Crystal structure of bis­(μ-3-nitro­benzoato)-κ3O,O′:O;κ3O:O,O′-bis­[bis­(3-cyano­pyridine-κN1)(3-nitro­benzoato-κ2O,O′)cadmium]

Hökelek, T.; Akduran, N.; Özen, A.; Uğurlu, G.; Necefoğlu, H.

doi:10.1107/S2056989017002675

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ISSN: 2056-9890

Volume 73| Part 3| March 2017| Pages 413-416

https://doi.org/10.1107/S2056989017002675

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Crystal structure of bis(μ-3-nitrobenzoato)-κ³O,O′:O;κ³O:O,O′-bis[bis(3-cyanopyridine-κN¹)(3-nitrobenzoato-κ²O,O′)cadmium]

Tuncer Hökelek,^a ^* Nurcan Akduran,^b Azer Özen,^c Güventürk Uğurlu ^c and Hacali Necefoğlu ^c,^d

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bSANAEM, Saray Mahallesi, Atom Caddesi, No. 27, 06980 Saray-Kazan, Ankara, Turkey, ^cDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, and ^dInternational Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

Edited by M. Weil, Vienna University of Technology, Austria (Received 3 February 2017; accepted 16 February 2017; online 21 February 2017)

The asymmetric unit of the title compound, [Cd₂(C₇H₄NO₄)₄(C₆H₄N₂)₄], contains one Cd^II atom, two 3-nitrobenzoate (NB) anions and two 3-cyanopyridine (CPy) ligands. The two CPy ligands act as monodentate N(pyridine)-bonding ligands, while the two NB anions act as bidentate ligands through the carboxylate O atoms. The centrosymmetric dinuclear complex is generated by application of inversion symmetry, whereby the Cd^II atoms are bridged by the carboxylate O atoms of two symmetry-related NB anions, thus completing the distorted N₂O₅ pentagonal–bipyramidal coordination sphere of each Cd^II atom. The benzene and pyridine rings are oriented at dihedral angles of 10.02 (7) and 5.76 (9)°, respectively. In the crystal, C—H⋯N hydrogen bonds link the molecules, enclosing R₂²(26) ring motifs, in which they are further linked via C—H⋯O hydrogen bonds, resulting in a three-dimensional network. In addition, π–π stacking interactions between parallel benzene rings and between parallel pyridine rings of adjacent molecules [shortest centroid-to-centroid distances = 3.885 (1) and 3.712 (1) Å, respectively], as well as a weak C—H⋯π interaction, may further stabilize the crystal structure.

Keywords: crystal structure; cadmium; transition metal complex; benzoic acid.

CCDC reference: 1533101

1. Chemical context

In the last two decades, research on metal–organic frameworks (MOFs) has received considerable attention due to their extensive structural chemistry (Li et al., 2016 ) and their potential applications, including gas storage, nonlinear optics and ion exchange (Carlucci et al., 2003 ). In the syntheses of compounds having MOF structures, various carboxylate ligands have been used (Li et al., 2004 ).

On the other hand, transition-metal complexes with biochemically active molecules show interesting physical and/or chemical properties, through which they may find applications in biological systems (Antolini et al., 1982 ). Some benzoic acid derivatives, such as 4-aminobenzoic acid, have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes (Chen & Chen, 2002 ; Amiraslanov et al., 1979 ; Hauptmann et al., 2000 ).

The structure–function–coordination relationships of arylcarboxylate ions in Zn^II complexes of benzoic acid derivatives change depending on the nature and position of the substituted groups on the benzene ring, the nature of the additional ligand molecule or solvent, and the pH range and temperature of the synthesis (Shnulin et al., 1981 ; Nadzhafov et al., 1981 ; Antsyshkina et al., 1980 ; Adiwidjaja et al., 1978 ). When pyridine and its derivatives are used instead of water molecules, the structure is completely different (Catterick et al., 1974 ).

The structures of some dinuclear complexes obtained from the reactions of transition metal(II) ions with nicotinamide (NA; C₆H₆N₂O) and some benzoic acid derivatives as ligands, e.g. [Zn₂(C₇H₄FO₂)₄(C₆H₆N₂O)₂]·C₇H₅FO₂ [(II); Hökelek et al., 2009 ], [Cu₂(C₈H₇O₃)₄(C₆H₆N₂O)₂(H₂O)₂] [(III); Hökelek et al., 2010 ], [Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄] [(IV); Sertçelik et al., 2013 ], [Mn₂(C₇H₄BrO₂)₄(C₆H₆N₂O)₂(H₂O)₂] [(V); Necefoğlu et al., 2011 ] and [Cd₂(C₇H₄ClO₂)₄(C₆H₆N₂O)₂(H₂O)₂] [(VI); Bozkurt et al., 2013 ], have been determined previously. In this context, we have synthesized the Cd^II-containing title compound, bis(μ-3-nitrobenzoato)-κ³O,O′:O;κ³O:O,O′-bis[bis(3-cyanopyridine-κN)(3-nitrobenzoato-κ²O,O′)cadmium], [Cd₂(C₇H₄NO₄)₄(C₆H₄N₂)₄], and report herein its crystal structure.

2. Structural commentary

The asymmetric unit of the title complex contains one Cd^II atom, two 3-nitrobenzoate (NB) anions and two 3-cyanopyridine (CPy) ligands. The two CPy ligands are monodentate (through the pyridine N atoms), while both NB anions act as bidentate ligands through their carboxylate O atoms (Fig. 1). The centrosymmetric dinuclear molecule is completed by application of inversion symmerty. The Cd^II atoms are bridged by the carboxylate O atoms of one NB anions (O6 and O5) and its symmetry-related counterpart [symmetry code: (i) −x, −y + 1, −z + 1]. Hence, this carboxylate group not only chelates to one Cd^II atom but also bridges two Cd^II atoms (Fig. 2). Thus, each Cd^II atom is surrounded by three NB anions and two CPy ligands. The overall coordination sphere of the Cd^II atom is defined by the bridging/chelating NB anions (O5, O5ⁱ and O6), one chelating NB anion (O1 and O2) and two 3-cyanopyridine (CPy) ligands (N3 and N5), resulting in a distorted pentagonal–bipyramidal environment. The five carboxylate O atoms (O1, O2, O5, O5ⁱ and O6) of the three NB anions around the Cd^II atom form a distorted pentagonal arrangement, with an average Cd1—O bond length of 2.42 Å (Table 1). The distorted pentagonal–bipyramidal coordination is completed by pyridine atoms N3 and N5 of the CPy ligands at distances of 2.3186 (17) and 2.3435 (17) Å, respectively, in the axial positions (Table 1; Figs. 1 and 2). The Cd1 atom lies 0.1252 (1) Å above and 0.0326 (1) Å below of planar O1/O2/C1 and O5/O6/C8 carboxylate groups, respectively. The Cd1⋯Cd1ⁱ separation in the binuclear molecule is 3.9360 (15) Å and is comparable to the corresponding M—M distances (M is a metal) in the structurally related transition metal(II) complexes [7.1368 (3) Å in (III), 4.1554 (8) Å in (IV), 7.180 (2) Å in (V) and 7.1647 (3) Å in (VI)]. The metal atoms are bridged by two NA ligand N and O atoms in (III), (V) and (VI), while they are bridged by two carboxylate O atoms in (IV).

Table 1
Selected bond lengths (Å)

Cd1—O1	2.3017 (15)	Cd1—O6	2.3264 (15)
Cd1—O2	2.5072 (18)	Cd1—N3	2.3186 (17)
Cd1—O5	2.5367 (16)	Cd1—N5	2.3435 (17)
Cd1—O5ⁱ	2.4716 (16)
Symmetry code: (i) -x, -y+1, -z+1.

Figure 1
The asymmetric unit of the title molecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
The molecular structure of the binuclear title molecule. Symmetry-related atoms are related by the symmetry code (−x, −y + 1, −z + 1). H atoms have been omitted for clarity.

The near equalities of the C1—O1 [1.264 (3) Å], C1—O2 [1.241 (3) Å], C8—O5 [1.256 (3) Å] and C8—O6 [1.253 (3) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The O1—Cd1—O2 and O5—Cd1—O6 bite angles are reduced to 54.33 (5) and 53.47 (5)°, respectively. The corresponding O—M—O (M is a divalent metal) angles are 60.92 (12)° in (II), 53.50 (14)° in (IV), 57.61 (8)° in (V), and 54.22 (4) and 53.32 (5)° in (VI). The dihedral angles between the planar carboxylate groups (O1/O2/C1 and O5/O6/C8) and the adjacent benzene [A (C2–C7) and B (C9–C14)] rings in the title structure are 17.18 (13) and 3.36 (12)°, respectively, while the benzene (A and B) and pyridine [C (N3/C15–C19) and D (N5/C21–C25)] rings are oriented at dihedral angles of A/B = 10.02 (7)°, A/C = 72.70 (7)°, A/D = 74.72 (7)°, B/C = 82.28 (7)°, B/D = 84.54 (8)° and C/D = 5.76 (9)°.

3. Supramolecular features

Intramolecular C—H_cpy⋯O_c (cpy = cyanopyridine and c = carboxylate) and C—H_nb⋯O_c (nb = nitrobenzoate) hydrogen bonds (Table 2) link the cyanopyridine and nitrobenzoate ligands to the carboxylate O atoms. In the crystal, C—H_cpy⋯N_cpy hydrogen bonds (Table 2) link the molecules, enclosing R₂²(26) ring motifs (Bernstein et al., 1995 ) (Fig. 3), in which they are further linked via additional C—H_cpy⋯O_nb (nb = nitrobenzoate) hydrogen bonds (Table 2), resulting in a three-dimensional network. The π–π contacts between parallel benzene rings and between parallel pyridine rings of adjacent molecules, Cg1–Cg2ⁱ and Cg3–Cg4ⁱⁱ [symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x, −y + 1, −z + 1; Cg1, Cg2, Cg3 and Cg4 are the centroids of the rings A (atoms C2–C7), B (C9–C14), C (N3/C15–C19) and D (N5/C21–C25)] may further stabilize the structure, with centroid–centroid distances of 3.885 (1) and 3.712 (1) Å, respectively. A weak C—H⋯π interaction (Table 2) is also observed.

Table 2
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the N3/C15–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O1ⁱ	0.93	2.20	3.108 (3)	167
C15—H15⋯O2ⁱⁱ	0.93	2.32	3.111 (3)	143
C23—H23⋯N4ⁱⁱⁱ	0.93	2.38	3.236 (5)	154
C25—H25⋯O6	0.93	2.58	3.242 (3)	128
C10—H10⋯Cg3ⁱⁱ	0.93	3.26	4.186 (3)	176
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z+1; (iii) x-1, y, z-1.

Figure 3
Part of the crystal structure. Intramolecular (C—H_cpy⋯O_c and C—H_nb⋯O_c) and intermolecular (C—H_cpy⋯N_cpy and C—H_cpy⋯O_nb) (cpy = cyanopyridine, c = carboxylate and nb = nitrobenzoate) hydrogen bonds are shown as dashed lines. Nonbonding H atoms have been omitted for clarity.

4. Refinement

The experimental details including the crystal data, data collection and refinement are summarized in Table 3. Aromatic H atoms were positioned geometrically, with C—H = 0.93 Å, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C). The maximum and minimum electron densities were found at 1.43 and 0.80 Å from atoms O2 and Cd1, respectively.

Table 3
Experimental details

Crystal data
Chemical formula	[Cd₂(C₇H₄NO₄)₄(C₆H₄N₂)₄]
M_r	1305.72
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	8.5237 (3), 12.7145 (4), 13.0583 (5)
α, β, γ (°)	105.022 (3), 97.347 (3), 104.866 (2)
V (Å³)	1292.12 (8)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.91
Crystal size (mm)	0.28 × 0.20 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.615, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	65471, 6414, 5828
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.072, 1.22
No. of reflections	6414
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.01, −0.75
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012 ), WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

5. Synthesis and crystallization

The title compound was prepared by the reaction of 3CdSO₄·8H₂O (0.64 g, 2.5 mmol) in H₂O (50 ml) and 3-cyanopyridine (0.52 g, 5 mmol) in H₂O (50 ml) with sodium 3-nitrobenzoate (0.95 g, 5 mmol) in H₂O (100 ml) at 333 K. The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving colourless single crystals.

Supporting information

CCDC reference: 1533101

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989017002675/wm5366sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017002675/wm5366Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012)'; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Bis(µ-3-nitrobenzoato)-κ³O,O':O;κ³O:O,O'-bis[bis(3-cyanopyridine-κN¹)(3-nitrobenzoato-κ²O,O')cadmium] top

Crystal data top

[Cd₂(C₇H₄NO₄)₄(C₆H₄N₂)₄]	Z = 1
M_r = 1305.72	F(000) = 652
Triclinic, P1	D_x = 1.678 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5237 (3) Å	Cell parameters from 9607 reflections
b = 12.7145 (4) Å	θ = 3.1–28.3°
c = 13.0583 (5) Å	µ = 0.91 mm⁻¹
α = 105.022 (3)°	T = 296 K
β = 97.347 (3)°	Prism, colourless
γ = 104.866 (2)°	0.28 × 0.20 × 0.18 mm
V = 1292.12 (8) Å³

Data collection top

Bruker APEXII CCD diffractometer	6414 independent reflections
Radiation source: fine-focus sealed tube	5828 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
φ and ω scans	θ_max = 28.3°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −11→11
T_min = 0.615, T_max = 0.746	k = −16→16
65471 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.22	w = 1/[σ²(F_o²) + (0.0277P)² + 0.8651P] where P = (F_o² + 2F_c²)/3
6414 reflections	(Δ/σ)_max = 0.001
370 parameters	Δρ_max = 1.01 e Å⁻³
0 restraints	Δρ_min = −0.75 e Å⁻³

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cd1	0.151839 (18)	0.436274 (11)	0.419807 (11)	0.03200 (6)
O1	0.0821 (2)	0.25149 (13)	0.30752 (14)	0.0448 (4)
O2	0.3355 (2)	0.35240 (13)	0.30991 (15)	0.0480 (4)
O3	−0.0992 (3)	−0.15593 (16)	0.12938 (19)	0.0675 (6)
O4	0.0033 (3)	−0.22812 (15)	−0.00392 (17)	0.0646 (5)
O5	0.1364 (2)	0.61626 (13)	0.55320 (14)	0.0431 (4)
O6	0.3515 (2)	0.61460 (13)	0.47720 (13)	0.0414 (3)
O7	0.8058 (3)	0.9744 (2)	0.5573 (3)	0.1093 (12)
O8	0.7807 (3)	1.13029 (18)	0.6485 (3)	0.0928 (9)
N1	0.0007 (3)	−0.14806 (16)	0.07056 (17)	0.0435 (4)
N2	0.7303 (3)	1.02738 (18)	0.6099 (2)	0.0537 (5)
N3	0.2275 (2)	0.37248 (14)	0.56414 (14)	0.0320 (3)
N4	0.6329 (5)	0.5371 (3)	0.8932 (3)	0.1256 (18)
N5	0.0320 (2)	0.48389 (15)	0.27322 (14)	0.0358 (4)
N6	−0.3803 (3)	0.2705 (2)	−0.0491 (2)	0.0685 (7)
C1	0.2174 (3)	0.26302 (16)	0.27548 (16)	0.0324 (4)
C2	0.2308 (3)	0.16188 (17)	0.19015 (17)	0.0322 (4)
C3	0.1160 (3)	0.05585 (17)	0.17155 (17)	0.0330 (4)
H3	0.0350	0.0469	0.2127	0.040*
C4	0.1244 (3)	−0.03626 (17)	0.09058 (17)	0.0347 (4)
C5	0.2408 (3)	−0.0262 (2)	0.0267 (2)	0.0459 (5)
H5	0.2429	−0.0892	−0.0279	0.055*
C6	0.3544 (4)	0.0798 (2)	0.0456 (2)	0.0535 (6)
H6	0.4340	0.0886	0.0034	0.064*
C7	0.3498 (3)	0.1736 (2)	0.1279 (2)	0.0447 (5)
H7	0.4274	0.2445	0.1410	0.054*
C8	0.2760 (2)	0.66594 (16)	0.53913 (16)	0.0315 (4)
C9	0.3550 (2)	0.79211 (16)	0.59657 (16)	0.0312 (4)
C10	0.5053 (3)	0.84920 (17)	0.57676 (18)	0.0346 (4)
H10	0.5592	0.8106	0.5294	0.042*
C11	0.5721 (3)	0.96539 (17)	0.62989 (19)	0.0384 (5)
C12	0.4989 (3)	1.02590 (19)	0.7024 (2)	0.0491 (6)
H12	0.5479	1.1036	0.7373	0.059*
C13	0.3506 (4)	0.9677 (2)	0.7217 (2)	0.0565 (7)
H13	0.2988	1.0064	0.7706	0.068*
C14	0.2785 (3)	0.8520 (2)	0.6685 (2)	0.0453 (5)
H14	0.1776	0.8140	0.6811	0.054*
C15	0.3517 (3)	0.43881 (18)	0.64654 (18)	0.0360 (4)
H15	0.4061	0.5123	0.6466	0.043*
C16	0.4023 (3)	0.4017 (2)	0.73219 (19)	0.0414 (5)
C17	0.3240 (3)	0.2918 (2)	0.7327 (2)	0.0479 (6)
H17	0.3567	0.2653	0.7894	0.058*
C18	0.1962 (3)	0.2229 (2)	0.6465 (2)	0.0503 (6)
H18	0.1411	0.1486	0.6437	0.060*
C19	0.1517 (3)	0.26648 (19)	0.56478 (19)	0.0417 (5)
H19	0.0649	0.2200	0.5072	0.050*
C20	0.5330 (4)	0.4779 (3)	0.8215 (3)	0.0706 (10)
C21	−0.0872 (3)	0.40583 (18)	0.19319 (17)	0.0375 (4)
H21	−0.1240	0.3318	0.1971	0.045*
C22	−0.1584 (3)	0.43099 (19)	0.10448 (17)	0.0373 (4)
C23	−0.1049 (3)	0.5416 (2)	0.09792 (19)	0.0462 (5)
H23	−0.1512	0.5609	0.0397	0.055*
C24	0.0186 (4)	0.6213 (2)	0.1803 (2)	0.0541 (7)
H24	0.0579	0.6960	0.1787	0.065*
C25	0.0835 (3)	0.58913 (19)	0.26552 (19)	0.0460 (6)
H25	0.1675	0.6438	0.3204	0.055*
C26	−0.2833 (3)	0.3418 (2)	0.0192 (2)	0.0484 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03932 (9)	0.02142 (7)	0.02841 (8)	0.00423 (6)	0.00100 (6)	0.00389 (5)
O1	0.0451 (9)	0.0315 (8)	0.0489 (9)	0.0062 (7)	0.0178 (7)	−0.0009 (7)
O2	0.0433 (9)	0.0304 (8)	0.0549 (10)	−0.0010 (7)	0.0077 (8)	0.0003 (7)
O3	0.0779 (14)	0.0390 (10)	0.0778 (14)	0.0002 (9)	0.0284 (12)	0.0163 (10)
O4	0.0769 (14)	0.0324 (9)	0.0658 (13)	0.0110 (9)	0.0042 (10)	−0.0060 (8)
O5	0.0372 (8)	0.0272 (7)	0.0521 (9)	−0.0040 (6)	0.0057 (7)	0.0061 (7)
O6	0.0422 (8)	0.0266 (7)	0.0437 (8)	0.0026 (6)	0.0061 (7)	0.0000 (6)
O7	0.0819 (17)	0.0595 (14)	0.155 (3)	−0.0138 (12)	0.0739 (19)	−0.0093 (16)
O8	0.0713 (15)	0.0345 (10)	0.141 (2)	−0.0190 (10)	0.0299 (15)	0.0046 (13)
N1	0.0528 (11)	0.0276 (9)	0.0451 (11)	0.0108 (8)	−0.0003 (9)	0.0091 (8)
N2	0.0436 (11)	0.0353 (10)	0.0650 (14)	−0.0075 (9)	0.0087 (10)	0.0070 (10)
N3	0.0325 (8)	0.0287 (8)	0.0325 (8)	0.0070 (7)	0.0044 (7)	0.0091 (7)
N4	0.136 (3)	0.085 (2)	0.103 (3)	−0.028 (2)	−0.077 (2)	0.050 (2)
N5	0.0488 (10)	0.0272 (8)	0.0279 (8)	0.0093 (7)	0.0024 (7)	0.0072 (7)
N6	0.0717 (16)	0.0507 (14)	0.0597 (15)	−0.0003 (12)	−0.0179 (13)	0.0112 (12)
C1	0.0396 (10)	0.0240 (9)	0.0312 (9)	0.0086 (8)	0.0033 (8)	0.0072 (7)
C2	0.0361 (10)	0.0269 (9)	0.0346 (10)	0.0122 (8)	0.0055 (8)	0.0093 (8)
C3	0.0373 (10)	0.0282 (9)	0.0332 (10)	0.0105 (8)	0.0056 (8)	0.0092 (8)
C4	0.0411 (11)	0.0259 (9)	0.0348 (10)	0.0110 (8)	0.0006 (8)	0.0081 (8)
C5	0.0548 (14)	0.0371 (11)	0.0464 (13)	0.0196 (10)	0.0167 (11)	0.0048 (10)
C6	0.0565 (15)	0.0471 (14)	0.0628 (16)	0.0197 (12)	0.0313 (13)	0.0136 (12)
C7	0.0437 (12)	0.0347 (11)	0.0540 (14)	0.0086 (9)	0.0183 (10)	0.0098 (10)
C8	0.0323 (9)	0.0236 (9)	0.0298 (9)	0.0016 (7)	−0.0040 (7)	0.0055 (7)
C9	0.0303 (9)	0.0221 (8)	0.0321 (9)	0.0004 (7)	−0.0020 (7)	0.0045 (7)
C10	0.0331 (10)	0.0246 (9)	0.0387 (11)	0.0027 (7)	0.0041 (8)	0.0047 (8)
C11	0.0321 (10)	0.0261 (9)	0.0452 (12)	−0.0034 (8)	−0.0006 (9)	0.0071 (8)
C12	0.0485 (13)	0.0230 (10)	0.0587 (15)	0.0004 (9)	0.0032 (11)	−0.0023 (10)
C13	0.0547 (15)	0.0342 (12)	0.0656 (17)	0.0061 (11)	0.0202 (13)	−0.0062 (11)
C14	0.0387 (11)	0.0332 (11)	0.0509 (13)	−0.0005 (9)	0.0118 (10)	0.0007 (10)
C15	0.0334 (10)	0.0317 (10)	0.0388 (11)	0.0042 (8)	0.0001 (8)	0.0128 (8)
C16	0.0376 (11)	0.0411 (12)	0.0431 (12)	0.0086 (9)	−0.0002 (9)	0.0162 (10)
C17	0.0519 (14)	0.0486 (13)	0.0483 (13)	0.0137 (11)	0.0059 (11)	0.0269 (11)
C18	0.0567 (15)	0.0351 (12)	0.0568 (15)	0.0034 (10)	0.0089 (12)	0.0222 (11)
C19	0.0432 (12)	0.0323 (10)	0.0411 (12)	0.0017 (9)	0.0021 (9)	0.0095 (9)
C20	0.0715 (19)	0.0570 (17)	0.0665 (19)	−0.0031 (14)	−0.0272 (16)	0.0329 (15)
C21	0.0454 (12)	0.0296 (10)	0.0336 (10)	0.0072 (9)	0.0035 (9)	0.0093 (8)
C22	0.0408 (11)	0.0361 (11)	0.0310 (10)	0.0106 (9)	0.0019 (8)	0.0070 (8)
C23	0.0601 (15)	0.0393 (12)	0.0379 (11)	0.0157 (11)	−0.0025 (10)	0.0148 (10)
C24	0.0765 (18)	0.0296 (11)	0.0472 (13)	0.0060 (11)	−0.0058 (12)	0.0155 (10)
C25	0.0605 (15)	0.0284 (10)	0.0369 (11)	0.0030 (10)	−0.0055 (10)	0.0075 (9)
C26	0.0533 (14)	0.0412 (12)	0.0430 (12)	0.0080 (11)	−0.0028 (11)	0.0123 (10)

Geometric parameters (Å, º) top

Cd1—O1	2.3017 (15)	C7—H7	0.9300
Cd1—O2	2.5072 (18)	C8—C9	1.511 (3)
Cd1—O5	2.5367 (16)	C9—C10	1.393 (3)
Cd1—O5ⁱ	2.4716 (16)	C9—C14	1.389 (3)
Cd1—O6	2.3264 (15)	C10—C11	1.387 (3)
Cd1—N3	2.3186 (17)	C10—H10	0.9300
Cd1—N5	2.3435 (17)	C11—N2	1.470 (3)
Cd1—C1	2.733 (2)	C11—C12	1.377 (3)
O1—C1	1.264 (3)	C12—C13	1.381 (4)
O5—Cd1ⁱ	2.4716 (16)	C12—H12	0.9300
O5—C8	1.256 (3)	C13—H13	0.9300
O6—C8	1.253 (3)	C14—C13	1.386 (3)
O8—N2	1.210 (3)	C14—H14	0.9300
N1—O3	1.220 (3)	C15—C16	1.384 (3)
N1—O4	1.219 (3)	C15—H15	0.9300
N1—C4	1.472 (3)	C16—C17	1.387 (3)
N2—O7	1.198 (3)	C16—C20	1.438 (4)
N3—C15	1.330 (3)	C17—H17	0.9300
N3—C19	1.339 (3)	C18—C17	1.381 (4)
N4—C20	1.127 (4)	C18—H18	0.9300
N5—C21	1.335 (3)	C19—C18	1.379 (3)
N5—C25	1.331 (3)	C19—H19	0.9300
C1—O2	1.241 (3)	C21—C22	1.387 (3)
C1—C2	1.508 (3)	C21—H21	0.9300
C2—C7	1.381 (3)	C22—C23	1.391 (3)
C3—C2	1.388 (3)	C22—C26	1.443 (3)
C3—C4	1.384 (3)	C23—C24	1.375 (3)
C3—H3	0.9300	C23—H23	0.9300
C4—C5	1.378 (3)	C24—H24	0.9300
C5—C6	1.382 (4)	C25—C24	1.380 (3)
C5—H5	0.9300	C25—H25	0.9300
C6—H6	0.9300	C26—N6	1.144 (3)
C7—C6	1.397 (3)

O1—Cd1—O2	54.33 (5)	C4—C5—H5	120.8
O1—Cd1—O5	161.73 (6)	C6—C5—H5	120.8
O1—Cd1—O5ⁱ	85.39 (6)	C5—C6—C7	120.1 (2)
O1—Cd1—O6	144.74 (6)	C5—C6—H6	120.0
O1—Cd1—N3	88.63 (6)	C7—C6—H6	120.0
O1—Cd1—N5	87.92 (6)	C2—C7—C6	120.5 (2)
O1—Cd1—C1	27.40 (6)	C2—C7—H7	119.7
O2—Cd1—O5	143.94 (5)	C6—C7—H7	119.7
O2—Cd1—C1	26.95 (6)	O5—C8—C9	119.48 (19)
O5ⁱ—Cd1—O2	139.57 (5)	O6—C8—O5	122.10 (18)
O5ⁱ—Cd1—O5	76.40 (5)	O6—C8—C9	118.41 (18)
O5—Cd1—C1	170.87 (6)	C10—C9—C8	119.84 (19)
O5ⁱ—Cd1—C1	112.66 (6)	C14—C9—C8	120.56 (19)
O6—Cd1—O2	90.60 (5)	C14—C9—C10	119.60 (18)
O6—Cd1—O5	53.47 (5)	C9—C10—H10	121.0
O6—Cd1—O5ⁱ	129.14 (5)	C11—C10—C9	117.9 (2)
O6—Cd1—N5	89.46 (6)	C11—C10—H10	121.0
O6—Cd1—C1	117.41 (6)	C10—C11—N2	118.8 (2)
N3—Cd1—O2	93.62 (6)	C12—C11—N2	117.92 (19)
N3—Cd1—O5	89.29 (6)	C12—C11—C10	123.3 (2)
N3—Cd1—O5ⁱ	88.16 (6)	C11—C12—C13	118.0 (2)
N3—Cd1—O6	98.23 (6)	C11—C12—H12	121.0
N3—Cd1—N5	170.84 (6)	C13—C12—H12	121.0
N3—Cd1—C1	92.02 (6)	C12—C13—C14	120.3 (2)
N5—Cd1—O2	91.25 (6)	C12—C13—H13	119.8
N5—Cd1—O5	91.33 (6)	C14—C13—H13	119.8
N5—Cd1—O5ⁱ	83.11 (6)	C9—C14—H14	119.6
N5—Cd1—C1	88.81 (6)	C13—C14—C9	120.9 (2)
C1—O1—Cd1	95.65 (12)	C13—C14—H14	119.6
C1—O2—Cd1	86.70 (13)	N3—C15—C16	121.9 (2)
Cd1ⁱ—O5—Cd1	103.60 (5)	N3—C15—H15	119.0
C8—O5—Cd1ⁱ	165.65 (15)	C16—C15—H15	119.0
C8—O5—Cd1	87.27 (13)	C15—C16—C17	119.8 (2)
C8—O6—Cd1	97.16 (12)	C15—C16—C20	119.9 (2)
O3—N1—C4	118.33 (19)	C17—C16—C20	120.3 (2)
O4—N1—O3	123.3 (2)	C16—C17—H17	120.9
O4—N1—C4	118.4 (2)	C18—C17—C16	118.1 (2)
O7—N2—O8	122.4 (2)	C18—C17—H17	120.9
O7—N2—C11	119.0 (2)	C17—C18—H18	120.7
O8—N2—C11	118.6 (2)	C19—C18—C17	118.7 (2)
C15—N3—Cd1	120.77 (14)	C19—C18—H18	120.7
C15—N3—C19	118.26 (19)	N3—C19—C18	123.2 (2)
C19—N3—Cd1	120.93 (14)	N3—C19—H19	118.4
C21—N5—Cd1	121.21 (14)	C18—C19—H19	118.4
C25—N5—Cd1	121.09 (15)	N4—C20—C16	178.3 (5)
C25—N5—C21	117.68 (19)	N5—C21—C22	122.5 (2)
O1—C1—Cd1	56.96 (10)	N5—C21—H21	118.7
O1—C1—C2	116.79 (18)	C22—C21—H21	118.7
O2—C1—Cd1	66.35 (12)	C21—C22—C23	119.3 (2)
O2—C1—O1	123.24 (19)	C21—C22—C26	119.7 (2)
O2—C1—C2	120.0 (2)	C23—C22—C26	121.0 (2)
C2—C1—Cd1	172.89 (15)	C22—C23—H23	121.1
C3—C2—C1	118.64 (19)	C24—C23—C22	117.9 (2)
C7—C2—C1	121.51 (19)	C24—C23—H23	121.1
C7—C2—C3	119.80 (19)	C23—C24—C25	119.2 (2)
C2—C3—H3	120.6	C23—C24—H24	120.4
C4—C3—C2	118.7 (2)	C25—C24—H24	120.4
C4—C3—H3	120.6	N5—C25—C24	123.4 (2)
C3—C4—N1	118.3 (2)	N5—C25—H25	118.3
C5—C4—N1	119.2 (2)	C24—C25—H25	118.3
C5—C4—C3	122.4 (2)	N6—C26—C22	178.8 (3)
C4—C5—C6	118.5 (2)

O2—Cd1—O1—C1	−1.60 (12)	Cd1—O1—C1—C2	−176.08 (15)
O5—Cd1—O1—C1	179.36 (16)	Cd1—O5—C8—O6	−0.7 (2)
O5ⁱ—Cd1—O1—C1	174.69 (14)	Cd1ⁱ—O5—C8—O6	−140.5 (5)
O6—Cd1—O1—C1	5.3 (2)	Cd1—O5—C8—C9	178.05 (16)
N3—Cd1—O1—C1	−97.04 (14)	Cd1ⁱ—O5—C8—C9	38.3 (7)
N5—Cd1—O1—C1	91.44 (14)	Cd1—O6—C8—O5	0.8 (2)
O1—Cd1—O2—C1	1.62 (12)	Cd1—O6—C8—C9	−177.99 (15)
O5—Cd1—O2—C1	−178.89 (11)	O3—N1—C4—C3	−3.3 (3)
O5ⁱ—Cd1—O2—C1	−4.09 (18)	O3—N1—C4—C5	178.5 (2)
O6—Cd1—O2—C1	−174.39 (13)	O4—N1—C4—C3	176.7 (2)
N3—Cd1—O2—C1	87.33 (13)	O4—N1—C4—C5	−1.5 (3)
N5—Cd1—O2—C1	−84.92 (14)	Cd1—N3—C15—C16	−178.18 (17)
O1—Cd1—O5—Cd1ⁱ	−4.8 (2)	C19—N3—C15—C16	−0.7 (3)
O1—Cd1—O5—C8	−175.30 (18)	Cd1—N3—C19—C18	177.4 (2)
O2—Cd1—O5—Cd1ⁱ	176.53 (8)	C15—N3—C19—C18	0.0 (4)
O2—Cd1—O5—C8	6.03 (18)	Cd1—N5—C21—C22	−178.82 (17)
O5ⁱ—Cd1—O5—Cd1ⁱ	0.0	C25—N5—C21—C22	−0.5 (3)
O5ⁱ—Cd1—O5—C8	−170.51 (16)	Cd1—N5—C25—C24	179.2 (2)
O6—Cd1—O5—Cd1ⁱ	170.93 (10)	C21—N5—C25—C24	0.8 (4)
O6—Cd1—O5—C8	0.42 (12)	O1—C1—O2—Cd1	−2.9 (2)
N3—Cd1—O5—Cd1ⁱ	−88.28 (7)	C2—C1—O2—Cd1	176.33 (17)
N3—Cd1—O5—C8	101.21 (13)	O1—C1—C2—C3	−15.8 (3)
N5—Cd1—O5—Cd1ⁱ	82.58 (7)	O1—C1—C2—C7	161.6 (2)
N5—Cd1—O5—C8	−87.92 (13)	O2—C1—C2—C3	164.9 (2)
O1—Cd1—O6—C8	177.25 (12)	O2—C1—C2—C7	−17.6 (3)
O2—Cd1—O6—C8	−177.13 (13)	C1—C2—C7—C6	−176.7 (2)
O5—Cd1—O6—C8	−0.42 (12)	C3—C2—C7—C6	0.7 (4)
O5ⁱ—Cd1—O6—C8	10.98 (16)	C4—C3—C2—C1	177.69 (18)
N3—Cd1—O6—C8	−83.38 (13)	C4—C3—C2—C7	0.2 (3)
N5—Cd1—O6—C8	91.63 (13)	C2—C3—C4—N1	−179.25 (18)
C1—Cd1—O6—C8	−179.99 (12)	C2—C3—C4—C5	−1.1 (3)
O1—Cd1—N3—C15	146.88 (17)	N1—C4—C5—C6	179.1 (2)
O1—Cd1—N3—C19	−30.50 (17)	C3—C4—C5—C6	0.9 (4)
O2—Cd1—N3—C15	92.75 (17)	C4—C5—C6—C7	0.1 (4)
O2—Cd1—N3—C19	−84.63 (17)	C2—C7—C6—C5	−0.9 (4)
O5—Cd1—N3—C15	−51.27 (16)	O5—C8—C9—C10	−176.4 (2)
O5ⁱ—Cd1—N3—C15	−127.69 (17)	O5—C8—C9—C14	3.1 (3)
O5—Cd1—N3—C19	131.34 (17)	O6—C8—C9—C10	2.4 (3)
O5ⁱ—Cd1—N3—C19	54.93 (17)	O6—C8—C9—C14	−178.1 (2)
O6—Cd1—N3—C15	1.62 (17)	C8—C9—C10—C11	178.96 (19)
O6—Cd1—N3—C19	−175.77 (17)	C14—C9—C10—C11	−0.6 (3)
C1—Cd1—N3—C15	119.69 (17)	C8—C9—C14—C13	179.8 (2)
C1—Cd1—N3—C19	−57.69 (17)	C10—C9—C14—C13	−0.6 (4)
O1—Cd1—N5—C21	25.91 (17)	C9—C10—C11—N2	−179.8 (2)
O1—Cd1—N5—C25	−152.4 (2)	C9—C10—C11—C12	1.4 (4)
O2—Cd1—N5—C21	80.15 (18)	C10—C11—N2—O7	−7.6 (4)
O2—Cd1—N5—C25	−98.16 (19)	C10—C11—N2—O8	173.3 (3)
O5—Cd1—N5—C21	−135.83 (17)	C12—C11—N2—O7	171.3 (3)
O5—Cd1—N5—C25	45.86 (19)	C12—C11—N2—O8	−7.7 (4)
O5ⁱ—Cd1—N5—C25	122.0 (2)	N2—C11—C12—C13	−179.7 (3)
O5ⁱ—Cd1—N5—C21	−59.69 (17)	C10—C11—C12—C13	−0.9 (4)
O6—Cd1—N5—C25	−7.57 (19)	C11—C12—C13—C14	−0.4 (5)
O6—Cd1—N5—C21	170.74 (18)	C9—C14—C13—C12	1.2 (5)
C1—Cd1—N5—C21	53.30 (18)	N3—C15—C16—C17	0.9 (4)
C1—Cd1—N5—C25	−125.0 (2)	N3—C15—C16—C20	−177.6 (3)
O1—Cd1—C1—O2	−177.1 (2)	C15—C16—C17—C18	−0.2 (4)
O2—Cd1—C1—O1	177.1 (2)	C20—C16—C17—C18	178.2 (3)
O5ⁱ—Cd1—C1—O1	−5.74 (15)	C19—C18—C17—C16	−0.4 (4)
O5ⁱ—Cd1—C1—O2	177.13 (13)	N3—C19—C18—C17	0.6 (4)
O6—Cd1—C1—O1	−176.54 (13)	N5—C21—C22—C23	−0.3 (4)
O6—Cd1—C1—O2	6.33 (15)	N5—C21—C22—C26	178.2 (2)
N3—Cd1—C1—O1	83.11 (14)	C21—C22—C23—C24	0.6 (4)
N3—Cd1—C1—O2	−94.02 (14)	C26—C22—C23—C24	−177.8 (3)
N5—Cd1—C1—O1	−87.76 (14)	C22—C23—C24—C25	−0.3 (4)
N5—Cd1—C1—O2	95.10 (14)	N5—C25—C24—C23	−0.5 (5)
Cd1—O1—C1—O2	3.1 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O1ⁱ	0.93	2.20	3.108 (3)	167
C15—H15···O2ⁱⁱ	0.93	2.32	3.111 (3)	143
C23—H23···N4ⁱⁱⁱ	0.93	2.38	3.236 (5)	154
C25—H25···O6	0.93	2.58	3.242 (3)	128
C10—H10···Cg3ⁱⁱ	0.93	3.26	4.186 (3)	176

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

Acknowledgements

The authors acknowledge the Scientific and Technological Research Application and Research Center, Sinop University, Turkey, for the use of the Bruker D8 QUEST diffractometer.

References

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