A fluoro­phore-labelled copper complex: crystal structure, hybrid cyclic water–perchlorate cluster and biological properties

A fluoro­phore-labelled copper(II) complex, aqua­bis­(di­methyl­formamide-κO)(perchlorato-κO)[2-(quinolin-2-yl)-1,3-oxazolo[4,5-f][1,10]phenanthroline]copper(II) perchlorate monohydrate, [Cu(ClO₄)(C₂₂H₁₂N₄O)(C₃H₇NO)₂(H₂O)]ClO₄·H₂O, has been synthesized and characterized. A cyclic hydrogen-bonded water–perchlorate anionic cluster, i.e. [(ClO₄)₂(H₂O)₂]²⁻, has been identified within the structure. Each cyclic anionic cluster unit is inter­connected by hydrogen bonding to the cation. The cations join into an infinite hydrogen-bonded chain running in the [010] direction. Furthermore, inter­action of the complex with calf-thymus DNA (CT-DNA) and cellular localization within the cells was explored. Spectroscopic studies indicate that the compound has a good affinity for DNA and stains the nucleus of the cells.

Computing details

Data collection: SAINT (Bruker, 2010); cell refinement: SMART (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Aquabis(dimethylformamide-κO)(perchlorato-κO)[2-(quinolin-2-yl)-1,3-oxazolo[4,5-f][1,10]phenanthroline]copper(II) perchlorate monohydrate

Crystal data

[Cu(ClO4)(C22H12N4O)(C3H7NO)2(H2O)]ClO4·H2O	F(000) = 3256
Mr = 793.02	Dx = 1.612 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 48.675 (3) Å	Cell parameters from 4790 reflections
b = 8.3750 (5) Å	θ = 1.9–64.5°
c = 16.3155 (9) Å	µ = 3.12 mm^−1
β = 100.716 (2)°	T = 173 K
V = 6535.1 (6) Å^3	Rectangle, green
Z = 8	0.28 × 0.22 × 0.17 mm

Data collection

Bruker X8 Proteum diffractometer	4790 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.071
Absorption correction: multi-scan (SADABS; Bruker, 2010)	θmax = 64.5°, θmin = 5.4°
Tmin = 0.482, Tmax = 0.505	h = −56→54
29422 measured reflections	k = −9→9
5417 independent reflections	l = −15→19

Refinement

Refinement on F^2	157 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.132	w = 1/[σ^2(Fo^2) + (0.0731P)^2 + 16.1488P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.002
5417 reflections	Δρmax = 0.77 e Å^−3
504 parameters	Δρmin = −0.48 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)
Cu1	0.63808 (2)	0.76800 (5)	0.33515 (3)	0.01822 (15)
O2	0.67770 (4)	0.8210 (3)	0.37130 (13)	0.0231 (5)
O1	0.64467 (4)	0.6953 (3)	0.22641 (13)	0.0232 (5)
O3	0.54145 (4)	1.1271 (2)	0.48962 (12)	0.0212 (4)
O4	0.65005 (5)	0.5336 (3)	0.39334 (14)	0.0283 (5)
H4A	0.668680	0.514138	0.399543	0.042*
H4B	0.641311	0.452483	0.362216	0.042*
N2	0.59662 (5)	0.7598 (3)	0.29512 (15)	0.0172 (5)
N1	0.62665 (5)	0.8758 (3)	0.43273 (14)	0.0187 (5)
N4	0.51555 (5)	1.0462 (3)	0.36830 (15)	0.0176 (5)
N7	0.71619 (5)	0.9632 (3)	0.36123 (16)	0.0231 (6)
N5	0.49830 (5)	1.2951 (3)	0.53244 (15)	0.0189 (5)
O5	0.70583 (5)	0.4386 (3)	0.44686 (19)	0.0468 (7)
H5A	0.718900	0.438323	0.418626	0.070*
H5B	0.706890	0.347375	0.470057	0.070*
N6	0.66992 (5)	0.5341 (3)	0.15751 (17)	0.0284 (6)
C5	0.58248 (5)	0.8501 (3)	0.34240 (17)	0.0164 (6)
C6	0.59897 (6)	0.9109 (3)	0.41920 (18)	0.0171 (6)
C4	0.55404 (5)	0.8880 (3)	0.31771 (17)	0.0171 (6)
C1	0.58274 (6)	0.7023 (3)	0.22309 (18)	0.0195 (6)
H1	0.592133	0.636716	0.191453	0.023*
C26	0.68925 (6)	0.9459 (4)	0.35209 (19)	0.0236 (7)
H26	0.677914	1.030785	0.330107	0.028*
C3	0.54021 (6)	0.8312 (3)	0.23980 (18)	0.0196 (6)
H3	0.521589	0.857181	0.219960	0.024*
C11	0.55818 (6)	1.0365 (3)	0.44858 (18)	0.0183 (6)
C23	0.66611 (6)	0.6122 (4)	0.22322 (19)	0.0234 (7)
H23	0.679992	0.606736	0.270749	0.028*
C22	0.47685 (6)	1.3819 (3)	0.55422 (19)	0.0209 (6)
C7	0.58712 (6)	1.0027 (3)	0.47580 (18)	0.0186 (6)
C13	0.51640 (6)	1.1273 (3)	0.43692 (19)	0.0208 (6)
C12	0.54243 (6)	0.9866 (3)	0.37484 (18)	0.0184 (6)
C2	0.55461 (6)	0.7368 (4)	0.19342 (19)	0.0212 (6)
H2	0.545639	0.695999	0.142404	0.025*
C8	0.60458 (6)	1.0527 (4)	0.54982 (19)	0.0246 (7)
H8	0.597389	1.111196	0.589469	0.030*
C15	0.46711 (6)	1.2196 (4)	0.4050 (2)	0.0227 (6)
H15	0.464676	1.164073	0.354847	0.027*
C10	0.64288 (6)	0.9274 (4)	0.50227 (19)	0.0228 (6)
H10	0.661922	0.905087	0.511060	0.027*
C17	0.44993 (6)	1.3887 (4)	0.5025 (2)	0.0242 (7)
C14	0.49310 (6)	1.2182 (3)	0.46072 (18)	0.0181 (6)
C9	0.63232 (6)	1.0138 (4)	0.5625 (2)	0.0263 (7)
H9	0.644151	1.045097	0.611341	0.032*
C16	0.44565 (6)	1.3050 (4)	0.4270 (2)	0.0269 (7)
H16	0.428264	1.307446	0.391828	0.032*
C21	0.48177 (7)	1.4658 (4)	0.6303 (2)	0.0278 (7)
H21	0.499320	1.461098	0.664476	0.033*
C18	0.42873 (7)	1.4798 (4)	0.5304 (2)	0.0339 (8)
H18	0.410916	1.484971	0.497807	0.041*
C20	0.46102 (8)	1.5540 (4)	0.6545 (2)	0.0364 (9)
H20	0.464707	1.610582	0.704394	0.044*
C19	0.43436 (8)	1.5600 (4)	0.6050 (3)	0.0396 (9)
H19	0.420330	1.618773	0.622661	0.048*
C27	0.72853 (8)	1.1103 (4)	0.3384 (2)	0.0389 (8)
H27A	0.713995	1.185541	0.317883	0.058*
H27B	0.739200	1.088833	0.295681	0.058*
H27C	0.740586	1.153987	0.386435	0.058*
C24	0.64950 (9)	0.5388 (6)	0.0826 (3)	0.0556 (12)
H24A	0.632332	0.581308	0.094368	0.083*
H24B	0.646343	0.432703	0.060585	0.083*
H24C	0.656075	0.605475	0.042465	0.083*
C28	0.73515 (7)	0.8364 (5)	0.3937 (3)	0.0517 (11)
H28A	0.725217	0.755903	0.418378	0.078*
H28B	0.749954	0.878560	0.435268	0.078*
H28C	0.742904	0.790148	0.349225	0.078*
C25	0.69518 (9)	0.4426 (5)	0.1565 (3)	0.0512 (11)
H25A	0.707412	0.451478	0.209748	0.077*
H25B	0.704433	0.483256	0.113808	0.077*
H25C	0.690400	0.332488	0.145403	0.077*
Cl3	0.61575 (2)	1.19401 (9)	0.26661 (5)	0.0271 (2)
O32	0.62515 (6)	1.2378 (3)	0.35322 (16)	0.0436 (6)
O31	0.62935 (5)	1.0488 (3)	0.25143 (15)	0.0358 (6)
O33	0.62201 (5)	1.3185 (3)	0.21300 (17)	0.0414 (6)
O34	0.58625 (5)	1.1691 (4)	0.2537 (2)	0.0533 (8)
Cl2	0.72028 (14)	0.0671 (7)	0.6164 (4)	0.0330 (12)	0.6667
O6	0.72004 (11)	0.1404 (8)	0.5356 (3)	0.0508 (14)	0.6667
O7	0.74955 (14)	0.0373 (12)	0.6530 (4)	0.0347 (14)	0.6667
O8	0.70409 (11)	−0.0720 (6)	0.6185 (4)	0.0594 (13)	0.6667
O9	0.71221 (14)	0.1840 (7)	0.6718 (4)	0.0653 (18)	0.6667
Cl1	0.7185 (2)	0.0605 (13)	0.6059 (8)	0.0297 (19)	0.3333
O10	0.7077 (3)	0.1569 (17)	0.5390 (9)	0.075 (3)	0.3333
O11	0.7465 (3)	0.040 (3)	0.6321 (12)	0.061 (4)	0.3333
O13	0.71045 (14)	−0.0957 (9)	0.5766 (6)	0.0345 (16)	0.3333
O12	0.7028 (2)	0.1098 (15)	0.6623 (7)	0.062 (3)	0.3333

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0134 (2)	0.0240 (3)	0.0190 (3)	0.00191 (15)	0.00771 (17)	−0.00228 (17)
O2	0.0155 (10)	0.0281 (11)	0.0273 (11)	0.0012 (8)	0.0081 (8)	0.0001 (9)
O1	0.0179 (10)	0.0317 (11)	0.0217 (11)	0.0055 (8)	0.0081 (8)	−0.0015 (9)
O3	0.0188 (10)	0.0232 (11)	0.0244 (11)	0.0035 (8)	0.0116 (8)	−0.0004 (9)
O4	0.0319 (12)	0.0250 (11)	0.0287 (12)	0.0029 (9)	0.0075 (9)	0.0020 (9)
N2	0.0173 (12)	0.0187 (12)	0.0178 (13)	0.0007 (9)	0.0092 (10)	0.0011 (10)
N1	0.0174 (12)	0.0224 (12)	0.0177 (13)	−0.0008 (9)	0.0070 (10)	0.0009 (10)
N4	0.0168 (12)	0.0162 (12)	0.0230 (13)	0.0009 (9)	0.0125 (10)	0.0019 (10)
N7	0.0224 (13)	0.0245 (13)	0.0244 (14)	−0.0028 (10)	0.0091 (10)	−0.0018 (11)
N5	0.0196 (12)	0.0185 (12)	0.0212 (13)	0.0001 (9)	0.0111 (10)	0.0032 (10)
O5	0.0396 (15)	0.0463 (16)	0.0588 (18)	0.0157 (12)	0.0204 (13)	0.0135 (13)
N6	0.0282 (14)	0.0332 (15)	0.0278 (15)	0.0035 (11)	0.0152 (12)	−0.0062 (12)
C5	0.0171 (13)	0.0164 (14)	0.0177 (14)	−0.0015 (11)	0.0086 (11)	0.0019 (11)
C6	0.0164 (13)	0.0182 (14)	0.0188 (15)	−0.0014 (11)	0.0086 (11)	0.0016 (12)
C4	0.0168 (13)	0.0167 (14)	0.0206 (15)	−0.0028 (11)	0.0110 (11)	0.0036 (11)
C1	0.0210 (14)	0.0215 (15)	0.0185 (15)	−0.0017 (11)	0.0103 (12)	−0.0013 (12)
C26	0.0235 (16)	0.0230 (16)	0.0244 (17)	0.0019 (12)	0.0046 (12)	−0.0025 (13)
C3	0.0154 (13)	0.0228 (15)	0.0227 (16)	−0.0017 (11)	0.0086 (11)	0.0047 (12)
C11	0.0195 (14)	0.0162 (14)	0.0231 (16)	0.0006 (11)	0.0141 (12)	−0.0006 (12)
C23	0.0217 (15)	0.0276 (16)	0.0233 (16)	−0.0001 (12)	0.0105 (12)	−0.0010 (13)
C22	0.0253 (15)	0.0151 (14)	0.0263 (16)	0.0023 (11)	0.0154 (13)	0.0051 (12)
C7	0.0198 (14)	0.0198 (14)	0.0191 (15)	0.0005 (11)	0.0108 (12)	0.0007 (12)
C13	0.0173 (14)	0.0172 (14)	0.0310 (17)	0.0005 (11)	0.0129 (12)	0.0066 (13)
C12	0.0180 (14)	0.0164 (14)	0.0232 (16)	0.0009 (11)	0.0105 (12)	0.0038 (12)
C2	0.0213 (15)	0.0261 (16)	0.0173 (15)	−0.0061 (12)	0.0064 (12)	−0.0021 (12)
C8	0.0260 (16)	0.0299 (16)	0.0204 (16)	−0.0006 (13)	0.0105 (13)	−0.0041 (13)
C15	0.0220 (15)	0.0240 (16)	0.0236 (16)	−0.0015 (12)	0.0080 (12)	−0.0008 (12)
C10	0.0171 (14)	0.0299 (16)	0.0219 (16)	0.0008 (12)	0.0052 (12)	−0.0010 (13)
C17	0.0223 (15)	0.0200 (15)	0.0345 (18)	0.0022 (12)	0.0162 (13)	0.0059 (13)
C14	0.0191 (14)	0.0148 (14)	0.0234 (16)	0.0008 (11)	0.0119 (12)	0.0030 (12)
C9	0.0245 (15)	0.0362 (18)	0.0184 (16)	−0.0022 (13)	0.0043 (12)	−0.0046 (13)
C16	0.0164 (14)	0.0281 (17)	0.0368 (19)	0.0009 (12)	0.0063 (13)	0.0050 (14)
C21	0.0393 (18)	0.0216 (16)	0.0265 (18)	0.0007 (13)	0.0165 (14)	0.0055 (13)
C18	0.0248 (16)	0.0272 (17)	0.055 (2)	0.0093 (13)	0.0221 (16)	0.0100 (16)
C20	0.061 (2)	0.0200 (16)	0.037 (2)	0.0024 (15)	0.0318 (18)	0.0028 (14)
C19	0.049 (2)	0.0232 (17)	0.059 (3)	0.0109 (15)	0.042 (2)	0.0075 (17)
C27	0.0381 (19)	0.0350 (19)	0.044 (2)	−0.0129 (15)	0.0093 (16)	0.0012 (16)
C24	0.056 (3)	0.076 (3)	0.036 (2)	0.014 (2)	0.0115 (19)	−0.019 (2)
C28	0.0207 (17)	0.039 (2)	0.096 (3)	0.0010 (15)	0.0124 (19)	0.018 (2)
C25	0.057 (2)	0.054 (3)	0.049 (2)	0.027 (2)	0.029 (2)	−0.005 (2)
Cl3	0.0253 (4)	0.0231 (4)	0.0345 (4)	−0.0010 (3)	0.0093 (3)	0.0036 (3)
O32	0.0667 (18)	0.0310 (13)	0.0356 (15)	−0.0074 (12)	0.0161 (13)	−0.0069 (11)
O31	0.0470 (14)	0.0308 (13)	0.0329 (13)	0.0096 (10)	0.0157 (11)	0.0021 (10)
O33	0.0415 (14)	0.0339 (13)	0.0506 (16)	−0.0068 (11)	0.0132 (12)	0.0131 (12)
O34	0.0236 (13)	0.0569 (17)	0.078 (2)	−0.0019 (12)	0.0051 (12)	0.0301 (16)
Cl2	0.035 (2)	0.0304 (14)	0.0318 (15)	−0.0038 (10)	0.0015 (10)	0.0079 (10)
O6	0.058 (3)	0.061 (3)	0.031 (2)	0.020 (3)	0.003 (2)	0.013 (2)
O7	0.030 (3)	0.042 (3)	0.030 (3)	0.001 (2)	−0.0012 (19)	0.010 (2)
O8	0.0562 (19)	0.0482 (18)	0.068 (2)	−0.0204 (14)	−0.0038 (16)	0.0132 (16)
O9	0.087 (5)	0.054 (3)	0.069 (4)	0.010 (3)	0.049 (3)	0.000 (3)
Cl1	0.023 (3)	0.027 (2)	0.041 (4)	−0.0043 (18)	0.012 (3)	0.003 (2)
O10	0.108 (9)	0.052 (5)	0.063 (5)	0.023 (6)	0.013 (5)	0.026 (5)
O11	0.021 (3)	0.048 (7)	0.111 (12)	−0.004 (3)	0.006 (4)	−0.003 (8)
O13	0.019 (3)	0.030 (2)	0.052 (5)	0.000 (2)	0.000 (3)	0.001 (3)
O12	0.054 (6)	0.084 (7)	0.052 (4)	0.032 (5)	0.018 (5)	−0.005 (5)

Geometric parameters (Å, º)

Cu1—O2	1.960 (2)	C13—C14	1.477 (4)
Cu1—O1	1.958 (2)	C2—H2	0.9300
Cu1—O4	2.211 (2)	C8—H8	0.9300
Cu1—N2	2.003 (2)	C8—C9	1.367 (4)
Cu1—N1	1.997 (2)	C15—H15	0.9300
Cu1—O31	2.713 (2)	C15—C14	1.414 (4)
O2—C26	1.255 (4)	C15—C16	1.367 (4)
O1—C23	1.264 (4)	C10—H10	0.9300
O3—C11	1.375 (3)	C10—C9	1.393 (4)
O3—C13	1.355 (4)	C17—C16	1.399 (5)
O4—H4A	0.9082	C17—C18	1.425 (4)
O4—H4B	0.9052	C9—H9	0.9300
N2—C5	1.356 (4)	C16—H16	0.9300
N2—C1	1.332 (4)	C21—H21	0.9300
N1—C6	1.357 (4)	C21—C20	1.368 (5)
N1—C10	1.328 (4)	C18—H18	0.9300
N4—C13	1.303 (4)	C18—C19	1.372 (6)
N4—C12	1.386 (3)	C20—H20	0.9300
N7—C26	1.300 (4)	C20—C19	1.396 (6)
N7—C27	1.449 (4)	C19—H19	0.9300
N7—C28	1.442 (4)	C27—H27A	0.9600
N5—C22	1.372 (4)	C27—H27B	0.9600
N5—C14	1.319 (4)	C27—H27C	0.9600
O5—H5A	0.8521	C24—H24A	0.9600
O5—H5B	0.8497	C24—H24B	0.9600
N6—C23	1.298 (4)	C24—H24C	0.9600
N6—C24	1.425 (5)	C28—H28A	0.9600
N6—C25	1.451 (4)	C28—H28B	0.9600
C5—C6	1.449 (4)	C28—H28C	0.9600
C5—C4	1.404 (4)	C25—H25A	0.9600
C6—C7	1.405 (4)	C25—H25B	0.9600
C4—C3	1.406 (4)	C25—H25C	0.9600
C4—C12	1.437 (4)	Cl3—O32	1.449 (3)
C1—H1	0.9300	Cl3—O31	1.428 (2)
C1—C2	1.395 (4)	Cl3—O33	1.430 (2)
C26—H26	0.9300	Cl3—O34	1.427 (3)
C3—H3	0.9300	Cl2—O6	1.452 (6)
C3—C2	1.373 (4)	Cl2—O7	1.460 (6)
C11—C7	1.424 (4)	Cl2—O8	1.410 (7)
C11—C12	1.366 (4)	Cl2—O9	1.435 (7)
C23—H23	0.9300	Cl1—O10	1.380 (13)
C22—C17	1.421 (4)	Cl1—O11	1.358 (12)
C22—C21	1.407 (5)	Cl1—O13	1.423 (11)
C7—C8	1.405 (4)	Cl1—O12	1.365 (12)
O2—Cu1—O4	84.60 (9)	C9—C8—C7	118.8 (3)
O2—Cu1—N2	168.83 (9)	C9—C8—H8	120.6
O2—Cu1—N1	93.56 (9)	C14—C15—H15	120.9
O2—Cu1—O31	90.49 (8)	C16—C15—H15	120.9
O1—Cu1—O2	91.45 (8)	C16—C15—C14	118.2 (3)
O1—Cu1—O4	92.21 (8)	N1—C10—H10	118.9
O1—Cu1—N2	91.07 (9)	N1—C10—C9	122.2 (3)
O1—Cu1—N1	168.47 (9)	C9—C10—H10	118.9
O1—Cu1—O31	81.37 (8)	C22—C17—C18	118.3 (3)
O4—Cu1—O31	171.83 (8)	C16—C17—C22	118.2 (3)
N2—Cu1—O4	106.18 (9)	C16—C17—C18	123.5 (3)
N2—Cu1—O31	79.14 (8)	N5—C14—C13	117.1 (3)
N1—Cu1—O4	98.60 (9)	N5—C14—C15	124.6 (3)
N1—Cu1—N2	82.09 (9)	C15—C14—C13	118.3 (3)
N1—Cu1—O31	88.20 (8)	C8—C9—C10	120.1 (3)
C26—O2—Cu1	125.1 (2)	C8—C9—H9	120.0
C23—O1—Cu1	118.96 (19)	C10—C9—H9	120.0
C13—O3—C11	103.7 (2)	C15—C16—C17	119.8 (3)
Cu1—O4—H4A	112.6	C15—C16—H16	120.1
Cu1—O4—H4B	111.5	C17—C16—H16	120.1
H4A—O4—H4B	106.5	C22—C21—H21	119.6
C5—N2—Cu1	112.50 (19)	C20—C21—C22	120.7 (3)
C1—N2—Cu1	127.96 (19)	C20—C21—H21	119.6
C1—N2—C5	118.4 (2)	C17—C18—H18	119.7
C6—N1—Cu1	112.56 (18)	C19—C18—C17	120.5 (3)
C10—N1—Cu1	128.20 (19)	C19—C18—H18	119.7
C10—N1—C6	118.9 (2)	C21—C20—H20	119.7
C13—N4—C12	104.1 (2)	C21—C20—C19	120.6 (3)
C26—N7—C27	121.5 (3)	C19—C20—H20	119.7
C26—N7—C28	121.5 (3)	C18—C19—C20	120.4 (3)
C28—N7—C27	116.9 (3)	C18—C19—H19	119.8
C14—N5—C22	117.3 (3)	C20—C19—H19	119.8
H5A—O5—H5B	104.4	N7—C27—H27A	109.5
C23—N6—C24	120.7 (3)	N7—C27—H27B	109.5
C23—N6—C25	121.8 (3)	N7—C27—H27C	109.5
C24—N6—C25	117.5 (3)	H27A—C27—H27B	109.5
N2—C5—C6	115.5 (2)	H27A—C27—H27C	109.5
N2—C5—C4	122.7 (3)	H27B—C27—H27C	109.5
C4—C5—C6	121.8 (2)	N6—C24—H24A	109.5
N1—C6—C5	116.0 (2)	N6—C24—H24B	109.5
N1—C6—C7	121.9 (3)	N6—C24—H24C	109.5
C7—C6—C5	122.1 (2)	H24A—C24—H24B	109.5
C5—C4—C3	117.6 (2)	H24A—C24—H24C	109.5
C5—C4—C12	115.4 (3)	H24B—C24—H24C	109.5
C3—C4—C12	126.9 (3)	N7—C28—H28A	109.5
N2—C1—H1	118.8	N7—C28—H28B	109.5
N2—C1—C2	122.4 (3)	N7—C28—H28C	109.5
C2—C1—H1	118.8	H28A—C28—H28B	109.5
O2—C26—N7	123.6 (3)	H28A—C28—H28C	109.5
O2—C26—H26	118.2	H28B—C28—H28C	109.5
N7—C26—H26	118.2	N6—C25—H25A	109.5
C4—C3—H3	120.5	N6—C25—H25B	109.5
C2—C3—C4	119.1 (3)	N6—C25—H25C	109.5
C2—C3—H3	120.5	H25A—C25—H25B	109.5
O3—C11—C7	126.8 (3)	H25A—C25—H25C	109.5
C12—C11—O3	108.1 (2)	H25B—C25—H25C	109.5
C12—C11—C7	125.1 (2)	O31—Cl3—O32	108.18 (15)
O1—C23—N6	123.9 (3)	O31—Cl3—O33	110.89 (15)
O1—C23—H23	118.1	O33—Cl3—O32	110.35 (15)
N6—C23—H23	118.1	O34—Cl3—O32	107.92 (18)
N5—C22—C17	122.0 (3)	O34—Cl3—O31	109.61 (17)
N5—C22—C21	118.7 (3)	O34—Cl3—O33	109.82 (16)
C21—C22—C17	119.3 (3)	Cl3—O31—Cu1	133.25 (13)
C6—C7—C11	114.0 (3)	O6—Cl2—O7	106.6 (5)
C6—C7—C8	118.1 (3)	O8—Cl2—O6	117.4 (5)
C8—C7—C11	127.9 (3)	O8—Cl2—O7	110.9 (5)
O3—C13—C14	118.6 (3)	O8—Cl2—O9	109.2 (5)
N4—C13—O3	115.2 (2)	O9—Cl2—O6	109.0 (5)
N4—C13—C14	126.2 (3)	O9—Cl2—O7	102.7 (6)
N4—C12—C4	129.5 (3)	O10—Cl1—O13	103.4 (10)
C11—C12—N4	109.0 (2)	O11—Cl1—O10	122.3 (12)
C11—C12—C4	121.5 (3)	O11—Cl1—O13	101.0 (11)
C1—C2—H2	120.1	O11—Cl1—O12	118.5 (13)
C3—C2—C1	119.8 (3)	O12—Cl1—O10	100.2 (10)
C3—C2—H2	120.1	O12—Cl1—O13	110.5 (9)
C7—C8—H8	120.6
Cu1—O2—C26—N7	−164.5 (2)	C3—C4—C12—C11	−179.0 (3)
Cu1—O1—C23—N6	166.9 (2)	C11—O3—C13—N4	0.5 (3)
Cu1—N2—C5—C6	−10.3 (3)	C11—O3—C13—C14	−178.7 (2)
Cu1—N2—C5—C4	167.4 (2)	C11—C7—C8—C9	−176.7 (3)
Cu1—N2—C1—C2	−164.2 (2)	C22—N5—C14—C13	179.0 (2)
Cu1—N1—C6—C5	6.4 (3)	C22—N5—C14—C15	0.3 (4)
Cu1—N1—C6—C7	−172.7 (2)	C22—C17—C16—C15	0.2 (4)
Cu1—N1—C10—C9	174.1 (2)	C22—C17—C18—C19	0.6 (4)
O3—C11—C7—C6	−177.9 (3)	C22—C21—C20—C19	1.3 (5)
O3—C11—C7—C8	0.7 (5)	C7—C11—C12—N4	−178.0 (3)
O3—C11—C12—N4	0.3 (3)	C7—C11—C12—C4	2.0 (4)
O3—C11—C12—C4	−179.6 (2)	C7—C8—C9—C10	0.6 (5)
O3—C13—C14—N5	0.4 (4)	C13—O3—C11—C7	177.8 (3)
O3—C13—C14—C15	179.2 (2)	C13—O3—C11—C12	−0.5 (3)
N2—C5—C6—N1	2.6 (4)	C13—N4—C12—C4	179.9 (3)
N2—C5—C6—C7	−178.3 (2)	C13—N4—C12—C11	0.0 (3)
N2—C5—C4—C3	−1.2 (4)	C12—N4—C13—O3	−0.3 (3)
N2—C5—C4—C12	−179.2 (2)	C12—N4—C13—C14	178.8 (3)
N2—C1—C2—C3	−1.1 (4)	C12—C4—C3—C2	−179.6 (3)
N1—C6—C7—C11	175.9 (2)	C12—C11—C7—C6	0.1 (4)
N1—C6—C7—C8	−2.7 (4)	C12—C11—C7—C8	178.7 (3)
N1—C10—C9—C8	−2.2 (5)	C10—N1—C6—C5	−179.6 (3)
N4—C13—C14—N5	−178.7 (3)	C10—N1—C6—C7	1.3 (4)
N4—C13—C14—C15	0.0 (4)	C17—C22—C21—C20	−0.4 (4)
N5—C22—C17—C16	−0.7 (4)	C17—C18—C19—C20	0.3 (5)
N5—C22—C17—C18	179.1 (3)	C14—N5—C22—C17	0.5 (4)
N5—C22—C21—C20	179.9 (3)	C14—N5—C22—C21	−179.8 (2)
C5—N2—C1—C2	2.6 (4)	C14—C15—C16—C17	0.5 (4)
C5—C6—C7—C11	−3.1 (4)	C16—C15—C14—N5	−0.8 (4)
C5—C6—C7—C8	178.2 (3)	C16—C15—C14—C13	−179.5 (3)
C5—C4—C3—C2	2.7 (4)	C16—C17—C18—C19	−179.6 (3)
C5—C4—C12—N4	178.9 (3)	C21—C22—C17—C16	179.6 (3)
C5—C4—C12—C11	−1.2 (4)	C21—C22—C17—C18	−0.6 (4)
C6—N1—C10—C9	1.2 (4)	C21—C20—C19—C18	−1.3 (5)
C6—C5—C4—C3	176.3 (2)	C18—C17—C16—C15	−179.7 (3)
C6—C5—C4—C12	−1.8 (4)	C27—N7—C26—O2	−179.8 (3)
C6—C7—C8—C9	1.7 (4)	C24—N6—C23—O1	0.4 (5)
C4—C5—C6—N1	−175.0 (2)	C28—N7—C26—O2	0.9 (5)
C4—C5—C6—C7	4.1 (4)	C25—N6—C23—O1	178.9 (3)
C4—C3—C2—C1	−1.6 (4)	O32—Cl3—O31—Cu1	46.4 (2)
C1—N2—C5—C6	−179.0 (2)	O33—Cl3—O31—Cu1	167.57 (17)
C1—N2—C5—C4	−1.4 (4)	O34—Cl3—O31—Cu1	−71.0 (2)
C3—C4—C12—N4	1.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O5	0.91	1.94	2.808 (3)	160
O4—H4B···O32^i	0.91	1.96	2.782 (3)	151
O5—H5A···O11^ii	0.85	2.02	2.862 (18)	170
O5—H5B···O10	0.85	1.95	2.790 (13)	171
O5—H5A···O7^ii	0.85	2.11	2.954 (7)	174
O5—H5B···O6	0.85	2.07	2.905 (7)	165

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