A bi­pyridine-ligated zinc(II) complex with bridging flavonolate ligation: synthesis, characterization, and visible-light-induced CO release reactivity

Metal–flavonolate compounds are of significant current inter­est as synthetic models for quercetinase enzymes and as bioactive compounds of importance to human health. Zinc–3-hy­droxy­flavonolate compounds, including those of quercetin, kampferol, and morin, generally exhibit bidentate coordination to a single Zn^II center. The bi­pyridine-ligated zinc–flavonolate compound reported herein, namely bis­(μ-4-oxo-2-phenyl-4H-chromen-3-olato)-κ³O³:O³,O⁴;κ³O³,O⁴:O³-bis­[(2,2′-bi­pyridine-κ²N,N′)zinc(II)] bis­(perchlorate), {[Zn₂(C₁₅H₉O₃)₂(C₁₀H₈N₂)₂](ClO₄)₂}_n, (1), provides an unusual example of bridging 3-hy­droxy­flavonolate ligation in a dinuclear metal complex. The symmetry-related Zn^II centers of (1) exhibit a distorted octa­hedral geometry, with weak coordination of a perchlorate anion trans to the bridging deprotonated O atom of the flavonolate ligand. Variable-concentration conductivity measurements provide evidence that, when (1) is dissolved in CH₃CN, the complex dissociates into monomers. ¹H NMR resonances for (1) dissolved in d₆-DMSO were assigned via HMQC to the H atoms of the flavonolate and bi­pyridine ligands. In CH₃CN, (1) undergoes qu­anti­tative visible-light-induced CO release with a quantum yield [0.004 (1)] similar to that exhibited by other mononuclear zinc–3-hy­droxy­flavonolate complexes. Mass spectroscopic identification of the [(bpy)₂Zn(O-benzoyl­salicylate)]⁺ ion provides evidence of CO release from the flavonol and of ligand exchange at the Zn^II center.

Computing details

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997) and SIR97 (Altomare et al., 1999); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis(µ-4-oxo-2-phenyl-4H-chromen-3-olato)-κ³O³:O³,O⁴;κ³O³,O⁴:O³-bis[(2,2'-bipyridine-κ²N,N')zinc(II)] bis(perchlorate)

Crystal data

[Zn2(C15H9O3)2(C10H8N2)2](ClO4)2	F(000) = 1136
Mr = 1116.45	Dx = 1.622 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.6003 (2) Å	Cell parameters from 5179 reflections
b = 14.0573 (3) Å	θ = 1.0–27.5°
c = 15.8141 (2) Å	µ = 1.24 mm^−1
β = 104.0158 (10)°	T = 150 K
V = 2286.33 (7) Å^3	Prism, yellow
Z = 2	0.28 × 0.25 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer	4417 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
Phi and ω scan	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −13→13
Tmin = 0.722, Tmax = 0.789	k = −16→18
8971 measured reflections	l = −20→20
5225 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.038P)^2 + 2.5961P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
5225 reflections	Δρmax = 1.06 e Å^−3
341 parameters	Δρmin = −0.51 e Å^−3
28 restraints

Special details

Experimental. The program Denzo-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL-97 input file.

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	0.63071 (2)	0.45723 (2)	0.49175 (2)	0.02410 (9)
O1	0.50997 (14)	0.44202 (10)	0.57399 (9)	0.0211 (3)
O2	0.54863 (16)	0.33113 (11)	0.44544 (10)	0.0281 (3)
O3	0.36814 (17)	0.21939 (11)	0.62159 (10)	0.0299 (4)
N1	0.76003 (18)	0.47018 (13)	0.41398 (12)	0.0234 (4)
N2	0.75846 (17)	0.55667 (13)	0.56275 (11)	0.0216 (4)
C1	0.4701 (2)	0.35118 (15)	0.57078 (13)	0.0215 (4)
C2	0.4885 (2)	0.29575 (15)	0.49750 (14)	0.0238 (4)
C3	0.4322 (2)	0.20209 (16)	0.48603 (15)	0.0274 (5)
C4	0.4304 (3)	0.14514 (17)	0.41248 (16)	0.0339 (5)
H4	0.4686	0.1678	0.3679	0.041*
C5	0.3734 (3)	0.05677 (19)	0.40522 (18)	0.0410 (6)
H5	0.3722	0.0185	0.3555	0.049*
C6	0.3169 (3)	0.02282 (19)	0.47094 (19)	0.0421 (6)
H6	0.2794	−0.0389	0.4659	0.050*
C7	0.3152 (3)	0.07794 (19)	0.54257 (17)	0.0389 (6)
H7	0.2757	0.0553	0.5866	0.047*
C8	0.3727 (2)	0.16787 (17)	0.54928 (15)	0.0296 (5)
C9	0.4154 (2)	0.31063 (15)	0.63192 (14)	0.0240 (4)
C10	0.4020 (2)	0.35302 (16)	0.71466 (14)	0.0262 (5)
C11	0.4834 (3)	0.42693 (18)	0.75412 (15)	0.0323 (5)
H11	0.5430	0.4544	0.7249	0.039*
C12	0.4778 (3)	0.46066 (19)	0.83612 (16)	0.0382 (6)
H12	0.5327	0.5114	0.8622	0.046*
C13	0.3928 (3)	0.4203 (2)	0.87918 (16)	0.0409 (6)
H13	0.3919	0.4415	0.9361	0.049*
C14	0.3090 (3)	0.3495 (2)	0.84028 (17)	0.0398 (6)
H14	0.2492	0.3232	0.8699	0.048*
C15	0.3115 (2)	0.31615 (18)	0.75770 (16)	0.0310 (5)
H15	0.2519	0.2684	0.7306	0.037*
C16	0.7600 (2)	0.41937 (18)	0.34236 (16)	0.0319 (5)
H16	0.6993	0.3689	0.3263	0.038*
C17	0.8460 (3)	0.43842 (19)	0.29110 (16)	0.0356 (6)
H17	0.8446	0.4014	0.2407	0.043*
C18	0.9335 (2)	0.51187 (19)	0.31430 (16)	0.0327 (5)
H18	0.9930	0.5263	0.2798	0.039*
C19	0.9338 (2)	0.56433 (17)	0.38805 (15)	0.0275 (5)
H19	0.9936	0.6151	0.4051	0.033*
C20	0.8458 (2)	0.54196 (15)	0.43692 (13)	0.0206 (4)
C21	0.8386 (2)	0.59469 (16)	0.51706 (13)	0.0209 (4)
C22	0.9060 (2)	0.67780 (18)	0.54329 (15)	0.0287 (5)
H22	0.9606	0.7045	0.5099	0.034*
C23	0.8929 (2)	0.72163 (19)	0.61922 (16)	0.0353 (6)
H23	0.9373	0.7795	0.6378	0.042*
C24	0.8148 (2)	0.68084 (19)	0.66787 (15)	0.0344 (6)
H24	0.8073	0.7087	0.7212	0.041*
C25	0.7484 (2)	0.59883 (18)	0.63707 (14)	0.0286 (5)
H25	0.6934	0.5710	0.6696	0.034*
Cl1A	0.8773 (6)	0.2224 (3)	0.6510 (4)	0.0346 (2)	0.176 (2)
O4A	0.8000 (14)	0.1459 (9)	0.6684 (9)	0.0532 (7)	0.176 (2)
O5A	0.8154 (13)	0.3096 (9)	0.6666 (13)	0.0697 (9)	0.176 (2)
O6A	0.9914 (17)	0.2401 (16)	0.7179 (12)	0.0824 (12)	0.176 (2)
O7A	0.9252 (19)	0.204 (2)	0.5791 (11)	0.0714 (13)	0.176 (2)
Cl1	0.82388 (10)	0.24761 (7)	0.62407 (6)	0.0346 (2)	0.824 (2)
O4	0.7164 (3)	0.18804 (19)	0.63012 (18)	0.0532 (7)	0.824 (2)
O5	0.7794 (3)	0.3426 (2)	0.6089 (3)	0.0697 (9)	0.824 (2)
O6	0.9246 (4)	0.2448 (3)	0.7016 (2)	0.0824 (12)	0.824 (2)
O7	0.8706 (3)	0.2153 (4)	0.5529 (2)	0.0714 (13)	0.824 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02362 (14)	0.01885 (14)	0.03314 (15)	−0.00616 (10)	0.01330 (10)	−0.00421 (10)
O1	0.0244 (7)	0.0154 (7)	0.0250 (7)	−0.0041 (6)	0.0088 (6)	0.0008 (6)
O2	0.0371 (9)	0.0208 (8)	0.0307 (8)	−0.0088 (7)	0.0166 (7)	−0.0038 (6)
O3	0.0450 (10)	0.0189 (8)	0.0281 (8)	−0.0085 (7)	0.0135 (7)	0.0042 (6)
N1	0.0225 (9)	0.0212 (9)	0.0277 (9)	0.0006 (7)	0.0083 (7)	−0.0030 (7)
N2	0.0215 (9)	0.0224 (9)	0.0217 (8)	−0.0049 (7)	0.0066 (7)	0.0011 (7)
C1	0.0237 (10)	0.0169 (10)	0.0235 (10)	−0.0007 (8)	0.0051 (8)	0.0030 (8)
C2	0.0280 (11)	0.0191 (11)	0.0247 (10)	−0.0028 (9)	0.0073 (9)	0.0021 (8)
C3	0.0330 (12)	0.0185 (11)	0.0306 (11)	−0.0053 (9)	0.0076 (9)	0.0007 (9)
C4	0.0425 (14)	0.0242 (12)	0.0372 (13)	−0.0076 (11)	0.0140 (11)	−0.0047 (10)
C5	0.0532 (17)	0.0270 (14)	0.0439 (15)	−0.0112 (12)	0.0141 (13)	−0.0108 (11)
C6	0.0549 (17)	0.0228 (13)	0.0485 (15)	−0.0158 (12)	0.0127 (13)	−0.0018 (11)
C7	0.0546 (16)	0.0255 (13)	0.0383 (13)	−0.0153 (12)	0.0146 (12)	0.0042 (11)
C8	0.0387 (13)	0.0201 (11)	0.0296 (12)	−0.0055 (10)	0.0077 (10)	0.0017 (9)
C9	0.0292 (11)	0.0167 (10)	0.0256 (10)	−0.0014 (9)	0.0061 (9)	0.0040 (8)
C10	0.0328 (12)	0.0223 (11)	0.0238 (10)	0.0070 (9)	0.0075 (9)	0.0083 (9)
C11	0.0426 (14)	0.0282 (12)	0.0254 (11)	0.0015 (11)	0.0066 (10)	0.0042 (9)
C12	0.0497 (16)	0.0329 (14)	0.0287 (12)	0.0109 (12)	0.0031 (11)	−0.0008 (10)
C13	0.0493 (16)	0.0460 (16)	0.0277 (12)	0.0247 (14)	0.0101 (11)	0.0028 (11)
C14	0.0409 (14)	0.0472 (16)	0.0381 (13)	0.0206 (13)	0.0227 (12)	0.0125 (12)
C15	0.0311 (12)	0.0299 (13)	0.0342 (12)	0.0093 (10)	0.0121 (10)	0.0090 (10)
C16	0.0337 (12)	0.0265 (12)	0.0363 (12)	0.0025 (10)	0.0100 (10)	−0.0094 (10)
C17	0.0411 (14)	0.0385 (15)	0.0297 (12)	0.0115 (11)	0.0138 (11)	−0.0055 (10)
C18	0.0322 (12)	0.0389 (14)	0.0319 (12)	0.0097 (11)	0.0172 (10)	0.0064 (10)
C19	0.0235 (11)	0.0315 (13)	0.0288 (11)	0.0012 (9)	0.0089 (9)	0.0062 (9)
C20	0.0198 (10)	0.0195 (10)	0.0227 (10)	0.0022 (8)	0.0055 (8)	0.0029 (8)
C21	0.0195 (10)	0.0225 (11)	0.0208 (9)	−0.0015 (8)	0.0051 (8)	0.0040 (8)
C22	0.0266 (11)	0.0310 (13)	0.0285 (11)	−0.0095 (10)	0.0071 (9)	0.0000 (10)
C23	0.0347 (13)	0.0357 (14)	0.0341 (13)	−0.0144 (11)	0.0055 (10)	−0.0108 (11)
C24	0.0354 (13)	0.0420 (15)	0.0259 (11)	−0.0061 (11)	0.0077 (10)	−0.0100 (10)
C25	0.0283 (11)	0.0354 (13)	0.0239 (10)	−0.0051 (10)	0.0096 (9)	−0.0005 (9)
Cl1A	0.0377 (5)	0.0353 (5)	0.0355 (5)	−0.0105 (4)	0.0178 (4)	−0.0056 (3)
O4A	0.0634 (18)	0.0483 (16)	0.0586 (16)	−0.0300 (13)	0.0354 (14)	−0.0149 (12)
O5A	0.0449 (16)	0.0405 (16)	0.117 (3)	−0.0064 (13)	0.0076 (17)	0.0004 (17)
O6A	0.080 (3)	0.089 (2)	0.059 (2)	−0.026 (3)	−0.021 (2)	0.0048 (18)
O7A	0.078 (3)	0.085 (2)	0.070 (2)	−0.025 (3)	0.054 (2)	−0.027 (2)
Cl1	0.0377 (5)	0.0353 (5)	0.0355 (5)	−0.0105 (4)	0.0178 (4)	−0.0056 (3)
O4	0.0634 (18)	0.0483 (16)	0.0586 (16)	−0.0300 (13)	0.0354 (14)	−0.0149 (12)
O5	0.0449 (16)	0.0405 (16)	0.117 (3)	−0.0064 (13)	0.0076 (17)	0.0004 (17)
O6	0.080 (3)	0.089 (2)	0.059 (2)	−0.026 (3)	−0.021 (2)	0.0048 (18)
O7	0.078 (3)	0.085 (2)	0.070 (2)	−0.025 (3)	0.054 (2)	−0.027 (2)

Geometric parameters (Å, º)

Zn1—O1	2.0448 (14)	C12—H12	0.9500
Zn1—O2	2.0315 (16)	C12—C13	1.377 (4)
Zn1—O1^i	2.1353 (15)	C13—H13	0.9500
Zn1—N1	2.0595 (18)	C13—C14	1.376 (4)
Zn1—N2	2.0765 (18)	C14—H14	0.9500
Zn1—Zn1^i	3.0891 (5)	C14—C15	1.394 (4)
O1—Zn1^i	2.1352 (15)	C15—H15	0.9500
O1—C1	1.342 (3)	C16—H16	0.9500
O2—C2	1.259 (3)	C16—C17	1.385 (3)
O3—C8	1.364 (3)	C17—H17	0.9500
O3—C9	1.372 (3)	C17—C18	1.377 (4)
N1—C16	1.339 (3)	C18—H18	0.9500
N1—C20	1.348 (3)	C18—C19	1.379 (3)
N2—C21	1.351 (3)	C19—H19	0.9500
N2—C25	1.343 (3)	C19—C20	1.384 (3)
C1—C2	1.448 (3)	C20—C21	1.486 (3)
C1—C9	1.367 (3)	C21—C22	1.380 (3)
C2—C3	1.439 (3)	C22—H22	0.9500
C3—C4	1.408 (3)	C22—C23	1.386 (3)
C3—C8	1.391 (3)	C23—H23	0.9500
C4—H4	0.9500	C23—C24	1.383 (3)
C4—C5	1.374 (3)	C24—H24	0.9500
C5—H5	0.9500	C24—C25	1.377 (3)
C5—C6	1.403 (4)	C25—H25	0.9500
C6—H6	0.9500	Cl1A—O4A	1.419 (10)
C6—C7	1.376 (4)	Cl1A—O5A	1.440 (11)
C7—H7	0.9500	Cl1A—O6A	1.422 (11)
C7—C8	1.396 (3)	Cl1A—O7A	1.377 (13)
C9—C10	1.476 (3)	Cl1—O4	1.436 (2)
C10—C11	1.398 (3)	Cl1—O5	1.417 (3)
C10—C15	1.403 (3)	Cl1—O6	1.418 (3)
C11—H11	0.9500	Cl1—O7	1.410 (3)
C11—C12	1.395 (3)
O2—Zn1—O1	81.87 (6)	C10—C11—H11	119.8
O2—Zn1—N1	98.67 (7)	C12—C11—C10	120.5 (2)
O1—Zn1—N1	177.08 (7)	C12—C11—H11	119.8
O2—Zn1—N2	161.55 (7)	C11—C12—H12	120.0
O1—Zn1—N2	98.81 (6)	C13—C12—C11	120.0 (3)
N1—Zn1—N2	79.76 (7)	C13—C12—H12	120.0
O2—Zn1—O1^i	102.45 (6)	C12—C13—H13	119.8
O1—Zn1—O1^i	84.73 (6)	C14—C13—C12	120.4 (2)
N1—Zn1—O1^i	97.93 (6)	C14—C13—H13	119.8
N2—Zn1—O1^i	95.96 (6)	C13—C14—H14	119.8
O1—Zn1—Zn1^i	43.49 (4)	C13—C14—C15	120.4 (2)
O1^i—Zn1—Zn1^i	41.23 (4)	C15—C14—H14	119.8
O1—Zn1—N2	98.81 (6)	C10—C15—H15	120.0
O2—Zn1—Zn1^i	93.18 (5)	C14—C15—C10	120.0 (3)
N1—Zn1—Zn1^i	139.15 (5)	C14—C15—H15	120.0
N2—Zn1—Zn1^i	99.97 (5)	N1—C16—H16	119.1
Zn1—O1—Zn1^i	95.27 (6)	N1—C16—C17	121.8 (2)
C1—O1—Zn1	108.39 (12)	C17—C16—H16	119.1
C1—O1—Zn1^i	115.85 (13)	C16—C17—H17	120.5
C2—O2—Zn1	110.45 (14)	C18—C17—C16	119.0 (2)
C8—O3—C9	120.67 (17)	C18—C17—H17	120.5
C16—N1—Zn1	126.44 (16)	C17—C18—H18	120.3
C16—N1—C20	119.29 (19)	C17—C18—C19	119.3 (2)
C20—N1—Zn1	114.12 (14)	C19—C18—H18	120.3
C21—N2—Zn1	112.90 (14)	C18—C19—H19	120.4
C25—N2—Zn1	126.19 (15)	C18—C19—C20	119.1 (2)
C25—N2—C21	119.11 (19)	C20—C19—H19	120.4
O1—C1—C2	116.09 (18)	N1—C20—C19	121.5 (2)
O1—C1—C9	123.63 (19)	N1—C20—C21	115.60 (18)
C9—C1—C2	120.3 (2)	C19—C20—C21	122.9 (2)
O2—C2—C1	119.88 (19)	N2—C21—C20	115.31 (18)
O2—C2—C3	122.6 (2)	N2—C21—C22	121.4 (2)
C3—C2—C1	117.46 (19)	C22—C21—C20	123.26 (19)
C4—C3—C2	123.1 (2)	C21—C22—H22	120.6
C8—C3—C2	118.2 (2)	C21—C22—C23	118.9 (2)
C8—C3—C4	118.6 (2)	C23—C22—H22	120.6
C3—C4—H4	120.0	C22—C23—H23	120.1
C5—C4—C3	120.1 (2)	C24—C23—C22	119.8 (2)
C5—C4—H4	120.0	C24—C23—H23	120.1
C4—C5—H5	119.9	C23—C24—H24	120.9
C4—C5—C6	120.2 (2)	C25—C24—C23	118.3 (2)
C6—C5—H5	119.9	C25—C24—H24	120.9
C5—C6—H6	119.6	N2—C25—C24	122.5 (2)
C7—C6—C5	120.7 (2)	N2—C25—H25	118.8
C7—C6—H6	119.6	C24—C25—H25	118.8
C6—C7—H7	120.7	O4A—Cl1A—O5A	107.6 (9)
C6—C7—C8	118.7 (2)	O4A—Cl1A—O6A	114.5 (11)
C8—C7—H7	120.7	O6A—Cl1A—O5A	93.7 (12)
O3—C8—C3	122.2 (2)	O7A—Cl1A—O4A	111.2 (13)
O3—C8—C7	116.2 (2)	O7A—Cl1A—O5A	125.4 (15)
C3—C8—C7	121.6 (2)	O7A—Cl1A—O6A	103.3 (14)
O3—C9—C10	111.86 (18)	O5—Cl1—O4	108.93 (18)
C1—C9—O3	120.71 (19)	O5—Cl1—O6	108.8 (2)
C1—C9—C10	127.4 (2)	O6—Cl1—O4	111.7 (2)
C11—C10—C9	121.0 (2)	O7—Cl1—O4	107.7 (2)
C11—C10—C15	118.6 (2)	O7—Cl1—O5	109.6 (3)
C15—C10—C9	120.3 (2)	O7—Cl1—O6	110.2 (2)
Zn1^i—O1—C1—C2	89.22 (19)	C4—C5—C6—C7	1.4 (5)
Zn1—O1—C1—C2	−16.4 (2)	C5—C6—C7—C8	−1.0 (4)
Zn1^i—O1—C1—C9	−91.0 (2)	C6—C7—C8—O3	180.0 (2)
Zn1—O1—C1—C9	163.38 (18)	C6—C7—C8—C3	−0.6 (4)
Zn1—O2—C2—C1	8.7 (3)	C8—O3—C9—C1	−1.2 (3)
Zn1—O2—C2—C3	−173.41 (18)	C8—O3—C9—C10	−179.5 (2)
Zn1—N1—C16—C17	175.30 (18)	C8—C3—C4—C5	−1.5 (4)
Zn1—N1—C20—C19	−175.72 (16)	C9—O3—C8—C3	4.3 (3)
Zn1—N1—C20—C21	4.0 (2)	C9—O3—C8—C7	−176.3 (2)
Zn1—N2—C21—C20	−15.7 (2)	C9—C1—C2—O2	−174.1 (2)
Zn1—N2—C21—C22	163.08 (17)	C9—C1—C2—C3	7.9 (3)
Zn1—N2—C25—C24	−162.27 (19)	C9—C10—C11—C12	−174.2 (2)
O1—C1—C2—O2	5.6 (3)	C9—C10—C15—C14	173.0 (2)
O1—C1—C2—C3	−172.35 (19)	C10—C11—C12—C13	0.8 (4)
O1—C1—C9—O3	175.31 (19)	C11—C10—C15—C14	−3.6 (3)
O1—C1—C9—C10	−6.6 (4)	C11—C12—C13—C14	−2.8 (4)
O2—C2—C3—C4	−5.2 (4)	C12—C13—C14—C15	1.6 (4)
O2—C2—C3—C8	177.2 (2)	C13—C14—C15—C10	1.6 (4)
O3—C9—C10—C11	155.6 (2)	C15—C10—C11—C12	2.4 (3)
O3—C9—C10—C15	−20.9 (3)	C16—N1—C20—C19	0.0 (3)
N1—C16—C17—C18	−0.3 (4)	C16—N1—C20—C21	179.8 (2)
N1—C20—C21—N2	8.0 (3)	C16—C17—C18—C19	0.3 (4)
N1—C20—C21—C22	−170.8 (2)	C17—C18—C19—C20	−0.2 (4)
N2—C21—C22—C23	1.4 (3)	C18—C19—C20—N1	0.0 (3)
C1—C2—C3—C4	172.7 (2)	C18—C19—C20—C21	−179.7 (2)
C1—C2—C3—C8	−4.9 (3)	C19—C20—C21—N2	−172.3 (2)
C1—C9—C10—C11	−22.6 (4)	C19—C20—C21—C22	9.0 (3)
C1—C9—C10—C15	160.9 (2)	C20—N1—C16—C17	0.1 (3)
C2—C1—C9—O3	−5.0 (3)	C20—C21—C22—C23	−179.9 (2)
C2—C1—C9—C10	173.1 (2)	C21—N2—C25—C24	1.4 (3)
C2—C3—C4—C5	−179.1 (2)	C21—C22—C23—C24	1.1 (4)
C2—C3—C8—O3	−1.0 (4)	C22—C23—C24—C25	−2.3 (4)
C2—C3—C8—C7	179.6 (2)	C23—C24—C25—N2	1.1 (4)
C3—C4—C5—C6	−0.1 (4)	C25—N2—C21—C20	178.60 (19)
C4—C3—C8—O3	−178.7 (2)	C25—N2—C21—C22	−2.6 (3)
C4—C3—C8—C7	1.9 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.