Synthesis, crystal structure and properties of poly[di-μ3-chlorido-di-μ2-chlorido-bis­[4-methyl-N-(pyridin-2-yl­methyl­idene)aniline]dicadmium(II)]

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

doi:10.1107/S2056989024004274

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ISSN: 2056-9890

Volume 80| Part 6| June 2024| Pages 636-640

https://doi.org/10.1107/S2056989024004274

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Synthesis, crystal structure and properties of poly[di-μ₃-chlorido-di-μ₂-chlorido-bis[4-methyl-N-(pyridin-2-ylmethylidene)aniline]dicadmium(II)]

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

^aThammasat University Research Unit in Multifunctional Crystalline Materials and Applications (TU-MCMA), Faculty of Science and Technology, Thammasat University, Pathum Thani 12121, Thailand, ^bOffice of Research, Chulabhorn Research Institute, Laksi, Bangkok 10210, Thailand, and ^cNuclear Technology Research and Development Center, Thailand Institute of Nuclear Technology (Public Organization), Nakhon Nayok 26120, Thailand
^*Correspondence e-mail: kc@tu.ac.th

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 April 2024; accepted 8 May 2024; online 21 May 2024)

The title coordination polymer with the 4-methyl-N-(pyridin-2-ylmethylidene)aniline Schiff base ligand (L, C₁₃H₁₂N₂), [Cd₂Cl₄(C₁₃H₁₂N₂)]_n (1), exhibits a columnar structure extending parallel to [100]. The columns are aligned in parallel and are decorated with chelating L ligands on both sides. They are elongated into a supramolecular sheet extending parallel to (01 $[\overline{1}]$ ) through π–π stacking interactions involving L ligands of neighbouring columns. Adjacent sheets are packed into the tri-periodic supramolecular network through weak C—H⋯Cl hydrogen-bonding interactions that involve the phenyl CH groups and chlorido ligands. The thermal stability and photoluminescent properties of (1) have also been examined.

Keywords: crystal structure; coordination polymers; cadmium(II); Schiff base.

CCDC reference: 2354120

1. Chemical context

The design and construction of coordination polymers (CPs) have received continuous attention over the past three decades due to their intriguing functionalities (Batten et al., 2008 ). These materials are assembled through the coordination bonds between metal ions and organic linkers, whereby their topologies and dimensionalities are highly dependent on synthetic parameters as well as the chemical nature of starting materials (Jiajaroen et al., 2022 ; Li et al., 2022 ). Among many others, CPs of group 12 metal ions have attracted great interest for their potential applications in photoluminescence and optoelectronics (Ren et al., 2014 ; Shang et al., 2020 ). In this context, organic linkers containing carboxylates and/or nitrogen heterocycles on their backbone have been widely used due to their abundant coordination sites when reacting with d¹⁰ metal ions (Zhang et al., 2020 ). On the other hand, inorganic halogenidometallates have also shown great potential as building blocks in various functional materials (Chen & Beatty, 2007 ; Zhai et al., 2011 ; Freudenmann & Feldmann, 2014 ; Chen et al., 2015 ). Specifically, chloridocadmate(II) anions are known to exist in various forms such as [CdCl₃], [CdCl₄], and [CdCl₆] within different structural motifs (Gridley et al., 2013 ; Mobin et al., 2014 ; Wang et al., 2017 ; Hu et al., 2021 ). Notably, some of the corresponding materials exhibit high luminescence brightness (Zhai et al., 2011).

In this work, a coordination polymer, [Cd₂Cl₄(L)]_n (1), has formed through self-assembly from CdCl₂ and the 4-methyl-N-(pyridin-2-ylmethylidene)aniline (L) Schiff base ligand. Next to the structural set-up, the thermal stability and solid-state photoluminescence properties of (1) were investigated and are discussed in detail.

2. Structural commentary

The asymmetric unit of (1) contains two Cd^II atoms, one Schiff base ligand L, and four chlorido ligands. Both Cd1 and Cd2 have a distorted octahedral coordination environment. As depicted in Fig. 1, Cd1 displays a [Cl₄N₂] coordination set defined by two μ₃-Cl atoms in the equatorial plane, two μ₂-Cl atoms in the axial positions and two N atoms from the chelating ligand L in the remaining equatorial sites, whereas Cd2 is in a [Cl₆] coordination set by two μ₂- and four μ₃-Cl atoms. The corresponding bond angles around the central Cd1 and Cd2 atoms vary from 72.51 (12) to 176.14 (3)° and 81.21 (3) to 176.84 (3)°, respectively. The Cd—Cl bond lengths are in the range 2.5729 (10) – 2.7555 (10) Å, expectedly longer than those of the Cd—N bonds (2.311 (3) and 2.378 (3) Å). These values are in the normal range reported for related Cd^II compounds (Zhai et al., 2011).

Figure 1
The expanded asymmetric unit of (1) showing the full coordination spheres of the two Cd^II atoms. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) −x, −y, −z; (ii) x − 1, y, z.]

The μ₂- and μ₃-bridging character of the chlorido ligands leads to a columnar motif with composition [Cd₂Cl₄(L)]_n running parallel to [100], as shown in Fig. 2. The columns contain a cubane-like [Cd₂Cl₄] unit with a missing vertex with diagonal Cd⋯Cd separations in the range from 3.853 (3) to 3.973 (3) Å. The chelating ligands L are arranged on both sides of the column motif.

Figure 2
The columnar structure of (1) extending parallel to [100]. Hydrogen atoms are omitted for clarity.

3. Supramolecular features

In the crystal, ligands L interact with those from neighbouring columns through π–π stacking interactions, where parallel planes of phenyl/pyridyl rings are slightly offset (slippage 1.518 and 1.810 Å) with a centroid-to-centroid distance of 3.700 (3) Å and a dihedral angle of 5.61 (3)°. This arrangement leads to the formation of supramolecular sheets extending parallel to (01 $[\overline{1}]$ ) (Fig. 3). There is also a weak C—H⋯Cl hydrogen bond between the phenyl CH group and a chlorido ligand in adjacent columns [C9—H9⋯Cl4⁽ⁱ⁾ = 3.552 (2) Å, C9—H9⋯Cl4⁽ⁱ⁾ = 146°, symmetry code: (i) 2 − x, 1 − y, 1 − z). The sheets are connected by additional C—H⋯Cl hydrogen bonds (C2—H2⋯Cl4⁽ⁱⁱ⁾ = 3.697 (3) Å, C2—H2⋯Cl4⁽ⁱⁱ⁾ = 159°, symmetry code: (ii) 1 − x, 1 − y, −z), resulting in a tri-periodic supramolecular structure. It is noteworthy that no significant Cl⋯Cl halogen-bonding interactions occur. This likely is a result of the bidentate L ligands establishing steric hindrance within the coordination sphere of the Cd1 atom.

Figure 3
A view of the supramolecular sheet structure in (1) with π–π interactions shown as dashed lines. Hydrogen atoms are omitted for clarity.

4. Powder X-ray diffraction (PXRD) and thermogravimetry (TG)

The phase purity of (1) was revealed by room-temperature PXRD measurements with a good match between experimental and simulated peak positions (Fig. 4). It should be noted that the differences in the intensity may be due to preferred orientation of the crystallites in the sample.

Figure 4
Comparison of experimental and simulated PXRD patterns of (1) at room temperature.

The thermal stability of (1) was studied by TG measurements. As can be seen in Fig. 5, the TG curve of (1) shows three consecutive steps of mass loss in the range of 530–920 K. However, these steps cannot be assigned clearly. There is no mass loss from room temperature to 520 K, indicating that solvent molecules are not incorporated.

Figure 5
TG curve of (1).

5. Solid-state photoluminescence properties

The solid-state photoluminescence spectra of the Schiff base ligand L and coordination polymer (1) were recorded at room temperature (Fig. 6). Upon excitation at 325 nm, the free ligand L displays a broad blue fluorescent emission at 456 nm, while (1) exhibits photoluminescence with a maximum at 457 nm upon excitation at 340 nm. Because metal ions with d¹⁰ configuration usually are stable, the luminescence of complex (1) can solely be attributed to the intra-ligand π → π* emission state (i.e. ligand-based emission), which is also found in the free ligand L itself (Zhao et al., 2017 ).

Figure 6
The solid-state photoluminescence spectra of ligand L and (1) at room temperature.

6. Database survey

A search of the Cambridge Structural Database (CSD, version 5.44, last update in April 2023; Groom et al., 2016 ) using the ConQuest software (Bruno et al., 2002 ) yielded 17 hits for a fragment of a chlorido-bridged tetranuclear cadmium(II) compound with a defect cubane-like core. There are two mono-periodic coordination polymers that include organic ligands organised on both sides of the chain motif, similar to the arrangement in (1), viz. IQATAY (Hu et al., 2021) and SOGREN (Biet & Avarvari, 2014 ). In addition, 50 complexes of the title Schiff base ligand 4-methyl-N-(pyridin-2-ylmethylidene)aniline appear in the CSD. All these complexes are mononuclear with the Schiff base ligands acting in a bidentate chelating fashion. In the crystal packing of these compounds, π–π stacking and weak C—H⋯π interactions are frequently observed.

7. Synthesis and crystallization

A solution of 4-methyl-N-(2-pyridylmethylene)aniline (61.6 mg, 0.2 mmol) in dry dichloromethane (2 ml) was placed in a test tube. A mixture of acetonitrile and dichloromethane solution (6 ml, 1:1, v/v) was carefully added on the top. A solution of CdCl₂·6H₂O (19.8 mg, 0.2 mmol) in dry acetonitrile (2 ml) was then carefully layered on the top of the acetonitrile/dichloromethane mixed solution. After slow diffusion at room temperature for a week, light-yellow block-shaped crystals of (1) were obtained. Yield: 57% based on Cd. Analysis calculated for C₁₃H₁₂Cd₂Cl₄N₂: C, 27.74; H, 2.15; N, 4.98%; found: C, 27.69; H, 2.18; N, 4.72%. IR (ATR mode, cm⁻¹): 3027 (w), 2943 (w), 1899 (w), 1590 (m), 1504 (m), 1441 (m), 1268 (m), 1158 (m), 1015 (m), 908 (m), 817 (s), 781 (s), 638 (m), 539 (s), 412 (m).

Experimental details

All commercially available chemicals and solvents were of reagent grade and were used as received without further purification. Elemental (C, H, N) analysis was performed on a LECO CHNS 932 elemental analyser. IR spectra were recorded on a Bruker model INVENIO R spectrometer using ATR mode, in the range of 650–4000 cm⁻¹. PXRD measurements were performed on a Bruker D2 Phaser X-ray diffractometer equipped with graphite monochromatized Cu Kα radiation (λ = 1.54056 Å) at 30 kV and 10 mA. Simulated PXRD pattern were calculated from single-crystal X-ray diffraction data and processed with Mercury (Macrae et al., 2020 ). The TG measurements were performed in an N₂ atmosphere on a TGA 55 TA Instrument from ambient temperature up to 1223 K with a heating rate of 10 K min⁻¹. The solid-state photoluminescence spectra were measured at room temperature using a Horiba Scientific model FluoroMax-4 spectrofluorometer.

8. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 1. The carbon-bound H atoms were placed in geometrically calculated positions and refined as riding with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Table 1
Experimental details

Crystal data
Chemical formula	[Cd₂Cl₄(C₁₃H₁₂N₂)]
M_r	562.85
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	6.8597 (2), 10.8855 (4), 12.8106 (5)
α, β, γ (°)	107.566 (1), 100.523 (1), 106.799 (1)
V (Å³)	834.02 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	3.18
Crystal size (mm)	0.18 × 0.14 × 0.14

Data collection
Diffractometer	Bruker D8 QUEST CMOS PHOTON II
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.696, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	20153, 3418, 2553
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.066, 1.03
No. of reflections	3418
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.41
Computer programs: APEX4 and SAINT (Bruker, 2019 ), SHELXT2014/4 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2354120

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024004274/wm5718sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024004274/wm5718Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024004274/wm5718Isup3.cdx

checkCIF report

Computing details top

Poly[di-µ₃-chlorido-di-µ₂-chlorido-[4-methyl-N-(pyridin-2-ylmethylidene)aniline]dicadmium(II)] top

Crystal data top

[Cd₂Cl₄(C₁₃H₁₂N₂)]	Z = 2
M_r = 562.85	F(000) = 536
Triclinic, P1	D_x = 2.241 Mg m⁻³
a = 6.8597 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8855 (4) Å	Cell parameters from 1412 reflections
c = 12.8106 (5) Å	θ = 3.2–25.2°
α = 107.566 (1)°	µ = 3.18 mm⁻¹
β = 100.523 (1)°	T = 296 K
γ = 106.799 (1)°	Block, yellow
V = 834.02 (5) Å³	0.18 × 0.14 × 0.14 mm

Data collection top

Bruker D8 QUEST CMOS PHOTON II diffractometer	3418 independent reflections
Radiation source: sealed x-ray tube, Mo	2553 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 7.39 pixels mm^-1	θ_max = 26.4°, θ_min = 3.2°
ω and φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −13→13
T_min = 0.696, T_max = 0.745	l = −15→15
20153 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0267P)² + 0.7296P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3418 reflections	Δρ_max = 0.73 e Å⁻³
191 parameters	Δρ_min = −0.41 e Å⁻³
0 restraints

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
Cd1	0.43896 (5)	0.25775 (3)	0.19523 (2)	0.03039 (10)
Cd2	−0.17441 (5)	0.09278 (3)	0.07673 (2)	0.03114 (10)
Cl1	0.11124 (16)	0.18034 (11)	0.27038 (9)	0.0364 (3)
Cl3	0.46812 (15)	0.00951 (10)	0.13602 (8)	0.0274 (2)
Cl4	0.76831 (17)	0.31838 (11)	0.11374 (9)	0.0369 (3)
Cl2	0.15327 (15)	0.15624 (10)	−0.01197 (8)	0.0294 (2)
N1	0.4732 (6)	0.4839 (3)	0.2237 (3)	0.0345 (8)
N2	0.6415 (5)	0.3967 (3)	0.3893 (3)	0.0298 (8)
C1	0.4082 (8)	0.5310 (5)	0.1449 (4)	0.0456 (12)
H1	0.322184	0.467069	0.072599	0.055*
C2	0.4618 (8)	0.6699 (5)	0.1650 (4)	0.0522 (13)
H2	0.415590	0.698893	0.107078	0.063*
C3	0.5849 (8)	0.7646 (5)	0.2725 (5)	0.0525 (13)
H3	0.622400	0.859025	0.288606	0.063*
C4	0.6520 (7)	0.7183 (5)	0.3561 (4)	0.0424 (11)
H4	0.733459	0.780776	0.429718	0.051*
C5	0.5963 (6)	0.5771 (4)	0.3286 (3)	0.0322 (10)
C6	0.6732 (6)	0.5254 (4)	0.4146 (4)	0.0334 (10)
H6	0.746876	0.587535	0.489373	0.040*
C7	0.7158 (6)	0.3456 (4)	0.4728 (3)	0.0303 (9)
C8	0.8273 (7)	0.4274 (5)	0.5868 (4)	0.0365 (10)
H8	0.863455	0.522899	0.613147	0.044*
C9	0.8839 (7)	0.3655 (5)	0.6609 (4)	0.0416 (11)
H9	0.959473	0.421358	0.736998	0.050*
C10	0.8331 (7)	0.2238 (5)	0.6266 (4)	0.0427 (11)
C11	0.7295 (9)	0.1463 (5)	0.5128 (4)	0.0563 (14)
H11	0.700061	0.051484	0.485576	0.068*
C12	0.6677 (8)	0.2051 (5)	0.4378 (4)	0.0512 (14)
H12	0.591889	0.148618	0.361789	0.061*
C13	0.8854 (9)	0.1584 (6)	0.7100 (5)	0.0617 (15)
H13A	0.989813	0.228147	0.779111	0.093*
H13B	0.941330	0.089598	0.676953	0.093*
H13C	0.758629	0.115638	0.727315	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03240 (18)	0.02790 (18)	0.02645 (17)	0.01212 (14)	0.00518 (13)	0.00540 (13)
Cd2	0.02639 (17)	0.03096 (18)	0.03128 (19)	0.01317 (14)	0.00606 (14)	0.00424 (14)
Cl1	0.0329 (6)	0.0427 (6)	0.0300 (5)	0.0128 (5)	0.0076 (4)	0.0107 (5)
Cl3	0.0302 (5)	0.0259 (5)	0.0252 (5)	0.0115 (4)	0.0081 (4)	0.0075 (4)
Cl4	0.0367 (6)	0.0292 (6)	0.0432 (6)	0.0126 (5)	0.0138 (5)	0.0096 (5)
Cl2	0.0305 (5)	0.0300 (5)	0.0262 (5)	0.0126 (4)	0.0056 (4)	0.0087 (4)
N1	0.039 (2)	0.031 (2)	0.036 (2)	0.0180 (17)	0.0102 (17)	0.0116 (17)
N2	0.0279 (18)	0.031 (2)	0.0265 (18)	0.0080 (16)	0.0069 (15)	0.0093 (15)
C1	0.060 (3)	0.046 (3)	0.039 (3)	0.030 (3)	0.013 (2)	0.018 (2)
C2	0.067 (4)	0.057 (3)	0.053 (3)	0.034 (3)	0.022 (3)	0.036 (3)
C3	0.060 (3)	0.038 (3)	0.069 (4)	0.021 (3)	0.023 (3)	0.027 (3)
C4	0.044 (3)	0.033 (3)	0.049 (3)	0.015 (2)	0.014 (2)	0.014 (2)
C5	0.032 (2)	0.032 (2)	0.032 (2)	0.0137 (19)	0.0112 (19)	0.0095 (19)
C6	0.031 (2)	0.033 (3)	0.030 (2)	0.009 (2)	0.0087 (18)	0.0076 (19)
C7	0.030 (2)	0.032 (2)	0.028 (2)	0.0112 (19)	0.0059 (18)	0.0099 (18)
C8	0.034 (2)	0.034 (2)	0.033 (2)	0.006 (2)	0.0050 (19)	0.011 (2)
C9	0.035 (2)	0.050 (3)	0.030 (2)	0.007 (2)	0.003 (2)	0.014 (2)
C10	0.037 (3)	0.052 (3)	0.040 (3)	0.017 (2)	0.011 (2)	0.018 (2)
C11	0.087 (4)	0.038 (3)	0.044 (3)	0.029 (3)	0.010 (3)	0.015 (2)
C12	0.079 (4)	0.034 (3)	0.029 (2)	0.021 (3)	0.002 (2)	0.004 (2)
C13	0.059 (3)	0.075 (4)	0.065 (4)	0.022 (3)	0.016 (3)	0.047 (3)

Geometric parameters (Å, º) top

Cd1—Cl1	2.6221 (11)	C3—H3	0.9300
Cd1—Cl3	2.6548 (10)	C3—C4	1.375 (7)
Cd1—Cl4	2.6543 (11)	C4—H4	0.9300
Cd1—Cl2	2.6805 (10)	C4—C5	1.385 (6)
Cd1—N1	2.311 (3)	C5—C6	1.463 (6)
Cd1—N2	2.378 (3)	C6—H6	0.9300
Cd2—Cl1	2.5729 (10)	C7—C8	1.388 (6)
Cd2—Cl3ⁱ	2.7555 (10)	C7—C12	1.375 (6)
Cd2—Cl3ⁱⁱ	2.6874 (10)	C8—H8	0.9300
Cd2—Cl4ⁱⁱ	2.5165 (11)	C8—C9	1.381 (6)
Cd2—Cl2	2.7074 (11)	C9—H9	0.9300
Cd2—Cl2ⁱ	2.6404 (10)	C9—C10	1.385 (6)
N1—C1	1.327 (5)	C10—C11	1.369 (6)
N1—C5	1.348 (5)	C10—C13	1.497 (6)
N2—C6	1.281 (5)	C11—H11	0.9300
N2—C7	1.426 (5)	C11—C12	1.376 (6)
C1—H1	0.9300	C12—H12	0.9300
C1—C2	1.377 (6)	C13—H13A	0.9600
C2—H2	0.9300	C13—H13B	0.9600
C2—C3	1.374 (7)	C13—H13C	0.9600

Cl1—Cd1—Cl3	93.00 (3)	C7—N2—Cd1	125.1 (2)
Cl1—Cd1—Cl4	176.14 (3)	N1—C1—H1	118.4
Cl1—Cd1—Cl2	86.03 (3)	N1—C1—C2	123.2 (4)
Cl3—Cd1—Cl2	85.58 (3)	C2—C1—H1	118.4
Cl4—Cd1—Cl3	83.17 (3)	C1—C2—H2	120.7
Cl4—Cd1—Cl2	93.13 (3)	C3—C2—C1	118.6 (5)
N1—Cd1—Cl1	100.54 (9)	C3—C2—H2	120.7
N1—Cd1—Cl3	166.29 (9)	C2—C3—H3	120.4
N1—Cd1—Cl4	83.26 (9)	C2—C3—C4	119.3 (5)
N1—Cd1—Cl2	93.16 (9)	C4—C3—H3	120.4
N1—Cd1—N2	72.51 (12)	C3—C4—H4	120.6
N2—Cd1—Cl1	87.37 (8)	C3—C4—C5	118.8 (4)
N2—Cd1—Cl3	110.60 (9)	C5—C4—H4	120.6
N2—Cd1—Cl4	94.46 (8)	N1—C5—C4	122.0 (4)
N2—Cd1—Cl2	162.83 (8)	N1—C5—C6	118.1 (4)
Cl1—Cd2—Cl3ⁱⁱ	100.81 (3)	C4—C5—C6	119.9 (4)
Cl1—Cd2—Cl3ⁱ	176.84 (3)	N2—C6—C5	121.6 (4)
Cl1—Cd2—Cl2ⁱ	93.06 (3)	N2—C6—H6	119.2
Cl1—Cd2—Cl2	86.45 (3)	C5—C6—H6	119.2
Cl3ⁱⁱ—Cd2—Cl3ⁱ	81.21 (3)	C8—C7—N2	124.5 (4)
Cl3ⁱⁱ—Cd2—Cl2	172.42 (3)	C12—C7—N2	117.3 (4)
Cl4ⁱⁱ—Cd2—Cl1	94.45 (4)	C12—C7—C8	118.2 (4)
Cl4ⁱⁱ—Cd2—Cl3ⁱⁱ	85.18 (3)	C7—C8—H8	120.3
Cl4ⁱⁱ—Cd2—Cl3ⁱ	88.13 (3)	C9—C8—C7	119.3 (4)
Cl4ⁱⁱ—Cd2—Cl2ⁱ	172.49 (3)	C9—C8—H8	120.3
Cl4ⁱⁱ—Cd2—Cl2	96.53 (3)	C8—C9—H9	118.6
Cl2ⁱ—Cd2—Cl3ⁱ	84.37 (3)	C8—C9—C10	122.8 (4)
Cl2ⁱ—Cd2—Cl3ⁱⁱ	93.30 (3)	C10—C9—H9	118.6
Cl2—Cd2—Cl3ⁱ	91.45 (3)	C9—C10—C13	121.8 (4)
Cl2ⁱ—Cd2—Cl2	84.04 (3)	C11—C10—C9	116.5 (4)
Cd2—Cl1—Cd1	95.92 (4)	C11—C10—C13	121.7 (5)
Cd1—Cl3—Cd2ⁱⁱⁱ	93.50 (3)	C10—C11—H11	119.1
Cd1—Cl3—Cd2ⁱ	93.98 (3)	C10—C11—C12	121.7 (5)
Cd2ⁱⁱⁱ—Cl3—Cd2ⁱ	98.79 (3)	C12—C11—H11	119.1
Cd2ⁱⁱⁱ—Cl4—Cd1	97.59 (4)	C7—C12—C11	121.3 (4)
Cd1—Cl2—Cd2	91.47 (3)	C7—C12—H12	119.3
Cd2ⁱ—Cl2—Cd1	96.07 (3)	C11—C12—H12	119.3
Cd2ⁱ—Cl2—Cd2	95.96 (3)	C10—C13—H13A	109.5
C1—N1—Cd1	126.8 (3)	C10—C13—H13B	109.5
C1—N1—C5	118.1 (4)	C10—C13—H13C	109.5
C5—N1—Cd1	114.5 (3)	H13A—C13—H13B	109.5
C6—N2—Cd1	113.0 (3)	H13A—C13—H13C	109.5
C6—N2—C7	121.8 (3)	H13B—C13—H13C	109.5

Cd1—N1—C1—C2	−170.1 (4)	C3—C4—C5—C6	177.4 (4)
Cd1—N1—C5—C4	173.0 (3)	C4—C5—C6—N2	−173.4 (4)
Cd1—N1—C5—C6	−6.4 (5)	C5—N1—C1—C2	0.6 (7)
Cd1—N2—C6—C5	−2.2 (5)	C6—N2—C7—C8	−0.1 (6)
Cd1—N2—C7—C8	−177.5 (3)	C6—N2—C7—C12	178.0 (4)
Cd1—N2—C7—C12	0.5 (5)	C7—N2—C6—C5	−179.9 (4)
N1—C1—C2—C3	−1.4 (8)	C7—C8—C9—C10	−0.4 (7)
N1—C5—C6—N2	6.0 (6)	C8—C7—C12—C11	−0.6 (8)
N2—C7—C8—C9	177.5 (4)	C8—C9—C10—C11	2.6 (7)
N2—C7—C12—C11	−178.8 (5)	C8—C9—C10—C13	−176.4 (4)
C1—N1—C5—C4	1.2 (6)	C9—C10—C11—C12	−3.8 (8)
C1—N1—C5—C6	−178.3 (4)	C10—C11—C12—C7	2.9 (9)
C1—C2—C3—C4	0.5 (8)	C12—C7—C8—C9	−0.6 (7)
C2—C3—C4—C5	1.1 (7)	C13—C10—C11—C12	175.2 (5)
C3—C4—C5—N1	−2.0 (7)

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

Acknowledgements

We are grateful for the kind support provided by the Thammasat University Research Unit in Multifunctional Crystalline Materials and Applications (TU-McMa) and the Thailand Institute of Nuclear Technology (Public Organisation) through their TINT to University programme.

Funding information

Funding for this research was provided by: Faculty of Science and Technology, Thammasat University (contract No. SciGR6/2565).

References

Batten, S. R., Neville, S. M. & Turner, D. R. (2008). Coordination Polymers: Design, Analysis and Application. Cambridge: The Royal Society of Chemistry. Google Scholar
Biet, T. & Avarvari, N. (2014). CrystEngComm, 16, 6612–6620. CSD CrossRef CAS Google Scholar
Bruker (2019). APEX4 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397. Web of Science CrossRef CAS IUCr Journals Google Scholar
Chen, C.-L. & Beatty, A. M. (2007). Chem. Commun. pp. 76–78. Web of Science CSD CrossRef Google Scholar
Chen, K.-J., Perry Iv, J. J., Scott, H. S., Yang, Q.-Y. & Zaworotko, M. J. (2015). Chem. Sci. 6, 4784–4789. CSD CrossRef PubMed Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Freudenmann, D. & Feldmann, C. (2014). Dalton Trans. 43, 14109–14113. CSD CrossRef CAS PubMed Google Scholar
Gridley, B. M., Blundell, T. J., Moxey, J. G., Lewis, W., Blake, A. J. & Kays, D. L. (2013). Chem. Commun. 49, 9752–9754. CSD CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hu, J., Qi, J., Luo, Y., Yin, T., Wang, J., Wang, C., Li, W. & Liang, L. (2021). Arab. J. Chem. 14, 103117. CSD CrossRef Google Scholar
Jiajaroen, S., Dungkaew, W., Kielar, F., Sukwattanasinitt, M., Sahasithiwat, S., Zenno, H., Hayami, S., Azam, M., Al-Resayes, S. I. & Chainok, K. (2022). Dalton Trans. 51, 7420–7435. Web of Science CSD CrossRef CAS PubMed Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Li, A., Chamoreau, L.-M., Baptiste, B., Delbes, L., Li, Y., Lloret, F., Journaux, Y. & Lisnard, L. (2022). Cryst. Growth Des. 22, 7518–7526. CSD CrossRef CAS Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Mobin, M., Mishra, V., Chaudhary, A., Rai, D. K., Golov, A. A. & Mathur, P. (2014). Cryst. Growth Des. 14, 4124–4137. CSD CrossRef CAS Google Scholar
Ren, H.-Y., Han, C.-Y., Qu, M. & Zhang, X.-M. (2014). RSC Adv. 4, 49090–49097. CSD CrossRef CAS Google Scholar
Shang, W., Zhu, X., Liang, T., Du, C., Hu, L., Li, T. & Liu, M. (2020). Angew. Chem. Int. Ed. 59, 12811–12816. CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Wang, R.-Y., Huo, Q.-S., Yu, J.-H. & Xu, J.-Q. (2017). Polyhedron, 128, 160–168. CSD CrossRef CAS Google Scholar
Zhai, Q.-G., Gao, X., Li, S.-N., Jiang, Y.-C. & Hu, M.-C. (2011). CrystEngComm, 13, 1602–1616. CSD CrossRef CAS Google Scholar
Zhang, X., Yang, Q., Yun, M., Si, C., An, N., Jia, M., Liu, J. & Dong, X. (2020). Acta Cryst. B76, 1001–1017. CSD CrossRef IUCr Journals Google Scholar
Zhao, H.-Y., Yang, F.-L., Li, N. & Wang, X.-J. (2017). J. Mol. Struct. 1148, 62–72. CSD CrossRef CAS Google Scholar

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