Poly[(μ₄-2,5-dimeth­oxy­benzene-1,4-di­carboxyl­ato)manganese(II)] and its zinc(II) analogue: three-dimensional coordination polymers containing unusually coordinated metal centres

The title compounds, [Mn(C₁₀H₈O₆)]_n and [Zn(C₁₀H₈O₆)]_n, are isomorphous coordination polymers prepared from 2,5-dimeth­oxy­terephthalic acid (H₂dmt) and the respective metal(II) salts. Both complexes form three-dimensional metal–organic frameworks with each M^II centre bridged by four 2,5-dimeth­oxy­terephthalate (dmt²⁻) anions, resulting in the same type of network topology. The asymmetric unit consists of one M^II cation on a twofold axis and one half of a dmt²⁻ anion (located on a centre of inversion). In the crystal structure, the M^II centres are coordinated in a rather unusual way, as there is a distorted tetra­hedral inner coordination sphere formed by four carboxyl­ate O atoms of four different dmt²⁻ anions, and an additional outer coordination sphere formed by two meth­oxy and two carboxyl­ate O atoms, with each of the O atoms belonging to one of the four different dmt²⁻ anions forming the inner coordination sphere. Consideration of both coordination spheres results in a super-dodeca­hedral coordination geometry for the M^II centres. Besides the numerous M^II...O inter­actions, both structures are further stabilized by weak C—H...O contacts.

S1. Comment

Metal–organic coordination polymers (MOCPs) are crystalline frameworks composed of metal ions or clusters of metal ions called secondary building units (SBUs) and organic molecules called linkers, to form one-, two- or three-dimensional structures possessing cavities (Li et al., 1999). In specific cases, knowledge of the SBU and linker geometries, in conjunction with their interaction principles, allows the prediction of network topologies and thus supports rational framework design. It is known that specific reaction conditions such as temperature, solvent and moisture can influence SBU formation (Hausdorf et al., 2008). Nevertheless, generation of SBUs subject to linker properties has only rarely been investigated (Choi et al., 2009).

While the reaction of 2,5-dihydroxyterephthalic acid and Zn(NO₃)₂.4H₂O [carried out under conditions (Tranchemontagne et al., 2008) comparable with those used here] leads to MOF-74 (Rosi et al., 2005) type networks, the reaction of 2,5-di-n-propoxyterephthalic acid and Zn(NO₃)₂.4H₂O gives rise to IRMOF (Eddaoudi et al., 2002) type structures. However, three-dimensional coordination polymers containing the dmt^2- anion as a linker with Zn^II or Mn^II as metal ions for the SBU have not been reported so far. This prompted us to use the dmt^2- anion as a rigid dicarboxylate with small weakly coordinating substituents for our investigations to form appropriate new types of MOCPs.

The title compounds, [Mn(dmt)]_n, (I), and [Zn(dmt)]_n, (II), crystallize in the monoclinic space group C2/c with asymmetric units containing one M^II cation (M = Mn or Zn) and one half of a dmt^2- anion (Fig. 1). Indeed, the two compounds are isomorphous, which is shown in the molecular overlay plot in Fig. 2. Besides a slight difference in the monoclinic angle β, the unit-cell dimensions do not differ significantly from each other.

As shown in Fig. 1, each of the M^II cations adopts a distorted M^IIO₄ tetrahedral geometry, coordinated by four O atoms from four different dmt^2- anions. The Mn1—O1 and Mn1—O2 bond lengths of 2.1391 (6) and 2.0761 (5) Å, respectively, in (I) are in accordance with those reported for related manganese(II) terephthalates [Mn—O = 2.100 (4)–2.188 (3) Å; Xu et al., 2010; Luo et al., 2008]. The corresponding O—Mn—O angles range from 93.73 (2) to 141.52 (3)°, thus deviating considerably from the ideal value of 109.4° for a tetrahedral coordination sphere. The Zn—O bond lengths in (II) range from 2.0023 (13) Å for Zn1—O1 to 1.9547 (13) Å for Zn1—O2 and do not vary significantly from literature values for related zinc(II) terephthalate-based MOCPs [1.935 (2)–2.104 (5) Å; Higuchi et al., 2009; Wang et al., 2008]. However, the distortion of the O—Zn—O angles from ideal tetrahedral geometry in (II), ranging from 99.51 (5) to 137.03 (8)°, is smaller than in (I). These structural differences between (I) and (II) may be caused by the different sizes of the Mn^II and Zn^II cations (0.91 and 0.83 Å, respectively; Reference for standard values?).

The uncommon values for the O—M^II—O bond angles mentioned above can be explained by the existence of a second coordination sphere formed by weak interactions between the M^II cations and O atoms of the methoxy and carboxylate groups (Fig. 1). This leads to a distorted [M^IIO₄(O)₂(OMe)₂] super dodecahedron (Fig. 3), where the methoxy O atoms are located in trans positions to each other, while the two bidentate and two monodentate carboxylates coordinate in a cis position to each other (Fig. 4).

The bond lengths for M—OMe [Mn1—O3 = 2.5596 (6) Å and Zn1—O3 = 2.6224 (17) Å] and M—O2' [Mn1—O2' = 2.7570 (6) Å and Zn1—O2' = 2.8772 (16) Å] reveal that these bonds are much weaker than the M—O bonds of the inner coordination sphere. Similar coordination modes have already been reported for Cd^II complexes (Li et al., 2008). The M^IIO₈ super dodecahedra are edge-sharing, to give a one-dimensional chain along the c axis (Fig. 3). Two adjacent one-dimensional chains are interconnected by dmt^2- anions to obtain a three-dimensional coordination network, with shortest Mn1A···Mn1B and Zn1A···Zn1B distances between the one-dimensional chains of 8.0793 (3) and 8.0552 (2) Å, respectively. Apart from these M^II—O interactions, there are weak intermolecular C—H···O hydrogen-bonding interactions in both networks, involving C3—H3···O1ⁱ and C5—H5B···O2ⁱⁱ for both (I) and (II), contributing to the stabilization of the crystal structures (symmetry codes are given in Tables 1 and 2).

One dimensional rhombic channels of 9.1 × 13.1 Å in diameter (measured between atoms in opposite corners) are located along the c axis in the networks of (I) and (II). The methoxy groups point inside these channels and subdivide them into two smaller pores, shown as balls in the network structure (Fig. 5). Taking the van der Waals radii into account, their size is reduced to about 1.2 Å, which is much too small for the uptake of any solvent molecules or nitrogen. A better understanding of the network structures of (I) and (II) can be achieved by a topological investigation, reducing complex network structures to simple SBU-and-linker networks (Rosi et al., 2005) (Fig. 6). To derive the nets of (I) and (II), the SBUs were reduced to rods of shaded quadrangles linked by sharing opposite edges, which leads to a ladder-like conformation of the one-dimensional SBU chains. The linkers are represented by rungs to form a 4-connected net with parallel rungs, analogous to the Al net in SrAl₂. This is called a network with sra¹² topology, also found in metal–organic frameworks such as MIL-47 (Barthelet et al., 2002), MIL-53 (Loiseau et al., 2004) and MOF-71 (Rosi et al., 2005).

The main reason for the generation of the more or less unusual isomorphous structures of (I) and (II) may be the formation of metal centres with high coordination numbers. The reaction of Zn(NO₃)₂.4H₂O and a rigid dicarboxylic acid in N,N-dimethyl formamide usually leads to an IRMOF-type framework (Eddaoudi et al., 2002) containing a four-coordinated Zn metal centre. Performing these reactions with 2,5-dihydroxyterephthalic acid instead leads to MOF-74-type frameworks, caused by the linker molecule facilitating the formation of a much more stable five-coordinated metal species. The frameworks of (I) and (II) discussed here exhibit eight-coordinated metal centres, which seems to be the most stable coordination geometry under these conditions.

Related literature

For related literature, see: Barthelet et al. (2002); Choi et al. (2009); Eddaoudi et al. (2002); Hausdorf et al. (2008); Higuchi et al. (2009); Li et al. (1999, 2008); Loiseau et al. (2004); Luo et al. (2008); Passaniti et al. (2002); Rosi et al. (2005); Tranchemontagne et al. (2008); Wang et al. (2008); Xu et al. (2010).

S2. Experimental

All chemicals and solvents were commercially available and used without further purification. 2,5-Dimethoxyterephthalic acid was synthesized according to the procedure published by Passaniti et al. (2002).

For the synthesis of [Mn(dmt)]_n, (I), MnCl₂.4H₂O (105 mg, 0.53 mmol) and 2,5-dimethoxyterephthalic acid (40 mg, 0.18 mmol) were dissolved in N,N-dimethyl formamide (40 ml) and heated in a sealed tube for 24 h at 373 K. Yellow crystals of (I) [Colourless given in CIF tables - please clarify] precipitated after 24 h (yield 72%).

For the synthesis of [Zn(dmt)]_n, (II), the same procedure was used as for (I), using Zn(NO₃)₂.4H₂O (140 mg, 0.53 mmol) instead of MnCl₂.4H₂O. Colourless crystals of (II) precipitated after 18 h (yield 79%).

S3. Refinement

For both compounds, H atoms were positioned geometrically and allowed to ride on their respective parent atoms, with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl H, and C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aryl H atoms.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The asymmetric units of (a) (I) and (b) (II), showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 50% probability level. Singly, doubly and triply primed atoms are at the symmetry positions ? [Please complete]
	Fig. 2. A molecular overlay of the asymmetric units of (I) and (II), showing only minor differences in the atom positions. The atoms of (I) are shown as shaded balls and the atoms of (II) as white balls with shaded borders. H atoms have been omitted for clarity.
	Fig. 3. The one-dimensional chains of (a) [Mn-(µ-CO2)2-Mn]n and (b) [Zn-(µ-CO2)2-Zn]n. The M^II—O bonds of the second coordination spheres are shown as dashed lines. The inorganic M^IIO8 SBUs are chains of edge-sharing dodecahedra [in the electronic version of the journal, purple for Mn in (a), turquoise for Zn in (b)], in which the C atoms can be connected to form a zigzag ladder (c).
	Fig. 4. The super-dodecahedral coordination spheres (a) MnO4(O)2(OMe)2 and (b) ZnO4(O)2(OMe)2, showing the coordination modes of the anions. The M^II—O bonds of the second coordination spheres are shown as dashed lines.
	Fig. 5. A view of the network of (I) and (II) along the c, axis with shaded M^IIO4(O)2(OMe)2 super dodecahedrons. The large balls show the accessible pores. The atom coordinates from (I) were used as the example to create the diagram.
	Fig. 6. The topology of the network, reduced to a simple SBU-and-linker geometry model. The M^IIO4(OMe)2 SBUs are reduced to rods of shaded quadrangles and the dmt^2- linkers are represented by thin grey rods.

(I) Poly[(µ₄-2,5-dimethoxybenzene-1,4-dicarboxylato)manganese(II)]

Crystal data

[Mn(C10H8O6)]	F(000) = 564
Mr = 279.10	Dx = 1.776 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8637 reflections
a = 16.7686 (6) Å	θ = 2.5–34.5°
b = 8.4646 (3) Å	µ = 1.28 mm^−1
c = 7.4464 (3) Å	T = 153 K
β = 99.093 (1)°	Block, yellow
V = 1043.66 (7) Å^3	0.52 × 0.35 × 0.33 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer	2156 independent reflections
Radiation source: fine-focus sealed tube	2084 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 34.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −26→26
Tmin = 0.633, Tmax = 0.747	k = −13→13
11427 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.052	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0264P)^2 + 0.4525P] where P = (Fo^2 + 2Fc^2)/3
2156 reflections	(Δ/σ)max = 0.001
79 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

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

	x	y	z	Uiso*/Ueq
Mn1	1.0000	−0.076459 (18)	0.2500	0.01459 (5)
O1	0.88960 (4)	0.05007 (7)	0.25036 (9)	0.02221 (11)
O2	0.96699 (3)	0.15728 (7)	0.48546 (7)	0.01809 (10)
O3	0.89455 (3)	0.29664 (7)	0.73532 (8)	0.02100 (11)
C1	0.82337 (4)	0.19593 (8)	0.45428 (9)	0.01336 (10)
C2	0.82294 (4)	0.27479 (8)	0.62019 (9)	0.01438 (10)
C3	0.74941 (4)	0.32770 (8)	0.66249 (9)	0.01502 (11)
H3	0.7488	0.3815	0.7742	0.018*
C4	0.89808 (4)	0.13108 (8)	0.39354 (9)	0.01460 (11)
C5	0.89157 (6)	0.38382 (13)	0.89920 (15)	0.0369 (2)
H5A	0.8689	0.4889	0.8685	0.055*
H5B	0.9463	0.3945	0.9675	0.055*
H5C	0.8575	0.3276	0.9736	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.00888 (7)	0.02125 (8)	0.01397 (7)	0.000	0.00279 (4)	0.000
O1	0.0159 (2)	0.0270 (3)	0.0246 (3)	0.00280 (19)	0.00613 (19)	−0.0088 (2)
O2	0.0104 (2)	0.0248 (2)	0.0194 (2)	0.00177 (17)	0.00324 (16)	0.00496 (18)
O3	0.0127 (2)	0.0239 (3)	0.0241 (2)	0.00429 (18)	−0.00405 (18)	−0.0099 (2)
C1	0.0106 (2)	0.0138 (2)	0.0157 (2)	0.00215 (18)	0.00227 (18)	−0.00033 (18)
C2	0.0106 (2)	0.0149 (2)	0.0169 (2)	0.00198 (19)	−0.00020 (19)	−0.0019 (2)
C3	0.0121 (3)	0.0171 (3)	0.0155 (2)	0.0033 (2)	0.00114 (19)	−0.0026 (2)
C4	0.0123 (3)	0.0144 (2)	0.0179 (3)	0.00228 (19)	0.0048 (2)	0.0022 (2)
C5	0.0255 (4)	0.0425 (5)	0.0370 (5)	0.0149 (4)	−0.0124 (3)	−0.0265 (4)

Geometric parameters (Å, º)

Mn1—O2^i	2.0761 (5)	C1—C3^iv	1.3965 (9)
Mn1—O2^ii	2.0761 (5)	C1—C2	1.4052 (9)
Mn1—O1^iii	2.1391 (6)	C1—C4	1.5015 (9)
Mn1—O1	2.1391 (6)	C2—C3	1.3938 (9)
O1—C4	1.2567 (9)	C3—C1^iv	1.3965 (9)
O2—C4	1.2660 (8)	C3—H3	0.9500
O2—Mn1^ii	2.0761 (5)	C5—H5A	0.9800
O3—C2	1.3733 (8)	C5—H5B	0.9800
O3—C5	1.4337 (10)	C5—H5C	0.9800
O2^i—Mn1—O2^ii	141.52 (3)	C3—C2—C1	118.61 (6)
O2^i—Mn1—O1^iii	105.36 (2)	C2—C3—C1^iv	122.04 (6)
O2^ii—Mn1—O1^iii	93.73 (2)	C2—C3—H3	119.0
O2^i—Mn1—O1	93.73 (2)	C1^iv—C3—H3	119.0
O2^ii—Mn1—O1	105.36 (2)	O1—C4—O2	121.70 (6)
O1^iii—Mn1—O1	119.91 (4)	O1—C4—C1	117.85 (6)
C4—O1—Mn1	107.00 (5)	O2—C4—C1	120.45 (6)
C4—O2—Mn1^ii	122.61 (4)	O3—C5—H5A	109.5
C2—O3—C5	117.13 (6)	O3—C5—H5B	109.5
C3^iv—C1—C2	119.35 (6)	H5A—C5—H5B	109.5
C3^iv—C1—C4	116.66 (6)	O3—C5—H5C	109.5
C2—C1—C4	123.98 (6)	H5A—C5—H5C	109.5
O3—C2—C3	122.21 (6)	H5B—C5—H5C	109.5
O3—C2—C1	119.17 (6)
O2^i—Mn1—O1—C4	−171.27 (5)	C1—C2—C3—C1^iv	0.28 (11)
O2^ii—Mn1—O1—C4	42.48 (5)	Mn1—O1—C4—O2	16.20 (8)
O1^iii—Mn1—O1—C4	−61.16 (5)	Mn1—O1—C4—C1	−163.40 (5)
C5—O3—C2—C3	−2.96 (11)	Mn1^ii—O2—C4—O1	−116.47 (7)
C5—O3—C2—C1	177.31 (8)	Mn1^ii—O2—C4—C1	63.11 (8)
C3^iv—C1—C2—O3	179.47 (6)	C3^iv—C1—C4—O1	−5.41 (9)
C4—C1—C2—O3	0.65 (10)	C2—C1—C4—O1	173.44 (7)
C3^iv—C1—C2—C3	−0.27 (11)	C3^iv—C1—C4—O2	174.99 (6)
C4—C1—C2—C3	−179.09 (6)	C2—C1—C4—O2	−6.16 (10)
O3—C2—C3—C1^iv	−179.45 (6)

Symmetry codes: (i) x, −y, z−1/2; (ii) −x+2, −y, −z+1; (iii) −x+2, y, −z+1/2; (iv) −x+3/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1^iv	0.95	2.37	2.7209 (8)	101
C5—H5B···O2^v	0.98	2.47	3.0654 (11)	119

Symmetry codes: (iv) −x+3/2, −y+1/2, −z+1; (v) −x+2, y, −z+3/2.

(II) Poly[(µ₄-2,5-dimethoxybenzene-1,4-dicarboxylato)zinc(II)]

Crystal data

[Zn(C10H8O6)]	F(000) = 584
Mr = 289.53	Dx = 1.851 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2923 reflections
a = 16.5936 (6) Å	θ = 2.5–26.0°
b = 8.4438 (3) Å	µ = 2.38 mm^−1
c = 7.4838 (3) Å	T = 153 K
β = 97.649 (2)°	Block, colourless
V = 1039.25 (7) Å^3	0.21 × 0.15 × 0.13 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer	1005 independent reflections
Radiation source: fine-focus sealed tube	898 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ϕ and ω scans	θmax = 25.8°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −19→20
Tmin = 0.695, Tmax = 0.746	k = −9→10
6781 measured reflections	l = −9→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.049	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0227P)^2 + 0.9295P] where P = (Fo^2 + 2Fc^2)/3
1005 reflections	(Δ/σ)max < 0.001
79 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

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 > σ(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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	1.0000	−0.07765 (4)	0.2500	0.01735 (12)
O1	0.89943 (8)	0.04802 (17)	0.27162 (18)	0.0206 (3)
O2	0.97106 (7)	0.16244 (16)	0.50689 (17)	0.0175 (3)
O3	0.88909 (8)	0.29952 (17)	0.74397 (19)	0.0223 (3)
C1	0.82575 (11)	0.1943 (2)	0.4642 (3)	0.0161 (4)
C2	0.81990 (11)	0.2758 (2)	0.6249 (3)	0.0167 (4)
C3	0.74429 (11)	0.3298 (2)	0.6580 (3)	0.0173 (4)
H3	0.7401	0.3848	0.7672	0.021*
C4	0.90393 (11)	0.1308 (2)	0.4121 (3)	0.0157 (4)
C5	0.88121 (14)	0.3818 (3)	0.9077 (3)	0.0407 (7)
H5A	0.8602	0.4887	0.8795	0.061*
H5B	0.9345	0.3890	0.9814	0.061*
H5C	0.8435	0.3243	0.9745	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01064 (17)	0.0276 (2)	0.01397 (18)	0.000	0.00223 (12)	0.000
O1	0.0149 (7)	0.0303 (9)	0.0166 (7)	0.0026 (6)	0.0023 (6)	−0.0049 (6)
O2	0.0116 (6)	0.0232 (8)	0.0177 (7)	−0.0003 (5)	0.0020 (6)	0.0025 (6)
O3	0.0140 (7)	0.0305 (8)	0.0210 (8)	0.0039 (6)	−0.0025 (6)	−0.0093 (7)
C1	0.0144 (9)	0.0172 (10)	0.0170 (10)	0.0000 (8)	0.0030 (8)	0.0027 (8)
C2	0.0131 (9)	0.0176 (10)	0.0186 (10)	0.0001 (8)	−0.0014 (8)	0.0009 (8)
C3	0.0165 (10)	0.0196 (11)	0.0157 (10)	0.0014 (8)	0.0024 (8)	−0.0013 (8)
C4	0.0147 (10)	0.0179 (10)	0.0148 (10)	−0.0007 (8)	0.0030 (8)	0.0051 (8)
C5	0.0272 (13)	0.0553 (17)	0.0352 (14)	0.0159 (11)	−0.0120 (10)	−0.0260 (12)

Geometric parameters (Å, º)

Zn1—O2^i	1.9547 (13)	C1—C3^iv	1.395 (3)
Zn1—O2^ii	1.9547 (13)	C1—C2	1.401 (3)
Zn1—O1^iii	2.0023 (13)	C1—C4	1.502 (3)
Zn1—O1	2.0023 (13)	C2—C3	1.388 (3)
O1—C4	1.256 (2)	C3—C1^iv	1.395 (3)
O2—C4	1.267 (2)	C3—H3	0.9500
O2—Zn1^ii	1.9547 (13)	C5—H5A	0.9800
O3—C2	1.371 (2)	C5—H5B	0.9800
O3—C5	1.430 (3)	C5—H5C	0.9800
O2^i—Zn1—O2^ii	137.03 (8)	C3—C2—C1	118.85 (17)
O2^i—Zn1—O1^iii	102.89 (5)	C2—C3—C1^iv	121.94 (19)
O2^ii—Zn1—O1^iii	99.51 (5)	C2—C3—H3	119.0
O2^i—Zn1—O1	99.51 (5)	C1^iv—C3—H3	119.0
O2^ii—Zn1—O1	102.89 (5)	O1—C4—O2	122.41 (17)
O1^iii—Zn1—O1	116.00 (8)	O1—C4—C1	117.28 (17)
C4—O1—Zn1	113.89 (12)	O2—C4—C1	120.30 (17)
C4—O2—Zn1^ii	122.20 (12)	O3—C5—H5A	109.5
C2—O3—C5	117.63 (15)	O3—C5—H5B	109.5
C3^iv—C1—C2	119.21 (17)	H5A—C5—H5B	109.5
C3^iv—C1—C4	116.79 (18)	O3—C5—H5C	109.5
C2—C1—C4	124.00 (17)	H5A—C5—H5C	109.5
O3—C2—C3	122.32 (18)	H5B—C5—H5C	109.5
O3—C2—C1	118.83 (16)
O2^i—Zn1—O1—C4	−173.31 (13)	C1—C2—C3—C1^iv	−0.2 (3)
O2^ii—Zn1—O1—C4	43.62 (14)	Zn1—O1—C4—O2	16.5 (2)
O1^iii—Zn1—O1—C4	−63.84 (12)	Zn1—O1—C4—C1	−164.29 (13)
C5—O3—C2—C3	0.6 (3)	Zn1^ii—O2—C4—O1	−112.14 (18)
C5—O3—C2—C1	−179.4 (2)	Zn1^ii—O2—C4—C1	68.6 (2)
C3^iv—C1—C2—O3	−179.77 (17)	C3^iv—C1—C4—O1	−6.6 (3)
C4—C1—C2—O3	−0.3 (3)	C2—C1—C4—O1	173.91 (18)
C3^iv—C1—C2—C3	0.2 (3)	C3^iv—C1—C4—O2	172.60 (17)
C4—C1—C2—C3	179.64 (18)	C2—C1—C4—O2	−6.8 (3)
O3—C2—C3—C1^iv	179.76 (17)

Symmetry codes: (i) x, −y, z−1/2; (ii) −x+2, −y, −z+1; (iii) −x+2, y, −z+1/2; (iv) −x+3/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1^iv	0.95	2.36	2.713 (2)	101
C5—H5B···O2^v	0.98	2.47	3.071 (3)	120

Symmetry codes: (iv) −x+3/2, −y+1/2, −z+1; (v) −x+2, y, −z+3/2.