Bis(9-amino-acridinium) bis-(pyridine-2,6-dicarboxyl-ato)cuprate(II) trihydrate.

The asymmetric unit of the title compound, (C(13)H(11)N(2))(2)[Cu(C(7)H(3)NO(4))(2)]·3H(2)O or (9-aminoAcr)[Cu(pydc)(2)]·3H(2)O, contains a Cu(pydc)(2) (pydc = pyridine-2,6-dicarboxyl-ate) anion, two protonated 9-amino-acridine (9-aminoAcr)(+) counter-ions and three uncoordinated water mol-ecules. The anion contains a six-coordinated Cu(II) atom within a distorted octa-hedral geometry. Non-covalent inter-actions i.e. N-H⋯O and O-H⋯O hydrogen bonds and inter-molecular π-π contacts between the pyridine rings [centroid-centroid distance = 3.7773 (13) Å] and acridine rings [centroid-centroid distance = 3.4897 (13), 3.7784 (14) and 3.8627 (15) Å] result in the formation of a three-dimensional network.

Related literature

For related structures, see: Aghabozorg et al. (2008 ▶, 2010 ▶); Eshtiagh-Hosseini et al. (2010 ▶); Tabatabaee et al. (2009 ▶). An independent determination of the title compound is reported in the preceeding paper by Derikvand et al. (2010 ▶).

Experimental

Crystal data

(C13H11N2)2[Cu(C7H3NO4)2]·3H2O

M = 838.27

Triclinic,

a = 10.921 (2) Å

b = 13.299 (3) Å

c = 14.008 (3) Å

α = 102.09 (3)°

β = 103.96 (3)°

γ = 105.38 (3)°

V = 1820.6 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.67 mm−1

T = 298 K

0.38 × 0.30 × 0.25 mm

Data collection

STOE IPDS II diffractometer

Absorption correction: numerical [shape of crystal determined optically (X-RED32 and X-SHAPE; Stoe & Cie, 2005 ▶)] T min = 0.787, T max = 0.849

21686 measured reflections

9767 independent reflections

7989 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.094

S = 1.03

9767 reflections

571 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.38 e Å−3

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536810037499/vm2039sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037499/vm2039Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C13H11N2)2[Cu(C7H3NO4)2]·3H2O	Z = 2
Mr = 838.27	F(000) = 866
Triclinic, P1	Dx = 1.529 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.921 (2) Å	Cell parameters from 342 reflections
b = 13.299 (3) Å	θ = 1.7–29.3°
c = 14.008 (3) Å	µ = 0.67 mm−1
α = 102.09 (3)°	T = 298 K
β = 103.96 (3)°	Block, green
γ = 105.38 (3)°	0.38 × 0.30 × 0.25 mm
V = 1820.6 (9) Å3

STOE IPDS II diffractometer	9767 independent reflections
Radiation source: fine-focus sealed tube	7989 reflections with I > 2σ(I)
graphite	Rint = 0.027
Detector resolution: 0.15 mm pixels mm-1	θmax = 29.3°, θmin = 1.7°
rotation method scans	h = −14→14
Absorption correction: numerical [shape of crystal determined optically (X-RED32 and X-SHAPE; Stoe & Cie, 2005)]	k = −18→17
Tmin = 0.787, Tmax = 0.849	l = −19→19
21686 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0426P)2 + 0.6394P] where P = (Fo2 + 2Fc2)/3
9767 reflections	(Δ/σ)max = 0.009
571 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.92667 (19)	0.60711 (13)	0.42626 (12)	0.0349 (3)
C2	0.82734 (19)	0.52885 (13)	0.45838 (12)	0.0336 (3)
C3	0.7771 (2)	0.41642 (14)	0.42011 (14)	0.0434 (4)
H3	0.8050	0.3797	0.3699	0.052*
C4	0.6839 (2)	0.36009 (15)	0.45865 (16)	0.0518 (5)
H4	0.6483	0.2844	0.4338	0.062*
C5	0.6433 (2)	0.41524 (15)	0.53371 (16)	0.0479 (5)
H5	0.5793	0.3777	0.5586	0.057*
C6	0.70022 (19)	0.52775 (14)	0.57088 (13)	0.0365 (4)
C7	0.6773 (2)	0.60503 (15)	0.65600 (14)	0.0405 (4)
C8	1.12179 (19)	0.88335 (15)	0.73752 (13)	0.0374 (4)
C9	1.05336 (17)	0.95035 (13)	0.68217 (12)	0.0300 (3)
C10	1.11455 (18)	1.06105 (14)	0.69997 (13)	0.0359 (4)
H10	1.2007	1.0969	0.7456	0.043*
C11	1.04499 (19)	1.11726 (13)	0.64861 (14)	0.0375 (4)
H11	1.0844	1.1914	0.6585	0.045*
C12	0.91678 (18)	1.06222 (13)	0.58267 (13)	0.0333 (3)
H12	0.8681	1.0990	0.5485	0.040*
C13	0.86124 (17)	0.95140 (12)	0.56785 (12)	0.0289 (3)
C14	0.72275 (18)	0.88280 (14)	0.49429 (13)	0.0347 (3)
C15	1.37185 (16)	0.95961 (13)	1.07213 (13)	0.0324 (3)
C16	1.32913 (19)	1.05136 (15)	1.07799 (16)	0.0418 (4)
H16	1.2923	1.0673	1.0182	0.050*
C17	1.3422 (2)	1.11666 (16)	1.17189 (18)	0.0495 (5)
H17	1.3137	1.1769	1.1756	0.059*
C18	1.3977 (2)	1.09398 (18)	1.26218 (17)	0.0540 (5)
H18	1.4055	1.1389	1.3255	0.065*
C19	1.4404 (2)	1.00637 (17)	1.25805 (15)	0.0478 (5)
H19	1.4777	0.9924	1.3188	0.057*
C20	1.42907 (17)	0.93619 (14)	1.16281 (13)	0.0356 (3)
C21	1.46778 (17)	0.84053 (14)	1.15464 (13)	0.0341 (3)
C22	1.45007 (16)	0.77425 (13)	1.05444 (13)	0.0312 (3)
C23	1.48653 (18)	0.67858 (15)	1.03790 (15)	0.0387 (4)
H23	1.5244	0.6573	1.0939	0.046*
C24	1.4666 (2)	0.61789 (16)	0.94107 (16)	0.0437 (4)
H24	1.4893	0.5547	0.9313	0.052*
C25	1.4119 (2)	0.64989 (16)	0.85545 (15)	0.0441 (4)
H25	1.4005	0.6084	0.7896	0.053*
C26	1.37570 (19)	0.74056 (15)	0.86782 (14)	0.0386 (4)
H26	1.3390	0.7607	0.8107	0.046*
C27	1.39373 (16)	0.80415 (13)	0.96740 (13)	0.0308 (3)
C28	1.17771 (16)	0.58124 (14)	1.05864 (13)	0.0338 (3)
C29	1.23228 (18)	0.51486 (17)	1.10920 (16)	0.0436 (4)
H29	1.2597	0.5332	1.1806	0.052*
C30	1.24485 (19)	0.42350 (17)	1.05313 (18)	0.0492 (5)
H30	1.2795	0.3789	1.0866	0.059*
C31	1.2062 (2)	0.39600 (16)	0.94593 (19)	0.0476 (5)
H31	1.2161	0.3336	0.9087	0.057*
C32	1.15397 (18)	0.46015 (14)	0.89518 (15)	0.0384 (4)
H32	1.1294	0.4415	0.8238	0.046*
C33	1.13709 (16)	0.55450 (13)	0.95054 (13)	0.0308 (3)
C34	1.08234 (16)	0.62463 (12)	0.90149 (12)	0.0288 (3)
C35	1.06314 (16)	0.71546 (13)	0.96518 (12)	0.0302 (3)
C36	0.99460 (19)	0.78033 (14)	0.92334 (14)	0.0368 (4)
H36	0.9628	0.7663	0.8524	0.044*
C37	0.9746 (2)	0.86353 (15)	0.98634 (17)	0.0467 (5)
H37	0.9281	0.9052	0.9581	0.056*
C38	1.0236 (2)	0.88633 (16)	1.09302 (17)	0.0517 (5)
H38	1.0117	0.9447	1.1351	0.062*
C39	1.0883 (2)	0.82497 (16)	1.13650 (15)	0.0455 (4)
H39	1.1200	0.8409	1.2077	0.055*
C40	1.10684 (17)	0.73667 (14)	1.07256 (13)	0.0339 (3)
N1	0.78860 (15)	0.57997 (11)	0.53151 (10)	0.0326 (3)
N2	0.93015 (14)	0.89696 (10)	0.61670 (10)	0.0279 (3)
N3	1.35654 (15)	0.89429 (12)	0.97868 (11)	0.0333 (3)
H3B	1.318 (2)	0.9069 (17)	0.9258 (18)	0.042 (6)*
N4	1.51724 (19)	0.81276 (16)	1.23737 (14)	0.0467 (4)
H4B	1.528 (2)	0.748 (2)	1.2318 (19)	0.057 (7)*
H4C	1.528 (3)	0.850 (2)	1.291 (2)	0.067 (8)*
N5	1.16460 (15)	0.67181 (13)	1.11570 (12)	0.0373 (3)
H5B	1.176 (2)	0.6785 (19)	1.1757 (19)	0.048 (6)*
N6	1.04770 (17)	0.60697 (13)	0.80144 (12)	0.0378 (3)
H6A	1.054 (2)	0.5511 (19)	0.7603 (17)	0.044 (6)*
H6B	1.030 (2)	0.654 (2)	0.7758 (19)	0.054 (7)*
O1	0.95524 (15)	0.70686 (9)	0.47217 (10)	0.0418 (3)
O2	0.97283 (16)	0.57032 (11)	0.35961 (11)	0.0493 (3)
O3	0.74543 (16)	0.70499 (11)	0.67476 (11)	0.0478 (3)
O4	0.59948 (17)	0.56796 (13)	0.70047 (12)	0.0566 (4)
O5	1.06120 (15)	0.78245 (10)	0.70856 (10)	0.0442 (3)
O6	1.22946 (16)	0.93578 (13)	0.80681 (12)	0.0601 (4)
O7	0.69467 (15)	0.78226 (10)	0.47402 (11)	0.0497 (3)
O8	0.64709 (14)	0.93215 (11)	0.45968 (11)	0.0454 (3)
O1W	0.5812 (2)	0.62222 (17)	0.27969 (14)	0.0649 (5)
H1WA	0.618 (3)	0.663 (3)	0.343 (3)	0.082 (10)*
H1WB	0.538 (3)	0.574 (3)	0.288 (3)	0.085 (12)*
O2W	0.61462 (19)	1.13490 (14)	0.52765 (15)	0.0605 (4)
H2WA	0.536 (3)	1.119 (2)	0.531 (2)	0.069 (9)*
H2WB	0.627 (3)	1.075 (3)	0.512 (3)	0.091 (11)*
O3W	1.1854 (2)	0.70163 (17)	1.31659 (12)	0.0679 (5)
H3WA	1.132 (3)	0.668 (2)	1.337 (2)	0.063 (8)*
H3WB	1.248 (3)	0.749 (2)	1.366 (2)	0.066 (8)*
Cu1	0.85947 (2)	0.735741 (15)	0.580449 (16)	0.03269 (6)

	U11	U22	U33	U12	U13	U23
C1	0.0476 (10)	0.0303 (7)	0.0268 (7)	0.0145 (7)	0.0114 (7)	0.0070 (6)
C2	0.0465 (10)	0.0275 (7)	0.0262 (7)	0.0145 (7)	0.0087 (7)	0.0069 (6)
C3	0.0631 (12)	0.0274 (8)	0.0353 (9)	0.0142 (8)	0.0131 (9)	0.0040 (7)
C4	0.0692 (14)	0.0252 (8)	0.0489 (11)	0.0057 (8)	0.0124 (10)	0.0064 (7)
C5	0.0574 (12)	0.0342 (9)	0.0487 (11)	0.0061 (8)	0.0179 (10)	0.0156 (8)
C6	0.0449 (10)	0.0332 (8)	0.0330 (8)	0.0125 (7)	0.0117 (7)	0.0144 (7)
C7	0.0496 (11)	0.0411 (9)	0.0363 (9)	0.0173 (8)	0.0176 (8)	0.0153 (7)
C8	0.0445 (10)	0.0427 (9)	0.0312 (8)	0.0203 (8)	0.0099 (7)	0.0182 (7)
C9	0.0377 (8)	0.0313 (7)	0.0243 (7)	0.0147 (6)	0.0103 (6)	0.0098 (6)
C10	0.0358 (9)	0.0340 (8)	0.0330 (8)	0.0080 (7)	0.0057 (7)	0.0102 (6)
C11	0.0452 (10)	0.0275 (7)	0.0399 (9)	0.0103 (7)	0.0131 (8)	0.0125 (7)
C12	0.0421 (9)	0.0297 (7)	0.0338 (8)	0.0179 (7)	0.0118 (7)	0.0134 (6)
C13	0.0368 (8)	0.0278 (7)	0.0258 (7)	0.0158 (6)	0.0105 (6)	0.0079 (5)
C14	0.0388 (9)	0.0341 (8)	0.0302 (8)	0.0141 (7)	0.0078 (7)	0.0088 (6)
C15	0.0272 (8)	0.0317 (7)	0.0355 (8)	0.0074 (6)	0.0078 (6)	0.0098 (6)
C16	0.0402 (10)	0.0376 (9)	0.0483 (10)	0.0147 (7)	0.0123 (8)	0.0139 (8)
C17	0.0500 (12)	0.0358 (9)	0.0604 (13)	0.0164 (8)	0.0178 (10)	0.0059 (8)
C18	0.0597 (13)	0.0473 (11)	0.0450 (11)	0.0165 (10)	0.0130 (10)	−0.0011 (9)
C19	0.0531 (12)	0.0484 (11)	0.0329 (9)	0.0151 (9)	0.0063 (8)	0.0039 (8)
C20	0.0327 (8)	0.0362 (8)	0.0331 (8)	0.0085 (7)	0.0068 (7)	0.0081 (7)
C21	0.0269 (8)	0.0380 (8)	0.0327 (8)	0.0073 (6)	0.0045 (6)	0.0110 (7)
C22	0.0256 (7)	0.0339 (8)	0.0339 (8)	0.0097 (6)	0.0075 (6)	0.0120 (6)
C23	0.0327 (9)	0.0425 (9)	0.0452 (10)	0.0172 (7)	0.0105 (8)	0.0173 (8)
C24	0.0392 (10)	0.0427 (9)	0.0541 (11)	0.0202 (8)	0.0176 (9)	0.0124 (8)
C25	0.0465 (11)	0.0472 (10)	0.0386 (9)	0.0188 (8)	0.0157 (8)	0.0059 (8)
C26	0.0394 (9)	0.0441 (9)	0.0321 (8)	0.0153 (8)	0.0097 (7)	0.0107 (7)
C27	0.0251 (7)	0.0333 (7)	0.0329 (8)	0.0081 (6)	0.0083 (6)	0.0103 (6)
C28	0.0247 (8)	0.0403 (8)	0.0370 (8)	0.0071 (6)	0.0103 (7)	0.0168 (7)
C29	0.0315 (9)	0.0562 (11)	0.0479 (10)	0.0122 (8)	0.0106 (8)	0.0303 (9)
C30	0.0346 (10)	0.0521 (11)	0.0726 (14)	0.0173 (8)	0.0172 (10)	0.0382 (11)
C31	0.0388 (10)	0.0374 (9)	0.0721 (14)	0.0165 (8)	0.0181 (10)	0.0214 (9)
C32	0.0366 (9)	0.0340 (8)	0.0459 (10)	0.0139 (7)	0.0129 (8)	0.0119 (7)
C33	0.0274 (8)	0.0309 (7)	0.0359 (8)	0.0089 (6)	0.0112 (6)	0.0126 (6)
C34	0.0276 (7)	0.0285 (7)	0.0297 (7)	0.0082 (6)	0.0105 (6)	0.0076 (6)
C35	0.0304 (8)	0.0289 (7)	0.0313 (8)	0.0085 (6)	0.0122 (6)	0.0077 (6)
C36	0.0413 (9)	0.0339 (8)	0.0383 (9)	0.0145 (7)	0.0157 (8)	0.0110 (7)
C37	0.0541 (12)	0.0359 (9)	0.0586 (12)	0.0215 (8)	0.0256 (10)	0.0137 (8)
C38	0.0686 (14)	0.0380 (9)	0.0547 (12)	0.0198 (9)	0.0348 (11)	0.0055 (8)
C39	0.0558 (12)	0.0419 (9)	0.0355 (9)	0.0106 (8)	0.0217 (9)	0.0033 (7)
C40	0.0319 (8)	0.0351 (8)	0.0319 (8)	0.0062 (6)	0.0128 (7)	0.0072 (6)
N1	0.0453 (8)	0.0257 (6)	0.0286 (6)	0.0130 (6)	0.0116 (6)	0.0098 (5)
N2	0.0364 (7)	0.0258 (6)	0.0236 (6)	0.0139 (5)	0.0095 (5)	0.0069 (5)
N3	0.0337 (7)	0.0358 (7)	0.0306 (7)	0.0125 (6)	0.0070 (6)	0.0125 (6)
N4	0.0556 (11)	0.0490 (10)	0.0319 (8)	0.0210 (8)	0.0027 (7)	0.0129 (7)
N5	0.0361 (8)	0.0462 (8)	0.0268 (7)	0.0098 (6)	0.0092 (6)	0.0106 (6)
N6	0.0538 (10)	0.0346 (7)	0.0295 (7)	0.0224 (7)	0.0134 (7)	0.0085 (6)
O1	0.0649 (9)	0.0268 (5)	0.0394 (7)	0.0151 (6)	0.0258 (6)	0.0101 (5)
O2	0.0661 (9)	0.0417 (7)	0.0405 (7)	0.0155 (6)	0.0283 (7)	0.0026 (6)
O3	0.0672 (9)	0.0363 (6)	0.0461 (7)	0.0177 (6)	0.0302 (7)	0.0097 (6)
O4	0.0685 (10)	0.0577 (9)	0.0557 (9)	0.0193 (8)	0.0371 (8)	0.0230 (7)
O5	0.0600 (9)	0.0390 (7)	0.0414 (7)	0.0248 (6)	0.0132 (6)	0.0202 (5)
O6	0.0558 (9)	0.0604 (9)	0.0535 (9)	0.0176 (7)	−0.0084 (7)	0.0267 (7)
O7	0.0516 (8)	0.0318 (6)	0.0496 (8)	0.0099 (6)	−0.0026 (7)	0.0055 (6)
O8	0.0411 (7)	0.0431 (7)	0.0471 (7)	0.0201 (6)	0.0009 (6)	0.0107 (6)
O1W	0.0835 (13)	0.0531 (10)	0.0467 (9)	0.0119 (9)	0.0106 (9)	0.0166 (8)
O2W	0.0492 (10)	0.0411 (8)	0.0809 (12)	0.0085 (7)	0.0180 (9)	0.0082 (8)
O3W	0.0691 (12)	0.0796 (12)	0.0318 (8)	−0.0060 (10)	0.0135 (8)	0.0114 (8)
Cu1	0.04830 (13)	0.02337 (9)	0.02931 (10)	0.01400 (8)	0.01495 (9)	0.00781 (7)

C1—O2	1.238 (2)	C24—H24	0.9300
C1—O1	1.264 (2)	C25—C26	1.356 (3)
C1—C2	1.515 (2)	C25—H25	0.9300
C2—N1	1.327 (2)	C26—C27	1.409 (2)
C2—C3	1.382 (2)	C26—H26	0.9300
C3—C4	1.385 (3)	C27—N3	1.355 (2)
C3—H3	0.9300	C28—N5	1.361 (2)
C4—C5	1.384 (3)	C28—C29	1.405 (3)
C4—H4	0.9300	C28—C33	1.408 (2)
C5—C6	1.386 (3)	C29—C30	1.361 (3)
C5—H5	0.9300	C29—H29	0.9300
C6—N1	1.334 (2)	C30—C31	1.396 (3)
C6—C7	1.519 (3)	C30—H30	0.9300
C7—O4	1.231 (2)	C31—C32	1.370 (3)
C7—O3	1.275 (2)	C31—H31	0.9300
C8—O6	1.242 (2)	C32—C33	1.412 (2)
C8—O5	1.255 (2)	C32—H32	0.9300
C8—C9	1.522 (2)	C33—C34	1.437 (2)
C9—N2	1.334 (2)	C34—N6	1.312 (2)
C9—C10	1.386 (2)	C34—C35	1.439 (2)
C10—C11	1.384 (3)	C35—C40	1.405 (2)
C10—H10	0.9300	C35—C36	1.411 (2)
C11—C12	1.378 (3)	C36—C37	1.365 (2)
C11—H11	0.9300	C36—H36	0.9300
C12—C13	1.386 (2)	C37—C38	1.396 (3)
C12—H12	0.9300	C37—H37	0.9300
C13—N2	1.344 (2)	C38—C39	1.357 (3)
C13—C14	1.518 (3)	C38—H38	0.9300
C14—O7	1.243 (2)	C39—C40	1.413 (2)
C14—O8	1.256 (2)	C39—H39	0.9300
C15—N3	1.355 (2)	C40—N5	1.353 (2)
C15—C20	1.410 (2)	N1—Cu1	1.9128 (15)
C15—C16	1.411 (2)	N2—Cu1	1.9818 (14)
C16—C17	1.367 (3)	N3—H3B	0.83 (2)
C16—H16	0.9300	N4—H4B	0.89 (3)
C17—C18	1.395 (3)	N4—H4C	0.78 (3)
C17—H17	0.9300	N5—H5B	0.80 (2)
C18—C19	1.361 (3)	N6—H6A	0.87 (2)
C18—H18	0.9300	N6—H6B	0.83 (3)
C19—C20	1.415 (3)	O1—Cu1	2.0680 (14)
C19—H19	0.9300	O3—Cu1	2.0529 (15)
C20—C21	1.434 (2)	O5—Cu1	2.3150 (18)
C21—N4	1.324 (2)	O7—Cu1	2.3509 (16)
C21—C22	1.430 (2)	O1W—H1WA	0.87 (3)
C22—C27	1.412 (2)	O1W—H1WB	0.74 (3)
C22—C23	1.422 (2)	O2W—H2WA	0.85 (3)
C23—C24	1.358 (3)	O2W—H2WB	0.84 (3)
C23—H23	0.9300	O3W—H3WA	0.79 (3)
C24—C25	1.407 (3)	O3W—H3WB	0.84 (3)
O2—C1—O1	125.65 (17)	C26—C27—C22	120.30 (16)
O2—C1—C2	119.24 (15)	N5—C28—C29	119.02 (17)
O1—C1—C2	115.11 (15)	N5—C28—C33	120.47 (16)
N1—C2—C3	120.24 (17)	C29—C28—C33	120.51 (17)
N1—C2—C1	112.35 (14)	C30—C29—C28	119.69 (19)
C3—C2—C1	127.41 (16)	C30—C29—H29	120.2
C2—C3—C4	118.10 (18)	C28—C29—H29	120.2
C2—C3—H3	120.9	C29—C30—C31	120.72 (18)
C4—C3—H3	120.9	C29—C30—H30	119.6
C5—C4—C3	120.66 (17)	C31—C30—H30	119.6
C5—C4—H4	119.7	C32—C31—C30	120.51 (19)
C3—C4—H4	119.7	C32—C31—H31	119.7
C4—C5—C6	118.41 (18)	C30—C31—H31	119.7
C4—C5—H5	120.8	C31—C32—C33	120.44 (19)
C6—C5—H5	120.8	C31—C32—H32	119.8
N1—C6—C5	119.60 (17)	C33—C32—H32	119.8
N1—C6—C7	112.28 (15)	C28—C33—C32	118.12 (16)
C5—C6—C7	128.11 (17)	C28—C33—C34	118.97 (15)
O4—C7—O3	126.43 (18)	C32—C33—C34	122.91 (16)
O4—C7—C6	119.43 (17)	N6—C34—C33	122.09 (15)
O3—C7—C6	114.13 (16)	N6—C34—C35	119.76 (15)
O6—C8—O5	128.25 (17)	C33—C34—C35	118.14 (14)
O6—C8—C9	115.80 (16)	C40—C35—C36	118.52 (15)
O5—C8—C9	115.94 (16)	C40—C35—C34	119.16 (15)
N2—C9—C10	121.76 (15)	C36—C35—C34	122.21 (15)
N2—C9—C8	116.30 (14)	C37—C36—C35	120.43 (18)
C10—C9—C8	121.93 (16)	C37—C36—H36	119.8
C11—C10—C9	118.74 (16)	C35—C36—H36	119.8
C11—C10—H10	120.6	C36—C37—C38	120.26 (19)
C9—C10—H10	120.6	C36—C37—H37	119.9
C12—C11—C10	119.29 (16)	C38—C37—H37	119.9
C12—C11—H11	120.4	C39—C38—C37	121.25 (18)
C10—C11—H11	120.4	C39—C38—H38	119.4
C11—C12—C13	119.24 (16)	C37—C38—H38	119.4
C11—C12—H12	120.4	C38—C39—C40	119.34 (18)
C13—C12—H12	120.4	C38—C39—H39	120.3
N2—C13—C12	121.16 (15)	C40—C39—H39	120.3
N2—C13—C14	115.54 (14)	N5—C40—C35	120.55 (15)
C12—C13—C14	123.27 (15)	N5—C40—C39	119.33 (17)
O7—C14—O8	125.93 (17)	C35—C40—C39	120.11 (17)
O7—C14—C13	116.55 (16)	C2—N1—C6	122.94 (15)
O8—C14—C13	117.52 (15)	C2—N1—Cu1	118.54 (12)
N3—C15—C20	120.58 (16)	C6—N1—Cu1	118.50 (12)
N3—C15—C16	119.34 (17)	C9—N2—C13	119.80 (14)
C20—C15—C16	120.07 (17)	C9—N2—Cu1	119.28 (11)
C17—C16—C15	119.72 (19)	C13—N2—Cu1	120.54 (11)
C17—C16—H16	120.1	C27—N3—C15	122.43 (15)
C15—C16—H16	120.1	C27—N3—H3B	118.2 (15)
C16—C17—C18	120.81 (19)	C15—N3—H3B	119.2 (15)
C16—C17—H17	119.6	C21—N4—H4B	121.0 (16)
C18—C17—H17	119.6	C21—N4—H4C	119 (2)
C19—C18—C17	120.29 (19)	H4B—N4—H4C	119 (3)
C19—C18—H18	119.9	C40—N5—C28	122.49 (15)
C17—C18—H18	119.9	C40—N5—H5B	118.6 (17)
C18—C19—C20	121.1 (2)	C28—N5—H5B	117.4 (17)
C18—C19—H19	119.4	C34—N6—H6A	122.4 (15)
C20—C19—H19	119.4	C34—N6—H6B	120.2 (17)
C15—C20—C19	117.99 (17)	H6A—N6—H6B	117 (2)
C15—C20—C21	118.98 (16)	C1—O1—Cu1	114.16 (11)
C19—C20—C21	122.98 (17)	C7—O3—Cu1	115.04 (12)
N4—C21—C22	120.31 (17)	C8—O5—Cu1	111.55 (11)
N4—C21—C20	121.26 (17)	C14—O7—Cu1	111.16 (12)
C22—C21—C20	118.43 (15)	H1WA—O1W—H1WB	99 (3)
C27—C22—C23	117.95 (16)	H2WA—O2W—H2WB	105 (3)
C27—C22—C21	119.13 (15)	H3WA—O3W—H3WB	110 (3)
C23—C22—C21	122.92 (16)	N1—Cu1—N2	174.31 (6)
C24—C23—C22	120.64 (17)	N1—Cu1—O3	79.84 (6)
C24—C23—H23	119.7	N2—Cu1—O3	104.50 (6)
C22—C23—H23	119.7	N1—Cu1—O1	79.84 (6)
C23—C24—C25	120.51 (18)	N2—Cu1—O1	95.97 (6)
C23—C24—H24	119.7	O3—Cu1—O1	159.47 (5)
C25—C24—H24	119.7	N1—Cu1—O5	107.30 (7)
C26—C25—C24	120.74 (18)	N2—Cu1—O5	76.29 (6)
C26—C25—H25	119.6	O3—Cu1—O5	94.39 (6)
C24—C25—H25	119.6	O1—Cu1—O5	88.91 (6)
C25—C26—C27	119.86 (18)	N1—Cu1—O7	101.06 (7)
C25—C26—H26	120.1	N2—Cu1—O7	75.34 (6)
C27—C26—H26	120.1	O3—Cu1—O7	91.72 (6)
N3—C27—C26	119.27 (16)	O1—Cu1—O7	94.95 (6)
N3—C27—C22	120.43 (15)	O5—Cu1—O7	151.61 (5)
O2—C1—C2—N1	178.92 (17)	C34—C35—C36—C37	177.81 (17)
O1—C1—C2—N1	−0.9 (2)	C35—C36—C37—C38	1.0 (3)
O2—C1—C2—C3	−1.3 (3)	C36—C37—C38—C39	−2.0 (3)
O1—C1—C2—C3	178.93 (18)	C37—C38—C39—C40	0.3 (3)
N1—C2—C3—C4	1.4 (3)	C36—C35—C40—N5	175.36 (16)
C1—C2—C3—C4	−178.39 (19)	C34—C35—C40—N5	−0.9 (2)
C2—C3—C4—C5	−0.3 (3)	C36—C35—C40—C39	−3.3 (2)
C3—C4—C5—C6	−1.4 (3)	C34—C35—C40—C39	−179.61 (16)
C4—C5—C6—N1	2.2 (3)	C38—C39—C40—N5	−176.33 (18)
C4—C5—C6—C7	−176.8 (2)	C38—C39—C40—C35	2.4 (3)
N1—C6—C7—O4	−178.97 (18)	C3—C2—N1—C6	−0.7 (3)
C5—C6—C7—O4	0.0 (3)	C1—C2—N1—C6	179.14 (16)
N1—C6—C7—O3	0.0 (2)	C3—C2—N1—Cu1	−179.19 (14)
C5—C6—C7—O3	179.0 (2)	C1—C2—N1—Cu1	0.6 (2)
O6—C8—C9—N2	−171.91 (16)	C5—C6—N1—C2	−1.1 (3)
O5—C8—C9—N2	6.9 (2)	C7—C6—N1—C2	177.94 (16)
O6—C8—C9—C10	7.0 (3)	C5—C6—N1—Cu1	177.36 (15)
O5—C8—C9—C10	−174.13 (16)	C7—C6—N1—Cu1	−3.6 (2)
N2—C9—C10—C11	0.4 (3)	C10—C9—N2—C13	−1.5 (2)
C8—C9—C10—C11	−178.49 (16)	C8—C9—N2—C13	177.47 (14)
C9—C10—C11—C12	0.9 (3)	C10—C9—N2—Cu1	171.40 (13)
C10—C11—C12—C13	−1.1 (3)	C8—C9—N2—Cu1	−9.66 (18)
C11—C12—C13—N2	0.1 (2)	C12—C13—N2—C9	1.2 (2)
C11—C12—C13—C14	−177.93 (16)	C14—C13—N2—C9	179.38 (13)
N2—C13—C14—O7	−10.9 (2)	C12—C13—N2—Cu1	−171.55 (12)
C12—C13—C14—O7	167.20 (17)	C14—C13—N2—Cu1	6.61 (18)
N2—C13—C14—O8	168.95 (15)	C26—C27—N3—C15	−179.52 (16)
C12—C13—C14—O8	−12.9 (2)	C22—C27—N3—C15	0.4 (2)
N3—C15—C16—C17	178.92 (17)	C20—C15—N3—C27	0.5 (2)
C20—C15—C16—C17	−0.7 (3)	C16—C15—N3—C27	−179.13 (16)
C15—C16—C17—C18	0.2 (3)	C35—C40—N5—C28	−3.1 (3)
C16—C17—C18—C19	0.3 (4)	C39—C40—N5—C28	175.61 (16)
C17—C18—C19—C20	−0.4 (3)	C29—C28—N5—C40	−176.57 (16)
N3—C15—C20—C19	−178.98 (17)	C33—C28—N5—C40	3.4 (2)
C16—C15—C20—C19	0.6 (3)	O2—C1—O1—Cu1	−179.08 (16)
N3—C15—C20—C21	−1.6 (2)	C2—C1—O1—Cu1	0.7 (2)
C16—C15—C20—C21	178.05 (16)	O4—C7—O3—Cu1	−177.91 (17)
C18—C19—C20—C15	−0.1 (3)	C6—C7—O3—Cu1	3.2 (2)
C18—C19—C20—C21	−177.4 (2)	O6—C8—O5—Cu1	177.28 (18)
C15—C20—C21—N4	−177.40 (17)	C9—C8—O5—Cu1	−1.39 (19)
C19—C20—C21—N4	−0.1 (3)	O8—C14—O7—Cu1	−170.74 (15)
C15—C20—C21—C22	1.7 (2)	C13—C14—O7—Cu1	9.11 (19)
C19—C20—C21—C22	178.99 (17)	C2—N1—Cu1—O3	−177.34 (14)
N4—C21—C22—C27	178.29 (17)	C6—N1—Cu1—O3	4.08 (13)
C20—C21—C22—C27	−0.9 (2)	C2—N1—Cu1—O1	−0.23 (13)
N4—C21—C22—C23	−1.6 (3)	C6—N1—Cu1—O1	−178.81 (14)
C20—C21—C22—C23	179.26 (16)	C2—N1—Cu1—O5	−85.87 (14)
C27—C22—C23—C24	−0.4 (3)	C6—N1—Cu1—O5	95.56 (14)
C21—C22—C23—C24	179.45 (17)	C2—N1—Cu1—O7	92.88 (14)
C22—C23—C24—C25	1.3 (3)	C6—N1—Cu1—O7	−85.69 (14)
C23—C24—C25—C26	−1.3 (3)	C9—N2—Cu1—O3	97.70 (12)
C24—C25—C26—C27	0.5 (3)	C13—N2—Cu1—O3	−89.48 (13)
C25—C26—C27—N3	−179.69 (17)	C9—N2—Cu1—O1	−80.76 (12)
C25—C26—C27—C22	0.4 (3)	C13—N2—Cu1—O1	92.06 (12)
C23—C22—C27—N3	179.67 (15)	C9—N2—Cu1—O5	6.65 (11)
C21—C22—C27—N3	−0.2 (2)	C13—N2—Cu1—O5	179.47 (13)
C23—C22—C27—C26	−0.4 (2)	C9—N2—Cu1—O7	−174.33 (13)
C21—C22—C27—C26	179.73 (16)	C13—N2—Cu1—O7	−1.52 (12)
N5—C28—C29—C30	179.39 (17)	C7—O3—Cu1—N1	−3.98 (14)
C33—C28—C29—C30	−0.6 (3)	C7—O3—Cu1—N2	172.25 (14)
C28—C29—C30—C31	1.1 (3)	C7—O3—Cu1—O1	−12.1 (3)
C29—C30—C31—C32	−0.5 (3)	C7—O3—Cu1—O5	−110.80 (15)
C30—C31—C32—C33	−0.7 (3)	C7—O3—Cu1—O7	96.94 (15)
N5—C28—C33—C32	179.48 (15)	C1—O1—Cu1—N1	−0.30 (13)
C29—C28—C33—C32	−0.6 (2)	C1—O1—Cu1—N2	−176.41 (13)
N5—C28—C33—C34	0.4 (2)	C1—O1—Cu1—O3	7.8 (3)
C29—C28—C33—C34	−179.68 (15)	C1—O1—Cu1—O5	107.50 (14)
C31—C32—C33—C28	1.2 (3)	C1—O1—Cu1—O7	−100.67 (14)
C31—C32—C33—C34	−179.76 (17)	C8—O5—Cu1—N1	172.87 (12)
C28—C33—C34—N6	177.13 (16)	C8—O5—Cu1—N2	−2.54 (12)
C32—C33—C34—N6	−1.9 (3)	C8—O5—Cu1—O3	−106.42 (13)
C28—C33—C34—C35	−4.1 (2)	C8—O5—Cu1—O1	93.87 (13)
C32—C33—C34—C35	176.79 (15)	C8—O5—Cu1—O7	−4.55 (19)
N6—C34—C35—C40	−176.82 (16)	C14—O7—Cu1—N1	179.90 (13)
C33—C34—C35—C40	4.4 (2)	C14—O7—Cu1—N2	−4.63 (13)
N6—C34—C35—C36	7.1 (2)	C14—O7—Cu1—O3	99.91 (14)
C33—C34—C35—C36	−171.71 (15)	C14—O7—Cu1—O1	−99.52 (14)
C40—C35—C36—C37	1.7 (3)	C14—O7—Cu1—O5	−2.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O7	0.87 (4)	1.98 (4)	2.832 (2)	167 (4)
O1W—H1WB···O4i	0.74 (4)	2.14 (4)	2.877 (3)	175 (4)
O2W—H2WA···O8ii	0.84 (3)	1.98 (3)	2.820 (3)	174 (3)
O2W—H2WB···O8	0.84 (4)	1.98 (4)	2.810 (3)	174 (4)
O3W—H3WA···O2iii	0.79 (3)	2.01 (3)	2.787 (3)	169 (3)
O3W—H3WB···O2Wiv	0.84 (3)	1.89 (3)	2.730 (3)	175 (3)
N3—H3B···O6	0.83 (2)	1.88 (2)	2.716 (2)	179 (3)
N4—H4B···O1Wv	0.89 (3)	2.09 (3)	2.938 (3)	158 (2)
N4—H4C···O8v	0.77 (3)	2.27 (3)	2.972 (2)	152 (3)
N5—H5B···O3W	0.80 (2)	1.91 (2)	2.703 (2)	173 (2)
N6—H6A···O2vi	0.87 (2)	1.97 (2)	2.819 (2)	164 (2)
N6—H6B···O5	0.83 (3)	2.11 (3)	2.888 (2)	158 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O7	0.87 (4)	1.98 (4)	2.832 (2)	167 (4)
O1W—H1WB⋯O4i	0.74 (4)	2.14 (4)	2.877 (3)	175 (4)
O2W—H2WA⋯O8ii	0.84 (3)	1.98 (3)	2.820 (3)	174 (3)
O2W—H2WB⋯O8	0.84 (4)	1.98 (4)	2.810 (3)	174 (4)
O3W—H3WA⋯O2iii	0.79 (3)	2.01 (3)	2.787 (3)	169 (3)
O3W—H3WB⋯O2Wiv	0.84 (3)	1.89 (3)	2.730 (3)	175 (3)
N3—H3B⋯O6	0.83 (2)	1.88 (2)	2.716 (2)	179 (3)
N4—H4B⋯O1Wv	0.89 (3)	2.09 (3)	2.938 (3)	158 (2)
N4—H4C⋯O8v	0.77 (3)	2.27 (3)	2.972 (2)	152 (3)
N5—H5B⋯O3W	0.80 (2)	1.91 (2)	2.703 (2)	173 (2)
N6—H6A⋯O2vi	0.87 (2)	1.97 (2)	2.819 (2)	164 (2)
N6—H6B⋯O5	0.83 (3)	2.11 (3)	2.888 (2)	158 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .