Bis(8-hy-droxy-2-methyl-quinolinium) bis-(pyridine-2,6-dicarboxyl-ato)cuprate(II) methanol monosolvate monohydrate.

The title compound, (C(10)H(10)NO)(2)[Cu(C(7)H(3)NO(4))(2)]·CH(3)OH·H(2)O was prepared by the reaction of copper(II) nitrate hexa-hydrate, 8-hy-droxy-2-methyl-quinoline, and pyridine-2,6-dicarb-oxy-lic acid in a 1:2:2 molar ratio in an aqueous solution. The geometry of the resulting CuN(2)O(4) coordination can be described as distorted octa-hedral. In the crystal, there are several inter-molecular O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds. An intra-molecular N-H⋯O hydrogen bond occurs in one of the cations. Considerable π-π stacking inter-actions are also observed between the aromatic rings of the cations, with centroid-centroid distances of 3.4567 (13), 3.5342 (14), 3.6941 (14) and 3.4568 (13) Å. These non-covalent inter-actions connect the components, forming a three-dimensional supra-molecular structure.

Related literature

For background to proton-transfer compounds, see: Aghabozorg et al. (2008 ▶). For examples of proton transfer from pyridine-2,6-dicarb­oxy­lic acid (pydcH2) to different amine base ligands, see: Eshtiagh-Hosseini et al. (2010a ▶, ▶).

Experimental

Crystal data

(C10H10NO)2[Cu(C7H3NO4)2]·CH4O·H2O

M = 764.20

Triclinic,

a = 10.116 (2) Å

b = 12.895 (3) Å

c = 14.816 (3) Å

α = 64.45 (3)°

β = 76.23 (3)°

γ = 83.74 (3)°

V = 1693.5 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.72 mm−1

T = 298 K

0.5 × 0.4 × 0.3 mm

Data collection

Stoe IPDS II diffractometer

Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005 ▶) T min = 0.714, T max = 0.803

18924 measured reflections

9061 independent reflections

7185 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.109

S = 1.01

9061 reflections

498 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.70 e Å−3

Δρmin = −0.45 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, global. DOI: 10.1107/S160053681100674X/vm2078sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100674X/vm2078Isup2.hkl

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

(C10H10NO)2[Cu(C7H3NO4)2]·CH4O·H2O	Z = 2
Mr = 764.20	F(000) = 790
Triclinic, P1	Dx = 1.499 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.116 (2) Å	Cell parameters from 9061 reflections
b = 12.895 (3) Å	θ = 2.3–29.2°
c = 14.816 (3) Å	µ = 0.72 mm−1
α = 64.45 (3)°	T = 298 K
β = 76.23 (3)°	Block, green
γ = 83.74 (3)°	0.5 × 0.4 × 0.3 mm
V = 1693.5 (8) Å3

Stoe IPDS II diffractometer	9061 independent reflections
Radiation source: fine-focus sealed tube	7185 reflections with I > 2σ(I)
graphite	Rint = 0.028
Detector resolution: 0.15 mm pixels mm-1	θmax = 29.2°, θmin = 2.3°
rotation method scans	h = −13→13
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005)	k = −17→17
Tmin = 0.714, Tmax = 0.803	l = −20→18
18924 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) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0728P)2] where P = (Fo2 + 2Fc2)/3
9061 reflections	(Δ/σ)max = 0.002
498 parameters	Δρmax = 0.70 e Å−3
2 restraints	Δρmin = −0.45 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
Cu1	0.987953 (19)	0.531740 (17)	0.743974 (16)	0.03101 (7)
N1	0.88383 (13)	0.54422 (11)	0.86756 (11)	0.0300 (3)
N2	1.09007 (13)	0.53417 (11)	0.61416 (10)	0.0279 (3)
O5	0.89361 (13)	0.67395 (12)	0.63268 (11)	0.0447 (3)
O3	0.81065 (14)	0.42206 (13)	0.78562 (11)	0.0460 (3)
O1	1.11637 (13)	0.64363 (13)	0.76480 (11)	0.0440 (3)
O7	1.12019 (15)	0.38075 (12)	0.79369 (10)	0.0450 (3)
O8	1.28336 (16)	0.28824 (13)	0.72425 (12)	0.0545 (4)
O2	1.11205 (17)	0.73177 (15)	0.86636 (13)	0.0587 (4)
O4	0.61123 (14)	0.37723 (14)	0.89804 (13)	0.0536 (4)
C1	0.92907 (16)	0.61020 (14)	0.90270 (13)	0.0317 (3)
C5	0.76455 (16)	0.48968 (14)	0.91421 (13)	0.0331 (3)
C7	0.72560 (18)	0.42323 (15)	0.86147 (14)	0.0371 (4)
C6	1.06461 (17)	0.66757 (15)	0.84037 (14)	0.0368 (4)
C8	1.06465 (16)	0.61551 (13)	0.52592 (13)	0.0305 (3)
C14	1.19898 (18)	0.36591 (15)	0.72033 (14)	0.0351 (3)
C2	0.8541 (2)	0.62252 (17)	0.98891 (15)	0.0420 (4)
H2	0.8858	0.6685	1.0132	0.050*
C12	1.18579 (16)	0.45418 (14)	0.61431 (13)	0.0313 (3)
O9	0.66369 (14)	0.76955 (12)	0.66892 (13)	0.0495 (4)
O6	0.92311 (15)	0.77708 (13)	0.46303 (12)	0.0573 (4)
C9	1.13573 (19)	0.61976 (16)	0.43302 (14)	0.0400 (4)
H9	1.1166	0.6763	0.3723	0.048*
C10	1.2365 (2)	0.53816 (19)	0.43151 (15)	0.0481 (5)
H10	1.2865	0.5394	0.3696	0.058*
N3	0.45289 (14)	0.91753 (13)	0.63308 (11)	0.0325 (3)
C23	0.68490 (17)	0.87638 (16)	0.65494 (15)	0.0375 (4)
C24	0.57362 (16)	0.95441 (15)	0.63553 (13)	0.0325 (3)
C11	1.2618 (2)	0.45481 (18)	0.52344 (15)	0.0452 (4)
H11	1.3295	0.3998	0.5239	0.054*
C16	0.34540 (17)	0.98636 (16)	0.61397 (13)	0.0372 (4)
C3	0.7318 (2)	0.5658 (2)	1.03830 (16)	0.0487 (5)
H3	0.6807	0.5730	1.0965	0.058*
C15	0.21709 (19)	0.9375 (2)	0.61694 (17)	0.0477 (5)
H15A	0.2375	0.8892	0.5809	0.072*
H15B	0.1575	0.9988	0.5850	0.072*
H15C	0.1735	0.8929	0.6868	0.072*
C4	0.68596 (19)	0.49856 (19)	1.00097 (15)	0.0452 (4)
H4	0.6038	0.4598	1.0334	0.054*
O10	0.52372 (17)	0.25204 (13)	0.83028 (15)	0.0587 (4)
N4	0.38002 (15)	0.08098 (13)	0.84401 (12)	0.0349 (3)
C21	0.8161 (2)	1.0311 (2)	0.64068 (19)	0.0548 (5)
H21	0.8979	1.0560	0.6426	0.066*
C26	0.30049 (18)	0.00004 (17)	0.85244 (14)	0.0400 (4)
C19	0.58640 (19)	1.06926 (16)	0.61857 (14)	0.0389 (4)
C33	0.58524 (19)	0.14932 (17)	0.85447 (16)	0.0415 (4)
C25	0.1594 (2)	0.0336 (2)	0.83583 (19)	0.0551 (5)
H25A	0.1027	0.0378	0.8961	0.083*
H25B	0.1237	−0.0227	0.8219	0.083*
H25C	0.1609	0.1072	0.7787	0.083*
C17	0.3561 (2)	1.10237 (18)	0.59373 (15)	0.0460 (5)
H17	0.2828	1.1521	0.5778	0.055*
C22	0.80401 (19)	0.9164 (2)	0.65722 (18)	0.0490 (5)
H22	0.8780	0.8667	0.6700	0.059*
C34	0.50978 (17)	0.05901 (15)	0.86173 (13)	0.0337 (3)
C18	0.4726 (2)	1.14235 (17)	0.59722 (16)	0.0475 (5)
H18	0.4775	1.2189	0.5854	0.057*
C20	0.7101 (2)	1.10638 (19)	0.62198 (18)	0.0508 (5)
H20	0.7194	1.1819	0.6115	0.061*
C32	0.7142 (2)	0.1243 (2)	0.87438 (17)	0.0510 (5)
H32	0.7665	0.1821	0.8698	0.061*
C29	0.56299 (19)	−0.05345 (16)	0.88863 (14)	0.0399 (4)
C27	0.3516 (2)	−0.11168 (18)	0.87752 (16)	0.0474 (5)
H27	0.2976	−0.1686	0.8825	0.057*
C28	0.4794 (2)	−0.13769 (17)	0.89464 (16)	0.0478 (5)
H28	0.5124	−0.2123	0.9106	0.057*
C31	0.7666 (2)	0.0131 (2)	0.90131 (18)	0.0567 (6)
H31	0.8536	−0.0018	0.9148	0.068*
C30	0.6951 (2)	−0.0749 (2)	0.90864 (18)	0.0537 (5)
H30	0.7330	−0.1482	0.9266	0.064*
C13	0.95099 (17)	0.69800 (15)	0.53946 (15)	0.0371 (4)
O11	0.37869 (17)	0.70218 (16)	0.6708 (2)	0.0806 (7)
C35	0.4497 (3)	0.6032 (2)	0.6755 (3)	0.0786 (9)
H35A	0.5415	0.6223	0.6374	0.118*
H35B	0.4066	0.5655	0.6467	0.118*
H35C	0.4505	0.5528	0.7456	0.118*
O12	0.9690 (3)	0.1914 (2)	0.96545 (19)	0.0947 (8)
H3A	0.446 (2)	0.8493 (19)	0.6449 (16)	0.035 (5)*
H4A	0.342 (2)	0.156 (2)	0.8246 (19)	0.054 (7)*
H9A	0.732 (3)	0.738 (3)	0.660 (2)	0.070 (9)*
H10A	0.564 (3)	0.296 (3)	0.846 (2)	0.075 (9)*
H11A	0.298 (4)	0.689 (3)	0.702 (3)	0.094 (11)*
H12A	1.029 (3)	0.227 (3)	0.917 (2)	0.113*
H12B	0.927 (4)	0.221 (3)	1.003 (3)	0.113*

	U11	U22	U33	U12	U13	U23
Cu1	0.02831 (10)	0.03006 (11)	0.03525 (12)	0.00009 (7)	−0.00293 (7)	−0.01629 (8)
N1	0.0281 (6)	0.0299 (6)	0.0327 (7)	−0.0011 (5)	−0.0045 (5)	−0.0146 (6)
N2	0.0274 (6)	0.0269 (6)	0.0296 (7)	0.0023 (5)	−0.0063 (5)	−0.0126 (5)
O5	0.0377 (6)	0.0417 (7)	0.0478 (8)	0.0125 (5)	−0.0056 (6)	−0.0172 (6)
O3	0.0490 (7)	0.0507 (8)	0.0423 (8)	−0.0129 (6)	0.0001 (6)	−0.0253 (6)
O1	0.0337 (6)	0.0550 (8)	0.0484 (8)	−0.0097 (5)	0.0033 (5)	−0.0304 (7)
O7	0.0557 (8)	0.0449 (7)	0.0320 (7)	0.0042 (6)	−0.0071 (6)	−0.0161 (6)
O8	0.0634 (9)	0.0454 (8)	0.0517 (9)	0.0267 (7)	−0.0230 (7)	−0.0183 (7)
O2	0.0605 (9)	0.0664 (10)	0.0627 (10)	−0.0269 (8)	−0.0034 (7)	−0.0386 (8)
O4	0.0424 (7)	0.0590 (9)	0.0635 (10)	−0.0217 (6)	0.0021 (7)	−0.0316 (8)
C1	0.0317 (7)	0.0315 (8)	0.0344 (8)	0.0016 (6)	−0.0082 (6)	−0.0160 (7)
C5	0.0301 (7)	0.0335 (8)	0.0335 (8)	−0.0038 (6)	−0.0032 (6)	−0.0130 (7)
C7	0.0377 (8)	0.0354 (9)	0.0378 (9)	−0.0072 (7)	−0.0048 (7)	−0.0149 (7)
C6	0.0349 (8)	0.0376 (9)	0.0413 (10)	−0.0057 (7)	−0.0065 (7)	−0.0194 (8)
C8	0.0291 (7)	0.0269 (7)	0.0348 (8)	0.0005 (6)	−0.0098 (6)	−0.0108 (6)
C14	0.0390 (8)	0.0329 (8)	0.0356 (9)	0.0057 (6)	−0.0129 (7)	−0.0153 (7)
C2	0.0466 (10)	0.0473 (10)	0.0410 (10)	0.0029 (8)	−0.0099 (8)	−0.0273 (9)
C12	0.0329 (7)	0.0307 (8)	0.0335 (8)	0.0061 (6)	−0.0093 (6)	−0.0167 (7)
O9	0.0309 (6)	0.0377 (7)	0.0792 (11)	0.0076 (5)	−0.0099 (7)	−0.0266 (7)
O6	0.0513 (8)	0.0447 (8)	0.0548 (9)	0.0159 (6)	−0.0168 (7)	−0.0022 (7)
C9	0.0460 (9)	0.0398 (9)	0.0307 (9)	0.0008 (7)	−0.0107 (7)	−0.0105 (7)
C10	0.0538 (11)	0.0567 (12)	0.0327 (9)	0.0082 (9)	−0.0030 (8)	−0.0229 (9)
N3	0.0306 (7)	0.0334 (7)	0.0327 (7)	0.0039 (5)	−0.0044 (5)	−0.0153 (6)
C23	0.0317 (8)	0.0381 (9)	0.0422 (10)	0.0035 (7)	−0.0053 (7)	−0.0186 (8)
C24	0.0308 (7)	0.0367 (8)	0.0302 (8)	0.0021 (6)	−0.0037 (6)	−0.0162 (7)
C11	0.0467 (10)	0.0489 (11)	0.0414 (10)	0.0176 (8)	−0.0082 (8)	−0.0249 (9)
C16	0.0310 (8)	0.0473 (10)	0.0292 (8)	0.0087 (7)	−0.0048 (6)	−0.0151 (7)
C3	0.0452 (10)	0.0655 (13)	0.0383 (10)	0.0003 (9)	0.0021 (8)	−0.0302 (10)
C15	0.0321 (8)	0.0600 (12)	0.0479 (11)	0.0052 (8)	−0.0096 (8)	−0.0207 (10)
C4	0.0350 (9)	0.0570 (12)	0.0390 (10)	−0.0082 (8)	0.0031 (7)	−0.0197 (9)
O10	0.0600 (9)	0.0412 (8)	0.0869 (13)	−0.0020 (7)	−0.0339 (9)	−0.0282 (8)
N4	0.0353 (7)	0.0378 (8)	0.0338 (8)	−0.0020 (6)	−0.0096 (6)	−0.0155 (6)
C21	0.0419 (10)	0.0660 (14)	0.0639 (14)	−0.0103 (9)	−0.0095 (9)	−0.0328 (12)
C26	0.0380 (9)	0.0491 (10)	0.0346 (9)	−0.0105 (7)	−0.0024 (7)	−0.0195 (8)
C19	0.0434 (9)	0.0373 (9)	0.0353 (9)	0.0007 (7)	−0.0040 (7)	−0.0171 (7)
C33	0.0429 (9)	0.0444 (10)	0.0429 (10)	−0.0047 (8)	−0.0140 (8)	−0.0201 (8)
C25	0.0367 (10)	0.0753 (15)	0.0601 (14)	−0.0075 (9)	−0.0082 (9)	−0.0341 (12)
C17	0.0470 (10)	0.0436 (10)	0.0400 (10)	0.0173 (8)	−0.0110 (8)	−0.0139 (8)
C22	0.0334 (9)	0.0571 (12)	0.0597 (13)	0.0040 (8)	−0.0121 (8)	−0.0275 (10)
C34	0.0360 (8)	0.0367 (8)	0.0297 (8)	−0.0025 (6)	−0.0090 (6)	−0.0136 (7)
C18	0.0566 (12)	0.0333 (9)	0.0472 (11)	0.0059 (8)	−0.0067 (9)	−0.0155 (8)
C20	0.0561 (12)	0.0436 (11)	0.0563 (13)	−0.0106 (9)	−0.0070 (10)	−0.0246 (10)
C32	0.0411 (10)	0.0705 (14)	0.0522 (12)	−0.0073 (9)	−0.0134 (9)	−0.0323 (11)
C29	0.0444 (9)	0.0401 (9)	0.0322 (9)	0.0020 (7)	−0.0087 (7)	−0.0128 (7)
C27	0.0549 (11)	0.0419 (10)	0.0439 (11)	−0.0167 (8)	−0.0006 (9)	−0.0181 (9)
C28	0.0617 (12)	0.0349 (9)	0.0419 (11)	−0.0013 (8)	−0.0065 (9)	−0.0138 (8)
C31	0.0369 (10)	0.0833 (17)	0.0556 (13)	0.0081 (10)	−0.0177 (9)	−0.0323 (12)
C30	0.0521 (11)	0.0576 (13)	0.0495 (12)	0.0180 (10)	−0.0198 (10)	−0.0203 (10)
C13	0.0302 (8)	0.0301 (8)	0.0455 (10)	0.0033 (6)	−0.0095 (7)	−0.0107 (7)
O11	0.0351 (8)	0.0562 (10)	0.139 (2)	−0.0101 (7)	0.0123 (10)	−0.0444 (12)
C35	0.0630 (15)	0.0560 (15)	0.107 (2)	−0.0065 (12)	0.0113 (15)	−0.0386 (16)
O12	0.125 (2)	0.0851 (16)	0.0707 (15)	−0.0470 (14)	0.0092 (13)	−0.0350 (12)

Cu1—N2	1.9433 (15)	C15—H15A	0.9600
Cu1—N1	1.9461 (15)	C15—H15B	0.9600
Cu1—O5	2.1799 (16)	C15—H15C	0.9600
Cu1—O7	2.1880 (16)	C4—H4	0.9300
Cu1—O1	2.2018 (14)	O10—C33	1.337 (3)
Cu1—O3	2.2070 (16)	O10—H10A	0.87 (3)
N1—C1	1.336 (2)	N4—C26	1.332 (2)
N1—C5	1.341 (2)	N4—C34	1.375 (2)
N2—C12	1.335 (2)	N4—H4A	0.95 (3)
N2—C8	1.339 (2)	C21—C20	1.360 (3)
O5—C13	1.276 (2)	C21—C22	1.405 (3)
O3—C7	1.247 (2)	C21—H21	0.9300
O1—C6	1.268 (2)	C26—C27	1.396 (3)
O7—C14	1.260 (2)	C26—C25	1.492 (3)
O8—C14	1.234 (2)	C19—C20	1.407 (3)
O2—C6	1.230 (2)	C19—C18	1.412 (3)
O4—C7	1.248 (2)	C33—C32	1.379 (3)
C1—C2	1.386 (3)	C33—C34	1.413 (3)
C1—C6	1.520 (2)	C25—H25A	0.9600
C5—C4	1.385 (3)	C25—H25B	0.9600
C5—C7	1.516 (2)	C25—H25C	0.9600
C8—C9	1.374 (3)	C17—C18	1.357 (3)
C8—C13	1.517 (2)	C17—H17	0.9300
C14—C12	1.518 (2)	C22—H22	0.9300
C2—C3	1.380 (3)	C34—C29	1.409 (3)
C2—H2	0.9300	C18—H18	0.9300
C12—C11	1.380 (3)	C20—H20	0.9300
O9—C23	1.336 (2)	C32—C31	1.392 (3)
O9—H9A	0.78 (3)	C32—H32	0.9300
O6—C13	1.223 (2)	C29—C28	1.409 (3)
C9—C10	1.387 (3)	C29—C30	1.410 (3)
C9—H9	0.9300	C27—C28	1.355 (3)
C10—C11	1.385 (3)	C27—H27	0.9300
C10—H10	0.9300	C28—H28	0.9300
N3—C16	1.330 (2)	C31—C30	1.362 (4)
N3—C24	1.372 (2)	C31—H31	0.9300
N3—H3A	0.83 (2)	C30—H30	0.9300
C23—C22	1.375 (3)	O11—C35	1.378 (3)
C23—C24	1.421 (2)	O11—H11A	0.83 (4)
C24—C19	1.407 (3)	C35—H35A	0.9600
C11—H11	0.9300	C35—H35B	0.9600
C16—C17	1.404 (3)	C35—H35C	0.9600
C16—C15	1.487 (3)	O12—H12A	0.82 (3)
C3—C4	1.378 (3)	O12—H12B	0.82 (4)
C3—H3	0.9300
N2—Cu1—N1	174.84 (5)	C16—C15—H15B	109.5
N2—Cu1—O5	77.26 (6)	H15A—C15—H15B	109.5
N1—Cu1—O5	98.34 (6)	C16—C15—H15C	109.5
N2—Cu1—O7	78.01 (6)	H15A—C15—H15C	109.5
N1—Cu1—O7	106.57 (6)	H15B—C15—H15C	109.5
O5—Cu1—O7	154.84 (6)	C3—C4—C5	118.75 (18)
N2—Cu1—O1	100.11 (6)	C3—C4—H4	120.6
N1—Cu1—O1	77.38 (6)	C5—C4—H4	120.6
O5—Cu1—O1	94.25 (6)	C33—O10—H10A	110.9 (19)
O7—Cu1—O1	94.57 (6)	C26—N4—C34	122.97 (16)
N2—Cu1—O3	104.79 (6)	C26—N4—H4A	115.8 (15)
N1—Cu1—O3	77.75 (6)	C34—N4—H4A	121.2 (15)
O5—Cu1—O3	90.63 (6)	C20—C21—C22	121.13 (19)
O7—Cu1—O3	91.22 (6)	C20—C21—H21	119.4
O1—Cu1—O3	155.09 (5)	C22—C21—H21	119.4
C1—N1—C5	120.77 (15)	N4—C26—C27	118.97 (17)
C1—N1—Cu1	119.89 (12)	N4—C26—C25	117.88 (18)
C5—N1—Cu1	119.29 (12)	C27—C26—C25	123.14 (19)
C12—N2—C8	120.70 (15)	C24—C19—C20	119.47 (17)
C12—N2—Cu1	119.15 (12)	C24—C19—C18	117.23 (18)
C8—N2—Cu1	120.15 (11)	C20—C19—C18	123.29 (19)
C13—O5—Cu1	114.39 (11)	O10—C33—C32	125.54 (19)
C7—O3—Cu1	112.59 (12)	O10—C33—C34	116.62 (17)
C6—O1—Cu1	113.61 (11)	C32—C33—C34	117.83 (19)
C14—O7—Cu1	113.22 (11)	C26—C25—H25A	109.5
N1—C1—C2	120.51 (16)	C26—C25—H25B	109.5
N1—C1—C6	114.34 (15)	H25A—C25—H25B	109.5
C2—C1—C6	125.15 (16)	C26—C25—H25C	109.5
N1—C5—C4	121.03 (17)	H25A—C25—H25C	109.5
N1—C5—C7	113.87 (15)	H25B—C25—H25C	109.5
C4—C5—C7	125.08 (16)	C18—C17—C16	120.42 (17)
O3—C7—O4	127.36 (18)	C18—C17—H17	119.8
O3—C7—C5	116.32 (15)	C16—C17—H17	119.8
O4—C7—C5	116.30 (17)	C23—C22—C21	121.22 (19)
O2—C6—O1	126.85 (17)	C23—C22—H22	119.4
O2—C6—C1	118.45 (17)	C21—C22—H22	119.4
O1—C6—C1	114.70 (15)	N4—C34—C29	119.13 (16)
N2—C8—C9	121.44 (15)	N4—C34—C33	119.13 (16)
N2—C8—C13	113.94 (15)	C29—C34—C33	121.73 (17)
C9—C8—C13	124.61 (15)	C17—C18—C19	120.87 (19)
O8—C14—O7	128.10 (17)	C17—C18—H18	119.6
O8—C14—C12	116.60 (16)	C19—C18—H18	119.6
O7—C14—C12	115.30 (14)	C21—C20—C19	119.6 (2)
C3—C2—C1	119.29 (18)	C21—C20—H20	120.2
C3—C2—H2	120.4	C19—C20—H20	120.2
C1—C2—H2	120.4	C33—C32—C31	120.5 (2)
N2—C12—C11	120.58 (16)	C33—C32—H32	119.8
N2—C12—C14	114.29 (15)	C31—C32—H32	119.8
C11—C12—C14	125.13 (15)	C28—C29—C34	117.42 (17)
C23—O9—H9A	111 (2)	C28—C29—C30	124.26 (19)
C8—C9—C10	118.74 (17)	C34—C29—C30	118.31 (19)
C8—C9—H9	120.6	C28—C27—C26	120.44 (19)
C10—C9—H9	120.6	C28—C27—H27	119.8
C11—C10—C9	119.10 (18)	C26—C27—H27	119.8
C11—C10—H10	120.5	C27—C28—C29	121.04 (19)
C9—C10—H10	120.5	C27—C28—H28	119.5
C16—N3—C24	122.87 (16)	C29—C28—H28	119.5
C16—N3—H3A	118.3 (14)	C30—C31—C32	122.37 (19)
C24—N3—H3A	118.8 (14)	C30—C31—H31	118.8
O9—C23—C22	125.73 (17)	C32—C31—H31	118.8
O9—C23—C24	116.22 (16)	C31—C30—C29	119.3 (2)
C22—C23—C24	118.04 (18)	C31—C30—H30	120.3
N3—C24—C19	119.72 (15)	C29—C30—H30	120.3
N3—C24—C23	119.76 (16)	O6—C13—O5	127.45 (17)
C19—C24—C23	120.52 (16)	O6—C13—C8	118.55 (18)
C12—C11—C10	119.43 (16)	O5—C13—C8	113.99 (15)
C12—C11—H11	120.3	C35—O11—H11A	112 (2)
C10—C11—H11	120.3	O11—C35—H35A	109.5
N3—C16—C17	118.85 (18)	O11—C35—H35B	109.5
N3—C16—C15	118.99 (18)	H35A—C35—H35B	109.5
C17—C16—C15	122.15 (16)	O11—C35—H35C	109.5
C4—C3—C2	119.63 (18)	H35A—C35—H35C	109.5
C4—C3—H3	120.2	H35B—C35—H35C	109.5
C2—C3—H3	120.2	H12A—O12—H12B	120 (4)
C16—C15—H15A	109.5
O5—Cu1—N1—C1	−90.30 (13)	Cu1—N2—C12—C14	2.18 (19)
O7—Cu1—N1—C1	93.28 (13)	O8—C14—C12—N2	177.89 (16)
O1—Cu1—N1—C1	2.21 (12)	O7—C14—C12—N2	−1.2 (2)
O3—Cu1—N1—C1	−179.13 (13)	O8—C14—C12—C11	−1.1 (3)
O5—Cu1—N1—C5	87.16 (13)	O7—C14—C12—C11	179.80 (18)
O7—Cu1—N1—C5	−89.26 (13)	N2—C8—C9—C10	−0.5 (3)
O1—Cu1—N1—C5	179.67 (13)	C13—C8—C9—C10	−179.33 (18)
O3—Cu1—N1—C5	−1.67 (12)	C8—C9—C10—C11	0.3 (3)
O5—Cu1—N2—C12	−177.07 (13)	C16—N3—C24—C19	0.8 (3)
O7—Cu1—N2—C12	−1.75 (12)	C16—N3—C24—C23	−179.05 (16)
O1—Cu1—N2—C12	90.82 (13)	O9—C23—C24—N3	0.6 (3)
O3—Cu1—N2—C12	−89.82 (13)	C22—C23—C24—N3	−179.72 (18)
O5—Cu1—N2—C8	3.17 (12)	O9—C23—C24—C19	−179.23 (17)
O7—Cu1—N2—C8	178.49 (13)	C22—C23—C24—C19	0.4 (3)
O1—Cu1—N2—C8	−88.94 (13)	N2—C12—C11—C10	−1.2 (3)
O3—Cu1—N2—C8	90.42 (13)	C14—C12—C11—C10	177.78 (19)
N2—Cu1—O5—C13	−4.78 (13)	C9—C10—C11—C12	0.5 (3)
N1—Cu1—O5—C13	172.49 (13)	C24—N3—C16—C17	1.1 (3)
O7—Cu1—O5—C13	−15.6 (2)	C24—N3—C16—C15	−177.64 (17)
O1—Cu1—O5—C13	94.64 (14)	C1—C2—C3—C4	−0.4 (3)
O3—Cu1—O5—C13	−109.81 (14)	C2—C3—C4—C5	0.0 (3)
N2—Cu1—O3—C7	−171.70 (13)	N1—C5—C4—C3	0.7 (3)
N1—Cu1—O3—C7	3.68 (13)	C7—C5—C4—C3	−177.43 (18)
O5—Cu1—O3—C7	−94.71 (14)	C34—N4—C26—C27	−1.9 (3)
O7—Cu1—O3—C7	110.38 (14)	C34—N4—C26—C25	177.28 (18)
O1—Cu1—O3—C7	6.8 (2)	N3—C24—C19—C20	179.49 (17)
N2—Cu1—O1—C6	172.75 (13)	C23—C24—C19—C20	−0.6 (3)
N1—Cu1—O1—C6	−2.65 (13)	N3—C24—C19—C18	−1.4 (3)
O5—Cu1—O1—C6	94.96 (14)	C23—C24—C19—C18	178.43 (17)
O7—Cu1—O1—C6	−108.63 (14)	N3—C16—C17—C18	−2.3 (3)
O3—Cu1—O1—C6	−5.8 (2)	C15—C16—C17—C18	176.36 (19)
N2—Cu1—O7—C14	1.00 (13)	O9—C23—C22—C21	179.5 (2)
N1—Cu1—O7—C14	−176.57 (13)	C24—C23—C22—C21	−0.1 (3)
O5—Cu1—O7—C14	11.8 (2)	C20—C21—C22—C23	0.1 (4)
O1—Cu1—O7—C14	−98.39 (14)	C26—N4—C34—C29	0.9 (3)
O3—Cu1—O7—C14	105.86 (14)	C26—N4—C34—C33	−177.81 (18)
C5—N1—C1—C2	0.7 (2)	O10—C33—C34—N4	0.0 (3)
Cu1—N1—C1—C2	178.13 (13)	C32—C33—C34—N4	178.91 (18)
C5—N1—C1—C6	−179.02 (14)	O10—C33—C34—C29	−178.76 (18)
Cu1—N1—C1—C6	−1.60 (19)	C32—C33—C34—C29	0.2 (3)
C1—N1—C5—C4	−1.1 (3)	C16—C17—C18—C19	1.7 (3)
Cu1—N1—C5—C4	−178.51 (14)	C24—C19—C18—C17	0.2 (3)
C1—N1—C5—C7	177.25 (14)	C20—C19—C18—C17	179.2 (2)
Cu1—N1—C5—C7	−0.19 (19)	C22—C21—C20—C19	−0.3 (4)
Cu1—O3—C7—O4	174.11 (17)	C24—C19—C20—C21	0.6 (3)
Cu1—O3—C7—C5	−4.8 (2)	C18—C19—C20—C21	−178.4 (2)
N1—C5—C7—O3	3.6 (2)	O10—C33—C32—C31	178.4 (2)
C4—C5—C7—O3	−178.13 (18)	C34—C33—C32—C31	−0.4 (3)
N1—C5—C7—O4	−175.40 (16)	N4—C34—C29—C28	0.8 (3)
C4—C5—C7—O4	2.8 (3)	C33—C34—C29—C28	179.49 (19)
Cu1—O1—C6—O2	−176.75 (17)	N4—C34—C29—C30	−178.67 (17)
Cu1—O1—C6—C1	2.55 (19)	C33—C34—C29—C30	0.1 (3)
N1—C1—C6—O2	178.49 (17)	N4—C26—C27—C28	1.1 (3)
C2—C1—C6—O2	−1.2 (3)	C25—C26—C27—C28	−178.0 (2)
N1—C1—C6—O1	−0.9 (2)	C26—C27—C28—C29	0.6 (3)
C2—C1—C6—O1	179.41 (17)	C34—C29—C28—C27	−1.5 (3)
C12—N2—C8—C9	−0.1 (2)	C30—C29—C28—C27	177.9 (2)
Cu1—N2—C8—C9	179.63 (13)	C33—C32—C31—C30	0.4 (4)
C12—N2—C8—C13	178.78 (14)	C32—C31—C30—C29	−0.2 (4)
Cu1—N2—C8—C13	−1.46 (19)	C28—C29—C30—C31	−179.5 (2)
Cu1—O7—C14—O8	−179.14 (17)	C34—C29—C30—C31	−0.1 (3)
Cu1—O7—C14—C12	−0.18 (19)	Cu1—O5—C13—O6	−175.71 (17)
N1—C1—C2—C3	0.0 (3)	Cu1—O5—C13—C8	5.28 (19)
C6—C1—C2—C3	179.72 (18)	N2—C8—C13—O6	178.03 (17)
C8—N2—C12—C11	1.0 (3)	C9—C8—C13—O6	−3.1 (3)
Cu1—N2—C12—C11	−178.77 (14)	N2—C8—C13—O5	−2.9 (2)
C8—N2—C12—C14	−178.06 (14)	C9—C8—C13—O5	176.01 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O9	0.83 (3)	2.37 (2)	2.692 (2)	104.3 (17)
N3—H3A···O11	0.83 (3)	1.93 (3)	2.739 (3)	164 (2)
N4—H4A···O8i	0.95 (3)	1.87 (3)	2.723 (2)	149 (2)
O9—H9A···O5	0.78 (3)	1.79 (3)	2.563 (2)	176 (3)
O10—H10A···O4	0.87 (4)	1.70 (4)	2.555 (3)	167 (3)
O11—H11A···O1i	0.83 (4)	1.88 (4)	2.706 (3)	172 (4)
O12—H12A···O7	0.82 (3)	2.14 (3)	2.895 (3)	154 (4)
O12—H12B···O2ii	0.82 (4)	2.21 (4)	2.974 (3)	156 (4)
C10—H10···O3iii	0.93	2.55	3.177 (3)	125
C15—H15C···O2i	0.96	2.55	3.480 (3)	163
C17—H17···O6iv	0.93	2.29	3.185 (3)	161
C25—H25C···O8i	0.96	2.48	3.212 (3)	133
C27—H27···O2v	0.93	2.50	3.394 (3)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O9	0.83 (3)	2.37 (2)	2.692 (2)	104.3 (17)
N3—H3A⋯O11	0.83 (3)	1.93 (3)	2.739 (3)	164 (2)
N4—H4A⋯O8i	0.95 (3)	1.87 (3)	2.723 (2)	149 (2)
O9—H9A⋯O5	0.78 (3)	1.79 (3)	2.563 (2)	176 (3)
O10—H10A⋯O4	0.87 (4)	1.70 (4)	2.555 (3)	167 (3)
O11—H11A⋯O1i	0.83 (4)	1.88 (4)	2.706 (3)	172 (4)
O12—H12A⋯O7	0.82 (3)	2.14 (3)	2.895 (3)	154 (4)
O12—H12B⋯O2ii	0.82 (4)	2.21 (4)	2.974 (3)	156 (4)
C10—H10⋯O3iii	0.93	2.55	3.177 (3)	125
C15—H15C⋯O2i	0.96	2.55	3.480 (3)	163
C17—H17⋯O6iv	0.93	2.29	3.185 (3)	161
C25—H25C⋯O8i	0.96	2.48	3.212 (3)	133
C27—H27⋯O2v	0.93	2.50	3.394 (3)	162

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