Syntheses, crystal structures and Hirshfeld surface analysis of (Z)-3-[(3-acetyl-2-hy­droxy­phen­yl)amino]-2-bromo­prop-2-enal and a novel Zn^II com­plex

A novel zero-dimensional dinuclear zinc com­plex, di-μ-acetato-1:2κ⁴O:O′-(μ-2-acetyl-6-{[(Z)-2-bromo-3-oxoprop-1-en-1-yl]aza­nid­yl}phenolato-1κ²O¹,O²:2κ³O¹,N,O⁶)(N,N-di­methyl­acetamide-1κO)dizinc(II), [Zn₂(C₁₁H₈BrNO₃)(CH₃COO)₂(C₄H₉NO)] or [Zn₂(L)(CH₃COO)₂(DMA)], 1, was synthesized using (Z)-3-[(3-acetyl-2-hy­droxy­phen­yl)amino]-2-bromo­prop-2-enal (H₂L), which was synthesized from 1-(3-amino-2-hy­droxy­phen­yl)ethanone and 2-bromo­malonaldehyde. H₂L and 1 were characterized by single-crystal X-ray diffraction, FT–IR spectroscopy and elemental analysis. Theoretical calculations of the bond orders and excited state of H₂L confirmed that there is extensive electron delocalization in the H₂L mol­ecules. Single-crystal X-ray diffraction shows that the two Zn atoms are penta­coordinated in distorted trigonal bipyramidal configurations in the crystals of 1. The thermogravimetric analysis of 1 shows that the main frame of the com­plex remains stable to about 190 °C. Powder X-ray diffraction (PXRD) analysis shows that 1 possesses high purity and acid and alkali resistance. The inter­molecular inter­actions of H₂L and 1 were analyzed using Hirshfeld surface analysis and the results indicate that the H...H and O...H inter­actions of H₂L and 1 play a considerable role in stabilizing the self-assembly process.

Computing details

Data collection: APEX2 (Bruker, 2016) for Sm; CrysAlis PRO (Rigaku OD, 2018) for px2. Cell refinement: SAINT (Bruker, 2016) for Sm; CrysAlis PRO (Rigaku OD, 2018) for px2. Data reduction: SAINT (Bruker, 2016) for Sm; CrysAlis PRO (Rigaku OD, 2018) for px2. For both structures, program(s) used to solve structure: olex2.solve (Bourhis et al., 2015) and OLEX2 (Dolomanov et al., 2009); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(Z)-3-[(3-Acetyl-2-hydroxyphenyl)amino]-2-bromoprop-2-enal (Sm)

Crystal data

C11H10BrNO3	F(000) = 568
Mr = 284.11	Dx = 1.690 Mg m^−3
Triclinic, P1	Melting point: 403.35 K
a = 9.8671 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6765 (8) Å	Cell parameters from 8447 reflections
c = 11.8719 (8) Å	θ = 3.0–26.0°
α = 85.770 (2)°	µ = 3.67 mm^−1
β = 86.907 (2)°	T = 273 K
γ = 63.586 (2)°	Irregular, orange
V = 1116.73 (14) Å^3	0.25 × 0.15 × 0.08 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	3058 reflections with I > 2σ(I)
Detector resolution: 16.0233 pixels mm^-1	Rint = 0.031
φ and ω scans	θmax = 25.1°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −11→11
Tmin = 0.533, Tmax = 0.746	k = −12→12
19863 measured reflections	l = −14→14
3956 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0313P)^2 + 0.7701P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
3956 reflections	Δρmax = 0.38 e Å^−3
292 parameters	Δρmin = −0.41 e Å^−3

Special details

Experimental. SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1097 before and 0.0476 after correction. The Ratio of minimum to maximum transmission is 0.7154. The λ/2 correction factor is Not present.

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
Br1	0.16665 (4)	0.62157 (4)	0.72653 (3)	0.05801 (12)
O1	0.2875 (3)	0.7949 (3)	0.56457 (19)	0.0763 (7)
N1	0.1587 (3)	0.7602 (3)	0.95138 (18)	0.0461 (6)
H1	0.1350	0.6933	0.9422	0.055*
C1	0.2849 (4)	0.8174 (3)	0.6639 (3)	0.0566 (8)
H1A	0.3217	0.8801	0.6811	0.068*
Br2	0.48752 (5)	0.93823 (4)	0.37672 (3)	0.06600 (13)
O2	0.0242 (3)	0.6586 (2)	1.10169 (18)	0.0607 (6)
H2	−0.0131	0.6292	1.1542	0.091*
N2	0.4378 (3)	0.6752 (2)	0.32647 (19)	0.0431 (6)
H2A	0.4159	0.7196	0.3875	0.052*
C2	0.2315 (3)	0.7577 (3)	0.7562 (2)	0.0434 (7)
O3	−0.0753 (3)	0.6459 (3)	1.3025 (2)	0.0751 (7)
C3	0.2167 (3)	0.8032 (3)	0.8615 (2)	0.0452 (7)
H3	0.2500	0.8703	0.8720	0.054*
O4	0.6521 (3)	0.9619 (3)	0.1490 (2)	0.0838 (8)
C4	0.1322 (3)	0.8127 (3)	1.0598 (2)	0.0412 (7)
O5	0.4446 (3)	0.5331 (2)	0.13048 (15)	0.0507 (5)
H5A	0.4402	0.4848	0.0815	0.076*
C5	0.1711 (3)	0.9136 (3)	1.0911 (2)	0.0466 (7)
H5	0.2171	0.9525	1.0387	0.056*
O6	0.3822 (3)	0.3576 (3)	0.04444 (18)	0.0802 (8)
C6	0.1419 (3)	0.9575 (3)	1.2007 (3)	0.0516 (8)
H6	0.1683	1.0261	1.2211	0.062*
C7	0.0749 (3)	0.9010 (3)	1.2792 (3)	0.0496 (7)
H7	0.0576	0.9304	1.3526	0.060*
C8	0.0609 (3)	0.7567 (3)	1.1384 (2)	0.0432 (7)
C9	0.0321 (3)	0.7993 (3)	1.2495 (2)	0.0446 (7)
C10	−0.0394 (4)	0.7359 (4)	1.3315 (3)	0.0583 (8)
C11	−0.0681 (5)	0.7794 (5)	1.4509 (3)	0.0827 (12)
H11A	−0.1480	0.8730	1.4530	0.124*
H11B	0.0224	0.7765	1.4798	0.124*
H11C	−0.0969	0.7167	1.4964	0.124*
C12	0.6158 (4)	0.8655 (4)	0.1585 (3)	0.0644 (10)
H12	0.6413	0.8089	0.0973	0.077*
C13	0.5411 (3)	0.8294 (3)	0.2491 (2)	0.0460 (7)
C14	0.5073 (3)	0.7195 (3)	0.2459 (2)	0.0435 (7)
H14	0.5358	0.6702	0.1804	0.052*
C15	0.3946 (3)	0.5659 (3)	0.3264 (2)	0.0369 (6)
C16	0.3950 (3)	0.4978 (3)	0.2302 (2)	0.0371 (6)
C17	0.3440 (3)	0.5285 (3)	0.4280 (2)	0.0470 (7)
H17	0.3435	0.5736	0.4922	0.056*
C18	0.2940 (4)	0.4262 (3)	0.4371 (2)	0.0551 (8)
H18	0.2620	0.4019	0.5068	0.066*
C19	0.2918 (4)	0.3609 (3)	0.3427 (2)	0.0520 (8)
H19	0.2573	0.2926	0.3484	0.062*
C20	0.3410 (3)	0.3957 (3)	0.2379 (2)	0.0408 (6)
C21	0.3321 (4)	0.3320 (3)	0.1352 (3)	0.0540 (8)
C22	0.2604 (5)	0.2335 (4)	0.1402 (3)	0.0760 (11)
H22A	0.2267	0.2238	0.2163	0.114*
H22B	0.1755	0.2703	0.0912	0.114*
H22C	0.3333	0.1437	0.1164	0.114*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0756 (2)	0.0634 (2)	0.0491 (2)	−0.04348 (18)	0.00968 (16)	−0.01078 (15)
O1	0.122 (2)	0.0772 (17)	0.0453 (14)	−0.0591 (16)	0.0280 (14)	−0.0159 (12)
N1	0.0591 (16)	0.0494 (14)	0.0363 (13)	−0.0305 (13)	0.0028 (11)	−0.0016 (11)
C1	0.073 (2)	0.0518 (19)	0.052 (2)	−0.0343 (17)	0.0166 (16)	−0.0112 (15)
Br2	0.1083 (3)	0.0653 (2)	0.0454 (2)	−0.0560 (2)	0.01018 (18)	−0.02145 (16)
O2	0.0862 (17)	0.0686 (15)	0.0500 (13)	−0.0551 (13)	0.0016 (12)	−0.0031 (11)
N2	0.0586 (15)	0.0395 (13)	0.0375 (13)	−0.0271 (12)	0.0038 (11)	−0.0078 (10)
C2	0.0468 (17)	0.0398 (16)	0.0441 (17)	−0.0200 (13)	0.0063 (13)	−0.0049 (13)
O3	0.0957 (19)	0.0926 (19)	0.0642 (15)	−0.0685 (16)	0.0018 (13)	0.0087 (13)
C3	0.0467 (17)	0.0446 (17)	0.0456 (17)	−0.0216 (14)	0.0006 (14)	−0.0025 (13)
O4	0.123 (2)	0.0930 (19)	0.0789 (17)	−0.0868 (18)	0.0304 (15)	−0.0271 (14)
C4	0.0428 (16)	0.0438 (16)	0.0373 (16)	−0.0198 (13)	−0.0033 (13)	0.0026 (13)
O5	0.0826 (15)	0.0568 (13)	0.0331 (11)	−0.0498 (12)	0.0113 (10)	−0.0079 (9)
C5	0.0503 (18)	0.0512 (18)	0.0454 (17)	−0.0298 (15)	0.0031 (14)	0.0004 (14)
O6	0.144 (2)	0.107 (2)	0.0410 (13)	−0.1013 (19)	0.0297 (14)	−0.0265 (13)
C6	0.059 (2)	0.0548 (19)	0.0531 (19)	−0.0352 (16)	0.0000 (15)	−0.0062 (15)
C7	0.0502 (18)	0.0593 (19)	0.0415 (16)	−0.0258 (16)	0.0001 (14)	−0.0061 (14)
C8	0.0459 (17)	0.0440 (17)	0.0434 (17)	−0.0236 (14)	−0.0042 (13)	0.0019 (13)
C9	0.0431 (17)	0.0521 (18)	0.0405 (16)	−0.0235 (14)	−0.0029 (13)	0.0034 (13)
C10	0.056 (2)	0.077 (2)	0.0489 (19)	−0.0366 (18)	−0.0025 (15)	0.0072 (17)
C11	0.098 (3)	0.123 (3)	0.048 (2)	−0.070 (3)	0.016 (2)	0.001 (2)
C12	0.091 (3)	0.073 (2)	0.055 (2)	−0.059 (2)	0.0251 (18)	−0.0305 (18)
C13	0.0609 (19)	0.0490 (17)	0.0404 (16)	−0.0341 (15)	0.0078 (14)	−0.0176 (13)
C14	0.0501 (17)	0.0433 (16)	0.0432 (16)	−0.0253 (14)	0.0043 (13)	−0.0123 (13)
C15	0.0411 (16)	0.0345 (14)	0.0370 (15)	−0.0185 (12)	0.0007 (12)	−0.0031 (12)
C16	0.0463 (16)	0.0393 (15)	0.0300 (14)	−0.0234 (13)	0.0039 (12)	−0.0005 (11)
C17	0.0602 (19)	0.0537 (18)	0.0326 (15)	−0.0297 (15)	0.0037 (14)	−0.0096 (13)
C18	0.078 (2)	0.068 (2)	0.0346 (16)	−0.0471 (19)	0.0100 (15)	−0.0033 (15)
C19	0.070 (2)	0.0568 (19)	0.0448 (17)	−0.0437 (17)	0.0126 (15)	−0.0060 (15)
C20	0.0498 (17)	0.0440 (16)	0.0373 (15)	−0.0291 (14)	0.0074 (13)	−0.0048 (12)
C21	0.075 (2)	0.062 (2)	0.0447 (17)	−0.0479 (18)	0.0121 (16)	−0.0130 (15)
C22	0.116 (3)	0.101 (3)	0.055 (2)	−0.088 (3)	0.017 (2)	−0.022 (2)

Geometric parameters (Å, º)

Br1—C2	1.890 (3)	C7—C9	1.401 (4)
O1—C1	1.217 (4)	C7—H7	0.9300
N1—C3	1.331 (3)	C8—C9	1.399 (4)
N1—C4	1.407 (3)	C9—C10	1.469 (4)
N1—H1	0.8600	C10—C11	1.497 (5)
C1—C2	1.421 (4)	C11—H11A	0.9600
C1—H1A	0.9300	C11—H11B	0.9600
Br2—C13	1.885 (3)	C11—H11C	0.9600
O2—C8	1.356 (3)	C12—C13	1.398 (4)
O2—H2	0.8200	C12—H12	0.9300
N2—C14	1.327 (3)	C13—C14	1.359 (4)
N2—C15	1.409 (3)	C14—H14	0.9300
N2—H2A	0.8600	C15—C17	1.380 (4)
C2—C3	1.351 (4)	C15—C16	1.397 (4)
O3—C10	1.238 (4)	C16—C20	1.406 (4)
C3—H3	0.9300	C17—C18	1.380 (4)
O4—C12	1.228 (4)	C17—H17	0.9300
C4—C5	1.374 (4)	C18—C19	1.369 (4)
C4—C8	1.395 (4)	C18—H18	0.9300
O5—C16	1.349 (3)	C19—C20	1.396 (4)
O5—H5A	0.8200	C19—H19	0.9300
C5—C6	1.387 (4)	C20—C21	1.465 (4)
C5—H5	0.9300	C21—C22	1.502 (4)
O6—C21	1.224 (3)	C22—H22A	0.9600
C6—C7	1.369 (4)	C22—H22B	0.9600
C6—H6	0.9300	C22—H22C	0.9600
C3—N1—C4	126.9 (2)	H11A—C11—H11B	109.5
C3—N1—H1	116.6	C10—C11—H11C	109.5
C4—N1—H1	116.6	H11A—C11—H11C	109.5
O1—C1—C2	126.6 (3)	H11B—C11—H11C	109.5
O1—C1—H1A	116.7	O4—C12—C13	128.6 (3)
C2—C1—H1A	116.7	O4—C12—H12	115.7
C8—O2—H2	109.5	C13—C12—H12	115.7
C14—N2—C15	129.3 (2)	C14—C13—C12	121.4 (3)
C14—N2—H2A	115.3	C14—C13—Br2	120.5 (2)
C15—N2—H2A	115.3	C12—C13—Br2	118.1 (2)
C3—C2—C1	121.4 (3)	N2—C14—C13	126.7 (3)
C3—C2—Br1	120.1 (2)	N2—C14—H14	116.6
C1—C2—Br1	118.3 (2)	C13—C14—H14	116.6
N1—C3—C2	125.7 (3)	C17—C15—C16	118.7 (2)
N1—C3—H3	117.1	C17—C15—N2	117.0 (2)
C2—C3—H3	117.1	C16—C15—N2	124.3 (2)
C5—C4—C8	119.5 (3)	O5—C16—C15	119.3 (2)
C5—C4—N1	124.4 (3)	O5—C16—C20	120.9 (2)
C8—C4—N1	116.2 (2)	C15—C16—C20	119.8 (2)
C16—O5—H5A	109.5	C18—C17—C15	122.0 (3)
C4—C5—C6	120.2 (3)	C18—C17—H17	119.0
C4—C5—H5	119.9	C15—C17—H17	119.0
C6—C5—H5	119.9	C19—C18—C17	119.4 (3)
C7—C6—C5	120.8 (3)	C19—C18—H18	120.3
C7—C6—H6	119.6	C17—C18—H18	120.3
C5—C6—H6	119.6	C18—C19—C20	120.7 (3)
C6—C7—C9	120.4 (3)	C18—C19—H19	119.6
C6—C7—H7	119.8	C20—C19—H19	119.6
C9—C7—H7	119.8	C19—C20—C16	119.3 (3)
O2—C8—C4	116.5 (3)	C19—C20—C21	121.3 (3)
O2—C8—C9	122.7 (3)	C16—C20—C21	119.3 (2)
C4—C8—C9	120.8 (3)	O6—C21—C20	121.2 (3)
C8—C9—C7	118.3 (3)	O6—C21—C22	118.9 (3)
C8—C9—C10	119.7 (3)	C20—C21—C22	119.9 (3)
C7—C9—C10	121.9 (3)	C21—C22—H22A	109.5
O3—C10—C9	120.3 (3)	C21—C22—H22B	109.5
O3—C10—C11	119.8 (3)	H22A—C22—H22B	109.5
C9—C10—C11	120.0 (3)	C21—C22—H22C	109.5
C10—C11—H11A	109.5	H22A—C22—H22C	109.5
C10—C11—H11B	109.5	H22B—C22—H22C	109.5
O1—C1—C2—C3	−171.7 (3)	O4—C12—C13—C14	179.2 (4)
O1—C1—C2—Br1	3.6 (5)	O4—C12—C13—Br2	−0.6 (6)
C4—N1—C3—C2	−175.1 (3)	C15—N2—C14—C13	177.3 (3)
C1—C2—C3—N1	175.4 (3)	C12—C13—C14—N2	179.7 (3)
Br1—C2—C3—N1	0.1 (4)	Br2—C13—C14—N2	−0.5 (4)
C3—N1—C4—C5	−3.9 (5)	C14—N2—C15—C17	170.5 (3)
C3—N1—C4—C8	175.9 (3)	C14—N2—C15—C16	−11.8 (5)
C8—C4—C5—C6	1.1 (4)	C17—C15—C16—O5	−179.8 (3)
N1—C4—C5—C6	−179.2 (3)	N2—C15—C16—O5	2.5 (4)
C4—C5—C6—C7	0.3 (5)	C17—C15—C16—C20	1.5 (4)
C5—C6—C7—C9	−1.1 (5)	N2—C15—C16—C20	−176.1 (3)
C5—C4—C8—O2	179.4 (3)	C16—C15—C17—C18	0.0 (4)
N1—C4—C8—O2	−0.3 (4)	N2—C15—C17—C18	177.8 (3)
C5—C4—C8—C9	−1.7 (4)	C15—C17—C18—C19	−1.1 (5)
N1—C4—C8—C9	178.6 (3)	C17—C18—C19—C20	0.6 (5)
O2—C8—C9—C7	179.8 (3)	C18—C19—C20—C16	0.9 (5)
C4—C8—C9—C7	0.9 (4)	C18—C19—C20—C21	−176.8 (3)
O2—C8—C9—C10	0.5 (4)	O5—C16—C20—C19	179.5 (3)
C4—C8—C9—C10	−178.3 (3)	C15—C16—C20—C19	−2.0 (4)
C6—C7—C9—C8	0.5 (4)	O5—C16—C20—C21	−2.8 (4)
C6—C7—C9—C10	179.7 (3)	C15—C16—C20—C21	175.8 (3)
C8—C9—C10—O3	−0.6 (5)	C19—C20—C21—O6	−176.3 (3)
C7—C9—C10—O3	−179.8 (3)	C16—C20—C21—O6	6.0 (5)
C8—C9—C10—C11	179.0 (3)	C19—C20—C21—C22	3.7 (5)
C7—C9—C10—C11	−0.2 (5)	C16—C20—C21—C22	−174.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.86	2.69	3.127 (2)	113
O2—H2···O3	0.82	1.83	2.547 (3)	146
N2—H2A···O1	0.86	2.39	3.196 (3)	156
N2—H2A···Br2	0.86	2.72	3.160 (2)	114
C3—H3···O4^i	0.93	2.38	3.288 (4)	166
O5—H5A···O6	0.82	1.78	2.513 (3)	148
C12—H12···O6^ii	0.93	2.63	3.503 (4)	158
C14—H14···O5	0.93	2.16	2.794 (3)	125
C17—H17···O1	0.93	2.39	3.194 (4)	145

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

Di-µ-acetato-1:2κ⁴O:O'-(µ-2-acetyl-6-{[(Z)-2-bromo-3-oxoprop-1-en-1-yl]azanidyl}phenolato-1κ²O¹,O²:2κ³O¹,N,O⁶)(N,N-dimethyl-acetamide-1κO)dizinc(II) (px2)

Crystal data

[Zn2(C11H8BrNO3)(C2H3O2)2(C4H9NO)]	Z = 2
Mr = 618.04	F(000) = 620
Triclinic, P1	Dx = 1.759 Mg m^−3
a = 8.0300 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1184 (10) Å	Cell parameters from 2035 reflections
c = 14.4723 (14) Å	θ = 3.7–25.2°
α = 87.217 (8)°	µ = 3.81 mm^−1
β = 89.232 (7)°	T = 293 K
γ = 83.518 (7)°	Needle, orange
V = 1166.95 (18) Å^3	0.21 × 0.13 × 0.06 mm

Data collection

Rigaku OD SuperNova Single source diffractometer with an Eos detector	4142 independent reflections
Radiation source: micro-focus sealed X-ray tube	3027 reflections with I > 2σ(I)
Detector resolution: 16.0233 pixels mm^-1	Rint = 0.027
ω scans	θmax = 25.1°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −9→9
Tmin = 0.557, Tmax = 0.796	k = −10→12
7311 measured reflections	l = −17→13

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0366P)^2 + 0.1413P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.002
4142 reflections	Δρmax = 0.32 e Å^−3
295 parameters	Δρmin = −0.49 e Å^−3

Special details

Experimental. CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Zn1	0.68765 (6)	0.69170 (5)	0.67187 (3)	0.04309 (16)
Br1	0.64484 (7)	0.13167 (5)	1.11694 (4)	0.06499 (18)
O1	0.5393 (4)	0.2610 (3)	0.8539 (2)	0.0616 (9)
N1	0.7054 (4)	0.4572 (3)	0.9468 (2)	0.0400 (8)
C1	0.5575 (5)	0.2019 (5)	0.9320 (3)	0.0517 (12)
H1	0.5142	0.1206	0.9399	0.062*
Zn2	0.62359 (6)	0.43658 (5)	0.81579 (3)	0.04353 (16)
O2	0.7241 (4)	0.6165 (3)	0.8007 (2)	0.0523 (8)
N2	0.6575 (5)	0.8954 (5)	0.4111 (3)	0.0649 (12)
C2	0.6357 (5)	0.2458 (4)	1.0078 (3)	0.0443 (11)
O3	0.7827 (4)	0.8552 (3)	0.7231 (2)	0.0573 (9)
C3	0.7025 (5)	0.3669 (4)	1.0129 (3)	0.0416 (10)
H3	0.7492	0.3840	1.0689	0.050*
O4	0.7673 (4)	0.3595 (3)	0.7134 (2)	0.0593 (9)
C4	0.7707 (5)	0.5788 (4)	0.9595 (3)	0.0390 (10)
O5	0.8095 (4)	0.5304 (3)	0.6163 (2)	0.0563 (8)
C5	0.8246 (5)	0.6219 (5)	1.0417 (3)	0.0528 (12)
H5	0.8222	0.5673	1.0952	0.063*
O6	0.3989 (3)	0.5142 (3)	0.7658 (2)	0.0545 (8)
C6	0.8824 (6)	0.7453 (5)	1.0456 (3)	0.0633 (14)
H6	0.9191	0.7722	1.1017	0.076*
O7	0.4412 (3)	0.6849 (3)	0.6677 (2)	0.0547 (8)
C7	0.8862 (5)	0.8277 (5)	0.9688 (3)	0.0557 (13)
H7	0.9254	0.9102	0.9732	0.067*
O8	0.6958 (4)	0.8040 (3)	0.5514 (2)	0.0571 (8)
C8	0.7751 (5)	0.6631 (4)	0.8778 (3)	0.0389 (10)
C9	0.8311 (5)	0.7899 (4)	0.8816 (3)	0.0416 (10)
C10	0.8308 (5)	0.8810 (4)	0.8014 (3)	0.0466 (11)
C11	0.8921 (6)	1.0151 (5)	0.8074 (4)	0.0654 (14)
H11A	1.0075	1.0039	0.8256	0.098*
H11B	0.8263	1.0652	0.8524	0.098*
H11C	0.8815	1.0620	0.7481	0.098*
C12	0.9477 (7)	0.3202 (6)	0.5861 (4)	0.097 (2)
H12A	1.0255	0.2662	0.6258	0.145*
H12B	1.0081	0.3723	0.5429	0.145*
H12C	0.8834	0.2639	0.5529	0.145*
C13	0.8313 (5)	0.4117 (5)	0.6437 (4)	0.0528 (12)
C14	0.3511 (5)	0.6114 (5)	0.7124 (3)	0.0471 (11)
C15	0.1634 (5)	0.6422 (6)	0.7005 (4)	0.0778 (17)
H15A	0.1067	0.5994	0.7503	0.117*
H15B	0.1314	0.6100	0.6427	0.117*
H15C	0.1331	0.7367	0.7007	0.117*
C16	0.5588 (7)	0.6796 (6)	0.4448 (4)	0.0852 (18)
H16A	0.6136	0.6004	0.4754	0.128*
H16B	0.5678	0.6718	0.3790	0.128*
H16C	0.4427	0.6906	0.4627	0.128*
C17	0.6408 (5)	0.7983 (5)	0.4720 (3)	0.0521 (12)
C18	0.5994 (9)	0.8999 (8)	0.3153 (4)	0.126 (3)
H18A	0.6782	0.8453	0.2789	0.189*
H18B	0.5902	0.9900	0.2903	0.189*
H18C	0.4919	0.8672	0.3138	0.189*
C19	0.7426 (7)	1.0085 (5)	0.4376 (4)	0.0897 (19)
H19A	0.7562	1.0045	0.5036	0.135*
H19B	0.6766	1.0902	0.4188	0.135*
H19C	0.8506	1.0047	0.4080	0.135*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0489 (3)	0.0399 (3)	0.0410 (3)	−0.0086 (2)	−0.0020 (2)	0.0022 (2)
Br1	0.0821 (4)	0.0524 (3)	0.0597 (4)	−0.0117 (3)	−0.0034 (3)	0.0146 (3)
O1	0.085 (2)	0.054 (2)	0.050 (2)	−0.0310 (18)	−0.0088 (17)	0.0050 (18)
N1	0.0429 (19)	0.039 (2)	0.039 (2)	−0.0049 (16)	0.0007 (16)	−0.0043 (18)
C1	0.059 (3)	0.037 (3)	0.063 (3)	−0.020 (2)	0.003 (2)	−0.004 (3)
Zn2	0.0536 (3)	0.0394 (3)	0.0395 (3)	−0.0131 (2)	−0.0029 (2)	−0.0023 (2)
O2	0.080 (2)	0.0406 (19)	0.0401 (18)	−0.0219 (15)	−0.0128 (16)	0.0004 (15)
N2	0.069 (3)	0.072 (3)	0.050 (3)	0.001 (2)	−0.006 (2)	0.017 (2)
C2	0.050 (3)	0.036 (3)	0.047 (3)	−0.007 (2)	0.001 (2)	0.003 (2)
O3	0.074 (2)	0.045 (2)	0.055 (2)	−0.0167 (16)	−0.0108 (17)	0.0020 (17)
C3	0.044 (2)	0.040 (3)	0.040 (3)	−0.001 (2)	−0.003 (2)	−0.002 (2)
O4	0.076 (2)	0.043 (2)	0.059 (2)	−0.0104 (17)	0.0162 (18)	−0.0048 (17)
C4	0.038 (2)	0.039 (3)	0.041 (3)	−0.0033 (19)	−0.0021 (19)	−0.009 (2)
O5	0.063 (2)	0.050 (2)	0.053 (2)	−0.0003 (16)	0.0110 (15)	0.0002 (17)
C5	0.063 (3)	0.056 (3)	0.041 (3)	−0.014 (2)	−0.003 (2)	−0.001 (2)
O6	0.0490 (18)	0.057 (2)	0.058 (2)	−0.0102 (15)	−0.0056 (15)	0.0047 (18)
C6	0.082 (4)	0.070 (4)	0.046 (3)	−0.034 (3)	−0.003 (3)	−0.015 (3)
O7	0.0457 (18)	0.064 (2)	0.053 (2)	−0.0046 (16)	−0.0005 (15)	0.0091 (18)
C7	0.064 (3)	0.048 (3)	0.061 (3)	−0.026 (2)	−0.002 (2)	−0.018 (3)
O8	0.080 (2)	0.053 (2)	0.0399 (19)	−0.0193 (17)	−0.0074 (16)	0.0088 (16)
C8	0.036 (2)	0.045 (3)	0.037 (2)	−0.0038 (19)	0.0005 (18)	−0.009 (2)
C9	0.040 (2)	0.037 (3)	0.049 (3)	−0.0076 (19)	0.002 (2)	−0.008 (2)
C10	0.040 (2)	0.039 (3)	0.061 (3)	−0.005 (2)	0.003 (2)	−0.005 (2)
C11	0.082 (3)	0.039 (3)	0.078 (4)	−0.016 (3)	−0.010 (3)	−0.003 (3)
C12	0.099 (4)	0.085 (5)	0.101 (5)	0.015 (4)	0.048 (4)	−0.021 (4)
C13	0.048 (3)	0.051 (3)	0.059 (3)	−0.004 (2)	0.003 (2)	−0.007 (3)
C14	0.043 (3)	0.057 (3)	0.041 (3)	0.000 (2)	−0.002 (2)	−0.011 (2)
C15	0.047 (3)	0.104 (5)	0.081 (4)	−0.008 (3)	−0.004 (3)	0.013 (4)
C16	0.091 (4)	0.094 (5)	0.077 (4)	−0.034 (4)	−0.015 (3)	−0.016 (4)
C17	0.046 (3)	0.055 (3)	0.053 (3)	0.000 (2)	0.001 (2)	0.001 (3)
C18	0.152 (6)	0.164 (8)	0.053 (4)	0.002 (6)	−0.025 (4)	0.035 (5)
C19	0.101 (4)	0.052 (4)	0.112 (5)	−0.006 (3)	0.017 (4)	0.021 (4)

Geometric parameters (Å, º)

Zn1—O7	1.989 (3)	C6—C7	1.359 (6)
Zn1—O2	1.992 (3)	C6—H6	0.9300
Zn1—O5	2.003 (3)	O7—C14	1.248 (5)
Zn1—O8	2.039 (3)	C7—C9	1.427 (6)
Zn1—O3	2.072 (3)	C7—H7	0.9300
Br1—C2	1.908 (4)	O8—C17	1.244 (5)
O1—C1	1.255 (5)	C8—C9	1.411 (6)
O1—Zn2	2.022 (3)	C9—C10	1.446 (6)
N1—C3	1.292 (5)	C10—C11	1.501 (6)
N1—C4	1.412 (5)	C11—H11A	0.9600
N1—Zn2	2.043 (3)	C11—H11B	0.9600
C1—C2	1.388 (6)	C11—H11C	0.9600
C1—H1	0.9300	C12—C13	1.512 (6)
Zn2—O4	2.000 (3)	C12—H12A	0.9600
Zn2—O6	2.014 (3)	C12—H12B	0.9600
Zn2—O2	2.074 (3)	C12—H12C	0.9600
O2—C8	1.319 (5)	C14—C15	1.515 (6)
N2—C17	1.305 (6)	C15—H15A	0.9600
N2—C18	1.466 (6)	C15—H15B	0.9600
N2—C19	1.466 (7)	C15—H15C	0.9600
C2—C3	1.397 (6)	C16—C17	1.505 (7)
O3—C10	1.250 (5)	C16—H16A	0.9600
C3—H3	0.9300	C16—H16B	0.9600
O4—C13	1.247 (6)	C16—H16C	0.9600
C4—C5	1.378 (6)	C18—H18A	0.9600
C4—C8	1.427 (6)	C18—H18B	0.9600
O5—C13	1.241 (5)	C18—H18C	0.9600
C5—C6	1.384 (6)	C19—H19A	0.9600
C5—H5	0.9300	C19—H19B	0.9600
O6—C14	1.249 (5)	C19—H19C	0.9600
O7—Zn1—O2	97.62 (12)	C17—O8—Zn1	135.4 (3)
O7—Zn1—O5	110.42 (13)	O2—C8—C9	122.9 (4)
O2—Zn1—O5	92.97 (12)	O2—C8—C4	116.8 (4)
O7—Zn1—O8	94.36 (13)	C9—C8—C4	120.3 (4)
O2—Zn1—O8	163.92 (12)	C8—C9—C7	117.5 (4)
O5—Zn1—O8	92.86 (13)	C8—C9—C10	122.2 (4)
O7—Zn1—O3	120.19 (13)	C7—C9—C10	120.3 (4)
O2—Zn1—O3	83.31 (12)	O3—C10—C9	123.8 (4)
O5—Zn1—O3	129.32 (13)	O3—C10—C11	115.2 (4)
O8—Zn1—O3	81.39 (13)	C9—C10—C11	121.0 (4)
C1—O1—Zn2	125.6 (3)	C10—C11—H11A	109.5
C3—N1—C4	121.8 (4)	C10—C11—H11B	109.5
C3—N1—Zn2	123.9 (3)	H11A—C11—H11B	109.5
C4—N1—Zn2	114.2 (3)	C10—C11—H11C	109.5
O1—C1—C2	126.5 (4)	H11A—C11—H11C	109.5
O1—C1—H1	116.7	H11B—C11—H11C	109.5
C2—C1—H1	116.7	C13—C12—H12A	109.5
O4—Zn2—O6	109.83 (13)	C13—C12—H12B	109.5
O4—Zn2—O1	93.61 (14)	H12A—C12—H12B	109.5
O6—Zn2—O1	92.73 (13)	C13—C12—H12C	109.5
O4—Zn2—N1	124.52 (13)	H12A—C12—H12C	109.5
O6—Zn2—N1	125.10 (13)	H12B—C12—H12C	109.5
O1—Zn2—N1	91.22 (14)	O5—C13—O4	127.2 (5)
O4—Zn2—O2	91.95 (13)	O5—C13—C12	116.4 (5)
O6—Zn2—O2	93.35 (12)	O4—C13—C12	116.5 (5)
O1—Zn2—O2	169.87 (12)	O7—C14—O6	127.0 (4)
N1—Zn2—O2	78.65 (13)	O7—C14—C15	116.8 (4)
C8—O2—Zn1	134.3 (3)	O6—C14—C15	116.2 (5)
C8—O2—Zn2	115.5 (3)	C14—C15—H15A	109.5
Zn1—O2—Zn2	109.40 (13)	C14—C15—H15B	109.5
C17—N2—C18	124.7 (5)	H15A—C15—H15B	109.5
C17—N2—C19	119.1 (4)	C14—C15—H15C	109.5
C18—N2—C19	116.2 (5)	H15A—C15—H15C	109.5
C1—C2—C3	126.4 (4)	H15B—C15—H15C	109.5
C1—C2—Br1	116.3 (3)	C17—C16—H16A	109.5
C3—C2—Br1	117.2 (3)	C17—C16—H16B	109.5
C10—O3—Zn1	133.3 (3)	H16A—C16—H16B	109.5
N1—C3—C2	125.9 (4)	C17—C16—H16C	109.5
N1—C3—H3	117.0	H16A—C16—H16C	109.5
C2—C3—H3	117.0	H16B—C16—H16C	109.5
C13—O4—Zn2	132.1 (3)	O8—C17—N2	119.5 (5)
C5—C4—N1	126.3 (4)	O8—C17—C16	120.8 (5)
C5—C4—C8	119.2 (4)	N2—C17—C16	119.7 (5)
N1—C4—C8	114.5 (3)	N2—C18—H18A	109.5
C13—O5—Zn1	132.0 (3)	N2—C18—H18B	109.5
C4—C5—C6	120.8 (5)	H18A—C18—H18B	109.5
C4—C5—H5	119.6	N2—C18—H18C	109.5
C6—C5—H5	119.6	H18A—C18—H18C	109.5
C14—O6—Zn2	134.0 (3)	H18B—C18—H18C	109.5
C7—C6—C5	121.0 (5)	N2—C19—H19A	109.5
C7—C6—H6	119.5	N2—C19—H19B	109.5
C5—C6—H6	119.5	H19A—C19—H19B	109.5
C14—O7—Zn1	130.1 (3)	N2—C19—H19C	109.5
C6—C7—C9	121.2 (4)	H19A—C19—H19C	109.5
C6—C7—H7	119.4	H19B—C19—H19C	109.5
C9—C7—H7	119.4
Zn2—O1—C1—C2	1.2 (7)	O2—C8—C9—C10	2.4 (6)
O1—C1—C2—C3	3.1 (7)	C4—C8—C9—C10	−177.2 (4)
O1—C1—C2—Br1	−179.4 (4)	C6—C7—C9—C8	−1.0 (6)
C4—N1—C3—C2	177.8 (4)	C6—C7—C9—C10	177.9 (4)
Zn2—N1—C3—C2	−3.9 (6)	Zn1—O3—C10—C9	0.7 (6)
C1—C2—C3—N1	−1.5 (7)	Zn1—O3—C10—C11	179.9 (3)
Br1—C2—C3—N1	−179.0 (3)	C8—C9—C10—O3	−0.4 (6)
C3—N1—C4—C5	−5.8 (6)	C7—C9—C10—O3	−179.2 (4)
Zn2—N1—C4—C5	175.7 (3)	C8—C9—C10—C11	−179.7 (4)
C3—N1—C4—C8	175.8 (3)	C7—C9—C10—C11	1.5 (6)
Zn2—N1—C4—C8	−2.7 (4)	Zn1—O5—C13—O4	6.6 (8)
N1—C4—C5—C6	−178.3 (4)	Zn1—O5—C13—C12	−173.7 (3)
C8—C4—C5—C6	0.1 (7)	Zn2—O4—C13—O5	−6.0 (8)
C4—C5—C6—C7	0.5 (7)	Zn2—O4—C13—C12	174.3 (3)
C5—C6—C7—C9	−0.1 (7)	Zn1—O7—C14—O6	−7.1 (7)
Zn1—O2—C8—C9	−4.9 (6)	Zn1—O7—C14—C15	173.3 (3)
Zn2—O2—C8—C9	−173.5 (3)	Zn2—O6—C14—O7	6.3 (8)
Zn1—O2—C8—C4	174.7 (3)	Zn2—O6—C14—C15	−174.2 (3)
Zn2—O2—C8—C4	6.1 (4)	Zn1—O8—C17—N2	174.3 (3)
C5—C4—C8—O2	179.2 (4)	Zn1—O8—C17—C16	−7.0 (7)
N1—C4—C8—O2	−2.2 (5)	C18—N2—C17—O8	179.5 (5)
C5—C4—C8—C9	−1.2 (6)	C19—N2—C17—O8	0.7 (7)
N1—C4—C8—C9	177.4 (3)	C18—N2—C17—C16	0.7 (7)
O2—C8—C9—C7	−178.8 (4)	C19—N2—C17—C16	−178.0 (5)
C4—C8—C9—C7	1.6 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Br1^i	0.93	3.13	4.005 (5)	158
C11—H11A···Br1^ii	0.96	3.07	3.992 (5)	160
C16—H16A···O5	0.96	2.61	3.401 (6)	140
C18—H18B···Br1^iii	0.96	2.88	3.658 (7)	139
C19—H19B···O7^iv	0.96	2.63	3.563 (6)	165

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