Crystal structure and Hirshfeld surface analysis of tris­(acetohydrazide-κ2N,O)(nitrato-κO)(nitrato-κ2O,O′)terbium(III) nitrate

Theppitak, C.; Laksee, S.; Chainok, K.

doi:10.1107/S2056989022002298

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Volume 78| Part 4| April 2022| Pages 354-358

https://doi.org/10.1107/S2056989022002298

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Crystal structure and Hirshfeld surface analysis of tris(acetohydrazide-κ²N,O)(nitrato-κO)(nitrato-κ²O,O′)terbium(III) nitrate

Chatphorn Theppitak,^a Sakchai Laksee ^b and Kittipong Chainok ^a ^*

^aThammasat University Research Unit in Multifunctional Crystalline Materials and Applications (TU-McMa), Faculty of Science and Technology, Thammasat University, Khlong Luang, Pathum Thani, 12121, Thailand, and ^bNuclear Technology Research and Development Center, Thailand Institute of Nuclear Technology (Public Organization), Ongkharak, Nakon Nayok, 26120, Thailand
^*Correspondence e-mail: kc@tu.ac.th

Edited by C. Schulzke, Universität Greifswald, Germany (Received 29 December 2021; accepted 27 February 2022; online 8 March 2022)

In the title lanthanide(III) compound, [Tb(NO₃)₂(C₂H₆N₂O)₃]NO₃, the asymmetric unit contains one Tb³⁺ ion, three acetohydrazide (C₂H₆N₂O) ligands, two coordinated nitrate anions, and an isolated nitrate anion. The Tb³⁺ ion is in a ninefold coordinated distorted tricapped trigonal–prismatic geometry formed by three oxygen atoms and three nitrogen atoms from three different acetohydrazide ligands and three oxygen atoms from two nitrate anions. In the crystal, the complex molecules and the non-coordinated nitrate anions are assembled into a three-dimensional supramolecular architecture through extensive N—H⋯O hydrogen-bonding interactions between the amine NH groups of the acetohydrazide ligands and the nitrate oxygen atoms. Hirshfeld surface analysis was performed to aid in the visualization of intermolecular contacts.

Keywords: crystal structure; acetohydrazide; Hirshfeld surface analysis; lanthanide(III) ion; terbium(III).

CCDC reference: 2101422

1. Chemical context

Over the past two decades, there has been increasing interest in the construction of new lanthanide-based coordination compounds, not only because of their structural diversity but also because of their fascinating potential applications in luminescence, magnetism, adsorption, and similar areas (Roy et al., 2014 ; Cui et al., 2018 ; Kuwamura et al., 2021 ). It is well known that lanthanide(III) ions have a high affinity for and prefer binding to hard donor atoms. Thus, organic ligands with oxygen donor atoms such as aromatic polycarboxylic acids have been used extensively for the formation of these coordination materials (Janicki et al., 2017 ) whereas organohydrazide ligands have received far less attention. Accordingly, a ConQuest search of the Cambridge Structural Database (CSD, Version 5.42, September 2021 update; Bruno et al., 2002 ; Groom et al., 2016 ) reveals only 23 entries for hydrazide-containing lanthanide complexes. Among them, 15 lanthanide coordination complexes have recently been reported by our groups. Some of these complexes exhibited a high CO₂ uptake ability at high pressure (Theppitak et al., 2021a ), and have shown great potential as luminescent sensors for acetone and the Co²⁺ ion with good recyclability (Theppitak et al., 2021b ). In this work, we present the molecular structure of a new terbium(III) complex, [Tb(C₂H₆N₂O)₃(NO₃)₂]NO₃ (1), synthesized with acetohydrazide (C₂H₆N₂O) as the organic ligand. In addition, a Hirshfeld surface analysis and two-dimensional fingerprint plots were used to quantify the intermolecular contacts in the crystal structure.

2. Structural commentary

The molecular structure of 1 is shown in Fig. 1. The asymmetric unit contains one Tb³⁺ ion, three acetohydrazide ligands, two coordinated nitrate anions, and a non-coordinated nitrate counter-anion. The Tb³⁺ ion is ninefold coordinated (TbN₃O₆) by three nitrogen atoms and three oxygen atoms from three different acetohydrazide ligands, two oxygen atoms from one chelate nitrate anion, and one oxygen atom from another nitrate anion. As can be seen in Fig. 2, the coordination polyhedron of the Tb³⁺ ion is best described as having a distorted tricapped trigonal–prismatic geometry, wherein the N3, N5, O1, O3, O4, and O7 atoms form a trigonal prism, while the N1, O2, and O5 atoms act as caps. The Tb—O bond lengths of 2.353 (2)–2.496 (2) Å are slightly shorter than the Tb—N bond lengths [2.553 (2)–2.586 (2) Å]. The bond angles around the central Tb³⁺ ion fall into the range of 50.93 (7)–150.97 (7)°. These values are comparable to those reported for other ninefold-coordinated Tb³⁺ compounds containing oxygen/nitrogen-donor ligands such as [Tb(C₁₇H₁₃N₃)(NO₃)₂(DMSO)]·CH₃OH (VUKNEW, Chen et al., 2015 ) and [Tb(C₁₃H₂₂N₃)(NO₃)₃]·MeCN (SEZTOJ, Long et al., 2018 ).

Figure 1
Molecular structure of 1, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
View of the distorted tricapped trigonal–prismatic coordination geometry of the central Tb³⁺ atom in 1.

3. Supramolecular features

Extensive hydrogen-bonding interactions involving the three components of the hydrazide group of the acetohydrazide ligand and the coordinated and non-coordinated nitrate ions contribute to the stabilization of the supramolecular structure of 1 (Table 1; the N—H distances are all fixed with N—H = 0.86 ± 0.02 Å). A closer inspection of the structure reveals that the [Tb(C₂H₆N₂O)₃(NO₃)₂]⁺ complex molecules form centrosymmetric dimers via pairs of symmetry-related N3—H3B⋯O6 hydrogen bonds involving the amine NH group of the acetohydrazide ligand and the coordinated nitrate oxygen atom, Fig. 3. Notably, the amine NH donor and the coordinated nitrate oxygen acceptor is also involved in an intramolecular N1—H1A⋯O8 hydrogen bond. The dimers are further held together through an intermolecular N3—H3A⋯O9 hydrogen bond between the amine NH and the coordinated nitrate oxygen (O9), resulting in the formation of a two-dimensional supramolecular layer that propagates in the [100] direction, Fig. 4. Ultimately, adjacent layers are connected into a three-dimensional supramolecular architecture via the other two complementary N—H⋯O hydrogen-bonding interactions (i.e. N5—H5B⋯O3 and N6—H6⋯O7) occurring between the acetohydrazide ligands and the coordinated nitrate ions, Fig. 5. In addition, the non-coordinated nitrate anion is located in cavities along the b axis and serves as the acceptor site for six N—H⋯O hydrogen-bonding interactions (i.e. N1—H1B⋯O10, N2—H2⋯O12, N4—H4⋯O10, N4—H4⋯O11, N5—H5A⋯O10, and N5—H5A⋯O12) as shown in Fig. 6.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O8	0.84 (2)	2.37 (2)	2.950 (3)	126 (2)
N1—H1B⋯O10ⁱ	0.85 (2)	2.36 (2)	3.136 (3)	153 (3)
N2—H2⋯O11	0.85 (2)	2.69 (3)	3.070 (3)	109 (2)
N2—H2⋯O12	0.85 (2)	2.09 (2)	2.891 (2)	156 (3)
N3—H3A⋯O8	0.87 (2)	2.46 (3)	2.866 (3)	110 (2)
N3—H3A⋯O9ⁱⁱ	0.87 (2)	2.33 (2)	3.146 (3)	157 (2)
N3—H3B⋯O6ⁱⁱⁱ	0.85 (2)	2.25 (2)	3.089 (3)	168 (3)
N4—H4⋯O10^iv	0.87 (2)	2.34 (2)	3.102 (3)	147 (3)
N4—H4⋯O11^iv	0.87 (2)	2.17 (2)	2.984 (3)	156 (3)
N5—H5A⋯O10^v	0.86 (2)	2.58 (2)	3.176 (3)	128 (2)
N5—H5A⋯O12^v	0.86 (2)	2.11 (2)	2.964 (2)	173 (3)
N5—H5B⋯O3^vi	0.85 (2)	2.51 (2)	3.211 (2)	140 (2)
N6—H6⋯O7^vi	0.85 (2)	2.17 (2)	2.999 (2)	166 (2)
N6—H6⋯O10^v	0.85 (2)	2.74 (2)	3.170 (3)	114 (2)
Symmetry codes: (i) ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 3
Dimer formation through N—H⋯O hydrogen bonds (dashed lines) in 1 (hydrogen atoms, except those forming hydrogen bonds, are omitted for clarity).

Figure 4
The two-dimensional hydrogen bonded layer in 1 (hydrogen atoms, except those forming hydrogen bonds, are omitted for clarity).

Figure 5
The three-dimensional hydrogen-bonded network in 1 (hydrogen atoms, except those forming hydrogen bonds, are omitted for clarity).

Figure 6
View of 1 approximately along the b-axis direction, showing the N—H⋯O hydrogen-bonding interactions involving the non-coordinated nitrate ion and the complex molecules (hydrogen atoms, except those forming hydrogen bonds, are omitted for clarity).

4. Hirshfeld surface analysis

The Hirshfeld surface analysis (McKinnon et al., 2007 ) and the associated two-dimensional fingerprint plot generation (Spackman & McKinnon, 2002 ) were carried out using CrystalExplorer17 (Turner et al., 2017 ) in order to quantify the nature of the intermolecular interactions present in the crystal structure, and the results are shown in Figs. 7 and 8. The most significant contributions to the d_norm surfaces are H⋯O/O⋯H contacts (i.e. N—H⋯O hydrogen bonds), contributing 62.8% to the overall crystal packing of the title compound. The H⋯H contacts (representing van der Waals interactions) with a 22.8% contribution play a minor role in the stabilization of the crystal packing. All other N⋯O/O⋯N, O⋯O and H⋯N/N⋯H contacts make only negligible contributions to the Hirshfeld surface.

Figure 7
Two-dimensional fingerprint plots of 1, showing (a) all interactions, and those delineated into (b) H⋯O/O⋯H, (c) H⋯H, (d) N⋯O/O⋯N, (e) O⋯O, and (f) H⋯N/N⋯H contacts [d_e and d_i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (internal) the surface, respectively].

Figure 8
Quantitative results of different intermolecular contacts contributing to the Hirshfeld surface of 1.

5. Database survey

A ConQuest search of the Cambridge Structural Database (CSD, Version 5.42, September 2021 update; Bruno et al., 2002; Groom et al., 2016) for the structures of lanthanide complexes with acetohydrazide ligands gave ten hits, viz. Er [CECLEB (Pangani et al., 1983 ), CECLEB10 (Agre et al., 1984 )], Dy [CECLIF (Pangani et al., 1983), CECLIF10 (Pangani, Agre et al., 1984 )], Ho [CECLOL (Pangani et al., 1983), CECLOL10 (Pangani, Agre et al., 1984)], Pr (CUWFAB; Pangani, Machhoshvili et al., 1984 ), Gd (FOYGIM; Brandão et al., 2020 ), and Sm [ISNHSM (Zinner et al., 1979 ), QITBIH (Theppitak et al., 2018 )]. In all of these complexes, the acetohydrazide ligand adopts a μ₂-κ¹:κ¹ bidentate chelating coordination mode to bind the lanthanide(III) ion and the amine NH moiety of the acetohydrazide ligand can act as a donor site for intermolecular hydrogen-bonding interactions, similar to that of the title compound.

6. Synthesis and crystallization

A mixture of Tb(NO₃)₃·6H₂O (45.3 mg, 0.1 mmol), acetohydrazide (14.8 mg, 0.2 mmol), and isopropyl alcohol (4 ml) was sealed in a 15 ml Teflon-lined steel autoclave and heated at 373 K for 24 h. The mixture was cooled to room temperature and colorless block-shaped crystals of the title compound (1) were obtained in 87% yield (39.3 mg, based on Tb³⁺ source). Analysis calculated (%) for C₆H₁₈N₉O₁₂Tb: C 12.71; H 3.20; N 22.23%. Found: C 12.44; H 3.96; N 21.89%.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were located in difference-Fourier maps. All carbon-bound hydrogen atoms were placed in calculated positions and refined using a riding-model approximation with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C). All nitrogen-bound hydrogen atoms were refined with a fixed distance N—H = 0.86 ± 0.02 Å.

Table 2
Experimental details

Crystal data
Chemical formula	[Tb(NO₃)₂(C₂H₆N₂O)₃]NO₃
M_r	567.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	10.9076 (3), 9.7786 (3), 16.8578 (5)
β (°)	90.791 (1)
V (Å³)	1797.90 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	4.02
Crystal size (mm)	0.28 × 0.21 × 0.2

Data collection
Diffractometer	Bruker D8 QUEST CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.471, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	47511, 6876, 5752
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.770

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.044, 1.08
No. of reflections	6876
No. of parameters	293
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.12, −1.13
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2101422

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022002298/yz2015sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989022002298/yz2015Isup3.cdx

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022002298/yz2015Isup4.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Tris(acetohydrazide-κ²N,O)(nitrato-κO)(nitrato-κ²O,O')terbium(III) nitrate] top

Crystal data top

[Tb(NO₃)₂(C₂H₆N₂O)₃]NO₃	F(000) = 1112
M_r = 567.21	D_x = 2.096 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.9076 (3) Å	Cell parameters from 9937 reflections
b = 9.7786 (3) Å	θ = 3.0–33.1°
c = 16.8578 (5) Å	µ = 4.01 mm⁻¹
β = 90.791 (1)°	T = 296 K
V = 1797.90 (9) Å³	Block, colourless
Z = 4	0.28 × 0.21 × 0.2 mm

Data collection top

Bruker D8 QUEST CMOS diffractometer	6876 independent reflections
Radiation source: sealed x-ray tube, Mo	5752 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 7.39 pixels mm^-1	θ_max = 33.2°, θ_min = 2.8°
ω and φ scans	h = −16→14
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −15→14
T_min = 0.471, T_max = 0.747	l = −25→25
47511 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.027	w = 1/[σ²(F_o²) + (0.0127P)² + 1.6017P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.044	(Δ/σ)_max = 0.003
S = 1.08	Δρ_max = 1.12 e Å⁻³
6876 reflections	Δρ_min = −1.13 e Å⁻³
293 parameters	Extinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
9 restraints	Extinction coefficient: 0.00248 (11)

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Tb1	0.53793 (2)	0.69267 (2)	0.81234 (2)	0.01794 (3)
O1	0.53302 (15)	0.88900 (15)	0.73061 (9)	0.0316 (3)
O2	0.48569 (13)	0.88947 (16)	0.88653 (10)	0.0310 (3)
O3	0.68110 (13)	0.63211 (16)	0.71532 (9)	0.0275 (3)
O4	0.5610 (2)	0.6421 (2)	0.95580 (11)	0.0535 (5)
O5	0.68865 (16)	0.53978 (19)	0.88111 (12)	0.0425 (4)
O6	0.7062 (2)	0.5199 (3)	1.00927 (15)	0.0780 (8)
O7	0.47104 (13)	0.45766 (15)	0.79809 (10)	0.0297 (3)
O8	0.27693 (15)	0.46317 (18)	0.76534 (12)	0.0430 (4)
O9	0.37120 (17)	0.26983 (17)	0.77663 (12)	0.0431 (4)
O10	0.51235 (17)	0.6218 (2)	0.38477 (11)	0.0446 (4)
O11	0.57284 (17)	0.6504 (3)	0.50502 (13)	0.0598 (6)
O12	0.38755 (14)	0.70400 (18)	0.47151 (9)	0.0337 (4)
N1	0.4200 (2)	0.6697 (2)	0.67879 (12)	0.0302 (4)
H1A	0.3464 (17)	0.647 (3)	0.6859 (16)	0.040 (8)*
H1B	0.454 (3)	0.608 (3)	0.6519 (16)	0.050 (9)*
N2	0.42249 (18)	0.7916 (2)	0.63406 (11)	0.0294 (4)
H2	0.401 (3)	0.789 (3)	0.5854 (11)	0.048 (9)*
N3	0.31650 (17)	0.7017 (2)	0.86115 (13)	0.0301 (4)
H3A	0.265 (2)	0.694 (3)	0.8222 (13)	0.038 (7)*
H3B	0.302 (3)	0.635 (2)	0.8919 (16)	0.051 (9)*
N4	0.29181 (17)	0.8249 (2)	0.90180 (12)	0.0327 (4)
H4	0.2186 (19)	0.842 (3)	0.9187 (18)	0.060 (10)*
N5	0.74028 (16)	0.82302 (19)	0.82323 (11)	0.0243 (4)
H5A	0.786 (2)	0.809 (3)	0.8643 (13)	0.040 (8)*
H5B	0.722 (2)	0.9075 (18)	0.8197 (16)	0.040 (8)*
N6	0.81190 (16)	0.79567 (19)	0.75554 (12)	0.0274 (4)
H6	0.8761 (18)	0.842 (2)	0.7489 (15)	0.035 (7)*
N7	0.6533 (2)	0.5651 (2)	0.95054 (14)	0.0433 (5)
N8	0.36977 (17)	0.39549 (19)	0.77997 (11)	0.0290 (4)
N9	0.49126 (17)	0.6579 (2)	0.45403 (11)	0.0286 (4)
C1	0.48401 (19)	0.8957 (2)	0.66389 (13)	0.0258 (4)
C2	0.4922 (3)	1.0227 (3)	0.61533 (16)	0.0426 (6)
H2A	0.472625	1.100447	0.647550	0.064*
H2B	0.435281	1.017233	0.571491	0.064*
H2C	0.573927	1.032232	0.595665	0.064*
C3	0.38049 (19)	0.9150 (2)	0.90919 (12)	0.0246 (4)
C4	0.3478 (2)	1.0492 (3)	0.94566 (15)	0.0376 (5)
H4A	0.401145	1.066733	0.990255	0.056*
H4B	0.264351	1.046395	0.963032	0.056*
H4C	0.356757	1.120640	0.907122	0.056*
C5	0.77501 (18)	0.7031 (2)	0.70400 (13)	0.0246 (4)
C6	0.8488 (2)	0.6862 (3)	0.63059 (16)	0.0421 (6)
H6A	0.895336	0.603072	0.634062	0.063*
H6B	0.903604	0.762411	0.625384	0.063*
H6C	0.794817	0.682378	0.585182	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.01473 (4)	0.01950 (5)	0.01956 (5)	0.00037 (4)	−0.00101 (3)	−0.00128 (4)
O1	0.0418 (9)	0.0248 (8)	0.0279 (8)	−0.0019 (7)	−0.0130 (7)	0.0027 (6)
O2	0.0230 (7)	0.0316 (8)	0.0386 (9)	−0.0015 (6)	0.0073 (6)	−0.0121 (7)
O3	0.0225 (7)	0.0280 (8)	0.0321 (8)	−0.0051 (6)	0.0061 (6)	−0.0090 (6)
O4	0.0599 (13)	0.0684 (13)	0.0320 (10)	0.0158 (11)	−0.0029 (9)	0.0067 (9)
O5	0.0319 (9)	0.0424 (10)	0.0530 (12)	0.0057 (8)	−0.0068 (8)	0.0097 (9)
O6	0.0641 (14)	0.102 (2)	0.0668 (15)	−0.0119 (14)	−0.0300 (12)	0.0547 (14)
O7	0.0236 (7)	0.0240 (7)	0.0414 (9)	−0.0037 (6)	−0.0017 (6)	−0.0023 (7)
O8	0.0224 (8)	0.0387 (10)	0.0679 (13)	0.0003 (7)	−0.0027 (8)	0.0016 (9)
O9	0.0467 (11)	0.0227 (8)	0.0598 (12)	−0.0082 (8)	−0.0065 (9)	0.0001 (8)
O10	0.0487 (11)	0.0525 (11)	0.0331 (9)	0.0088 (9)	0.0142 (8)	−0.0051 (8)
O11	0.0280 (9)	0.1001 (17)	0.0510 (12)	0.0141 (10)	−0.0115 (9)	−0.0132 (12)
O12	0.0214 (7)	0.0512 (10)	0.0284 (8)	0.0049 (7)	0.0009 (6)	−0.0029 (7)
N1	0.0331 (10)	0.0294 (10)	0.0278 (9)	−0.0056 (8)	−0.0048 (8)	−0.0015 (8)
N2	0.0332 (10)	0.0370 (11)	0.0178 (8)	−0.0010 (8)	−0.0041 (7)	0.0008 (8)
N3	0.0217 (8)	0.0310 (10)	0.0377 (11)	−0.0035 (8)	0.0021 (8)	−0.0029 (9)
N4	0.0198 (8)	0.0376 (11)	0.0410 (11)	0.0027 (8)	0.0094 (8)	−0.0069 (9)
N5	0.0234 (8)	0.0233 (9)	0.0261 (9)	−0.0011 (7)	−0.0032 (7)	−0.0024 (7)
N6	0.0213 (8)	0.0257 (9)	0.0352 (10)	−0.0075 (7)	0.0036 (7)	−0.0022 (8)
N7	0.0389 (11)	0.0437 (13)	0.0470 (13)	−0.0100 (10)	−0.0171 (10)	0.0220 (11)
N8	0.0277 (9)	0.0257 (9)	0.0337 (10)	−0.0065 (8)	0.0027 (8)	−0.0008 (8)
N9	0.0237 (9)	0.0321 (10)	0.0300 (9)	−0.0011 (7)	0.0041 (7)	0.0022 (8)
C1	0.0233 (10)	0.0299 (11)	0.0242 (9)	0.0054 (8)	0.0013 (8)	0.0019 (8)
C2	0.0429 (14)	0.0443 (14)	0.0404 (14)	−0.0028 (12)	−0.0072 (11)	0.0157 (12)
C3	0.0248 (9)	0.0301 (10)	0.0189 (9)	0.0048 (9)	0.0016 (7)	−0.0013 (8)
C4	0.0361 (12)	0.0364 (13)	0.0403 (13)	0.0112 (10)	0.0027 (10)	−0.0104 (11)
C5	0.0221 (9)	0.0221 (9)	0.0296 (10)	0.0016 (8)	0.0035 (8)	0.0010 (8)
C6	0.0414 (13)	0.0411 (14)	0.0445 (14)	−0.0059 (12)	0.0206 (11)	−0.0097 (12)

Geometric parameters (Å, º) top

Tb1—O1	2.3632 (15)	N2—H2	0.849 (17)
Tb1—O2	2.3690 (15)	N2—C1	1.316 (3)
Tb1—O3	2.3525 (14)	N3—H3A	0.865 (17)
Tb1—O4	2.4779 (19)	N3—H3B	0.850 (17)
Tb1—O5	2.4959 (17)	N3—N4	1.414 (3)
Tb1—O7	2.4220 (15)	N4—H4	0.867 (17)
Tb1—N1	2.587 (2)	N4—C3	1.313 (3)
Tb1—N3	2.5640 (19)	N5—H5A	0.857 (17)
Tb1—N5	2.5532 (18)	N5—H5B	0.851 (17)
O1—C1	1.240 (2)	N5—N6	1.417 (3)
O2—C3	1.240 (2)	N6—H6	0.845 (17)
O3—C5	1.254 (2)	N6—C5	1.314 (3)
O4—N7	1.261 (3)	C1—C2	1.491 (3)
O5—N7	1.262 (3)	C2—H2A	0.9600
O6—N7	1.222 (3)	C2—H2B	0.9600
O7—N8	1.294 (2)	C2—H2C	0.9600
O8—N8	1.232 (2)	C3—C4	1.494 (3)
O9—N8	1.230 (2)	C4—H4A	0.9600
O10—N9	1.244 (2)	C4—H4B	0.9600
O11—N9	1.231 (3)	C4—H4C	0.9600
O12—N9	1.257 (2)	C5—C6	1.494 (3)
N1—H1A	0.844 (17)	C6—H6A	0.9600
N1—H1B	0.845 (17)	C6—H6B	0.9600
N1—N2	1.411 (3)	C6—H6C	0.9600

O1—Tb1—O2	69.15 (6)	H3A—N3—H3B	106 (3)
O1—Tb1—O4	137.09 (7)	N4—N3—Tb1	111.81 (13)
O1—Tb1—O5	140.08 (6)	N4—N3—H3A	108.2 (18)
O1—Tb1—O7	135.12 (5)	N4—N3—H3B	109 (2)
O1—Tb1—N1	63.66 (6)	N3—N4—H4	120 (2)
O1—Tb1—N3	98.35 (6)	C3—N4—N3	118.22 (18)
O1—Tb1—N5	69.45 (6)	C3—N4—H4	121 (2)
O2—Tb1—O4	70.66 (7)	Tb1—N5—H5A	118.0 (19)
O2—Tb1—O5	113.77 (6)	Tb1—N5—H5B	106.4 (19)
O2—Tb1—O7	138.48 (5)	H5A—N5—H5B	110 (3)
O2—Tb1—N1	114.19 (6)	N6—N5—Tb1	109.48 (12)
O2—Tb1—N3	64.41 (6)	N6—N5—H5A	107.6 (19)
O2—Tb1—N5	76.73 (5)	N6—N5—H5B	104.8 (19)
O3—Tb1—O1	79.00 (6)	N5—N6—H6	118.1 (18)
O3—Tb1—O2	137.59 (5)	C5—N6—N5	119.68 (17)
O3—Tb1—O4	124.67 (6)	C5—N6—H6	122.1 (18)
O3—Tb1—O5	74.51 (6)	O4—N7—O5	115.89 (19)
O3—Tb1—O7	83.93 (5)	O6—N7—O4	121.8 (3)
O3—Tb1—N1	72.54 (6)	O6—N7—O5	122.3 (3)
O3—Tb1—N3	150.36 (6)	O8—N8—O7	119.45 (18)
O3—Tb1—N5	66.06 (5)	O9—N8—O7	117.96 (19)
O4—Tb1—O5	50.93 (7)	O9—N8—O8	122.57 (19)
O4—Tb1—N1	150.97 (7)	O10—N9—O12	120.03 (19)
O4—Tb1—N3	77.11 (7)	O11—N9—O10	119.8 (2)
O4—Tb1—N5	87.34 (7)	O11—N9—O12	120.1 (2)
O5—Tb1—N1	131.95 (7)	O1—C1—N2	121.1 (2)
O5—Tb1—N3	119.27 (7)	O1—C1—C2	120.9 (2)
O5—Tb1—N5	72.69 (6)	N2—C1—C2	118.0 (2)
O7—Tb1—O4	86.19 (7)	C1—C2—H2A	109.5
O7—Tb1—O5	70.93 (6)	C1—C2—H2B	109.5
O7—Tb1—N1	71.68 (6)	C1—C2—H2C	109.5
O7—Tb1—N3	77.33 (6)	H2A—C2—H2B	109.5
O7—Tb1—N5	137.71 (5)	H2A—C2—H2C	109.5
N3—Tb1—N1	79.81 (7)	H2B—C2—H2C	109.5
N5—Tb1—N1	121.66 (6)	O2—C3—N4	121.3 (2)
N5—Tb1—N3	140.98 (6)	O2—C3—C4	122.1 (2)
C1—O1—Tb1	125.30 (14)	N4—C3—C4	116.64 (19)
C3—O2—Tb1	123.84 (14)	C3—C4—H4A	109.5
C5—O3—Tb1	121.19 (13)	C3—C4—H4B	109.5
N7—O4—Tb1	96.95 (15)	C3—C4—H4C	109.5
N7—O5—Tb1	96.06 (14)	H4A—C4—H4B	109.5
N8—O7—Tb1	136.41 (13)	H4A—C4—H4C	109.5
Tb1—N1—H1A	111.2 (19)	H4B—C4—H4C	109.5
Tb1—N1—H1B	108 (2)	O3—C5—N6	121.60 (19)
H1A—N1—H1B	108 (3)	O3—C5—C6	121.0 (2)
N2—N1—Tb1	112.25 (13)	N6—C5—C6	117.39 (19)
N2—N1—H1A	109.1 (19)	C5—C6—H6A	109.5
N2—N1—H1B	108 (2)	C5—C6—H6B	109.5
N1—N2—H2	119 (2)	C5—C6—H6C	109.5
C1—N2—N1	117.60 (18)	H6A—C6—H6B	109.5
C1—N2—H2	122 (2)	H6A—C6—H6C	109.5
Tb1—N3—H3A	111.3 (19)	H6B—C6—H6C	109.5
Tb1—N3—H3B	110 (2)

Tb1—O1—C1—N2	3.9 (3)	Tb1—O7—N8—O9	178.18 (15)
Tb1—O1—C1—C2	−176.58 (17)	Tb1—N1—N2—C1	1.4 (2)
Tb1—O2—C3—N4	8.5 (3)	Tb1—N3—N4—C3	0.0 (3)
Tb1—O2—C3—C4	−171.10 (16)	Tb1—N5—N6—C5	−6.9 (2)
Tb1—O3—C5—N6	14.8 (3)	N1—N2—C1—O1	−3.4 (3)
Tb1—O3—C5—C6	−164.56 (17)	N1—N2—C1—C2	177.1 (2)
Tb1—O4—N7—O5	−4.1 (2)	N3—N4—C3—O2	−5.3 (3)
Tb1—O4—N7—O6	174.7 (2)	N3—N4—C3—C4	174.4 (2)
Tb1—O5—N7—O4	4.0 (2)	N5—N6—C5—O3	−4.1 (3)
Tb1—O5—N7—O6	−174.7 (2)	N5—N6—C5—C6	175.3 (2)
Tb1—O7—N8—O8	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O8	0.84 (2)	2.37 (2)	2.950 (3)	126 (2)
N1—H1B···O10ⁱ	0.85 (2)	2.36 (2)	3.136 (3)	153 (3)
N2—H2···O11	0.85 (2)	2.69 (3)	3.070 (3)	109 (2)
N2—H2···O12	0.85 (2)	2.09 (2)	2.891 (2)	156 (3)
N3—H3A···O8	0.87 (2)	2.46 (3)	2.866 (3)	110 (2)
N3—H3A···O9ⁱⁱ	0.87 (2)	2.33 (2)	3.146 (3)	157 (2)
N3—H3B···O6ⁱⁱⁱ	0.85 (2)	2.25 (2)	3.089 (3)	168 (3)
N4—H4···O10^iv	0.87 (2)	2.34 (2)	3.102 (3)	147 (3)
N4—H4···O11^iv	0.87 (2)	2.17 (2)	2.984 (3)	156 (3)
N5—H5A···O10^v	0.86 (2)	2.58 (2)	3.176 (3)	128 (2)
N5—H5A···O12^v	0.86 (2)	2.11 (2)	2.964 (2)	173 (3)
N5—H5B···O3^vi	0.85 (2)	2.51 (2)	3.211 (2)	140 (2)
N6—H6···O7^vi	0.85 (2)	2.17 (2)	2.999 (2)	166 (2)
N6—H6···O10^v	0.85 (2)	2.74 (2)	3.170 (3)	114 (2)

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

Funding information

The authors gratefully acknowledge the financial support provided by the Thailand Institute of Nuclear Technology (Public Organization), through its program of TINT to University (grant to KC). This study was also partially supported by the Thammasat University Research Unit in Multifunctional Crystalline Materials and Applications (TU-McMa). CT would like to acknowledge a Graduate Development Scholarship 2020, National Research Council of Thailand (contract No. 15/2563).

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