Diaqua­tetra­kis(pyrazine-2-carboxyl­ato-κ²O,N)thorium(IV) trihydrate

The structure of the title compound, [Th(C₅H₃N₂O₂)₄(H₂O)₂]·3H₂O, contains monomeric mol­ecules composed of a thorium(IV) ion coordinated by N,O-chelating groups donated by four pyrazine-2-carboxyl­ate ligands [mean Th—N = 2.773 (30) Å and mean Th—O = 2.391 (17) Å] and two water O atoms [mean Th—O = 2.517 (30) Å]. The coordination polyhedron around the Th^IV ion is an irregular hexa­deca­hedron.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.042
• wR factor = 0.124
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95
PLAT731_ALERT_1_B Bond    Calc     0.84(9), Rep     0.84(2) ......       4.50 su-Rat
              O2   -H21     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.84(9), Rep     0.84(2) ......       4.50 su-Rat
              O2   -H21     1.555   1.555

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT220_ALERT_2_C Large Non-Solvent    N     Ueq(max)/Ueq(min) ...       2.56 Ratio
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         12
PLAT417_ALERT_2_C Short Inter D-H..H-D       H301   ..  H401    ..       2.10 Ang.
PLAT731_ALERT_1_C Bond    Calc     0.84(8), Rep     0.85(2) ......       4.00 su-Rat
              O1   -H11     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(8), Rep     0.85(2) ......       4.00 su-Rat
              O1   -H11     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc    1.87(10), Rep     1.87(3) ......       3.33 su-Rat
              H21  -O12     1.555   1.655
PLAT751_ALERT_4_C Bond    Calc     0.86000, Rep    0.856(5) ......  Senseless su
              O1   -H12     1.555   1.555
PLAT751_ALERT_4_C Bond    Calc     0.83000, Rep    0.825(6) ......  Senseless su
              O3   -H301    1.555   1.555
PLAT751_ALERT_4_C Bond    Calc     0.83000, Rep    0.832(6) ......  Senseless su
              O3   -H302    1.555   1.555
PLAT751_ALERT_4_C Bond    Calc     0.91000, Rep   0.908(12) ......  Senseless su
              O4   -H402    1.555   1.555
PLAT751_ALERT_4_C Bond    Calc     0.89000, Rep    0.888(9) ......  Senseless su
              O4   -H401    1.555   1.555
PLAT751_ALERT_4_C Bond    Calc     0.85000, Rep   0.849(12) ......  Senseless su
              O5   -H502    1.555   1.555
PLAT751_ALERT_4_C Bond    Calc     0.85000, Rep   0.848(13) ......  Senseless su
              O5   -H501    1.555   1.555

Alert level G
ABSTM02_ALERT_3_G  The ratio of expected to reported Tmax/Tmin(RR) is > 1.50
            Tmin and Tmax reported:      0.240     0.379
            Tmin and Tmax expected:      0.143     0.351
            RR =      1.563
            Please check that your absorption correction is appropriate.

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
  17 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   8 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

The structures and properties of divalent 3d transition metal complexes with the pyrazine-2-carboxylate ligand still attract much interest. In contrast, the structure of only one complex with the trivalent La^III ion has been reported (Leciejewicz et al., 2004). Its structure is polymeric, with three bridging pathways via the pyrazine-2-carboxylate ligands.

The structure of a complex with a tetravalent ion, Th^IV, is described here. It contains monomeric molecules in which four pyrazine-2-carboxylate ligands are chelated to a Th^IV ion using their N,O-bonding groups. Two water O atoms complete the ten-coordination. Fig. 1 shows the complex molecule with the ligand and atom numbering, and Fig. 2 is a packing diagram.

Each acid ligand is almost coplanar since the relevant r.m.s. deviations from the mean plane are 0.027 (1), 0.049 (1), 0.073 (1) and 0.040 (1) Å for the ligands PYR1, PYR2, PYR3 and PYR4, respectively. The dihedral angles between ligand planes are PYR1/PYR2 = 63.0 (2)°, PYR2/PYR3 = 78.0 (2)°, PYR3/PYR4 = 75.9 (2)° and PYR4/PYR1 = 34.0 (2)°. The bond lengths and bond angles in the ligands are close to those reported for pyrazine-2-carboxylate acid (Takusagawa et al., 1974).

The coordination polyhedron around the Th^IV ion is an irregular decahexahedron and the geometry is composed of two monocapped square pyramids rotated by ca 45° around O21—Th—N41 axis [O21—Th—N41 = 171.28 (18)°].

Fig. 3 shows the atom alignment in the polyhedron viewed along the O21—Th—N41 axis. The base of the upper pyramid consists of atoms N11, N21, N31 and O2; its apex is atom O21. The base of the lower pyramid is formed by atoms O11, O31, O41 and O1, the apex being atom N41. The bond distances and bond angles observed within this polyhedron are listed in Table 1.

The same coordination geometry has been reported in the structure of the Th^IV complex with pyridine-2,6-dicarboxylate and water, in which the metal ion is coordinated by the O,O',N-bonding groups donated by two pyridine-2,6-dicarboxylate ligands and four water O atoms, forming a monomeric molecule (Degetto et al., 1978).

S2. Experimental

An aqueous solution of thorium nitrate pentahydrate (0.570 g in 25 ml) was added to a solution of pyrazine-2,3-dicarboxylic acid (0.745 g in 25 ml H₂O) and 10% hydrazine hydrate (2 ml). The pH of the resulting solution was mantained at 3 by adding a few drops of 10% hydrazine hydrate. After concentration over a steam bath to one-half of the initial volume, the turbid solution was filtered and the clear filtrate was left for crystallization at room temperature. Pale-yellow plate-shaped crystals were found in the mother liquid after a week. They were washed with a cold (1:1) water–ethanol mixture and dried in air.

S3. Refinement

The positions of H atoms attached to the coordinated water O atoms (O1 and O2) and to the solvation water O atoms (O3, O4 and O5) were not observed directly in Fourier maps. To insert them and construct the hydrogen-bond network, the method of Nardelli (1999) as implemented in the WinGX software (Faruggia, 1999) has been adopted. The full structure of (I) was then refined using constraints on the O—H distances and H—O—H angles [please specify values]. The hydrogen bonds listed in Table 2 have reasonable geometric parameters, so they can be considered as physical. Pyrazine ring H atoms were inserted by HFIX, each at a distance of 0.93 Å from the respective C atom, and refined adopting a riding model. Small intensities of reflections in the range of large Bragg scattering angles resulted in a completeness factor of 0.95.

Computing details

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1992); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecule of (I) with ligand and atom labelling schemes. Non-H atoms are shown as 50% probability displacement ellipsoids. For clarity, ligand molecules are marked as PYR1, PYR2, PYR3 and PYR4.
	Fig. 2. The packing diagram of (I). Solvation water O atoms are marked as O3, O4 and O5.
	Fig. 3. The coordination polyhedron around the Th^IV ion in (I), viewed along the O21—Th—N41 axis.

Diaquatetrakis(pyrazine-2-carboxylato-κ²O,N)thorium(IV) trihydrate

Crystal data

[Th(C5H3N2O2)4(H2O)2]·3H2O	F(000) = 1568
Mr = 814.50	Dx = 1.968 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.9080 (16) Å	Cell parameters from 25 reflections
b = 18.014 (4) Å	θ = 6–15°
c = 19.391 (4) Å	µ = 5.50 mm^−1
β = 95.70 (3)°	T = 293 K
V = 2748.7 (10) Å^3	Rectangular plate, pale yellow
Z = 4	0.41 × 0.31 × 0.19 mm

Data collection

Kuma KM-4 diffractometer	4872 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.067
Graphite monochromator	θmax = 30.1°, θmin = 1.6°
ω/2θ scans	h = 0→11
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2000)	k = 0→25
Tmin = 0.241, Tmax = 0.379	l = −26→26
7144 measured reflections	3 standard reflections every 200 reflections
5768 independent reflections	intensity decay: 9.7%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0835P)^2 + 2.9776P] where P = (Fo^2 + 2Fc^2)/3
5768 reflections	(Δ/σ)max = 0.002
388 parameters	Δρmax = 1.54 e Å^−3
13 restraints	Δρmin = −3.93 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Th1	1.03088 (3)	0.943782 (13)	0.253092 (13)	0.02560 (9)
N11	0.9713 (8)	0.8032 (3)	0.2023 (3)	0.0312 (13)
C12	0.8124 (10)	0.7804 (4)	0.2022 (4)	0.0344 (16)
C13	0.7640 (12)	0.7096 (5)	0.1793 (5)	0.047 (2)
H13	0.6515	0.6951	0.1806	0.056*
N12	0.8727 (11)	0.6618 (5)	0.1555 (5)	0.060 (2)
C15	1.0309 (13)	0.6856 (5)	0.1557 (5)	0.053 (2)
H15	1.1105	0.6539	0.1392	0.063*
C16	1.0843 (11)	0.7551 (5)	0.1793 (4)	0.0419 (19)
H16	1.1978	0.7686	0.1793	0.050*
C17	0.6878 (9)	0.8349 (4)	0.2270 (4)	0.0312 (14)
O11	0.7433 (7)	0.8987 (3)	0.2420 (3)	0.0341 (11)
O12	0.5403 (7)	0.8137 (3)	0.2305 (4)	0.0458 (15)
N21	0.9077 (10)	0.9384 (4)	0.1146 (4)	0.0413 (16)
C22	1.0214 (12)	0.9177 (5)	0.0712 (4)	0.0411 (18)
C23	0.9713 (14)	0.9059 (7)	0.0004 (5)	0.060 (3)
H23	1.0539	0.8924	−0.0281	0.072*
N22	0.8153 (13)	0.9129 (7)	−0.0272 (5)	0.068 (3)
C25	0.7009 (16)	0.9340 (7)	0.0170 (6)	0.064 (3)
H25	0.5879	0.9406	−0.0002	0.077*
C26	0.7470 (13)	0.9457 (6)	0.0858 (5)	0.056 (3)
H26	0.6636	0.9593	0.1139	0.068*
C27	1.2021 (11)	0.9092 (6)	0.1019 (5)	0.046 (2)
O21	1.2227 (7)	0.9143 (3)	0.1680 (3)	0.0386 (12)
O22	1.3152 (9)	0.8966 (5)	0.0658 (4)	0.070 (2)
N31	1.2036 (9)	1.0643 (4)	0.2043 (4)	0.0352 (14)
N32	1.3387 (10)	1.1983 (5)	0.1615 (4)	0.0457 (18)
C32	1.1049 (9)	1.1227 (4)	0.1864 (4)	0.0318 (15)
C33	1.1724 (11)	1.1898 (5)	0.1655 (4)	0.0395 (18)
H33	1.0997	1.2295	0.1542	0.047*
C35	1.4358 (10)	1.1374 (6)	0.1780 (5)	0.046 (2)
H35	1.5525	1.1401	0.1755	0.056*
C36	1.3656 (11)	1.0709 (5)	0.1985 (5)	0.046 (2)
H36	1.4363	1.0302	0.2082	0.055*
C37	0.9172 (9)	1.1132 (4)	0.1891 (4)	0.0320 (15)
O31	0.8742 (7)	1.0537 (3)	0.2205 (3)	0.0349 (11)
O32	0.8185 (8)	1.1597 (4)	0.1625 (4)	0.062 (2)
N41	0.8422 (7)	0.9956 (3)	0.3582 (3)	0.0266 (12)
C42	0.9275 (10)	1.0386 (4)	0.4055 (4)	0.0304 (15)
C43	0.8550 (11)	1.0694 (5)	0.4612 (5)	0.0394 (18)
H43	0.9204	1.0989	0.4929	0.047*
N42	0.6925 (9)	1.0568 (4)	0.4696 (4)	0.0379 (15)
C45	0.6056 (10)	1.0161 (4)	0.4228 (4)	0.0365 (17)
H45	0.4908	1.0080	0.4267	0.044*
C46	0.6785 (10)	0.9842 (4)	0.3673 (4)	0.0361 (17)
H46	0.6123	0.9546	0.3360	0.043*
C47	1.1119 (11)	1.0529 (5)	0.3943 (4)	0.0370 (16)
O41	1.1650 (7)	1.0177 (3)	0.3436 (3)	0.0381 (12)
O42	1.1934 (9)	1.0973 (5)	0.4307 (4)	0.071 (3)
O1	1.0106 (7)	0.8497 (3)	0.3499 (3)	0.0413 (13)
H11	1.079 (11)	0.814 (4)	0.357 (6)	0.062*
H12	0.9274	0.8328	0.3702	0.062*
O2	1.3021 (8)	0.8844 (4)	0.2961 (3)	0.0432 (14)
H21	1.364 (12)	0.861 (5)	0.271 (5)	0.065*
H22	1.323 (14)	0.881 (6)	0.3398 (13)	0.065*
O3	0.4182 (8)	0.8464 (4)	0.4251 (3)	0.0514 (16)
H301	0.5217	0.8430	0.4355	0.077*
H302	0.4030	0.8647	0.4634	0.077*
O4	0.7484 (13)	0.7966 (6)	0.4160 (6)	0.131 (5)
H402	0.7266	0.7545	0.3910	0.197*
H401	0.7289	0.7701	0.4530	0.197*
O5	0.920 (2)	0.7488 (7)	0.5269 (7)	0.172 (7)
H502	0.8893	0.7071	0.5417	0.258*
H501	0.9002	0.7789	0.5587	0.258*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Th1	0.01934 (12)	0.02827 (12)	0.03041 (13)	0.00152 (10)	0.00859 (8)	−0.00275 (11)
N11	0.023 (3)	0.032 (3)	0.039 (3)	0.005 (2)	0.007 (2)	−0.006 (3)
C12	0.028 (4)	0.038 (4)	0.038 (4)	−0.001 (3)	0.008 (3)	−0.004 (3)
C13	0.042 (5)	0.038 (4)	0.060 (6)	−0.001 (4)	0.008 (4)	−0.021 (4)
N12	0.058 (5)	0.040 (4)	0.083 (6)	−0.002 (4)	0.021 (5)	−0.023 (4)
C15	0.052 (6)	0.045 (5)	0.065 (6)	0.018 (4)	0.022 (5)	−0.009 (4)
C16	0.038 (4)	0.043 (4)	0.047 (5)	0.009 (4)	0.016 (4)	−0.002 (4)
C17	0.025 (3)	0.039 (4)	0.031 (4)	0.004 (3)	0.008 (3)	0.002 (3)
O11	0.028 (3)	0.034 (3)	0.041 (3)	0.006 (2)	0.008 (2)	−0.008 (2)
O12	0.027 (3)	0.047 (3)	0.066 (4)	−0.003 (2)	0.016 (3)	−0.014 (3)
N21	0.039 (4)	0.054 (4)	0.032 (3)	0.005 (3)	0.008 (3)	0.001 (3)
C22	0.045 (5)	0.044 (4)	0.036 (4)	0.004 (4)	0.015 (4)	0.001 (3)
C23	0.055 (6)	0.090 (8)	0.038 (5)	0.011 (6)	0.018 (4)	−0.008 (5)
N22	0.052 (6)	0.093 (7)	0.057 (6)	0.004 (5)	−0.003 (4)	−0.009 (5)
C25	0.047 (6)	0.094 (9)	0.052 (6)	0.014 (6)	0.001 (5)	0.008 (6)
C26	0.038 (5)	0.082 (7)	0.048 (5)	0.010 (5)	0.002 (4)	0.005 (5)
C27	0.036 (4)	0.060 (5)	0.044 (5)	0.006 (4)	0.019 (4)	0.000 (4)
O21	0.027 (3)	0.049 (3)	0.042 (3)	−0.001 (2)	0.011 (2)	−0.007 (3)
O22	0.048 (4)	0.119 (7)	0.048 (4)	0.011 (4)	0.025 (3)	−0.017 (4)
N31	0.027 (3)	0.039 (3)	0.042 (4)	0.003 (3)	0.012 (3)	0.000 (3)
N32	0.034 (4)	0.056 (4)	0.048 (4)	−0.016 (3)	0.011 (3)	0.003 (3)
C32	0.029 (4)	0.033 (3)	0.035 (4)	−0.007 (3)	0.010 (3)	0.000 (3)
C33	0.029 (4)	0.043 (4)	0.047 (5)	−0.008 (3)	0.004 (3)	0.003 (3)
C35	0.019 (3)	0.063 (5)	0.059 (5)	−0.012 (4)	0.009 (3)	0.001 (4)
C36	0.026 (4)	0.051 (5)	0.061 (6)	0.006 (3)	0.007 (4)	0.007 (4)
C37	0.021 (3)	0.030 (3)	0.046 (4)	0.006 (3)	0.006 (3)	0.010 (3)
O31	0.023 (3)	0.037 (3)	0.047 (3)	0.003 (2)	0.013 (2)	0.002 (2)
O32	0.035 (3)	0.052 (4)	0.101 (6)	0.002 (3)	0.013 (3)	0.029 (4)
N41	0.026 (3)	0.024 (3)	0.032 (3)	0.001 (2)	0.014 (2)	−0.002 (2)
C42	0.028 (4)	0.031 (3)	0.034 (4)	0.002 (3)	0.008 (3)	−0.002 (3)
C43	0.034 (4)	0.048 (5)	0.037 (4)	−0.003 (3)	0.012 (3)	−0.008 (3)
N42	0.033 (4)	0.047 (4)	0.036 (3)	0.006 (3)	0.015 (3)	0.000 (3)
C45	0.032 (4)	0.036 (4)	0.045 (4)	−0.004 (3)	0.020 (3)	−0.002 (3)
C46	0.026 (4)	0.034 (4)	0.050 (5)	−0.004 (3)	0.013 (3)	−0.002 (3)
C47	0.031 (4)	0.043 (4)	0.038 (4)	−0.002 (3)	0.010 (3)	−0.004 (3)
O41	0.025 (3)	0.047 (3)	0.044 (3)	−0.004 (2)	0.014 (2)	−0.012 (3)
O42	0.042 (4)	0.095 (6)	0.081 (5)	−0.032 (4)	0.028 (4)	−0.057 (5)
O1	0.033 (3)	0.041 (3)	0.053 (3)	0.008 (2)	0.018 (3)	0.003 (3)
O2	0.031 (3)	0.059 (4)	0.040 (3)	0.017 (3)	0.010 (2)	−0.004 (3)
O3	0.043 (4)	0.061 (4)	0.052 (4)	0.004 (3)	0.007 (3)	−0.013 (3)
O4	0.081 (7)	0.148 (10)	0.178 (12)	0.035 (7)	0.072 (8)	0.095 (9)
O5	0.22 (2)	0.121 (11)	0.174 (15)	0.008 (12)	0.019 (14)	0.018 (10)

Geometric parameters (Å, º)

Th1—O41	2.369 (6)	N31—C36	1.303 (11)
Th1—O31	2.388 (5)	N31—C32	1.334 (10)
Th1—O11	2.405 (6)	N32—C33	1.334 (11)
Th1—O21	2.409 (5)	N32—C35	1.359 (13)
Th1—O2	2.466 (6)	C32—C33	1.399 (10)
Th1—O1	2.545 (6)	C32—C37	1.501 (10)
Th1—N11	2.742 (6)	C33—H33	0.9300
Th1—N21	2.766 (7)	C35—C36	1.395 (12)
Th1—N31	2.781 (6)	C35—H35	0.9300
Th1—N41	2.804 (5)	C36—H36	0.9300
N11—C12	1.322 (10)	C37—O32	1.223 (9)
N11—C16	1.352 (9)	C37—O31	1.295 (9)
C12—C13	1.392 (11)	N41—C42	1.331 (9)
C12—C17	1.503 (10)	N41—C46	1.339 (9)
C13—N12	1.330 (11)	C42—C43	1.388 (10)
C13—H13	0.9300	C42—C47	1.517 (11)
N12—C15	1.322 (13)	C43—N42	1.331 (11)
C15—C16	1.384 (12)	C43—H43	0.9300
C15—H15	0.9300	N42—C45	1.308 (11)
C16—H16	0.9300	C45—C46	1.394 (10)
C17—O12	1.235 (9)	C45—H45	0.9300
C17—O11	1.254 (9)	C46—H46	0.9300
N21—C26	1.343 (13)	C47—O42	1.210 (10)
N21—C22	1.343 (10)	C47—O41	1.274 (9)
C22—C23	1.407 (13)	O1—H11	0.85 (2)
C22—C27	1.500 (14)	O1—H12	0.856 (5)
C23—N22	1.301 (15)	O2—H21	0.84 (2)
C23—H23	0.9300	O2—H22	0.85 (2)
N22—C25	1.361 (15)	O3—H301	0.825 (6)
C25—C26	1.363 (15)	O3—H302	0.832 (6)
C25—H25	0.9300	O4—H402	0.908 (12)
C26—H26	0.9300	O4—H401	0.888 (9)
C27—O22	1.211 (10)	O5—H502	0.849 (12)
C27—O21	1.278 (10)	O5—H501	0.848 (13)
O41—Th1—O31	85.0 (2)	C22—N21—Th1	115.1 (6)
O41—Th1—O11	127.31 (17)	N21—C22—C23	120.8 (9)
O31—Th1—O11	78.20 (18)	N21—C22—C27	116.8 (8)
O41—Th1—O21	111.44 (19)	C23—C22—C27	122.4 (8)
O31—Th1—O21	110.3 (2)	N22—C23—C22	123.4 (9)
O11—Th1—O21	121.24 (19)	N22—C23—H23	118.3
O41—Th1—O2	71.5 (2)	C22—C23—H23	118.3
O31—Th1—O2	149.3 (2)	C23—N22—C25	115.5 (9)
O11—Th1—O2	131.8 (2)	N22—C25—C26	121.9 (11)
O21—Th1—O2	63.3 (2)	N22—C25—H25	119.0
O41—Th1—O1	83.3 (2)	C26—C25—H25	119.0
O31—Th1—O1	132.72 (17)	N21—C26—C25	122.8 (10)
O11—Th1—O1	73.3 (2)	N21—C26—H26	118.6
O21—Th1—O1	116.63 (19)	C25—C26—H26	118.6
O2—Th1—O1	65.1 (2)	O22—C27—O21	124.3 (9)
O41—Th1—N11	146.5 (2)	O22—C27—C22	121.3 (9)
O31—Th1—N11	127.2 (2)	O21—C27—C22	114.3 (7)
O11—Th1—N11	61.86 (17)	C27—O21—Th1	132.5 (5)
O21—Th1—N11	69.35 (19)	C36—N31—C32	117.5 (7)
O2—Th1—N11	80.4 (2)	C36—N31—Th1	128.4 (6)
O1—Th1—N11	68.2 (2)	C32—N31—Th1	114.1 (5)
O41—Th1—N21	145.9 (2)	C33—N32—C35	115.5 (7)
O31—Th1—N21	69.4 (2)	N31—C32—C33	121.8 (7)
O11—Th1—N21	70.3 (2)	N31—C32—C37	117.2 (6)
O21—Th1—N21	60.8 (2)	C33—C32—C37	121.0 (7)
O2—Th1—N21	121.6 (2)	N32—C33—C32	121.5 (8)
O1—Th1—N21	130.6 (2)	N32—C33—H33	119.3
N11—Th1—N21	65.6 (2)	C32—C33—H33	119.3
O41—Th1—N31	67.3 (2)	N32—C35—C36	122.0 (7)
O31—Th1—N31	61.43 (19)	N32—C35—H35	119.0
O11—Th1—N31	136.5 (2)	C36—C35—H35	119.0
O21—Th1—N31	64.8 (2)	N31—C36—C35	121.7 (8)
O2—Th1—N31	90.8 (2)	N31—C36—H36	119.2
O1—Th1—N31	147.1 (2)	C35—C36—H36	119.2
N11—Th1—N31	132.19 (19)	O32—C37—O31	125.4 (7)
N21—Th1—N31	80.5 (2)	O32—C37—C32	120.0 (7)
O41—Th1—N41	60.34 (17)	O31—C37—C32	114.6 (6)
O31—Th1—N41	67.46 (18)	C37—O31—Th1	131.1 (4)
O11—Th1—N41	67.08 (18)	C42—N41—C46	115.5 (6)
O21—Th1—N41	171.28 (18)	C42—N41—Th1	115.1 (4)
O2—Th1—N41	113.98 (19)	C46—N41—Th1	129.4 (5)
O1—Th1—N41	66.95 (17)	N41—C42—C43	123.2 (7)
N11—Th1—N41	118.96 (17)	N41—C42—C47	115.4 (6)
N21—Th1—N41	123.8 (2)	C43—C42—C47	121.4 (7)
N31—Th1—N41	107.61 (17)	N42—C43—C42	120.4 (8)
C12—N11—C16	117.4 (7)	N42—C43—H43	119.8
C12—N11—Th1	114.6 (5)	C42—C43—H43	119.8
C16—N11—Th1	128.0 (5)	C45—N42—C43	117.3 (7)
N11—C12—C13	121.1 (7)	N42—C45—C46	122.5 (7)
N11—C12—C17	116.8 (7)	N42—C45—H45	118.8
C13—C12—C17	122.1 (7)	C46—C45—H45	118.8
N12—C13—C12	122.4 (9)	N41—C46—C45	121.2 (8)
N12—C13—H13	118.8	N41—C46—H46	119.4
C12—C13—H13	118.8	C45—C46—H46	119.4
C15—N12—C13	115.7 (8)	O42—C47—O41	125.6 (8)
N12—C15—C16	123.5 (8)	O42—C47—C42	119.5 (7)
N12—C15—H15	118.3	O41—C47—C42	114.9 (7)
C16—C15—H15	118.3	C47—O41—Th1	133.9 (5)
N11—C16—C15	119.9 (8)	Th1—O1—H11	123 (8)
N11—C16—H16	120.1	Th1—O1—H12	133.2
C15—C16—H16	120.1	H11—O1—H12	99
O12—C17—O11	125.5 (7)	Th1—O2—H21	124 (8)
O12—C17—C12	117.9 (7)	Th1—O2—H22	116 (8)
O11—C17—C12	116.5 (6)	H21—O2—H22	119 (10)
C17—O11—Th1	129.6 (4)	H301—O3—H302	92.3
C26—N21—C22	115.5 (8)	H402—O4—H401	86.8
C26—N21—Th1	128.9 (6)	H502—O5—H501	103.9

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···N32^i	0.85 (2)	2.22 (6)	2.994 (9)	152 (10)
O1—H12···O4	0.86	1.86	2.718 (10)	179
O2—H21···O12^ii	0.84 (2)	1.87 (3)	2.696 (8)	167 (11)
O2—H22···O3^ii	0.85 (2)	1.86 (5)	2.668 (9)	159 (11)
O3—H301···O4	0.83	2.05	2.783 (12)	148
O3—H302···N42^iii	0.83	2.11	2.886 (9)	155
O4—H402···O32^iv	0.91	2.01	2.919 (14)	179
O4—H401···O5	0.89	2.01	2.574 (19)	120
O5—H502···O22^v	0.85	2.03	2.871 (15)	174
O5—H501···O42^vi	0.85	2.36	3.051 (15)	138

Symmetry codes: (i) −x+5/2, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+1, −y+2, −z+1; (iv) −x+3/2, y−1/2, −z+1/2; (v) x−1/2, −y+3/2, z+1/2; (vi) −x+2, −y+2, −z+1.