Crystal structure and Hirshfeld surface analysis of aqua­bis­(nicotinamide-κN1)bis­(2,4,6-tri­methyl­benzoato-κ2O,O′)cadmium(II)

Hökelek, T.; Özkaya, S.; Necefoğlu, H.

doi:10.1107/S2056989018001494

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ISSN: 2056-9890

Volume 74| Part 2| February 2018| Pages 246-251

https://doi.org/10.1107/S2056989018001494

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Crystal structure and Hirshfeld surface analysis of aquabis(nicotinamide-κN¹)bis(2,4,6-trimethylbenzoato-κ²O,O′)cadmium(II)

Tuncer Hökelek,^a ^* Safiye Özkaya ^b and Hacali Necefoğlu ^b,^c

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, and ^cInternational Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 18 January 2018; accepted 23 January 2018; online 31 January 2018)

The asymmetric unit of the title complex, [Cd(C₁₀H₁₁O₂)₂(C₆H₆N₂O)₂(H₂O)], contains one half of the complex molecule, with the Cd^II cation and the coordinated water O atom residing on a twofold rotation axis. The Cd^II cation is coordinated in a bidentate manner to the carboxylate O atoms of the two symmetry-related 2,4,6-trimethylbenzoate (TMB) anions and to the water O atom at distances of 2.297 (2), 2.527 (2) and 2.306 (3) Å to form a distorted pentagonal arrangement, while the distorted pentagonal–bipyramidal coordination sphere is completed by the two pyridine N atoms of the two symmetry-related monodentate nicotinamide (NA) ligands at distances of 2.371 (3) Å in the axial positions. In the crystal, molecules are linked via intermolecular N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds with R₂²(12), R₃³(8), R₃³(14), R₃³(16), R₃³(20), R₃³(22), R₄⁴(22), R₅⁵(16), R₆⁶(16) and R₆⁶(18) ring motifs, forming a three-dimensional architecture. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are H⋯H (56.9%), H⋯C/C⋯H (21.3%) and H⋯O/O⋯H (19.0%) interactions.

Keywords: crystal structure; cadmium(II); transition metal complexes of benzoic acid and nicotinamide derivatives.

CCDC reference: 1818756

1. Chemical context

Nicotinamide (NA) is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels (Krishnamachari, 1974 ). The crystal structure of NA was first determined by Wright & King (1954 ). The NA ring is the reactive part of nicotinamide adenine dinucleotide (NAD) and its phosphate (NADP), which are the major electron carriers in many biological oxidation–reduction reactions (You et al., 1978 ). The nicotinic acid derivative N,N-diethylnicotinamide (DENA) is an important respiratory stimulant (Bigoli et al., 1972 ).

Transition metal complexes with ligands of biochemical interest such as imidazole and some N-protected amino acids show interesting physical and/or chemical properties, through which they may find applications in biological systems (Antolini et al., 1982 ). Crystal structures of metal complexes with benzoic acid derivatives have been reported extensively because of the varieties of the coordination modes. For example, Co and Cd complexes with 4-aminobenzoic acid (Chen & Chen, 2002 ), Co complexes with benzoic acid (Catterick et al., 1974 ), 4-nitrobenzoic acid (Nadzhafov et al., 1981 ) and phthalic acid (Adiwidjaja et al., 1978 ), and Cu complexes with 4-hydrochloric acid (Shnulin et al., 1981 ) have been described.

The structure–function–coordination relationships of the arylcarboxylate ion in Cd^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 and temperature of synthesis (Shnulin et al., 1981). When pyridine and its derivatives are used instead of water molecules, the structure is completely different (Catterick et al., 1974).

The structures of some mononuclear complexes obtained from the reactions of transition metal(II) ions with nicotinamide (NA) and some benzoic acid derivatives as ligands have been determined previously, e.g. [Zn(C₇H₅O₃)₂(C₆H₆N₂O)₂] [(II); Necefoğlu et al., 2002 ], [Mn(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] [(III); Hökelek et al., 2008 ], [Zn(C₈H₈NO₂)₂(C₆H₆N₂O)₂]·H₂O [(IV); Hökelek et al., 2009a ], [Mn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂] [(V); Hökelek et al., 2009b ] and [Co(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂] [(VI); Hökelek et al., 2009c ]. The structure determination of the title compound, (I), a cadmium complex with two 2,4,6-trimethylbenzoate (TMB) and two nicotinamide (NA) ligands and one coordinated water molecule, was undertaken in order to compare the results obtained with those reported previously. In this context, we synthesized the Cd^II-containing title compound and report herein its crystal and molecular structures along with the Hirshfeld surface analysis.

2. Structural commentary

The asymmetric unit of the crystal structure of the mononuclear title complex contains half of a Cd^II cation (site symmetry 2), one 2,4,6-trimethylbenzoate (TMB) anion and one nicotinamide (NA) molecule together with half of a water molecule (point group symmetry 2), the TMB and NA ligands coordinating in bidentate and monodentate manners, respectively (Fig. 1).

Figure 1
The molecular structure of the title complex with the atom-numbering scheme. Unlabelled atoms are related to labelled atoms by the symmetry operation (1 − x, y, $[{1\over 2}]$ − z). Displacement ellipsoids are drawn at the 50% probability level.

The Cd^II cation is coordinated bidentately to the carboxylate O atoms (O1, O2, O1ⁱ and O2ⁱ) of two symmetry-related 2,4,6-trimethylbenzoate (TMB) anions and to the water O atom (O4) at distances of 2.297 (2), 2.527 (2) and 2.306 (3) Å, respectively, to form a distorted pentagonal arrangement. The sum of the bond angles O1—Cd1—O1ⁱ [87.57 (11)°], O1—Cd1—O2 [53.63 (7)°], O1ⁱ—Cd1—O2ⁱ [53.63 (7)°], O2—Cd1—O4 [84.47 (5)°] and O2ⁱ—Cd1—O4 [84.47 (5)°] in the basal plane around Cd^II cation is 363.77° [symmetry code: (i) 1 − x, y, $[{1\over 2}]$ − z]. This confirms the presence of the Cd^II cation with a small deviation from the basal plane. The distorted pentagonal–bipyramidal coordination sphere is completed by the two pyridine N atoms (N1 and N1ⁱ) of the two symmetry-related monodentate nicotinamide (NA) ligands at distances of 2.371 (3) Å in the axial positions (Fig. 1).

The near equalities of the C1—O1 [1.249 (4) Å] and C1—O2 [1.253 (3) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The O2—C1—O1 bond angle [121.7 (3)°] seems to be slightly decreased than that present in a free acid [122.2°]. The O2—C1—O1 bond angle may be compared with the corresponding values of 123.5 (2) and 120.4 (2)° in (II), 125.2 (5)° in (III), 119.2 (3) and 123.8 (2)° in (IV), 123.6 (3) and 119.4 (3)° in (V) and 123.86 (13) and 118.49 (14)° in (VI), where the benzoate ions are coordinated to the metal atoms only monodentately in (III), and both monodentately and bidentately in (II), (IV), (V) and (VI). The Cd1 atom lies 0.0192 (1) Å above of the planar (O1/O2/C1) carboxylate group. The O1—Cd1—O2 angle is 53.63 (7)°. The corresponding O—M—O angles are 58.79 (6)° in (II), 59.02 (8)° in (IV), 58.45 (9)° in (V) and 60.70 (4)° in (VI). In the TMB anion, the carboxylate group is twisted away from the attached benzene ring, A (C2–C7), ring by 60.94 (18)°, while the benzene and pyridine rings [pyridine = B (N1/C11–C15)], are oriented at a dihedral angle of 50.32 (11)°. The four-membered ring D (Cd1/O1/O2/C1) is nearly planar with a maximum deviation of 0.0029 (30) Å (for C1) from the mean plane, and it is oriented at dihedral angles of 60.98 (11) and 81.91 (7)°, with respect to the A and B rings.

3. Supramolecular features

In the crystal, the molecules are linked via intermolecular N—H_NA⋯O_NA, N—H_NA⋯O_C, O—H_W⋯O_NA and C—H_TMB⋯O_C (NA = nicotinamide, C = carboxylate, W = water and TMB = 2,4,6-trimethylbenzoate) hydrogen bonds (Table 1) with R₂²(12), R₃³(8), R₃³(14), R₃³(16), R₃³(20), R₃³(22), R₄⁴(22), R₅⁵(16), R₆⁶(16) and R₆⁶(18) ring motifs (Fig. 2), forming a three-dimensional architecture. Hydrogen-bonding and van der Waals contacts are the dominant interactions in the crystal packing. No significant π–π or C—H⋯π interactions are observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3^vi	0.89 (3)	2.26 (4)	3.047 (4)	147 (3)
N2—H2B⋯O2^vii	0.81 (3)	2.03 (3)	2.830 (4)	168 (4)
O4—H41⋯O3ⁱⁱⁱ	0.80 (3)	1.92 (3)	2.714 (3)	170 (3)
C8—H8C⋯O1^viii	0.96	2.55	3.468 (5)	161
Symmetry codes: (iii) -x+1, -y+2, -z+1; (vi) $[x, -y+2, z+{\script{1\over 2}}]$ ; (vii) x, y, z+1; (viii) $[x, -y+1, z-{\script{1\over 2}}]$ .

Figure 2
Part of the crystal structure. O—H_W⋯O_NA, N—H_NA⋯O_C and N—H_NA⋯O_NA (W = water, C = carboxylate and NA = nicotinamide) hydrogen bonds, enclosing R₂²(12), R₃³(8), R₃³(14), R₃³(16), R₃³(20), R₃³(22), R₄⁴(22), R₅⁵(16), R₆⁶(16) and R₆⁶(18) ring motifs are shown as dashed lines. C-bound H atoms have been omitted for clarity.

4. Hirshfeld surface analysis

Visulization and exploration of intermolecular close contacts of a structure is invaluable, and this can be achieved using Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ; Spackman & Jayatilaka, 2009 ). An HS analysis was carried out by using CrystalExplorer17.5 (Turner et al., 2017 ) to investigate the locations of atom⋯atom short contacts with the potential to form hydrogen bonds and the quantitative ratios of these interactions and the π-stacking interactions in the crystal structure of the title complex.

In the HS plotted over d_norm (Fig. 3), the white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact) than the van der Waals radii, respectively (Venkatesan et al., 2016 ). The bright-red spots appearing near NA-O3, TMB-O1 and O2, and hydrogen atoms H2A, H2B, H41 and H8C indicate their role as the respective donors and acceptors in the dominant O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds; they also appear as blue and red regions corresponding to positive and negative potentials on the HS mapped over electrostatic potential (Spackman et al., 2008 ; Jayatilaka et al., 2005 ) as shown in Fig. 4. The blue regions indicate the positive electrostatic potential (hydrogen-bond donors), while the red regions indicate the negative electrostatic potential (hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 5 clearly suggests that there are no π–π interactions in (I).

Figure 3
View of the three-dimensional Hirshfeld surface of the title complex plotted over d_norm in the range −0.6741 to 1.6440 a.u.

Figure 4
View of the three-dimensional Hirshfeld surface of the title complex plotted over electrostatic potential energy in the range −0.1379 to 0.1988 a.u. using the STO-3G basis set at the Hartree–Fock level of theory. The N—H⋯O, O—H⋯O and C—H⋯O hydrogen-bond donors and acceptors are viewed as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.

Figure 5
Hirshfeld surface of the title complex plotted over shape-index.

The overall two-dimensional fingerprint plot, Fig. 6a, and those delineated into H⋯H, H⋯C/C⋯H, H⋯O/O⋯H, H⋯N/N⋯H, C⋯C and O⋯C/C⋯O contacts (McKinnon et al., 2007 ) are illustrated in Fig. 6b–g, respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯H, contributing 56.9% to the overall crystal packing, which is reflected in Fig. 6b as widely scattered points of high density due to the large hydrogen content of the molecule. The single spike in the centre at d_e = d_i = 1.2 Å in Fig. 6b is due to a short interatomic H⋯H contact (Table 2). In the absence of C—H⋯π interactions in the crystal, the pair of characteristic wings resulting in the fingerprint plot delineated into H⋯C/C⋯H contacts, with 21.3% contribution to the HS, Fig. 6c; the pair of thin edges at d_e + d_i ∼ 1.67 Å result from short interatomic H⋯C/C⋯H contacts (Table 2). In the fingerprint plot delineated into H⋯O/O⋯H contacts, Fig. 6d, the 19.0% contribution to the HS arises from intermolecular O—H⋯O hydrogen bonding and is viewed as a pair of spikes with the tip at d_e + d_i ∼ 1.74 Å. The short H⋯O/O⋯H contacts are masked by strong O—H⋯O hydrogen bonding in this plot. The H⋯N/N⋯H contacts in the structure, with a 1.9% contribution to the HS, has a symmetrical distribution of points, Fig. 6e, with the tips at d_e + d_i ∼ 2.96 Å arising from the short interatomic H⋯N/N⋯H contact listed in Table 2. The Hirshfeld surface representations with the function d_norm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H, H⋯O/O⋯H and H⋯N/N⋯H interactions in Fig. 7a–d, respectively.

Table 2
Selected interatomic distances (Å)

O1⋯H8Cⁱ	2.55	N2⋯H13	2.75
O2⋯H2Bⁱⁱ	2.03 (3)	C6⋯H14ⁱⁱ	2.80
O3⋯H41ⁱⁱⁱ	1.92 (3)	C16⋯H41ⁱⁱⁱ	2.85 (3)
O3⋯H2A^iv	2.26 (4)	H8A⋯H8A^v	2.54
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) x, y, z-1; (iii) -x+1, -y+2, -z+1; (iv) $[x, -y+2, z-{\script{1\over 2}}]$ ; (v) -x+1, -y+1, -z.

Figure 6
The full two-dimensional fingerprint plots for the title complex, showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯O/O⋯H, (e) H⋯N/N⋯H, (f) C⋯C and (g) O⋯C/C⋯O interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

Figure 7
The Hirshfeld surface representations with the function d_norm plotted onto the surface for (a) H⋯H, (b) H⋯C/C⋯H, (c) H⋯O/O⋯H and (d) H⋯N/N⋯H interactions.

The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

5. Synthesis and crystallization

The title compound was prepared by the reaction of 3CdSO₄·8H₂O (0.64 g, 2.5 mmol) in water (50 ml) and nicotinamide (0.61 g, 5 mmol) in water (25 ml) with sodium 2,4,6-trimethylbenzoate (0.93 g, 5 mmol) in water (150 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for six weeks, giving colourless single crystals (yield: 1.42 g, 85%). Combustion analysis: found; C, 57.07, H, 5.67, N, 7.92%. Calculated: C₃₂H₃₆CdN₄O₇ C, 57.42; H, 5.43, N, 8.34%. FT–IR: 3390, 3122, 2921, 1669, 1619, 1539, 1445, 1399, 1113, 1038, 847, 731, 641 cm⁻¹.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The H atoms of the NH₂ group and of the water molecule were located in difference-Fourier maps and refined freely. The C-bound H atoms were positioned geometrically with C—H = 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with U_iso(H) = k × U_eq(C), where k = 1.5 for methyl H-atoms and k = 1.2 for aromatic H-atoms.

Table 3
Experimental details

Crystal data
Chemical formula	[Cd(C₁₀H₁₁O₂)₂(C₆H₆N₂O)₂(H₂O)]
M_r	701.05
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	296
a, b, c (Å)	23.6876 (5), 15.6711 (4), 9.0682 (2)
V (Å³)	3366.21 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.70
Crystal size (mm)	0.45 × 0.28 × 0.21

Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.784, 0.867
No. of measured, independent and observed [I > 2σ(I)] reflections	68263, 4213, 3681
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.099, 1.32
No. of reflections	4213
No. of parameters	215
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.47
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1818756

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018001494/xu5916sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018001494/xu5916Isup2.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).

Aquabis(nicotinamide-κN¹)bis(2,4,6-trimethylbenzoato-κ²O,O')cadmium(II) top

Crystal data top

[Cd(C₁₀H₁₁O₂)₂(C₆H₆N₂O)₂(H₂O)]	F(000) = 1440
M_r = 701.05	D_x = 1.383 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 9766 reflections
a = 23.6876 (5) Å	θ = 2.6–28.4°
b = 15.6711 (4) Å	µ = 0.70 mm⁻¹
c = 9.0682 (2) Å	T = 296 K
V = 3366.21 (13) Å³	Block, colorless
Z = 4	0.45 × 0.28 × 0.21 mm

Data collection top

Bruker SMART BREEZE CCD diffractometer	4213 independent reflections
Radiation source: fine-focus sealed tube	3681 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
φ and ω scans	θ_max = 28.4°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −31→31
T_min = 0.784, T_max = 0.867	k = −20→20
68263 measured reflections	l = −11→12

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.32	w = 1/[σ²(F_o²) + (0.0171P)² + 5.5549P] where P = (F_o² + 2F_c²)/3
4213 reflections	(Δ/σ)_max = 0.001
215 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.47 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	0.5000	0.746100 (17)	0.2500	0.03358 (9)
O1	0.43935 (10)	0.64030 (14)	0.1751 (3)	0.0472 (6)
O2	0.42005 (10)	0.76163 (14)	0.0676 (3)	0.0468 (6)
O3	0.42068 (10)	0.98712 (14)	0.6880 (3)	0.0471 (5)
O4	0.5000	0.8932 (2)	0.2500	0.0481 (8)
H41	0.5257 (14)	0.924 (2)	0.272 (4)	0.041 (10)*
N1	0.44028 (11)	0.75971 (16)	0.4585 (3)	0.0392 (6)
N2	0.41074 (13)	0.91347 (19)	0.9004 (3)	0.0434 (7)
H2A	0.4139 (15)	0.960 (2)	0.957 (4)	0.053 (11)*
H2B	0.4105 (15)	0.867 (2)	0.939 (4)	0.050 (11)*
C1	0.41017 (13)	0.68404 (18)	0.0888 (3)	0.0344 (6)
C2	0.36190 (13)	0.64076 (19)	0.0124 (3)	0.0387 (7)
C3	0.30699 (16)	0.6685 (3)	0.0358 (5)	0.0587 (10)
C4	0.26341 (18)	0.6243 (4)	−0.0346 (6)	0.0812 (15)
H4	0.2264	0.6419	−0.0194	0.097*
C5	0.2733 (2)	0.5561 (4)	−0.1254 (6)	0.0801 (15)
C6	0.32799 (19)	0.5306 (3)	−0.1478 (5)	0.0662 (12)
H6	0.3351	0.4847	−0.2100	0.079*
C7	0.37317 (16)	0.5717 (2)	−0.0798 (4)	0.0475 (8)
C8	0.43251 (18)	0.5435 (3)	−0.1127 (5)	0.0715 (13)
H8A	0.4488	0.5186	−0.0259	0.107*
H8B	0.4546	0.5919	−0.1425	0.107*
H8C	0.4320	0.5021	−0.1907	0.107*
C9	0.2941 (2)	0.7424 (4)	0.1375 (7)	0.099 (2)
H9A	0.3084	0.7301	0.2343	0.149*
H9B	0.2540	0.7509	0.1424	0.149*
H9C	0.3118	0.7932	0.1004	0.149*
C10	0.2234 (3)	0.5105 (5)	−0.1995 (8)	0.143 (3)
H10A	0.2204	0.4535	−0.1614	0.214*
H10B	0.2295	0.5083	−0.3041	0.214*
H10C	0.1892	0.5411	−0.1792	0.214*
C11	0.44160 (12)	0.82871 (18)	0.5440 (3)	0.0361 (6)
H11	0.4655	0.8732	0.5176	0.043*
C12	0.40932 (12)	0.83775 (17)	0.6698 (3)	0.0314 (6)
C13	0.37296 (15)	0.7725 (2)	0.7083 (4)	0.0445 (8)
H13	0.3509	0.7761	0.7929	0.053*
C14	0.37015 (16)	0.7016 (2)	0.6178 (4)	0.0529 (9)
H14	0.3455	0.6572	0.6398	0.064*
C15	0.40397 (16)	0.6973 (2)	0.4953 (4)	0.0470 (8)
H15	0.4017	0.6493	0.4353	0.056*
C16	0.41406 (12)	0.91928 (18)	0.7553 (3)	0.0357 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03990 (16)	0.02586 (14)	0.03497 (16)	0.000	−0.00070 (14)	0.000
O1	0.0606 (14)	0.0357 (11)	0.0452 (13)	−0.0048 (10)	−0.0166 (11)	0.0054 (10)
O2	0.0552 (14)	0.0349 (11)	0.0504 (14)	−0.0075 (10)	−0.0097 (12)	0.0037 (10)
O3	0.0675 (15)	0.0323 (11)	0.0413 (12)	−0.0071 (10)	−0.0008 (12)	0.0041 (10)
O4	0.0467 (19)	0.0269 (14)	0.071 (2)	0.000	−0.0015 (19)	0.000
N1	0.0449 (14)	0.0373 (13)	0.0356 (14)	−0.0081 (11)	0.0017 (11)	−0.0062 (11)
N2	0.0645 (19)	0.0310 (13)	0.0346 (14)	0.0058 (13)	−0.0028 (13)	−0.0019 (12)
C1	0.0408 (15)	0.0326 (14)	0.0299 (14)	−0.0032 (12)	0.0014 (12)	−0.0019 (12)
C2	0.0418 (16)	0.0375 (15)	0.0369 (16)	−0.0074 (13)	−0.0042 (13)	0.0058 (13)
C3	0.0457 (19)	0.073 (3)	0.057 (2)	−0.0045 (18)	0.0016 (17)	−0.003 (2)
C4	0.042 (2)	0.121 (4)	0.081 (3)	−0.018 (2)	−0.003 (2)	0.005 (3)
C5	0.072 (3)	0.101 (4)	0.067 (3)	−0.043 (3)	−0.016 (2)	0.001 (3)
C6	0.085 (3)	0.056 (2)	0.058 (2)	−0.030 (2)	−0.011 (2)	−0.0060 (19)
C7	0.061 (2)	0.0349 (16)	0.0465 (19)	−0.0115 (15)	−0.0078 (16)	0.0007 (14)
C8	0.074 (3)	0.057 (2)	0.083 (3)	0.010 (2)	−0.005 (2)	−0.032 (2)
C9	0.055 (3)	0.130 (5)	0.113 (5)	0.017 (3)	0.009 (3)	−0.042 (4)
C10	0.103 (4)	0.189 (7)	0.137 (6)	−0.085 (5)	−0.034 (4)	−0.022 (5)
C11	0.0391 (15)	0.0323 (14)	0.0368 (15)	−0.0100 (12)	0.0041 (13)	0.0004 (12)
C12	0.0359 (14)	0.0310 (13)	0.0274 (13)	−0.0027 (11)	−0.0015 (11)	0.0032 (11)
C13	0.0507 (19)	0.0490 (18)	0.0340 (16)	−0.0122 (15)	0.0065 (14)	0.0034 (14)
C14	0.068 (2)	0.0449 (18)	0.0457 (19)	−0.0277 (17)	0.0084 (17)	0.0038 (15)
C15	0.067 (2)	0.0339 (15)	0.0403 (17)	−0.0140 (15)	0.0006 (16)	−0.0033 (14)
C16	0.0361 (14)	0.0356 (14)	0.0353 (14)	0.0009 (11)	−0.0012 (13)	0.0013 (13)

Geometric parameters (Å, º) top

Cd1—O1	2.297 (2)	C4—H4	0.9300
Cd1—O1ⁱ	2.297 (2)	C5—C10	1.536 (6)
Cd1—O2	2.527 (2)	C6—C5	1.371 (7)
Cd1—O2ⁱ	2.527 (2)	C6—H6	0.9300
Cd1—O4	2.306 (3)	C7—C6	1.392 (5)
Cd1—N1	2.371 (3)	C7—C8	1.503 (5)
Cd1—N1ⁱ	2.371 (3)	C8—H8A	0.9600
Cd1—C1	2.759 (3)	C8—H8B	0.9600
Cd1—C1ⁱ	2.759 (3)	C8—H8C	0.9600
O1—C1	1.249 (4)	C11—H11	0.9300
O2—C1	1.253 (3)	C12—C11	1.380 (4)
O3—C16	1.236 (4)	C12—C13	1.382 (4)
O4—H41	0.80 (3)	C12—C16	1.499 (4)
N1—C11	1.331 (4)	C13—C14	1.382 (5)
N1—C15	1.344 (4)	C13—H13	0.9300
N2—C16	1.321 (4)	C14—H14	0.9300
N2—H2A	0.90 (4)	C15—C14	1.371 (5)
N2—H2B	0.81 (4)	C15—H15	0.9300
C1—C2	1.499 (4)	C9—H9A	0.9600
C2—C3	1.388 (5)	C9—H9B	0.9600
C2—C7	1.394 (5)	C9—H9C	0.9600
C3—C4	1.397 (6)	C10—H10A	0.9600
C3—C9	1.512 (6)	C10—H10B	0.9600
C4—C5	1.370 (7)	C10—H10C	0.9600

O1···H8Cⁱⁱ	2.55	N2···H13	2.75
O2···H2Bⁱⁱⁱ	2.03 (3)	C6···H14ⁱⁱⁱ	2.80
O3···H41^iv	1.92 (3)	C16···H41^iv	2.85 (3)
O3···H2A^v	2.26 (4)	H8A···H8A^vi	2.54

O1—Cd1—O1ⁱ	87.57 (11)	C7—C2—C1	118.9 (3)
O1—Cd1—O2	53.63 (7)	C2—C3—C4	117.9 (4)
O1ⁱ—Cd1—O2	137.06 (8)	C2—C3—C9	121.5 (4)
O1—Cd1—O2ⁱ	137.06 (8)	C4—C3—C9	120.6 (4)
O1ⁱ—Cd1—O2ⁱ	53.63 (7)	C3—C4—H4	118.8
O1—Cd1—O4	136.22 (6)	C5—C4—C3	122.3 (4)
O1ⁱ—Cd1—O4	136.22 (6)	C5—C4—H4	118.8
O1—Cd1—N1	85.85 (9)	C4—C5—C6	118.6 (4)
O1ⁱ—Cd1—N1	101.67 (9)	C4—C5—C10	119.7 (5)
O1—Cd1—N1ⁱ	101.67 (9)	C6—C5—C10	121.8 (5)
O1ⁱ—Cd1—N1ⁱ	85.85 (9)	C5—C6—C7	121.8 (4)
O1—Cd1—C1	26.66 (8)	C5—C6—H6	119.1
O1ⁱ—Cd1—C1	112.62 (9)	C7—C6—H6	119.1
O1—Cd1—C1ⁱ	112.62 (9)	C2—C7—C8	121.7 (3)
O1ⁱ—Cd1—C1ⁱ	26.66 (8)	C6—C7—C2	118.5 (4)
O2—Cd1—O2ⁱ	168.94 (10)	C6—C7—C8	119.7 (4)
O2—Cd1—C1	26.97 (7)	C7—C8—H8A	109.5
O2ⁱ—Cd1—C1	163.57 (8)	C7—C8—H8B	109.5
O2—Cd1—C1ⁱ	163.57 (8)	C7—C8—H8C	109.5
O2ⁱ—Cd1—C1ⁱ	26.97 (7)	H8A—C8—H8B	109.5
O4—Cd1—O2	84.47 (5)	H8A—C8—H8C	109.5
O4—Cd1—O2ⁱ	84.47 (5)	H8B—C8—H8C	109.5
O4—Cd1—N1	84.84 (6)	C3—C9—H9A	109.5
O4—Cd1—N1ⁱ	84.84 (6)	C3—C9—H9B	109.5
O4—Cd1—C1	110.64 (6)	C3—C9—H9C	109.5
O4—Cd1—C1ⁱ	110.64 (6)	H9A—C9—H9B	109.5
N1—Cd1—O2	93.81 (9)	H9A—C9—H9C	109.5
N1ⁱ—Cd1—O2	85.20 (9)	H9B—C9—H9C	109.5
N1—Cd1—O2ⁱ	85.20 (9)	C5—C10—H10A	109.5
N1ⁱ—Cd1—O2ⁱ	93.81 (9)	C5—C10—H10B	109.5
N1—Cd1—N1ⁱ	169.68 (12)	C5—C10—H10C	109.5
N1—Cd1—C1	89.67 (9)	H10A—C10—H10B	109.5
N1ⁱ—Cd1—C1	93.97 (9)	H10A—C10—H10C	109.5
N1—Cd1—C1ⁱ	93.97 (9)	H10B—C10—H10C	109.5
N1ⁱ—Cd1—C1ⁱ	89.67 (9)	N1—C11—C12	123.5 (3)
C1—Cd1—C1ⁱ	138.71 (12)	N1—C11—H11	118.3
C1—O1—Cd1	97.78 (18)	C12—C11—H11	118.3
C1—O2—Cd1	86.90 (18)	C11—C12—C13	118.6 (3)
Cd1—O4—H41	127 (2)	C11—C12—C16	118.3 (3)
C11—N1—Cd1	121.6 (2)	C13—C12—C16	123.1 (3)
C11—N1—C15	117.5 (3)	C12—C13—C14	118.3 (3)
C15—N1—Cd1	120.9 (2)	C12—C13—H13	120.8
C16—N2—H2A	121 (2)	C14—C13—H13	120.8
C16—N2—H2B	120 (3)	C13—C14—H14	120.3
H2A—N2—H2B	119 (4)	C15—C14—C13	119.5 (3)
O1—C1—Cd1	55.57 (15)	C15—C14—H14	120.3
O1—C1—O2	121.7 (3)	N1—C15—C14	122.6 (3)
O1—C1—C2	117.6 (3)	N1—C15—H15	118.7
O2—C1—Cd1	66.13 (17)	C14—C15—H15	118.7
O2—C1—C2	120.7 (3)	O3—C16—N2	124.0 (3)
C2—C1—Cd1	173.1 (2)	O3—C16—C12	119.1 (3)
C3—C2—C1	120.2 (3)	N2—C16—C12	116.9 (3)
C3—C2—C7	121.0 (3)

O1ⁱ—Cd1—O1—C1	−160.5 (2)	N1ⁱ—Cd1—C1—O2	−71.26 (19)
O2—Cd1—O1—C1	−0.25 (18)	C1ⁱ—Cd1—C1—O1	14.27 (18)
O2ⁱ—Cd1—O1—C1	175.96 (17)	C1ⁱ—Cd1—C1—O2	−165.28 (19)
O4—Cd1—O1—C1	19.5 (2)	Cd1—O1—C1—O2	0.5 (3)
N1—Cd1—O1—C1	97.6 (2)	Cd1—O1—C1—C2	−178.5 (2)
N1ⁱ—Cd1—O1—C1	−75.3 (2)	Cd1—O2—C1—O1	−0.4 (3)
C1ⁱ—Cd1—O1—C1	−169.85 (13)	Cd1—O2—C1—C2	178.6 (3)
O1—Cd1—O2—C1	0.25 (17)	Cd1—N1—C11—C12	−177.2 (2)
O1ⁱ—Cd1—O2—C1	29.9 (2)	C15—N1—C11—C12	2.4 (5)
O2ⁱ—Cd1—O2—C1	−166.18 (18)	Cd1—N1—C15—C14	177.8 (3)
O4—Cd1—O2—C1	−166.18 (18)	C11—N1—C15—C14	−1.8 (5)
N1—Cd1—O2—C1	−81.75 (19)	O1—C1—C2—C3	118.2 (4)
N1ⁱ—Cd1—O2—C1	108.55 (19)	O1—C1—C2—C7	−60.7 (4)
C1ⁱ—Cd1—O2—C1	36.3 (5)	O2—C1—C2—C3	−60.9 (4)
O1—Cd1—N1—C11	−162.7 (3)	O2—C1—C2—C7	120.2 (3)
O1ⁱ—Cd1—N1—C11	110.6 (2)	C1—C2—C3—C4	−178.2 (4)
O1—Cd1—N1—C15	17.7 (3)	C1—C2—C3—C9	0.1 (6)
O1ⁱ—Cd1—N1—C15	−68.9 (3)	C7—C2—C3—C4	0.7 (6)
O2—Cd1—N1—C11	−109.6 (2)	C7—C2—C3—C9	179.0 (4)
O2ⁱ—Cd1—N1—C11	59.3 (2)	C3—C2—C7—C6	−0.3 (5)
O2—Cd1—N1—C15	70.8 (3)	C1—C2—C7—C6	178.6 (3)
O2ⁱ—Cd1—N1—C15	−120.2 (3)	C3—C2—C7—C8	176.8 (4)
O4—Cd1—N1—C11	−25.6 (2)	C1—C2—C7—C8	−4.3 (5)
O4—Cd1—N1—C15	154.9 (3)	C2—C3—C4—C5	−0.5 (7)
N1ⁱ—Cd1—N1—C11	−25.6 (2)	C9—C3—C4—C5	−178.8 (5)
N1ⁱ—Cd1—N1—C15	154.9 (3)	C3—C4—C5—C6	−0.2 (8)
C1—Cd1—N1—C11	−136.3 (2)	C3—C4—C5—C10	−180.0 (5)
C1ⁱ—Cd1—N1—C11	84.8 (3)	C7—C6—C5—C4	0.6 (7)
C1—Cd1—N1—C15	44.1 (3)	C7—C6—C5—C10	−179.6 (5)
C1ⁱ—Cd1—N1—C15	−94.7 (3)	C2—C7—C6—C5	−0.4 (6)
O1ⁱ—Cd1—C1—O1	21.1 (3)	C8—C7—C6—C5	−177.6 (4)
O1—Cd1—C1—O2	−179.6 (3)	C13—C12—C11—N1	−1.1 (5)
O1ⁱ—Cd1—C1—O2	−158.40 (18)	C16—C12—C11—N1	−179.1 (3)
O2—Cd1—C1—O1	179.6 (3)	C11—C12—C13—C14	−0.8 (5)
O2ⁱ—Cd1—C1—O1	−9.8 (4)	C16—C12—C13—C14	177.1 (3)
O2ⁱ—Cd1—C1—O2	170.68 (14)	C11—C12—C16—O3	36.2 (4)
O4—Cd1—C1—O1	−165.73 (18)	C11—C12—C16—N2	−143.9 (3)
O4—Cd1—C1—O2	14.72 (19)	C13—C12—C16—O3	−141.7 (3)
N1—Cd1—C1—O1	−81.4 (2)	C13—C12—C16—N2	38.2 (4)
N1ⁱ—Cd1—C1—O1	108.3 (2)	C12—C13—C14—C15	1.3 (6)
N1—Cd1—C1—O2	99.07 (19)	N1—C15—C14—C13	0.0 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3^vii	0.89 (3)	2.26 (4)	3.047 (4)	147 (3)
N2—H2B···O2^viii	0.81 (3)	2.03 (3)	2.830 (4)	168 (4)
O4—H41···O3^iv	0.80 (3)	1.92 (3)	2.714 (3)	170 (3)
C8—H8C···O1^ix	0.96	2.55	3.468 (5)	161

Symmetry codes: (iv) −x+1, −y+2, −z+1; (vii) x, −y+2, z+1/2; (viii) x, y, z+1; (ix) x, −y+1, z−1/2.

Acknowledgements

The authors acknowledge the Aksaray University, Science and Technology Application and Research Center, Aksaray, Turkey, for the use of the Bruker SMART BREEZE CCD diffractometer (purchased under grant No. 2010K120480 of the State Planning Organization).

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