Poly[[aqua-μ3-picolinato-μ2-picolinato-dipicolinatopotassium(I)terbium(III)] 2.5-hydrate]

Cunha-Silva, L.; Soares-Santos, P.C.R.; Nogueira, H.I.S.; Trindade, T.; Klinowski, J.; Rocha, J.; Almeida Paz, F.A.

doi:10.1107/S1600536808005758

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 4| April 2008| Pages m529-m530

doi:10.1107/S1600536808005758

Open

access

Poly[[aqua-μ₃-picolinato-μ₂-picolinato-dipicolinatopotassium(I)terbium(III)] 2.5-hydrate]

Luís Cunha-Silva,^a Paula C. R. Soares-Santos,^a Helena I. S. Nogueira,^a Tito Trindade,^a Jacek Klinowski,^b João Rocha ^a and Filipe A. Almeida Paz ^a ^*

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193, Aveiro, Portugal, and ^bDepartment of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW, Cambridge, England
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 28 November 2007; accepted 29 February 2008; online 7 March 2008)

In the title compound, [KTb(C₆H₄NO₂)₄(H₂O)]·2.5H₂O, each Tb³⁺ centre is coordinated by four N and five O atoms from five distinct picolinate ligands in a geometry resembling a highly distorted tricapped trigonal prism. One of the ligands establishes a skew bridge between neighbouring Tb³⁺ centres, leading to the formation of one-dimensional anionic polymeric chains, {[(C₆H₄NO₂)₄Tb]⁻}_n, running along the direction [010]. Each K⁺ cation is seven-coordinated by six O atoms from one anionic polymeric chain and one water molecule [K⋯O 2.676 (3)–3.208 (4) Å]. The uncoordinated water molecules are involved in O—H⋯O hydrogen bonding.

Related literature

For recent research on metal–organic frameworks (MOFs) or coordination polymers from our research group, see: Shi et al. (2008 ); Cunha-Silva et al. (2007 ); Paz & Klinowski (2007 ); Soares-Santos et al. (2006 ); Paz et al. (2005 ). For relevant examples of discrete complexes or MOFs incorporating lanthanide centres and pyridine–carboxylic acid derivative ligands, see: Sendor et al. (2003 ); Jian-Fang et al. (1996 ); Starynowicz (1993 ).

Experimental

Crystal data

[KTb(C₆H₄NO₂)₄(H₂O)]·2.5H₂O
M_r = 749.49
Hexagonal, P 6₅ 22
a = 12.7187 (2) Å
c = 62.2321 (9) Å
V = 8718.3 (2) Å³
Z = 12
Mo Kα radiation
μ = 2.64 mm⁻¹
T = 180 (2) K
0.39 × 0.28 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.426, T_max = 0.582 (expected range = 0.398–0.545)
31023 measured reflections
5031 independent reflections
4488 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.094
S = 1.14
5031 reflections
377 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 1.00 e Å⁻³
Δρ_min = −0.70 e Å⁻³
Absolute structure: Flack (1983 ), 1938 Friedel pairs
Flack parameter: −0.020 (15)

Table 1
Selected bond lengths (Å)

Tb1—O1	2.380 (2)
Tb1—O3	2.354 (2)
Tb1—O5	2.333 (2)
Tb1—O7ⁱ	2.352 (3)
Tb1—O8	2.385 (3)
Tb1—N1	2.640 (3)
Tb1—N2	2.575 (3)
Tb1—N3	2.736 (4)
Tb1—N4	2.626 (3)
K1—O1	2.676 (3)
K1—O2	3.208 (4)
K1—O3	2.972 (2)
K1—O5ⁱ	2.725 (3)
K1—O6ⁱ	2.985 (4)
K1—O8ⁱ	2.959 (2)
K1—O3W	2.661 (5)
Symmetry code: (i) x-y, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O4	0.84	2.09	2.858 (4)	152
O2W—H2W⋯O6ⁱⁱ	0.85	2.48	3.219 (5)	146
O3W—H3WA⋯O6ⁱⁱⁱ	0.86	2.09	2.647 (5)	121
O4W—H4WB⋯O2^iv	0.86	1.92	2.711 (6)	152
O5W—H5W⋯O4W	0.85	2.34	3.080 (13)	145
Symmetry codes: (ii) x-y+1, -y+1, -z; (iii) $[y-1, -x+y, z+{\script{1\over 6}}]$ ; (iv) x+1, y, z.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808005758/cv2369sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808005758/cv2369Isup2.hkl

checkCIF report

Comment top

In the last years research on multidimensional Metal-Organic Frameworks (MOFs), or coordination polymers, has received a remarkable interest as consequence of the their fascinating structural architectures which, in many cases, are also associated with interesting potential applications (e.g., gas storage, separation, catalysis, guest exchange, magnetic or optical sensors). Following our ongoing research focused on the preparation and structural characterization of these interesting compounds (for recent examples see: Shi et al., 2008; Cunha-Silva et al., 2007; Paz & Klinowski, 2007; Soares-Santos et al., 2006; Paz et al., 2005), we report in this short communication the crystalline structure of the title compound, K₂[Tb₂(pic)₆(µ-pic)₂].7(H₂O) [where pic^- stands for the picolinate anion, C₆H₄NO₂^-].

The crystalline structure of the title compound contains a single crystallographically independent Tb³⁺site, Tb1, which is coordinated to four N and five O-donor atoms belonging to five distinct picolinate anionic (pic^-) ligands, with a nine-coordination sphere {TbN₄O₅} resembling a highly distorted tricapped trigonal prism (Figure 1). The Tb—O and Tb—N bond distances are found in the 2.333 (2)–2.385 (3) Å and 2.575 (3)–2.736 (4) Å, respectively. The O—Tb—O, O—Tb—N and N—Tb—N angles are ranging from 68.75 (9) to 142.62 (9)°, 62.59 (10) to 142.63 (9)° and 69.62 (10) to 150.65 (10)°, respectively (see Figure 1 and Table 1).

As usually found in related compounds (see for example: Soares-Santos et al., 2006; Sendor et al., 2003; Starynowicz, 1993; Jian-Fang et al., 1996), all pic^- ligands are coordinated to the Tb³⁺ metal centre via the typical N,O-chelation mode (Figure 1). Furthermore, one pic^- establishes a skew-bridge (through the O7 atom; Figure 1) with a neighbouring Tb³⁺, thus completing the nine-coordination environment of the lanthanide centre and leading to the formation of the one-dimensional (one-dimensional) anionic coordination polymer (chain), [Tb₂(pic)₆(µ-pic)₂]_n²ⁿ^-, running along the [010] direction (Figure 2). The skew-bridge is also responsible for the zigzag distribution of the Tb³⁺centres along the aforementioned crystallographic direction, imposing an intermetallic Tb1···Tb1ⁱ distance of 6.4375 (4) Å [symmetry code: (i) 1 + x-y, 1 - y, -z]. Adjacent polymers close pack along the [001] direction of the unit cell with an arrangement resembling a layered-like structure. The water molecules of crystallization and the potassion cations are housed in the interchain empty spaces (Figure 2c with the K⁺ cations being omitted for clarity).

Related literature top

For recent research on metal–organic frameworks (MOF) or coordination polymers from our research group, see: Shi et al. (2008); Cunha-Silva et al. (2007); Paz & Klinowski (2007); Soares-Santos et al. (2006); Paz et al. (2005). For relevant examples of discrete complexes or MOFs incorporating lanthanide centres and pyridine–carboxilic acid derivative ligands, see: Sendor et al. (2003); Jian-Fang et al. (1996); Starynowicz (1993).

Experimental top

Starting materials were purchased from commercial sources and were used as received without further purification. The title compound has been prepared by adding an aqueous solution (5 ml) of TbCl₃.6H₂O (1 mmol, 373 mg) to a solution of picolinic acid (Hpic, 4 mmol, 492 mg) and KOH (4 mmol, 220 mg) in distilled water (20 ml, pH = 6.8). After stirring the mixture for 1 h, an aqueous solution (5 ml) of tetrabutylammonium chloride hydrate (ⁿBu₄NCl.nH₂O, 4 mmol, 1.12 g) was added drop wise. The resulting mixture was heated and the formed white precipitate was collected by vacuum filtering. Colourless crystals suitable for single-crystal X-ray analysis were obtained from the mother solution after three days.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Schematic representation of a fragment of the title compound, emphasizing the coordination environment of the crystallographically unique Tb centre, showing the labelling scheme for all atoms composing the first coordination sphere. Displacement ellipsoids are drawn at the 30% probability level and H atoms associated with the water molecules are represented as spheres with arbitrary radii. All H-atoms bound to carbon were omitted for clarity. Symmetry code used to generate equivalent atoms (represented in the ball-and-stick mode): (i) x, 1 + y, z.

Fig. 2. Perspective views of the one-dimensional anionic [Tb₂(pic)₆(µ-pic)₂]_n²ⁿ^- coordination polymer viewed along the (a) [010] and (b) [001] directions of the unit cell. (c) Crystal packing of the title compound viewed in perspective along the [010] direction of the unit cell (K⁺ cations and H-atoms were omitted for clarity).

Poly[[aqua-µ₃-picolinato-µ₂-picolinato- dipicolinatopotassium(I)terbium(III)] 2.5-hydrate] top

Crystal data top

[KTb(C₆H₄NO₂)₄(H₂O)]·2.5H₂O	D_x = 1.713 Mg m⁻³
M_r = 1498.97	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₅22	Cell parameters from 28400 reflections
Hall symbol: P 65 2 (0 0 1)	θ = 1.0–25.0°
a = 12.7187 (2) Å	µ = 2.64 mm⁻¹
c = 62.2321 (9) Å	T = 180 K
V = 8718.3 (2) Å³	Block, colourless
Z = 12	0.39 × 0.28 × 0.23 mm
F(000) = 4452

Data collection top

Nonius KappaCCD diffractometer	4488 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.062
Thin slice ω and ϕ scans	θ_max = 25.0°, θ_min = 3.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −14→15
T_min = 0.426, T_max = 0.582	k = −15→14
31023 measured reflections	l = −67→73
5031 independent 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)] = 0.032	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.059P)² + 2.1846P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max = 0.004
5031 reflections	Δρ_max = 1.00 e Å⁻³
377 parameters	Δρ_min = −0.70 e Å⁻³
14 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.020 (15)

Crystal data top

[KTb(C₆H₄NO₂)₄(H₂O)]·2.5H₂O	Z = 12
M_r = 1498.97	Mo Kα radiation
Hexagonal, P6₅22	µ = 2.64 mm⁻¹
a = 12.7187 (2) Å	T = 180 K
c = 62.2321 (9) Å	0.39 × 0.28 × 0.23 mm
V = 8718.3 (2) Å³

Data collection top

Nonius KappaCCD diffractometer	5031 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	4488 reflections with I > 2σ(I)
T_min = 0.426, T_max = 0.582	R_int = 0.062
31023 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.094	Δρ_max = 1.00 e Å⁻³
S = 1.14	Δρ_min = −0.70 e Å⁻³
5031 reflections	Absolute structure: Flack (1983)
377 parameters	Absolute structure parameter: −0.020 (15)
14 restraints

Special details top

Experimental. Please see the details in the main paper

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 (Å²) top

	x	y	z	U_iso*/U_eq
Tb1	0.078634 (13)	0.533458 (14)	0.005432 (2)	0.03612 (4)
K1	−0.23692 (8)	0.38564 (10)	0.040543 (15)	0.0593 (3)
O1	−0.0725 (2)	0.3470 (2)	0.02072 (4)	0.0505 (7)
O2	−0.2334 (3)	0.1630 (3)	0.01703 (6)	0.0757 (11)
O3	0.00810 (19)	0.6012 (2)	0.03429 (4)	0.0404 (6)
O4	0.0360 (2)	0.7288 (3)	0.06104 (4)	0.0560 (8)
O5	0.1777 (2)	0.6215 (2)	−0.02676 (4)	0.0507 (7)
O6	0.2602 (3)	0.7599 (3)	−0.05195 (5)	0.0925 (10)
O7	0.4239 (2)	0.5234 (2)	0.01432 (4)	0.0454 (7)
O8	0.2598 (2)	0.5230 (2)	0.00168 (4)	0.0413 (6)
N1	0.0152 (3)	0.3362 (3)	−0.01757 (5)	0.0512 (9)
N2	0.2430 (2)	0.7330 (3)	0.02245 (5)	0.0428 (8)
N3	0.0606 (3)	0.7255 (3)	−0.00984 (5)	0.0445 (8)
N4	0.1596 (2)	0.4834 (3)	0.04055 (5)	0.0423 (8)
C1	−0.1366 (4)	0.2477 (4)	0.01065 (7)	0.0565 (12)
C2	−0.0837 (3)	0.2389 (3)	−0.01096 (7)	0.0514 (10)
C3	−0.1393 (4)	0.1320 (4)	−0.02296 (9)	0.0729 (14)
H3	−0.2113	0.0629	−0.0180	0.087*
C4	−0.0875 (4)	0.1287 (5)	−0.04229 (8)	0.0797 (15)
H4	−0.1221	0.0570	−0.0507	0.096*
C5	0.0153 (4)	0.2318 (5)	−0.04897 (8)	0.0765 (15)
H5	0.0527	0.2326	−0.0622	0.092*
C6	0.0631 (4)	0.3330 (4)	−0.03634 (7)	0.0663 (13)
H6	0.1336	0.4042	−0.0412	0.080*
C7	0.0742 (3)	0.6955 (4)	0.04553 (6)	0.0476 (10)
C8	0.2077 (3)	0.7708 (4)	0.03953 (6)	0.0472 (10)
C9	0.2864 (4)	0.8706 (4)	0.05138 (7)	0.0605 (13)
H9	0.2593	0.8927	0.0639	0.073*
C10	0.4059 (4)	0.9384 (4)	0.04475 (8)	0.0684 (15)
H10	0.4620	1.0087	0.0525	0.082*
C11	0.4415 (4)	0.9027 (4)	0.02702 (8)	0.0592 (13)
H11	0.5228	0.9482	0.0220	0.071*
C12	0.3585 (3)	0.7999 (4)	0.01633 (7)	0.0489 (11)
H12	0.3847	0.7752	0.0040	0.059*
C13	0.1919 (4)	0.7149 (4)	−0.03693 (6)	0.0528 (11)
C14	0.1186 (3)	0.7695 (3)	−0.02886 (7)	0.0500 (11)
C15	0.1069 (4)	0.8548 (4)	−0.04020 (8)	0.0673 (13)
H15	0.1495	0.8849	−0.0533	0.081*
C16	0.0336 (4)	0.8974 (5)	−0.03266 (9)	0.0832 (16)
H16	0.0237	0.9560	−0.0405	0.100*
C17	−0.0243 (4)	0.8527 (4)	−0.01355 (10)	0.0710 (15)
H17	−0.0758	0.8802	−0.0079	0.085*
C18	−0.0092 (3)	0.7700 (4)	−0.00260 (8)	0.0546 (12)
H18	−0.0495	0.7418	0.0108	0.066*
C19	0.3216 (3)	0.5129 (3)	0.01674 (6)	0.0361 (9)
C20	0.2693 (3)	0.4904 (3)	0.03900 (6)	0.0379 (9)
C21	0.3275 (3)	0.4709 (4)	0.05577 (6)	0.0529 (10)
H21	0.4045	0.4771	0.0538	0.063*
C22	0.2705 (4)	0.4417 (5)	0.07585 (7)	0.0629 (13)
H22	0.3083	0.4275	0.0878	0.075*
C23	0.1574 (4)	0.4335 (4)	0.07812 (7)	0.0610 (13)
H23	0.1165	0.4145	0.0916	0.073*
C24	0.1061 (3)	0.4547 (4)	0.05951 (6)	0.0539 (11)
H24	0.0285	0.4478	0.0608	0.065*
O1W	0.06278 (19)	0.93722 (19)	0.0833	0.0632 (11)
H1W	0.0617	0.8930	0.0732	0.095*
O2W	0.5413 (3)	0.4587 (3)	0.0833	0.134 (2)
H2W	0.5540	0.4285	0.0722	0.200*
O3W	−0.1780 (4)	0.5373 (5)	0.07365 (6)	0.145 (3)
H3WA	−0.1443	0.5384	0.0857	0.218*
H3WB	−0.2010	0.5906	0.0761	0.218*
O4W	0.7402 (6)	0.1052 (5)	0.05936 (7)	0.188 (4)
H4WA	0.7373	0.1610	0.0670	0.282*
H4WB	0.7729	0.1408	0.0475	0.282*
O5W	0.9314 (6)	0.0686 (6)	0.0833	0.262 (6)
H5W	0.9021	0.0847	0.0723	0.393*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.03522 (7)	0.04700 (8)	0.03202 (8)	0.02495 (6)	0.00027 (6)	−0.00075 (7)
K1	0.0491 (4)	0.0827 (5)	0.0514 (5)	0.0369 (4)	−0.0055 (4)	0.0029 (5)
O1	0.0550 (13)	0.0407 (12)	0.0521 (15)	0.0211 (10)	−0.0067 (13)	0.0005 (11)
O2	0.0649 (18)	0.0485 (16)	0.088 (2)	0.0088 (14)	−0.0043 (18)	−0.0049 (16)
O3	0.0358 (10)	0.0519 (12)	0.0356 (12)	0.0235 (9)	0.0025 (10)	−0.0050 (10)
O4	0.0474 (13)	0.0689 (15)	0.0482 (15)	0.0264 (11)	0.0052 (12)	−0.0175 (12)
O5	0.0628 (12)	0.0699 (13)	0.0379 (13)	0.0471 (10)	0.0083 (11)	0.0070 (11)
O6	0.154 (2)	0.1116 (19)	0.0538 (17)	0.0975 (16)	0.0544 (17)	0.0407 (14)
O7	0.0386 (10)	0.0549 (13)	0.0459 (14)	0.0257 (9)	0.0029 (10)	−0.0006 (11)
O8	0.0426 (9)	0.0566 (12)	0.0356 (12)	0.0330 (9)	0.0007 (10)	0.0010 (10)
N1	0.0494 (14)	0.0641 (16)	0.0513 (18)	0.0368 (12)	−0.0120 (14)	−0.0162 (15)
N2	0.0384 (13)	0.0492 (15)	0.0416 (16)	0.0226 (11)	0.0020 (13)	−0.0011 (13)
N3	0.0409 (13)	0.0536 (14)	0.0439 (16)	0.0271 (12)	0.0000 (13)	−0.0008 (13)
N4	0.0395 (12)	0.0607 (16)	0.0319 (14)	0.0290 (11)	0.0025 (12)	0.0060 (13)
C1	0.0606 (19)	0.0488 (18)	0.066 (3)	0.0320 (16)	−0.021 (2)	−0.0019 (19)
C2	0.0586 (17)	0.0459 (16)	0.063 (2)	0.0366 (13)	−0.0211 (18)	−0.0112 (16)
C3	0.082 (2)	0.058 (2)	0.088 (3)	0.0421 (18)	−0.028 (2)	−0.021 (2)
C4	0.090 (3)	0.085 (3)	0.082 (3)	0.057 (2)	−0.039 (2)	−0.043 (2)
C5	0.069 (2)	0.111 (3)	0.067 (3)	0.058 (2)	−0.023 (2)	−0.045 (2)
C6	0.0546 (19)	0.084 (2)	0.071 (3)	0.0421 (18)	−0.011 (2)	−0.025 (2)
C7	0.0425 (16)	0.066 (2)	0.042 (2)	0.0323 (14)	−0.0012 (16)	−0.0020 (17)
C8	0.0493 (18)	0.0567 (19)	0.0365 (19)	0.0271 (15)	−0.0025 (16)	−0.0033 (16)
C9	0.058 (2)	0.062 (2)	0.062 (3)	0.0294 (17)	−0.006 (2)	−0.0259 (19)
C10	0.050 (2)	0.058 (2)	0.085 (3)	0.0187 (19)	−0.011 (2)	−0.019 (2)
C11	0.0401 (18)	0.055 (2)	0.074 (3)	0.0179 (16)	0.006 (2)	0.005 (2)
C12	0.0437 (17)	0.060 (2)	0.044 (2)	0.0267 (15)	0.0059 (17)	0.0056 (18)
C13	0.069 (2)	0.067 (2)	0.037 (2)	0.0454 (16)	0.0036 (17)	0.0095 (17)
C14	0.0554 (19)	0.053 (2)	0.046 (2)	0.0308 (15)	−0.0032 (17)	0.0009 (17)
C15	0.083 (2)	0.068 (2)	0.066 (3)	0.0491 (18)	0.013 (2)	0.019 (2)
C16	0.093 (2)	0.087 (2)	0.099 (4)	0.067 (2)	0.026 (3)	0.032 (3)
C17	0.061 (2)	0.056 (2)	0.110 (4)	0.0400 (16)	0.015 (2)	0.005 (2)
C18	0.0450 (17)	0.0511 (19)	0.071 (3)	0.0263 (15)	−0.001 (2)	−0.0019 (19)
C19	0.0285 (14)	0.0402 (16)	0.0403 (19)	0.0178 (12)	0.0058 (14)	0.0015 (14)
C20	0.0377 (15)	0.0406 (16)	0.0370 (18)	0.0209 (12)	0.0009 (14)	0.0014 (14)
C21	0.0492 (16)	0.077 (2)	0.045 (2)	0.0410 (15)	0.0004 (16)	0.0020 (19)
C22	0.070 (2)	0.093 (3)	0.038 (2)	0.0504 (19)	−0.0038 (18)	0.008 (2)
C23	0.059 (2)	0.082 (3)	0.044 (2)	0.0368 (19)	0.0064 (18)	0.0116 (19)
C24	0.0479 (17)	0.078 (2)	0.043 (2)	0.0369 (16)	0.0033 (16)	0.0074 (18)
O1W	0.0694 (12)	0.0694 (12)	0.059 (2)	0.0408 (16)	−0.008 (2)	−0.008 (2)
O2W	0.171 (2)	0.171 (2)	0.121 (5)	0.133 (3)	−0.048 (4)	−0.048 (4)
O3W	0.102 (3)	0.166 (5)	0.055 (2)	−0.018 (3)	0.010 (2)	−0.023 (3)
O4W	0.199 (6)	0.164 (6)	0.119 (4)	0.029 (5)	−0.018 (5)	0.028 (4)
O5W	0.281 (6)	0.281 (6)	0.282 (12)	0.184 (8)	−0.151 (8)	−0.151 (8)

Geometric parameters (Å, º) top

Tb1—O1	2.380 (2)	C3—H3	0.9500
Tb1—O3	2.354 (2)	C4—C5	1.373 (7)
Tb1—O5	2.333 (2)	C4—H4	0.9500
Tb1—O7ⁱ	2.352 (3)	C5—C6	1.365 (7)
Tb1—O8	2.385 (3)	C5—H5	0.9500
Tb1—N1	2.640 (3)	C6—H6	0.9500
Tb1—N2	2.575 (3)	C7—C8	1.520 (5)
Tb1—N3	2.736 (4)	C8—C9	1.374 (5)
Tb1—N4	2.626 (3)	C9—C10	1.383 (6)
K1—O1	2.676 (3)	C9—H9	0.9500
K1—O2	3.208 (4)	C10—C11	1.354 (7)
K1—O3	2.972 (2)	C10—H10	0.9500
K1—O5ⁱ	2.725 (3)	C11—C12	1.373 (6)
K1—O6ⁱ	2.985 (4)	C11—H11	0.9500
K1—O8ⁱ	2.959 (2)	C12—H12	0.9500
K1—O3W	2.661 (5)	C13—C14	1.501 (7)
Tb1—K1	4.1075 (9)	C13—K1ⁱⁱ	3.204 (5)
Tb1—K1ⁱⁱ	4.4471 (10)	C14—C15	1.364 (6)
K1—Tb1ⁱ	4.4471 (10)	C15—C16	1.374 (8)
O1—C1	1.274 (5)	C15—H15	0.9500
O2—C1	1.228 (5)	C16—C17	1.364 (8)
O3—C7	1.276 (4)	C16—H16	0.9500
O4—C7	1.246 (5)	C17—C18	1.345 (7)
O5—C13	1.276 (5)	C17—H17	0.9500
O5—K1ⁱⁱ	2.725 (3)	C18—H18	0.9500
O6—C13	1.207 (5)	C19—C20	1.501 (5)
O6—K1ⁱⁱ	2.985 (4)	C20—C21	1.372 (6)
O7—C19	1.248 (4)	C21—C22	1.398 (6)
O7—Tb1ⁱⁱ	2.352 (3)	C21—H21	0.9500
O8—C19	1.271 (4)	C22—C23	1.397 (7)
O8—K1ⁱⁱ	2.959 (2)	C22—H22	0.9500
N1—C2	1.314 (5)	C23—C24	1.420 (6)
N1—C6	1.327 (5)	C23—H23	0.9500
N2—C12	1.333 (5)	C24—H24	0.9500
N2—C8	1.334 (5)	O1W—H1W	0.8423
N3—C18	1.347 (6)	O2W—H2W	0.8472
N3—C14	1.358 (5)	O3W—H3WA	0.8616
N4—C24	1.319 (5)	O3W—H3WB	0.8749
N4—C20	1.356 (5)	O4W—H4WA	0.8712
C1—C2	1.532 (6)	O4W—H4WB	0.8598
C2—C3	1.394 (6)	O5W—H5W	0.8517
C3—C4	1.383 (7)

O5—Tb1—O7ⁱ	84.54 (9)	C1—O1—Tb1	126.1 (3)
O5—Tb1—O3	133.84 (9)	C1—O1—K1	103.8 (3)
O7ⁱ—Tb1—O3	91.51 (8)	Tb1—O1—K1	108.51 (11)
O5—Tb1—O1	142.62 (9)	C1—O2—K1	79.9 (3)
O7ⁱ—Tb1—O1	74.24 (9)	C7—O3—Tb1	124.7 (2)
O3—Tb1—O1	78.10 (9)	C7—O3—K1	133.6 (2)
O5—Tb1—O8	68.75 (9)	Tb1—O3—K1	100.26 (8)
O7ⁱ—Tb1—O8	137.81 (8)	C13—O5—Tb1	131.6 (3)
O3—Tb1—O8	130.58 (8)	C13—O5—K1ⁱⁱ	100.0 (2)
O1—Tb1—O8	107.77 (9)	Tb1—O5—K1ⁱⁱ	122.89 (12)
O5—Tb1—N2	84.42 (9)	C13—O6—K1ⁱⁱ	89.2 (3)
O7ⁱ—Tb1—N2	134.49 (10)	C19—O7—Tb1ⁱⁱ	147.0 (2)
O3—Tb1—N2	66.16 (8)	C19—O8—Tb1	126.7 (2)
O1—Tb1—N2	132.14 (9)	C19—O8—K1ⁱⁱ	118.6 (2)
O8—Tb1—N2	76.37 (9)	Tb1—O8—K1ⁱⁱ	112.22 (9)
O5—Tb1—N4	130.37 (9)	C2—N1—C6	119.0 (4)
O7ⁱ—Tb1—N4	142.63 (9)	C2—N1—Tb1	114.8 (3)
O3—Tb1—N4	73.81 (10)	C6—N1—Tb1	125.4 (3)
O1—Tb1—N4	69.22 (9)	C12—N2—C8	117.4 (3)
O8—Tb1—N4	63.97 (9)	C12—N2—Tb1	127.1 (3)
N2—Tb1—N4	70.92 (10)	C8—N2—Tb1	115.4 (2)
O5—Tb1—N1	79.95 (10)	C18—N3—C14	117.1 (4)
O7ⁱ—Tb1—N1	68.57 (9)	C18—N3—Tb1	128.8 (3)
O3—Tb1—N1	140.33 (8)	C14—N3—Tb1	113.5 (3)
O1—Tb1—N1	63.84 (10)	C24—N4—C20	116.9 (3)
O8—Tb1—N1	74.85 (9)	C24—N4—Tb1	126.9 (3)
N2—Tb1—N1	150.65 (10)	C20—N4—Tb1	116.1 (2)
N4—Tb1—N1	101.03 (11)	O2—C1—O1	125.0 (4)
O5—Tb1—N3	62.59 (10)	O2—C1—C2	120.2 (4)
O7ⁱ—Tb1—N3	66.11 (8)	O1—C1—C2	114.7 (3)
O3—Tb1—N3	73.80 (9)	O2—C1—K1	78.1 (3)
O1—Tb1—N3	129.94 (10)	O1—C1—K1	53.7 (2)
O8—Tb1—N3	122.04 (8)	C2—C1—K1	148.5 (3)
N2—Tb1—N3	69.62 (10)	N1—C2—C3	122.1 (4)
N4—Tb1—N3	136.35 (9)	N1—C2—C1	117.0 (3)
N1—Tb1—N3	122.56 (10)	C3—C2—C1	120.9 (4)
O5—Tb1—K1	147.78 (7)	C4—C3—C2	118.6 (4)
O7ⁱ—Tb1—K1	64.31 (7)	C4—C3—H3	120.7
O3—Tb1—K1	45.40 (5)	C2—C3—H3	120.7
O1—Tb1—K1	38.16 (8)	C5—C4—C3	118.4 (4)
O8—Tb1—K1	140.97 (6)	C5—C4—H4	120.8
N2—Tb1—K1	111.00 (7)	C3—C4—H4	120.8
N4—Tb1—K1	81.85 (6)	C6—C5—C4	119.2 (5)
N1—Tb1—K1	95.11 (7)	C6—C5—H5	120.4
N3—Tb1—K1	95.42 (6)	C4—C5—H5	120.4
O5—Tb1—K1ⁱⁱ	30.97 (7)	N1—C6—C5	122.7 (4)
O7ⁱ—Tb1—K1ⁱⁱ	108.39 (7)	N1—C6—H6	118.6
O3—Tb1—K1ⁱⁱ	147.55 (5)	C5—C6—H6	118.6
O1—Tb1—K1ⁱⁱ	131.21 (7)	O4—C7—O3	123.9 (3)
O8—Tb1—K1ⁱⁱ	38.02 (6)	O4—C7—C8	118.6 (3)
N2—Tb1—K1ⁱⁱ	81.83 (7)	O3—C7—C8	117.5 (3)
N4—Tb1—K1ⁱⁱ	101.43 (6)	N2—C8—C9	122.7 (4)
N1—Tb1—K1ⁱⁱ	71.99 (7)	N2—C8—C7	116.1 (3)
N3—Tb1—K1ⁱⁱ	90.77 (6)	C9—C8—C7	121.3 (4)
K1—Tb1—K1ⁱⁱ	167.044 (5)	C8—C9—C10	118.8 (4)
O3W—K1—O1	121.80 (14)	C8—C9—H9	120.6
O3W—K1—O5ⁱ	100.66 (15)	C10—C9—H9	120.6
O1—K1—O5ⁱ	132.75 (8)	C11—C10—C9	118.8 (4)
O3W—K1—O8ⁱ	116.68 (14)	C11—C10—H10	120.6
O1—K1—O8ⁱ	85.12 (8)	C9—C10—H10	120.6
O5ⁱ—K1—O8ⁱ	55.72 (8)	C10—C11—C12	119.2 (4)
O3W—K1—O3	69.35 (11)	C10—C11—H11	120.4
O1—K1—O3	63.49 (7)	C12—C11—H11	120.4
O5ⁱ—K1—O3	122.62 (9)	N2—C12—C11	123.1 (4)
O8ⁱ—K1—O3	78.10 (8)	N2—C12—H12	118.5
O3W—K1—O6ⁱ	95.03 (12)	C11—C12—H12	118.5
O1—K1—O6ⁱ	136.98 (9)	O6—C13—O5	124.0 (5)
O5ⁱ—K1—O6ⁱ	44.88 (8)	O6—C13—C14	120.4 (4)
O8ⁱ—K1—O6ⁱ	98.24 (8)	O5—C13—C14	115.6 (3)
O3—K1—O6ⁱ	159.29 (9)	O6—C13—K1ⁱⁱ	68.7 (3)
O3W—K1—C13ⁱ	101.29 (14)	O5—C13—K1ⁱⁱ	56.9 (2)
O1—K1—C13ⁱ	136.87 (9)	C14—C13—K1ⁱⁱ	163.7 (3)
O5ⁱ—K1—C13ⁱ	23.10 (9)	N3—C14—C15	121.7 (4)
O8ⁱ—K1—C13ⁱ	76.45 (9)	N3—C14—C13	115.9 (4)
O3—K1—C13ⁱ	144.73 (10)	C15—C14—C13	122.4 (4)
O6ⁱ—K1—C13ⁱ	22.14 (9)	C14—C15—C16	120.2 (5)
O3W—K1—O2	150.45 (16)	C14—C15—H15	119.9
O1—K1—O2	43.17 (8)	C16—C15—H15	119.9
O5ⁱ—K1—O2	105.46 (9)	C17—C16—C15	117.7 (5)
O8ⁱ—K1—O2	89.76 (8)	C17—C16—H16	121.2
O3—K1—O2	106.46 (8)	C15—C16—H16	121.2
O6ⁱ—K1—O2	93.82 (9)	C18—C17—C16	120.6 (5)
C13ⁱ—K1—O2	97.47 (10)	C18—C17—H17	119.7
O3W—K1—C1	142.75 (15)	C16—C17—H17	119.7
O1—K1—C1	22.56 (8)	C17—C18—N3	122.7 (4)
O5ⁱ—K1—C1	116.01 (9)	C17—C18—H18	118.6
O8ⁱ—K1—C1	81.64 (9)	N3—C18—H18	118.6
O3—K1—C1	84.75 (9)	O7—C19—O8	124.3 (3)
O6ⁱ—K1—C1	115.13 (10)	O7—C19—C20	118.1 (3)
C13ⁱ—K1—C1	114.93 (10)	O8—C19—C20	117.6 (3)
O2—K1—C1	22.01 (9)	N4—C20—C21	124.4 (3)
O3W—K1—Tb1	102.90 (10)	N4—C20—C19	114.9 (3)
O1—K1—Tb1	33.33 (5)	C21—C20—C19	120.6 (3)
O5ⁱ—K1—Tb1	123.64 (6)	C20—C21—C22	118.3 (4)
O8ⁱ—K1—Tb1	67.93 (5)	C20—C21—H21	120.9
O3—K1—Tb1	34.34 (5)	C22—C21—H21	120.9
O6ⁱ—K1—Tb1	160.91 (7)	C23—C22—C21	119.2 (4)
C13ⁱ—K1—Tb1	143.12 (7)	C23—C22—H22	120.4
O2—K1—Tb1	73.72 (6)	C21—C22—H22	120.4
C1—K1—Tb1	51.71 (7)	C22—C23—C24	117.2 (4)
O3W—K1—Tb1ⁱ	108.22 (14)	C22—C23—H23	121.4
O1—K1—Tb1ⁱ	112.36 (6)	C24—C23—H23	121.4
O5ⁱ—K1—Tb1ⁱ	26.14 (6)	N4—C24—C23	124.1 (4)
O8ⁱ—K1—Tb1ⁱ	29.77 (5)	N4—C24—H24	118.0
O3—K1—Tb1ⁱ	100.94 (6)	C23—C24—H24	118.0
O6ⁱ—K1—Tb1ⁱ	70.27 (6)	K1—O3W—H3WA	130.1
C13ⁱ—K1—Tb1ⁱ	48.14 (7)	K1—O3W—H3WB	127.8
O2—K1—Tb1ⁱ	101.31 (7)	H3WA—O3W—H3WB	101.2
C1—K1—Tb1ⁱ	102.51 (8)	H4WA—O4W—H4WB	104.4
Tb1—K1—Tb1ⁱ	97.539 (19)

O5—Tb1—K1—O3W	−117.41 (19)	K1—Tb1—O8—C19	−39.4 (3)
O7ⁱ—Tb1—K1—O3W	−133.39 (16)	K1ⁱⁱ—Tb1—O8—C19	161.4 (3)
O3—Tb1—K1—O3W	−12.35 (17)	O5—Tb1—O8—K1ⁱⁱ	−4.91 (9)
O1—Tb1—K1—O3W	129.46 (18)	O7ⁱ—Tb1—O8—K1ⁱⁱ	49.58 (15)
O8—Tb1—K1—O3W	91.20 (17)	O3—Tb1—O8—K1ⁱⁱ	−135.11 (9)
N2—Tb1—K1—O3W	−2.97 (16)	O1—Tb1—O8—K1ⁱⁱ	135.50 (9)
N4—Tb1—K1—O3W	62.91 (16)	N2—Tb1—O8—K1ⁱⁱ	−94.16 (10)
N1—Tb1—K1—O3W	163.36 (16)	N4—Tb1—O8—K1ⁱⁱ	−169.33 (13)
N3—Tb1—K1—O3W	−73.19 (15)	N1—Tb1—O8—K1ⁱⁱ	80.00 (10)
K1ⁱⁱ—Tb1—K1—O3W	168.59 (15)	N3—Tb1—O8—K1ⁱⁱ	−39.22 (13)
O5—Tb1—K1—O1	113.13 (17)	K1—Tb1—O8—K1ⁱⁱ	159.19 (3)
O7ⁱ—Tb1—K1—O1	97.15 (12)	O5—Tb1—N1—C2	−157.6 (3)
O3—Tb1—K1—O1	−141.81 (14)	O7ⁱ—Tb1—N1—C2	−69.6 (3)
O8—Tb1—K1—O1	−38.26 (14)	O3—Tb1—N1—C2	−5.0 (4)
N2—Tb1—K1—O1	−132.43 (13)	O1—Tb1—N1—C2	12.8 (3)
N4—Tb1—K1—O1	−66.55 (12)	O8—Tb1—N1—C2	131.9 (3)
N1—Tb1—K1—O1	33.90 (13)	N2—Tb1—N1—C2	143.5 (3)
N3—Tb1—K1—O1	157.35 (12)	N4—Tb1—N1—C2	72.9 (3)
K1ⁱⁱ—Tb1—K1—O1	39.13 (14)	N3—Tb1—N1—C2	−109.5 (3)
O5—Tb1—K1—O5ⁱ	−5.0 (2)	K1—Tb1—N1—C2	−9.8 (3)
O7ⁱ—Tb1—K1—O5ⁱ	−21.03 (9)	K1ⁱⁱ—Tb1—N1—C2	171.5 (3)
O3—Tb1—K1—O5ⁱ	100.01 (12)	O5—Tb1—N1—C6	11.7 (3)
O1—Tb1—K1—O5ⁱ	−118.18 (13)	O7ⁱ—Tb1—N1—C6	99.7 (4)
O8—Tb1—K1—O5ⁱ	−156.44 (11)	O3—Tb1—N1—C6	164.4 (3)
N2—Tb1—K1—O5ⁱ	109.39 (11)	O1—Tb1—N1—C6	−177.9 (4)
N4—Tb1—K1—O5ⁱ	175.27 (11)	O8—Tb1—N1—C6	−58.8 (4)
N1—Tb1—K1—O5ⁱ	−84.28 (11)	N2—Tb1—N1—C6	−47.2 (5)
N3—Tb1—K1—O5ⁱ	39.17 (10)	N4—Tb1—N1—C6	−117.8 (4)
K1ⁱⁱ—Tb1—K1—O5ⁱ	−79.04 (12)	N3—Tb1—N1—C6	59.8 (4)
O5—Tb1—K1—O8ⁱ	−3.57 (15)	K1—Tb1—N1—C6	159.6 (3)
O7ⁱ—Tb1—K1—O8ⁱ	−19.55 (8)	K1ⁱⁱ—Tb1—N1—C6	−19.2 (3)
O3—Tb1—K1—O8ⁱ	101.48 (11)	O5—Tb1—N2—C12	−34.9 (3)
O1—Tb1—K1—O8ⁱ	−116.70 (11)	O7ⁱ—Tb1—N2—C12	−111.6 (3)
O8—Tb1—K1—O8ⁱ	−154.96 (5)	O3—Tb1—N2—C12	−178.4 (4)
N2—Tb1—K1—O8ⁱ	110.87 (10)	O1—Tb1—N2—C12	136.4 (3)
N4—Tb1—K1—O8ⁱ	176.75 (9)	O8—Tb1—N2—C12	34.6 (3)
N1—Tb1—K1—O8ⁱ	−82.81 (9)	N4—Tb1—N2—C12	101.4 (4)
N3—Tb1—K1—O8ⁱ	40.64 (8)	N1—Tb1—N2—C12	23.0 (5)
K1ⁱⁱ—Tb1—K1—O8ⁱ	−77.57 (10)	N3—Tb1—N2—C12	−97.7 (4)
O5—Tb1—K1—O3	−105.06 (16)	K1—Tb1—N2—C12	174.3 (3)
O7ⁱ—Tb1—K1—O3	−121.03 (11)	K1ⁱⁱ—Tb1—N2—C12	−3.8 (3)
O1—Tb1—K1—O3	141.81 (14)	O5—Tb1—N2—C8	146.8 (3)
O8—Tb1—K1—O3	103.56 (13)	O7ⁱ—Tb1—N2—C8	70.0 (3)
N2—Tb1—K1—O3	9.39 (12)	O3—Tb1—N2—C8	3.2 (3)
N4—Tb1—K1—O3	75.26 (12)	O1—Tb1—N2—C8	−42.0 (3)
N1—Tb1—K1—O3	175.71 (12)	O8—Tb1—N2—C8	−143.8 (3)
N3—Tb1—K1—O3	−60.84 (11)	N4—Tb1—N2—C8	−77.0 (3)
O5—Tb1—K1—O6ⁱ	42.1 (3)	N1—Tb1—N2—C8	−155.3 (3)
O7ⁱ—Tb1—K1—O6ⁱ	26.1 (2)	N3—Tb1—N2—C8	84.0 (3)
O3—Tb1—K1—O6ⁱ	147.2 (2)	K1—Tb1—N2—C8	−4.1 (3)
O1—Tb1—K1—O6ⁱ	−71.0 (2)	K1ⁱⁱ—Tb1—N2—C8	177.8 (3)
O8—Tb1—K1—O6ⁱ	−109.3 (2)	O5—Tb1—N3—C18	171.9 (3)
N2—Tb1—K1—O6ⁱ	156.6 (2)	O7ⁱ—Tb1—N3—C18	75.5 (3)
N4—Tb1—K1—O6ⁱ	−137.6 (2)	O3—Tb1—N3—C18	−23.6 (3)
N1—Tb1—K1—O6ⁱ	−37.1 (2)	O1—Tb1—N3—C18	34.8 (3)
N3—Tb1—K1—O6ⁱ	86.3 (2)	O8—Tb1—N3—C18	−151.8 (3)
K1ⁱⁱ—Tb1—K1—O6ⁱ	−31.9 (3)	N2—Tb1—N3—C18	−93.7 (3)
O5—Tb1—K1—C13ⁱ	12.37 (19)	N4—Tb1—N3—C18	−67.2 (3)
O7ⁱ—Tb1—K1—C13ⁱ	−3.61 (14)	N1—Tb1—N3—C18	116.3 (3)
O3—Tb1—K1—C13ⁱ	117.43 (16)	K1—Tb1—N3—C18	16.7 (3)
O1—Tb1—K1—C13ⁱ	−100.76 (17)	K1ⁱⁱ—Tb1—N3—C18	−174.7 (3)
O8—Tb1—K1—C13ⁱ	−139.01 (15)	O5—Tb1—N3—C14	1.4 (2)
N2—Tb1—K1—C13ⁱ	126.81 (15)	O7ⁱ—Tb1—N3—C14	−95.1 (2)
N4—Tb1—K1—C13ⁱ	−167.31 (15)	O3—Tb1—N3—C14	165.8 (2)
N1—Tb1—K1—C13ⁱ	−66.86 (15)	O1—Tb1—N3—C14	−135.8 (2)
N3—Tb1—K1—C13ⁱ	56.59 (14)	O8—Tb1—N3—C14	37.7 (3)
K1ⁱⁱ—Tb1—K1—C13ⁱ	−61.62 (17)	N2—Tb1—N3—C14	95.7 (2)
O5—Tb1—K1—O2	92.95 (15)	N4—Tb1—N3—C14	122.3 (2)
O7ⁱ—Tb1—K1—O2	76.97 (9)	N1—Tb1—N3—C14	−54.3 (3)
O3—Tb1—K1—O2	−161.99 (12)	K1—Tb1—N3—C14	−153.9 (2)
O1—Tb1—K1—O2	−20.18 (13)	K1ⁱⁱ—Tb1—N3—C14	14.7 (2)
O8—Tb1—K1—O2	−58.43 (11)	O5—Tb1—N4—C24	166.3 (3)
N2—Tb1—K1—O2	−152.61 (11)	O7ⁱ—Tb1—N4—C24	−38.5 (4)
N4—Tb1—K1—O2	−86.73 (10)	O3—Tb1—N4—C24	31.9 (3)
N1—Tb1—K1—O2	13.72 (11)	O1—Tb1—N4—C24	−51.2 (3)
N3—Tb1—K1—O2	137.17 (9)	O8—Tb1—N4—C24	−174.5 (4)
K1ⁱⁱ—Tb1—K1—O2	18.96 (12)	N2—Tb1—N4—C24	101.7 (3)
O5—Tb1—K1—C1	93.33 (16)	N1—Tb1—N4—C24	−107.5 (3)
O7ⁱ—Tb1—K1—C1	77.35 (12)	N3—Tb1—N4—C24	75.4 (3)
O3—Tb1—K1—C1	−161.61 (13)	K1—Tb1—N4—C24	−13.9 (3)
O1—Tb1—K1—C1	−19.80 (14)	K1ⁱⁱ—Tb1—N4—C24	178.8 (3)
O8—Tb1—K1—C1	−58.05 (13)	O5—Tb1—N4—C20	−12.3 (3)
N2—Tb1—K1—C1	−152.23 (13)	O7ⁱ—Tb1—N4—C20	142.9 (2)
N4—Tb1—K1—C1	−86.35 (12)	O3—Tb1—N4—C20	−146.7 (3)
N1—Tb1—K1—C1	14.10 (12)	O1—Tb1—N4—C20	130.2 (3)
N3—Tb1—K1—C1	137.55 (11)	O8—Tb1—N4—C20	6.9 (2)
K1ⁱⁱ—Tb1—K1—C1	19.34 (13)	N2—Tb1—N4—C20	−76.9 (3)
O5—Tb1—K1—Tb1ⁱ	−6.69 (14)	N1—Tb1—N4—C20	73.8 (3)
O7ⁱ—Tb1—K1—Tb1ⁱ	−22.67 (6)	N3—Tb1—N4—C20	−103.2 (3)
O3—Tb1—K1—Tb1ⁱ	98.37 (9)	K1—Tb1—N4—C20	167.5 (3)
O1—Tb1—K1—Tb1ⁱ	−119.82 (10)	K1ⁱⁱ—Tb1—N4—C20	0.2 (3)
O8—Tb1—K1—Tb1ⁱ	−158.07 (9)	K1—O2—C1—O1	27.6 (4)
N2—Tb1—K1—Tb1ⁱ	107.75 (8)	K1—O2—C1—C2	−152.4 (4)
N4—Tb1—K1—Tb1ⁱ	173.63 (7)	Tb1—O1—C1—O2	−159.8 (4)
N1—Tb1—K1—Tb1ⁱ	−85.92 (8)	K1—O1—C1—O2	−34.2 (5)
N3—Tb1—K1—Tb1ⁱ	37.53 (6)	Tb1—O1—C1—C2	20.2 (5)
K1ⁱⁱ—Tb1—K1—Tb1ⁱ	−80.68 (9)	K1—O1—C1—C2	145.8 (3)
O5—Tb1—O1—C1	−2.5 (4)	Tb1—O1—C1—K1	−125.6 (3)
O7ⁱ—Tb1—O1—C1	55.4 (3)	O3W—K1—C1—O2	125.6 (3)
O3—Tb1—O1—C1	150.4 (4)	O1—K1—C1—O2	152.0 (4)
O8—Tb1—O1—C1	−80.5 (4)	O5ⁱ—K1—C1—O2	−65.4 (3)
N2—Tb1—O1—C1	−168.0 (3)	O8ⁱ—K1—C1—O2	−110.6 (3)
N4—Tb1—O1—C1	−132.6 (4)	O3—K1—C1—O2	170.7 (3)
N1—Tb1—O1—C1	−18.1 (3)	O6ⁱ—K1—C1—O2	−15.4 (3)
N3—Tb1—O1—C1	93.6 (4)	C13ⁱ—K1—C1—O2	−39.8 (3)
K1—Tb1—O1—C1	123.6 (4)	Tb1—K1—C1—O2	−179.0 (3)
K1ⁱⁱ—Tb1—O1—C1	−45.5 (4)	Tb1ⁱ—K1—C1—O2	−89.3 (3)
O5—Tb1—O1—K1	−126.14 (15)	O3W—K1—C1—O1	−26.4 (4)
O7ⁱ—Tb1—O1—K1	−68.28 (10)	O5ⁱ—K1—C1—O1	142.6 (2)
O3—Tb1—O1—K1	26.73 (9)	O8ⁱ—K1—C1—O1	97.4 (2)
O8—Tb1—O1—K1	155.83 (9)	O3—K1—C1—O1	18.7 (2)
N2—Tb1—O1—K1	68.33 (16)	O6ⁱ—K1—C1—O1	−167.3 (2)
N4—Tb1—O1—K1	103.74 (12)	C13ⁱ—K1—C1—O1	168.2 (2)
N1—Tb1—O1—K1	−141.77 (14)	O2—K1—C1—O1	−152.0 (4)
N3—Tb1—O1—K1	−30.01 (15)	Tb1—K1—C1—O1	29.0 (2)
K1ⁱⁱ—Tb1—O1—K1	−169.16 (4)	Tb1ⁱ—K1—C1—O1	118.8 (2)
O3W—K1—O1—C1	161.6 (3)	O3W—K1—C1—C2	−104.4 (5)
O5ⁱ—K1—O1—C1	−48.0 (3)	O1—K1—C1—C2	−78.0 (5)
O8ⁱ—K1—O1—C1	−79.9 (2)	O5ⁱ—K1—C1—C2	64.6 (5)
O3—K1—O1—C1	−159.1 (3)	O8ⁱ—K1—C1—C2	19.4 (5)
O6ⁱ—K1—O1—C1	16.9 (3)	O3—K1—C1—C2	−59.3 (5)
C13ⁱ—K1—O1—C1	−15.7 (3)	O6ⁱ—K1—C1—C2	114.6 (5)
O2—K1—O1—C1	14.9 (2)	C13ⁱ—K1—C1—C2	90.2 (5)
Tb1—K1—O1—C1	−136.1 (3)	O2—K1—C1—C2	130.0 (6)
Tb1ⁱ—K1—O1—C1	−67.7 (3)	Tb1—K1—C1—C2	−49.0 (4)
O3W—K1—O1—Tb1	−62.31 (18)	Tb1ⁱ—K1—C1—C2	40.8 (5)
O5ⁱ—K1—O1—Tb1	88.12 (13)	C6—N1—C2—C3	0.6 (7)
O8ⁱ—K1—O1—Tb1	56.19 (10)	Tb1—N1—C2—C3	170.7 (4)
O3—K1—O1—Tb1	−22.93 (8)	C6—N1—C2—C1	−179.1 (4)
O6ⁱ—K1—O1—Tb1	153.05 (10)	Tb1—N1—C2—C1	−9.1 (5)
C13ⁱ—K1—O1—Tb1	120.40 (13)	O2—C1—C2—N1	174.9 (4)
O2—K1—O1—Tb1	151.06 (18)	O1—C1—C2—N1	−5.1 (6)
C1—K1—O1—Tb1	136.1 (3)	K1—C1—C2—N1	55.1 (7)
Tb1ⁱ—K1—O1—Tb1	68.45 (10)	O2—C1—C2—C3	−4.9 (7)
O3W—K1—O2—C1	−86.7 (3)	O1—C1—C2—C3	175.1 (4)
O1—K1—O2—C1	−15.3 (2)	K1—C1—C2—C3	−124.7 (5)
O5ⁱ—K1—O2—C1	122.0 (3)	N1—C2—C3—C4	0.6 (7)
O8ⁱ—K1—O2—C1	67.8 (3)	C1—C2—C3—C4	−179.6 (5)
O3—K1—O2—C1	−9.7 (3)	C2—C3—C4—C5	−1.2 (8)
O6ⁱ—K1—O2—C1	166.1 (3)	C3—C4—C5—C6	0.5 (8)
C13ⁱ—K1—O2—C1	144.1 (3)	C2—N1—C6—C5	−1.4 (7)
Tb1—K1—O2—C1	0.8 (3)	Tb1—N1—C6—C5	−170.3 (4)
Tb1ⁱ—K1—O2—C1	95.4 (3)	C4—C5—C6—N1	0.8 (8)
O5—Tb1—O3—C7	−57.5 (3)	Tb1—O3—C7—O4	−178.5 (3)
O7ⁱ—Tb1—O3—C7	−141.4 (3)	K1—O3—C7—O4	−14.8 (6)
O1—Tb1—O3—C7	145.1 (3)	Tb1—O3—C7—C8	1.3 (5)
O8—Tb1—O3—C7	41.8 (3)	K1—O3—C7—C8	165.0 (3)
N2—Tb1—O3—C7	−2.3 (3)	C12—N2—C8—C9	−3.4 (7)
N4—Tb1—O3—C7	73.5 (3)	Tb1—N2—C8—C9	175.2 (4)
N1—Tb1—O3—C7	161.4 (3)	C12—N2—C8—C7	177.6 (4)
N3—Tb1—O3—C7	−76.8 (3)	Tb1—N2—C8—C7	−3.9 (5)
K1—Tb1—O3—C7	168.1 (3)	O4—C7—C8—N2	−178.2 (4)
K1ⁱⁱ—Tb1—O3—C7	−12.3 (4)	O3—C7—C8—N2	2.0 (6)
O5—Tb1—O3—K1	134.46 (10)	O4—C7—C8—C9	2.7 (7)
O7ⁱ—Tb1—O3—K1	50.57 (9)	O3—C7—C8—C9	−177.0 (4)
O1—Tb1—O3—K1	−22.98 (9)	N2—C8—C9—C10	3.3 (8)
O8—Tb1—O3—K1	−126.28 (9)	C7—C8—C9—C10	−177.7 (5)
N2—Tb1—O3—K1	−170.42 (12)	C8—C9—C10—C11	−1.1 (8)
N4—Tb1—O3—K1	−94.53 (9)	C9—C10—C11—C12	−0.7 (8)
N1—Tb1—O3—K1	−6.70 (19)	C8—N2—C12—C11	1.4 (7)
N3—Tb1—O3—K1	115.13 (10)	Tb1—N2—C12—C11	−177.0 (3)
K1ⁱⁱ—Tb1—O3—K1	179.60 (5)	C10—C11—C12—N2	0.6 (8)
O3W—K1—O3—C7	0.7 (4)	K1ⁱⁱ—O6—C13—O5	−14.1 (4)
O1—K1—O3—C7	−144.1 (4)	K1ⁱⁱ—O6—C13—C14	165.0 (3)
O5ⁱ—K1—O3—C7	90.3 (4)	Tb1—O5—C13—O6	169.0 (3)
O8ⁱ—K1—O3—C7	125.4 (4)	K1ⁱⁱ—O5—C13—O6	15.7 (4)
O6ⁱ—K1—O3—C7	43.6 (5)	Tb1—O5—C13—C14	−10.1 (5)
C13ⁱ—K1—O3—C7	80.9 (4)	K1ⁱⁱ—O5—C13—C14	−163.4 (3)
O2—K1—O3—C7	−148.4 (4)	Tb1—O5—C13—K1ⁱⁱ	153.3 (3)
C1—K1—O3—C7	−152.0 (4)	C18—N3—C14—C15	0.0 (5)
Tb1—K1—O3—C7	−166.4 (4)	Tb1—N3—C14—C15	171.7 (3)
Tb1ⁱ—K1—O3—C7	106.2 (4)	C18—N3—C14—C13	−177.8 (3)
O3W—K1—O3—Tb1	167.12 (17)	Tb1—N3—C14—C13	−6.0 (4)
O1—K1—O3—Tb1	22.31 (8)	O6—C13—C14—N3	−169.3 (4)
O5ⁱ—K1—O3—Tb1	−103.24 (11)	O5—C13—C14—N3	9.9 (5)
O8ⁱ—K1—O3—Tb1	−68.14 (8)	K1ⁱⁱ—C13—C14—N3	−48.9 (10)
O6ⁱ—K1—O3—Tb1	−149.9 (2)	O6—C13—C14—C15	13.0 (6)
C13ⁱ—K1—O3—Tb1	−112.70 (15)	O5—C13—C14—C15	−167.9 (4)
O2—K1—O3—Tb1	18.03 (11)	K1ⁱⁱ—C13—C14—C15	133.4 (8)
C1—K1—O3—Tb1	14.40 (11)	N3—C14—C15—C16	−1.0 (6)
Tb1ⁱ—K1—O3—Tb1	−87.37 (8)	C13—C14—C15—C16	176.6 (4)
O7ⁱ—Tb1—O5—C13	70.9 (3)	C14—C15—C16—C17	0.9 (7)
O3—Tb1—O5—C13	−15.9 (4)	C15—C16—C17—C18	0.2 (7)
O1—Tb1—O5—C13	125.9 (3)	C16—C17—C18—N3	−1.3 (7)
O8—Tb1—O5—C13	−142.4 (3)	C14—N3—C18—C17	1.2 (5)
N2—Tb1—O5—C13	−64.8 (3)	Tb1—N3—C18—C17	−169.1 (3)
N4—Tb1—O5—C13	−123.9 (3)	Tb1ⁱⁱ—O7—C19—O8	−49.3 (6)
N1—Tb1—O5—C13	140.1 (3)	Tb1ⁱⁱ—O7—C19—C20	132.6 (4)
N3—Tb1—O5—C13	5.1 (3)	Tb1—O8—C19—O7	−170.3 (2)
K1—Tb1—O5—C13	56.5 (4)	K1ⁱⁱ—O8—C19—O7	−9.9 (4)
K1ⁱⁱ—Tb1—O5—C13	−148.2 (4)	Tb1—O8—C19—C20	7.8 (4)
O7ⁱ—Tb1—O5—K1ⁱⁱ	−140.81 (13)	K1ⁱⁱ—O8—C19—C20	168.2 (2)
O3—Tb1—O5—K1ⁱⁱ	132.34 (12)	C24—N4—C20—C21	−0.7 (6)
O1—Tb1—O5—K1ⁱⁱ	−85.86 (18)	Tb1—N4—C20—C21	178.0 (3)
O8—Tb1—O5—K1ⁱⁱ	5.88 (10)	C24—N4—C20—C19	175.1 (3)
N2—Tb1—O5—K1ⁱⁱ	83.41 (13)	Tb1—N4—C20—C19	−6.2 (4)
N4—Tb1—O5—K1ⁱⁱ	24.35 (19)	O7—C19—C20—N4	178.1 (3)
N1—Tb1—O5—K1ⁱⁱ	−71.65 (13)	O8—C19—C20—N4	−0.1 (5)
N3—Tb1—O5—K1ⁱⁱ	153.31 (15)	O7—C19—C20—C21	−5.9 (5)
K1—Tb1—O5—K1ⁱⁱ	−155.24 (5)	O8—C19—C20—C21	175.9 (3)
O5—Tb1—O8—C19	156.5 (3)	N4—C20—C21—C22	0.2 (6)
O7ⁱ—Tb1—O8—C19	−149.0 (2)	C19—C20—C21—C22	−175.4 (4)
O3—Tb1—O8—C19	26.3 (3)	C20—C21—C22—C23	−0.1 (7)
O1—Tb1—O8—C19	−63.1 (3)	C21—C22—C23—C24	0.6 (7)
N2—Tb1—O8—C19	67.3 (3)	C20—N4—C24—C23	1.3 (6)
N4—Tb1—O8—C19	−7.9 (2)	Tb1—N4—C24—C23	−177.3 (3)
N1—Tb1—O8—C19	−118.6 (3)	C22—C23—C24—N4	−1.2 (7)
N3—Tb1—O8—C19	122.2 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O4	0.84	2.09	2.858 (4)	152
O2W—H2W···O6ⁱⁱ	0.85	2.48	3.219 (5)	146
O3W—H3WA···O6ⁱⁱⁱ	0.86	2.09	2.647 (5)	121
O4W—H4WB···O2^iv	0.86	1.92	2.711 (6)	152
O5W—H5W···O4W	0.85	2.34	3.080 (13)	145

Symmetry codes: (ii) x−y+1, −y+1, −z; (iii) y−1, −x+y, z+1/6; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[KTb(C₆H₄NO₂)₄(H₂O)]·2.5H₂O
M_r	1498.97
Crystal system, space group	Hexagonal, P6₅22
Temperature (K)	180
a, c (Å)	12.7187 (2), 62.2321 (9)
V (Å³)	8718.3 (2)
Z	12
Radiation type	Mo Kα
µ (mm⁻¹)	2.64
Crystal size (mm)	0.39 × 0.28 × 0.23

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.426, 0.582
No. of measured, independent and observed [I > 2σ(I)] reflections	31023, 5031, 4488
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.094, 1.14
No. of reflections	5031
No. of parameters	377
No. of restraints	14
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.00, −0.70
Absolute structure	Flack (1983)
Absolute structure parameter	−0.020 (15)

Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

Selected bond lengths (Å) top

Tb1—O1	2.380 (2)	Tb1—N4	2.626 (3)
Tb1—O3	2.354 (2)	K1—O1	2.676 (3)
Tb1—O5	2.333 (2)	K1—O2	3.208 (4)
Tb1—O7ⁱ	2.352 (3)	K1—O3	2.972 (2)
Tb1—O8	2.385 (3)	K1—O5ⁱ	2.725 (3)
Tb1—N1	2.640 (3)	K1—O6ⁱ	2.985 (4)
Tb1—N2	2.575 (3)	K1—O8ⁱ	2.959 (2)
Tb1—N3	2.736 (4)	K1—O3W	2.661 (5)

Symmetry code: (i) x−y, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O4	0.84	2.09	2.858 (4)	151.9
O2W—H2W···O6ⁱⁱ	0.85	2.48	3.219 (5)	146.2
O3W—H3WA···O6ⁱⁱⁱ	0.86	2.09	2.647 (5)	121.4
O4W—H4WB···O2^iv	0.86	1.92	2.711 (6)	151.9
O5W—H5W···O4W	0.85	2.34	3.080 (13)	144.9

Symmetry codes: (ii) x−y+1, −y+1, −z; (iii) y−1, −x+y, z+1/6; (iv) x+1, y, z.

Acknowledgements

The authors are grateful to Fundação para a Ciência e a Tecnologia (FCT, Portugal) for general financial support (grant No. POCI-PPCDT/QUI/58377/2004 supported by FEDER), for specific funding towards the purchase of the single-crystal diffractometer and also for the postdoctoral research grants referenced as SFRH/BPD/14410/2003 (to LC-S) and SFRH/BPD/14954/2004 (to PCRS-S).

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Version 3.1e. Crystal Impact GbR, Bonn, Germany. Google Scholar
Cunha-Silva, L., Mafra, L., Ananias, D., Carlos, L. D., Rocha, J. & Paz, F. A. A. (2007). Chem. Mater. 19, 3527–3538. Web of Science CSD CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jian-Fang, M., Ning-Hai, H. & Jia-Zuan, N. (1996). Polyhedron, 15, 1797–1799. CSD CrossRef CAS Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Paz, F. A. A. & Klinowski, J. (2007). Pure Appl. Chem. 79, 1097–1110. Web of Science CrossRef CAS Google Scholar
Paz, F. A. A., Rocha, J., Klinowski, J., Trindade, T., Shi, F.-N. & Mafra, L. (2005). Prog. Solid State Chem. 33, 113–125. Web of Science CrossRef CAS Google Scholar
Sendor, D., Hilder, M., Juestel, T., Junk, P. & Kynast, U. (2003). New J. Chem. 27, 1070–1077. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, F.-N., Cunha-Silva, L., Sá Ferreira, R. A., Mafra, L., Trindade, T., Carlos, L. D., Paz, F. A. A. & Rocha, J. (2008). J. Am. Chem. Soc. 130, 150–167. Web of Science CSD CrossRef PubMed CAS Google Scholar
Soares-Santos, P. C. R., Almeida Paz, F. A., Sá Ferreira, R. A., Klinowski, J., Carlos, L. D., Trindade, T. & Nogueira, H. I. S. (2006). Polyhedron, 25, 2471–2482. Web of Science CSD CrossRef CAS Google Scholar
Starynowicz, P. (1993). Acta Cryst. C49, 1895–1897. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.