Synthesis, crystal structure and biological properties of a fluoro­phore-labelled mixed-ligand copper(II) complex incorporating N-hy­droxy­naph­tha­lene-1,8-di­car­box­imide

The mixed-ligand fluoro­phore-labelled copper(II) complex aqua­[2,4-dioxo-3-aza­tri­cyclo­[7.3.1.0^5,13]trideca-1(12),5,7,9(13),10-pentaen-3-olato-κ²O²,O³](1,10-phenanthroline-κ²N,N′)copper(II) nitrate, [Cu(C₁₂H₆NO₃)(C₁₂H₈N₂)(H₂O)]NO₃·CH₃OH or [Cu(L)(phen)(H₂O)]NO₃·CH₃OH (where phen is 1,10-phen­anthroline and HL is N-hy­droxy­naph­tha­lene-1,8-di­car­box­imide), (1), was synthesized and structurally characterized. The structure of (1) was confirmed by single-crystal X-ray structure determination. The complex crystallized in the triclinic space group P. The geometry around the copper centre is distorted square pyramidal, with the apical position occupied by a water mol­ecule. The complex is highly fluorescent in organic and aqueous solutions. It has good anti­cancer activity, with an IC₅₀ value of 17 µM, which is almost five times greater than cis­platin (IC₅₀ = 82 µM) under identical experimental conditions.

Computing details

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015) and SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Aqua[2,4-dioxo-3-azatricyclo[7.3.1.0^5,13]trideca-1(12),5,7,9(13),10-pentaen-3-olato-κO²,O³](1,10-phenanthroline-κN,N')copper(II) nitrate methanol monosolvate

Crystal data

[Cu(C12H6NO3)(C12H8N2)(H2O)]NO3·CH4O	Z = 2
Mr = 567.99	F(000) = 582
Triclinic, P1	Dx = 1.649 Mg m^−3
a = 10.4795 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.1326 (4) Å	Cell parameters from 6405 reflections
c = 12.1768 (7) Å	θ = 2.2–27.8°
α = 101.393 (3)°	µ = 1.02 mm^−1
β = 105.793 (3)°	T = 296 K
γ = 115.958 (2)°	Block, clear dark blue
V = 1143.78 (9) Å^3	0.23 × 0.21 × 0.2 mm

Data collection

Bruker SMART X2S benchtop diffractometer	5312 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
φ and ω scans	θmax = 31.9°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −15→15
Tmin = 0.618, Tmax = 0.746	k = −16→16
27013 measured reflections	l = −18→17
7598 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.0591P)^2 + 0.0324P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.116	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.51 e Å^−3
7598 reflections	Δρmin = −0.52 e Å^−3
424 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0026 (8)
Primary atom site location: iterative

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. Single crystal data of complex (1) was collected on a Bruker SMART X2S benchtop crystallographic system. Intensity measurements were performed using monochromated (doubly curved silicon crystal) Mo Kα radiation (λ = 0.71073 Å) from a sealed microfocus tube. Generator settings were 50 kV, 1 mA. APEX2 software was used for preliminary determination of the unit cell. Determination of integrated intensities and unit cell refinement were performed using SAINT (Bruker, 2010). Data were corrected for absorption effects with SADABS (Bruker, 2010) using the multiscan technique. The structure was resolved on Olex2.0 (Dolomanov et al., 2009) package using ShelxT (Sheldrick, 2015a) and refined by full-matrix least squares based on F², using ShelexL (Sheldrick, 2015b). Crystal data, data collection and structurerefinementdetails for complex (1) were summarized in Table1. All non-H atoms were refined anisotropically.

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

	x	y	z	Uiso*/Ueq
Cu1	0.64849 (3)	0.47282 (2)	0.09574 (2)	0.03270 (9)
O2	0.60399 (16)	0.59194 (13)	0.20029 (13)	0.0378 (3)
O1	0.82505 (16)	0.65190 (13)	0.12556 (13)	0.0378 (3)
O3	1.05760 (17)	0.92025 (15)	0.20820 (14)	0.0444 (3)
N3	0.83009 (18)	0.75864 (15)	0.20769 (14)	0.0300 (3)
O4	0.7782 (2)	0.4286 (2)	0.25361 (19)	0.0527 (4)
N1	0.67338 (18)	0.35070 (16)	−0.02946 (14)	0.0313 (3)
N2	0.44867 (18)	0.29220 (16)	0.04833 (14)	0.0314 (3)
N4	1.1322 (2)	0.4470 (2)	0.26569 (18)	0.0502 (5)
O6	1.2572 (2)	0.4545 (2)	0.2942 (2)	0.0767 (6)
C13	0.7114 (2)	0.72106 (19)	0.24422 (16)	0.0296 (4)
C11	0.4391 (2)	0.17856 (18)	−0.02764 (15)	0.0292 (4)
O7	1.1117 (3)	0.5264 (2)	0.33672 (19)	0.0781 (6)
C12	0.5604 (2)	0.21025 (18)	−0.06963 (16)	0.0295 (4)
C24	0.8370 (2)	0.97461 (19)	0.37522 (16)	0.0301 (4)
C14	0.7135 (2)	0.83134 (19)	0.33304 (16)	0.0302 (4)
C4	0.5598 (2)	0.1002 (2)	−0.14860 (16)	0.0335 (4)
C22	0.9561 (2)	1.01076 (19)	0.33264 (16)	0.0311 (4)
O5	1.0225 (3)	0.3588 (2)	0.16730 (19)	0.0938 (8)
C23	0.9582 (2)	0.89902 (19)	0.24617 (17)	0.0310 (4)
C7	0.3184 (2)	0.03686 (19)	−0.06388 (17)	0.0342 (4)
C10	0.3371 (2)	0.2677 (2)	0.08843 (18)	0.0378 (4)
C18	0.8392 (2)	1.0827 (2)	0.46117 (17)	0.0370 (4)
C1	0.7878 (2)	0.3845 (2)	−0.06660 (19)	0.0394 (4)
C15	0.5978 (3)	0.7963 (2)	0.37510 (19)	0.0380 (4)
C3	0.6844 (3)	0.1400 (2)	−0.18313 (19)	0.0419 (5)
C21	1.0734 (3)	1.1519 (2)	0.3729 (2)	0.0409 (5)
C19	0.9624 (3)	1.2259 (2)	0.5010 (2)	0.0465 (5)
C5	0.4337 (3)	−0.0446 (2)	−0.18556 (19)	0.0413 (5)
C6	0.3202 (3)	−0.0743 (2)	−0.14541 (19)	0.0406 (5)
C8	0.2061 (2)	0.0145 (2)	−0.0164 (2)	0.0423 (5)
C9	0.2157 (3)	0.1295 (2)	0.0591 (2)	0.0450 (5)
C17	0.7203 (3)	1.0430 (2)	0.5032 (2)	0.0443 (5)
C2	0.7980 (3)	0.2812 (2)	−0.1430 (2)	0.0446 (5)
C16	0.6031 (3)	0.9044 (3)	0.4617 (2)	0.0456 (5)
C20	1.0754 (3)	1.2593 (2)	0.4568 (2)	0.0488 (6)
O8	0.6589 (3)	0.3415 (2)	0.42340 (19)	0.0636 (5)
C25	0.5354 (4)	0.3651 (4)	0.4039 (3)	0.0671 (7)
H9	0.146 (3)	0.119 (2)	0.094 (2)	0.039 (6)*
H1	0.863 (2)	0.483 (2)	−0.0347 (18)	0.035 (5)*
H16	0.535 (3)	0.881 (2)	0.489 (2)	0.035 (6)*
H21	1.147 (3)	1.171 (2)	0.3417 (19)	0.035 (6)*
H3	0.691 (3)	0.076 (3)	−0.229 (2)	0.052 (7)*
H2	0.885 (3)	0.309 (2)	−0.165 (2)	0.051 (7)*
H10	0.347 (3)	0.345 (2)	0.141 (2)	0.041 (6)*
H17	0.713 (3)	1.106 (3)	0.558 (2)	0.054 (7)*
H8	0.131 (3)	−0.073 (3)	−0.035 (3)	0.069 (8)*
H15	0.513 (3)	0.705 (3)	0.346 (2)	0.048 (7)*
H25A	0.554 (4)	0.439 (4)	0.366 (3)	0.097 (11)*
H6	0.242 (3)	−0.168 (3)	−0.163 (2)	0.053 (7)*
H20	1.147 (4)	1.358 (3)	0.480 (3)	0.081 (9)*
H5	0.437 (3)	−0.117 (3)	−0.240 (2)	0.059 (7)*
H19	0.959 (3)	1.284 (3)	0.556 (2)	0.061 (8)*
H25B	0.436 (4)	0.283 (4)	0.345 (3)	0.098 (11)*
H25C	0.513 (4)	0.385 (4)	0.475 (3)	0.095 (11)*
H8A	0.712 (3)	0.372 (3)	0.492 (3)	0.068 (10)*
H4A	0.769 (3)	0.410 (3)	0.308 (2)	0.041 (7)*
H4B	0.845 (3)	0.443 (3)	0.257 (3)	0.042 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03265 (14)	0.02420 (12)	0.03814 (14)	0.01289 (9)	0.01809 (10)	0.00498 (9)
O2	0.0349 (7)	0.0276 (6)	0.0519 (8)	0.0143 (6)	0.0258 (6)	0.0097 (6)
O1	0.0407 (8)	0.0268 (6)	0.0485 (8)	0.0169 (6)	0.0281 (6)	0.0063 (5)
O3	0.0376 (8)	0.0369 (7)	0.0583 (9)	0.0159 (6)	0.0296 (7)	0.0112 (6)
N3	0.0321 (8)	0.0254 (7)	0.0349 (8)	0.0154 (6)	0.0184 (6)	0.0080 (6)
O4	0.0438 (11)	0.0670 (12)	0.0522 (11)	0.0299 (9)	0.0220 (9)	0.0250 (9)
N1	0.0318 (8)	0.0275 (7)	0.0338 (8)	0.0146 (6)	0.0161 (6)	0.0081 (6)
N2	0.0285 (7)	0.0313 (7)	0.0306 (7)	0.0136 (6)	0.0129 (6)	0.0076 (6)
N4	0.0464 (11)	0.0515 (11)	0.0468 (11)	0.0189 (9)	0.0219 (9)	0.0189 (9)
O6	0.0591 (12)	0.0926 (15)	0.0833 (14)	0.0443 (12)	0.0350 (11)	0.0218 (11)
C13	0.0312 (9)	0.0288 (8)	0.0318 (8)	0.0175 (7)	0.0148 (7)	0.0097 (7)
C11	0.0272 (8)	0.0276 (8)	0.0273 (8)	0.0123 (7)	0.0085 (7)	0.0077 (6)
O7	0.0967 (16)	0.0973 (16)	0.0668 (12)	0.0713 (14)	0.0359 (11)	0.0263 (11)
C12	0.0318 (9)	0.0272 (8)	0.0280 (8)	0.0158 (7)	0.0108 (7)	0.0079 (6)
C24	0.0347 (9)	0.0286 (8)	0.0289 (8)	0.0197 (7)	0.0111 (7)	0.0088 (7)
C14	0.0323 (9)	0.0311 (8)	0.0321 (9)	0.0196 (7)	0.0152 (7)	0.0106 (7)
C4	0.0382 (10)	0.0322 (9)	0.0291 (8)	0.0217 (8)	0.0100 (7)	0.0066 (7)
C22	0.0325 (9)	0.0276 (8)	0.0314 (9)	0.0160 (7)	0.0114 (7)	0.0085 (7)
O5	0.0658 (13)	0.0812 (14)	0.0640 (12)	−0.0015 (11)	0.0078 (11)	0.0156 (11)
C23	0.0310 (9)	0.0279 (8)	0.0343 (9)	0.0154 (7)	0.0139 (7)	0.0109 (7)
C7	0.0283 (9)	0.0296 (9)	0.0351 (9)	0.0119 (7)	0.0066 (7)	0.0101 (7)
C10	0.0306 (9)	0.0427 (11)	0.0354 (10)	0.0169 (8)	0.0150 (8)	0.0081 (8)
C18	0.0447 (11)	0.0374 (10)	0.0325 (9)	0.0269 (9)	0.0141 (8)	0.0081 (8)
C1	0.0377 (11)	0.0360 (10)	0.0418 (10)	0.0162 (9)	0.0209 (9)	0.0098 (8)
C15	0.0373 (10)	0.0410 (11)	0.0417 (10)	0.0235 (9)	0.0203 (9)	0.0129 (9)
C3	0.0494 (12)	0.0440 (11)	0.0363 (10)	0.0305 (10)	0.0185 (9)	0.0060 (9)
C21	0.0404 (11)	0.0311 (9)	0.0452 (11)	0.0153 (8)	0.0168 (9)	0.0111 (8)
C19	0.0574 (14)	0.0317 (10)	0.0435 (11)	0.0255 (10)	0.0155 (10)	0.0021 (9)
C5	0.0438 (11)	0.0289 (9)	0.0404 (10)	0.0197 (9)	0.0086 (9)	0.0023 (8)
C6	0.0370 (10)	0.0248 (9)	0.0430 (11)	0.0122 (8)	0.0053 (9)	0.0052 (8)
C8	0.0280 (10)	0.0381 (11)	0.0476 (12)	0.0095 (8)	0.0110 (9)	0.0155 (9)
C9	0.0313 (10)	0.0529 (13)	0.0473 (12)	0.0170 (9)	0.0202 (9)	0.0177 (10)
C17	0.0554 (13)	0.0465 (12)	0.0395 (10)	0.0352 (11)	0.0220 (10)	0.0075 (9)
C2	0.0435 (12)	0.0507 (12)	0.0464 (12)	0.0257 (10)	0.0274 (10)	0.0153 (10)
C16	0.0484 (13)	0.0562 (13)	0.0467 (12)	0.0337 (11)	0.0295 (10)	0.0165 (10)
C20	0.0524 (14)	0.0298 (10)	0.0500 (12)	0.0162 (10)	0.0159 (10)	0.0069 (9)
O8	0.0681 (13)	0.0665 (12)	0.0513 (11)	0.0357 (10)	0.0237 (10)	0.0115 (9)
C25	0.0637 (19)	0.080 (2)	0.0540 (16)	0.0337 (17)	0.0247 (14)	0.0257 (15)

Geometric parameters (Å, º)

Cu1—O2	1.9480 (13)	C7—C8	1.397 (3)
Cu1—O1	1.9102 (14)	C10—C9	1.391 (3)
Cu1—O4	2.307 (2)	C10—H10	0.91 (2)
Cu1—N1	1.9870 (15)	C18—C19	1.412 (3)
Cu1—N2	1.9897 (15)	C18—C17	1.401 (3)
O2—C13	1.254 (2)	C1—C2	1.392 (3)
O1—N3	1.3645 (18)	C1—H1	0.94 (2)
O3—C23	1.202 (2)	C15—C16	1.404 (3)
N3—C13	1.356 (2)	C15—H15	0.92 (2)
N3—C23	1.413 (2)	C3—C2	1.367 (3)
O4—H4A	0.75 (3)	C3—H3	0.85 (2)
O4—H4B	0.63 (3)	C21—C20	1.399 (3)
N1—C12	1.359 (2)	C21—H21	0.92 (2)
N1—C1	1.324 (3)	C19—C20	1.368 (4)
N2—C11	1.358 (2)	C19—H19	0.85 (3)
N2—C10	1.328 (3)	C5—C6	1.341 (3)
N4—O6	1.220 (3)	C5—H5	0.96 (3)
N4—O7	1.242 (3)	C6—H6	0.94 (3)
N4—O5	1.232 (3)	C8—C9	1.367 (3)
C13—C14	1.455 (2)	C8—H8	0.87 (3)
C11—C12	1.426 (3)	C9—H9	0.91 (2)
C11—C7	1.399 (2)	C17—C16	1.356 (3)
C12—C4	1.397 (2)	C17—H17	0.92 (3)
C24—C14	1.411 (3)	C2—H2	0.96 (3)
C24—C22	1.408 (3)	C16—H16	0.83 (2)
C24—C18	1.417 (2)	C20—H20	0.94 (3)
C14—C15	1.374 (3)	O8—C25	1.399 (4)
C4—C3	1.394 (3)	O8—H8A	0.77 (3)
C4—C5	1.439 (3)	C25—H25A	0.99 (4)
C22—C23	1.475 (2)	C25—H25B	0.97 (4)
C22—C21	1.377 (3)	C25—H25C	0.97 (4)
C7—C6	1.436 (3)
O2—Cu1—O4	94.28 (7)	C8—C7—C6	125.03 (17)
O2—Cu1—N1	172.42 (6)	N2—C10—C9	122.01 (19)
O2—Cu1—N2	94.60 (6)	N2—C10—H10	116.8 (14)
O1—Cu1—O2	84.06 (5)	C9—C10—H10	121.1 (14)
O1—Cu1—O4	94.95 (7)	C19—C18—C24	118.1 (2)
O1—Cu1—N1	97.09 (6)	C17—C18—C24	118.80 (19)
O1—Cu1—N2	172.46 (6)	C17—C18—C19	123.07 (18)
N1—Cu1—O4	93.08 (7)	N1—C1—C2	122.31 (19)
N1—Cu1—N2	83.28 (6)	N1—C1—H1	114.7 (13)
N2—Cu1—O4	92.55 (7)	C2—C1—H1	123.0 (13)
C13—O2—Cu1	111.09 (12)	C14—C15—C16	119.5 (2)
N3—O1—Cu1	108.65 (10)	C14—C15—H15	122.9 (15)
O1—N3—C23	116.88 (14)	C16—C15—H15	117.5 (16)
C13—N3—O1	117.31 (14)	C4—C3—H3	120.0 (17)
C13—N3—C23	125.81 (14)	C2—C3—C4	120.54 (18)
Cu1—O4—H4A	138 (2)	C2—C3—H3	119.4 (17)
Cu1—O4—H4B	113 (3)	C22—C21—C20	120.3 (2)
H4A—O4—H4B	109 (3)	C22—C21—H21	117.0 (13)
C12—N1—Cu1	111.23 (12)	C20—C21—H21	122.7 (14)
C1—N1—Cu1	129.78 (13)	C18—C19—H19	112.9 (19)
C1—N1—C12	118.58 (16)	C20—C19—C18	120.86 (19)
C11—N2—Cu1	111.38 (12)	C20—C19—H19	126.1 (19)
C10—N2—Cu1	129.86 (13)	C4—C5—H5	115.3 (16)
C10—N2—C11	118.40 (16)	C6—C5—C4	121.54 (18)
O6—N4—O7	120.5 (2)	C6—C5—H5	123.1 (16)
O6—N4—O5	121.1 (2)	C7—C6—H6	115.5 (16)
O5—N4—O7	118.4 (2)	C5—C6—C7	121.63 (18)
O2—C13—N3	118.53 (15)	C5—C6—H6	122.7 (16)
O2—C13—C14	122.44 (17)	C7—C8—H8	119.9 (19)
N3—C13—C14	119.03 (16)	C9—C8—C7	119.58 (19)
N2—C11—C12	116.43 (15)	C9—C8—H8	120.5 (19)
N2—C11—C7	122.90 (17)	C10—C9—H9	117.7 (14)
C7—C11—C12	120.67 (16)	C8—C9—C10	119.9 (2)
N1—C12—C11	116.76 (15)	C8—C9—H9	122.4 (14)
N1—C12—C4	122.81 (17)	C18—C17—H17	124.5 (17)
C4—C12—C11	120.43 (16)	C16—C17—C18	121.25 (19)
C14—C24—C18	118.88 (18)	C16—C17—H17	114.3 (17)
C22—C24—C14	120.95 (16)	C1—C2—H2	120.1 (14)
C22—C24—C18	120.16 (17)	C3—C2—C1	119.0 (2)
C24—C14—C13	118.60 (17)	C3—C2—H2	121.0 (14)
C15—C14—C13	120.57 (17)	C15—C16—H16	118.4 (15)
C15—C14—C24	120.83 (17)	C17—C16—C15	120.7 (2)
C12—C4—C5	117.93 (18)	C17—C16—H16	120.8 (15)
C3—C4—C12	116.77 (17)	C21—C20—H20	123 (2)
C3—C4—C5	125.29 (17)	C19—C20—C21	120.7 (2)
C24—C22—C23	120.86 (16)	C19—C20—H20	115.9 (19)
C21—C22—C24	119.87 (17)	C25—O8—H8A	111 (2)
C21—C22—C23	119.26 (18)	O8—C25—H25A	108 (2)
O3—C23—N3	120.30 (16)	O8—C25—H25B	114 (2)
O3—C23—C22	125.03 (17)	O8—C25—H25C	115 (2)
N3—C23—C22	114.67 (16)	H25A—C25—H25B	104 (3)
C11—C7—C6	117.80 (19)	H25A—C25—H25C	114 (3)
C8—C7—C11	117.16 (18)	H25B—C25—H25C	101 (3)
Cu1—O2—C13—N3	4.6 (2)	C24—C22—C23—N3	2.6 (2)
Cu1—O2—C13—C14	−175.06 (13)	C24—C22—C21—C20	0.6 (3)
Cu1—O1—N3—C13	−3.82 (18)	C24—C18—C19—C20	0.7 (3)
Cu1—O1—N3—C23	176.80 (12)	C24—C18—C17—C16	−1.0 (3)
Cu1—N1—C12—C11	6.80 (19)	C14—C24—C22—C23	−2.3 (3)
Cu1—N1—C12—C4	−173.48 (14)	C14—C24—C22—C21	178.44 (17)
Cu1—N1—C1—C2	170.53 (15)	C14—C24—C18—C19	−179.05 (17)
Cu1—N2—C11—C12	−6.89 (19)	C14—C24—C18—C17	1.3 (3)
Cu1—N2—C11—C7	172.88 (13)	C14—C15—C16—C17	0.7 (3)
Cu1—N2—C10—C9	−169.80 (15)	C4—C3—C2—C1	0.3 (3)
O2—C13—C14—C24	−178.36 (16)	C4—C5—C6—C7	0.2 (3)
O2—C13—C14—C15	1.8 (3)	C22—C24—C14—C13	0.0 (3)
O1—N3—C13—O2	−0.6 (2)	C22—C24—C14—C15	179.76 (17)
O1—N3—C13—C14	179.13 (14)	C22—C24—C18—C19	0.6 (3)
O1—N3—C23—O3	−1.0 (3)	C22—C24—C18—C17	−179.06 (17)
O1—N3—C23—C22	178.62 (14)	C22—C21—C20—C19	0.7 (3)
N3—C13—C14—C24	1.9 (2)	C23—N3—C13—O2	178.74 (16)
N3—C13—C14—C15	−177.86 (17)	C23—N3—C13—C14	−1.6 (3)
N1—C12—C4—C3	1.6 (3)	C23—C22—C21—C20	−178.73 (18)
N1—C12—C4—C5	−179.70 (16)	C7—C11—C12—N1	−179.71 (15)
N1—C1—C2—C3	1.3 (3)	C7—C11—C12—C4	0.6 (3)
N2—C11—C12—N1	0.1 (2)	C7—C8—C9—C10	−0.2 (3)
N2—C11—C12—C4	−179.67 (15)	C10—N2—C11—C12	179.21 (16)
N2—C11—C7—C6	179.49 (17)	C10—N2—C11—C7	−1.0 (3)
N2—C11—C7—C8	−1.3 (3)	C18—C24—C14—C13	179.60 (16)
N2—C10—C9—C8	−2.2 (3)	C18—C24—C14—C15	−0.6 (3)
C13—N3—C23—O3	179.71 (18)	C18—C24—C22—C23	178.07 (16)
C13—N3—C23—C22	−0.7 (3)	C18—C24—C22—C21	−1.2 (3)
C13—C14—C15—C16	179.38 (17)	C18—C19—C20—C21	−1.3 (3)
C11—N2—C10—C9	2.8 (3)	C18—C17—C16—C15	0.0 (3)
C11—C12—C4—C3	−178.64 (17)	C1—N1—C12—C11	−179.86 (17)
C11—C12—C4—C5	0.0 (3)	C1—N1—C12—C4	−0.1 (3)
C11—C7—C6—C5	0.4 (3)	C3—C4—C5—C6	178.1 (2)
C11—C7—C8—C9	1.8 (3)	C21—C22—C23—O3	1.5 (3)
C12—N1—C1—C2	−1.4 (3)	C21—C22—C23—N3	−178.10 (17)
C12—C11—C7—C6	−0.7 (2)	C19—C18—C17—C16	179.4 (2)
C12—C11—C7—C8	178.49 (17)	C5—C4—C3—C2	179.77 (19)
C12—C4—C3—C2	−1.7 (3)	C6—C7—C8—C9	−179.00 (19)
C12—C4—C5—C6	−0.4 (3)	C8—C7—C6—C5	−178.8 (2)
C24—C14—C15—C16	−0.4 (3)	C17—C18—C19—C20	−179.7 (2)
C24—C22—C23—O3	−177.80 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O7^i	0.77 (3)	2.05 (3)	2.804 (3)	168 (3)
O4—H4A···O8	0.75 (3)	2.10 (3)	2.813 (3)	159 (3)

Symmetry code: (i) −x+2, −y+1, −z+1.