metal-organic papers
Acta Cryst.(2006). E62, m109–m110 doi:10.1107/S1600536805041310 Maroszova´et al. [Cu(C
7H3N2O6)(C6H7NO)2](C7H3N2O6)
m109
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
(3,5-Dinitrobenzoato-
j
O
)bis[(2-pyridyl)-methanol-
j
2N
,
O
]copper(II) 3,5-dinitrobenzoate
Jaroslava Maroszova´, Petra Stachova´, Zuzana Vaskova´, Dusˇan Valigura and Marian Koman*
Department of Inorganic Chemistry, Slovak University of Technology, Radlinske´ho 9, SK-812 37 Bratislava, Slovak Republic
Correspondence e-mail: jaroslava.maroszova@stuba.sk
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C–C) = 0.004 A˚ Disorder in main residue
Rfactor = 0.042
wRfactor = 0.111
Data-to-parameter ratio = 15.1
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2006 International Union of Crystallography Printed in Great Britain – all rights reserved
In the title compound, [Cu(C7H3N2O6)(C6H7NO)2](C7H3
-N2O6), the Cu II
atom is coordinated by two chelating 2-pyridylmethanol ligands and a monodentate 3,5-dinitro-benzoate 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.
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 ligand (also known as 2-pyridylcarbinol and abbreviated as 2-pycarb) prefers a chelating mode, in
contrast with the bridging mode found for
(3-pyrid-yl)methanol (known as ronicol) in copper(II) complexes (Stachova´ 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 CuO2N2O0 coordination polyhedron. The
basal plane is formed by carboxylate atom O1 from the coordinating 3,5-dinitrobenzoate ligand, atom O31 from one
[image:1.610.232.429.322.419.2] [image:1.610.207.462.592.720.2]Received 3 November 2005 Accepted 9 December 2005 Online 14 December 2005
Figure 1
2-pycarb ligand and two mutuallytranspyridine atoms, N5 and N6, from two 2-pycarb ligands. The apical 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) A˚ 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) A˚ 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-dinitro-benzoate (Sundberget 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
(Turpeinenet 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 (Senet al., 2000, Sundberg & Klinga, 1994).
Experimental
(2-Pyridyl)methanol (2 mmol) was added to copper(II) acetate (1 mmol) in aqueous solution (20 ml). 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 over a period of a few weeks.
Crystal data
[Cu(C7H3N2O6)(C6H7NO)2
]-(C7H3N2O6)
Mr= 704.02 Triclinic,P1 a= 9.870 (1) A˚ b= 12.181 (1) A˚ c= 12.732 (1) A˚ = 95.29 (1)
= 108.68 (1)
= 91.80 (1)
V= 1440.9 (2) A˚3
Z= 2
Dx= 1.623 Mg m3 MoKradiation Cell parameters from 25
reflections = 4.2–12.0
= 0.84 mm1
T= 293 (2) K Prism, blue
0.550.450.30 mm
Data collection
SiemensP4 diffractometer ’scans
Absorption correction: scan (XEMP; Siemens, 1990) Tmin= 0.641,Tmax= 0.777
7697 measured reflections 6556 independent reflections
Rint= 0.029
max= 27.5
h=1!12 k=15!15 l=16!16 2 standard reflections
every 100 reflections
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.042
wR(F2) = 0.111 S= 1.04 6556 reflections 433 parameters
H-atom parameters constrained
w= 1/[2
(Fo2) + (0.0601P)2
+ 0.292P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001 max= 0.52 e A˚
3 min=0.63 e A˚ 3
Table 1
Selected geometric parameters (A˚ ,).
Cu1—O1 1.967 (2)
Cu1—N5 1.972 (2)
Cu1—N6 1.993 (2)
Cu1—O31 2.000 (2)
Cu1—O41 2.301 (2)
O1—C11 1.274 (3)
O2—C11 1.224 (3)
O1—Cu1—N5 92.43 (7)
O1—Cu1—N6 93.46 (7)
N5—Cu1—N6 173.81 (7)
O1—Cu1—O31 162.24 (7)
N5—Cu1—O31 81.75 (7)
N6—Cu1—O31 93.16 (7)
O1—Cu1—O41 96.50 (7)
N5—Cu1—O41 99.99 (7)
N6—Cu1—O41 77.45 (8)
O31—Cu1—O41 101.02 (6)
Table 2
Hydrogen-bond geometry (A˚ ,).
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
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 A˚ (methylene). TheUiso value for all H atoms was fixed at 0.05 A˚
2
. Atom O11 of an NO2group 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.
Data collection, cell refinement and data reduction: XSCANS (Siemens, 1994); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure:SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); publication material:WinGX(Farrugia, 1999).
This work was supported by VEGA grant 1/2452/05.
References
Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838..
Krabbes, I., Seichter, W., Breuning, T., Otschik, P. & Gloe, K. (1999).Z. Anorg. Allg. Chem.625, 1562–1565.
Sen, S., Saha, M. K., Mitra, S., Edwards, A. J. & Clegg, W. (2000).Polyhedron, 19, 1881–1885.
Sheldrick, G. M. (1985).SHELXS86.Crystallographic Computing 3, edited by G. M. Sheldrick, C. Kru¨ger & R. Goddard, pp. 175-189. Oxford University Press.
Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany. Siemens (1990).XEMP. Version 4.2. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Siemens (1994). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Stachova´, P., Valigura, D., Koman, M. & Glowiak, T. (2005).Acta Cryst.E61, m994–m996.
Sundberg, M. R. & Klinga, M. (1994).Polyhedron,13, 1099–1100.
supporting information
sup-1
Acta Cryst. (2006). E62, m109–m110
supporting information
Acta Cryst. (2006). E62, m109–m110 [doi:10.1107/S1600536805041310]
(3,5-Dinitrobenzoato-
κ
O
)bis[(2-pyridyl)methanol-
κ
2N
,
O
]copper(II)
3,5-dinitro-benzoate
Jaroslava Maroszov
á
, Petra Stachov
á
, Zuzana Vaskov
á
, Du
š
an Valigura and Marian Koman
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-di-nitrobenzoate (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-Dinitro-benzoic 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
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 Uiso value for all H atoms was fixed at 0.05 Å2. 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),
[image:4.610.124.484.170.357.2]but later fixed at 0.5 each.
Figure 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)
Mr = 704.02
Triclinic, P1 Hall symbol: -P 1
a = 9.870 (1) Å
b = 12.181 (1) Å
c = 12.732 (1) Å
α = 95.29 (1)°
β = 108.68 (1)°
γ = 91.80 (1)°
V = 1440.9 (2) Å3
Z = 2
F(000) = 718
Dx = 1.623 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections
θ = 4.2–12.0°
µ = 0.84 mm−1
T = 293 K Prism, blue
0.55 × 0.45 × 0.30 mm
Data collection
Siemens P4 diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ scans
Absorption correction: ψ scan (XEMP; Siemens, 1990)
Tmin = 0.641, Tmax = 0.777
7697 measured reflections
6556 independent reflections 5266 reflections with I > 2σ(I)
Rint = 0.029
θmax = 27.5°, θmin = 1.7°
h = −1→12
k = −15→15
l = −16→16
supporting information
sup-3
Acta Cryst. (2006). E62, m109–m110
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.042
wR(F2) = 0.111
S = 1.04 6556 reflections 433 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0601P)2 + 0.292P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.52 e Å−3
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 (Å2)
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)
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 (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-5
Acta Cryst. (2006). E62, m109–m110
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)
supporting information
sup-7
Acta Cryst. (2006). E62, m109–m110
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—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
