Two Zn^II-based MOFs constructed with biphenyl-2,2′,5,5′-tetra­carb­oxy­lic acid and flexible N-donor ligands: syntheses, structures and properties

Two new Zn²⁺-based metal–organic frameworks (MOFs) based on biphenyl-2,2′,5,5′-tetra­carb­oxy­lic acid, i.e. H₄(o,m-bpta), and N-donor ligands, namely, poly[[(μ₄-biphenyl-2,2′,5,5′-tetra­carboxyl­ato)bis{[1,3-phenyl­enebis(methyl­ene)]bis­(1H-imidazole)}dizinc(II)] di­methyl­formamide monosolvate dihydrate], {[Zn₂(C₁₆H₆O₈)(C₁₄H₁₄N₄)₂]·C₃H₇NO·2H₂O}_n or {[Zn₂(o,m-bpta)(1,3-bimb)₂]·C₃H₇NO·2H₂O}_n (1) {1,3-bimb = [1,3-phenyl­enebis(methyl­ene)]bis­(1H-imidazole)}, and poly[[(μ₄-biphenyl-2,2′,5,5′-tetra­carboxyl­ato)bis{[1,4-phenyl­ene­bis(methyl­ene)]bis­(1H-imidazole)}dizinc(II)] monohydrate], {[Zn₂(C₁₆H₆O₈)(C₁₄H₁₄N₄)₂]·H₂O}_n or {[Zn₂(o,m-bpta)(1,4-bimb)₂]·H₂O}_n (2) {1,4-bimb = [1,4-phenyl­enebis(methyl­ene)]bis­(1H-imidazole)}, have been synthesized under solvothermal conditions. The com­plexes were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction and powder X-ray diffraction analysis. Structurally, the (o,m-bpta)⁴⁻ ligands are fully deprotonated and com­bine with Zn²⁺ ions in μ₄-coordination modes. Com­plex 1 is a (3,4)-connected porous network with honeycomb-like [Zn₂(o,m-bpta)]_n sheets formed by 4-connected (o,m-bpta)⁴⁻ ligands. Com­plex 2 exhibits a (2,4)-con­­nected network formed by 4-connected (o,m-bpta)⁴⁻ ligands linking Zn²⁺ ions in left-handed helical chains. The cis-configured 1,3-bimb and 1,4-bimb ligands bridge Zn²⁺ ions to form multi-membered [Zn₂(bimb)₂] loops. Optically, the com­plexes show strong fluorescence and display larger red shifts compared to free H₄(o,m-bpta). Com­plex 2 shows ferroelectric properties due to crystallizing in the C_2v polar point group.

Computing details

For both structures, data collection: APEX3 (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: SHELXL2018 (Sheldrick, 2015). Molecular graphics: SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2005) and PLATON (Spek, 2020) for sf170323a-15_a_sq; SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005) for sf170602b-43_a. For both structures, software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[[(µ₄-biphenyl-2,2',5,5'-tetracarboxylato)bis{[1,3-phenylenebis(methylene)]bis(1H-imidazole)}dizinc(II)] dimethylformamide monosolvate dihydrate] (sf170323a-15_a_sq)

Crystal data

[Zn2(C16H6O8)(C14H14N4)2]·C3H7NO·2H2O	F(000) = 1912
Mr = 1042.34	Dx = 1.358 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.3143 (14) Å	Cell parameters from 8069 reflections
b = 16.3192 (19) Å	θ = 2.7–21.7°
c = 23.367 (3) Å	µ = 1.11 mm^−1
β = 103.545 (3)°	T = 296 K
V = 4565.3 (9) Å^3	Block, colourless
Z = 4	0.32 × 0.30 × 0.30 mm

Data collection

Bruker Quest APEX III diffractometer	2808 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.099
φ and ω scans	θmax = 26.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −15→15
Tmin = 0.654, Tmax = 0.745	k = −20→20
37836 measured reflections	l = −29→29
4709 independent reflections

Refinement

Refinement on F^2	13 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0459P)^2 + 5.6151P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
4709 reflections	Δρmax = 0.34 e Å^−3
289 parameters	Δρmin = −0.27 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.58999 (3)	0.62562 (3)	0.35543 (2)	0.04334 (16)
O1	0.6413 (2)	0.53400 (16)	0.31723 (12)	0.0624 (8)
O2	0.8127 (19)	0.5856 (12)	0.3472 (8)	0.074 (5)	0.4
O2'	0.8131 (13)	0.5609 (9)	0.3652 (5)	0.075 (3)	0.6
O3	0.8712 (2)	0.21893 (16)	0.18763 (11)	0.0554 (7)
O4	0.9680 (2)	0.30720 (17)	0.14785 (12)	0.0655 (8)
N1	0.4261 (2)	0.60926 (18)	0.34787 (13)	0.0435 (8)
N2	0.2471 (2)	0.6334 (2)	0.32756 (13)	0.0493 (8)
N3	−0.1433 (3)	0.7991 (2)	0.47281 (13)	0.0549 (9)
N4	−0.1406 (2)	0.8578 (2)	0.55730 (13)	0.0520 (9)
C1	0.7458 (4)	0.5309 (3)	0.3228 (2)	0.0579 (11)
C2	0.7852 (3)	0.4719 (2)	0.28289 (17)	0.0454 (10)
C3	0.8971 (3)	0.4693 (2)	0.28231 (17)	0.0469 (10)
H3	0.945897	0.506688	0.305018	0.056*
C4	0.9387 (3)	0.4125 (2)	0.24872 (15)	0.0363 (8)
C5	0.8666 (3)	0.3558 (2)	0.21582 (15)	0.0376 (9)
C6	0.7532 (3)	0.3593 (2)	0.21561 (16)	0.0492 (10)
H6	0.704150	0.321801	0.193282	0.059*
C7	0.7132 (3)	0.4173 (3)	0.24785 (18)	0.0542 (10)
H7	0.637026	0.419981	0.246126	0.065*
C8	0.9070 (3)	0.2905 (2)	0.18075 (15)	0.0411 (9)
C9	0.3778 (3)	0.5638 (3)	0.3842 (2)	0.0667 (13)
H9	0.415565	0.527456	0.412672	0.080*
C10	0.2685 (4)	0.5792 (3)	0.3729 (2)	0.0713 (13)
H10	0.217241	0.557178	0.392229	0.086*
C11	0.3444 (3)	0.6495 (2)	0.31421 (15)	0.0424 (9)
H11	0.352824	0.685156	0.284501	0.051*
C12	0.1406 (3)	0.6728 (3)	0.30224 (18)	0.0698 (13)
H12A	0.083405	0.631162	0.290535	0.084*
H12B	0.146192	0.702965	0.267301	0.084*
C13	0.1070 (3)	0.7303 (3)	0.34523 (18)	0.0600 (12)
C14	0.0141 (3)	0.7149 (3)	0.36667 (16)	0.0548 (11)
H14	−0.029671	0.669303	0.353119	0.066*
C15	−0.0156 (3)	0.7651 (3)	0.40757 (17)	0.0547 (11)
C16	0.0488 (4)	0.8324 (3)	0.4280 (3)	0.0914 (17)
H16	0.027989	0.867610	0.454883	0.110*
C17	0.1459 (5)	0.8481 (3)	0.4082 (3)	0.123 (3)
H17	0.191519	0.892335	0.422955	0.148*
C18	0.1728 (5)	0.7967 (3)	0.3666 (3)	0.1001 (19)
H18	0.236459	0.807224	0.352832	0.120*
C19	−0.1157 (3)	0.7407 (3)	0.43097 (18)	0.0675 (13)
H19A	−0.179872	0.734819	0.398062	0.081*
H19B	−0.101116	0.687731	0.449990	0.081*
C20	−0.2117 (4)	0.8659 (3)	0.46161 (18)	0.0680 (13)
H20	−0.251998	0.883509	0.424914	0.082*
C21	−0.2098 (3)	0.9012 (3)	0.51369 (19)	0.0624 (12)
H21	−0.249482	0.947868	0.519187	0.075*
C22	−0.1019 (3)	0.7972 (3)	0.53078 (17)	0.0558 (11)
H22	−0.051710	0.757993	0.550109	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0381 (2)	0.0553 (3)	0.0419 (3)	0.0072 (2)	0.01987 (19)	0.0041 (2)
O1	0.0487 (17)	0.0572 (18)	0.094 (2)	0.0108 (14)	0.0423 (15)	0.0036 (16)
O2	0.065 (7)	0.081 (10)	0.088 (12)	0.002 (7)	0.040 (9)	−0.030 (8)
O2'	0.065 (5)	0.104 (8)	0.060 (5)	0.019 (5)	0.022 (4)	−0.014 (5)
O3	0.0703 (19)	0.0457 (17)	0.0585 (17)	0.0004 (14)	0.0315 (15)	−0.0025 (14)
O4	0.0709 (19)	0.073 (2)	0.0656 (19)	−0.0252 (16)	0.0415 (16)	−0.0198 (15)
N1	0.0398 (18)	0.046 (2)	0.0491 (18)	0.0028 (15)	0.0199 (16)	0.0018 (15)
N2	0.0331 (17)	0.069 (2)	0.0484 (19)	−0.0017 (17)	0.0153 (14)	−0.0024 (18)
N3	0.0430 (19)	0.089 (3)	0.0377 (19)	0.0040 (19)	0.0194 (16)	0.0050 (19)
N4	0.0403 (18)	0.079 (3)	0.0406 (18)	0.0075 (17)	0.0172 (16)	0.0058 (18)
C1	0.062 (3)	0.053 (3)	0.069 (3)	0.018 (2)	0.035 (3)	0.009 (2)
C2	0.040 (2)	0.045 (2)	0.060 (2)	0.0106 (19)	0.0272 (19)	0.010 (2)
C3	0.043 (2)	0.034 (2)	0.070 (3)	0.0000 (17)	0.025 (2)	−0.0002 (19)
C4	0.0323 (18)	0.0287 (19)	0.052 (2)	0.0032 (16)	0.0186 (18)	0.0061 (18)
C5	0.036 (2)	0.038 (2)	0.040 (2)	0.0014 (16)	0.0135 (17)	0.0063 (17)
C6	0.034 (2)	0.062 (3)	0.053 (2)	−0.0024 (19)	0.0121 (18)	−0.003 (2)
C7	0.035 (2)	0.071 (3)	0.061 (3)	0.006 (2)	0.020 (2)	0.008 (2)
C8	0.033 (2)	0.051 (3)	0.037 (2)	−0.0030 (18)	0.0056 (17)	−0.0010 (18)
C9	0.058 (3)	0.060 (3)	0.088 (3)	0.010 (2)	0.029 (2)	0.034 (3)
C10	0.053 (3)	0.080 (3)	0.089 (3)	−0.004 (2)	0.034 (3)	0.026 (3)
C11	0.037 (2)	0.056 (3)	0.038 (2)	0.0002 (18)	0.0176 (18)	0.0013 (18)
C12	0.041 (2)	0.118 (4)	0.053 (3)	0.008 (3)	0.017 (2)	0.002 (3)
C13	0.039 (2)	0.083 (3)	0.064 (3)	0.010 (2)	0.025 (2)	0.009 (2)
C14	0.036 (2)	0.089 (3)	0.040 (2)	−0.001 (2)	0.0099 (18)	0.004 (2)
C15	0.044 (2)	0.075 (3)	0.052 (2)	0.003 (2)	0.023 (2)	0.006 (2)
C16	0.105 (4)	0.064 (3)	0.134 (5)	−0.005 (3)	0.085 (4)	−0.011 (3)
C17	0.138 (5)	0.070 (4)	0.202 (7)	−0.035 (3)	0.120 (5)	−0.029 (4)
C18	0.103 (4)	0.077 (4)	0.153 (5)	−0.009 (3)	0.097 (4)	−0.004 (4)
C19	0.053 (3)	0.105 (4)	0.052 (3)	−0.010 (2)	0.027 (2)	−0.009 (3)
C20	0.059 (3)	0.103 (4)	0.041 (2)	0.014 (3)	0.007 (2)	0.015 (3)
C21	0.052 (3)	0.081 (3)	0.054 (3)	0.015 (2)	0.014 (2)	0.014 (2)
C22	0.044 (2)	0.087 (3)	0.040 (2)	0.011 (2)	0.017 (2)	0.013 (2)

Geometric parameters (Å, º)

Zn1—O1	1.923 (3)	C5—C8	1.498 (5)
Zn1—O3^i	1.945 (2)	C6—C7	1.372 (5)
Zn1—N1	2.002 (3)	C6—H6	0.9300
Zn1—N4^ii	2.006 (3)	C7—H7	0.9300
O1—C1	1.263 (5)	C9—C10	1.333 (5)
O2—O2'	0.58 (2)	C9—H9	0.9300
O2—C1	1.257 (16)	C10—H10	0.9300
O2'—C1	1.234 (13)	C11—H11	0.9300
O3—C8	1.272 (4)	C12—C13	1.502 (6)
O4—C8	1.225 (4)	C12—H12A	0.9700
N1—C11	1.301 (4)	C12—H12B	0.9700
N1—C9	1.365 (4)	C13—C14	1.375 (5)
N2—C11	1.333 (4)	C13—C18	1.376 (6)
N2—C10	1.358 (5)	C14—C15	1.372 (5)
N2—C12	1.457 (5)	C14—H14	0.9300
N3—C22	1.331 (5)	C15—C16	1.373 (6)
N3—C20	1.366 (5)	C15—C19	1.514 (5)
N3—C19	1.460 (5)	C16—C17	1.403 (6)
N4—C22	1.314 (5)	C16—H16	0.9300
N4—C21	1.364 (5)	C17—C18	1.382 (7)
C1—C2	1.499 (5)	C17—H17	0.9300
C2—C7	1.382 (5)	C18—H18	0.9300
C2—C3	1.382 (5)	C19—H19A	0.9700
C3—C4	1.388 (4)	C19—H19B	0.9700
C3—H3	0.9300	C20—C21	1.342 (5)
C4—C5	1.383 (5)	C20—H20	0.9300
C4—C4^iii	1.498 (6)	C21—H21	0.9300
C5—C6	1.396 (5)	C22—H22	0.9300
O1—Zn1—O3^i	102.79 (11)	C10—C9—N1	110.0 (4)
O1—Zn1—N1	106.83 (12)	C10—C9—H9	125.0
O3^i—Zn1—N1	115.04 (12)	N1—C9—H9	125.0
O1—Zn1—N4^ii	121.29 (13)	C9—C10—N2	106.2 (3)
O3^i—Zn1—N4^ii	111.37 (12)	C9—C10—H10	126.9
N1—Zn1—N4^ii	100.06 (12)	N2—C10—H10	126.9
C1—O1—Zn1	114.9 (3)	N1—C11—N2	111.7 (3)
O2'—O2—C1	74 (3)	N1—C11—H11	124.2
O2—O2'—C1	79 (3)	N2—C11—H11	124.2
C8—O3—Zn1^iv	121.3 (2)	N2—C12—C13	111.5 (3)
C11—N1—C9	105.2 (3)	N2—C12—H12A	109.3
C11—N1—Zn1	127.4 (2)	C13—C12—H12A	109.3
C9—N1—Zn1	126.5 (3)	N2—C12—H12B	109.3
C11—N2—C10	106.9 (3)	C13—C12—H12B	109.3
C11—N2—C12	126.3 (3)	H12A—C12—H12B	108.0
C10—N2—C12	126.6 (3)	C14—C13—C18	118.8 (4)
C22—N3—C20	106.6 (3)	C14—C13—C12	120.8 (4)
C22—N3—C19	125.0 (4)	C18—C13—C12	120.3 (4)
C20—N3—C19	128.5 (4)	C15—C14—C13	121.7 (4)
C22—N4—C21	105.7 (3)	C15—C14—H14	119.2
C22—N4—Zn1^ii	121.4 (3)	C13—C14—H14	119.2
C21—N4—Zn1^ii	132.9 (3)	C14—C15—C16	119.6 (4)
O2'—C1—O1	122.9 (9)	C14—C15—C19	117.8 (4)
O2—C1—O1	124.2 (12)	C16—C15—C19	122.5 (4)
O2'—C1—C2	120.0 (9)	C15—C16—C17	119.9 (5)
O2—C1—C2	117.7 (12)	C15—C16—H16	120.1
O1—C1—C2	115.6 (4)	C17—C16—H16	120.1
C7—C2—C3	118.6 (3)	C18—C17—C16	119.0 (5)
C7—C2—C1	121.8 (3)	C18—C17—H17	120.5
C3—C2—C1	119.6 (4)	C16—C17—H17	120.5
C2—C3—C4	121.7 (3)	C13—C18—C17	121.0 (4)
C2—C3—H3	119.1	C13—C18—H18	119.5
C4—C3—H3	119.1	C17—C18—H18	119.5
C5—C4—C3	119.2 (3)	N3—C19—C15	114.0 (4)
C5—C4—C4^iii	122.1 (3)	N3—C19—H19A	108.7
C3—C4—C4^iii	118.6 (3)	C15—C19—H19A	108.7
C4—C5—C6	119.0 (3)	N3—C19—H19B	108.7
C4—C5—C8	121.8 (3)	C15—C19—H19B	108.7
C6—C5—C8	119.1 (3)	H19A—C19—H19B	107.6
C7—C6—C5	121.0 (4)	C21—C20—N3	106.9 (4)
C7—C6—H6	119.5	C21—C20—H20	126.6
C5—C6—H6	119.5	N3—C20—H20	126.6
C6—C7—C2	120.4 (3)	C20—C21—N4	109.3 (4)
C6—C7—H7	119.8	C20—C21—H21	125.4
C2—C7—H7	119.8	N4—C21—H21	125.4
O4—C8—O3	124.4 (3)	N4—C22—N3	111.6 (4)
O4—C8—C5	121.1 (3)	N4—C22—H22	124.2
O3—C8—C5	114.5 (3)	N3—C22—H22	124.2
O2—O2'—C1—O1	−102 (4)	N1—C9—C10—N2	1.8 (5)
O2—O2'—C1—C2	93 (4)	C11—N2—C10—C9	−1.1 (5)
O2'—O2—C1—O1	96 (4)	C12—N2—C10—C9	−175.5 (4)
O2'—O2—C1—C2	−102 (4)	C9—N1—C11—N2	1.0 (4)
Zn1—O1—C1—O2'	27.1 (9)	Zn1—N1—C11—N2	−168.7 (2)
Zn1—O1—C1—O2	−5.3 (11)	C10—N2—C11—N1	0.1 (4)
Zn1—O1—C1—C2	−166.9 (3)	C12—N2—C11—N1	174.5 (4)
O2'—C1—C2—C7	158.5 (7)	C11—N2—C12—C13	−107.0 (4)
O2—C1—C2—C7	−170.7 (10)	C10—N2—C12—C13	66.3 (6)
O1—C1—C2—C7	−7.9 (6)	N2—C12—C13—C14	−114.4 (4)
O2'—C1—C2—C3	−19.1 (9)	N2—C12—C13—C18	61.5 (6)
O2—C1—C2—C3	11.7 (12)	C18—C13—C14—C15	1.6 (7)
O1—C1—C2—C3	174.5 (3)	C12—C13—C14—C15	177.6 (4)
C7—C2—C3—C4	−1.6 (5)	C13—C14—C15—C16	−0.2 (6)
C1—C2—C3—C4	176.1 (3)	C13—C14—C15—C19	−176.8 (4)
C2—C3—C4—C5	−1.3 (5)	C14—C15—C16—C17	−1.8 (8)
C2—C3—C4—C4^iii	−178.8 (3)	C19—C15—C16—C17	174.6 (5)
C3—C4—C5—C6	2.3 (5)	C15—C16—C17—C18	2.4 (10)
C4^iii—C4—C5—C6	179.8 (3)	C14—C13—C18—C17	−0.9 (8)
C3—C4—C5—C8	−177.3 (3)	C12—C13—C18—C17	−177.0 (5)
C4^iii—C4—C5—C8	0.2 (5)	C16—C17—C18—C13	−1.1 (10)
C4—C5—C6—C7	−0.6 (5)	C22—N3—C19—C15	−89.2 (5)
C8—C5—C6—C7	179.0 (3)	C20—N3—C19—C15	88.9 (5)
C5—C6—C7—C2	−2.2 (6)	C14—C15—C19—N3	−178.1 (4)
C3—C2—C7—C6	3.3 (6)	C16—C15—C19—N3	5.4 (6)
C1—C2—C7—C6	−174.3 (4)	C22—N3—C20—C21	−0.8 (5)
Zn1^iv—O3—C8—O4	−0.6 (5)	C19—N3—C20—C21	−179.1 (4)
Zn1^iv—O3—C8—C5	178.3 (2)	N3—C20—C21—N4	0.4 (5)
C4—C5—C8—O4	−48.7 (5)	C22—N4—C21—C20	0.1 (5)
C6—C5—C8—O4	131.7 (4)	Zn1^ii—N4—C21—C20	176.9 (3)
C4—C5—C8—O3	132.3 (3)	C21—N4—C22—N3	−0.6 (4)
C6—C5—C8—O3	−47.3 (4)	Zn1^ii—N4—C22—N3	−177.8 (2)
C11—N1—C9—C10	−1.7 (5)	C20—N3—C22—N4	0.9 (4)
Zn1—N1—C9—C10	168.1 (3)	C19—N3—C22—N4	179.3 (3)

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

Poly[[(µ₄-biphenyl-2,2',5,5'-tetracarboxylato)bis{[1,4-πhenylenebis(methylene)]bis(1H-imidazole)}dizinc(II)] monohydrate] (sf170602b-43_a)

Crystal data

[Zn2(C16H6O8)(C14H14N4)2]·H2O	Dx = 1.486 Mg m^−3
Mr = 951.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 9983 reflections
a = 12.4360 (7) Å	θ = 2.8–23.7°
b = 24.0412 (13) Å	µ = 1.19 mm^−1
c = 28.4613 (15) Å	T = 296 K
V = 8509.3 (8) Å^3	Block, colourless
Z = 8	0.35 × 0.32 × 0.30 mm
F(000) = 3904

Data collection

Bruker Quest APEX III diffractometer	3544 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.056
φ and ω scans	θmax = 26.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −15→15
Tmin = 0.693, Tmax = 0.745	k = −30→30
36150 measured reflections	l = −35→35
4388 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.051	w = 1/[σ^2(Fo^2) + (0.0809P)^2 + 17.9128P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.133	(Δ/σ)max = 0.001
S = 1.01	Δρmax = 0.77 e Å^−3
4388 reflections	Δρmin = −0.35 e Å^−3
290 parameters	Absolute structure: Refined as an inversion twin
44 restraints	Absolute structure parameter: 0.06 (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. Refined as a 2-component inversion twin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.65012 (7)	0.62783 (3)	0.19424 (3)	0.0386 (2)
O1	0.7507 (4)	0.5942 (2)	0.2384 (2)	0.0580 (15)
O2	0.6024 (6)	0.5523 (3)	0.2593 (3)	0.091 (2)
O3	1.0113 (4)	0.4278 (2)	0.40604 (19)	0.0471 (13)
O4	0.9483 (5)	0.3567 (2)	0.3659 (2)	0.0651 (17)
O5	0.2247 (17)	0.7073 (9)	0.3335 (7)	0.125 (6)	0.5
H5A	0.175990	0.687782	0.343791	0.188*	0.5
H5B	0.245583	0.692869	0.309030	0.188*	0.5
N1	−0.0573 (5)	0.8107 (3)	0.2224 (2)	0.0447 (15)
N2	−0.0055 (5)	0.7265 (3)	0.2391 (3)	0.0541 (16)
N3	0.3934 (5)	0.5521 (3)	0.1310 (3)	0.0576 (18)
N4	0.5476 (5)	0.5866 (2)	0.1524 (2)	0.0430 (14)
C1	0.7010 (6)	0.5586 (4)	0.2621 (3)	0.054 (2)
C2	0.7662 (6)	0.5209 (3)	0.2928 (3)	0.0457 (17)
C3	0.7200 (7)	0.4743 (4)	0.3124 (3)	0.062 (2)
H3	0.647029	0.467257	0.308469	0.075*
C4	0.7838 (6)	0.4381 (4)	0.3383 (3)	0.059 (2)
H4	0.752810	0.406645	0.351691	0.071*
C5	0.8930 (6)	0.4478 (3)	0.3446 (2)	0.0411 (16)
C6	0.9406 (5)	0.4948 (3)	0.3247 (2)	0.0323 (13)
C7	0.8752 (5)	0.5306 (3)	0.2987 (2)	0.0367 (15)
H7	0.905615	0.562037	0.285060	0.044*
C8	0.9555 (6)	0.4069 (3)	0.3735 (3)	0.0435 (16)
C9	0.0331 (7)	0.8132 (4)	0.2489 (3)	0.063 (2)
H9	0.067591	0.845775	0.258087	0.075*
C10	0.0650 (7)	0.7621 (4)	0.2599 (4)	0.068 (2)
H10	0.124071	0.752503	0.278259	0.081*
C11	−0.0790 (6)	0.7578 (3)	0.2172 (3)	0.0455 (17)
H11	−0.137442	0.743827	0.200594	0.055*
C12	−0.0093 (7)	0.6659 (4)	0.2438 (4)	0.067 (2)
H12A	−0.082035	0.653523	0.237367	0.080*
H12B	0.007345	0.656146	0.276021	0.080*
C13	0.0676 (7)	0.6345 (4)	0.2113 (3)	0.058 (2)
C14	0.1557 (9)	0.6556 (4)	0.1897 (6)	0.098 (2)
H14	0.170598	0.693318	0.193200	0.118*
C15	0.2244 (11)	0.6236 (4)	0.1627 (6)	0.096 (2)
H15	0.280060	0.640224	0.146080	0.116*
C16	0.2099 (9)	0.5678 (5)	0.1608 (5)	0.094 (2)
C17	0.1231 (10)	0.5475 (5)	0.1799 (5)	0.099 (2)
H17	0.109881	0.509499	0.177367	0.119*
C18	0.0497 (10)	0.5805 (5)	0.2039 (5)	0.102 (2)
H18	−0.013497	0.564594	0.215105	0.123*
C19	0.2845 (7)	0.5293 (4)	0.1349 (5)	0.082 (3)
H19A	0.287495	0.493939	0.151178	0.099*
H19B	0.256307	0.522636	0.103605	0.099*
C20	0.4433 (9)	0.5722 (4)	0.0916 (4)	0.081 (3)
H20	0.417106	0.571397	0.060967	0.098*
C21	0.5361 (8)	0.5929 (4)	0.1057 (3)	0.071 (3)
H21	0.586524	0.609518	0.086152	0.086*
C22	0.4601 (6)	0.5616 (3)	0.1671 (3)	0.0494 (18)
H22	0.446333	0.551873	0.198179	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0331 (4)	0.0390 (4)	0.0438 (4)	−0.0013 (3)	−0.0033 (3)	0.0115 (4)
O1	0.047 (3)	0.063 (4)	0.064 (4)	0.003 (3)	−0.011 (3)	0.033 (3)
O2	0.068 (4)	0.098 (4)	0.108 (4)	0.000 (3)	−0.026 (3)	0.039 (4)
O3	0.052 (3)	0.041 (3)	0.049 (3)	0.002 (2)	−0.015 (3)	0.007 (2)
O4	0.067 (4)	0.036 (3)	0.092 (5)	0.002 (3)	−0.027 (3)	0.004 (3)
O5	0.121 (8)	0.131 (8)	0.124 (8)	0.000 (5)	0.000 (5)	0.014 (5)
N1	0.031 (3)	0.051 (4)	0.052 (4)	0.001 (3)	0.005 (3)	−0.007 (3)
N2	0.040 (3)	0.059 (4)	0.063 (4)	0.004 (3)	−0.003 (3)	0.011 (3)
N3	0.045 (4)	0.041 (4)	0.087 (5)	0.000 (3)	−0.014 (4)	−0.015 (3)
N4	0.038 (3)	0.040 (3)	0.051 (4)	−0.003 (3)	0.000 (3)	0.006 (3)
C1	0.036 (4)	0.059 (5)	0.067 (5)	0.001 (4)	−0.016 (4)	0.018 (4)
C2	0.039 (4)	0.045 (4)	0.053 (4)	0.001 (3)	−0.009 (3)	0.010 (3)
C3	0.038 (4)	0.065 (5)	0.083 (6)	−0.012 (4)	−0.020 (4)	0.023 (5)
C4	0.043 (4)	0.053 (5)	0.081 (6)	−0.013 (4)	−0.014 (4)	0.028 (4)
C5	0.038 (4)	0.039 (4)	0.046 (4)	0.001 (3)	−0.008 (3)	0.014 (3)
C6	0.031 (3)	0.031 (3)	0.035 (3)	−0.003 (3)	−0.001 (3)	−0.003 (3)
C7	0.038 (3)	0.032 (3)	0.040 (4)	0.002 (3)	−0.004 (3)	0.003 (3)
C8	0.040 (4)	0.040 (4)	0.050 (4)	0.001 (3)	−0.001 (3)	0.012 (3)
C9	0.046 (5)	0.073 (6)	0.069 (6)	−0.014 (4)	−0.012 (4)	−0.008 (5)
C10	0.044 (5)	0.072 (6)	0.087 (7)	0.008 (4)	−0.016 (5)	0.000 (5)
C11	0.038 (4)	0.053 (5)	0.046 (4)	0.003 (3)	0.002 (3)	−0.004 (3)
C12	0.050 (5)	0.056 (5)	0.094 (7)	0.001 (4)	0.008 (5)	0.016 (5)
C13	0.048 (4)	0.050 (5)	0.076 (6)	0.002 (4)	−0.005 (4)	0.022 (4)
C14	0.074 (4)	0.060 (4)	0.159 (6)	−0.012 (3)	0.039 (4)	−0.011 (4)
C15	0.074 (4)	0.060 (3)	0.155 (6)	−0.015 (3)	0.038 (4)	−0.014 (4)
C16	0.075 (4)	0.060 (3)	0.147 (6)	−0.021 (3)	0.034 (4)	−0.017 (4)
C17	0.085 (4)	0.068 (3)	0.145 (6)	−0.026 (3)	0.041 (4)	−0.020 (4)
C18	0.088 (4)	0.074 (4)	0.146 (6)	−0.029 (3)	0.046 (4)	−0.022 (4)
C19	0.045 (5)	0.054 (5)	0.148 (10)	−0.008 (4)	−0.007 (6)	−0.020 (6)
C20	0.103 (8)	0.074 (7)	0.067 (6)	−0.026 (6)	−0.034 (6)	0.015 (5)
C21	0.081 (7)	0.071 (6)	0.061 (6)	−0.025 (5)	−0.012 (5)	0.017 (5)
C22	0.040 (4)	0.049 (4)	0.059 (5)	0.000 (3)	0.003 (4)	−0.009 (4)

Geometric parameters (Å, º)

Zn1—O1	1.950 (5)	C5—C8	1.499 (9)
Zn1—O3^i	1.960 (5)	C6—C7	1.396 (9)
Zn1—N4	2.006 (6)	C6—C6^iii	1.498 (12)
Zn1—N1^ii	2.039 (7)	C7—H7	0.9300
O1—C1	1.251 (10)	C9—C10	1.328 (13)
O2—C1	1.239 (10)	C9—H9	0.9300
O3—C8	1.262 (9)	C10—H10	0.9300
O4—C8	1.228 (9)	C11—H11	0.9300
O5—H5A	0.8204	C12—C13	1.528 (14)
O5—H5B	0.8204	C12—H12A	0.9700
N1—C11	1.308 (10)	C12—H12B	0.9700
N1—C9	1.356 (10)	C13—C18	1.335 (13)
N2—C11	1.338 (10)	C13—C14	1.354 (14)
N2—C10	1.360 (12)	C14—C15	1.383 (16)
N2—C12	1.463 (11)	C14—H14	0.9300
N3—C22	1.340 (10)	C15—C16	1.354 (15)
N3—C20	1.372 (13)	C15—H15	0.9300
N3—C19	1.464 (11)	C16—C17	1.304 (15)
N4—C22	1.311 (9)	C16—C19	1.504 (15)
N4—C21	1.345 (11)	C17—C18	1.391 (16)
C1—C2	1.497 (10)	C17—H17	0.9300
C2—C3	1.377 (11)	C18—H18	0.9300
C2—C7	1.385 (9)	C19—H19A	0.9700
C3—C4	1.390 (11)	C19—H19B	0.9700
C3—H3	0.9300	C20—C21	1.319 (14)
C4—C5	1.389 (10)	C20—H20	0.9300
C4—H4	0.9300	C21—H21	0.9300
C5—C6	1.397 (9)	C22—H22	0.9300
O1—Zn1—O3^i	104.6 (2)	N1—C9—H9	125.1
O1—Zn1—N4	125.8 (2)	C9—C10—N2	106.7 (8)
O3^i—Zn1—N4	109.4 (2)	C9—C10—H10	126.7
O1—Zn1—N1^ii	114.3 (3)	N2—C10—H10	126.7
O3^i—Zn1—N1^ii	95.3 (2)	N1—C11—N2	110.7 (7)
N4—Zn1—N1^ii	103.3 (2)	N1—C11—H11	124.7
C1—O1—Zn1	108.4 (5)	N2—C11—H11	124.7
C8—O3—Zn1^iv	118.1 (5)	N2—C12—C13	114.6 (7)
H5A—O5—H5B	107.1	N2—C12—H12A	108.6
C11—N1—C9	106.1 (7)	C13—C12—H12A	108.6
C11—N1—Zn1^ii	122.9 (5)	N2—C12—H12B	108.6
C9—N1—Zn1^ii	131.0 (6)	C13—C12—H12B	108.6
C11—N2—C10	106.8 (7)	H12A—C12—H12B	107.6
C11—N2—C12	125.4 (8)	C18—C13—C14	115.4 (10)
C10—N2—C12	127.4 (8)	C18—C13—C12	118.1 (9)
C22—N3—C20	106.7 (7)	C14—C13—C12	126.5 (9)
C22—N3—C19	125.4 (9)	C13—C14—C15	122.9 (10)
C20—N3—C19	127.7 (9)	C13—C14—H14	118.6
C22—N4—C21	106.1 (7)	C15—C14—H14	118.6
C22—N4—Zn1	124.4 (6)	C16—C15—C14	119.5 (11)
C21—N4—Zn1	126.8 (5)	C16—C15—H15	120.2
O2—C1—O1	122.5 (7)	C14—C15—H15	120.2
O2—C1—C2	120.0 (7)	C17—C16—C15	117.7 (12)
O1—C1—C2	117.4 (6)	C17—C16—C19	119.0 (10)
C3—C2—C7	119.7 (7)	C15—C16—C19	123.2 (10)
C3—C2—C1	120.2 (7)	C16—C17—C18	122.3 (10)
C7—C2—C1	119.9 (7)	C16—C17—H17	118.9
C2—C3—C4	119.1 (7)	C18—C17—H17	118.9
C2—C3—H3	120.4	C13—C18—C17	121.6 (10)
C4—C3—H3	120.4	C13—C18—H18	119.2
C5—C4—C3	121.4 (7)	C17—C18—H18	119.2
C5—C4—H4	119.3	N3—C19—C16	112.2 (8)
C3—C4—H4	119.3	N3—C19—H19A	109.2
C4—C5—C6	119.8 (6)	C16—C19—H19A	109.2
C4—C5—C8	117.9 (6)	N3—C19—H19B	109.2
C6—C5—C8	122.3 (6)	C16—C19—H19B	109.2
C7—C6—C5	117.8 (6)	H19A—C19—H19B	107.9
C7—C6—C6^iii	118.2 (6)	C21—C20—N3	106.1 (8)
C5—C6—C6^iii	123.5 (7)	C21—C20—H20	126.9
C2—C7—C6	122.1 (6)	N3—C20—H20	126.9
C2—C7—H7	119.0	C20—C21—N4	110.7 (9)
C6—C7—H7	119.0	C20—C21—H21	124.7
O4—C8—O3	124.1 (6)	N4—C21—H21	124.7
O4—C8—C5	120.7 (7)	N4—C22—N3	110.3 (7)
O3—C8—C5	115.1 (6)	N4—C22—H22	124.8
C10—C9—N1	109.7 (8)	N3—C22—H22	124.8
C10—C9—H9	125.1
Zn1—O1—C1—O2	−6.7 (12)	Zn1^ii—N1—C11—N2	−180.0 (5)
Zn1—O1—C1—C2	170.1 (6)	C10—N2—C11—N1	1.2 (9)
O2—C1—C2—C3	9.5 (13)	C12—N2—C11—N1	175.0 (8)
O1—C1—C2—C3	−167.4 (8)	C11—N2—C12—C13	104.2 (9)
O2—C1—C2—C7	−174.9 (9)	C10—N2—C12—C13	−83.3 (12)
O1—C1—C2—C7	8.2 (12)	N2—C12—C13—C18	−162.2 (11)
C7—C2—C3—C4	0.4 (13)	N2—C12—C13—C14	19.7 (16)
C1—C2—C3—C4	175.9 (9)	C18—C13—C14—C15	−2 (2)
C2—C3—C4—C5	−0.1 (15)	C12—C13—C14—C15	176.6 (13)
C3—C4—C5—C6	−0.1 (14)	C13—C14—C15—C16	−6 (3)
C3—C4—C5—C8	179.4 (8)	C14—C15—C16—C17	8 (2)
C4—C5—C6—C7	0.0 (11)	C14—C15—C16—C19	−176.1 (14)
C8—C5—C6—C7	−179.5 (7)	C15—C16—C17—C18	−4 (2)
C4—C5—C6—C6^iii	−172.4 (7)	C19—C16—C17—C18	−179.2 (13)
C8—C5—C6—C6^iii	8.1 (10)	C14—C13—C18—C17	7 (2)
C3—C2—C7—C6	−0.5 (12)	C12—C13—C18—C17	−171.7 (12)
C1—C2—C7—C6	−176.1 (7)	C16—C17—C18—C13	−4 (2)
C5—C6—C7—C2	0.3 (10)	C22—N3—C19—C16	65.1 (13)
C6^iii—C6—C7—C2	173.1 (6)	C20—N3—C19—C16	−108.6 (13)
Zn1^iv—O3—C8—O4	4.5 (10)	C17—C16—C19—N3	−158.5 (13)
Zn1^iv—O3—C8—C5	−177.9 (5)	C15—C16—C19—N3	26 (2)
C4—C5—C8—O4	49.1 (11)	C22—N3—C20—C21	−0.4 (11)
C6—C5—C8—O4	−131.4 (8)	C19—N3—C20—C21	174.3 (8)
C4—C5—C8—O3	−128.7 (8)	N3—C20—C21—N4	0.3 (12)
C6—C5—C8—O3	50.8 (10)	C22—N4—C21—C20	0.0 (11)
C11—N1—C9—C10	−0.4 (11)	Zn1—N4—C21—C20	−161.8 (7)
Zn1^ii—N1—C9—C10	179.0 (6)	C21—N4—C22—N3	−0.2 (9)
N1—C9—C10—N2	1.1 (11)	Zn1—N4—C22—N3	162.1 (5)
C11—N2—C10—C9	−1.4 (10)	C20—N3—C22—N4	0.4 (9)
C12—N2—C10—C9	−175.0 (9)	C19—N3—C22—N4	−174.4 (7)
C9—N1—C11—N2	−0.5 (9)

Symmetry codes: (i) −x+7/4, y+1/4, z−1/4; (ii) −x+1/2, −y+3/2, z; (iii) −x+2, −y+1, z; (iv) −x+7/4, y−1/4, z+1/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···O2	0.93	2.61	3.172 (11)	120
C12—H12B···O4^v	0.97	2.63	3.598 (13)	173
C12—H12A···O1^vi	0.97	2.52	3.452 (11)	160
C11—H11···O3^vii	0.93	2.55	3.445 (10)	162
C11—H11···O3^viii	0.93	2.60	3.062 (9)	112
C10—H10···O5^ii	0.93	2.63	3.43 (2)	144
C10—H10···O5	0.93	2.28	3.17 (2)	160
O5—H5A···O4^v	0.82	1.98	2.80 (2)	176

Symmetry codes: (ii) −x+1/2, −y+3/2, z; (v) −x+1, −y+1, z; (vi) x−1, y, z; (vii) −x+3/4, y+1/4, z−1/4; (viii) x−5/4, −y+5/4, z−1/4.