Crystal structure of a cadmium sulfate coordination polymer based on the 3,6-bis­(pyrimidin-2-yl)-1,4-di­hydro-1,2,4,5-tetra­zine ligand

Jiajaroen, S.; Chainok, K.

doi:10.1107/S2056989020006830

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Volume 76| Part 6| June 2020| Pages 958-961

https://doi.org/10.1107/S2056989020006830

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Crystal structure of a cadmium sulfate coordination polymer based on the 3,6-bis(pyrimidin-2-yl)-1,4-dihydro-1,2,4,5-tetrazine ligand

Suwadee Jiajaroen ^a 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
^*Correspondence e-mail: kc@tu.ac.th

Edited by M. Weil, Vienna University of Technology, Austria (Received 7 February 2020; accepted 20 May 2020; online 29 May 2020)

The polymeric title compound, poly[aquahemi[μ₂-3,6-bis(pyrimidin-2-yl)-1,4-dihydro-1,2,4,5-tetrazine](μ₃-sulfato)cadmium(II)], [Cd(SO₄)(C₁₀H₈N₈)_0.5(H₂O)]_n, (I), represents an example of a three-dimensional coordination polymer resulting from the reaction of CdSO₄·8/3H₂O with 3,6-bis(pyrimidin-2-yl)-1,4-dihydro-1,2,4,5-tetrazine (H₂bmtz, C₁₀H₈N₈) under hydrothermal conditions. The Cd^II atom has a distorted octahedral coordination environment defined by two nitrogen atoms from one H₂bmtz ligand, three oxygen atoms from three different sulfate anions, and one oxygen atom from a coordinating water molecule. The 1,4-dihydro-1,2,4,5-tetrazine ring of the H₂bmtz ligand is located about an inversion center, with the NH group being equally disordered over two sites. The sulfate anion acts as a μ₃-bridging ligand to connect three Cd^II atoms, resulting in the formation of [Cd(SO₄)(H₂O)] sheets propagating parallel to the bc plane. Adjacent sheets are interconnected across the H₂bmtz ligands, which coordinate the Cd^II atoms in a bis-bidentate coordination mode, to form a three-dimensional framework structure. The framework is further stabilized by classical O—H⋯O hydrogen bonds involving the coordinating water molecules and the sulfate groups, and by N—H⋯O hydrogen bonds between the disordered tetrazine NH groups and sulfate oxygen atom, along with C—H⋯π and π–π stacking [centroid-to-centroid separation = 3.5954 (15) Å] interactions between parallel pyrimidine rings of the H₂bmtz ligand.

Keywords: crystal structure; coordination polymers; cadmium(II); bis-bidentate coordination mode; tetrazine.

CCDC reference: 2004950

1. Chemical context

Coordination polymers (CPs) are a class of organic–inorganic hybrid materials formed from metal ions or metal clusters and organic linkers through covalent bonds. The structural organization of CPs can result in chains, sheets or three-dimensional frameworks (Batten et al., 2009 ). These hybrid materials have received extensive attention over the past three decades owing to their structural features and useful applications in the fields of gas storage and separation, catalysis, chemical sensing, magnetism or proton conduction (Furukawa et al., 2010 ; Ye & Johnson, 2016 ; Espallargas & Coronado, 2018 ; Xu et al., 2016 ; Zhang et al., 2017 ). Nowadays, many multi-dimensional CPs with structural and topological diversity have been synthesized through the tremendous possibilities of choices for building blocks, and some of them seem promising as candidate materials, for instance, in gas purification (Duan et al., 2015 ). In the context of the crystal engineering of CPs, the most feasible strategy for the construction of such infinite hybrid networks is by the careful selection of metal coordination arrangements and suitable organic linkers. Among the most common ligands, the rigid organic carboxylate- and pyridyl-based ligands have by far been the most widely used to control the structural motifs of these solids (Glöckle et al., 2001 ).

In this work, to explore the synthesis of novel CPs using 3,6-bis(pyrimidin-2-yl)-1,4-dihydro-1,2,4,5-tetrazine, C₁₀H₈N₈ or H₂bmtz (Kaim & Fees, 1995 ; Chainok et al., 2012 ) as a polydentate nitrogen-donor ligand with cadmium(II) sulfate, a new CP [Cd(SO₄)(H₂bmtz)_0.5(H₂O)]_n (I) was isolated under hydrothermal conditions. The crystal structure and supramolecular interactions of (I) are reported herein.

2. Structural commentary

The asymmetric unit of the title compound consists of one Cd^II cation, one-half of the H₂bmtz ligand, one sulfate anion and one coordinating water molecule. The 1,4-dihydro-1,2,4,5-tetrazine ring of the H₂bmtz ligand is located about an inversion centre, with the NH group (N4) being equally disordered over two sites. As shown in Fig. 1, the Cd^II atom exhibits a distorted octahedral [CdN₂O₄] coordination environment with two nitrogen atoms from the H₂bmtz ligand, three oxygen atoms from three different sulfate anions and one oxygen atom from the coordinating water molecule. The bond angles around the central Cd^II atom range from 69.69 (5) to 168.46 (5)°. The Cd—O and Cd—N bond lengths fall in the range of 2.2321 (12)–2.3790 (13) Å, which is comparable with those of reported cadmium(II) sulfate compounds containing additional nitrogen donor ligands such as [Cd₂(SO₄)₂(C₁₆H₁₂N₆)₂(H₂O)₂]·4H₂O (GADLON; Harvey et al., 2003 ), [Cd₂(C₂H₃O₂)₂(S₂O₈)(C₁₅H₁₁N₂)₂(H₂O)₂]·7H₂O (FOMBUF; Díaz de Vivar et al., 2005 ) and [Cd₂(C₁₅H₉N₉)(H₂O)₆(SO₄)₂]·H₂O (DIQCOX; Safin et al., 2013 ). The complete H₂bmtz molecule is not planar (r.m.s. deviation = 0.111 Å) with the central six-membered ring of the 1,4-dihydro-1,2,4,5-tetrazine moiety in a twist-boat conformation; the C5—N3—N4Aⁱ—C5ⁱ torsion angle is 36.4 (4)° [symmetry code: (i) 2 − x, 1 − y, 1 − z]. The sulfate anion acts as a μ₃-bridging ligand to connect three Cd^II atoms to form a sheet-like structure of [Cd(SO₄)(H₂O)] units, propagating parallel to the bc plane, Fig. 2. Adjacent sheets are interconnected across the H₂bmtz ligands, which exhibit a bis-bidentate coordination mode, giving rise to a three-dimensional framework structure, Fig. 3.

Figure 1
Molecular structure of (I), showing the atom-labelling scheme. Only one orientation of the disordered N4—H group is shown. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (ii) 1 − x, 1 − y, 1 − z].

Figure 2
View of the [Cd(SO₄)(H₂O)] sheet in (I) propagating parallel to the bc plane. Classical O—H⋯O hydrogen-bonding interactions are shown as dashed lines.

Figure 3
Packing diagram of (I), showing N—H⋯O hydrogen bonding as dashed lines.

3. Supramolecular features

In the crystal, classical O—H⋯O hydrogen bonds exist between the coordinating water molecules and the sulfate groups, and N—H⋯O hydrogen bonds involving the disordered tetrazine NH group and sulfate oxygen atoms. In this way, rings with R₁¹(8) and R₄⁴(16) graph-set motifs are formed, Table 1. Additionally, C—H⋯π [H⋯Cg = 3.34 (2) Å; Cg is the centroid of the pyrimidine ring] and π–π stacking [centroid-to-centroid separation = 3.5954 (15) Å, slippage between parallel pyrimidine rings = 1.131 Å] interactions between the pyrimidine rings of the H₂bmtz ligand are also observed, Fig. 4.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/N2/C1–C4 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3ⁱ	0.84 (2)	1.92 (2)	2.710 (2)	159 (2)
O1—H1B⋯O4ⁱⁱ	0.84 (2)	1.91 (2)	2.743 (2)	174 (3)
N4A—H4A⋯O3ⁱⁱⁱ	0.87 (2)	2.09 (2)	2.889 (3)	153 (2)
N4B—H4A⋯O3ⁱⁱⁱ	0.87 (2)	2.09 (2)	2.828 (3)	143 (2)
C2—H2⋯Cg1^iv	0.93	3.34 (2)	4.091 (3)	140 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y-1, z; (iii) -x+2, -y+1, -z+1; (iv) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 4
Partial packing diagram of (I), showing C—H⋯π and π–π stacking interactions (dashed lines) between the H₂bmtz ligands.

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.41, November 2019 update; Groom et al., 2016 ) gave only two hits for H₂bmtz complexes with transition metals ions, viz. with Cu^I (QORNAM; Glöckle et al., 2001) and Ag^I (ZASTAQ; Chainok et al., 2012). In these structures, the coordination mode of the H₂bmtz ligands is bis-bidentate through nitrogen atoms.

5. Synthesis and crystallization

All reagents were of analytical grade and were used as received without further purification. The ligand 3,6-bis(pyrimidin-2-yl)-1,4-dihydro-1,2,4,5-tetrazine was synthesized according to a literature method (Kaim & Fees, 1995). A mixture solution of CdSO₄·8/3H₂O (41.7 mg, 0.2 mmol) and the H₂bmtz ligand (36.7 mg, 0.1 mmol) in water (5 ml) was added into a 15 ml Teflon-lined reactor, stirred at room temperature for 10 min, sealed in a stainless steel autoclave and placed in an oven. The mixture was heated to 383 K under autogenous pressure for 48 h, and then cooled down to room temperature. After filtration, brown block-shaped crystals were obtained in 80% yield (33.4 mg) based on the cadmium(II) source.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Nitrogen atom N4 of the 1,4-dihydro-1,2,4,5-tetrazine ring was found to be disordered about an inversion centre; restraints (SADI and RIGU with esd 0.001 Å²) were used for its refinement. All hydrogen atoms were found in difference-Fourier maps. H atoms attached to C atoms were refined in the riding-model approximation with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The H atoms bound to O or N atoms were refined with distance restraints of O—H = 0.84 ± 0.01 Å and N—H = 0.86 ± 0.01 Å and with U_iso(H) = 1.5U_eq(O) and 1.2U_eq(N), respectively.

Table 2
Experimental details

Crystal data
Chemical formula	[Cd(SO₄)(C₁₀H₈N₈)_0.5(H₂O)]
M_r	346.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.3000 (3), 7.9798 (2), 13.2586 (4)
β (°)	106.872 (1)
V (Å³)	941.60 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.56
Crystal size (mm)	0.28 × 0.24 × 0.18

Data collection
Diffractometer	Bruker D8 QUEST CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.660, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	24280, 2357, 2338
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.014, 0.037, 1.12
No. of reflections	2357
No. of parameters	167
No. of restraints	11
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.37
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2004950

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020006830/wm5546sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020006830/wm5546Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020006830/wm5546Isup3.cdx

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).

Poly[aquahemi[µ₂-3,6-bis(pyrimidin-2-yl)-1,4-dihydro-1,2,4,5-tetrazine](µ₃-sulfato)cadmium(II)] top

Crystal data top

[Cd(SO₄)(C₁₀H₈N₈)_0.5(H₂O)]	F(000) = 672
M_r = 346.60	D_x = 2.445 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.3000 (3) Å	Cell parameters from 9940 reflections
b = 7.9798 (2) Å	θ = 3.4–28.4°
c = 13.2586 (4) Å	µ = 2.56 mm⁻¹
β = 106.872 (1)°	T = 296 K
V = 941.60 (5) Å³	Block, brown
Z = 4	0.28 × 0.24 × 0.18 mm

Data collection top

Bruker D8 QUEST CMOS diffractometer	2357 independent reflections
Radiation source: sealed x-ray tube	2338 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 7.39 pixels mm^-1	θ_max = 28.4°, θ_min = 3.2°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −10→10
T_min = 0.660, T_max = 0.746	l = −17→17
24280 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)] = 0.014	w = 1/[σ²(F_o²) + (0.0176P)² + 0.6173P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.037	(Δ/σ)_max = 0.002
S = 1.12	Δρ_max = 0.41 e Å⁻³
2357 reflections	Δρ_min = −0.37 e Å⁻³
167 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
11 restraints	Extinction coefficient: 0.0013 (3)
Primary atom site location: dual

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	Occ. (<1)
Cd1	0.61850 (2)	0.31497 (2)	0.37692 (2)	0.01977 (5)
S1	0.46994 (4)	0.71617 (4)	0.38900 (3)	0.01921 (8)
O1	0.40176 (15)	0.17176 (15)	0.34420 (10)	0.0290 (2)
H1A	0.378 (3)	0.170 (3)	0.4004 (13)	0.046 (7)*
H1B	0.408 (3)	0.0706 (15)	0.329 (2)	0.049 (7)*
O2	0.49134 (16)	0.55557 (15)	0.34172 (10)	0.0389 (3)
O3	0.61350 (13)	0.77844 (18)	0.45697 (10)	0.0327 (3)
O4	0.40858 (15)	0.83595 (14)	0.30158 (9)	0.0276 (2)
O5	0.35993 (14)	0.70011 (18)	0.44827 (9)	0.0338 (3)
N1	0.81264 (15)	0.12667 (17)	0.37110 (10)	0.0254 (3)
N2	1.07599 (16)	0.1093 (2)	0.39678 (13)	0.0342 (3)
N3	0.85731 (15)	0.44436 (17)	0.44639 (13)	0.0321 (3)
N4A	1.1157 (3)	0.4194 (4)	0.4718 (3)	0.0326 (6)	0.5
H4A	1.180 (2)	0.345 (3)	0.5064 (15)	0.070 (9)*
N4B	1.1132 (3)	0.3849 (4)	0.5340 (3)	0.0320 (6)	0.5
C1	0.7954 (2)	−0.0244 (2)	0.32666 (14)	0.0337 (4)
H1	0.699820	−0.071019	0.303463	0.040*
C2	0.9168 (2)	−0.1135 (3)	0.31425 (17)	0.0427 (4)
H2	0.904140	−0.217907	0.281657	0.051*
C3	1.0573 (2)	−0.0420 (3)	0.35194 (17)	0.0410 (4)
H3	1.140880	−0.100588	0.345972	0.049*
C4	0.95337 (18)	0.18608 (18)	0.40350 (13)	0.0243 (3)
C5	0.97378 (19)	0.3543 (2)	0.45278 (17)	0.0354 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01945 (7)	0.02157 (7)	0.01864 (7)	0.00090 (3)	0.00607 (4)	0.00089 (3)
S1	0.02314 (16)	0.01938 (15)	0.01601 (15)	0.00267 (12)	0.00708 (12)	0.00085 (12)
O1	0.0335 (6)	0.0267 (6)	0.0300 (6)	−0.0058 (4)	0.0145 (5)	−0.0068 (4)
O2	0.0544 (8)	0.0226 (6)	0.0341 (6)	0.0142 (5)	0.0042 (6)	−0.0037 (5)
O3	0.0235 (5)	0.0464 (7)	0.0285 (6)	−0.0025 (5)	0.0081 (5)	−0.0066 (5)
O4	0.0458 (7)	0.0195 (5)	0.0182 (5)	0.0052 (5)	0.0102 (5)	0.0032 (4)
O5	0.0249 (6)	0.0580 (8)	0.0200 (5)	−0.0031 (5)	0.0090 (4)	0.0059 (5)
N1	0.0235 (6)	0.0253 (6)	0.0262 (6)	0.0015 (5)	0.0053 (5)	−0.0010 (5)
N2	0.0250 (6)	0.0319 (7)	0.0456 (8)	0.0029 (6)	0.0101 (6)	−0.0042 (6)
N3	0.0208 (6)	0.0213 (6)	0.0537 (9)	−0.0026 (5)	0.0101 (6)	−0.0076 (6)
N4A	0.0192 (11)	0.0255 (14)	0.0529 (19)	−0.0017 (10)	0.0102 (12)	−0.0135 (14)
N4B	0.0227 (12)	0.0210 (13)	0.0506 (18)	−0.0004 (10)	0.0079 (11)	−0.0084 (13)
C1	0.0292 (8)	0.0321 (8)	0.0356 (9)	−0.0019 (7)	0.0025 (7)	−0.0077 (7)
C2	0.0421 (10)	0.0341 (9)	0.0480 (11)	0.0047 (8)	0.0067 (8)	−0.0178 (8)
C3	0.0331 (9)	0.0400 (10)	0.0498 (11)	0.0091 (8)	0.0119 (8)	−0.0117 (8)
C4	0.0235 (7)	0.0233 (7)	0.0262 (7)	0.0011 (5)	0.0072 (6)	0.0009 (5)
C5	0.0203 (7)	0.0228 (7)	0.0613 (11)	−0.0022 (6)	0.0087 (7)	−0.0069 (7)

Geometric parameters (Å, º) top

Cd1—O1	2.2472 (12)	N2—C4	1.320 (2)
Cd1—O2	2.2321 (12)	N3—N4Aⁱⁱⁱ	1.505 (3)
Cd1—O4ⁱ	2.3122 (11)	N3—N4Bⁱⁱⁱ	1.399 (3)
Cd1—O5ⁱⁱ	2.2708 (12)	N3—C5	1.282 (2)
Cd1—N1	2.3674 (13)	N4A—H4A	0.871 (10)
Cd1—N3	2.3790 (13)	N4A—C5	1.372 (3)
S1—O2	1.4653 (12)	N4B—H4A	0.866 (10)
S1—O3	1.4640 (12)	N4B—C5	1.445 (3)
S1—O4	1.4828 (11)	C1—H1	0.9300
S1—O5	1.4654 (12)	C1—C2	1.384 (3)
O1—H1A	0.835 (10)	C2—H2	0.9300
O1—H1B	0.839 (10)	C2—C3	1.379 (3)
N1—C1	1.331 (2)	C3—H3	0.9300
N1—C4	1.340 (2)	C4—C5	1.481 (2)
N2—C3	1.335 (2)

O1—Cd1—O4ⁱ	90.81 (5)	C4—N2—C3	116.51 (15)
O1—Cd1—O5ⁱⁱ	88.77 (5)	N4Aⁱⁱⁱ—N3—Cd1	122.32 (13)
O1—Cd1—N1	108.71 (5)	N4Bⁱⁱⁱ—N3—Cd1	127.25 (15)
O1—Cd1—N3	168.46 (5)	C5—N3—Cd1	117.26 (11)
O2—Cd1—O1	90.34 (5)	C5—N3—N4Aⁱⁱⁱ	113.35 (17)
O2—Cd1—O4ⁱ	80.21 (5)	C5—N3—N4Bⁱⁱⁱ	114.67 (17)
O2—Cd1—O5ⁱⁱ	98.25 (5)	N3ⁱⁱⁱ—N4A—H4A	99.5 (18)
O2—Cd1—N1	154.41 (5)	C5—N4A—N3ⁱⁱⁱ	110.9 (2)
O2—Cd1—N3	94.94 (5)	C5—N4A—H4A	108.3 (19)
O4ⁱ—Cd1—N1	82.54 (5)	N3ⁱⁱⁱ—N4B—H4A	108.1 (19)
O4ⁱ—Cd1—N3	100.19 (5)	N3ⁱⁱⁱ—N4B—C5	112.9 (2)
O5ⁱⁱ—Cd1—O4ⁱ	178.41 (4)	C5—N4B—H4A	102.7 (18)
O5ⁱⁱ—Cd1—N1	99.05 (5)	N1—C1—H1	119.3
O5ⁱⁱ—Cd1—N3	80.32 (5)	N1—C1—C2	121.38 (16)
N1—Cd1—N3	69.69 (5)	C2—C1—H1	119.3
O2—S1—O4	107.38 (7)	C1—C2—H2	121.2
O2—S1—O5	110.83 (9)	C3—C2—C1	117.63 (17)
O3—S1—O2	110.33 (8)	C3—C2—H2	121.2
O3—S1—O4	109.74 (8)	N2—C3—C2	121.52 (17)
O3—S1—O5	110.69 (7)	N2—C3—H3	119.2
O5—S1—O4	107.78 (7)	C2—C3—H3	119.2
Cd1—O1—H1A	106.8 (18)	N1—C4—C5	116.76 (14)
Cd1—O1—H1B	114.6 (17)	N2—C4—N1	126.64 (15)
H1A—O1—H1B	105 (2)	N2—C4—C5	116.60 (15)
S1—O2—Cd1	142.41 (8)	N3—C5—N4A	123.30 (19)
S1—O4—Cd1^iv	131.02 (7)	N3—C5—N4B	120.8 (2)
S1—O5—Cd1ⁱⁱ	133.11 (8)	N3—C5—C4	118.78 (15)
C1—N1—Cd1	126.47 (11)	N4A—C5—C4	114.68 (18)
C1—N1—C4	116.31 (14)	N4B—C5—C4	117.02 (18)
C4—N1—Cd1	116.63 (10)

Cd1—N1—C1—C2	170.31 (15)	N2—C4—C5—N3	169.24 (18)
Cd1—N1—C4—N2	−172.52 (14)	N2—C4—C5—N4A	8.9 (3)
Cd1—N1—C4—C5	8.10 (19)	N2—C4—C5—N4B	−31.3 (3)
Cd1—N3—C5—N4A	167.1 (2)	N3ⁱⁱⁱ—N4A—C5—N3	40.7 (4)
Cd1—N3—C5—N4B	−150.1 (2)	N3ⁱⁱⁱ—N4A—C5—C4	−160.0 (2)
Cd1—N3—C5—C4	8.5 (2)	N3ⁱⁱⁱ—N4B—C5—N3	−38.9 (4)
O2—S1—O4—Cd1^iv	−10.01 (13)	N3ⁱⁱⁱ—N4B—C5—C4	162.2 (2)
O2—S1—O5—Cd1ⁱⁱ	103.95 (11)	N4Aⁱⁱⁱ—N3—C5—N4A	−41.6 (4)
O3—S1—O2—Cd1	38.91 (17)	N4Aⁱⁱⁱ—N3—C5—C4	159.9 (2)
O3—S1—O4—Cd1^iv	109.93 (10)	N4Bⁱⁱⁱ—N3—C5—N4B	39.5 (4)
O3—S1—O5—Cd1ⁱⁱ	−18.81 (14)	N4Bⁱⁱⁱ—N3—C5—C4	−161.9 (2)
O4—S1—O2—Cd1	158.47 (14)	C1—N1—C4—N2	−0.8 (3)
O4—S1—O5—Cd1ⁱⁱ	−138.82 (10)	C1—N1—C4—C5	179.83 (16)
O5—S1—O2—Cd1	−84.06 (16)	C1—C2—C3—N2	−1.5 (3)
O5—S1—O4—Cd1^iv	−129.45 (10)	C3—N2—C4—N1	0.9 (3)
N1—C1—C2—C3	1.5 (3)	C3—N2—C4—C5	−179.74 (18)
N1—C4—C5—N3	−11.3 (3)	C4—N1—C1—C2	−0.5 (3)
N1—C4—C5—N4A	−171.7 (2)	C4—N2—C3—C2	0.3 (3)
N1—C4—C5—N4B	148.1 (2)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/N2/C1–C4 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ⁱⁱ	0.84 (2)	1.92 (2)	2.710 (2)	159 (2)
O1—H1B···O4^v	0.84 (2)	1.91 (2)	2.743 (2)	174 (3)
N4A—H4A···O3ⁱⁱⁱ	0.87 (2)	2.09 (2)	2.889 (3)	153 (2)
N4B—H4A···O3ⁱⁱⁱ	0.87 (2)	2.09 (2)	2.828 (3)	143 (2)
C2—H2···Cg1^vi	0.93	3.34 (2)	4.091 (3)	140 (2)

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

Acknowledgements

The authors thank the Faculty of Science and Technology, Thammasat University, for funds to purchase the X-ray diffractometer.

Funding information

Funding for this research was provided by: Thailand Research Fund (contract No. RSA5780056 to KC); The Research Professional Development Project Under the Science Achievement Scholarship of Thailand (SAST) (award to SJ).

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