Preparation, characterization and luminescence-sensing properties of two Zn^II MOFs with mixed 5-amino-2,4,6-tri­bromo­isophthalic acid and bipyridyl-type ligands

The bromo-substituted aromatic di­carb­oxy­lic acid 5-amino-2,4,6-tri­bromo­isophthalic acid (H₂ATBIP), in the presence of the N-donor flexible bipyridyl-type ligands 1,3-bis­(pyridin-4-yl)propane (bpp) and N,N′-bis­(pyridin-4-ylmeth­yl)oxalamide (4-bpme) and Zn^II ions, was used as an O-donor ligand to assemble two novel luminescent metal–organic frameworks (MOFs), namely poly[[(μ-5-amino-2,4,6-tri­bromo­isophthalato-κ²O¹:O³)[μ-1,3-bis­(pyridin-4-yl)propane-κ²N:N′]zinc(II)] di­methyl­formamide monosolvate], {[Zn(C₈H₂Br₃NO₄)(C₁₃H₁₄N₂)]·C₃H₇NO}_n, (1), and poly[[(μ-5-amino-2,4,6-tri­bromo­isophthalato-κ²O¹:O³)di­aqua­[μ-N,N′-bis­(pyridin-4-ylmeth­yl)oxalamide-κ²N:N′]zinc(II)] monohydrate], {[Zn(C₈H₂Br₃NO₄)(C₁₄H₁₄N₄O₂)(H₂O)₂]·H₂O}_n, (2), using the solution eva­poration method. Both (1) and (2) were characterized by FT–IR spectroscopy, elemental analysis (EA), solid-state diffuse-reflectance UV–Vis spectroscopy, and powder and single-crystal X-ray diffraction analysis. Complex (1) shows a two-dimensional (2D) corrugated layer simplified as a 2D (4,4) topological network. The supra­molecular inter­actions (π–π stacking, hydrogen bonding and C—Br...Br halogen bonding) play significant roles in the formation of an extended three-dimensional (3D) supra­molecular network of (1). Complex (2) crystallizes in the chiral space group P2₁2₁2₁ and exhibits a novel 3D homochiral framework, showing a diamond-like topology with Schläfli symbol 6⁶. The homochirality of (2) is further confirmed by the solid-state circular dichroism (CD) spectrum. The second harmonic generation (SHG) property of (2) was also investigated. The hydrogen and C—Br...Br/O halogen bonding further stabilize the framework of (2). The central Zn^II ions in (1) and (2) show tetra­hedral and octa­hedral coordination geometries, respectively. The coordinated and uncoordinated water mol­ecules in (2) could be removed selectively upon heating. Most importantly, (1) and (2) show rapid and highly sensitive sensing for a large pool of nitro­aromatic explosives (NAEs).

Computing details

For both structures, data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXL2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b). Molecular graphics: SHELXTL (Bruker, 2008) and DIAMOND (Brandenburg, 2005) for (1); SHELXTL (Bruker, 2008) for (2). For both structures, software used to prepare material for publication: SHELXTL (Bruker, 2008).

Poly[[(µ-5-amino-2,4,6-tribromoisophthalato-κ²O¹:O³)[µ-1,3-bis(pyridin-4-yl)propane-κ²N:N']zinc(II)] dimethylformamide monosolvate] (1)

Crystal data

[Zn(C8H2Br3NO4)(C13H14N2)]·C3H7NO	F(000) = 370
Mr = 752.55	Dx = 1.809 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.6877 (2) Å	Cell parameters from 9941 reflections
b = 15.1790 (3) Å	θ = 2.4–27.1°
c = 20.9944 (4) Å	µ = 5.27 mm^−1
β = 93.6833 (6)°	T = 293 K
V = 2762.83 (10) Å^3	Block, white
Z = 4	0.25 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area detector diffractometer	4467 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.056
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2008)	θmax = 27.5°, θmin = 1.9°
Tmin = 0.294, Tmax = 0.387	h = −11→11
41610 measured reflections	k = −16→19
6330 independent reflections	l = −27→25

Refinement

Refinement on F^2	50 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0346P)^2 + 2.4762P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.052
6330 reflections	Δρmax = 0.73 e Å^−3
362 parameters	Δρmin = −0.75 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. X-ray single-crystal diffraction data for complexes (1) and (2) were collected on a Bruker SMART 1000 CCD diffractometer at 293 K with Mo-Kα radiation (λ = 0.71073 Å) by the ω-scan mode. Empirical absorption corrections were applied to raw intensities with the SADABS program, and the SAINT program was used for integration of the diffraction profiles (Bruker, 2008). Both structures were solved by direct methods using the SHELXT-2016 program and subsequently refined by full-matrix least-squares techniques based on ?F?² with the SHELXTL crystallographic software package (Sheldrick, 2015a, 2015b).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.86338 (4)	0.37101 (3)	0.23143 (2)	0.04459 (11)
Br2	0.22688 (4)	0.32238 (3)	0.17188 (2)	0.05811 (13)
Br3	0.54121 (5)	0.59819 (2)	0.05516 (2)	0.04653 (11)
Zn1	0.48951 (4)	0.17498 (2)	0.33387 (2)	0.03178 (10)
O1	0.5200 (3)	0.28967 (16)	0.29222 (11)	0.0418 (6)
O2	0.5657 (3)	0.20373 (17)	0.21029 (12)	0.0496 (7)
O3	0.8367 (3)	0.59635 (16)	0.16649 (12)	0.0446 (6)
O4	0.9241 (3)	0.49862 (16)	0.09939 (14)	0.0532 (7)
O5'	0.133 (5)	0.4957 (17)	0.4294 (17)	0.228 (7)	0.294 (17)
O5	0.233 (2)	0.5196 (9)	0.4446 (7)	0.228 (7)	0.706 (17)
N1	0.2694 (4)	0.4803 (2)	0.08417 (16)	0.0464 (8)
H11	0.186 (3)	0.455 (2)	0.0963 (16)	0.043 (11)*
H12	0.280 (4)	0.5225 (19)	0.0560 (14)	0.055 (12)*
N2	0.4473 (4)	0.22129 (18)	0.42213 (13)	0.0386 (7)
N3	0.7913 (3)	0.37468 (18)	0.79249 (13)	0.0354 (6)
C1	0.5450 (4)	0.2757 (2)	0.23445 (17)	0.0342 (8)
C2	0.5454 (3)	0.3563 (2)	0.19169 (15)	0.0283 (7)
C3	0.6798 (3)	0.4037 (2)	0.18290 (15)	0.0287 (7)
C4	0.6818 (3)	0.4746 (2)	0.14207 (15)	0.0268 (7)
C5	0.5442 (4)	0.4986 (2)	0.10955 (14)	0.0290 (7)
C6	0.4040 (3)	0.4548 (2)	0.11663 (15)	0.0304 (7)
C7	0.4120 (3)	0.3837 (2)	0.15864 (16)	0.0308 (7)
C8	0.8290 (4)	0.5266 (2)	0.13411 (16)	0.0331 (8)
C9	0.4156 (6)	0.3062 (3)	0.4297 (2)	0.0666 (14)
H9	0.407699	0.342012	0.393675	0.080*
C10	0.3939 (7)	0.3438 (3)	0.4881 (2)	0.0759 (16)
H10	0.372740	0.403658	0.490944	0.091*
C11	0.4036 (5)	0.2927 (3)	0.54230 (17)	0.0473 (10)
C12	0.4284 (4)	0.2043 (2)	0.53401 (17)	0.0440 (9)
H12A	0.429491	0.166495	0.568905	0.053*
C13	0.4515 (4)	0.1713 (2)	0.47457 (16)	0.0394 (8)
H13	0.470954	0.111387	0.470590	0.047*
C14	0.3881 (6)	0.3294 (3)	0.60899 (19)	0.0598 (12)
H14A	0.293853	0.306435	0.625010	0.072*
H14B	0.473447	0.307474	0.636575	0.072*
C15	0.3852 (5)	0.4283 (3)	0.61429 (19)	0.0564 (11)
H15A	0.295359	0.450822	0.589662	0.068*
H15B	0.476187	0.452396	0.596246	0.068*
C16	0.3803 (5)	0.4592 (3)	0.68355 (19)	0.0562 (11)
H16A	0.371507	0.522871	0.684437	0.067*
H16B	0.289966	0.434645	0.701814	0.067*
C17	0.7944 (5)	0.4401 (3)	0.75046 (19)	0.0496 (10)
H17	0.888434	0.467001	0.744237	0.059*
C18	0.6651 (5)	0.4699 (3)	0.7157 (2)	0.0548 (11)
H18	0.673199	0.515969	0.686985	0.066*
C19	0.5230 (4)	0.4315 (3)	0.72345 (17)	0.0427 (9)
C20	0.5198 (4)	0.3650 (3)	0.76821 (18)	0.0440 (9)
H20	0.426884	0.338033	0.776082	0.053*
C21	0.6536 (4)	0.3387 (2)	0.80116 (17)	0.0400 (8)
H21	0.648241	0.293718	0.830974	0.048*
N4'	0.083 (6)	0.6312 (18)	0.4711 (14)	0.103 (3)	0.294 (17)
C23'	0.083 (4)	0.5706 (15)	0.4228 (12)	0.131 (4)	0.294 (17)
H23'	0.043435	0.587602	0.382475	0.158*	0.294 (17)
C24'	0.079 (5)	0.602 (2)	0.5371 (11)	0.167 (6)	0.294 (17)
H24D	0.077818	0.538624	0.538428	0.251*	0.294 (17)
H24E	−0.011459	0.624476	0.555125	0.251*	0.294 (17)
H24F	0.169313	0.623076	0.561354	0.251*	0.294 (17)
C25'	0.091 (4)	0.7240 (14)	0.4599 (14)	0.097 (3)	0.294 (17)
H25D	0.089484	0.734865	0.414819	0.145*	0.294 (17)
H25E	0.184112	0.747193	0.480337	0.145*	0.294 (17)
H25F	0.003551	0.752338	0.477008	0.145*	0.294 (17)
N4	0.114 (2)	0.6446 (8)	0.4763 (6)	0.103 (3)	0.706 (17)
C23	0.1582 (17)	0.5848 (7)	0.4320 (6)	0.131 (4)	0.706 (17)
H23	0.128414	0.595471	0.389388	0.158*	0.706 (17)
C24	0.1568 (18)	0.6401 (11)	0.5419 (5)	0.167 (6)	0.706 (17)
H24A	0.194004	0.581969	0.552432	0.251*	0.706 (17)
H24B	0.068807	0.652825	0.565789	0.251*	0.706 (17)
H24C	0.236625	0.682326	0.552415	0.251*	0.706 (17)
C25	0.0143 (16)	0.7171 (8)	0.4543 (5)	0.097 (3)	0.706 (17)
H25A	−0.012988	0.710239	0.409500	0.145*	0.706 (17)
H25B	0.067627	0.771930	0.461424	0.145*	0.706 (17)
H25C	−0.077579	0.716814	0.477365	0.145*	0.706 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.02718 (18)	0.0473 (2)	0.0585 (3)	0.00293 (15)	−0.00296 (15)	0.00770 (18)
Br2	0.02844 (19)	0.0711 (3)	0.0748 (3)	−0.01611 (18)	0.00314 (18)	0.0215 (2)
Br3	0.0617 (3)	0.0372 (2)	0.0408 (2)	−0.00153 (17)	0.00487 (18)	0.01167 (16)
Zn1	0.0341 (2)	0.0303 (2)	0.0313 (2)	0.00512 (16)	0.00464 (16)	0.00230 (16)
O1	0.0547 (16)	0.0397 (14)	0.0319 (14)	−0.0001 (11)	0.0092 (11)	0.0063 (11)
O2	0.0678 (18)	0.0321 (15)	0.0501 (17)	0.0017 (12)	0.0139 (13)	0.0036 (12)
O3	0.0420 (15)	0.0406 (15)	0.0520 (16)	−0.0169 (11)	0.0097 (12)	−0.0134 (12)
O4	0.0460 (16)	0.0401 (15)	0.078 (2)	−0.0091 (12)	0.0353 (15)	−0.0063 (14)
O5'	0.239 (14)	0.154 (8)	0.293 (11)	0.118 (10)	0.031 (10)	0.053 (7)
O5	0.239 (14)	0.154 (8)	0.293 (11)	0.118 (10)	0.031 (10)	0.053 (7)
N1	0.0320 (17)	0.062 (2)	0.045 (2)	0.0036 (16)	0.0004 (15)	0.0146 (17)
N2	0.0572 (19)	0.0304 (16)	0.0286 (16)	0.0054 (13)	0.0057 (13)	0.0019 (13)
N3	0.0376 (16)	0.0335 (16)	0.0356 (17)	−0.0008 (13)	0.0057 (12)	−0.0054 (13)
C1	0.0278 (17)	0.034 (2)	0.041 (2)	−0.0041 (14)	0.0053 (15)	0.0072 (16)
C2	0.0290 (16)	0.0283 (17)	0.0284 (18)	−0.0002 (13)	0.0080 (13)	−0.0003 (14)
C3	0.0233 (15)	0.0300 (17)	0.0331 (18)	0.0024 (13)	0.0039 (13)	−0.0035 (14)
C4	0.0278 (16)	0.0258 (17)	0.0280 (17)	−0.0010 (13)	0.0103 (13)	−0.0046 (13)
C5	0.0373 (18)	0.0262 (17)	0.0245 (17)	0.0012 (13)	0.0104 (14)	−0.0004 (13)
C6	0.0275 (16)	0.0343 (18)	0.0297 (18)	0.0023 (14)	0.0039 (13)	−0.0046 (14)
C7	0.0233 (16)	0.0356 (19)	0.0343 (19)	−0.0035 (13)	0.0077 (13)	−0.0002 (15)
C8	0.0303 (17)	0.0299 (19)	0.040 (2)	−0.0042 (14)	0.0082 (15)	0.0026 (15)
C9	0.125 (4)	0.038 (2)	0.037 (2)	0.022 (2)	0.011 (2)	0.0075 (18)
C10	0.152 (5)	0.036 (2)	0.041 (3)	0.030 (3)	0.019 (3)	−0.0001 (19)
C11	0.069 (3)	0.042 (2)	0.031 (2)	0.0138 (19)	0.0058 (18)	−0.0011 (17)
C12	0.063 (3)	0.035 (2)	0.034 (2)	0.0020 (17)	0.0013 (18)	0.0073 (16)
C13	0.050 (2)	0.0325 (19)	0.035 (2)	0.0042 (16)	0.0021 (16)	−0.0028 (16)
C14	0.090 (3)	0.053 (3)	0.037 (2)	0.010 (2)	0.007 (2)	−0.0058 (19)
C15	0.073 (3)	0.053 (3)	0.042 (2)	0.022 (2)	−0.006 (2)	−0.0097 (19)
C16	0.060 (3)	0.060 (3)	0.048 (2)	0.024 (2)	−0.0084 (19)	−0.017 (2)
C17	0.046 (2)	0.043 (2)	0.059 (3)	−0.0066 (18)	0.0017 (19)	0.009 (2)
C18	0.062 (3)	0.045 (2)	0.056 (3)	0.003 (2)	0.000 (2)	0.012 (2)
C19	0.050 (2)	0.045 (2)	0.033 (2)	0.0135 (18)	0.0039 (16)	−0.0182 (17)
C20	0.039 (2)	0.051 (2)	0.042 (2)	0.0004 (17)	0.0110 (17)	−0.0123 (19)
C21	0.042 (2)	0.045 (2)	0.034 (2)	−0.0004 (16)	0.0093 (16)	−0.0022 (16)
N4'	0.106 (8)	0.089 (5)	0.114 (5)	0.016 (5)	0.005 (4)	0.011 (4)
C23'	0.133 (9)	0.104 (6)	0.160 (7)	0.031 (6)	0.027 (7)	0.016 (5)
C24'	0.192 (13)	0.164 (12)	0.139 (8)	−0.017 (9)	−0.051 (8)	0.059 (8)
C25'	0.103 (9)	0.100 (5)	0.086 (5)	0.025 (7)	−0.011 (6)	−0.010 (4)
N4	0.106 (8)	0.089 (5)	0.114 (5)	0.016 (5)	0.005 (4)	0.011 (4)
C23	0.133 (9)	0.104 (6)	0.160 (7)	0.031 (6)	0.027 (7)	0.016 (5)
C24	0.192 (13)	0.164 (12)	0.139 (8)	−0.017 (9)	−0.051 (8)	0.059 (8)
C25	0.103 (9)	0.100 (5)	0.086 (5)	0.025 (7)	−0.011 (6)	−0.010 (4)

Geometric parameters (Å, º)

Br1—C3	1.902 (3)	C14—C15	1.506 (6)
Br2—C7	1.895 (3)	C14—H14A	0.9700
Br3—C5	1.893 (3)	C14—H14B	0.9700
Zn1—O3^i	1.925 (2)	C15—C16	1.531 (5)
Zn1—O1	1.974 (2)	C15—H15A	0.9700
Zn1—N3^ii	2.024 (3)	C15—H15B	0.9700
Zn1—N2	2.037 (3)	C16—C19	1.511 (5)
O1—C1	1.264 (4)	C16—H16A	0.9700
O2—C1	1.223 (4)	C16—H16B	0.9700
O3—C8	1.258 (4)	C17—C18	1.375 (5)
O4—C8	1.213 (4)	C17—H17	0.9300
O5'—C23'	1.220 (10)	C18—C19	1.384 (6)
O5—C23	1.204 (7)	C18—H18	0.9300
N1—C6	1.371 (4)	C19—C20	1.380 (6)
N1—H11	0.871 (10)	C20—C21	1.373 (5)
N1—H12	0.880 (10)	C20—H20	0.9300
N2—C9	1.330 (5)	C21—H21	0.9300
N2—C13	1.336 (4)	N4'—C23'	1.370 (9)
N3—C17	1.330 (5)	N4'—C25'	1.43 (3)
N3—C21	1.338 (4)	N4'—C24'	1.46 (3)
C1—C2	1.518 (5)	C23'—H23'	0.9300
C2—C7	1.376 (4)	C24'—H24D	0.9600
C2—C3	1.394 (4)	C24'—H24E	0.9600
C3—C4	1.377 (4)	C24'—H24F	0.9600
C4—C5	1.387 (4)	C25'—H25D	0.9600
C4—C8	1.521 (4)	C25'—H25E	0.9600
C5—C6	1.405 (4)	C25'—H25F	0.9600
C6—C7	1.392 (5)	N4—C23	1.370 (7)
C9—C10	1.377 (6)	N4—C24	1.405 (13)
C9—H9	0.9300	N4—C25	1.459 (13)
C10—C11	1.374 (6)	C23—H23	0.9300
C10—H10	0.9300	C24—H24A	0.9600
C11—C12	1.372 (5)	C24—H24B	0.9600
C11—C14	1.521 (5)	C24—H24C	0.9600
C12—C13	1.371 (5)	C25—H25A	0.9600
C12—H12A	0.9300	C25—H25B	0.9600
C13—H13	0.9300	C25—H25C	0.9600
O3^i—Zn1—O1	114.68 (10)	C14—C15—H15A	109.2
O3^i—Zn1—N3^ii	114.41 (11)	C16—C15—H15A	109.2
O1—Zn1—N3^ii	105.85 (11)	C14—C15—H15B	109.2
O3^i—Zn1—N2	113.85 (11)	C16—C15—H15B	109.2
O1—Zn1—N2	97.80 (11)	H15A—C15—H15B	107.9
N3^ii—Zn1—N2	108.74 (12)	C19—C16—C15	111.7 (3)
C1—O1—Zn1	108.3 (2)	C19—C16—H16A	109.3
C8—O3—Zn1^iii	122.3 (2)	C15—C16—H16A	109.3
C6—N1—H11	115 (2)	C19—C16—H16B	109.3
C6—N1—H12	114 (3)	C15—C16—H16B	109.3
H11—N1—H12	130 (4)	H16A—C16—H16B	107.9
C9—N2—C13	116.6 (3)	N3—C17—C18	123.1 (4)
C9—N2—Zn1	119.6 (3)	N3—C17—H17	118.4
C13—N2—Zn1	123.9 (2)	C18—C17—H17	118.4
C17—N3—C21	116.8 (3)	C17—C18—C19	120.3 (4)
C17—N3—Zn1^iv	120.7 (2)	C17—C18—H18	119.9
C21—N3—Zn1^iv	122.2 (2)	C19—C18—H18	119.9
O2—C1—O1	125.9 (3)	C20—C19—C18	116.4 (3)
O2—C1—C2	118.0 (3)	C20—C19—C16	122.0 (4)
O1—C1—C2	116.1 (3)	C18—C19—C16	121.6 (4)
C7—C2—C3	117.5 (3)	C21—C20—C19	120.1 (4)
C7—C2—C1	120.6 (3)	C21—C20—H20	119.9
C3—C2—C1	121.9 (3)	C19—C20—H20	119.9
C4—C3—C2	122.0 (3)	N3—C21—C20	123.2 (4)
C4—C3—Br1	119.6 (2)	N3—C21—H21	118.4
C2—C3—Br1	118.3 (2)	C20—C21—H21	118.4
C3—C4—C5	117.8 (3)	C23'—N4'—C25'	122 (2)
C3—C4—C8	121.2 (3)	C23'—N4'—C24'	120.0 (18)
C5—C4—C8	120.9 (3)	C25'—N4'—C24'	117.5 (9)
C4—C5—C6	123.3 (3)	O5'—C23'—N4'	124.0 (13)
C4—C5—Br3	119.0 (2)	O5'—C23'—H23'	118.0
C6—C5—Br3	117.6 (2)	N4'—C23'—H23'	118.0
N1—C6—C7	122.7 (3)	N4'—C24'—H24D	109.5
N1—C6—C5	122.1 (3)	N4'—C24'—H24E	109.5
C7—C6—C5	115.2 (3)	H24D—C24'—H24E	109.5
C2—C7—C6	124.1 (3)	N4'—C24'—H24F	109.5
C2—C7—Br2	118.2 (2)	H24D—C24'—H24F	109.5
C6—C7—Br2	117.7 (2)	H24E—C24'—H24F	109.5
O4—C8—O3	127.2 (3)	N4'—C25'—H25D	109.4
O4—C8—C4	119.6 (3)	N4'—C25'—H25E	109.6
O3—C8—C4	113.2 (3)	H25D—C25'—H25E	109.5
N2—C9—C10	123.3 (4)	N4'—C25'—H25F	109.4
N2—C9—H9	118.4	H25D—C25'—H25F	109.5
C10—C9—H9	118.4	H25E—C25'—H25F	109.5
C11—C10—C9	119.9 (4)	C23—N4—C24	124.5 (9)
C11—C10—H10	120.0	C23—N4—C25	118.0 (9)
C9—C10—H10	120.0	C24—N4—C25	117.5 (6)
C12—C11—C10	116.6 (3)	O5—C23—N4	124.5 (9)
C12—C11—C14	119.9 (3)	O5—C23—H23	117.8
C10—C11—C14	123.4 (4)	N4—C23—H23	117.8
C13—C12—C11	120.4 (3)	N4—C24—H24A	109.5
C13—C12—H12A	119.8	N4—C24—H24B	109.5
C11—C12—H12A	119.8	H24A—C24—H24B	109.5
N2—C13—C12	123.0 (3)	N4—C24—H24C	109.4
N2—C13—H13	118.5	H24A—C24—H24C	109.5
C12—C13—H13	118.5	H24B—C24—H24C	109.5
C15—C14—C11	115.9 (4)	N4—C25—H25A	109.5
C15—C14—H14A	108.3	N4—C25—H25B	109.5
C11—C14—H14A	108.3	H25A—C25—H25B	109.5
C15—C14—H14B	108.3	N4—C25—H25C	109.4
C11—C14—H14B	108.3	H25A—C25—H25C	109.5
H14A—C14—H14B	107.4	H25B—C25—H25C	109.5
C14—C15—C16	112.1 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O4^v	0.87 (1)	2.38 (3)	3.050 (4)	134 (3)
C25—H25B···Br3^vi	0.96	2.81	3.513 (12)	131
C25—H25A···O2^vii	0.96	2.53	3.486 (11)	174
C12—H12A···O4^viii	0.93	2.59	3.373 (4)	142
C13—H13···O4^i	0.93	2.47	3.266 (4)	144

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

Poly[[(µ-5-amino-2,4,6-tribromoisophthalato-κ²O¹:O³)diaqua[µ-N,N'-bis(pyridin-4-ylmethyl)oxalamide-κ²N:N']zinc(II)] monohydrate] (2)

Crystal data

[Zn(C8H2Br3NO4)(C14H14N4O2)(H2O)2]·H2O	Dx = 2.019 Mg m^−3
Mr = 805.54	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 6891 reflections
a = 8.5083 (5) Å	θ = 2.3–27.1°
b = 13.8444 (10) Å	µ = 5.51 mm^−1
c = 22.4960 (12) Å	T = 293 K
V = 2649.9 (3) Å^3	Needle, white
Z = 4	0.28 × 0.25 × 0.21 mm
F(000) = 396

Data collection

Bruker SMART CCD area detector diffractometer	4032 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.083
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2008)	θmax = 27.5°, θmin = 2.3°
Tmin = 0.233, Tmax = 0.314	h = −11→10
24793 measured reflections	k = −18→17
6064 independent reflections	l = −29→27

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.046	w = 1/[σ^2(Fo^2) + (0.032P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.079	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 1.70 e Å^−3
6064 reflections	Δρmin = −1.13 e Å^−3
361 parameters	Absolute structure: Flack x determined using 1290 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.0 (4)

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. X-ray single-crystal diffraction data for complexes (1) and (2) were collected on a Bruker SMART 1000 CCD diffractometer at 293 K with Mo-Kα radiation (λ = 0.71073 Å) by the ω-scan mode. Empirical absorption corrections were applied to raw intensities with the SADABS program, and the SAINT program was used for integration of the diffraction profiles (Bruker, 2008). Both structures were solved by direct methods using the SHELXT-2016 program and subsequently refined by full-matrix least-squares techniques based on ?F?² with the SHELXTL crystallographic software package (Sheldrick, 2015a, 2015b).

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

	x	y	z	Uiso*/Ueq
O4	0.4005 (5)	0.2397 (4)	0.1546 (2)	0.0296 (12)
Br1	0.99478 (8)	0.57628 (7)	0.15189 (4)	0.0427 (2)
Br2	0.35951 (8)	0.48257 (6)	0.19278 (3)	0.0366 (2)
Br3	0.73899 (10)	0.22488 (7)	0.06256 (3)	0.0433 (2)
C1	0.6730 (7)	0.5926 (6)	0.2160 (3)	0.0239 (18)
C2	0.6855 (7)	0.5101 (5)	0.1714 (3)	0.0182 (16)
C3	0.5602 (7)	0.4487 (6)	0.1620 (3)	0.0214 (18)
C4	0.5711 (7)	0.3654 (6)	0.1287 (3)	0.0190 (16)
C5	0.7190 (8)	0.3436 (6)	0.1048 (3)	0.0257 (18)
C6	0.8488 (7)	0.4030 (6)	0.1108 (3)	0.0249 (18)
C7	0.8258 (7)	0.4873 (6)	0.1440 (3)	0.0233 (17)
C8	0.4307 (8)	0.3028 (6)	0.1168 (3)	0.0250 (19)
C9	0.9309 (8)	0.7739 (6)	0.2730 (3)	0.031 (2)
H9	0.831663	0.802030	0.272725	0.037*
C10	1.0500 (8)	0.8171 (6)	0.2400 (3)	0.032 (2)
H10	1.030355	0.872952	0.218270	0.038*
C11	1.1969 (7)	0.7761 (6)	0.2400 (3)	0.0214 (17)
C12	1.2195 (8)	0.6955 (6)	0.2736 (3)	0.0287 (19)
H12	1.318121	0.666639	0.275046	0.034*
C13	1.0965 (7)	0.6564 (6)	0.3054 (3)	0.0302 (19)
H13	1.114525	0.601386	0.328136	0.036*
C14	1.3314 (7)	0.8195 (6)	0.2041 (3)	0.0269 (18)
H14A	1.304531	0.885056	0.192818	0.032*
H14B	1.425171	0.822048	0.228578	0.032*
C15	1.2795 (7)	0.7720 (6)	0.1016 (3)	0.0240 (17)
C16	1.3338 (8)	0.7122 (6)	0.0487 (3)	0.0276 (19)
C17	1.2693 (9)	0.6794 (6)	−0.0558 (3)	0.035 (2)
H17A	1.373986	0.651669	−0.055767	0.042*
H17B	1.266971	0.729025	−0.086261	0.042*
C18	1.1536 (7)	0.6015 (5)	−0.0726 (3)	0.0249 (18)
C19	1.1562 (8)	0.5633 (6)	−0.1288 (3)	0.031 (2)
H19	1.233512	0.582581	−0.155478	0.037*
C20	0.5686 (9)	0.4989 (7)	0.4448 (3)	0.040 (2)
H20	0.645206	0.520586	0.471084	0.048*
C21	0.4619 (8)	0.4325 (7)	0.4654 (3)	0.033 (2)
H21	0.467101	0.410624	0.504389	0.040*
C22	0.4545 (7)	0.5034 (6)	0.3541 (3)	0.034 (2)
H22	0.448721	0.528192	0.315696	0.041*
N1	0.9523 (6)	0.6947 (5)	0.3047 (2)	0.0236 (15)
N2	1.3644 (6)	0.7628 (4)	0.1503 (2)	0.0225 (13)
H2	1.441254	0.722437	0.150657	0.027*
N3	1.2426 (7)	0.7247 (5)	0.0010 (2)	0.0330 (16)
H3	1.162610	0.762205	0.004460	0.040*
N4	0.9902 (7)	0.3819 (5)	0.0837 (2)	0.0387 (17)
H4A	0.999273	0.330692	0.062304	0.046*
H4B	1.069191	0.419958	0.088133	0.046*
N5	0.5701 (6)	0.5346 (5)	0.3894 (2)	0.0269 (16)
O1	0.7049 (5)	0.5629 (4)	0.26869 (18)	0.0280 (12)
O2	0.6369 (6)	0.6733 (4)	0.2001 (2)	0.0402 (14)
O3	0.3538 (6)	0.3231 (4)	0.0713 (2)	0.0415 (15)
O5	1.1627 (6)	0.8236 (4)	0.0972 (2)	0.0371 (14)
O6	1.4525 (6)	0.6604 (4)	0.0509 (2)	0.0391 (15)
O1W	0.9225 (6)	0.5070 (4)	0.3767 (2)	0.0403 (15)
H1WA	0.881540	0.442380	0.378767	0.060*
H1WB	1.012260	0.516110	0.404962	0.060*
O3W	0.0223 (7)	0.5344 (4)	0.4972 (2)	0.0499 (16)
H3WA	−0.002527	0.481500	0.513991	0.075*
H3WB	0.054357	0.574599	0.522777	0.075*
Zn1	0.75588 (9)	0.62528 (6)	0.34771 (3)	0.0247 (2)
O2W	0.8396 (6)	0.6769 (4)	0.4316 (2)	0.0474 (15)
H2WA	0.782861	0.713443	0.453277	0.071*
H2WB	0.863352	0.626235	0.451095	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.032 (3)	0.031 (4)	0.026 (2)	−0.005 (3)	0.000 (2)	0.003 (3)
Br1	0.0229 (3)	0.0483 (6)	0.0569 (5)	−0.0115 (4)	0.0055 (4)	−0.0114 (5)
Br2	0.0189 (3)	0.0381 (6)	0.0528 (4)	−0.0018 (4)	0.0053 (3)	−0.0180 (4)
Br3	0.0553 (5)	0.0375 (6)	0.0371 (4)	0.0066 (5)	0.0045 (4)	−0.0168 (4)
C1	0.007 (3)	0.029 (6)	0.036 (4)	−0.006 (3)	−0.001 (3)	−0.005 (4)
C2	0.024 (3)	0.013 (5)	0.018 (3)	0.001 (3)	−0.005 (2)	0.000 (3)
C3	0.023 (3)	0.023 (5)	0.019 (3)	0.005 (3)	0.001 (3)	−0.004 (3)
C4	0.025 (3)	0.016 (5)	0.016 (3)	−0.001 (3)	−0.005 (3)	0.002 (3)
C5	0.034 (4)	0.025 (5)	0.018 (3)	0.007 (4)	0.002 (3)	−0.004 (3)
C6	0.023 (3)	0.034 (6)	0.017 (3)	0.005 (4)	0.010 (3)	−0.003 (4)
C7	0.020 (3)	0.026 (5)	0.023 (3)	0.001 (3)	−0.001 (3)	−0.001 (4)
C8	0.029 (4)	0.025 (6)	0.021 (4)	−0.006 (4)	0.006 (3)	−0.006 (4)
C9	0.029 (4)	0.029 (6)	0.035 (4)	0.009 (4)	0.004 (3)	0.005 (4)
C10	0.035 (4)	0.030 (6)	0.031 (4)	0.004 (4)	0.002 (3)	0.015 (4)
C11	0.028 (4)	0.024 (5)	0.013 (3)	0.001 (3)	0.000 (3)	−0.008 (3)
C12	0.023 (4)	0.031 (6)	0.032 (4)	0.005 (4)	−0.005 (3)	0.004 (4)
C13	0.028 (4)	0.029 (6)	0.033 (4)	0.002 (4)	−0.004 (3)	0.008 (4)
C14	0.024 (4)	0.034 (5)	0.022 (4)	−0.002 (4)	0.001 (3)	−0.003 (4)
C15	0.022 (4)	0.022 (5)	0.028 (4)	−0.003 (4)	0.007 (3)	−0.001 (4)
C16	0.031 (4)	0.024 (5)	0.028 (4)	−0.003 (4)	0.001 (3)	−0.002 (4)
C17	0.035 (4)	0.044 (6)	0.026 (4)	−0.008 (4)	−0.003 (3)	−0.012 (4)
C18	0.025 (3)	0.021 (5)	0.030 (4)	0.008 (3)	−0.005 (3)	−0.004 (3)
C19	0.023 (3)	0.046 (6)	0.024 (4)	−0.006 (4)	0.000 (3)	−0.011 (4)
C20	0.048 (4)	0.053 (7)	0.019 (4)	−0.016 (5)	0.000 (3)	−0.011 (4)
C21	0.041 (4)	0.035 (6)	0.024 (4)	−0.010 (4)	0.004 (3)	−0.002 (4)
C22	0.027 (3)	0.046 (7)	0.031 (4)	0.005 (4)	0.003 (3)	0.013 (4)
N1	0.029 (3)	0.019 (4)	0.023 (3)	−0.001 (3)	0.000 (2)	0.001 (3)
N2	0.022 (3)	0.025 (4)	0.021 (3)	0.001 (3)	0.002 (3)	0.003 (3)
N3	0.022 (3)	0.043 (5)	0.034 (3)	0.002 (4)	−0.004 (3)	−0.013 (3)
N4	0.031 (3)	0.043 (5)	0.042 (3)	0.002 (4)	0.014 (3)	−0.008 (3)
N5	0.030 (3)	0.022 (5)	0.029 (3)	0.001 (3)	0.005 (3)	0.001 (3)
O1	0.038 (3)	0.024 (3)	0.022 (2)	−0.008 (2)	0.004 (2)	−0.005 (2)
O2	0.049 (3)	0.023 (4)	0.049 (3)	0.012 (3)	−0.013 (3)	−0.005 (3)
O3	0.052 (3)	0.042 (4)	0.031 (3)	−0.027 (3)	−0.020 (3)	0.011 (3)
O5	0.034 (3)	0.044 (4)	0.033 (3)	0.012 (3)	−0.006 (2)	−0.015 (3)
O6	0.042 (3)	0.047 (4)	0.028 (3)	0.017 (3)	−0.002 (2)	−0.009 (3)
O1W	0.045 (3)	0.032 (4)	0.044 (3)	−0.004 (3)	−0.009 (2)	0.015 (3)
O3W	0.079 (4)	0.035 (4)	0.035 (3)	−0.001 (3)	−0.017 (3)	0.001 (3)
Zn1	0.0297 (4)	0.0217 (5)	0.0227 (4)	−0.0015 (4)	0.0045 (4)	−0.0018 (4)
O2W	0.051 (3)	0.049 (4)	0.042 (3)	0.010 (3)	−0.007 (3)	0.000 (3)

Geometric parameters (Å, º)

O4—C8	1.245 (8)	C15—C16	1.522 (10)
O4—Zn1^i	2.070 (5)	C16—O6	1.240 (8)
Br1—C7	1.902 (7)	C16—N3	1.334 (8)
Br2—C3	1.902 (6)	C17—N3	1.442 (8)
Br3—C5	1.905 (7)	C17—C18	1.508 (10)
C1—O2	1.213 (9)	C17—H17A	0.9700
C1—O1	1.284 (8)	C17—H17B	0.9700
C1—C2	1.523 (10)	C18—C19	1.371 (9)
C2—C7	1.380 (8)	C18—C21^ii	1.384 (9)
C2—C3	1.380 (9)	C19—C22^ii	1.375 (10)
C3—C4	1.378 (10)	C19—H19	0.9300
C4—C5	1.401 (9)	C20—N5	1.340 (9)
C4—C8	1.500 (9)	C20—C21	1.372 (11)
C5—C6	1.384 (10)	C20—H20	0.9300
C6—N4	1.380 (8)	C21—H21	0.9300
C6—C7	1.400 (10)	C22—N5	1.337 (8)
C8—O3	1.246 (8)	C22—H22	0.9300
C9—N1	1.321 (9)	N1—Zn1	2.157 (5)
C9—C10	1.391 (9)	N2—H2	0.8600
C9—H9	0.9300	N3—H3	0.8600
C10—C11	1.373 (9)	N4—H4A	0.8600
C10—H10	0.9300	N4—H4B	0.8600
C11—C12	1.361 (10)	N5—Zn1	2.226 (6)
C11—C14	1.525 (9)	O1—Zn1	2.024 (4)
C12—C13	1.378 (9)	O1W—Zn1	2.262 (5)
C12—H12	0.9300	O1W—H1WA	0.9619
C13—N1	1.337 (8)	O1W—H1WB	1.0017
C13—H13	0.9300	O3W—H3WA	0.8506
C14—N2	1.468 (8)	O3W—H3WB	0.8458
C14—H14A	0.9700	Zn1—O2W	2.139 (5)
C14—H14B	0.9700	O2W—H2WA	0.8533
C15—O5	1.228 (8)	O2W—H2WB	0.8519
C15—N2	1.319 (8)
C8—O4—Zn1^i	130.7 (4)	C18—C17—H17B	108.4
O2—C1—O1	128.4 (7)	H17A—C17—H17B	107.5
O2—C1—C2	121.0 (6)	C19—C18—C21^ii	116.6 (7)
O1—C1—C2	110.7 (7)	C19—C18—C17	119.8 (6)
C7—C2—C3	117.3 (6)	C21^ii—C18—C17	123.5 (6)
C7—C2—C1	121.7 (6)	C18—C19—C22^ii	120.5 (7)
C3—C2—C1	120.6 (5)	C18—C19—H19	119.7
C4—C3—C2	123.2 (6)	C22^ii—C19—H19	119.7
C4—C3—Br2	117.7 (5)	N5—C20—C21	124.5 (7)
C2—C3—Br2	119.0 (5)	N5—C20—H20	117.7
C3—C4—C5	116.7 (6)	C21—C20—H20	117.7
C3—C4—C8	121.8 (6)	C20—C21—C18^iii	119.3 (7)
C5—C4—C8	121.5 (7)	C20—C21—H21	120.3
C6—C5—C4	123.4 (7)	C18^iii—C21—H21	120.3
C6—C5—Br3	119.4 (5)	N5—C22—C19^iii	123.7 (6)
C4—C5—Br3	117.2 (5)	N5—C22—H22	118.2
N4—C6—C5	121.8 (7)	C19^iii—C22—H22	118.2
N4—C6—C7	122.3 (7)	C9—N1—C13	117.5 (6)
C5—C6—C7	115.9 (5)	C9—N1—Zn1	120.3 (4)
C2—C7—C6	123.4 (6)	C13—N1—Zn1	122.0 (5)
C2—C7—Br1	117.7 (5)	C15—N2—C14	121.9 (6)
C6—C7—Br1	118.9 (4)	C15—N2—H2	119.1
O4—C8—O3	127.6 (7)	C14—N2—H2	119.1
O4—C8—C4	116.6 (6)	C16—N3—C17	124.4 (6)
O3—C8—C4	115.7 (7)	C16—N3—H3	117.8
N1—C9—C10	123.0 (7)	C17—N3—H3	117.8
N1—C9—H9	118.5	C6—N4—H4A	120.0
C10—C9—H9	118.5	C6—N4—H4B	120.0
C11—C10—C9	119.0 (7)	H4A—N4—H4B	120.0
C11—C10—H10	120.5	C22—N5—C20	115.3 (6)
C9—C10—H10	120.5	C22—N5—Zn1	117.0 (5)
C12—C11—C10	117.9 (6)	C20—N5—Zn1	127.4 (5)
C12—C11—C14	120.8 (6)	C1—O1—Zn1	136.0 (5)
C10—C11—C14	121.4 (7)	Zn1—O1W—H1WA	117.4
C11—C12—C13	120.2 (7)	Zn1—O1W—H1WB	124.8
C11—C12—H12	119.9	H1WA—O1W—H1WB	111.2
C13—C12—H12	119.9	H3WA—O3W—H3WB	110.2
N1—C13—C12	122.4 (7)	O1—Zn1—O4^iv	99.63 (19)
N1—C13—H13	118.8	O1—Zn1—O2W	171.3 (2)
C12—C13—H13	118.8	O4^iv—Zn1—O2W	88.9 (2)
N2—C14—C11	111.7 (6)	O1—Zn1—N1	87.84 (19)
N2—C14—H14A	109.3	O4^iv—Zn1—N1	98.4 (2)
C11—C14—H14A	109.3	O2W—Zn1—N1	89.3 (2)
N2—C14—H14B	109.3	O1—Zn1—N5	88.7 (2)
C11—C14—H14B	109.3	O4^iv—Zn1—N5	89.2 (2)
H14A—C14—H14B	107.9	O2W—Zn1—N5	93.0 (2)
O5—C15—N2	124.5 (6)	N1—Zn1—N5	172.1 (2)
O5—C15—C16	119.9 (6)	O1—Zn1—O1W	94.5 (2)
N2—C15—C16	115.6 (6)	O4^iv—Zn1—O1W	164.67 (18)
O6—C16—N3	125.5 (6)	O2W—Zn1—O1W	77.2 (2)
O6—C16—C15	122.0 (6)	N1—Zn1—O1W	88.0 (2)
N3—C16—C15	112.4 (6)	N5—Zn1—O1W	85.2 (2)
N3—C17—C18	115.4 (6)	Zn1—O2W—H2WA	120.9
N3—C17—H17A	108.4	Zn1—O2W—H2WB	105.0
C18—C17—H17A	108.4	H2WA—O2W—H2WB	109.1
N3—C17—H17B	108.4
O2—C1—C2—C7	92.3 (8)	N1—C9—C10—C11	0.1 (12)
O1—C1—C2—C7	−87.8 (7)	C9—C10—C11—C12	−1.2 (11)
O2—C1—C2—C3	−95.0 (8)	C9—C10—C11—C14	179.2 (6)
O1—C1—C2—C3	84.9 (7)	C10—C11—C12—C13	1.1 (10)
C7—C2—C3—C4	2.3 (10)	C14—C11—C12—C13	−179.3 (6)
C1—C2—C3—C4	−170.7 (6)	C11—C12—C13—N1	0.2 (11)
C7—C2—C3—Br2	−174.5 (5)	C12—C11—C14—N2	75.7 (7)
C1—C2—C3—Br2	12.5 (9)	C10—C11—C14—N2	−104.8 (8)
C2—C3—C4—C5	1.1 (10)	O5—C15—C16—O6	178.8 (7)
Br2—C3—C4—C5	177.9 (5)	N2—C15—C16—O6	−1.9 (10)
C2—C3—C4—C8	−176.9 (7)	O5—C15—C16—N3	0.5 (10)
Br2—C3—C4—C8	−0.1 (9)	N2—C15—C16—N3	179.8 (6)
C3—C4—C5—C6	−3.0 (10)	N3—C17—C18—C19	171.4 (7)
C8—C4—C5—C6	175.0 (6)	N3—C17—C18—C21^ii	−6.2 (11)
C3—C4—C5—Br3	176.4 (5)	C21^ii—C18—C19—C22^ii	1.8 (11)
C8—C4—C5—Br3	−5.5 (9)	C17—C18—C19—C22^ii	−175.9 (7)
C4—C5—C6—N4	−176.0 (6)	N5—C20—C21—C18^iii	0.1 (13)
Br3—C5—C6—N4	4.5 (9)	C10—C9—N1—C13	1.2 (11)
C4—C5—C6—C7	1.4 (10)	C10—C9—N1—Zn1	−174.2 (6)
Br3—C5—C6—C7	−178.1 (5)	C12—C13—N1—C9	−1.3 (10)
C3—C2—C7—C6	−4.1 (10)	C12—C13—N1—Zn1	173.9 (5)
C1—C2—C7—C6	168.8 (7)	O5—C15—N2—C14	−3.8 (11)
C3—C2—C7—Br1	175.5 (5)	C16—C15—N2—C14	176.9 (6)
C1—C2—C7—Br1	−11.6 (9)	C11—C14—N2—C15	80.7 (8)
N4—C6—C7—C2	179.7 (6)	O6—C16—N3—C17	−0.2 (12)
C5—C6—C7—C2	2.3 (10)	C15—C16—N3—C17	178.0 (7)
N4—C6—C7—Br1	0.2 (9)	C18—C17—N3—C16	109.2 (8)
C5—C6—C7—Br1	−177.2 (5)	C19^iii—C22—N5—C20	−2.4 (11)
Zn1^i—O4—C8—O3	13.9 (11)	C19^iii—C22—N5—Zn1	171.0 (6)
Zn1^i—O4—C8—C4	−169.7 (4)	C21—C20—N5—C22	2.1 (12)
C3—C4—C8—O4	−87.4 (9)	C21—C20—N5—Zn1	−170.4 (6)
C5—C4—C8—O4	94.7 (8)	O2—C1—O1—Zn1	−14.4 (10)
C3—C4—C8—O3	89.5 (8)	C2—C1—O1—Zn1	165.7 (4)
C5—C4—C8—O3	−88.4 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H3WB···O3^v	0.85	1.95	2.790 (7)	171
O2W—H2WA···O3^iv	0.85	1.99	2.609 (8)	129
O2W—H2WB···O3W^vi	0.85	2.13	2.914 (7)	153
O1W—H1WB···O3W^vi	1.00	2.09	2.866 (6)	133
N2—H2···O2^vi	0.86	2.11	2.857 (8)	144
N3—H3···O6^vii	0.86	2.43	3.161 (8)	144
N4—H4A···O2W^viii	0.86	2.54	3.204 (9)	135
O1W—H1WA···O5^viii	0.96	1.77	2.706 (8)	163
C21—H21···N3^iii	0.93	2.59	2.900 (10)	100
O2W—H2WA···Br3^iii	0.85	2.61	3.314 (5)	141
O3W—H3WA···O6^iii	0.85	2.17	2.963 (8)	154

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