0.0180 (16)0.0007 (15)0.0035 (16)
C530.0180 (17)0.0313 (19)0.043 (2)0.0099 (15)0.0009 (15)0.0067 (16)
C290.0235 (18)0.0271 (19)0.043 (2)0.0126 (16)0.0039 (15)0.0055 (16)
C360.062 (3)0.048 (3)0.047 (3)0.022 (2)−0.007 (2)0.002 (2)
C350.038 (2)0.0324 (19)0.041 (2)0.0218 (17)0.0045 (16)0.0015 (16)
C230.0342 (19)0.036 (2)0.0346 (19)0.0199 (17)0.0069 (15)0.0036 (15)
C120.069 (3)0.059 (3)0.063 (3)0.045 (3)0.028 (2)0.022 (2)
C420.043 (2)0.055 (3)0.036 (2)0.028 (2)−0.0060 (17)−0.0014 (18)
C430.053 (3)0.067 (3)0.040 (2)0.034 (2)−0.002 (2)−0.009 (2)
C480.057 (3)0.042 (2)0.044 (2)0.028 (2)−0.010 (2)−0.0026 (18)
N30.070 (3)0.047 (2)0.034 (2)0.029 (2)0.0062 (19)0.0161 (17)
C590.046 (2)0.0294 (19)0.0328 (19)0.0219 (17)0.0011 (16)0.0016 (15)
C440.050 (3)0.060 (3)0.060 (3)0.034 (2)0.007 (2)−0.003 (2)
C580.085 (3)0.036 (2)0.042 (2)0.029 (2)0.008 (2)0.0042 (18)
C660.051 (2)0.041 (2)0.042 (2)0.011 (2)−0.0079 (19)−0.0028 (18)
C700.039 (2)0.044 (2)0.036 (2)0.0202 (18)0.0063 (16)0.0088 (16)
C460.043 (2)0.059 (3)0.034 (2)0.032 (2)−0.0090 (17)−0.0064 (18)
C200.029 (2)0.075 (3)0.052 (3)0.012 (2)−0.0016 (19)−0.001 (2)
C160.061 (3)0.045 (2)0.044 (2)0.031 (2)−0.0032 (19)−0.0009 (18)
C500.093 (4)0.032 (2)0.048 (3)0.024 (2)0.011 (2)0.0078 (19)
C60.036 (2)0.043 (2)0.046 (2)0.0121 (18)−0.0032 (17)0.0041 (18)
C190.034 (2)0.078 (3)0.049 (2)0.031 (2)0.0008 (18)0.003 (2)
C520.033 (2)0.031 (2)0.057 (2)0.0065 (17)0.0045 (18)0.0075 (18)
C670.072 (3)0.052 (3)0.057 (3)0.020 (3)−0.019 (3)−0.008 (2)
C210.044 (3)0.055 (3)0.066 (3)0.011 (2)−0.005 (2)−0.015 (2)
C370.071 (4)0.073 (4)0.058 (3)0.036 (3)−0.024 (3)−0.011 (3)
C90.047 (2)0.054 (3)0.038 (2)0.026 (2)0.0035 (18)−0.0012 (18)
C30.038 (2)0.044 (2)0.037 (2)0.020 (2)0.0037 (17)0.0036 (19)
C720.042 (2)0.049 (3)0.067 (3)0.020 (2)0.003 (2)0.005 (2)
C80.054 (3)0.056 (3)0.037 (2)0.036 (2)−0.0105 (19)−0.0101 (19)
C610.095 (4)0.067 (3)0.045 (2)0.061 (3)0.004 (2)0.016 (2)
C450.048 (2)0.076 (3)0.054 (3)0.043 (2)−0.009 (2)−0.005 (2)
C400.044 (2)0.046 (2)0.048 (2)0.015 (2)0.0056 (19)0.0000 (19)
N10.052 (2)0.059 (3)0.049 (2)0.020 (2)−0.021 (2)−0.009 (2)
C100.035 (2)0.048 (2)0.039 (2)0.0201 (19)0.0016 (16)−0.0058 (17)
C380.046 (3)0.088 (4)0.075 (4)0.032 (3)−0.017 (2)−0.032 (3)
C600.072 (3)0.061 (3)0.037 (2)0.047 (2)0.0126 (19)0.0192 (19)
C390.045 (3)0.060 (3)0.075 (3)0.002 (2)0.016 (2)−0.007 (3)
C240.043 (2)0.034 (2)0.056 (2)0.0246 (18)−0.0016 (18)−0.0013 (17)
C140.076 (4)0.050 (3)0.101 (4)0.036 (3)−0.001 (3)0.021 (3)
C680.095 (4)0.077 (3)0.031 (2)0.058 (3)−0.008 (2)−0.003 (2)
C320.062 (3)0.082 (3)0.040 (2)0.047 (3)0.004 (2)−0.004 (2)
C300.092 (3)0.070 (3)0.039 (2)0.063 (3)0.013 (2)0.014 (2)
C250.073 (3)0.056 (3)0.062 (3)0.049 (3)−0.003 (2)−0.006 (2)
C690.058 (3)0.062 (3)0.044 (2)0.034 (2)0.012 (2)0.015 (2)
C310.081 (3)0.084 (3)0.043 (2)0.061 (3)0.015 (2)0.020 (2)
C340.094 (4)0.067 (3)0.049 (3)0.065 (3)−0.005 (2)−0.004 (2)
C70.041 (2)0.050 (3)0.055 (3)0.016 (2)−0.017 (2)−0.006 (2)
C260.054 (3)0.089 (4)0.060 (3)0.050 (3)−0.001 (2)−0.016 (3)
C150.090 (4)0.053 (3)0.065 (3)0.048 (3)−0.020 (3)−0.012 (2)
C630.117 (4)0.076 (3)0.055 (3)0.076 (3)0.040 (3)0.026 (2)
C10.068 (3)0.055 (3)0.047 (3)0.045 (3)−0.023 (2)−0.018 (2)
C620.099 (4)0.072 (3)0.053 (3)0.069 (3)0.015 (2)0.009 (2)
C20.046 (3)0.032 (2)0.049 (3)0.020 (2)0.000 (2)−0.0019 (18)
N20.058 (2)0.065 (3)0.041 (2)0.041 (2)0.0095 (18)−0.0047 (19)
C280.038 (2)0.040 (2)0.094 (3)0.015 (2)0.019 (2)0.000 (2)
C490.101 (4)0.052 (3)0.052 (3)0.051 (3)−0.006 (3)0.010 (2)
C640.089 (3)0.053 (3)0.040 (2)0.052 (3)0.019 (2)0.014 (2)
C540.059 (3)0.033 (2)0.044 (2)0.001 (2)0.002 (2)0.0010 (18)
C550.069 (3)0.055 (3)0.041 (2)−0.001 (2)0.005 (2)−0.007 (2)
C730.039 (3)0.074 (3)0.077 (3)0.017 (2)−0.009 (2)0.007 (3)
C560.046 (3)0.077 (3)0.035 (2)0.014 (2)−0.0027 (19)0.008 (2)
C570.089 (4)0.054 (3)0.054 (3)0.040 (3)0.015 (3)0.020 (2)
C740.057 (3)0.080 (4)0.081 (4)0.003 (3)−0.029 (3)−0.004 (3)
C270.037 (2)0.071 (3)0.117 (5)0.023 (2)0.014 (3)−0.014 (3)
C330.135 (5)0.094 (4)0.057 (3)0.095 (4)0.003 (3)−0.009 (3)
C760.081 (4)0.039 (3)0.143 (5)0.023 (3)−0.056 (4)−0.024 (3)
C130.094 (4)0.074 (4)0.097 (4)0.057 (3)0.048 (3)0.047 (3)
C750.104 (5)0.041 (3)0.205 (8)0.015 (3)−0.093 (5)−0.033 (4)
Geometric parameters (Å, º) top
Tb1—O12.265 (3)C20—C191.379 (6)
Tb1—O22.246 (3)C20—C211.380 (6)
Tb1—O32.243 (3)C16—H160.9300
Tb1—N12.350 (4)C16—C151.369 (5)
Tb1—N22.359 (4)C50—H500.9300
Tb1—N32.356 (4)C50—C491.379 (6)
Tb2—N42.355 (4)C6—H60.9300
Tb2—O42.267 (3)C6—C71.364 (5)
P3—O31.509 (3)C19—H190.9300
P3—C411.797 (3)C52—H520.9300
P3—C471.794 (3)C67—H670.9300
P3—C531.793 (4)C67—C681.349 (6)
P1—O11.508 (3)C21—H210.9300
P1—C171.791 (3)C37—H370.9300
P1—C51.782 (4)C37—C381.362 (7)
P1—C111.801 (4)C9—H90.9300
P4—O41.505 (3)C9—C81.389 (5)
P4—C651.786 (4)C9—C101.369 (5)
P4—C711.778 (4)C72—H720.9300
P4—C591.799 (4)C72—C731.376 (5)
S3—C31.621 (4)C8—H80.9300
S2—C21.619 (4)C8—C71.360 (5)
S4—C41.613 (4)C61—H610.9300
C4—N41.148 (5)C61—C601.370 (5)
C51—H510.9300C61—C621.374 (6)
C51—C501.371 (6)C45—H450.9300
C51—C521.380 (5)C40—H400.9300
P2—O21.504 (3)C40—C391.378 (6)
P2—C291.784 (4)N1—C11.123 (5)
P2—C351.792 (4)C10—H100.9300
P2—C231.784 (3)C38—H380.9300
C65—C661.371 (5)C38—C391.381 (6)
C65—C701.402 (5)C60—H600.9300
S1—C11.602 (5)C39—H390.9300
C71—C721.385 (5)C24—H240.9300
C71—C761.381 (5)C24—C251.386 (5)
C22—H220.9300C14—H140.9300
C22—C171.377 (5)C14—C151.379 (7)
C22—C211.382 (5)C14—C131.372 (7)
C17—C181.401 (5)C68—H680.9300
C18—H180.9300C68—C691.384 (6)
C18—C191.382 (5)C32—H320.9300
C41—C421.381 (5)C32—C311.360 (5)
C41—C461.378 (5)C32—C331.353 (6)
C47—C481.373 (5)C30—H300.9300
C47—C521.401 (5)C30—C311.363 (5)
C5—C61.389 (5)C25—H250.9300
C5—C101.404 (5)C25—C261.368 (6)
C11—C121.374 (5)C69—H690.9300
C11—C161.388 (5)C31—H310.9300
C53—C581.383 (5)C34—H340.9300
C53—C541.378 (5)C34—C331.359 (6)
C29—C301.389 (5)C7—H70.9300
C29—C341.374 (5)C26—H260.9300
C36—H360.9300C26—C271.358 (6)
C36—C351.376 (5)C15—H150.9300
C36—C371.371 (6)C63—H630.9300
C35—C401.391 (5)C63—C621.379 (5)
C23—C241.386 (5)C63—C641.377 (6)
C23—C281.382 (5)C62—H620.9300
C12—H120.9300C2—N21.152 (5)
C12—C131.383 (6)C28—H280.9300
C42—H420.9300C28—C271.388 (6)
C42—C431.393 (5)C49—H490.9300
C43—H430.9300C64—H640.9300
C43—C441.370 (6)C54—H540.9300
C48—H480.9300C54—C551.368 (5)
C48—C491.397 (5)C55—H550.9300
N3—C31.148 (5)C55—C561.368 (6)
C59—C601.390 (5)C73—H730.9300
C59—C641.384 (5)C73—C741.334 (7)
C44—H440.9300C56—H560.9300
C44—C451.368 (6)C56—C571.353 (6)
C58—H580.9300C57—H570.9300
C58—C571.367 (5)C74—H740.9300
C66—H660.9300C74—C751.389 (8)
C66—C671.379 (6)C27—H270.9300
C70—H700.9300C33—H330.9300
C70—C691.377 (5)C76—H760.9300
C46—H460.9300C76—C751.366 (6)
C46—C451.387 (5)C13—H130.9300
C20—H200.9300C75—H750.9300
O1—Tb1—N399.48 (12)C15—C16—H16119.8
O1—Tb1—N184.99 (12)C51—C50—H50119.5
O1—Tb1—N2171.36 (12)C51—C50—C49121.0 (4)
O3—Tb1—O187.18 (10)C49—C50—H50119.5
O3—Tb1—O291.69 (10)C5—C6—H6119.4
O3—Tb1—N384.97 (11)C7—C6—C5121.2 (4)
O3—Tb1—N1167.59 (12)C7—C6—H6119.4
O3—Tb1—N299.90 (11)C18—C19—H19120.0
O2—Tb1—O189.08 (10)C20—C19—C18120.0 (4)
O2—Tb1—N3170.63 (13)C20—C19—H19120.0
O2—Tb1—N197.79 (12)C51—C52—C47120.3 (4)
O2—Tb1—N285.77 (11)C51—C52—H52119.8
N3—Tb1—N286.18 (13)C47—C52—H52119.8
N1—Tb1—N386.84 (14)C66—C67—H67119.4
N1—Tb1—N288.83 (14)C68—C67—C66121.3 (4)
N4i—Tb2—N4ii88.40 (14)C68—C67—H67119.4
N4i—Tb2—N488.41 (14)C22—C21—H21119.9
N4ii—Tb2—N488.41 (14)C20—C21—C22120.1 (4)
O4—Tb2—N4ii97.42 (12)C20—C21—H21119.9
O4i—Tb2—N4ii172.71 (11)C36—C37—H37119.3
O4ii—Tb2—N4172.71 (11)C38—C37—C36121.3 (5)
O4i—Tb2—N497.42 (12)C38—C37—H37119.3
O4—Tb2—N487.38 (11)C8—C9—H9119.8
O4ii—Tb2—N4i97.41 (12)C10—C9—H9119.8
O4i—Tb2—N4i87.38 (11)C10—C9—C8120.3 (4)
O4—Tb2—N4i172.71 (12)N3—C3—S3179.0 (4)
O4ii—Tb2—N4ii87.38 (11)C71—C72—H72119.8
O4ii—Tb2—O4i87.27 (10)C73—C72—C71120.4 (4)
O4ii—Tb2—O487.27 (10)C73—C72—H72119.8
O4i—Tb2—O487.27 (10)C9—C8—H8120.2
O3—P3—C41109.19 (15)C7—C8—C9119.6 (4)
O3—P3—C47110.67 (16)C7—C8—H8120.2
O3—P3—C53111.18 (16)C60—C61—H61119.5
C47—P3—C41108.95 (15)C60—C61—C62120.9 (4)
C53—P3—C41108.10 (16)C62—C61—H61119.5
C53—P3—C47108.68 (16)C44—C45—C46120.6 (4)
O1—P1—C17110.64 (16)C44—C45—H45119.7
O1—P1—C5112.06 (16)C46—C45—H45119.7
O1—P1—C11109.36 (16)C35—C40—H40119.9
C17—P1—C11110.58 (16)C39—C40—C35120.3 (4)
C5—P1—C17108.41 (16)C39—C40—H40119.9
C5—P1—C11105.69 (16)C1—N1—Tb1174.7 (4)
O4—P4—C65110.52 (16)C5—C10—H10119.8
O4—P4—C71111.29 (16)C9—C10—C5120.4 (4)
O4—P4—C59110.95 (16)C9—C10—H10119.8
C65—P4—C59106.78 (16)C37—C38—H38120.3
C71—P4—C65108.68 (17)C37—C38—C39119.3 (4)
C71—P4—C59108.47 (17)C39—C38—H38120.3
N4—C4—S4179.7 (4)C59—C60—H60120.0
C50—C51—H51120.3C61—C60—C59120.0 (4)
C50—C51—C52119.5 (4)C61—C60—H60120.0
C52—C51—H51120.3C40—C39—C38120.0 (4)
P1—O1—Tb1168.67 (18)C40—C39—H39120.0
P3—O3—Tb1164.49 (17)C38—C39—H39120.0
C4—N4—Tb2170.0 (4)C23—C24—H24120.1
P4—O4—Tb2159.75 (17)C25—C24—C23119.8 (4)
O2—P2—C29110.55 (16)C25—C24—H24120.1
O2—P2—C35110.03 (17)C15—C14—H14120.1
O2—P2—C23111.66 (16)C13—C14—H14120.1
C29—P2—C35106.91 (16)C13—C14—C15119.8 (4)
C29—P2—C23106.70 (16)C67—C68—H68120.1
C23—P2—C35110.84 (16)C67—C68—C69119.8 (4)
P2—O2—Tb1168.4 (2)C69—C68—H68120.1
C66—C65—P4119.7 (3)C31—C32—H32120.5
C66—C65—C70118.8 (4)C33—C32—H32120.5
C70—C65—P4121.4 (3)C33—C32—C31119.0 (4)
C72—C71—P4119.6 (3)C29—C30—H30119.2
C76—C71—P4122.0 (3)C31—C30—C29121.6 (4)
C76—C71—C72118.4 (4)C31—C30—H30119.2
C17—C22—H22119.9C24—C25—H25119.6
C17—C22—C21120.2 (4)C26—C25—C24120.7 (4)
C21—C22—H22119.9C26—C25—H25119.6
C22—C17—P1119.3 (3)C70—C69—C68119.8 (4)
C22—C17—C18119.6 (3)C70—C69—H69120.1
C18—C17—P1121.2 (3)C68—C69—H69120.1
C17—C18—H18120.1C32—C31—C30120.0 (4)
C19—C18—C17119.8 (4)C32—C31—H31120.0
C19—C18—H18120.1C30—C31—H31120.0
C42—C41—P3117.5 (3)C29—C34—H34119.6
C46—C41—P3122.6 (3)C33—C34—C29120.8 (4)
C46—C41—C42119.8 (3)C33—C34—H34119.6
C48—C47—P3120.6 (3)C6—C7—H7119.6
C48—C47—C52119.7 (3)C8—C7—C6120.8 (4)
C52—C47—P3119.7 (3)C8—C7—H7119.6
C6—C5—P1119.4 (3)C25—C26—H26120.0
C6—C5—C10117.8 (3)C27—C26—C25119.9 (4)
C10—C5—P1122.9 (3)C27—C26—H26120.0
C12—C11—P1118.4 (3)C16—C15—C14120.2 (4)
C12—C11—C16119.1 (4)C16—C15—H15119.9
C16—C11—P1122.5 (3)C14—C15—H15119.9
C58—C53—P3117.6 (3)C62—C63—H63119.7
C54—C53—P3124.4 (3)C64—C63—H63119.7
C54—C53—C58118.0 (3)C64—C63—C62120.6 (4)
C30—C29—P2123.3 (3)N1—C1—S1178.6 (5)
C34—C29—P2119.7 (3)C61—C62—C63119.2 (4)
C34—C29—C30116.9 (4)C61—C62—H62120.4
C35—C36—H36119.9C63—C62—H62120.4
C37—C36—H36119.9N2—C2—S2179.1 (4)
C37—C36—C35120.1 (4)C2—N2—Tb1168.7 (3)
C36—C35—P2119.2 (3)C23—C28—H28119.7
C36—C35—C40118.9 (4)C23—C28—C27120.5 (4)
C40—C35—P2121.7 (3)C27—C28—H28119.7
C24—C23—P2121.9 (3)C48—C49—H49120.1
C28—C23—P2118.9 (3)C50—C49—C48119.7 (4)
C28—C23—C24118.7 (3)C50—C49—H49120.1
C11—C12—H12119.8C59—C64—H64120.0
C11—C12—C13120.5 (4)C63—C64—C59120.0 (4)
C13—C12—H12119.8C63—C64—H64120.0
C41—C42—H42120.0C53—C54—H54119.7
C41—C42—C43120.0 (3)C55—C54—C53120.7 (4)
C43—C42—H42120.0C55—C54—H54119.7
C42—C43—H43120.1C54—C55—H55119.7
C44—C43—C42119.8 (4)C56—C55—C54120.5 (4)
C44—C43—H43120.1C56—C55—H55119.7
C47—C48—H48120.1C72—C73—H73119.5
C47—C48—C49119.7 (4)C74—C73—C72121.0 (5)
C49—C48—H48120.1C74—C73—H73119.5
C3—N3—Tb1176.9 (3)C55—C56—H56120.4
C60—C59—P4122.0 (3)C57—C56—C55119.2 (4)
C64—C59—P4118.8 (3)C57—C56—H56120.4
C64—C59—C60119.2 (3)C58—C57—H57119.5
C43—C44—H44119.9C56—C57—C58121.0 (4)
C45—C44—C43120.2 (4)C56—C57—H57119.5
C45—C44—H44119.9C73—C74—H74120.2
C53—C58—H58119.8C73—C74—C75119.5 (5)
C57—C58—C53120.5 (4)C75—C74—H74120.2
C57—C58—H58119.8C26—C27—C28120.2 (4)
C65—C66—H66119.9C26—C27—H27119.9
C65—C66—C67120.2 (4)C28—C27—H27119.9
C67—C66—H66119.9C32—C33—C34121.6 (4)
C65—C70—H70119.9C32—C33—H33119.2
C69—C70—C65120.2 (4)C34—C33—H33119.2
C69—C70—H70119.9C71—C76—H76119.9
C41—C46—H46120.2C75—C76—C71120.1 (5)
C41—C46—C45119.7 (3)C75—C76—H76119.9
C45—C46—H46120.2C12—C13—H13120.0
C19—C20—H20119.9C14—C13—C12120.0 (5)
C19—C20—C21120.2 (4)C14—C13—H13120.0
C21—C20—H20119.9C74—C75—H75119.8
C11—C16—H16119.8C76—C75—C74120.5 (5)
C15—C16—C11120.4 (4)C76—C75—H75119.8
Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y, −x+1, z.
Selected bond lengths (Å) top
Tb1—O12.265 (3)Tb1—N22.359 (4)
Tb1—O22.246 (3)Tb1—N32.356 (4)
Tb1—O32.243 (3)Tb2—N42.355 (4)
Tb1—N12.350 (4)Tb2—O42.267 (3)
Acknowledgements top

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

references
References top

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Bowden, A., Singh, K. & Platt, A. (2012). Polyhedron, 42, 30–35.

Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244–247.

Cousins, D. R. & Hart, F. A. (1967). J. Inorg. Nucl. Chem. 29, 1745–1757.

Cousins, D. R. & Hart, F. A. (1968). J. Inorg. Nucl. Chem. 30, 3009–3015.

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.

Feazell, R. P., Gary, J. B., Kautz, J. A., Klausmeyer, K. K., Wong, C. W. & Zancanella, M. (2004). Acta Cryst. E60, m532–m534.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.