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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): m193–m194.
Published online 2010 January 23. doi:  10.1107/S1600536810002448
PMCID: PMC2979733

Tetra­kis-μ-l-alanine-κ8 O:O′-bis­[tetra­aqua­terbium(III)] hexa­perchlorate

Abstract

The asymmetric unit of the title compound, [Tb2(C3H7NO2)4(H2O)8](ClO4)6, contains a dinuclear cation and six perchlorate anions, one of which is disordered. In the cation, the four l-alanine mol­ecules are present in their zwitterionic form and bridge two Tb3+ ions through their carboxyl­ate O atoms. Each Tb atom is also coordinated by four water mol­ecules in a square-anti­prismatic geometry. In the crystal structure, the cations and anions are held together via inter­molecular O—H(...)O and N—H(...)O hydrogen bonds.

Related literature

For applications of terbium complexes, see: Ropp (2004 [triangle]). For complexes of rare-earth ions, see: Ngoan et al. (1988 [triangle]); Glowiak et al. (1991 [triangle], 1996 [triangle]); Hu et al. (1995 [triangle]); Tianzhu et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m193-scheme1.jpg

Experimental

Crystal data

  • [Tb2(C3H7NO2)4(H2O)8](ClO4)6
  • M r = 1415.05
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m193-efi1.jpg
  • a = 10.7703 (3) Å
  • b = 10.7766 (2) Å
  • c = 11.3521 (3) Å
  • α = 79.345 (2)°
  • β = 65.390 (3)°
  • γ = 67.658 (2)°
  • V = 1107.44 (5) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 3.65 mm−1
  • T = 100 K
  • 0.40 × 0.40 × 0.40 mm

Data collection

  • Oxford Diffraction Excalibur2 CCD diffractometer
  • Absorption correction: multi-scan (Blessing, 1995 [triangle], 1997 [triangle]) T min = 0.637, T max = 0.780
  • 11115 measured reflections
  • 8505 independent reflections
  • 8128 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.107
  • S = 1.09
  • 8505 reflections
  • 639 parameters
  • 47 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 1.42 e Å−3
  • Δρmin = −2.57 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 770 Friedel pairs
  • Flack parameter: 0.006 (9)

Data collection: CrysAlis CCD (Oxford Diffraction, 2003 [triangle]); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2003 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810002448/cv2689sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002448/cv2689Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Dr Kirsty Stewart, UKZN, for the data collection.

supplementary crystallographic information

Comment

Structural determinations of complexes of rare-earth metals with amino acids are of interest to understand the coordination chemistry of these important class of compounds and to utilize in different optical devices (Ropp, 2004).

In this regard, different complexes, with DL-alanine as the amino acid, containing chloride ions as the counter-ion with the rare-earth metal ion being holmium (Ngoan et al., 1988) and dysprosium (Glowiak et al., 1991) have been synthesized and characterized structurally. The commonly observed inorganic counterions are either perchlorate or chloride anions. It has been observed that depending on the counterion present, the crystal structure contains motifs forming either dimers, chains or network structure in the crystal lattice (Hu et al., 1995, and references therein). Keeping in mind the structural diversity associated with these complexes, we report here the structure of a terbium complex with L-alanine, (I), as extension of the already determined crystal structures.

The title compound (I) crystallizes in the triclinic non-centrosymmetric space group P1. Analogous complexes of neodymium (existing as dimorphs; Glowiak et al., 1996), yttrium (Tianzhu et al., 1987),and erbium (Hu et al., 1995) have also been characterized structurally. The present complex is isostructural with the triclinic form of the neodynium complex which also crystallizes in the triclinic space group P1. The dimeric structure of the complex is depicted in Fig.1. The terbium atom exists in a distorted square-antiprism geometry, having a coordination number of eight. The complex contains two eight-membered rings in the dinuclear cluster, the dihedral angles between these being 88.1 (1)°.

The crystal structure is composed of discrete dinuclear clusters of terbium metal atoms bridged by the carboxyl group of the L-alanine ligand. The ligand exists in the zwitterionic form. The Tb–O(carboxyl) distances lie in the range of 2.274 (6)-2.376 (6)Å while those of Tb–O(water) between 2.358 (8)Å and 2.539 (6)Å. The Tb—Tb distance is 4.367 (3)Å. The dinuclear cations are separated by perchlorate ions, which form hydrogen bonds between coordinated water molecules and the amino groups (Table 1).

Experimental

An aqueous solution of terbium perchlorate was prepared by digesting (0.15 gm) terbium oxide in concentrated perchloric acid (2 ml), a suitable concentration of terbium perchlorate (0.33 g, 2 mmol) was achieved by diluting the concentrated solution with 4 ml distilled water. L-alanine (0.10 g, 1 mmol) was added as solid to the above aqueous solution of terbium perchlorate. The mixture was stirred at about 80C on a heating plate while an aqueous solution of NaOH (0.5M) was added dropwise to cause an incipient but permanent precipitate, pH=4. The mixture was then filtered, and the filtrate was then reduced to about 4 ml. The hot solution was tightly covered and allowed to evaporate gradually at room temperature. The crystalline precipitate appeared in about 7 days. The solid was collected by filtration, washed with cold diethyl ether/THF 1:1 v/v, and dried under vacuum in a desiccator charged with silica gel. The melting point is 241C. The presence of terbium metal was detected by xylenol orange indicator.

Refinement

All the amino, methine and methyl hydrogen atoms were positioned geometrically and refined using a riding model with d(N—H) = 0.91Å, Uiso(H) = 1.2Ueq (N) and d(C—H) = 0.96Å and 0.98Å, Uiso(H)=1.5Ueq(C).

All the hydrogen atoms of the water molecule coordinated to the metal ion, were refined using geometrical bond restraints, the d(O—H) = 0.85 (5)Å and d(H···H) = 1.37 (2) Å, respectively.

The number of perchlorate ions present in the asymmetric unit is six, out of which one is disordered, the occupancies of the disoredred oxygen atom refined to 0.71 (10) and 0.29 (10), respectively. The Cl—O bond distances lie in the range of acceptable bond lengths, between 1.392 (10)-1.52 (5)Å.

Figures

Fig. 1.
View of the cation in (I) showing the atomic numbering and 50% probability displacement ellipsoids. H atoms have been omitted for clarity.

Crystal data

[Tb2(C3H7NO2)4(H2O)8](ClO4)6Z = 1
Mr = 1415.05F(000) = 696
Triclinic, P1Dx = 2.122 Mg m3
Hall symbol: P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.7703 (3) ÅCell parameters from 665 reflections
b = 10.7766 (2) Åθ = 1.7–25.9°
c = 11.3521 (3) ŵ = 3.65 mm1
α = 79.345 (2)°T = 100 K
β = 65.390 (3)°Block, colourless
γ = 67.658 (2)°0.40 × 0.40 × 0.40 mm
V = 1107.44 (5) Å3

Data collection

Oxford Diffraction Excalibur2 CCD diffractometer8505 independent reflections
Radiation source: fine-focus sealed tube8128 reflections with I > 2σ(I)
graphiteRint = 0.027
ω and 2θ scansθmax = 32.1°, θmin = 2.8°
Absorption correction: multi-scan (Blessing, 1995, 1997)h = −15→15
Tmin = 0.637, Tmax = 0.780k = −11→15
11115 measured reflectionsl = −16→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107w = 1/[σ2(Fo2) + (0.0814P)2 + 0.8066P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
8505 reflectionsΔρmax = 1.42 e Å3
639 parametersΔρmin = −2.57 e Å3
47 restraintsAbsolute structure: Flack (1983), 770 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.006 (9)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/UeqOcc. (<1)
C10.4190 (9)0.6940 (9)0.1555 (8)0.0145 (14)
C20.5789 (9)0.3191 (9)−0.1630 (7)0.0140 (14)
C30.4097 (9)0.6629 (9)−0.1672 (8)0.0150 (14)
C40.6005 (9)0.3273 (9)0.1564 (8)0.0168 (15)
C50.6141 (7)0.2316 (8)−0.2732 (7)0.0170 (12)
H50.59230.2941−0.34450.020*
C60.6109 (8)0.2245 (8)0.2672 (7)0.0193 (14)
H60.58860.14720.25430.023*
C70.3826 (7)0.7421 (8)−0.2844 (6)0.0158 (12)
H70.40930.6759−0.34950.019*
C80.3880 (7)0.8167 (8)0.2267 (7)0.0158 (11)
H80.40130.89180.16160.019*
N10.7733 (8)0.1558 (9)−0.3250 (8)0.0223 (16)
H110.82290.2139−0.34590.033*
H120.79760.1121−0.39700.033*
H130.79660.0950−0.26370.033*
N20.7634 (9)0.1745 (9)0.2602 (8)0.0240 (15)
H210.82520.14030.18080.036*
H220.77300.10930.32250.036*
H230.78500.24360.27300.036*
C90.4869 (8)0.7915 (9)0.2993 (7)0.0246 (14)
H9A0.46920.72340.36840.037*
H9C0.46660.87510.33720.037*
H9B0.58840.75990.23900.037*
C100.4726 (9)0.8325 (9)−0.3490 (8)0.0291 (16)
H10A0.44060.9054−0.29130.044*
H10B0.46020.8704−0.43040.044*
H10C0.57510.7803−0.36710.044*
N30.2240 (8)0.8194 (9)−0.2458 (8)0.0215 (14)
H310.17270.7626−0.20740.032*
H320.20550.8596−0.31750.032*
H330.19730.8832−0.18910.032*
N40.2318 (8)0.8572 (8)0.3187 (7)0.0176 (13)
H410.17400.87180.27400.026*
H420.20820.93370.35820.026*
H430.21850.79050.37970.026*
C110.5048 (9)0.2818 (10)0.3982 (7)0.0303 (17)
H11A0.40540.30850.40230.045*
H11B0.52220.36040.41070.045*
H11C0.51790.21370.46630.045*
C120.5248 (8)0.1422 (8)−0.2365 (8)0.0259 (14)
H12A0.42200.1973−0.21190.039*
H12B0.53900.0829−0.16310.039*
H12C0.55510.0880−0.31050.039*
O10.7135 (7)0.3573 (7)0.0837 (6)0.0216 (12)
Cl2S0.8570 (2)0.8811 (2)0.4648 (2)0.0180 (4)
O20.5450 (7)0.6491 (7)0.0736 (6)0.0228 (13)
O2S0.7578 (8)0.9092 (8)0.4010 (7)0.0311 (14)
Cl5S0.1466 (2)0.0542 (2)0.0312 (2)0.0203 (4)
O5S0.1243 (8)0.0075 (8)0.5644 (8)0.0317 (15)
O60.5399 (6)0.6135 (7)−0.1774 (6)0.0229 (12)
O6S0.0345 (10)0.2428 (10)0.5709 (11)0.045 (3)
O70.6865 (6)0.3358 (7)−0.1563 (6)0.0198 (11)
O30.9611 (7)0.3441 (8)−0.1569 (6)0.0239 (14)
H3A0.992 (7)0.293 (7)−0.101 (4)0.029*
H3B1.002 (7)0.310 (8)−0.231 (4)0.029*
O40.8468 (7)0.5258 (8)−0.3247 (6)0.0254 (14)
H4A0.940 (2)0.494 (10)−0.364 (4)0.030*
H4B0.808 (4)0.550 (11)−0.381 (3)0.030*
O50.7415 (7)0.7271 (7)−0.1561 (6)0.0208 (12)
H5A0.780 (10)0.754 (5)−0.235 (2)0.025*
H5B0.712 (10)0.790 (4)−0.106 (4)0.025*
O80.8528 (7)0.5495 (7)0.0278 (6)0.0198 (12)
H8A0.853 (10)0.629 (4)0.016 (7)0.024*
H8B0.817 (9)0.529 (8)0.108 (3)0.024*
O130.1579 (7)0.4609 (8)−0.0296 (6)0.0237 (14)
H13A0.065 (2)0.488 (10)−0.007 (5)0.028*
H13B0.196 (5)0.446 (11)−0.110 (3)0.028*
O140.2390 (11)0.2843 (8)0.1615 (8)0.0385 (19)
H14A0.277 (12)0.234 (6)0.214 (9)0.046*
H14B0.243 (13)0.241 (6)0.104 (6)0.046*
O150.0449 (6)0.6566 (7)0.1651 (6)0.0201 (12)
H15A0.028 (5)0.740 (2)0.152 (9)0.024*
H15B−0.034 (3)0.641 (4)0.196 (9)0.024*
O160.1667 (7)0.4676 (8)0.3269 (6)0.0219 (13)
H16A0.085 (6)0.456 (11)0.359 (5)0.026*
H16B0.181 (8)0.506 (9)0.375 (4)0.026*
O90.3161 (6)0.6520 (7)0.1832 (6)0.0193 (12)
O20S0.1478 (6)0.4809 (7)−0.4224 (6)0.0237 (12)
O100.4811 (7)0.3768 (7)0.1443 (6)0.0263 (13)
Cl3S0.7685 (2)0.4507 (2)0.41047 (19)0.0217 (4)
O110.3020 (7)0.6551 (7)−0.0709 (6)0.0230 (13)
O120.4490 (7)0.3679 (7)−0.0932 (6)0.0214 (12)
O9S0.8749 (14)0.5005 (13)0.4016 (16)0.090 (5)
Cl6S0.8241 (2)0.9367 (2)−0.0224 (2)0.0245 (4)
O13S0.6832 (9)0.9455 (9)−0.0124 (10)0.048 (2)
O14S0.9066 (9)0.7981 (7)−0.0050 (9)0.0415 (17)
O17S0.0746 (7)0.6455 (8)−0.2755 (7)0.0395 (16)
O18S0.2996 (7)0.4729 (8)−0.3200 (6)0.0281 (13)
O15S0.8045 (12)1.0152 (12)0.0727 (13)0.064 (4)
O23S0.0356 (7)0.1853 (7)0.0532 (7)0.0356 (14)
O24S0.0912 (7)−0.0414 (7)0.1209 (6)0.0329 (13)
O25S0.2664 (8)0.0614 (8)0.0544 (9)0.0421 (18)
O12S0.8133 (8)0.3067 (7)0.4314 (7)0.0385 (15)
O10S0.7326 (11)0.4879 (9)0.2992 (7)0.045 (2)
Cl1S0.1624 (2)0.1275 (2)0.5306 (2)0.0220 (4)
O7SA0.255 (5)0.1305 (19)0.3977 (15)0.057 (11)0.71 (10)
O7SB0.181 (10)0.130 (3)0.390 (3)0.037 (17)0.29 (10)
O16S0.9019 (9)0.9741 (11)−0.1509 (8)0.066 (3)
O19S0.2652 (8)0.6408 (9)−0.4749 (7)0.0414 (16)
O8S0.2530 (13)0.1202 (11)0.5942 (15)0.072 (4)
O22S0.1939 (15)0.0213 (13)−0.0991 (10)0.060 (3)
O26S0.6419 (13)0.5062 (8)0.5196 (8)0.078 (4)
Tb10.28195 (2)0.48987 (2)0.094542 (19)0.01289 (8)
Tb20.719556 (19)0.510671 (19)−0.093565 (17)0.01263 (8)
Cl4S0.1964 (2)0.5602 (2)−0.37293 (18)0.0218 (4)
O1S0.9780 (8)0.7615 (8)0.4134 (7)0.0265 (15)
O3S0.7844 (8)0.8652 (9)0.6027 (7)0.0308 (16)
O4S0.9085 (7)0.9956 (7)0.4380 (6)0.0219 (12)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.018 (3)0.011 (3)0.017 (3)−0.005 (3)−0.008 (3)−0.002 (3)
C20.019 (3)0.019 (4)0.005 (3)−0.008 (3)−0.004 (2)0.001 (3)
C30.020 (3)0.015 (3)0.015 (3)−0.005 (3)−0.012 (3)−0.002 (3)
C40.019 (3)0.017 (3)0.013 (3)−0.001 (3)−0.007 (2)−0.006 (3)
C50.015 (3)0.022 (3)0.012 (3)−0.005 (2)−0.003 (2)−0.005 (2)
C60.019 (3)0.020 (3)0.018 (3)−0.006 (3)−0.009 (2)0.005 (3)
C70.013 (3)0.021 (3)0.013 (3)−0.006 (2)−0.005 (2)0.004 (2)
C80.012 (3)0.021 (3)0.013 (3)−0.007 (2)−0.001 (2)−0.003 (2)
N10.018 (3)0.029 (4)0.020 (3)−0.005 (3)−0.006 (3)−0.011 (3)
N20.026 (4)0.025 (4)0.016 (3)−0.002 (3)−0.011 (3)0.001 (3)
C90.022 (3)0.035 (4)0.021 (3)−0.010 (3)−0.010 (2)−0.007 (3)
C100.030 (4)0.029 (4)0.026 (3)−0.013 (3)−0.011 (3)0.012 (3)
N30.014 (3)0.024 (3)0.027 (3)−0.001 (3)−0.012 (2)−0.003 (3)
N40.015 (3)0.018 (3)0.018 (3)−0.002 (3)−0.005 (2)−0.002 (3)
C110.022 (3)0.046 (5)0.016 (3)−0.012 (3)−0.002 (3)0.000 (3)
C120.023 (3)0.026 (3)0.028 (3)−0.011 (3)−0.005 (3)−0.005 (3)
O10.024 (3)0.021 (3)0.020 (3)−0.008 (2)−0.009 (2)0.001 (2)
Cl2S0.0172 (8)0.0215 (9)0.0129 (7)−0.0069 (7)−0.0037 (6)0.0006 (7)
O20.017 (3)0.024 (3)0.019 (3)−0.005 (2)−0.0014 (19)0.000 (2)
O2S0.033 (3)0.037 (3)0.036 (3)−0.019 (3)−0.023 (3)0.010 (3)
Cl5S0.0198 (8)0.0230 (8)0.0198 (7)−0.0055 (6)−0.0099 (6)−0.0024 (6)
O5S0.041 (4)0.026 (3)0.037 (3)−0.016 (3)−0.020 (3)−0.001 (3)
O60.021 (3)0.025 (3)0.029 (3)−0.008 (2)−0.018 (2)0.003 (2)
O6S0.026 (4)0.029 (4)0.078 (7)−0.001 (3)−0.019 (4)−0.017 (4)
O70.019 (2)0.024 (3)0.019 (2)−0.005 (2)−0.0081 (19)−0.006 (2)
O30.016 (3)0.029 (4)0.017 (3)0.000 (3)−0.003 (2)−0.004 (3)
O40.020 (3)0.036 (4)0.011 (2)−0.006 (3)0.001 (2)−0.006 (2)
O50.028 (3)0.026 (3)0.012 (2)−0.015 (2)−0.007 (2)0.004 (2)
O80.019 (3)0.024 (3)0.020 (3)−0.006 (2)−0.011 (2)−0.003 (2)
O130.017 (3)0.041 (4)0.015 (3)−0.010 (3)−0.006 (2)−0.004 (3)
O140.070 (6)0.028 (4)0.030 (4)−0.028 (4)−0.022 (4)0.004 (3)
O150.014 (3)0.021 (3)0.023 (3)−0.003 (2)−0.008 (2)0.000 (2)
O160.026 (3)0.025 (3)0.015 (3)−0.008 (3)−0.010 (2)0.001 (2)
O90.013 (2)0.027 (3)0.021 (3)−0.008 (2)−0.0069 (19)−0.006 (2)
O20S0.023 (3)0.034 (3)0.020 (2)−0.010 (2)−0.0084 (19)−0.011 (2)
O100.021 (3)0.031 (3)0.028 (3)−0.001 (2)−0.016 (2)−0.003 (2)
Cl3S0.0247 (9)0.0269 (9)0.0205 (9)−0.0134 (7)−0.0129 (7)0.0034 (7)
O110.023 (3)0.024 (3)0.013 (2)−0.003 (2)−0.004 (2)0.003 (2)
O120.017 (2)0.028 (3)0.020 (3)−0.007 (2)−0.006 (2)−0.007 (2)
O9S0.085 (8)0.076 (8)0.163 (13)−0.062 (7)−0.094 (9)0.064 (9)
Cl6S0.0279 (10)0.0223 (9)0.0229 (8)−0.0021 (7)−0.0127 (7)−0.0064 (7)
O13S0.045 (5)0.039 (4)0.071 (6)−0.004 (4)−0.035 (4)−0.014 (4)
O14S0.054 (5)0.024 (3)0.063 (5)−0.011 (3)−0.043 (4)0.007 (3)
O17S0.019 (3)0.047 (4)0.050 (4)−0.005 (3)−0.007 (2)−0.026 (3)
O18S0.030 (3)0.040 (4)0.020 (3)−0.012 (3)−0.015 (2)0.000 (2)
O15S0.054 (6)0.067 (7)0.088 (9)0.000 (5)−0.039 (6)−0.054 (7)
O23S0.030 (3)0.028 (3)0.034 (3)0.004 (3)−0.011 (3)−0.004 (3)
O24S0.036 (3)0.033 (3)0.034 (3)−0.017 (3)−0.017 (3)0.009 (3)
O25S0.029 (4)0.035 (4)0.068 (5)−0.004 (3)−0.027 (4)−0.010 (4)
O12S0.041 (4)0.028 (3)0.036 (3)−0.005 (3)−0.014 (3)0.005 (3)
O10S0.079 (6)0.040 (4)0.024 (3)−0.023 (4)−0.026 (4)0.002 (3)
Cl1S0.0220 (9)0.0201 (9)0.0185 (8)−0.0027 (7)−0.0064 (7)−0.0012 (7)
O7SA0.08 (2)0.034 (6)0.014 (5)−0.010 (8)0.006 (7)0.007 (4)
O7SB0.07 (3)0.014 (10)0.009 (9)−0.015 (14)0.005 (12)0.003 (7)
O16S0.042 (4)0.068 (6)0.041 (4)0.009 (4)−0.005 (3)0.020 (4)
O19S0.039 (4)0.053 (4)0.035 (3)−0.029 (3)−0.014 (3)0.023 (3)
O8S0.074 (7)0.051 (6)0.136 (10)−0.032 (5)−0.084 (8)0.023 (6)
O22S0.105 (9)0.054 (6)0.023 (3)−0.035 (6)−0.018 (4)−0.007 (3)
O26S0.105 (8)0.028 (4)0.042 (4)−0.009 (5)0.021 (5)−0.011 (3)
Tb10.01223 (14)0.01682 (17)0.01058 (14)−0.00513 (12)−0.00486 (11)−0.00088 (12)
Tb20.01099 (14)0.01639 (16)0.01099 (14)−0.00412 (12)−0.00485 (11)−0.00105 (11)
Cl4S0.0213 (8)0.0299 (9)0.0168 (8)−0.0127 (7)−0.0065 (6)0.0006 (7)
O1S0.023 (3)0.025 (4)0.027 (3)−0.005 (3)−0.004 (2)−0.011 (3)
O3S0.029 (4)0.033 (4)0.019 (3)−0.009 (3)−0.001 (3)0.002 (3)
O4S0.028 (3)0.022 (3)0.020 (2)−0.012 (2)−0.009 (2)−0.001 (2)

Geometric parameters (Å, °)

C1—O21.247 (10)O2—Tb22.304 (7)
C1—O91.254 (10)Cl5S—O22S1.415 (10)
C1—C81.533 (11)Cl5S—O24S1.424 (6)
C2—O121.238 (10)Cl5S—O23S1.444 (7)
C2—O71.272 (10)Cl5S—O25S1.451 (7)
C2—C51.539 (10)O5S—Cl1S1.442 (8)
C3—O111.238 (10)O6—Tb22.322 (6)
C3—O61.258 (10)O6S—Cl1S1.426 (9)
C3—C71.516 (10)O7—Tb22.324 (6)
C4—O101.247 (10)O3—Tb22.424 (7)
C4—O11.278 (11)O3—H3A0.85 (6)
C4—C61.525 (12)O3—H3B0.85 (5)
C5—N11.492 (10)O4—Tb22.410 (6)
C5—C121.500 (11)O4—H4A0.86 (6)
C5—H51.0000O4—H4B0.85 (6)
C6—N21.493 (11)O5—Tb22.380 (7)
C6—C111.512 (11)O5—H5A0.86 (2)
C6—H61.0000O5—H5B0.84 (5)
C7—N31.495 (10)O8—Tb22.539 (6)
C7—C101.513 (11)O8—H8A0.84 (6)
C7—H71.0000O8—H8B0.85 (2)
C8—N41.504 (9)O13—Tb12.432 (6)
C8—C91.521 (10)O13—H13A0.86 (6)
C8—H81.0000O13—H13B0.85 (2)
N1—H110.9100O14—Tb12.358 (8)
N1—H120.9100O14—H14A0.86 (11)
N1—H130.9100O14—H14B0.84 (6)
N2—H210.9100O15—Tb12.394 (6)
N2—H220.9100O15—H15A0.85 (2)
N2—H230.9100O15—H15B0.84 (6)
C9—H9A0.9800O16—Tb12.413 (6)
C9—H9C0.9800O16—H16A0.85 (8)
C9—H9B0.9800O16—H16B0.83 (8)
C10—H10A0.9800O9—Tb12.376 (6)
C10—H10B0.9800O20S—Cl4S1.442 (6)
C10—H10C0.9800O10—Tb12.274 (6)
N3—H310.9100Cl3S—O9S1.402 (9)
N3—H320.9100Cl3S—O26S1.414 (8)
N3—H330.9100Cl3S—O10S1.417 (8)
N4—H410.9100Cl3S—O12S1.444 (7)
N4—H420.9100O11—Tb12.337 (7)
N4—H430.9100O12—Tb12.356 (7)
C11—H11A0.9800Cl6S—O15S1.392 (10)
C11—H11B0.9800Cl6S—O16S1.419 (8)
C11—H11C0.9800Cl6S—O13S1.441 (8)
C12—H12A0.9800Cl6S—O14S1.445 (7)
C12—H12B0.9800O17S—Cl4S1.429 (7)
C12—H12C0.9800O18S—Cl4S1.426 (7)
O1—Tb22.352 (7)Cl1S—O8S1.410 (9)
Cl2S—O1S1.438 (8)Cl1S—O7SA1.422 (17)
Cl2S—O3S1.441 (7)Cl1S—O7SB1.52 (5)
Cl2S—O2S1.441 (7)O19S—Cl4S1.430 (6)
Cl2S—O4S1.470 (7)
O2—C1—O9127.5 (8)Tb2—O5—H5A125 (3)
O2—C1—C8115.2 (7)Tb2—O5—H5B126 (3)
O9—C1—C8117.3 (7)H5A—O5—H5B109 (5)
O12—C2—O7127.5 (7)Tb2—O8—H8A111 (4)
O12—C2—C5116.4 (7)Tb2—O8—H8B111 (4)
O7—C2—C5116.1 (7)H8A—O8—H8B112 (5)
O11—C3—O6126.7 (8)Tb1—O13—H13A125 (3)
O11—C3—C7117.0 (7)Tb1—O13—H13B125 (3)
O6—C3—C7116.3 (7)H13A—O13—H13B107 (5)
O10—C4—O1124.7 (9)Tb1—O14—H14A117 (5)
O10—C4—C6117.3 (8)Tb1—O14—H14B117 (5)
O1—C4—C6118.0 (7)H14A—O14—H14B114 (5)
N1—C5—C12112.6 (7)Tb1—O15—H15A125 (3)
N1—C5—C2108.5 (6)Tb1—O15—H15B125 (3)
C12—C5—C2114.1 (6)H15A—O15—H15B110 (5)
N1—C5—H5107.0Tb1—O16—H16A119 (3)
C12—C5—H5107.0Tb1—O16—H16B120 (4)
C2—C5—H5107.0H16A—O16—H16B115 (5)
N2—C6—C11111.0 (7)C1—O9—Tb1134.3 (5)
N2—C6—C4108.3 (6)C4—O10—Tb1170.1 (7)
C11—C6—C4112.3 (7)O9S—Cl3S—O26S108.3 (9)
N2—C6—H6108.4O9S—Cl3S—O10S111.4 (7)
C11—C6—H6108.4O26S—Cl3S—O10S108.1 (7)
C4—C6—H6108.4O9S—Cl3S—O12S111.3 (6)
N3—C7—C10111.4 (7)O26S—Cl3S—O12S106.9 (5)
N3—C7—C3109.0 (6)O10S—Cl3S—O12S110.6 (5)
C10—C7—C3113.9 (6)C3—O11—Tb1129.8 (6)
N3—C7—H7107.4C2—O12—Tb1145.5 (5)
C10—C7—H7107.4O15S—Cl6S—O16S114.4 (8)
C3—C7—H7107.4O15S—Cl6S—O13S108.3 (6)
N4—C8—C9110.5 (6)O16S—Cl6S—O13S108.8 (6)
N4—C8—C1107.4 (6)O15S—Cl6S—O14S110.9 (6)
C9—C8—C1113.4 (6)O16S—Cl6S—O14S105.2 (5)
N4—C8—H8108.5O13S—Cl6S—O14S109.2 (5)
C9—C8—H8108.5O8S—Cl1S—O7SA102 (3)
C1—C8—H8108.5O8S—Cl1S—O6S109.7 (7)
C5—N1—H11109.5O7SA—Cl1S—O6S115.0 (12)
C5—N1—H12109.5O8S—Cl1S—O5S108.2 (6)
H11—N1—H12109.5O7SA—Cl1S—O5S111.3 (16)
C5—N1—H13109.5O6S—Cl1S—O5S110.0 (5)
H11—N1—H13109.5O8S—Cl1S—O7SB135 (4)
H12—N1—H13109.5O6S—Cl1S—O7SB98 (3)
C6—N2—H21109.5O5S—Cl1S—O7SB94 (2)
C6—N2—H22109.5O10—Tb1—O11117.3 (2)
H21—N2—H22109.5O10—Tb1—O1276.9 (2)
C6—N2—H23109.5O11—Tb1—O1276.2 (2)
H21—N2—H23109.5O10—Tb1—O1482.4 (3)
H22—N2—H23109.5O11—Tb1—O14145.0 (3)
C8—C9—H9A109.5O12—Tb1—O1481.3 (3)
C8—C9—H9C109.5O10—Tb1—O974.7 (2)
H9A—C9—H9C109.5O11—Tb1—O977.3 (2)
C8—C9—H9B109.5O12—Tb1—O9125.8 (2)
H9A—C9—H9B109.5O14—Tb1—O9137.5 (2)
H9C—C9—H9B109.5O10—Tb1—O15144.7 (2)
C7—C10—H10A109.5O11—Tb1—O1576.9 (2)
C7—C10—H10B109.5O12—Tb1—O15138.1 (2)
H10A—C10—H10B109.5O14—Tb1—O15104.3 (3)
C7—C10—H10C109.5O9—Tb1—O1577.7 (2)
H10A—C10—H10C109.5O10—Tb1—O1680.1 (2)
H10B—C10—H10C109.5O11—Tb1—O16140.5 (2)
C7—N3—H31109.5O12—Tb1—O16143.2 (2)
C7—N3—H32109.5O14—Tb1—O1667.4 (3)
H31—N3—H32109.5O9—Tb1—O1673.7 (2)
C7—N3—H33109.5O15—Tb1—O1671.2 (2)
H31—N3—H33109.5O10—Tb1—O13139.5 (2)
H32—N3—H33109.5O11—Tb1—O1375.4 (2)
C8—N4—H41109.5O12—Tb1—O1368.9 (2)
C8—N4—H42109.5O14—Tb1—O1371.7 (3)
H41—N4—H42109.5O9—Tb1—O13144.0 (2)
C8—N4—H43109.5O15—Tb1—O1373.6 (2)
H41—N4—H43109.5O16—Tb1—O13115.7 (2)
H42—N4—H43109.5O2—Tb2—O679.9 (2)
C6—C11—H11A109.5O2—Tb2—O7123.2 (2)
C6—C11—H11B109.5O6—Tb2—O774.8 (2)
H11A—C11—H11B109.5O2—Tb2—O179.7 (2)
C6—C11—H11C109.5O6—Tb2—O1127.5 (2)
H11A—C11—H11C109.5O7—Tb2—O177.2 (2)
H11B—C11—H11C109.5O2—Tb2—O573.9 (2)
C5—C12—H12A109.5O6—Tb2—O578.4 (2)
C5—C12—H12B109.5O7—Tb2—O5144.1 (2)
H12A—C12—H12B109.5O1—Tb2—O5138.7 (2)
C5—C12—H12C109.5O2—Tb2—O4138.9 (3)
H12A—C12—H12C109.5O6—Tb2—O474.6 (2)
H12B—C12—H12C109.5O7—Tb2—O480.3 (2)
C4—O1—Tb2122.9 (6)O1—Tb2—O4141.3 (3)
O1S—Cl2S—O3S110.6 (5)O5—Tb2—O469.8 (2)
O1S—Cl2S—O2S109.2 (5)O2—Tb2—O3141.8 (2)
O3S—Cl2S—O2S110.3 (4)O6—Tb2—O3138.3 (2)
O1S—Cl2S—O4S109.7 (4)O7—Tb2—O378.0 (2)
O3S—Cl2S—O4S109.2 (5)O1—Tb2—O374.6 (2)
O2S—Cl2S—O4S107.9 (4)O5—Tb2—O3108.5 (2)
C1—O2—Tb2152.4 (6)O4—Tb2—O370.2 (2)
O22S—Cl5S—O24S112.3 (6)O2—Tb2—O873.8 (2)
O22S—Cl5S—O23S108.8 (6)O6—Tb2—O8144.5 (2)
O24S—Cl5S—O23S109.6 (4)O7—Tb2—O8140.1 (2)
O22S—Cl5S—O25S109.8 (7)O1—Tb2—O870.7 (2)
O24S—Cl5S—O25S108.6 (5)O5—Tb2—O871.7 (2)
O23S—Cl5S—O25S107.6 (5)O4—Tb2—O8111.2 (2)
C3—O6—Tb2153.0 (6)O3—Tb2—O871.3 (2)
C2—O7—Tb2134.3 (6)O18S—Cl4S—O17S110.3 (4)
Tb2—O3—H3A121 (3)O18S—Cl4S—O19S108.3 (4)
Tb2—O3—H3B120 (3)O17S—Cl4S—O19S109.3 (5)
H3A—O3—H3B113 (5)O18S—Cl4S—O20S109.2 (4)
Tb2—O4—H4A124 (3)O17S—Cl4S—O20S109.3 (4)
Tb2—O4—H4B126 (3)O19S—Cl4S—O20S110.5 (4)
H4A—O4—H4B109 (5)
O12—C2—C5—N1−166.3 (8)C2—O12—Tb1—O929.2 (12)
O7—C2—C5—N115.5 (10)C2—O12—Tb1—O15143.4 (10)
O12—C2—C5—C12−39.8 (11)C2—O12—Tb1—O16−83.4 (12)
O7—C2—C5—C12142.1 (8)C2—O12—Tb1—O13171.4 (12)
O10—C4—C6—N2177.7 (8)C1—O9—Tb1—O1056.8 (8)
O1—C4—C6—N2−3.0 (11)C1—O9—Tb1—O11−66.4 (8)
O10—C4—C6—C11−59.4 (10)C1—O9—Tb1—O12−4.1 (9)
O1—C4—C6—C11120.0 (8)C1—O9—Tb1—O14116.6 (8)
O11—C3—C7—N312.2 (10)C1—O9—Tb1—O15−145.5 (8)
O6—C3—C7—N3−166.7 (7)C1—O9—Tb1—O16140.7 (8)
O11—C3—C7—C10137.3 (8)C1—O9—Tb1—O13−107.9 (8)
O6—C3—C7—C10−41.6 (10)C1—O2—Tb2—O653.0 (13)
O2—C1—C8—N4179.1 (7)C1—O2—Tb2—O7−11.2 (15)
O9—C1—C8—N40.5 (10)C1—O2—Tb2—O1−78.4 (14)
O2—C1—C8—C9−58.6 (10)C1—O2—Tb2—O5133.8 (14)
O9—C1—C8—C9122.9 (8)C1—O2—Tb2—O4105.1 (14)
O10—C4—O1—Tb2−1.7 (13)C1—O2—Tb2—O3−126.6 (13)
C6—C4—O1—Tb2179.0 (5)C1—O2—Tb2—O8−151.1 (14)
O9—C1—O2—Tb27(2)C3—O6—Tb2—O2−36.5 (12)
C8—C1—O2—Tb2−170.9 (9)C3—O6—Tb2—O792.1 (13)
O11—C3—O6—Tb2−10.8 (19)C3—O6—Tb2—O132.0 (13)
C7—C3—O6—Tb2168.0 (9)C3—O6—Tb2—O5−112.0 (13)
O12—C2—O7—Tb2−31.1 (14)C3—O6—Tb2—O4176.0 (13)
C5—C2—O7—Tb2146.8 (6)C3—O6—Tb2—O3143.2 (12)
O2—C1—O9—Tb1−7.2 (15)C3—O6—Tb2—O8−78.9 (13)
C8—C1—O9—Tb1171.1 (5)C2—O7—Tb2—O236.1 (8)
O6—C3—O11—Tb1−27.6 (13)C2—O7—Tb2—O6−30.7 (7)
C7—C3—O11—Tb1153.6 (6)C2—O7—Tb2—O1104.5 (7)
O7—C2—O12—Tb1−8.9 (18)C2—O7—Tb2—O5−73.7 (8)
C5—C2—O12—Tb1173.2 (7)C2—O7—Tb2—O4−107.2 (7)
C3—O11—Tb1—O1029.4 (8)C2—O7—Tb2—O3−178.8 (8)
C3—O11—Tb1—O12−37.7 (7)C2—O7—Tb2—O8141.2 (7)
C3—O11—Tb1—O14−89.0 (9)C4—O1—Tb2—O262.2 (7)
C3—O11—Tb1—O994.6 (7)C4—O1—Tb2—O6−6.4 (8)
C3—O11—Tb1—O15174.7 (8)C4—O1—Tb2—O7−65.5 (7)
C3—O11—Tb1—O16138.0 (7)C4—O1—Tb2—O5112.9 (7)
C3—O11—Tb1—O13−109.2 (8)C4—O1—Tb2—O4−121.4 (7)
C2—O12—Tb1—O10−30.7 (11)C4—O1—Tb2—O3−146.4 (7)
C2—O12—Tb1—O1192.0 (11)C4—O1—Tb2—O8138.5 (7)
C2—O12—Tb1—O14−114.9 (11)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H23···O12S0.912.202.928 (15)136
N3—H31···O17S0.912.323.032 (15)136
O14—H14B···O25S0.85 (10)2.01 (9)2.754 (15)145 (6)
O5—H5A···O3Si0.86 (4)2.00 (4)2.809 (10)156 (3)
O4—H4B···O9Si0.85 (5)2.37 (6)3.048 (20)137 (3)
N2—H22···O4Sii0.912.233.022 (12)145
N2—H21···O15Sii0.912.112.768 (19)129
N1—H13···O16Sii0.912.022.906 (13)163
N2—H22···O2Sii0.912.223.016 (12)147
N4—H42···O7SBiii0.912.102.979 (51)163
N3—H33···O22Siii0.911.942.822 (19)164
N4—H41···O24Siii0.912.183.033 (12)156
N4—H42···O5Siii0.912.313.049 (13)139
N1—H11···O6Siv0.912.203.002 (15)147
O3—H3B···O6Siv0.85 (5)2.33 (7)3.149 (15)161 (4)
N1—H12···O4Sv0.912.092.981 (11)165
N2—H21···O23Svi0.912.302.924 (10)125
O3—H3A···O23Svi0.85 (6)2.04 (5)2.882 (10)171 (4)
O4—H4A···O20Svi0.86 (6)2.01 (4)2.826 (10)158 (5)
N4—H43···O19Svii0.912.163.017 (11)156
O16—H16B···O20Svii0.84 (10)2.16 (5)2.794 (11)133 (4)
N3—H32···O5Sviii0.912.062.926 (12)159
O13—H13A···O8ix0.86 (3)2.01 (3)2.863 (10)174 (5)

Symmetry codes: (i) x, y, z−1; (ii) x, y−1, z; (iii) x, y+1, z; (iv) x+1, y, z−1; (v) x, y−1, z−1; (vi) x+1, y, z; (vii) x, y, z+1; (viii) x, y+1, z−1; (ix) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2689).

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