research communications
Synthesis and 2(C3H2N3O3)4(H2O)8]
of a heterobimetallic cadmium–sodium complex of 1,3,5-triazine-2,4,6-trione, [CdNaaPG Department and Research Centre in Physics, M.G. College, University of Kerala, Thiruvananthapuram 695004, India, and bDepartment of Chemistry, Faculty of Science, Eastern University, Sri Lanka, Chenkalady, Sri Lanka
*Correspondence e-mail: msithambaresan@gmail.com
Heterobimetallic crystals of a cadmium–sodium complex of 1,3,5-triazine-2,4,6-trione, namely, μ-aqua-1:2κ2O:O-heptaaqua-1κ3O,2κ2O,3κ2O-bis(μ-4,6-dioxo-1,4,5,6-tetrahydro-1,3,5-triazin-2-olato)-1:2κ2O2:N1;2:3κ2N1:O2-bis(4,6-dioxo-1,4,5,6-tetrahydro-1,3,5-triazin-2-olato)-1κO2,3κO2-2-cadmium-1,3-disodium, [CdNa2(C3H2N3O3)4(H2O)8], were grown by the single gel diffusion technique. The of the title compound comprises four 1,3,5-triazine-2,4,6-trione ligands, two sodium atoms and one cadmium atom. Of the four ligands, two are monodentately coordinated to two Na atoms. The third ligand is coordinated bidentately to one Na and the Cd atom and the fourth is also coordinated bidentately to the Cd atom and the other Na atom. All the metal atoms are six-coordinate with a distorted octahedral geometry. The water molecules bridge the Na atoms, constructing coordination polymer chains along the a axis and hence are linked by two Cd and one Na coordinations through the cyanuric acid ligands present in the coordination polymer chains, generating a two-dimensional coordination polymer in the (110) plane. The polymer formation is further assisted by means of many intermolecular and intramolecular N—H⋯O, O—H⋯O and O–H⋯N hydrogen bonds between the water molecules and the ligands.
Keywords: crystal structure; heterobimetallic cadmium–sodium complex; gel growth; 1,3,5 triazine-2,4,6-trione; two-dimensional coordination polymer.
CCDC reference: 1576691
1. Chemical context
etc. In addition, reactions are utilized in the determination of cadmium toxicity (Flora & Pachauri, 2010) with 1,3,5-triazine-2,4,6-trione, also known as cyanuric acid, being the preferred ligand used for the as it has multiple hydrogen-bond donor centres (Mistri et al., 2014). 1,3,5-Triazine-2,4,6-trione exists in either the keto or enol form but the most stable isomer is the keto form (Reva, 2015). In this work, we report the of a heterobimetallic cadmium and sodium complex of 1,3,5-triazine-2,4,6-trione.
is considered as the preferred method for the reduction of toxic effects of heavy metals, in which the metals are removed in the form of stable complex chelates. Cadmium, one of the most toxic heavy metals, can accumulate in the human body, leading to renal dysfunction, lung cancer,2. Structural commentary
The title complex crystallizes in the triclinic P. Fig. 1 shows the of the crystal, which consists of four cyanuric acid ligands, two sodium atoms (Na1 and Na2) and one cadmium atom. Of the four ligands, two are monodentately coordinated to Na1 and Na2 atoms each. The third ligand is coordinated bidentately to Na1 and Cd1 atoms and the fourth one also coordinated bidentately to Na2 and Cd1 atoms. The sodium atom Na2 is coordinated to oxygen atoms of two cyanuric acid ligands [O5—Na2—O14 = 94.52 (6)°]. The Na1 atom is also coordinated to oxygen atoms of two cyanuric acid ligands [O10—Na1—O13 = 173.39 (7)°]. The Cd1 atom is coordinated to nitrogen atoms of two cyanuric acid ligands [N1—Cd1—N4 = 174.58 (6)]°. In addition to the ligand coordination, atoms Na1, Na2 and Cd1 are also coordinated by two, three and four water molecules, respectively.
The title compound forms a two dimensional coordination polymer. In the coordination environment of the polymer, the Na1 atom is six-coordinate with the coordination angle varying from 90° [78.82 (6)–90.60 (6)°], forming a distorted octahedral geometry. Atom Na2 also exhibits a distorted octahedral geometry, with the coordination angles ranging from 77.17 (6) to 91.77 (6)°. The cadmium atom also shows a distorted octahedral geometry with coordination angles in the range 87.94 (5) to 95.46 (6)°. A similar geometry is observed for the Cd atom in the heterobimetallic compound tetraaquabis(malonato)cadmium(II)copper(II) (Dhanya et al., 2014). Na1—O bond distances [2.3471 (16) to 2.4195 (18) Å] show a decrease compared to the value reported for a free Na—O bond (2.421 Å; Brown & Shannon, 1973). The Na2—O bonds, which vary from 2.3067 (17) to 2.4997 (18) Å, are longer than the reported value for a free Na—O bond. This observed range of Na—O bonds also shows close agreement with values reported for sodium 2-aminoterephthalate where the sodium atom adopts a similar six-coordinate geometry (2.326–2.505 Å; Sienkiewicz-Gromiuk et al., 2012). The Cd1—N4 bond distance [2.3210 (15) Å] is comparable to the reported value in a similar coordinated geometry (2.324 Å; Hashemian & Mangeli, 2017). The water molecules are tetrahedrally coordinated to the cadmium atom, forming bond angles ranging from 81.59 (5) to 111.45 (5)°. Three water molecules are coordinated to Na2, with bond angles ranging from 85.43 (6) to 102.25 (7)°. Two water molecules are coordinated to Na1, forming a bond angle of 170.94 (7)°. The two water molecules coordinated to Na1 bridge adjacent Na1 atoms on both sides, forming a coordination polymer chain along the a axis. These chains are interconnected by means of two Cd1 and Na2 coordinations through the cyanuric acid ligands present in the Na1 coordination polymer chain on both sides to build a 2D coordination polymer in the (110) plane.
3. Supramolecular features
There are 25 intramolecular and intermolecular hydrogen-bonding interactions involving the ligands and the coordinated water molecules with D⋯A distances ranging from 2.716 (2) to 3.236 (2) Å (Table 1). Two types of π–π interactions (Table 2) occur between the cyanurate rings of different units, having centroid–centroid distances of 3.5174 (12) and 3.4893 (11) Å, and two types of C—O⋯π interactions (Table 3) with different cyanurate rings with X⋯Cg distances of 3.6086 (2) and 3.4783 (2) Å are also present in the complex (Fig. 2). A packing diagram is presented in Fig. 3.
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4. Synthesis and crystallization
Needle-shaped transparent single crystals were obtained by the single gel diffusion method (Chandran et al., 2017). 1,3,5-Triazine-2,4,6-trione, acetic acid, sodium metasilicate and cadmium chloride hydrate were used for the growth in a single glass test tube of length 20 cm and diameter 2.5 cm. The preparation of silica gel of specific gravity 1.03–1.05 g cm−3 involved dissolution of sodium metasilicate (SMS) in double-distilled water to which 1,3,5-triazine-2,4,6-trione (0.01–0.02 M concentration) was added. The resulting SMS solution was acidified with drops of glacial acetic acid to adjust the pH to within the range 4–7. The test tubes were filled with 30 ml of the above solution for gel setting. Over the set gel, cadmium chloride solution (0.25–1 M) was added carefully along the sides of the test tube to prevent the gel breakage. Finally, the test tube was sealed with a transparent plastic sheet to prevent contamination and kept undisturbed for crystal growth. Crystals formed within the gel after two weeks and growth was completed in a month. A series of trials was undertaken to obtain the optimum conditions to grow well-defined single crystals. 1,3,5-Triazine-2,4,6-trione (0.02 M) was used as inner reactant and cadmium chloride (0.25 M) as the top solution. Well-defined good-quality single crystals suitable for single-crystal XRD studies were grown in a gel medium of pH 6 and density 1.03 g cm−3.
5. Refinement
Crystal data, data collection and structure . Some reflections truncated by beamstop were omitted. The nitrogen-bound H atoms were placed in calculated positions (N—H = 0.86 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2Ueq(N). H atoms attached to water molecules were located from difference-Fourier maps and were refined with isotropic displacement parameters [Uiso(H) = 1.5Ueq(O)].
details are summarized in Table 4
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Supporting information
CCDC reference: 1576691
https://doi.org/10.1107/S2056989021008148/jy2009sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021008148/jy2009Isup2.hkl
Data collection: APEX3 (Bruker, 2016); cell
APEX3 and SAINT (Bruker, 2016); data reduction: SAINT andXPREP (Bruker, 2016); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015b).[CdNa2(C3H2N3O3)4(H2O)8] | Z = 2 |
Mr = 814.81 | F(000) = 820 |
Triclinic, P1 | Dx = 2.016 Mg m−3 |
a = 7.0501 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.0314 (5) Å | Cell parameters from 9962 reflections |
c = 19.5058 (9) Å | θ = 3.1–29.6° |
α = 101.023 (1)° | µ = 0.96 mm−1 |
β = 90.468 (1)° | T = 293 K |
γ = 97.233 (1)° | Block, colourless |
V = 1342.53 (11) Å3 | 0.15 × 0.10 × 0.10 mm |
Bruker Kappa APEX3 CMOS diffractometer | 5912 independent reflections |
Radiation source: fine-focus sealed tube | 5460 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω and φ scan | θmax = 27.2°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −9→9 |
Tmin = 0.870, Tmax = 0.901 | k = −12→12 |
52745 measured reflections | l = −25→25 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.063 | w = 1/[σ2(Fo2) + (0.0277P)2 + 0.9925P] where P = (Fo2 + 2Fc2)/3 |
S = 1.20 | (Δ/σ)max = 0.001 |
5912 reflections | Δρmax = 0.88 e Å−3 |
430 parameters | Δρmin = −0.57 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8025 (3) | 0.33005 (19) | 0.28213 (10) | 0.0172 (4) | |
C2 | 0.8168 (3) | 0.4798 (2) | 0.39643 (11) | 0.0216 (4) | |
C3 | 0.6821 (3) | 0.24087 (19) | 0.37866 (10) | 0.0172 (4) | |
C4 | 0.5623 (3) | −0.32929 (19) | 0.20544 (10) | 0.0160 (4) | |
C5 | 0.6255 (3) | −0.4699 (2) | 0.09476 (10) | 0.0194 (4) | |
C6 | 0.6837 (3) | −0.22094 (19) | 0.11527 (10) | 0.0157 (4) | |
C7 | 0.9520 (3) | 0.33435 (19) | −0.20488 (10) | 0.0157 (4) | |
C8 | 0.8810 (3) | 0.4855 (2) | −0.09848 (10) | 0.0190 (4) | |
C9 | 0.8168 (3) | 0.23791 (19) | −0.11439 (10) | 0.0158 (4) | |
C10 | 0.1780 (3) | 0.23787 (19) | 0.37549 (10) | 0.0166 (4) | |
C11 | 0.3200 (3) | 0.4760 (2) | 0.39865 (11) | 0.0213 (4) | |
C12 | 0.3021 (3) | 0.3339 (2) | 0.28316 (10) | 0.0170 (4) | |
N1 | 0.7207 (2) | 0.22287 (16) | 0.30988 (8) | 0.0169 (3) | |
N2 | 0.7326 (3) | 0.36898 (17) | 0.42028 (9) | 0.0226 (4) | |
H2 | 0.709160 | 0.378905 | 0.464036 | 0.027* | |
N3 | 0.8481 (3) | 0.45615 (17) | 0.32672 (9) | 0.0215 (4) | |
H3 | 0.899616 | 0.523714 | 0.309038 | 0.026* | |
N4 | 0.6247 (2) | −0.21351 (16) | 0.18213 (8) | 0.0152 (3) | |
N5 | 0.5607 (2) | −0.45516 (16) | 0.16086 (8) | 0.0187 (3) | |
H5 | 0.516292 | −0.527734 | 0.175881 | 0.022* | |
N6 | 0.6887 (3) | −0.35041 (17) | 0.07445 (8) | 0.0195 (3) | |
H6 | 0.734942 | −0.354974 | 0.033533 | 0.023* | |
N7 | 0.8839 (2) | 0.22246 (16) | −0.17957 (8) | 0.0172 (3) | |
N8 | 0.9513 (2) | 0.46392 (16) | −0.16400 (9) | 0.0187 (3) | |
H8 | 0.997548 | 0.533894 | −0.180868 | 0.022* | |
N9 | 0.8147 (3) | 0.36876 (17) | −0.07555 (9) | 0.0203 (4) | |
H9 | 0.768803 | 0.376704 | −0.034471 | 0.024* | |
N10 | 0.3519 (3) | 0.45707 (17) | 0.32895 (9) | 0.0215 (4) | |
H10 | 0.406119 | 0.525452 | 0.312499 | 0.026* | |
N11 | 0.2119 (2) | 0.22607 (17) | 0.30703 (9) | 0.0188 (3) | |
N12 | 0.2315 (3) | 0.36306 (17) | 0.41995 (9) | 0.0219 (4) | |
H12 | 0.207301 | 0.369553 | 0.463517 | 0.026* | |
O1 | 0.9770 (2) | 0.03762 (14) | 0.20860 (7) | 0.0215 (3) | |
H1A | 1.065349 | 0.092864 | 0.245551 | 0.032* | |
H1B | 1.036161 | −0.047201 | 0.203744 | 0.032* | |
O2 | 0.4449 (2) | 0.06725 (15) | 0.18140 (8) | 0.0256 (3) | |
H2A | 0.363198 | −0.014609 | 0.156501 | 0.038* | |
H2B | 0.391157 | 0.153416 | 0.196860 | 0.038* | |
O3 | 0.8349 (2) | −0.08797 (15) | 0.33509 (8) | 0.0241 (3) | |
H3A | 0.939632 | −0.020504 | 0.358856 | 0.036* | |
H3B | 0.901723 | −0.163676 | 0.311768 | 0.036* | |
O4 | 0.3757 (2) | −0.08155 (17) | 0.30812 (8) | 0.0290 (3) | |
H4A | 0.369042 | −0.181741 | 0.301003 | 0.044* | |
H4B | 0.265442 | −0.057541 | 0.284123 | 0.044* | |
O5 | 0.6035 (2) | 0.14863 (15) | 0.40559 (8) | 0.0280 (3) | |
O6 | 0.8599 (3) | 0.59241 (16) | 0.43440 (8) | 0.0368 (4) | |
O7 | 0.8382 (2) | 0.32046 (15) | 0.21994 (8) | 0.0269 (3) | |
O8 | 0.5039 (2) | −0.32832 (15) | 0.26519 (8) | 0.0262 (3) | |
O9 | 0.6280 (3) | −0.58152 (15) | 0.05625 (8) | 0.0312 (4) | |
O10 | 0.7346 (2) | −0.11970 (15) | 0.09073 (8) | 0.0241 (3) | |
O11 | 1.0167 (2) | 0.32568 (15) | −0.26437 (8) | 0.0246 (3) | |
O12 | 0.8765 (3) | 0.59950 (15) | −0.06270 (8) | 0.0308 (4) | |
O13 | 0.7540 (2) | 0.13948 (15) | −0.08785 (8) | 0.0236 (3) | |
O14 | 0.1013 (2) | 0.14177 (14) | 0.40139 (8) | 0.0227 (3) | |
O15 | 0.3689 (3) | 0.58556 (16) | 0.43856 (8) | 0.0353 (4) | |
O16 | 0.3458 (2) | 0.32703 (15) | 0.22117 (7) | 0.0248 (3) | |
O17 | 0.5338 (2) | 0.13908 (16) | 0.05424 (9) | 0.0313 (4) | |
H17A | 0.559228 | 0.239151 | 0.059155 | 0.047* | |
H18A | 1.002488 | −0.103967 | −0.120403 | 0.047* | |
O18 | 0.9774 (2) | −0.12084 (16) | −0.07304 (8) | 0.0295 (4) | |
H18B | 0.956220 | −0.221324 | −0.079922 | 0.044* | |
H17B | 0.545676 | 0.133976 | 0.104027 | 0.044* | |
O19 | 0.5872 (2) | −0.13881 (16) | 0.44927 (8) | 0.0299 (3) | |
H19A | 0.537228 | −0.235403 | 0.447693 | 0.045* | |
H19B | 0.694698 | −0.133273 | 0.417733 | 0.045* | |
O20 | 0.0908 (3) | −0.14107 (19) | 0.46154 (10) | 0.0411 (4) | |
H20A | 0.081618 | −0.129379 | 0.512560 | 0.062* | |
H20B | 0.114905 | −0.236594 | 0.446586 | 0.062* | |
Na1 | 0.75518 (12) | 0.00016 (9) | −0.00173 (4) | 0.02498 (19) | |
Na2 | 0.34777 (12) | 0.00440 (9) | 0.43414 (5) | 0.02616 (19) | |
Cd1 | 0.66796 (2) | 0.00416 (2) | 0.25149 (2) | 0.01845 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0207 (9) | 0.0147 (9) | 0.0163 (9) | 0.0027 (7) | 0.0031 (7) | 0.0031 (7) |
C2 | 0.0283 (11) | 0.0171 (10) | 0.0170 (10) | −0.0031 (8) | 0.0054 (8) | 0.0010 (8) |
C3 | 0.0177 (9) | 0.0141 (9) | 0.0184 (9) | 0.0006 (7) | 0.0014 (7) | 0.0002 (7) |
C4 | 0.0190 (9) | 0.0123 (9) | 0.0156 (9) | 0.0004 (7) | 0.0014 (7) | 0.0015 (7) |
C5 | 0.0246 (10) | 0.0157 (9) | 0.0164 (9) | 0.0004 (8) | 0.0038 (8) | 0.0011 (7) |
C6 | 0.0175 (9) | 0.0145 (9) | 0.0146 (9) | 0.0003 (7) | 0.0000 (7) | 0.0030 (7) |
C7 | 0.0181 (9) | 0.0133 (9) | 0.0154 (9) | 0.0020 (7) | 0.0022 (7) | 0.0017 (7) |
C8 | 0.0241 (10) | 0.0162 (9) | 0.0158 (9) | 0.0003 (8) | 0.0036 (7) | 0.0022 (7) |
C9 | 0.0173 (9) | 0.0137 (9) | 0.0161 (9) | 0.0006 (7) | −0.0005 (7) | 0.0028 (7) |
C10 | 0.0166 (9) | 0.0156 (9) | 0.0173 (9) | 0.0020 (7) | −0.0002 (7) | 0.0023 (7) |
C11 | 0.0276 (11) | 0.0175 (10) | 0.0168 (9) | −0.0019 (8) | 0.0051 (8) | 0.0015 (8) |
C12 | 0.0190 (9) | 0.0164 (9) | 0.0156 (9) | 0.0033 (7) | 0.0021 (7) | 0.0020 (7) |
N1 | 0.0221 (8) | 0.0122 (8) | 0.0150 (8) | −0.0003 (6) | 0.0026 (6) | 0.0011 (6) |
N2 | 0.0357 (10) | 0.0150 (8) | 0.0140 (8) | −0.0052 (7) | 0.0074 (7) | 0.0000 (6) |
N3 | 0.0335 (10) | 0.0126 (8) | 0.0170 (8) | −0.0037 (7) | 0.0079 (7) | 0.0032 (6) |
N4 | 0.0220 (8) | 0.0107 (7) | 0.0120 (7) | −0.0003 (6) | 0.0023 (6) | 0.0011 (6) |
N5 | 0.0293 (9) | 0.0099 (7) | 0.0156 (8) | −0.0018 (6) | 0.0069 (7) | 0.0021 (6) |
N6 | 0.0301 (9) | 0.0149 (8) | 0.0121 (8) | −0.0006 (7) | 0.0074 (7) | 0.0006 (6) |
N7 | 0.0246 (9) | 0.0120 (7) | 0.0151 (8) | 0.0024 (6) | 0.0044 (6) | 0.0028 (6) |
N8 | 0.0284 (9) | 0.0109 (7) | 0.0169 (8) | 0.0001 (6) | 0.0072 (7) | 0.0040 (6) |
N9 | 0.0307 (9) | 0.0156 (8) | 0.0138 (8) | 0.0006 (7) | 0.0088 (7) | 0.0020 (6) |
N10 | 0.0332 (10) | 0.0135 (8) | 0.0159 (8) | −0.0042 (7) | 0.0076 (7) | 0.0028 (6) |
N11 | 0.0233 (8) | 0.0152 (8) | 0.0165 (8) | −0.0011 (6) | 0.0017 (6) | 0.0019 (6) |
N12 | 0.0335 (10) | 0.0159 (8) | 0.0138 (8) | −0.0046 (7) | 0.0059 (7) | 0.0016 (6) |
O1 | 0.0228 (7) | 0.0180 (7) | 0.0211 (7) | −0.0004 (6) | 0.0020 (6) | −0.0010 (6) |
O2 | 0.0313 (8) | 0.0192 (7) | 0.0241 (8) | 0.0063 (6) | −0.0049 (6) | −0.0029 (6) |
O3 | 0.0274 (8) | 0.0226 (7) | 0.0217 (7) | 0.0048 (6) | −0.0015 (6) | 0.0021 (6) |
O4 | 0.0302 (8) | 0.0309 (9) | 0.0235 (8) | −0.0006 (7) | 0.0018 (6) | 0.0020 (7) |
O5 | 0.0382 (9) | 0.0185 (7) | 0.0250 (8) | −0.0085 (6) | 0.0073 (7) | 0.0063 (6) |
O6 | 0.0630 (12) | 0.0175 (8) | 0.0222 (8) | −0.0136 (8) | 0.0136 (8) | −0.0040 (6) |
O7 | 0.0431 (9) | 0.0213 (7) | 0.0149 (7) | 0.0000 (7) | 0.0082 (6) | 0.0028 (6) |
O8 | 0.0443 (9) | 0.0171 (7) | 0.0162 (7) | −0.0007 (6) | 0.0125 (6) | 0.0029 (6) |
O9 | 0.0558 (11) | 0.0132 (7) | 0.0214 (8) | −0.0006 (7) | 0.0148 (7) | −0.0019 (6) |
O10 | 0.0374 (9) | 0.0163 (7) | 0.0186 (7) | −0.0023 (6) | 0.0030 (6) | 0.0071 (6) |
O11 | 0.0382 (9) | 0.0175 (7) | 0.0180 (7) | 0.0028 (6) | 0.0128 (6) | 0.0034 (6) |
O12 | 0.0530 (10) | 0.0135 (7) | 0.0232 (8) | −0.0003 (7) | 0.0145 (7) | −0.0008 (6) |
O13 | 0.0347 (8) | 0.0172 (7) | 0.0190 (7) | −0.0023 (6) | 0.0044 (6) | 0.0071 (6) |
O14 | 0.0279 (8) | 0.0171 (7) | 0.0229 (7) | −0.0046 (6) | 0.0026 (6) | 0.0079 (6) |
O15 | 0.0595 (11) | 0.0178 (8) | 0.0212 (8) | −0.0124 (7) | 0.0131 (7) | −0.0035 (6) |
O16 | 0.0374 (9) | 0.0206 (7) | 0.0155 (7) | 0.0013 (6) | 0.0071 (6) | 0.0025 (6) |
O17 | 0.0421 (10) | 0.0223 (8) | 0.0290 (9) | −0.0001 (7) | 0.0074 (7) | 0.0066 (7) |
O18 | 0.0414 (9) | 0.0196 (8) | 0.0263 (8) | −0.0002 (7) | 0.0064 (7) | 0.0039 (6) |
O19 | 0.0358 (9) | 0.0242 (8) | 0.0292 (8) | 0.0013 (7) | 0.0088 (7) | 0.0051 (6) |
O20 | 0.0497 (11) | 0.0333 (10) | 0.0365 (10) | −0.0116 (8) | 0.0067 (8) | 0.0078 (8) |
Na1 | 0.0304 (5) | 0.0240 (4) | 0.0226 (4) | 0.0034 (4) | 0.0040 (4) | 0.0096 (3) |
Na2 | 0.0257 (4) | 0.0243 (4) | 0.0284 (5) | −0.0008 (3) | 0.0033 (3) | 0.0073 (4) |
Cd1 | 0.02259 (8) | 0.01318 (8) | 0.01772 (8) | 0.00042 (5) | 0.00074 (5) | −0.00040 (5) |
C1—O7 | 1.229 (2) | N6—H6 | 0.8600 |
C1—N1 | 1.361 (2) | N8—H8 | 0.8600 |
C1—N3 | 1.390 (3) | N9—H9 | 0.8600 |
C2—O6 | 1.227 (3) | N10—H10 | 0.8600 |
C2—N2 | 1.357 (3) | N12—H12 | 0.8600 |
C2—N3 | 1.360 (3) | O1—Cd1 | 2.3478 (14) |
C3—O5 | 1.225 (2) | O1—H1A | 0.9836 |
C3—N1 | 1.354 (3) | O1—H1B | 0.9829 |
C3—N2 | 1.385 (2) | O2—Cd1 | 2.2996 (15) |
C4—O8 | 1.238 (2) | O2—H2A | 0.9828 |
C4—N4 | 1.351 (2) | O2—H2B | 0.9831 |
C4—N5 | 1.388 (2) | O3—Cd1 | 2.3913 (15) |
C5—O9 | 1.225 (2) | O3—H3A | 0.9830 |
C5—N6 | 1.357 (3) | O3—H3B | 0.9833 |
C5—N5 | 1.359 (3) | O4—Na2 | 2.4627 (18) |
C6—O10 | 1.219 (2) | O4—Cd1 | 2.4817 (16) |
C6—N4 | 1.363 (2) | O4—H4A | 0.9830 |
C6—N6 | 1.392 (2) | O4—H4B | 0.9828 |
C7—O11 | 1.242 (2) | O5—Na2 | 2.3067 (17) |
C7—N7 | 1.347 (2) | O10—Na1 | 2.3471 (16) |
C7—N8 | 1.389 (2) | O13—Na1 | 2.3824 (16) |
C8—O12 | 1.224 (2) | O14—Na2 | 2.4997 (18) |
C8—N9 | 1.363 (3) | O17—Na1 | 2.3584 (19) |
C8—N8 | 1.363 (2) | O17—Na1i | 2.4195 (19) |
C9—O13 | 1.236 (2) | O17—H17A | 0.9832 |
C9—N7 | 1.348 (2) | O17—H17B | 0.9857 |
C9—N9 | 1.386 (2) | O18—Na1 | 2.3939 (18) |
C10—O14 | 1.240 (2) | O18—Na1ii | 2.4192 (19) |
C10—N11 | 1.344 (3) | O18—H18A | 0.9841 |
C10—N12 | 1.389 (3) | O18—H18B | 0.9830 |
C11—O15 | 1.227 (3) | O19—Na2 | 2.4009 (19) |
C11—N12 | 1.361 (3) | O19—Na2iii | 2.4197 (18) |
C11—N10 | 1.361 (3) | O19—H19A | 0.9830 |
C12—O16 | 1.242 (2) | O19—H19B | 0.9830 |
C12—N11 | 1.347 (3) | O20—Na2 | 2.3118 (19) |
C12—N10 | 1.383 (3) | O20—H20A | 0.9831 |
N1—Cd1 | 2.2541 (16) | O20—H20B | 0.9833 |
N2—H2 | 0.8600 | Na1—Na1ii | 3.4526 (17) |
N3—H3 | 0.8600 | Na1—Na1i | 3.5988 (17) |
N4—Cd1 | 2.3210 (15) | Na2—Na2iii | 3.3557 (18) |
N5—H5 | 0.8600 | ||
O7—C1—N1 | 123.25 (18) | C10—O14—Na2 | 110.29 (13) |
O7—C1—N3 | 118.73 (18) | Na1—O17—Na1i | 97.73 (6) |
N1—C1—N3 | 118.01 (17) | Na1—O17—H17A | 119.9 |
O6—C2—N2 | 122.93 (19) | Na1i—O17—H17A | 124.6 |
O6—C2—N3 | 122.67 (19) | Na1—O17—H17B | 104.9 |
N2—C2—N3 | 114.40 (17) | Na1i—O17—H17B | 110.2 |
O5—C3—N1 | 122.71 (18) | H17A—O17—H17B | 98.3 |
O5—C3—N2 | 118.59 (18) | Na1—O18—Na1ii | 91.67 (6) |
N1—C3—N2 | 118.70 (17) | Na1—O18—H18A | 120.5 |
O8—C4—N4 | 122.70 (17) | Na1ii—O18—H18A | 107.0 |
O8—C4—N5 | 117.98 (17) | Na1—O18—H18B | 116.6 |
N4—C4—N5 | 119.31 (17) | Na1ii—O18—H18B | 118.1 |
O9—C5—N6 | 122.21 (18) | H18A—O18—H18B | 103.3 |
O9—C5—N5 | 123.24 (18) | Na2—O19—Na2iii | 88.23 (6) |
N6—C5—N5 | 114.55 (17) | Na2—O19—H19A | 114.5 |
O10—C6—N4 | 122.79 (17) | Na2iii—O19—H19A | 114.5 |
O10—C6—N6 | 119.38 (17) | Na2—O19—H19B | 114.5 |
N4—C6—N6 | 117.82 (16) | Na2iii—O19—H19B | 114.5 |
O11—C7—N7 | 121.84 (17) | H19A—O19—H19B | 109.5 |
O11—C7—N8 | 118.25 (17) | Na2—O20—H20A | 109.9 |
N7—C7—N8 | 119.91 (17) | Na2—O20—H20B | 109.5 |
O12—C8—N9 | 122.17 (18) | H20A—O20—H20B | 104.2 |
O12—C8—N8 | 123.57 (18) | O10—Na1—O17 | 88.93 (6) |
N9—C8—N8 | 114.26 (17) | O10—Na1—O13 | 173.39 (7) |
O13—C9—N7 | 122.52 (18) | O17—Na1—O13 | 84.51 (6) |
O13—C9—N9 | 118.21 (17) | O10—Na1—O18 | 100.11 (6) |
N7—C9—N9 | 119.27 (17) | O17—Na1—O18 | 170.94 (7) |
O14—C10—N11 | 123.13 (18) | O13—Na1—O18 | 86.45 (6) |
O14—C10—N12 | 117.85 (17) | O10—Na1—O17i | 89.31 (6) |
N11—C10—N12 | 119.02 (17) | O17—Na1—O17i | 82.27 (6) |
O15—C11—N12 | 123.32 (19) | O13—Na1—O17i | 90.60 (6) |
O15—C11—N10 | 122.43 (19) | O18—Na1—O17i | 97.21 (6) |
N12—C11—N10 | 114.24 (17) | O10—Na1—O18ii | 78.82 (6) |
O16—C12—N11 | 122.52 (18) | O17—Na1—O18ii | 93.97 (6) |
O16—C12—N10 | 117.89 (18) | O13—Na1—O18ii | 100.80 (6) |
N11—C12—N10 | 119.58 (17) | O18—Na1—O18ii | 88.33 (6) |
C3—N1—C1 | 120.31 (16) | O17i—Na1—O18ii | 167.64 (7) |
C3—N1—Cd1 | 114.93 (12) | O10—Na1—Na1ii | 89.19 (5) |
C1—N1—Cd1 | 124.46 (13) | O17—Na1—Na1ii | 137.16 (6) |
C2—N2—C3 | 124.18 (17) | O13—Na1—Na1ii | 95.07 (5) |
C2—N2—H2 | 117.9 | O18—Na1—Na1ii | 44.46 (4) |
C3—N2—H2 | 117.9 | O17i—Na1—Na1ii | 140.49 (6) |
C2—N3—C1 | 124.38 (17) | O18ii—Na1—Na1ii | 43.88 (4) |
C2—N3—H3 | 117.8 | O10—Na1—Na1i | 88.84 (5) |
C1—N3—H3 | 117.8 | O17—Na1—Na1i | 41.77 (4) |
C4—N4—C6 | 120.03 (16) | O13—Na1—Na1i | 86.81 (5) |
C4—N4—Cd1 | 124.47 (12) | O18—Na1—Na1i | 137.02 (6) |
C6—N4—Cd1 | 115.24 (12) | O17i—Na1—Na1i | 40.49 (4) |
C5—N5—C4 | 123.55 (16) | O18ii—Na1—Na1i | 134.60 (6) |
C5—N5—H5 | 118.2 | Na1ii—Na1—Na1i | 177.78 (5) |
C4—N5—H5 | 118.2 | O5—Na2—O20 | 179.41 (8) |
C5—N6—C6 | 124.54 (16) | O5—Na2—O19 | 83.92 (6) |
C5—N6—H6 | 117.7 | O20—Na2—O19 | 96.15 (7) |
C6—N6—H6 | 117.7 | O5—Na2—O19iii | 83.78 (6) |
C7—N7—C9 | 119.30 (16) | O20—Na2—O19iii | 96.81 (7) |
C8—N8—C7 | 123.21 (16) | O19—Na2—O19iii | 91.77 (6) |
C8—N8—H8 | 118.4 | O5—Na2—O4 | 77.17 (6) |
C7—N8—H8 | 118.4 | O20—Na2—O4 | 102.25 (7) |
C8—N9—C9 | 124.01 (17) | O19—Na2—O4 | 85.43 (6) |
C8—N9—H9 | 118.0 | O19iii—Na2—O4 | 160.92 (7) |
C9—N9—H9 | 118.0 | O5—Na2—O14 | 94.52 (6) |
C11—N10—C12 | 123.56 (17) | O20—Na2—O14 | 85.34 (7) |
C11—N10—H10 | 118.2 | O19—Na2—O14 | 172.40 (7) |
C12—N10—H10 | 118.2 | O19iii—Na2—O14 | 95.47 (6) |
C10—N11—C12 | 119.66 (17) | O4—Na2—O14 | 86.97 (6) |
C11—N12—C10 | 123.89 (17) | O5—Na2—Na2iii | 81.14 (5) |
C11—N12—H12 | 118.1 | O20—Na2—Na2iii | 99.33 (6) |
C10—N12—H12 | 118.1 | O19—Na2—Na2iii | 46.11 (4) |
Cd1—O1—H1A | 110.2 | O19iii—Na2—Na2iii | 45.65 (5) |
Cd1—O1—H1B | 110.1 | O4—Na2—Na2iii | 128.64 (6) |
H1A—O1—H1B | 97.0 | O14—Na2—Na2iii | 141.06 (6) |
Cd1—O2—H2A | 109.8 | N1—Cd1—O2 | 88.83 (6) |
Cd1—O2—H2B | 119.7 | N1—Cd1—N4 | 174.58 (6) |
H2A—O2—H2B | 120.2 | O2—Cd1—N4 | 88.80 (5) |
Cd1—O3—H3A | 111.0 | N1—Cd1—O1 | 87.44 (5) |
Cd1—O3—H3B | 110.8 | O2—Cd1—O1 | 111.45 (5) |
H3A—O3—H3B | 103.1 | N4—Cd1—O1 | 88.89 (5) |
Na2—O4—Cd1 | 117.77 (6) | N1—Cd1—O3 | 95.46 (6) |
Na2—O4—H4A | 107.4 | O2—Cd1—O3 | 166.49 (5) |
Cd1—O4—H4A | 107.4 | N4—Cd1—O3 | 87.94 (5) |
Na2—O4—H4B | 107.3 | O1—Cd1—O3 | 81.59 (5) |
Cd1—O4—H4B | 107.3 | N1—Cd1—O4 | 100.77 (6) |
H4A—O4—H4B | 109.5 | O2—Cd1—O4 | 81.82 (6) |
C3—O5—Na2 | 155.60 (16) | N4—Cd1—O4 | 83.72 (5) |
C6—O10—Na1 | 152.13 (14) | O1—Cd1—O4 | 164.73 (5) |
C9—O13—Na1 | 153.27 (14) | O3—Cd1—O4 | 84.79 (5) |
O5—C3—N1—C1 | 177.79 (19) | O11—C7—N7—C9 | 179.44 (18) |
N2—C3—N1—C1 | −1.9 (3) | N8—C7—N7—C9 | −0.5 (3) |
O5—C3—N1—Cd1 | −8.2 (3) | O13—C9—N7—C7 | −179.33 (19) |
N2—C3—N1—Cd1 | 172.08 (14) | N9—C9—N7—C7 | 1.7 (3) |
O7—C1—N1—C3 | −178.84 (19) | O12—C8—N8—C7 | −178.5 (2) |
N3—C1—N1—C3 | 1.4 (3) | N9—C8—N8—C7 | 1.4 (3) |
O7—C1—N1—Cd1 | 7.8 (3) | O11—C7—N8—C8 | 178.91 (19) |
N3—C1—N1—Cd1 | −172.02 (13) | N7—C7—N8—C8 | −1.2 (3) |
O6—C2—N2—C3 | 179.9 (2) | O12—C8—N9—C9 | 179.9 (2) |
N3—C2—N2—C3 | 0.4 (3) | N8—C8—N9—C9 | 0.0 (3) |
O5—C3—N2—C2 | −178.7 (2) | O13—C9—N9—C8 | 179.48 (19) |
N1—C3—N2—C2 | 1.0 (3) | N7—C9—N9—C8 | −1.5 (3) |
O6—C2—N3—C1 | 179.5 (2) | O15—C11—N10—C12 | 178.5 (2) |
N2—C2—N3—C1 | −0.9 (3) | N12—C11—N10—C12 | −0.8 (3) |
O7—C1—N3—C2 | −179.7 (2) | O16—C12—N10—C11 | −176.9 (2) |
N1—C1—N3—C2 | 0.1 (3) | N11—C12—N10—C11 | 1.9 (3) |
O8—C4—N4—C6 | −178.62 (19) | O14—C10—N11—C12 | −177.67 (19) |
N5—C4—N4—C6 | 0.6 (3) | N12—C10—N11—C12 | 2.1 (3) |
O8—C4—N4—Cd1 | 7.4 (3) | O16—C12—N11—C10 | 176.32 (19) |
N5—C4—N4—Cd1 | −173.39 (13) | N10—C12—N11—C10 | −2.5 (3) |
O10—C6—N4—C4 | 177.24 (19) | O15—C11—N12—C10 | −179.0 (2) |
N6—C6—N4—C4 | −4.1 (3) | N10—C11—N12—C10 | 0.3 (3) |
O10—C6—N4—Cd1 | −8.3 (2) | O14—C10—N12—C11 | 178.8 (2) |
N6—C6—N4—Cd1 | 170.42 (13) | N11—C10—N12—C11 | −1.0 (3) |
O9—C5—N5—C4 | 178.2 (2) | N1—C3—O5—Na2 | −79.6 (4) |
N6—C5—N5—C4 | −1.6 (3) | N2—C3—O5—Na2 | 100.1 (4) |
O8—C4—N5—C5 | −178.30 (19) | N4—C6—O10—Na1 | −143.5 (2) |
N4—C4—N5—C5 | 2.5 (3) | N6—C6—O10—Na1 | 37.8 (4) |
O9—C5—N6—C6 | 178.0 (2) | N7—C9—O13—Na1 | 118.8 (3) |
N5—C5—N6—C6 | −2.3 (3) | N9—C9—O13—Na1 | −62.3 (4) |
O10—C6—N6—C5 | −176.13 (19) | N11—C10—O14—Na2 | 87.6 (2) |
N4—C6—N6—C5 | 5.1 (3) | N12—C10—O14—Na2 | −92.13 (18) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y, −z; (iii) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N11iv | 0.98 | 1.82 | 2.788 (2) | 168 |
O1—H1B···N7ii | 0.98 | 1.89 | 2.860 (2) | 169 |
N2—H2···O15v | 0.86 | 1.96 | 2.817 (2) | 173 |
O2—H2A···O13i | 0.98 | 1.77 | 2.716 (2) | 161 |
O2—H2B···N11 | 0.98 | 2.53 | 3.236 (2) | 128 |
O2—H2B···O16 | 0.98 | 1.79 | 2.753 (2) | 167 |
N3—H3···O11vi | 0.86 | 1.92 | 2.773 (2) | 173 |
O3—H3A···O14iv | 0.98 | 1.91 | 2.871 (2) | 166 |
O3—H3B···O11ii | 0.98 | 1.87 | 2.842 (2) | 169 |
N5—H5···O16vii | 0.86 | 2.10 | 2.938 (2) | 164 |
N6—H6···O12vii | 0.86 | 2.13 | 2.979 (2) | 168 |
N10—H10···O8viii | 0.86 | 1.94 | 2.792 (2) | 172 |
N8—H8···O7vi | 0.86 | 2.02 | 2.862 (2) | 167 |
N12—H12···O6v | 0.86 | 2.03 | 2.882 (2) | 173 |
N9—H9···O9viii | 0.86 | 2.04 | 2.885 (2) | 169 |
O20—H20B···O6ix | 0.98 | 2.30 | 2.903 (2) | 119 |
O20—H20A···O14x | 0.98 | 2.14 | 3.008 (2) | 147 |
O4—H4A···O8 | 0.98 | 1.88 | 2.725 (2) | 143 |
O17—H17B···O2 | 0.99 | 1.87 | 2.768 (2) | 149 |
O17—H17A···O9viii | 0.98 | 1.81 | 2.790 (2) | 171 |
O18—H18B···O12vii | 0.98 | 1.91 | 2.852 (2) | 160 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y, −z; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x+2, −y+1, −z; (vii) x, y−1, z; (viii) x, y+1, z; (ix) x−1, y−1, z; (x) −x, −y, −z+1. |
α is the dihedral angle between planes I and J. Cg1, Cg2, Cg3 and Cg4 are the centroids of the N1–N3/C1–C3, N4–N6/C4–C6, N7–N9/C7–C9 and N10–N12/C10–C12 rings, respectively. |
Cg(I)···Cg(J) | Cg···Cg | α |
Cg1···Cg4i | 3.5174 (12) | 2.42 (10) |
Cg2···Cg3ii | 3.4893 (11) | 2.59 (9) |
Symmetry codes: (i) 1 + x, y, z; (ii) 2 - x, -y, -z. |
Y—X(I)···Cg(J) | X···Cg | Y—X···Cg | Y···Cg |
C4—O8···Cg3i | 3.6086 (2) | 68.07 (11) | 3.349 (2) |
C7—O11···Cg2ii | 3.4783 (2) | 68.37 (11) | 3.233 (2) |
Symmetry codes: (i) 1 - x, -y, -z; (ii) 2 - x, -y, -z. |
Acknowledgements
The authors thank the SAIF, IIT Madras, for the single crystal X-ray diffraction measurements. The authors are thankful to Professor M. R. P. Kurup, Cochin University of Science & Technology, Kochi-22, for the use of DIAMOND software.
Funding information
KRB is grateful to KSCSTE, Govt. of Kerala, India, for the award of an Emeritus Scientist fellowship.
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