Crystal structure and Hirshfeld surface analysis of bis­(μ-4-tert-but­oxy-4-oxobut-2-en-2-olato)bis­[(4-tert-but­oxy-4-oxobut-2-en-2-olato)ethano­lzinc(II)]

Shtokvysh, O.O.; Dyakonenko, V.V.; Koval, L.I.; Pekhnyo, V.I.

doi:10.1107/S2056989023003377

research communications

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ISSN: 2056-9890

Volume 79| Part 5| May 2023| Pages 478-481

https://doi.org/10.1107/S2056989023003377

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Crystal structure and Hirshfeld surface analysis of bis(μ-4-tert-butoxy-4-oxobut-2-en-2-olato)bis[(4-tert-butoxy-4-oxobut-2-en-2-olato)ethanolzinc(II)]

Olherd O. Shtokvysh,^a ^* Viktoriya V. Dyakonenko,^b,^a Lyudmila I. Koval ^a and Vasyl I. Pekhnyo ^a

^aV. I. Vernadskii Institute of General and Inorganic Chemistry, National Academy of Sciences of Ukraine, Akad. Palladin Ave 32/34, Kyiv 03142, Ukraine, and ^bSSI "Institute for Single Crystals" National Academy of Sciences of Ukraine, Nauki Ave 60, Kharkiv 61001, Ukraine
^*Correspondence e-mail: Olej@meta.ua

Edited by C. Schulzke, Universität Greifswald, Germany (Received 10 March 2023; accepted 12 April 2023; online 21 April 2023)

The molecular and crystal structure of the title binuclear Zn²⁺ complex, [Zn₂(C₈H₁₃O₃)₄(C₂H₅OH)₂], with enolated anionic tert-butylacetoacetate and ethanol was analysed. The coordination polyhedra of the Zn atoms are distorted octahedra formed by six oxygen atoms that belong to three ligand molecules and a coordinated ethanol molecule. In the crystal phase, alternating layers can be distinguished parallel to the ac plane. A Hirshfeld surface analysis showed that there are no strong intermolecular interactions in the structure. The most significant contributions to the overall crystal packing are from H⋯H intermolecular contacts.

Keywords: crystal structure; complex; zinc; tert-butyl acetoacetate; keto ester; ethanol; binuclear structure.

CCDC reference: 2255847

1. Chemical context

Metal complexes with β-dicarbonyl ligands are widely used for obtaining metal oxides and, less often, metal films by the metal–organic chemical vapor deposition (MOCVD) process and its variations (Wei et al., 2014 ; Han et al., 2017 , 2018 ; Nayak et al., 2007 ; Cosham et al., 2017 ; Kawazoe et al., 2006 ; Kamata et al., 1994 ), for the catalysis of reduction, oxidation, and oligomerization of unsaturated compounds and cross-coupling reacti& Nobile et al., 1994 ). They also exhibit antiviral activity (Sechi et al., 2006 ), in which interest has increased significantly in recent years. In addition, β-dicarbonyl complexes of zinc are studied as luminescent materials and antioxidants (Aliaga-Alcalde et al., 2012 ; Nie et al., 2014 ; Turra et al., 2010 ).

Our research group is developing coordination compounds soluble in non-polar organic solvents, including metal complexes of acetoacetic acid esters (Koval et al., 2009 ), which can potentially be used as environmentally friendly additives to industrial products. Previously, we reported the structure of a trimeric zinc complex synthesized in a rather complicated way using diethyl zinc (Shtokvish et al., 2014 ). After that, we developed a much simpler and relatively more efficient method for the synthesis of cobalt and nickel ketoesterates (Shtokvish et al., 2015 , 2017 , Shtokvysh et al., 2018 ). The use of this method for the synthesis of Zn complexes made it possible to obtain dimeric complexes with cyclohexylacetoacetate (Shtokvysh et al., 2020 ) and tert-butylacetoacetate. In the present work, we report the synthesis and structural analysis of the new complex [Zn₂(C₈H₁₀O₃)₄(C₂H₅OH)₂].

2. Structural commentary

The title compound, systematic name bis(μ-4-tert-butoxy-4-oxobut-2-en-2-olato)bis[(4-tert-butoxy-4-oxobut-2-en-2-olato)ethanolzinc(II)], is a binuclear complex that resides on a special position with the unit cell's central inversion centre being close to the refined zinc(II) atom and directly in between this and the symmetry-generated zinc atom [symmetry code: (i) −x + 1, −y + 1, −z + 1] (Fig. 1). The coordination polyhedron of the Zn centre is a distorted octahedron formed by six oxygen atoms. One bidentate acetylacetonate type ligand (O1, O2) binds only to one zinc centre. Its oxygen atoms occupy an axial (O1) and an equatorial position (O2). The second bidentate ligand (O4, O5) binds the zinc centre only equatorially, while O4 also binds the symmetry-generated second zinc atom of the binuclear complex. This also means that the symmetry-generated O4ⁱ atom occupies the fourth equatorial position. The octahedral coordination sphere is completed by axially coordinated ethanol (O7). The bonds of zinc atoms with the enol atom of the bridging ligand are not equivalent. The Zn1—O4 bond length in the chelate is shorter than the Zn1—O4ⁱ bond length with the symmetry-generated bridging ligand [2.076 (2) and 2.141 (3) Å, respectively; Table 1]. The Zn—O bond lengths of terminal ligands (O1, O2) are shorter than the Zn—O bonds of bridging ligands (O4, O5) with ranges of 2.031 (3) to 2.039 (3) and of 2.072 (3) to 2.076 (2) Å, respectively (Table 1). The Zn1—O7 bond length (the bond between the zinc atom and the oxygen of the coordinated ethanol molecule) is the longest in the coordination polyhedron at 2.201 (3) Å (Table 1). The values of the O—Zn—O bond angles lie in the range 85.30 (11) to 97.46 (12)° (Table 1). The connection between the nuclei of the complex is additionally stabilized by two intramolecular hydrogen bonds between the hydrogen atoms of the hydroxyl groups of ethanol and the enol oxygen atoms of the terminal ligands belonging to another nucleus (Table 2).

Table 1
Selected geometric parameters (Å, °)

Zn1—O1	2.031 (3)	Zn1—O4	2.076 (2)
Zn1—O2	2.039 (3)	Zn1—O5	2.072 (3)
Zn1—O4ⁱ	2.141 (3)	Zn1—O7	2.201 (3)

O1—Zn1—O2	90.99 (11)	O2—Zn1—O7	93.30 (12)
O1—Zn1—O4	90.61 (11)	O4—Zn1—O7	86.49 (12)
O1—Zn1—O5	97.46 (12)	O5—Zn1—O4	88.08 (11)
O2—Zn1—O5	85.30 (11)	O5—Zn1—O7	94.74 (12)
Symmetry code: (i) .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7⋯O1ⁱ	0.86 (1)	2.01 (1)	2.861 (4)	171 (4)
Symmetry code: (i) .

Figure 1
The molecular structure of the title compound, showing 30% probability displacement ellipsoids. H atoms and the minor occupancy disordered component have been omitted for clarity. Unlabelled atoms are related by the symmetry operation 1 − x, 1 − y, 1 − z.

3. Supramolecular features

There are no short intermolecular contacts between neighbouring molecules in the crystal phase. However, visually we can distinguish alternating layers parallel to the ac plane (Fig. 2a). Molecules in the layer are oriented identically with respect to each other and mirrored with respect to the molecules of the neighbouring layer (Fig. 2b).

Figure 2
(a) Crystal packing of the title compound and (b) differently-coloured layers in the same projection.

4. Hirshfeld surface analysis and finger print plots

A Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were generated using Crystal Explorer 21.5 software (Spackman et al., 2021 ), with a standard resolution of the three-dimensional d_norm surfaces plotted over a fixed colour scale of 0.0290 (white) to 1.706 (blue) a.u. (Fig. 3). Usually contacts shorter than the sums of van der Waals radii are shown in red, those longer in blue, and those approximately equal as white spots. There are no red spots on the d_norm surface. This indicates that there are no strong intermolecular interactions in the structure.

Figure 3
A projection of d_norm mapped on the Hirshfeld surface, showing the intermolecular interactions within the molecule.

The overall two-dimensional fingerprint plot, and those decomposed into various interactions are given Fig. 4. The most significant contributions to the overall crystal packing are from H⋯H (89.2%) proximities, which are located mostly in the middle region of the fingerprint plot. There is also a small contribution from H⋯O/O⋯H (6.5%) and H⋯C/C⋯H (4.3%) intermolecular `contacts'.

Figure 4
The overall two-dimensional fingerprint plot and those delineated into specified interactions.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.43, update November 2022; Groom et al., 2016 ; ConQuest 2022.3.0; Bruno et al., 2002 ) for binuclear complexes with different acetoacetic esters yielded seven structures that are very similar to the title compound. Among these structures are three structures with the metal being cobalt (refcodes BENNUG, BENPAO; Shtokvish et al., 2017; WARHAB; Shtokvish et al., 2015), three structures with nickel (refcodes WOCXOE, WOCXUK, WOCYAR; Shtokvysh et al., 2018) and one with zinc (refcode GARBOU; Shtokvysh et al., 2020). The coordination centres in all cases have an octahedral geometric environment. The M—O bond lengths (1.997 to 2.082 Å) are consistently shorter in the terminal ligand than the M—O bond lengths (2.088 to 2.184 Å) of the bridging ligands.

6. Synthesis and crystallization

The title compound was synthesized in accordance with the methodology reported earlier (Shtokvish et al., 2015). ZnCl₂ (0.1 g, 7 mmol) was dissolved in 2 ml of ethanol (azeotrope with water, 95.6% alcohol). Then liquid tert-butyl acetoacetate was added to the solution (0.244 ml, 14 mmol). The components were then mixed. The test tube with the reaction mixture was placed in a container together with a vessel containing triethylamine (0.4 ml, 28 mmol). The container was sealed and left in the refrigerator for 1–2 days at a temperature of 281 K. The structural study was performed for a crystal taken directly and immediately from the reaction mixture, since this compound is prone to degradeation. The crystals were filtered on a P2 (P100) fritted glass filter (to separate thin powders of by-products and degradeation products), then washed several times with ethanol and dried in air for no more than 1 h. The yield is 0.078 g, which is 25.3% of the theoretical value. The obtained crystals can be stored at 261 K and below.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were placed in calculated positions [C—H = 0.93 Å (0.96 Å for C-methyl)] and refined as riding with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C-methyl).

Table 3
Experimental details

Crystal data
Chemical formula	[Zn₂(C₈H₁₃O₃)₄(C₂H₆O)₂]
M_r	851.61
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	9.1689 (5), 22.8882 (10), 11.0743 (5)
β (°)	103.043 (5)
V (Å³)	2264.10 (19)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.12
Crystal size (mm)	0.5 × 0.4 × 0.2

Data collection
Diffractometer	Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.460, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18037, 4622, 3257
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.154, 1.09
No. of reflections	4622
No. of parameters	268
No. of restraints	53
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.34
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), OLEX2.solve (Bourhis et al., 2015 ), SHELXL2019/3 (Sheldrick, 2015 ), OLEX2(Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2020 ).

The C atoms of the coordinated ethanol molecule are disordered over two positions with an occupancy of 50%. Restraints were applied to the bond lengths in the disordered parts (O—C = 1.45 Å, C—C = 1.49 Å) within a standard deviation of 0.02 Å. The position of the O-bound hydrogen atom was determined from the electron-density map. The O-bound hydrogen atom was refined freely with full occupancy restraining only the O—H bond length to 0.86 Å within a standard deviation of 0.02 Å.

Supporting information

CCDC reference: 2255847

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989023003377/yz2031sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023003377/yz2031Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); cell refinement: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); data reduction: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018); program(s) used to solve structure: olex2.solve 1.5 (Bourhis et al., 2015); program(s) used to refine structure: SHELXL2019/3 (Sheldrick, 2015); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009), Mercury 2022.3.0 (Macrae et al., 2020); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

Bis(µ-4-tert-butoxy-4-oxobut-2-en-2-olato)bis[(4-tert-butoxy-4-oxobut-2-en-2-olato)ethanolzinc(II)] top

Crystal data top

[Zn₂(C₈H₁₃O₃)₄(C₂H₆O)₂]	F(000) = 904
M_r = 851.61	D_x = 1.249 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1689 (5) Å	Cell parameters from 2231 reflections
b = 22.8882 (10) Å	θ = 3.7–21.8°
c = 11.0743 (5) Å	µ = 1.12 mm⁻¹
β = 103.043 (5)°	T = 295 K
V = 2264.10 (19) Å³	Block, colourless
Z = 2	0.5 × 0.4 × 0.2 mm

Data collection top

Xcalibur, Sapphire3 diffractometer	3257 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	R_int = 0.051
ω scans	θ_max = 26.4°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	h = −11→11
T_min = 0.460, T_max = 1.000	k = −28→28
18037 measured reflections	l = −8→13
4622 independent reflections

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.0617P)² + 0.6818P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
4622 reflections	Δρ_max = 0.56 e Å⁻³
268 parameters	Δρ_min = −0.34 e Å⁻³
53 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.54544 (5)	0.44504 (2)	0.42445 (4)	0.0662 (2)
O1	0.3922 (3)	0.47158 (13)	0.2720 (3)	0.0764 (8)
O2	0.6833 (3)	0.41548 (12)	0.3169 (2)	0.0671 (7)
O3	0.7330 (3)	0.38286 (15)	0.1401 (3)	0.0882 (9)
O4	0.3987 (3)	0.46505 (12)	0.5364 (2)	0.0672 (7)
O5	0.4756 (3)	0.35898 (12)	0.4248 (3)	0.0772 (8)
O6	0.3134 (3)	0.28661 (12)	0.4379 (2)	0.0738 (7)
O7	0.7190 (4)	0.43704 (14)	0.5970 (3)	0.0911 (9)
C1	0.2636 (5)	0.4793 (2)	0.0629 (4)	0.0938 (15)
H1A	0.172653	0.468769	0.086530	0.141*
H1B	0.266070	0.461221	−0.014835	0.141*
H1C	0.267881	0.521015	0.054530	0.141*
C2	0.3957 (4)	0.45897 (18)	0.1606 (4)	0.0672 (10)
C3	0.5095 (4)	0.42909 (19)	0.1243 (4)	0.0706 (11)
H3	0.496600	0.421072	0.040242	0.085*
C4	0.6431 (4)	0.40970 (17)	0.2033 (4)	0.0666 (10)
C5	0.8841 (5)	0.3624 (2)	0.1982 (5)	0.0897 (14)
C6	0.9817 (5)	0.4121 (3)	0.2556 (6)	0.1108 (18)
H6A	0.963480	0.445332	0.201407	0.166*
H6B	1.084927	0.400825	0.268616	0.166*
H6C	0.959237	0.422025	0.333682	0.166*
C7	0.8762 (7)	0.3149 (3)	0.2906 (7)	0.131 (2)
H7A	0.845972	0.331407	0.360811	0.197*
H7B	0.972864	0.297042	0.317296	0.197*
H7C	0.804662	0.285930	0.252621	0.197*
C8	0.9363 (7)	0.3385 (4)	0.0867 (6)	0.155 (3)
H8A	0.862961	0.311646	0.042344	0.233*
H8B	1.030025	0.318583	0.114494	0.233*
H8C	0.948707	0.370145	0.033114	0.233*
C9	0.1984 (7)	0.4577 (2)	0.6368 (6)	0.123 (2)
H9A	0.256051	0.467295	0.717969	0.184*
H9B	0.120541	0.430766	0.643732	0.184*
H9C	0.154656	0.492652	0.596048	0.184*
C10	0.2986 (5)	0.43028 (19)	0.5624 (4)	0.0705 (11)
C11	0.2793 (5)	0.37331 (19)	0.5304 (4)	0.0739 (11)
H11	0.203184	0.353451	0.556179	0.089*
C12	0.3643 (5)	0.34110 (17)	0.4612 (3)	0.0652 (10)
C13	0.3831 (5)	0.24431 (19)	0.3696 (4)	0.0776 (12)
C14	0.2860 (7)	0.1908 (2)	0.3683 (5)	0.1141 (19)
H14A	0.285700	0.179792	0.451860	0.171*
H14B	0.325115	0.159240	0.327984	0.171*
H14C	0.185651	0.199405	0.324153	0.171*
C15	0.3773 (8)	0.2664 (3)	0.2393 (4)	0.122 (2)
H15A	0.275191	0.274108	0.198153	0.183*
H15B	0.418317	0.237424	0.193851	0.183*
H15C	0.434563	0.301784	0.243508	0.183*
C16	0.5409 (6)	0.2315 (2)	0.4396 (5)	0.1051 (17)
H16A	0.601067	0.265992	0.441878	0.158*
H16B	0.581885	0.200646	0.398803	0.158*
H16C	0.540080	0.219781	0.522665	0.158*
C17A	0.7360 (17)	0.3935 (4)	0.6946 (9)	0.120 (2)	0.502 (9)
H17A	0.640986	0.375180	0.695965	0.144*	0.502 (9)
H17B	0.777579	0.410583	0.775206	0.144*	0.502 (9)
C17B	0.7398 (17)	0.3790 (2)	0.6508 (10)	0.119 (2)	0.498 (9)
H17C	0.758504	0.352034	0.588523	0.142*	0.498 (9)
H17D	0.647661	0.367100	0.672769	0.142*	0.498 (9)
C18A	0.8418 (16)	0.3510 (6)	0.6591 (14)	0.151 (3)	0.502 (9)
H18A	0.939453	0.368299	0.671692	0.226*	0.502 (9)
H18B	0.807363	0.340685	0.573319	0.226*	0.502 (9)
H18C	0.846888	0.316516	0.709264	0.226*	0.502 (9)
C18B	0.8644 (15)	0.3742 (6)	0.7627 (12)	0.142 (3)	0.498 (9)
H18D	0.941201	0.349365	0.744778	0.212*	0.498 (9)
H18E	0.827299	0.357902	0.829736	0.212*	0.498 (9)
H18F	0.905194	0.412323	0.785632	0.212*	0.498 (9)
H7	0.692 (4)	0.4672 (10)	0.633 (3)	0.079 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0695 (3)	0.0780 (3)	0.0560 (3)	0.0014 (2)	0.0247 (2)	0.0122 (2)
O1	0.0709 (18)	0.101 (2)	0.0607 (17)	0.0149 (15)	0.0226 (14)	0.0153 (15)
O2	0.0607 (15)	0.0879 (18)	0.0556 (16)	0.0049 (13)	0.0193 (13)	0.0093 (14)
O3	0.0650 (18)	0.133 (3)	0.0683 (19)	0.0093 (17)	0.0196 (15)	−0.0132 (18)
O4	0.0752 (17)	0.0740 (16)	0.0594 (16)	−0.0039 (14)	0.0297 (14)	0.0126 (13)
O5	0.0866 (19)	0.0788 (18)	0.0735 (19)	−0.0078 (16)	0.0333 (16)	0.0084 (14)
O6	0.0857 (19)	0.0751 (18)	0.0636 (17)	−0.0105 (15)	0.0233 (15)	−0.0032 (14)
O7	0.110 (2)	0.090 (2)	0.073 (2)	0.0219 (18)	0.0186 (18)	0.0182 (16)
C1	0.067 (3)	0.141 (4)	0.072 (3)	0.006 (3)	0.012 (2)	0.020 (3)
C2	0.058 (2)	0.086 (3)	0.059 (2)	−0.008 (2)	0.015 (2)	0.016 (2)
C3	0.058 (2)	0.106 (3)	0.050 (2)	−0.004 (2)	0.0160 (19)	0.002 (2)
C4	0.062 (2)	0.081 (3)	0.063 (3)	−0.009 (2)	0.026 (2)	−0.001 (2)
C5	0.067 (3)	0.120 (4)	0.085 (3)	0.015 (3)	0.023 (3)	−0.001 (3)
C6	0.063 (3)	0.155 (5)	0.113 (4)	−0.004 (3)	0.019 (3)	0.009 (4)
C7	0.114 (5)	0.112 (4)	0.171 (7)	0.034 (4)	0.039 (5)	0.020 (4)
C8	0.090 (4)	0.257 (9)	0.123 (5)	0.050 (5)	0.032 (4)	−0.049 (5)
C9	0.135 (5)	0.100 (4)	0.169 (6)	−0.036 (3)	0.108 (5)	−0.027 (4)
C10	0.074 (3)	0.086 (3)	0.058 (2)	−0.010 (2)	0.027 (2)	0.008 (2)
C11	0.078 (3)	0.084 (3)	0.067 (3)	−0.020 (2)	0.031 (2)	−0.002 (2)
C12	0.075 (3)	0.073 (3)	0.046 (2)	−0.003 (2)	0.0083 (19)	0.0114 (18)
C13	0.097 (3)	0.084 (3)	0.053 (2)	−0.007 (3)	0.020 (2)	−0.001 (2)
C14	0.144 (5)	0.089 (3)	0.113 (4)	−0.024 (3)	0.037 (4)	−0.018 (3)
C15	0.186 (6)	0.125 (4)	0.056 (3)	0.002 (4)	0.030 (4)	−0.001 (3)
C16	0.109 (4)	0.107 (4)	0.103 (4)	0.005 (3)	0.032 (4)	−0.001 (3)
C17A	0.140 (4)	0.111 (4)	0.095 (4)	0.033 (4)	−0.005 (4)	−0.002 (3)
C17B	0.138 (4)	0.109 (4)	0.095 (4)	0.038 (4)	−0.003 (4)	0.000 (3)
C18A	0.159 (6)	0.139 (6)	0.132 (6)	0.027 (6)	−0.014 (6)	0.004 (6)
C18B	0.157 (6)	0.135 (6)	0.114 (6)	0.032 (5)	−0.008 (6)	0.006 (5)

Geometric parameters (Å, º) top

Zn1—O1	2.031 (3)	C8—H8B	0.9600
Zn1—O2	2.039 (3)	C8—H8C	0.9600
Zn1—O4ⁱ	2.141 (3)	C9—H9A	0.9600
Zn1—O4	2.076 (2)	C9—H9B	0.9600
Zn1—O5	2.072 (3)	C9—H9C	0.9600
Zn1—O7	2.201 (3)	C9—C10	1.503 (6)
O1—C2	1.273 (5)	C10—C11	1.352 (6)
O2—C4	1.235 (5)	C11—H11	0.9300
O3—C4	1.345 (5)	C11—C12	1.417 (6)
O3—C5	1.467 (5)	C13—C14	1.512 (6)
O4—C10	1.295 (4)	C13—C15	1.519 (6)
O5—C12	1.248 (5)	C13—C16	1.508 (6)
O6—C12	1.336 (5)	C14—H14A	0.9600
O6—C13	1.461 (5)	C14—H14B	0.9600
O7—C17A	1.452 (2)	C14—H14C	0.9600
O7—C17B	1.450 (2)	C15—H15A	0.9600
O7—H7	0.860 (2)	C15—H15B	0.9600
C1—H1A	0.9600	C15—H15C	0.9600
C1—H1B	0.9600	C16—H16A	0.9600
C1—H1C	0.9600	C16—H16B	0.9600
C1—C2	1.505 (6)	C16—H16C	0.9600
C2—C3	1.381 (5)	C17A—H17A	0.9700
C3—H3	0.9300	C17A—H17B	0.9700
C3—C4	1.407 (6)	C17A—C18A	1.489 (2)
C5—C6	1.498 (7)	C17B—H17C	0.9700
C5—C7	1.506 (7)	C17B—H17D	0.9700
C5—C8	1.522 (7)	C17B—C18B	1.487 (2)
C6—H6A	0.9600	C18A—H18A	0.9600
C6—H6B	0.9600	C18A—H18B	0.9600
C6—H6C	0.9600	C18A—H18C	0.9600
C7—H7A	0.9600	C18B—H18D	0.9600
C7—H7B	0.9600	C18B—H18E	0.9600
C7—H7C	0.9600	C18B—H18F	0.9600
C8—H8A	0.9600

O1—Zn1—O2	90.99 (11)	H8A—C8—H8C	109.5
O1—Zn1—O4ⁱ	88.27 (12)	H8B—C8—H8C	109.5
O1—Zn1—O4	90.61 (11)	H9A—C9—H9B	109.5
O1—Zn1—O5	97.46 (12)	H9A—C9—H9C	109.5
O1—Zn1—O7	167.36 (12)	H9B—C9—H9C	109.5
O2—Zn1—O4	173.35 (10)	C10—C9—H9A	109.5
O2—Zn1—O4ⁱ	106.60 (10)	C10—C9—H9B	109.5
O2—Zn1—O5	85.30 (11)	C10—C9—H9C	109.5
O2—Zn1—O7	93.30 (12)	O4—C10—C9	114.6 (4)
O4—Zn1—O4ⁱ	79.90 (10)	O4—C10—C11	126.3 (4)
O4ⁱ—Zn1—O7	79.11 (11)	C11—C10—C9	119.1 (4)
O4—Zn1—O7	86.49 (12)	C10—C11—H11	117.0
O5—Zn1—O4	88.08 (11)	C10—C11—C12	126.0 (4)
O5—Zn1—O4ⁱ	166.76 (10)	C12—C11—H11	117.0
O5—Zn1—O7	94.74 (12)	O5—C12—O6	121.2 (4)
C2—O1—Zn1	125.0 (3)	O5—C12—C11	126.4 (4)
C4—O2—Zn1	123.2 (3)	O6—C12—C11	112.3 (4)
C4—O3—C5	123.2 (3)	O6—C13—C14	102.5 (4)
Zn1—O4—Zn1ⁱ	100.10 (10)	O6—C13—C15	110.2 (4)
C10—O4—Zn1ⁱ	134.0 (3)	O6—C13—C16	110.1 (4)
C10—O4—Zn1	125.8 (3)	C14—C13—C15	111.5 (4)
C12—O5—Zn1	126.0 (3)	C16—C13—C14	110.0 (4)
C12—O6—C13	123.0 (3)	C16—C13—C15	112.2 (4)
Zn1—O7—H7	96 (3)	C13—C14—H14A	109.5
C17A—O7—Zn1	129.7 (7)	C13—C14—H14B	109.5
C17A—O7—H7	102 (3)	C13—C14—H14C	109.5
C17B—O7—Zn1	115.8 (5)	H14A—C14—H14B	109.5
C17B—O7—H7	125 (3)	H14A—C14—H14C	109.5
H1A—C1—H1B	109.5	H14B—C14—H14C	109.5
H1A—C1—H1C	109.5	C13—C15—H15A	109.5
H1B—C1—H1C	109.5	C13—C15—H15B	109.5
C2—C1—H1A	109.5	C13—C15—H15C	109.5
C2—C1—H1B	109.5	H15A—C15—H15B	109.5
C2—C1—H1C	109.5	H15A—C15—H15C	109.5
O1—C2—C1	115.7 (4)	H15B—C15—H15C	109.5
O1—C2—C3	125.4 (4)	C13—C16—H16A	109.5
C3—C2—C1	118.8 (4)	C13—C16—H16B	109.5
C2—C3—H3	117.1	C13—C16—H16C	109.5
C2—C3—C4	125.7 (4)	H16A—C16—H16B	109.5
C4—C3—H3	117.1	H16A—C16—H16C	109.5
O2—C4—O3	120.1 (4)	H16B—C16—H16C	109.5
O2—C4—C3	128.1 (4)	O7—C17A—H17A	111.2
O3—C4—C3	111.7 (4)	O7—C17A—H17B	111.2
O3—C5—C6	111.0 (4)	O7—C17A—C18A	102.6 (8)
O3—C5—C7	110.1 (4)	H17A—C17A—H17B	109.2
O3—C5—C8	101.4 (4)	C18A—C17A—H17A	111.2
C6—C5—C7	112.0 (5)	C18A—C17A—H17B	111.2
C6—C5—C8	110.5 (5)	O7—C17B—H17C	108.6
C7—C5—C8	111.4 (5)	O7—C17B—H17D	108.6
C5—C6—H6A	109.5	O7—C17B—C18B	114.5 (8)
C5—C6—H6B	109.5	H17C—C17B—H17D	107.6
C5—C6—H6C	109.5	C18B—C17B—H17C	108.6
H6A—C6—H6B	109.5	C18B—C17B—H17D	108.6
H6A—C6—H6C	109.5	C17A—C18A—H18A	109.5
H6B—C6—H6C	109.5	C17A—C18A—H18B	109.5
C5—C7—H7A	109.5	C17A—C18A—H18C	109.5
C5—C7—H7B	109.5	H18A—C18A—H18B	109.5
C5—C7—H7C	109.5	H18A—C18A—H18C	109.5
H7A—C7—H7B	109.5	H18B—C18A—H18C	109.5
H7A—C7—H7C	109.5	C17B—C18B—H18D	109.5
H7B—C7—H7C	109.5	C17B—C18B—H18E	109.5
C5—C8—H8A	109.5	C17B—C18B—H18F	109.5
C5—C8—H8B	109.5	H18D—C18B—H18E	109.5
C5—C8—H8C	109.5	H18D—C18B—H18F	109.5
H8A—C8—H8B	109.5	H18E—C18B—H18F	109.5

Zn1—O1—C2—C1	175.2 (3)	C2—C3—C4—O2	0.0 (7)
Zn1—O1—C2—C3	−5.2 (6)	C2—C3—C4—O3	−178.9 (4)
Zn1—O2—C4—O3	−171.2 (3)	C4—O3—C5—C6	−60.4 (6)
Zn1—O2—C4—C3	10.0 (6)	C4—O3—C5—C7	64.2 (6)
Zn1ⁱ—O4—C10—C9	−0.3 (6)	C4—O3—C5—C8	−177.8 (5)
Zn1—O4—C10—C9	−174.9 (4)	C5—O3—C4—O2	−3.7 (6)
Zn1ⁱ—O4—C10—C11	−179.5 (3)	C5—O3—C4—C3	175.2 (4)
Zn1—O4—C10—C11	5.9 (6)	C9—C10—C11—C12	−179.8 (5)
Zn1—O5—C12—O6	168.2 (3)	C10—C11—C12—O5	4.4 (7)
Zn1—O5—C12—C11	−12.6 (6)	C10—C11—C12—O6	−176.3 (4)
Zn1—O7—C17A—C18A	95.5 (12)	C12—O6—C13—C14	−180.0 (4)
Zn1—O7—C17B—C18B	176.2 (11)	C12—O6—C13—C15	−61.2 (5)
O1—C2—C3—C4	−2.8 (7)	C12—O6—C13—C16	63.0 (5)
O4—C10—C11—C12	−0.6 (8)	C13—O6—C12—O5	0.2 (6)
C1—C2—C3—C4	176.8 (4)	C13—O6—C12—C11	−179.1 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O1ⁱ	0.86 (1)	2.01 (1)	2.861 (4)	171 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

References

Aliaga-Alcalde, N., Rodríguez, L., Ferbinteanu, M., Höfer, P. & Weyhermüller, T. (2012). Inorg. Chem. 51, 864–873. CAS PubMed Google Scholar
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. Web of Science CrossRef IUCr Journals Google Scholar
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397. Web of Science CrossRef CAS IUCr Journals Google Scholar
Cosham, S. D., Richards, S. P., Manning, T., Hill, M. S., Johnson, A. L. & Molloy, K. C. (2017). Eur. J. Inorg. Chem. pp. 1868–1876. CrossRef Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Han, H., Wei, Zh., Barry, M. C., Carozza, J. C., Alkan, M., Rogachev, A. Yu., Filatov, A. S., Abakumov, A. M. & Dikarev, E. V. (2018). Chem. Sci. 9, 4736–4745. CSD CrossRef CAS PubMed Google Scholar
Han, H., Wei, Zh., Barry, M. C., Filatov, A. S. & Dikarev, E. V. (2017). Dalton Trans. 46, 5644–5649. CSD CrossRef CAS PubMed Google Scholar
Kamata, K., Nishino, J., Ohshio, S., Maruyama, K. & Ohtuki, M. (1994). J. Am. Ceram. Soc. 77, 505–508. CrossRef CAS Google Scholar
Kawazoe, T., Kobayashi, K. & Ohtsu, M. (2006). Appl. Phys. B, 84, 247–251. CrossRef CAS Google Scholar
Koval, L. I., Dzyuba, V. I., Bon, V. V., Ilnitska, O. L. & Pekhnyo, V. I. (2009). Polyhedron, 28, 2698–2702. Web of Science CSD CrossRef CAS Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Mastrorilli, P. & Nobile, C. F. (1994). J. Mol. Catal. 94, 19–26. CrossRef CAS Google Scholar
Nayak, S. K., Jena, A., Neelgund, G. M., Shivashankar, S. A. & Guru Row, T. N. (2007). Acta Cryst. E63, m1604. CSD CrossRef IUCr Journals Google Scholar
Nie, C., Zhang, Q., Ding, H., Huang, B., Wang, X., Zhao, X., Li, S., Zhou, H., Wu, J. & Tian, Y. (2014). Dalton Trans. 43, 599–608. CSD CrossRef CAS PubMed Google Scholar
Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Sechi, M., Bacchi, A., Carcelli, M., Compari, C., Duce, E., Fisicaro, E., Rogolino, D., Gates, P., Derudas, M., Al-Mawsawi, L. Q. & Neamati, N. (2006). J. Med. Chem. 49, 4248–4260. CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shtokvish, O. O., Koval, L. I., Dyakonenko, V. V. & Pekhnyo, V. I. (2017). Ukr. Chem. J. 83, 34–37. https://ucj.org.ua/index.php/journal/issue/view/95/5-2017 Google Scholar
Shtokvish, O. O., Koval, L. I. & Pekhnyo, V. I. (2014). Acta Cryst. E70, 483–485. CSD CrossRef IUCr Journals Google Scholar
Shtokvish, O. O., Koval, L. I. & Pekhnyo, V. I. (2015). Ukr. Chem. J. 81, 92–98. https://ucj.org.ua/index.php/journal/issue/view/43/12-2015 Google Scholar
Shtokvysh, O., Koval, L., Dyakonenko, V. & Pekhnyo, V. (2020). Bull. Taras Shevchenko Nat. Univ. Kyiv Chem. 1, 66–69. https://doi.org/10.17721/1728-2209.2020.1(57).16 Google Scholar
Shtokvysh, O. O., Koval, L. I., Dyakonenko, V. V. & Pekhnyo, V. I. (2018). Ukr. Chem. J. 84, 13–19. https://ucj.org.ua/index.php/journal/issue/view/3/3 Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Turrà, N., Neuenschwander, U., Baiker, A., Peeters, J. & Hermans, I. (2010). Chem. Eur. J. 16, 13226–13235. PubMed Google Scholar
Wei, Zh., Han, H., Filatov, A. S. & Dikarev, E. V. (2014). Chem. Sci. 5, 813–818. CSD CrossRef CAS Google Scholar

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Volume 79| Part 5| May 2023| Pages 478-481

https://doi.org/10.1107/S2056989023003377

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure and Hirshfeld surface analysis of bis­­(μ-4-tert-but­­oxy-4-oxobut-2-en-2-olato)bis­­[(4-tert-but­­oxy-4-oxobut-2-en-2-olato)ethano­lzinc(II)]

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis and finger print plots

5. Database survey

6. Synthesis and crystallization

7. Refinement

Supporting information

References

research communications

Crystal structure and Hirshfeld surface analysis of bis(μ-4-tert-butoxy-4-oxobut-2-en-2-olato)bis[(4-tert-butoxy-4-oxobut-2-en-2-olato)ethanolzinc(II)]

3. Supramolecular features