research communications
κN1)bis(2,4,6-trimethylbenzoato-κO)zinc
and Hirshfeld surface analysis of aquabis(nicotinamide-aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, bDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, and cDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, International Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan
*Correspondence e-mail:
The 10H11O2)2(C6H6N2O)2(H2O)], contains one half of the complex molecule, and the ZnII cation and the water O atom lie on a twofold rotation axis. The ZnII cation is coordinated by two carboxylate O atoms of the two symmetry-related 2,4,6-trimethylbenzoate (TMB) anions and by the water O atom at distances of 2.0311 (16) and 2.076 (2) Å to form a slightly distorted trigonal–planar arrangement, while the distorted trigonal–bipyramidal coordination sphere is completed by the two pyridine N atoms of the two symmetry-related monodentate nicotinamide (NA) ligands at distances of 2.2066 (19) Å in the axial positions. In the crystal, molecules are linked via intermolecular N—H⋯O and O—H⋯O hydrogen bonds with R22(12), R33(10) and R33(16) ring motifs, forming a double-column structure running along the c-axis direction. The Hirshfeld surface analysis of the indicates that the most important contributions for the crystal packing are from H⋯H (58.4%), H⋯C/C⋯H (20.3%) and H⋯O/O⋯H (18.3%) interactions.
of the title complex, [Zn(CKeywords: crystal structure; zinc; transition metal complex of benzoic acid and nicotinamide derivatives.
CCDC reference: 1567723
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 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). A nicotinic acid derivative, N,N-diethylnicotinamide (DENA), is an important respiratory stimulant (Bigoli et al., 1972).
The transition metal complexes with ligands of biochemical interest 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)]. 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, 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], [Ni(C7H4ClO2)2(C6H6N2O)2(H2O)2] [(VI); Hökelek et al., 2009c] and [Zn(C7H4BrO2)2(C6H6N2O)2(H2O)2] [(VII); Hökelek et al., 2009d], have been determined previously. The of the title compound, [Zn(C10H11O2)2(C6H6ON2)2(H2O)] (I), a zinc complex with two 2,4,6-trimethylbenzoate (TMB) and two nicotinamide (NA) ligands and one coordinating water molecule, was undertaken in order to compare the results obtained with those reported previously. In this context, we synthesized the title compound and report herein its crystal and molecular structures along with the Hirshfeld surface analysis.
2. Structural commentary
The II cation (site symmetry 2), one 2,4,6-trimethylbenzoate (TMB) anion and one nicotinamide (NA) molecule together with one water molecule (point group symmetry 2), all ligands coordinating in a monodentate manner (Fig. 1). The ZnII cation is penta-coordinated via two nitrogen atoms of NA and two oxygen atoms of TMB anions and one oxygen atom of the water molecule. The two carboxylate O atoms [O2 and O2i; symmetry code: (i) 1 − x, y, − z] of the two symmetry-related monodentate TMB anions and the coordinating water O atom (O4) are at distances of 2.0311 (16) and 2.076 (2) Å, respectively, around the Zn1 atom and form a slightly distorted triangular planar arrangement. The sum of the bond angles O2—Zn1—O2i [95.38 (9)°], O2—Zn1—O4 [132.31 (5)°] and O2—Zn1—O4i [132.31 (5)°] in the basal plane around ZnII cation is 360°. This confirms the presence of the ZnII cation with very slight deviation from the basal plane. The slightly distorted trigonal–bipyramidal coordination sphere is completed by the two pyridine N atoms (N1 and N1i) of the two symmetry-related monodentate NA ligands at distances of 2.2066 (19) Å in the axial positions. The index of trigonality τ [where τ = (β - α)/60, in which α and β are the two largest coordination angles; Addison et al. (1984)] was calculated as 0.65 by taking N1—Zn1—N1 as β [171.42 (8)°] and O2—Zn1—O4 as α [132.31 (5)°]. In general, τ = 0 for an ideal square pyramidal and τ = 1 for an ideal trigonal–pyramidal geometry. In the present case, the obtained τ value is slightly closer to a trigonal–pyramidal geometry.
of the of the mononuclear title complex contains one ZnThe near equalities of the C1—O1 [1.240 (3) Å] and C1—O2 [1.259 (3) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements rather than localized single and double bonds. The O2—C1—O1 bond angle [121.8 (2)°] seems to be slightly decreased than that present in a free acid [122.2°], in which 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), 124.4 (2)° in (VI) and 124.3 (2)° in (VII), where the benzoate ions coordinate to the metal atoms only monodentately in (III), (VI) and (VII), and both monodentately and bidentately in (II), (IV) and (V). The Zn1 atom lies 0.0817 (1) Å above of the planar (O1/O2/C1) carboxylate group. In the TMB anion, the carboxylate group is twisted away from the attached benzene C2–C7 ring by 61.32 (14)°, while the benzene ring and the pyridine N1/C11–C15 ring are oriented at a dihedral angle of 81.90 (8)°.
3. Supramolecular features
In the crystal, the NH2 group links to the non-coordinating carboxylate and NA oxygen atoms via intermolecular N—H⋯O hydrogen bonds, and the water molecule links to the NA oxygen atoms via intermolecular O—H⋯O hydrogen bonds (Table 1). These hydrogen bonds, enclosing R22(12), R33(10) and R33(16) ring motifs, link the molecules into a network consisting of a double-column structure running along the c-axis direction (Fig. 2). No significant π–π, C—H⋯π or C—H⋯O interactions are observed.
4. Hirshfeld surface analysis
A Hirshfeld surface (HS) analysis (Hirshfeld, 1977; Spackman & Jayatilaka, 2009) was carried out by using Crystal Explorer 17.5 (Turner et al., 2017) in order to visualize the intermolecular interactions in the crystal of the title complex. In the HS plotted over dnorm (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 (distant contact) than the van der Waals radii, respectively (Venkatesan et al., 2016). The bright-red spots appearing near atoms O1, O3, H21, H22 and H41 indicate their role as the respective donors and acceptors in the dominant O—H⋯O and N—H⋯O hydrogen bonds. These O and H atoms also appear as blue and red regions, respectively, 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 overall two-dimensional fingerprint plot and those delineated into H⋯H, H⋯C/C⋯H, H⋯O/O⋯H, H⋯N/N⋯H, C⋯C, O⋯C/C⋯O, O⋯N/N⋯O and O⋯O contacts (McKinnon et al., 2007) are illustrated in Fig. 5 a–i, respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯H contributing 58.4% to the overall crystal packing, which is reflected in Fig. 5b as widely scattered points of high density due to the large hydrogen content of the molecule. 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 20.3% contribution to the HS, Fig. 5c, and the pair of thin edges at de + di ∼2.9 Å result from short interatomic H⋯C/C⋯H contacts. In the fingerprint plot delineated into H⋯O/O⋯H contacts (Fig. 5d), the 18.3% contribution to the HS arises from the intermolecular O—H⋯O hydrogen bonding and is viewed as pair of spikes with the tip at de + di ∼1.9 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 1.9% contribution to the HS has a symmetrical distribution of points with the tips at de + di ∼2.8 Å arising from the short interatomic H⋯N/N⋯H contact (Fig. 5e). The HSs mapped over shape-index, curvedness and those with the function dnorm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H, H⋯O/O⋯H and H⋯N/N⋯H interactions are shown in Figs. s1–s3 in the Supporting Information.
5. Synthesis and crystallization
The title compound was prepared by the reaction of ZnSO4·7H2O (0.72 g, 2.5 mmol) in H2O (50 ml) and nicotinamide (0.61 g, 5 mmol) in H2O (25 ml) with sodium 2,4,6-trimethylbenzoate (0.93 g, 5 mmol) in H2O (150 ml) at room temperature. The mixture was set aside to crystallize at ambient temperature for ten weeks, giving colourless single crystals (yield: 1.39 g, 85%). FT–IR: 3396, 3111, 2953, 2919, 2740, 2321, 1947, 1693, 1665, 1621, 1601, 1584, 1445, 1397, 1199, 1113, 1047, 860, 839, 797, 731, 647, 614, 545, 559 cm−1.
6. Refinement
The experimental details including the crystal data, data collection and . The H atom of the water molecule was located in a difference-Fourier map and refined freely. H atoms of the NH2 group were also located in a difference Fourier map and the positions were refined with Uiso(H) = 1.5Ueq(N). 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 refined as riding with Uiso(H) = k × Ueq(C), where k = 1.5 for methyl H-atoms and k = 1.2 for aromatic H-atoms.
are summarized in Table 2Supporting information
CCDC reference: 1567723
https://doi.org/10.1107/S2056989017011690/is5478sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017011690/is5478Isup2.hkl
Hirsfeld surface plotted over shape-index. DOI: https://doi.org/10.1107/S2056989017011690/is5478sup3.pdf
Hirshfeld surface plotted over curvedness. DOI: https://doi.org/10.1107/S2056989017011690/is5478sup4.pdf
Hirshfeld surfaces plotted over dnorm. DOI: https://doi.org/10.1107/S2056989017011690/is5478sup5.pdf
Data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2012); data reduction: SAINT; 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, 2015).[Zn(C10H11O2)2(C6H6N2O)2(H2O)] | F(000) = 1368 |
Mr = 654.02 | Dx = 1.325 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 9891 reflections |
a = 23.4004 (5) Å | θ = 2.7–28.4° |
b = 15.1685 (4) Å | µ = 0.80 mm−1 |
c = 9.2353 (3) Å | T = 296 K |
V = 3278.06 (15) Å3 | Block, colourless |
Z = 4 | 0.42 × 0.36 × 0.21 mm |
Bruker SMART BREEZE CCD diffractometer | 4104 independent reflections |
Radiation source: fine-focus sealed tube | 3310 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
φ and ω scans | θmax = 28.4°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −29→31 |
Tmin = 0.730, Tmax = 0.850 | k = −20→18 |
44050 measured reflections | l = −12→11 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0569P)2 + 1.7904P] where P = (Fo2 + 2Fc2)/3 |
4104 reflections | (Δ/σ)max = 0.001 |
213 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.32 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. |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.5000 | 0.74469 (2) | 0.2500 | 0.04143 (13) | |
O1 | 0.41787 (9) | 0.77620 (12) | 0.4394 (2) | 0.0656 (5) | |
O2 | 0.44479 (7) | 0.65455 (11) | 0.33298 (16) | 0.0544 (4) | |
O3 | 0.57370 (8) | 0.99041 (10) | 0.66283 (17) | 0.0589 (4) | |
O4 | 0.5000 | 0.88159 (15) | 0.2500 | 0.0502 (5) | |
H41 | 0.5262 (12) | 0.9122 (18) | 0.222 (3) | 0.057 (8)* | |
N1 | 0.55509 (9) | 0.75557 (11) | 0.4431 (2) | 0.0449 (4) | |
N2 | 0.58656 (10) | 0.91889 (14) | 0.8743 (2) | 0.0522 (5) | |
H21 | 0.5893 (13) | 0.867 (2) | 0.924 (3) | 0.078* | |
H22 | 0.5842 (13) | 0.969 (2) | 0.920 (3) | 0.078* | |
C1 | 0.41195 (9) | 0.69614 (15) | 0.4166 (2) | 0.0436 (5) | |
C2 | 0.36403 (9) | 0.64607 (14) | 0.4853 (2) | 0.0433 (5) | |
C3 | 0.30732 (11) | 0.6708 (2) | 0.4566 (3) | 0.0657 (7) | |
C4 | 0.26398 (12) | 0.6235 (3) | 0.5224 (4) | 0.0879 (10) | |
H4 | 0.2263 | 0.6396 | 0.5041 | 0.106* | |
C5 | 0.27421 (13) | 0.5537 (3) | 0.6139 (4) | 0.0834 (10) | |
C6 | 0.33025 (13) | 0.53126 (19) | 0.6414 (3) | 0.0664 (7) | |
H6 | 0.3379 | 0.4846 | 0.7038 | 0.080* | |
C7 | 0.37565 (10) | 0.57607 (14) | 0.5789 (2) | 0.0481 (5) | |
C8 | 0.43568 (12) | 0.5514 (2) | 0.6170 (3) | 0.0692 (7) | |
H8A | 0.4354 | 0.5117 | 0.6980 | 0.104* | |
H8B | 0.4568 | 0.6035 | 0.6420 | 0.104* | |
H8C | 0.4534 | 0.5231 | 0.5356 | 0.104* | |
C9 | 0.29388 (16) | 0.7462 (3) | 0.3543 (5) | 0.1093 (15) | |
H9A | 0.2533 | 0.7555 | 0.3514 | 0.164* | |
H9B | 0.3074 | 0.7319 | 0.2589 | 0.164* | |
H9C | 0.3124 | 0.7988 | 0.3877 | 0.164* | |
C10 | 0.22443 (18) | 0.5042 (4) | 0.6832 (6) | 0.144 (2) | |
H10A | 0.1901 | 0.5384 | 0.6732 | 0.217* | |
H10B | 0.2323 | 0.4949 | 0.7840 | 0.217* | |
H10C | 0.2196 | 0.4484 | 0.6358 | 0.217* | |
C11 | 0.55380 (9) | 0.82679 (13) | 0.5282 (2) | 0.0431 (5) | |
H11 | 0.5294 | 0.8726 | 0.5026 | 0.052* | |
C12 | 0.58642 (9) | 0.83658 (13) | 0.6518 (2) | 0.0396 (4) | |
C13 | 0.62260 (11) | 0.76826 (16) | 0.6900 (3) | 0.0521 (5) | |
H13 | 0.6449 | 0.7718 | 0.7732 | 0.063* | |
C14 | 0.62482 (12) | 0.69502 (16) | 0.6023 (3) | 0.0605 (7) | |
H14 | 0.6492 | 0.6485 | 0.6248 | 0.073* | |
C15 | 0.59098 (11) | 0.69098 (15) | 0.4816 (2) | 0.0524 (6) | |
H15 | 0.5930 | 0.6410 | 0.4235 | 0.063* | |
C16 | 0.58181 (9) | 0.92186 (14) | 0.7316 (2) | 0.0427 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0472 (2) | 0.02853 (19) | 0.0485 (2) | 0.000 | 0.00026 (14) | 0.000 |
O1 | 0.0772 (12) | 0.0463 (10) | 0.0733 (12) | −0.0103 (9) | 0.0122 (10) | −0.0028 (9) |
O2 | 0.0569 (9) | 0.0608 (10) | 0.0456 (8) | −0.0090 (8) | 0.0146 (7) | −0.0075 (7) |
O3 | 0.0898 (12) | 0.0369 (8) | 0.0499 (9) | 0.0059 (8) | 0.0028 (8) | 0.0006 (7) |
O4 | 0.0559 (14) | 0.0318 (11) | 0.0630 (14) | 0.000 | 0.0037 (11) | 0.000 |
N1 | 0.0525 (11) | 0.0331 (9) | 0.0490 (10) | 0.0057 (7) | −0.0026 (8) | −0.0027 (7) |
N2 | 0.0718 (13) | 0.0428 (11) | 0.0422 (10) | −0.0075 (9) | 0.0027 (9) | −0.0030 (8) |
C1 | 0.0462 (11) | 0.0490 (12) | 0.0355 (9) | −0.0037 (9) | 0.0004 (8) | 0.0012 (8) |
C2 | 0.0450 (11) | 0.0459 (11) | 0.0389 (10) | −0.0030 (9) | 0.0039 (8) | −0.0067 (8) |
C3 | 0.0488 (13) | 0.087 (2) | 0.0613 (15) | 0.0026 (13) | −0.0020 (11) | 0.0045 (14) |
C4 | 0.0415 (14) | 0.135 (3) | 0.088 (2) | −0.0110 (17) | 0.0016 (13) | 0.002 (2) |
C5 | 0.0654 (18) | 0.105 (3) | 0.080 (2) | −0.0333 (17) | 0.0173 (15) | −0.0014 (19) |
C6 | 0.0767 (18) | 0.0598 (16) | 0.0626 (15) | −0.0218 (13) | 0.0108 (13) | 0.0010 (12) |
C7 | 0.0555 (13) | 0.0386 (11) | 0.0501 (11) | −0.0058 (9) | 0.0068 (10) | −0.0057 (9) |
C8 | 0.0644 (16) | 0.0619 (16) | 0.0814 (18) | 0.0082 (13) | 0.0039 (14) | 0.0188 (14) |
C9 | 0.070 (2) | 0.142 (4) | 0.116 (3) | 0.021 (2) | −0.014 (2) | 0.046 (3) |
C10 | 0.091 (3) | 0.186 (5) | 0.157 (4) | −0.069 (3) | 0.034 (3) | 0.024 (4) |
C11 | 0.0447 (11) | 0.0342 (10) | 0.0506 (11) | 0.0086 (8) | −0.0034 (9) | −0.0035 (8) |
C12 | 0.0422 (10) | 0.0376 (10) | 0.0391 (9) | 0.0020 (8) | 0.0046 (8) | 0.0031 (8) |
C13 | 0.0596 (14) | 0.0548 (13) | 0.0420 (11) | 0.0116 (11) | −0.0022 (10) | 0.0076 (10) |
C14 | 0.0782 (17) | 0.0474 (13) | 0.0559 (13) | 0.0274 (12) | −0.0024 (12) | 0.0056 (10) |
C15 | 0.0722 (15) | 0.0354 (11) | 0.0497 (12) | 0.0134 (10) | 0.0015 (11) | −0.0015 (9) |
C16 | 0.0467 (11) | 0.0384 (11) | 0.0431 (10) | −0.0022 (8) | 0.0034 (8) | −0.0006 (8) |
Zn1—O2i | 2.0311 (16) | C6—C5 | 1.379 (5) |
Zn1—O2 | 2.0311 (16) | C6—H6 | 0.9300 |
Zn1—O4 | 2.076 (2) | C7—C6 | 1.387 (3) |
Zn1—N1 | 2.2066 (19) | C7—C8 | 1.496 (4) |
Zn1—N1i | 2.2066 (19) | C8—H8A | 0.9600 |
O1—C1 | 1.240 (3) | C8—H8B | 0.9600 |
O2—C1 | 1.259 (3) | C8—H8C | 0.9600 |
O3—C16 | 1.233 (3) | C9—H9A | 0.9600 |
O4—H41 | 0.81 (3) | C9—H9B | 0.9600 |
N1—C11 | 1.336 (3) | C9—H9C | 0.9600 |
N1—C15 | 1.338 (3) | C10—H10A | 0.9600 |
N2—C16 | 1.324 (3) | C10—H10B | 0.9600 |
N2—H21 | 0.91 (3) | C10—H10C | 0.9600 |
N2—H22 | 0.87 (3) | C11—H11 | 0.9300 |
C2—C1 | 1.496 (3) | C12—C11 | 1.382 (3) |
C2—C3 | 1.404 (3) | C12—C13 | 1.384 (3) |
C2—C7 | 1.396 (3) | C12—C16 | 1.493 (3) |
C3—C4 | 1.383 (4) | C13—C14 | 1.376 (3) |
C3—C9 | 1.516 (4) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | C14—H14 | 0.9300 |
C5—C4 | 1.375 (5) | C15—C14 | 1.369 (3) |
C5—C10 | 1.526 (4) | C15—H15 | 0.9300 |
O2i—Zn1—O2 | 95.38 (9) | C6—C7—C8 | 119.9 (2) |
O2—Zn1—O4 | 132.31 (5) | C7—C8—H8A | 109.5 |
O2i—Zn1—O4 | 132.31 (5) | C7—C8—H8B | 109.5 |
O2—Zn1—N1 | 96.72 (7) | C7—C8—H8C | 109.5 |
O2i—Zn1—N1 | 89.07 (7) | H8A—C8—H8B | 109.5 |
O2—Zn1—N1i | 89.07 (7) | H8A—C8—H8C | 109.5 |
O2i—Zn1—N1i | 96.72 (7) | H8B—C8—H8C | 109.5 |
O4—Zn1—N1 | 85.71 (4) | C3—C9—H9A | 109.5 |
O4—Zn1—N1i | 85.71 (4) | C3—C9—H9B | 109.5 |
N1—Zn1—N1i | 171.42 (8) | C3—C9—H9C | 109.5 |
C1—O2—Zn1 | 106.41 (14) | H9A—C9—H9B | 109.5 |
Zn1—O4—H41 | 125 (2) | H9A—C9—H9C | 109.5 |
C11—N1—Zn1 | 121.50 (14) | H9B—C9—H9C | 109.5 |
C11—N1—C15 | 116.7 (2) | C5—C10—H10A | 109.5 |
C15—N1—Zn1 | 121.76 (15) | C5—C10—H10B | 109.5 |
C16—N2—H21 | 122.6 (19) | C5—C10—H10C | 109.5 |
C16—N2—H22 | 117 (2) | H10A—C10—H10B | 109.5 |
H21—N2—H22 | 121 (3) | H10A—C10—H10C | 109.5 |
O1—C1—O2 | 121.8 (2) | H10B—C10—H10C | 109.5 |
O1—C1—C2 | 120.6 (2) | N1—C11—C12 | 124.08 (19) |
O2—C1—C2 | 117.6 (2) | N1—C11—H11 | 118.0 |
C3—C2—C1 | 119.5 (2) | C12—C11—H11 | 118.0 |
C7—C2—C1 | 120.20 (19) | C11—C12—C13 | 117.9 (2) |
C7—C2—C3 | 120.3 (2) | C11—C12—C16 | 117.47 (18) |
C2—C3—C9 | 121.0 (3) | C13—C12—C16 | 124.6 (2) |
C4—C3—C2 | 118.1 (3) | C12—C13—H13 | 120.7 |
C4—C3—C9 | 120.9 (3) | C14—C13—C12 | 118.5 (2) |
C3—C4—H4 | 118.6 | C14—C13—H13 | 120.7 |
C5—C4—C3 | 122.8 (3) | C13—C14—H14 | 120.2 |
C5—C4—H4 | 118.6 | C15—C14—C13 | 119.6 (2) |
C4—C5—C6 | 118.0 (3) | C15—C14—H14 | 120.2 |
C4—C5—C10 | 120.2 (4) | N1—C15—C14 | 123.1 (2) |
C6—C5—C10 | 121.8 (4) | N1—C15—H15 | 118.4 |
C5—C6—C7 | 122.0 (3) | C14—C15—H15 | 118.4 |
C5—C6—H6 | 119.0 | O3—C16—N2 | 123.7 (2) |
C7—C6—H6 | 119.0 | O3—C16—C12 | 119.17 (18) |
C2—C7—C8 | 121.3 (2) | N2—C16—C12 | 117.14 (19) |
C6—C7—C2 | 118.8 (2) | ||
O2i—Zn1—O2—C1 | 166.98 (17) | C7—C2—C3—C9 | −179.5 (3) |
O4—Zn1—O2—C1 | −13.02 (17) | C1—C2—C7—C6 | 179.7 (2) |
N1—Zn1—O2—C1 | 77.29 (14) | C1—C2—C7—C8 | 2.2 (3) |
N1i—Zn1—O2—C1 | −96.36 (14) | C3—C2—C7—C6 | 0.6 (3) |
O2—Zn1—N1—C11 | −106.95 (18) | C3—C2—C7—C8 | −176.9 (2) |
O2i—Zn1—N1—C11 | 157.75 (18) | C2—C3—C4—C5 | −0.2 (5) |
O2—Zn1—N1—C15 | 72.40 (19) | C9—C3—C4—C5 | 178.8 (4) |
O2i—Zn1—N1—C15 | −22.91 (19) | C6—C5—C4—C3 | 0.7 (6) |
O4—Zn1—N1—C11 | 25.19 (17) | C10—C5—C4—C3 | 180.0 (4) |
O4—Zn1—N1—C15 | −155.46 (19) | C7—C6—C5—C4 | −0.7 (5) |
Zn1—O2—C1—O1 | −2.4 (3) | C7—C6—C5—C10 | −179.9 (3) |
Zn1—O2—C1—C2 | 175.91 (15) | C2—C7—C6—C5 | 0.1 (4) |
Zn1—N1—C11—C12 | 178.69 (16) | C8—C7—C6—C5 | 177.5 (3) |
C15—N1—C11—C12 | −0.7 (3) | C13—C12—C11—N1 | −0.1 (3) |
Zn1—N1—C15—C14 | −178.6 (2) | C16—C12—C11—N1 | 177.5 (2) |
C11—N1—C15—C14 | 0.8 (4) | C11—C12—C13—C14 | 0.9 (3) |
C3—C2—C1—O1 | 60.0 (3) | C16—C12—C13—C14 | −176.5 (2) |
C3—C2—C1—O2 | −118.4 (2) | C11—C12—C16—O3 | −33.6 (3) |
C7—C2—C1—O1 | −119.1 (2) | C11—C12—C16—N2 | 146.1 (2) |
C7—C2—C1—O2 | 62.5 (3) | C13—C12—C16—O3 | 143.8 (2) |
C1—C2—C3—C4 | −179.6 (3) | C13—C12—C16—N2 | −36.4 (3) |
C1—C2—C3—C9 | 1.4 (4) | C12—C13—C14—C15 | −0.9 (4) |
C7—C2—C3—C4 | −0.5 (4) | N1—C15—C14—C13 | 0.0 (4) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···O1ii | 0.91 (3) | 1.88 (3) | 2.766 (3) | 165 (3) |
N2—H22···O3iii | 0.87 (3) | 2.34 (3) | 3.013 (2) | 134 (2) |
O4—H41···O3iv | 0.81 (3) | 1.93 (3) | 2.719 (2) | 165 (3) |
Symmetry codes: (ii) −x+1, y, −z+3/2; (iii) x, −y+2, z+1/2; (iv) x, −y+2, z−1/2. |
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.
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