(3,5-Dinitro­benzoato-κO)bis­[(2-pyrid­yl)methanol-κ²N,O]copper(II) 3,5-dinitro­benzoate

In the title compound, [Cu(C₇H₃N₂O₆)(C₆H₇NO)₂](C₇H₃N₂O₆), the Cu^II atom is coordinated by two chelating 2-pyridylmethanol ligands and a monodentate 3,5-dinitro­benzoate anion, forming a square-pyramidal coordination polyhedron. The cation and neighbouring anion are connected by two very strong O—H...O hydrogen bonds to form an ion pair.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.042
• wR factor = 0.111
• Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.18
PLAT301_ALERT_3_C Main Residue  Disorder .........................       2.00 Perc.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C7 H3 N2 O6

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

As a part of our systematic study of copper(II) carboxylate complexes with biologically interesting molecular ligands, we report here the crystal structure of the title compound, (I).

The asymmetric unit of (I) is made up of a [Cu(C₆H₇NO)₂(C₇H₃N₂O₆)]⁺ cation and a C₇H₃N₂O₆⁻ anion. The (2-pyridyl)methanol (also known as 2-pyridylcarbinol and abbreviated as 2-pycarb) ligand prefers a chelating bonding mode, in contrast with the bridging bonding mode found for (3-pyridyl)methanol (known as ronicol) in copper(II) complexes (Stachová et al., 2005). The 3,5-dinitrobenzoate ligand is monodentate, coordinating through a carboxylate O atom to give a complex cation with distorted square-pyramidal geometry and a CuO₂N₂O' coordination polyhedron. The basal plane is formed by carboxylate atom O1 from the coordinating 3,5-dinitrobenzoate ligand, atom O31 from one 2-pycarb ligand and two mutually trans pyridine atoms, N5 and N6, from two 2-pycarb ligands. The axial position of the coordination polyhedron is occupied by atom O41 of a 2-pycarb ligand, with a Cu—O distance longer than those in the basal plane (Table 1). The Cu1—O2 distance of 2.735 (2) Å is longer than the Cu1—O1 distance. Also, the C11—O2 distance is significantly shorter than the C11—O1 distance. These confirm that atom O2 is not involved in coordination and the ligand is monodentate. Atom Cu1 is displaced out of the basal plane by 0.120 (1) Å in the direction of the apical O41 atom. The 3,5-dinitrobenzoate anion is uncoordinated. With the exception of the C—O distances in the carboxylate groups, there are no significant differences in bond lengths or angles between the coordinated and uncoordinated anions and the values are comparable with those observed for bis(1,3-diaminopropane)-3,5-dinitrobenzoatocopper(II) 3,5-dinitrobenzoate (Sundberg et al., 1994).

Two very strong hydrogen bonds link atoms O7 and O8 of the uncoordinated 3,5-dinitrobenzoate anion to hydroxyl atoms H41 and H31 of the coordinated 2-pycarb ligands (Table 2), giving rise to ion-pair formation. Similar hydrogen bonding is reported for bis(triethanolamine)copper(II) diacetate (Krabbes et al., 1999). In the closely related benzoatobis(dimethylaminoetanol)copper(II) benzoate (Turpeinen et al., 1985), the carboxylate anions form hydrogen bonds with hydroxyl H atoms of the coordinated ligands. Similar but weaker hydrogen bonds are found in copper(II) complexes containing coordinated NH groups (Sen et al., 2000, Sundberg & Klinga, 1994).

S2. Experimental

(2-Pyridyl)methanol (2 mmol) was added to copper(II) acetate (1 mmol) in aqueous solution (Volume?). 3,5-Dinitrobenzoic acid (2 mmol) was then added. The powdery blue product was filtered off and dried at room temperature. Blue prismatic crystals of (I) suitable for X-ray analysis were obtained from the mother liquor after slow room-temperature crystallization for a few weeks.

S3. Refinement

Atoms H31 and H41 were located in a difference Fourier map and their positions were not refined. The remaining H atoms were placed in geometrically calculated positions and allowed to ride on their parent atoms, with C—H distances of 0.93 (aromatic) or 0.97 Å (methylene). The U_iso value for all H atoms was fixed at 0.05 Ų. Atom O11 of an NO₂ group is disordered over two positions, O11A and O11B. The occupancy factors were initially refined to 0.502 (2) and 0.498 (2), but later fixed at 0.5 each.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The asymmetric unit of (I). Displacement ellipsoids are drawn at the 40% probability level. Dotted lines represent O—H···O hydrogen bonds.

(3,5-Dinitrobenzoato-κ²O,O')bis[(2-pyridyl)methanol-κ²N,O]copper(II) 3,5-dinitrobenzoate

Crystal data

[Cu(C7H3N2O6)(C6H7NO)2](C7H3N2O6)	Z = 2
Mr = 704.02	F(000) = 718
Triclinic, P1	Dx = 1.623 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.870 (1) Å	Cell parameters from 25 reflections
b = 12.181 (1) Å	θ = 4.2–12.0°
c = 12.732 (1) Å	µ = 0.84 mm^−1
α = 95.29 (1)°	T = 293 K
β = 108.68 (1)°	Prism, blue
γ = 91.80 (1)°	0.55 × 0.45 × 0.30 mm
V = 1440.9 (2) Å^3

Data collection

Siemens P4 diffractometer	5266 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 27.5°, θmin = 1.7°
ϕ scans	h = −1→12
Absorption correction: ψ scan (XEMP; Siemens, 1990)	k = −15→15
Tmin = 0.641, Tmax = 0.777	l = −16→16
7697 measured reflections	2 standard reflections every 100 reflections
6556 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0601P)^2 + 0.292P] where P = (Fo^2 + 2Fc^2)/3
6556 reflections	(Δ/σ)max = 0.001
433 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.24345 (3)	0.20701 (2)	0.07794 (2)	0.03324 (9)
O1	0.35754 (18)	0.19589 (14)	0.23424 (12)	0.0414 (4)
O2	0.1409 (2)	0.1750 (2)	0.24923 (16)	0.0662 (6)
O3	0.2916 (3)	0.0366 (3)	0.7348 (2)	0.0919 (9)
O4	0.1022 (2)	0.0602 (2)	0.60108 (18)	0.0700 (6)
O5	0.7777 (2)	0.1572 (2)	0.5571 (2)	0.0748 (7)
O6	0.7535 (2)	0.1458 (2)	0.71725 (17)	0.0717 (6)
O7	0.3371 (3)	0.3479 (2)	−0.17568 (17)	0.0740 (7)
O8	0.1061 (2)	0.28979 (18)	−0.22585 (15)	0.0577 (5)
O9	0.3235 (3)	0.5979 (2)	−0.5875 (2)	0.0910 (9)
O10	0.4646 (3)	0.59000 (19)	−0.4202 (2)	0.0742 (7)
O11A	−0.1383 (10)	0.2283 (8)	−0.6324 (9)	0.079 (3)	0.5
O11B	−0.1840 (10)	0.2716 (8)	−0.6236 (9)	0.079 (3)	0.5
O12	−0.1152 (2)	0.3650 (2)	−0.7290 (2)	0.0682 (6)
O31	0.08534 (17)	0.18756 (13)	−0.06853 (12)	0.0380 (3)
O41	0.42129 (19)	0.29544 (14)	0.03027 (13)	0.0438 (4)
N1	0.2311 (2)	0.0616 (2)	0.64227 (18)	0.0496 (5)
N2	0.7052 (2)	0.14946 (18)	0.61728 (17)	0.0457 (5)
N3	0.3560 (3)	0.5606 (2)	−0.4977 (2)	0.0599 (6)
N4	−0.0882 (3)	0.3228 (2)	−0.6427 (2)	0.0580 (6)
N5	0.2700 (2)	0.05234 (15)	0.03196 (14)	0.0331 (4)
N6	0.2107 (2)	0.36586 (16)	0.10705 (15)	0.0399 (4)
C11	0.2717 (3)	0.17695 (19)	0.28778 (17)	0.0385 (5)
C12	0.3406 (2)	0.15251 (17)	0.40698 (17)	0.0332 (4)
C13	0.2550 (2)	0.11972 (18)	0.46765 (18)	0.0352 (5)
H13	0.1558	0.1119	0.4355	0.05*
C14	0.3197 (2)	0.09860 (19)	0.57692 (18)	0.0362 (5)
C15	0.4665 (3)	0.10997 (18)	0.62806 (18)	0.0372 (5)
H15	0.5083	0.0972	0.7021	0.05*
C16	0.5475 (2)	0.14104 (18)	0.56520 (18)	0.0348 (5)
C17	0.4891 (2)	0.16214 (17)	0.45530 (17)	0.0337 (4)
H17	0.5475	0.1825	0.4148	0.05*
C21	0.2137 (3)	0.3307 (2)	−0.2428 (2)	0.0435 (6)
C22	0.1871 (3)	0.36606 (19)	−0.3591 (2)	0.0403 (5)
C23	0.2849 (3)	0.4393 (2)	−0.3773 (2)	0.0437 (5)
H23	0.3689	0.464	−0.3200	0.05*
C24	0.2565 (3)	0.4758 (2)	−0.4816 (2)	0.0445 (6)
C25	0.1353 (3)	0.4388 (2)	−0.5702 (2)	0.0450 (6)
H25	0.1173	0.4638	−0.6399	0.05*
C26	0.0430 (3)	0.3635 (2)	−0.5497 (2)	0.0418 (5)
C27	0.0637 (3)	0.3273 (2)	−0.4458 (2)	0.0416 (5)
H27	−0.0031	0.2782	−0.4344	0.05*
C31	0.0528 (2)	0.07582 (19)	−0.11763 (18)	0.0383 (5)
H311	0.0412	0.072	−0.1965	0.05*
H312	−0.0367	0.0487	−0.1101	0.05*
C32	0.1708 (2)	0.00433 (19)	−0.06115 (17)	0.0336 (4)
C33	0.1782 (3)	−0.1036 (2)	−0.1014 (2)	0.0469 (6)
H33	0.1076	−0.1365	−0.1652	0.05*
C34	0.2923 (3)	−0.1623 (2)	−0.0454 (2)	0.0522 (6)
H34	0.2999	−0.2349	−0.0717	0.05*
C35	0.3950 (3)	−0.1123 (2)	0.0503 (2)	0.0485 (6)
H35	0.4722	−0.1504	0.0892	0.05*
C36	0.3804 (3)	−0.0050 (2)	0.08645 (19)	0.0413 (5)
H36	0.4487	0.029	0.1509	0.05*
C41	0.4531 (3)	0.3936 (2)	0.1051 (2)	0.0520 (6)
H411	0.5045	0.448	0.0785	0.05*
H412	0.5145	0.3776	0.1777	0.05*
C42	0.0882 (3)	0.4004 (2)	0.1186 (2)	0.0511 (6)
H42	0.0139	0.3484	0.1117	0.05*
C43	0.0686 (4)	0.5103 (3)	0.1400 (2)	0.0648 (9)
H43	−0.017	0.5322	0.1485	0.05*
C44	0.1769 (4)	0.5870 (3)	0.1492 (3)	0.0708 (10)
H44	0.165	0.6618	0.1628	0.05*
C45	0.3034 (4)	0.5526 (2)	0.1374 (2)	0.0639 (8)
H45	0.3782	0.6039	0.1439	0.05*
C46	0.3182 (3)	0.4400 (2)	0.11589 (19)	0.0471 (6)
H31	0.0951	0.2276	−0.119	0.05*
H41	0.388	0.3175	−0.0407	0.05*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03677 (16)	0.03858 (15)	0.02142 (13)	0.00363 (11)	0.00477 (10)	0.00492 (9)
O1	0.0457 (9)	0.0521 (9)	0.0224 (7)	0.0046 (8)	0.0050 (7)	0.0053 (6)
O2	0.0363 (10)	0.1082 (17)	0.0447 (10)	−0.0038 (10)	−0.0063 (8)	0.0349 (11)
O3	0.0616 (14)	0.167 (3)	0.0590 (14)	0.0121 (16)	0.0228 (12)	0.0614 (17)
O4	0.0438 (12)	0.1122 (19)	0.0593 (13)	0.0013 (12)	0.0224 (10)	0.0164 (12)
O5	0.0358 (11)	0.118 (2)	0.0686 (14)	−0.0087 (12)	0.0116 (10)	0.0214 (13)
O6	0.0440 (11)	0.1083 (18)	0.0452 (11)	−0.0042 (11)	−0.0118 (9)	0.0186 (11)
O7	0.0654 (14)	0.1102 (18)	0.0374 (10)	−0.0176 (13)	0.0025 (10)	0.0223 (11)
O8	0.0624 (12)	0.0718 (13)	0.0392 (10)	−0.0053 (10)	0.0141 (9)	0.0194 (9)
O9	0.122 (2)	0.0874 (17)	0.0582 (14)	−0.0327 (16)	0.0198 (14)	0.0310 (13)
O10	0.0823 (17)	0.0710 (14)	0.0611 (13)	−0.0314 (13)	0.0167 (12)	0.0014 (11)
O11A	0.077 (6)	0.099 (6)	0.049 (3)	−0.040 (4)	0.011 (4)	−0.004 (4)
O11B	0.060 (5)	0.111 (7)	0.054 (4)	−0.031 (4)	0.003 (3)	0.019 (5)
O12	0.0659 (14)	0.0899 (16)	0.0382 (10)	0.0011 (12)	0.0019 (9)	0.0087 (10)
O31	0.0407 (9)	0.0445 (8)	0.0254 (7)	0.0046 (7)	0.0047 (6)	0.0088 (6)
O41	0.0440 (9)	0.0506 (9)	0.0355 (8)	0.0027 (8)	0.0116 (7)	0.0037 (7)
N1	0.0436 (12)	0.0684 (14)	0.0402 (11)	0.0042 (11)	0.0168 (10)	0.0119 (10)
N2	0.0340 (11)	0.0528 (12)	0.0402 (11)	−0.0020 (9)	−0.0024 (9)	0.0094 (9)
N3	0.0792 (18)	0.0527 (13)	0.0473 (13)	−0.0154 (13)	0.0216 (13)	0.0066 (10)
N4	0.0556 (15)	0.0805 (17)	0.0319 (11)	−0.0078 (13)	0.0093 (10)	−0.0018 (11)
N5	0.0334 (9)	0.0399 (9)	0.0236 (8)	0.0003 (8)	0.0057 (7)	0.0051 (7)
N6	0.0509 (12)	0.0428 (10)	0.0254 (8)	0.0063 (9)	0.0107 (8)	0.0065 (7)
C11	0.0412 (13)	0.0422 (12)	0.0249 (10)	−0.0018 (10)	0.0001 (9)	0.0075 (8)
C12	0.0342 (11)	0.0335 (10)	0.0257 (10)	0.0019 (9)	0.0013 (8)	0.0033 (8)
C13	0.0317 (11)	0.0403 (11)	0.0296 (10)	0.0033 (9)	0.0042 (8)	0.0040 (8)
C14	0.0371 (12)	0.0411 (11)	0.0301 (10)	0.0024 (9)	0.0103 (9)	0.0054 (8)
C15	0.0403 (12)	0.0416 (11)	0.0255 (10)	0.0030 (10)	0.0035 (9)	0.0083 (8)
C16	0.0306 (11)	0.0365 (11)	0.0302 (10)	−0.0013 (9)	0.0001 (8)	0.0046 (8)
C17	0.0342 (11)	0.0357 (10)	0.0277 (10)	−0.0025 (9)	0.0056 (8)	0.0040 (8)
C21	0.0578 (16)	0.0431 (12)	0.0283 (11)	0.0002 (11)	0.0126 (11)	0.0036 (9)
C22	0.0513 (14)	0.0396 (11)	0.0300 (11)	0.0023 (10)	0.0136 (10)	0.0032 (9)
C23	0.0538 (15)	0.0410 (12)	0.0332 (11)	−0.0040 (11)	0.0113 (10)	0.0016 (9)
C24	0.0583 (15)	0.0395 (12)	0.0364 (12)	−0.0035 (11)	0.0173 (11)	0.0039 (9)
C25	0.0609 (16)	0.0467 (13)	0.0288 (11)	0.0041 (12)	0.0162 (11)	0.0054 (9)
C26	0.0497 (14)	0.0458 (12)	0.0282 (10)	0.0030 (11)	0.0116 (10)	−0.0008 (9)
C27	0.0500 (14)	0.0430 (12)	0.0334 (11)	−0.0016 (10)	0.0166 (10)	0.0028 (9)
C31	0.0305 (11)	0.0492 (13)	0.0298 (10)	−0.0012 (9)	0.0020 (9)	0.0062 (9)
C32	0.0292 (10)	0.0453 (12)	0.0262 (9)	−0.0023 (9)	0.0086 (8)	0.0067 (8)
C33	0.0427 (14)	0.0485 (13)	0.0392 (12)	−0.0046 (11)	0.0027 (11)	−0.0061 (10)
C34	0.0524 (16)	0.0436 (13)	0.0526 (15)	0.0058 (12)	0.0088 (12)	−0.0058 (11)
C35	0.0459 (14)	0.0496 (14)	0.0449 (13)	0.0136 (11)	0.0063 (11)	0.0067 (11)
C36	0.0410 (13)	0.0479 (13)	0.0288 (10)	0.0051 (10)	0.0025 (9)	0.0034 (9)
C41	0.0496 (15)	0.0513 (14)	0.0487 (14)	−0.0074 (12)	0.0087 (12)	0.0023 (11)
C42	0.0604 (17)	0.0596 (16)	0.0373 (12)	0.0175 (13)	0.0190 (12)	0.0092 (11)
C43	0.086 (2)	0.072 (2)	0.0392 (14)	0.0367 (19)	0.0212 (15)	0.0074 (13)
C44	0.105 (3)	0.0486 (16)	0.0480 (16)	0.0265 (18)	0.0093 (17)	−0.0024 (12)
C45	0.087 (2)	0.0410 (14)	0.0490 (15)	−0.0006 (15)	0.0051 (15)	−0.0037 (12)
C46	0.0602 (16)	0.0447 (13)	0.0285 (11)	0.0026 (12)	0.0046 (11)	0.0009 (9)

Geometric parameters (Å, º)

Cu1—O1	1.967 (2)	C15—H15	0.93
Cu1—N5	1.972 (2)	C16—C17	1.384 (3)
Cu1—N6	1.993 (2)	C17—H17	0.93
Cu1—O31	2.000 (2)	C21—C22	1.524 (3)
Cu1—O41	2.301 (2)	C22—C23	1.381 (4)
O1—C11	1.274 (3)	C22—C27	1.390 (3)
O2—C11	1.224 (3)	C23—C24	1.386 (3)
O3—N1	1.210 (3)	C23—H23	0.93
O4—N1	1.210 (3)	C24—C25	1.383 (4)
O5—N2	1.212 (3)	C25—C26	1.372 (4)
O6—N2	1.214 (3)	C25—H25	0.93
O9—N3	1.219 (3)	C26—C27	1.387 (3)
O10—N3	1.219 (3)	C27—H27	0.93
O11A—N4	1.273 (1)	C31—C32	1.508 (3)
O11B—N4	1.217 (1)	C31—H311	0.97
O12—N4	1.212 (3)	C31—H312	0.97
O31—C31	1.426 (3)	C32—C33	1.380 (3)
O31—H31	0.87	C33—C34	1.384 (4)
O41—C41	1.418 (3)	C33—H33	0.93
O41—H41	0.92	C34—C35	1.385 (4)
N1—C14	1.474 (3)	C34—H34	0.93
N2—C16	1.479 (3)	C35—C36	1.373 (4)
N3—C24	1.475 (3)	C35—H35	0.93
N4—C26	1.482 (3)	C36—H36	0.93
N5—C32	1.341 (3)	C41—C46	1.504 (4)
N5—C36	1.345 (3)	C41—H411	0.97
N6—C42	1.339 (3)	C41—H412	0.97
N6—C46	1.341 (3)	C42—C43	1.373 (4)
C11—C12	1.513 (3)	C42—H42	0.93
C12—C13	1.387 (3)	C43—C44	1.367 (5)
C12—C17	1.392 (3)	C43—H43	0.93
C13—C14	1.384 (3)	C44—C45	1.377 (5)
C13—H13	0.93	C44—H44	0.93
C14—C15	1.381 (3)	C45—C46	1.395 (4)
C15—C16	1.368 (3)	C45—H45	0.93
O1—Cu1—N5	92.43 (7)	C23—C22—C27	120.1 (2)
O1—Cu1—N6	93.46 (7)	C23—C22—C21	119.5 (2)
N5—Cu1—N6	173.81 (7)	C27—C22—C21	120.4 (2)
O1—Cu1—O31	162.24 (7)	C22—C23—C24	119.3 (2)
N5—Cu1—O31	81.75 (7)	C22—C23—H23	120.4
N6—Cu1—O31	93.16 (7)	C24—C23—H23	120.3
O1—Cu1—O41	96.50 (7)	C25—C24—C23	122.4 (2)
N5—Cu1—O41	99.99 (7)	C25—C24—N3	118.7 (2)
N6—Cu1—O41	77.45 (8)	C23—C24—N3	118.8 (2)
O31—Cu1—O41	101.02 (6)	C26—C25—C24	116.5 (2)
C11—O1—Cu1	108.2 (1)	C26—C25—H25	121.8
O11B—O11A—N4	68.8 (2)	C24—C25—H25	121.7
O11A—O11B—N4	77.3 (2)	C25—C26—C27	123.4 (2)
C31—O31—Cu1	114.2 (2)	C25—C26—N4	117.8 (2)
C31—O31—H31	108	C27—C26—N4	118.7 (2)
Cu1—O31—H31	116.1	C26—C27—C22	118.3 (2)
C41—O41—Cu1	102.1 (2)	C26—C27—H27	121
C41—O41—H41	106.2	C22—C27—H27	120.8
Cu1—O41—H41	112.2	O31—C31—C32	110.4 (2)
O3—N1—O4	123.9 (2)	O31—C31—H311	109.8
O3—N1—C14	118.0 (2)	C32—C31—H311	109.7
O4—N1—C14	118.0 (2)	O31—C31—H312	109.4
O5—N2—O6	124.2 (2)	C32—C31—H312	109.5
O5—N2—C16	118.0 (2)	H311—C31—H312	108.1
O6—N2—C16	117.8 (2)	N5—C32—C33	121.3 (2)
O9—N3—O10	124.0 (3)	N5—C32—C31	115.7 (2)
O9—N3—C24	117.9 (3)	C33—C32—C31	123.0 (2)
O10—N3—C24	118.1 (2)	C32—C33—C34	119.0 (2)
O12—N4—O11B	118.9 (5)	C32—C33—H33	120.5
O12—N4—O11A	125.3 (5)	C34—C33—H33	120.5
O12—N4—C26	118.5 (2)	C33—C34—C35	119.5 (2)
O11B—N4—C26	119.6 (5)	C33—C34—H34	120.3
O11A—N4—C26	113.4 (5)	C35—C34—H34	120.1
C32—N5—C36	119.6 (2)	C36—C35—C34	118.4 (2)
C32—N5—Cu1	116.1 (2)	C36—C35—H35	120.7
C36—N5—Cu1	124.3 (2)	C34—C35—H35	120.8
C42—N6—C46	119.7 (2)	N5—C36—C35	122.1 (2)
C42—N6—Cu1	123.0 (2)	N5—C36—H36	119
C46—N6—Cu1	117.3 (2)	C35—C36—H36	118.9
O2—C11—O1	125.0 (2)	O41—C41—C46	110.9 (2)
O2—C11—C12	119.2 (2)	O41—C41—H411	109.6
O1—C11—C12	115.8 (2)	C46—C41—H411	109.5
C13—C12—C17	120.2 (2)	O41—C41—H412	109.3
C13—C12—C11	119.6 (2)	C46—C41—H412	109.5
C17—C12—C11	120.2 (2)	H411—C41—H412	108
C14—C13—C12	118.8 (2)	N6—C42—C43	122.1 (3)
C14—C13—H13	120.5	N6—C42—H42	119.1
C12—C13—H13	120.6	C43—C42—H42	118.9
C15—C14—C13	122.4 (2)	C44—C43—C42	119.1 (3)
C15—C14—N1	117.8 (2)	C44—C43—H43	120.4
C13—C14—N1	119.8 (2)	C42—C43—H43	120.5
C16—C15—C14	117.1 (2)	C43—C44—C45	119.4 (3)
C16—C15—H15	121.4	C43—C44—H44	120.2
C14—C15—H15	121.4	C45—C44—H44	120.3
C15—C16—C17	123.1 (2)	C44—C45—C46	119.3 (3)
C15—C16—N2	117.8 (2)	C44—C45—H45	120.4
C17—C16—N2	119.0 (2)	C46—C45—H45	120.3
C16—C17—C12	118.3 (2)	N6—C46—C45	120.4 (3)
C16—C17—H17	120.8	N6—C46—C41	116.0 (2)
C12—C17—H17	120.8	C45—C46—C41	123.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O31—H31···O8	0.87	1.65	2.512 (2)	173
O41—H41···O7	0.93	1.71	2.631 (3)	174