Bis(lysine-κ2N,O)hexa-μ2-oxido-hexa­oxidobis(1,10-phenanthroline-κ2N,N′)dicopper(II)tetravanadium(V) tetra­hydrate

Giron-Moreno, A.K.; Lara-Sánchez, N.; Moreno-Martínez, G.; Pastor-Ramírez, C.; Sánchez-Lara, E.; Sánchez-Morales, N.K.

doi:10.1107/S2414314617010501

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x171050

https://doi.org/10.1107/S2414314617010501

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Bis(lysine-κ²N,O)hexa-μ₂-oxido-hexaoxidobis(1,10-phenanthroline-κ²N,N′)dicopper(II)tetravanadium(V) tetrahydrate

Ana Karen Giron-Moreno,^a Nancy Lara-Sánchez,^a Gabriela Moreno-Martínez,^a Cándida Pastor-Ramírez,^a Eduardo Sánchez-Lara ^a ^* and Nailea Karina Sánchez-Morales ^a

^aCentro de Química, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico
^*Correspondence e-mail: eduardo.slara@alumno.buap.mx

Edited by A. J. Lough, University of Toronto, Canada (Received 2 June 2017; accepted 14 July 2017; online 25 July 2017)

The heterometallic coordination compound [Cu(Lys)(phen)]₂V₄O₁₂·4H₂O (Lys is the amino acid lysine, C₆H₁₄N₂O₂, and phen is 1,10-phenanthroline, C₁₂H₈N₂) lies across an inversion centre. Two [Cu(Lys)(phen)]²⁺ units coordinate to the cyclo-vanadate fragment and the formula unit is completed by four solvent water molecules. The lysine ligand is in the zwitterionic form and chelates the Cu^II atom via the α-NH₂ and α-COO⁻ donor groups, while the ∊-NH₃⁺ group is involved in intramolecular hydrogen bonds with the central [V₄O₁₂]⁴⁻ core and with solvent water molecules. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds connect the components of the structure to form a three-dimensional network. The crystal structure is further stabilized by π–π interactions involving the phen ligands. The lysine group is disordered over two sets of sites with refined occupancies of 0.534 (11) and 0.466 (11).

Keywords: crystal structure; mixed-ligand complex; cyclic oxovanadate; copper.

CCDC reference: 1562307

Structure description

Vanadate [VO₄]³⁻ is prone to condensation in aqueous solutions and forms oligomeric polyoxovanadate ions, whose formula and structure depend on pH, vanadate concentration, temperature and ionic strength. In basic media, predominant species are dimeric [V₂O₇]⁴⁻, tetrameric [V₄O₁₂]⁴⁻ and pentameric [V₅O₁₅]⁵⁻ anions, while the decameric cluster [V₁₀O₂₈]⁶⁻ is the most stable species in acidic media (Amado et al., 1993 ; Aureliano & Crans, 2009 ). The ring system [V₄O₁₂]⁴⁻ is of interest in coordination chemistry, given that this anion may behave as a bridging ligand, providing an entry to heterometallic complexes. Hence, the crystal structures of some V/Cu compounds, including [V₄O₁₂]⁴⁻, have been reported (Yucesan et al., 2006 ; Joniaková et al., 2006 ; Wang et al., 2007 ; Paredes-García et al., 2008 ). Within the sub-set of heterometallic complexes containing V and Cu as transition metals for which an X-ray characterization is available, the compound reported herein is the first one including an amino acid, namely lysine.

The asymmetric unit for [Cu(Lys)(phen)]₂V₄O₁₂·4H₂O, where Lys is lysine and phen is 1,10-phenanthroline, contains one half complex molecule and two solvent water molecules. The formula unit is completed by an inversion center (Fig. 1). The centrosymmetric [V₄O₁₂]⁴⁻ anion shows an eight-membered ring structure built up from four corner sharing tetrahedra and displays a chair-like conformation. The V—O bond lengths and V—O—V angles are found in normal ranges, in comparison with other structures containing this polyoxovanadate (e.g. Paredes-García et al., 2008).

Figure 1
Molecular entities in the crystal structure of the title compound with displacement ellipsoids for non-H atoms at the 30% probability level. Only the major component of disorder for the lysine group is presented and only the symmetry-unique water molecules are shown. Unlabelled atoms are generated by the symmetry operator (1 − x, 1 − y, −z).

The [V₄O₁₂]⁴⁻ anion serves as a bridge between two [Cu(Lys)(phen)]²⁺ moieties, a complex which has been shown to present a photo-induced DNA cleavage activity (Patra et al., 2005 ). The Cu^II atom displays the common distorted square pyramidal geometry: the α-amino N and α-carboxylate O atoms of lysine and the two N donors of phenanthroline are placed in basal positions, while the apical position is occupied by O3 belonging to the [V₄O₁₂]⁴⁻ anion, with a longer Cu—O bond length of 2.282 (2) Å. The value of the structural parameter τ₅ for Cu is 0.26, reflecting a limited distortion toward the trigonal–bipyramidal geometry (Addison et al., 1984 ). The Cu atom is displaced by 0.24 Å above the basal mean plane O1/N2A/N3/N4. The zwitterionic lysine is folded in such a way that both the ∊-NH₃⁺ and the α-NH₂ donor groups interact with the [V₄O₁₂]⁴⁻ core ring and the water molecule O10, via weak N—H⋯O hydrogen bonds (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A1⋯O5ⁱ	0.89	2.09	2.794 (7)	136
N1A—H1A2⋯O10ⁱⁱ	0.89	2.21	2.979 (7)	145
N1A—H1A3⋯O5ⁱⁱⁱ	0.89	1.89	2.769 (8)	169
N2A—H2AC⋯O4	0.89	2.25	3.094 (3)	159
N2A—H2AD⋯O10^iv	0.89	2.22	3.077 (3)	163
N2B—H2BC⋯O4	0.89	2.48	3.094 (3)	127
N2B—H2BC⋯O7	0.89	2.39	3.127 (4)	141
N2B—H2BD⋯O10^iv	0.89	2.23	3.077 (3)	159
O9—H91⋯O8	0.84	2.00	2.780 (6)	155
O9—H92⋯O8^v	0.84	2.21	2.861 (6)	135
O10—H101⋯O5^vi	0.84	2.09	2.837 (4)	148
O10—H102⋯O2	0.84	2.07	2.811 (4)	147
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y, z-1; (iii) x-1, y, z; (iv) -x, -y+1, -z+1; (v) -x+1, -y, -z; (vi) -x+1, -y+1, -z+1.

In the crystal, O—H⋯O and N—H⋯O hydrogen bonds involving the water molecules O9, O10 and the N atoms of the lysine molecule as donors connect the components of the structure forming a three-dimensional network (Table 1, Fig. 2). In addition, the crystal structure is further stabilized by π–π parallel-displaced stacking interactions between the phen ligands, characterized by a separation of 3.6446 (2) Å between the centroids of the central rings C10/C11/C12/C13/C17/C18 for two symmetry-related phen ligands (see Fig. 2, inset). The shortest Cu⋯Cu intermolecular distance is Cu⋯Cuⁱ = 6.2251 (7) Å [symmetry code: (i) 1 − x, 1 − y, 1 − z], large enough to avoid any significant magnetic interactions in the crystal.

Figure 2
Part of the crystal structure showing the O—H⋯O and N—H⋯O hydrogen bonds, which are represented by dotted green lines, and only H atoms involved in hydrogen bonds are shown. The inset displays two molecules interacting through π–π contacts between symmetry-related phenanthroline ligands.

Synthesis and crystallization

The title compound was prepared by a general synthetic method in which 1.0 mmol of 1,10-phenanthroline hydrochloride was added to an aqueous solution of lysine hydrochloride (0.18 g, 1.0 mmol in 30 ml H₂O) under stirring and slight warming in order to dissolve the heterocyclic base. An amount of CuCl₂·2H₂O (0.170 g, 1 mmol) was added to this mixture, and the pH of the resulting solution was adjusted to 9.5 by slow addition of KOH (10%), giving a dark-blue solution. Then, NH₄VO₃ (0.116 g, 1.0 mmol in 15 ml H₂O) was added dropwise to the solution, which was filtered and kept outdoors at room temperature for three days. Blue prismatic crystals were separated from the solution without any other impurity and used for X-ray diffraction. The final pH of the solution at 298 K was 8.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. ADPs for non-H atoms of the lysine ligand evidenced that this molecule is disordered over two positions. The disorder was modelled using independent sites A and B, and occupancies for each part were refined, which converged to 0.534 (11) and 0.466 (11) for sites A and B, respectively. Since atoms N2A and N2B, corresponding to the α-NH₂ group coordinating the metal, were difficult to resolve their sites were constrained to have the same coordinates and displacement parameters (EXYZ and EADP constrictions in SHELXL; Sheldrick, 2015b ).

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₈N₂)(C₆H₁₄N₂O₂)]₂[V₄O₁₂]·4H₂O
M_r	1247.69
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	295
a, b, c (Å)	9.2807 (4), 11.2960 (4), 12.7697 (5)
α, β, γ (°)	72.259 (3), 69.999 (3), 81.523 (3)
V (Å³)	1196.75 (9)
Z	1
Radiation type	Ag Kα, λ = 0.56083 Å
μ (mm⁻¹)	0.89
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Stoe Stadivari
No. of measured, independent and observed [I > 2σ(I)] reflections	46672, 7667, 5850
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.728

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.119, 1.04
No. of reflections	7667
No. of parameters	371
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.05, −1.04
Computer programs: X-AREA (Stoe & Cie, 2015 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b), XP in SHELXTL-Plus (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1562307

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617010501/lh4021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010501/lh4021Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2015); cell refinement: X-AREA (Stoe & Cie, 2015); data reduction: X-AREA (Stoe & Cie, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).

Bis(lysine-κ²N,O)hexa-µ₂-oxido-hexaoxidobis(1,10-phenanthroline-κ²N,N')dicopper(II)tetravanadium(V) tetrahydrate top

Crystal data top

[Cu(C₁₂H₈N₂)(C₆H₁₄N₂O₂)]₂[V₄O₁₂]·4H₂O	Z = 1
M_r = 1247.69	F(000) = 634
Triclinic, P1	D_x = 1.731 Mg m⁻³
a = 9.2807 (4) Å	Ag Kα radiation, λ = 0.56083 Å
b = 11.2960 (4) Å	Cell parameters from 29693 reflections
c = 12.7697 (5) Å	θ = 2.3–28.7°
α = 72.259 (3)°	µ = 0.89 mm⁻¹
β = 69.999 (3)°	T = 295 K
γ = 81.523 (3)°	Prism, blue
V = 1196.75 (9) Å³	0.30 × 0.20 × 0.20 mm

Data collection top

Stoe Stadivari diffractometer	5850 reflections with I > 2σ(I)
Radiation source: Sealed X-ray tube, Axo Microfocus source	R_int = 0.034
Mirror monochromator	θ_max = 24.1°, θ_min = 2.3°
Detector resolution: 5.81 pixels mm^-1	h = −13→13
ω scans	k = −16→16
46672 measured reflections	l = −18→18
7667 independent reflections

Refinement top

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)] = 0.044	Hydrogen site location: mixed
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0417P)² + 1.8611P] where P = (F_o² + 2F_c²)/3
7667 reflections	(Δ/σ)_max < 0.001
371 parameters	Δρ_max = 1.05 e Å⁻³
0 restraints	Δρ_min = −1.04 e Å⁻³
0 constraints

Special details top

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.

Refinement. The H atoms for water molecules O9 and O10 were located from a difference Fourier map, and then included with idealized O—H bond lengths of 0.84 Å. All other H atoms were placed in calculated positions and refined in the riding-motion approximation.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.28666 (4)	0.37528 (3)	0.42645 (3)	0.03113 (9)
V1	0.60736 (5)	0.45877 (4)	0.16289 (4)	0.03081 (11)
V2	0.48289 (8)	0.31044 (5)	0.03247 (4)	0.04600 (15)
O1	0.2405 (3)	0.52471 (18)	0.47897 (18)	0.0385 (4)
O2	0.0915 (3)	0.6963 (2)	0.4704 (2)	0.0553 (6)
O3	0.5310 (3)	0.4070 (2)	0.30298 (17)	0.0411 (5)
O4	0.4868 (3)	0.58607 (19)	0.11187 (16)	0.0383 (4)
O5	0.7830 (3)	0.4986 (3)	0.1340 (2)	0.0632 (7)
O6	0.6154 (3)	0.3387 (2)	0.0954 (2)	0.0565 (7)
O7	0.3068 (4)	0.3382 (3)	0.1098 (2)	0.0769 (9)
O8	0.5116 (6)	0.1674 (2)	0.0252 (3)	0.0980 (14)
N3	0.3584 (3)	0.2840 (2)	0.56278 (19)	0.0325 (5)
N4	0.2610 (3)	0.2000 (2)	0.42780 (19)	0.0321 (5)
N1A	−0.0245 (7)	0.6630 (7)	−0.0520 (5)	0.0511 (17)	0.534 (11)
H1A1	0.068783	0.628719	−0.053834	0.077*	0.534 (11)
H1A2	−0.036718	0.675570	−0.120727	0.077*	0.534 (11)
H1A3	−0.094914	0.612355	0.002064	0.077*	0.534 (11)
N2A	0.1937 (3)	0.4754 (2)	0.3046 (2)	0.0324 (5)	0.534 (11)
H2AC	0.267423	0.500729	0.237479	0.039*	0.534 (11)
H2AD	0.132401	0.428641	0.295082	0.039*	0.534 (11)
C1A	−0.0422 (15)	0.7850 (10)	−0.0239 (11)	0.065 (3)	0.534 (11)
H1AA	−0.151129	0.802817	0.009100	0.078*	0.534 (11)
H1AB	−0.006459	0.848649	−0.096551	0.078*	0.534 (11)
C2A	0.0364 (14)	0.8003 (7)	0.0564 (8)	0.052 (2)	0.534 (11)
H2AA	0.140387	0.824892	0.011591	0.062*	0.534 (11)
H2AB	−0.017196	0.866728	0.090425	0.062*	0.534 (11)
C3A	0.042 (3)	0.683 (3)	0.153 (2)	0.052 (5)	0.534 (11)
H3AA	0.106097	0.619819	0.118836	0.062*	0.534 (11)
H3AB	−0.060707	0.652883	0.191254	0.062*	0.534 (11)
C4A	0.1031 (13)	0.7010 (7)	0.2422 (8)	0.0430 (18)	0.534 (11)
H4AA	0.206876	0.729162	0.204135	0.052*	0.534 (11)
H4AB	0.040617	0.765710	0.274879	0.052*	0.534 (11)
C5A	0.1047 (10)	0.5842 (6)	0.3398 (7)	0.0349 (14)	0.534 (11)
H5AA	−0.002022	0.560109	0.377435	0.042*	0.534 (11)
N1B	−0.0843 (17)	0.7332 (13)	−0.0599 (9)	0.092 (4)	0.466 (11)
H1B1	−0.056330	0.653128	−0.053176	0.138*	0.466 (11)
H1B2	−0.103320	0.767266	−0.126794	0.138*	0.466 (11)
H1B3	−0.168642	0.740242	−0.001552	0.138*	0.466 (11)
N2B	0.1937 (3)	0.4754 (2)	0.3046 (2)	0.0324 (5)	0.466 (11)
H2BC	0.254448	0.469107	0.235269	0.039*	0.466 (11)
H2BD	0.103074	0.446448	0.317935	0.039*	0.466 (11)
C1B	0.0327 (15)	0.7939 (11)	−0.0569 (9)	0.055 (3)	0.466 (11)
H1BA	0.036663	0.880480	−0.101643	0.066*	0.466 (11)
H1BB	0.132517	0.751270	−0.078464	0.066*	0.466 (11)
C2B	−0.0450 (15)	0.7745 (13)	0.0883 (10)	0.062 (3)	0.466 (11)
H2BA	−0.060180	0.853549	0.106720	0.074*	0.466 (11)
H2BB	−0.142491	0.735132	0.118419	0.074*	0.466 (11)
C3B	0.073 (3)	0.692 (3)	0.136 (2)	0.040 (4)	0.466 (11)
H3BA	0.173286	0.725887	0.093264	0.048*	0.466 (11)
H3BB	0.076685	0.610213	0.124312	0.048*	0.466 (11)
C4B	0.0414 (11)	0.6762 (9)	0.2659 (8)	0.0365 (17)	0.466 (11)
H4BA	0.025226	0.757614	0.279834	0.044*	0.466 (11)
H4BB	−0.051585	0.631427	0.310312	0.044*	0.466 (11)
C5B	0.1740 (10)	0.6059 (6)	0.3064 (6)	0.0255 (13)	0.466 (11)
H5BA	0.268464	0.646941	0.254025	0.031*	0.466 (11)
C6	0.1564 (4)	0.6087 (3)	0.4323 (2)	0.0364 (6)
C7	0.4109 (4)	0.3304 (3)	0.6255 (3)	0.0407 (6)
H7A	0.419788	0.415905	0.606119	0.049*
C8	0.4533 (4)	0.2536 (3)	0.7205 (3)	0.0480 (8)
H8A	0.491515	0.288232	0.762469	0.058*
C9	0.4389 (4)	0.1284 (3)	0.7515 (3)	0.0498 (8)
H9A	0.465751	0.077469	0.815119	0.060*
C10	0.3828 (4)	0.0767 (3)	0.6865 (2)	0.0408 (6)
C11	0.3672 (5)	−0.0537 (3)	0.7089 (3)	0.0535 (9)
H11A	0.392773	−0.109731	0.771058	0.064*
C12	0.3157 (5)	−0.0964 (3)	0.6404 (3)	0.0552 (9)
H12A	0.304755	−0.181337	0.657416	0.066*
C13	0.2778 (4)	−0.0142 (3)	0.5428 (3)	0.0412 (6)
C14	0.2262 (4)	−0.0526 (3)	0.4671 (3)	0.0511 (8)
H14A	0.213642	−0.136481	0.479431	0.061*
C15	0.1949 (4)	0.0339 (3)	0.3756 (3)	0.0487 (8)
H15A	0.161247	0.009298	0.325069	0.058*
C16	0.2137 (4)	0.1603 (3)	0.3580 (3)	0.0404 (6)
H16A	0.192236	0.218353	0.295089	0.048*
C17	0.2930 (3)	0.1139 (2)	0.5187 (2)	0.0310 (5)
C18	0.3457 (3)	0.1596 (2)	0.5914 (2)	0.0312 (5)
O9	0.2826 (5)	0.0017 (5)	0.0903 (4)	0.1215 (16)
H91	0.332940	0.065801	0.060048	0.182*
H92	0.308060	−0.029729	0.034468	0.182*
O10	0.0727 (3)	0.6510 (3)	0.7036 (2)	0.0613 (7)
H101	0.130220	0.593952	0.729652	0.092*
H102	0.115531	0.669602	0.631782	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0444 (2)	0.02394 (14)	0.02671 (15)	−0.00129 (12)	−0.01526 (14)	−0.00487 (11)
V1	0.0309 (2)	0.0383 (2)	0.0236 (2)	0.00036 (17)	−0.01121 (17)	−0.00697 (16)
V2	0.0816 (4)	0.0301 (2)	0.0266 (2)	−0.0047 (2)	−0.0206 (3)	−0.00322 (18)
O1	0.0528 (12)	0.0331 (9)	0.0374 (10)	0.0036 (8)	−0.0229 (9)	−0.0134 (8)
O2	0.0801 (18)	0.0393 (12)	0.0570 (15)	0.0152 (11)	−0.0316 (13)	−0.0251 (11)
O3	0.0470 (12)	0.0459 (11)	0.0264 (9)	−0.0012 (9)	−0.0135 (9)	−0.0024 (8)
O4	0.0475 (12)	0.0371 (10)	0.0266 (9)	0.0023 (8)	−0.0133 (8)	−0.0038 (7)
O5	0.0394 (13)	0.091 (2)	0.0561 (15)	−0.0165 (13)	−0.0183 (12)	−0.0059 (14)
O6	0.089 (2)	0.0452 (12)	0.0485 (13)	0.0218 (12)	−0.0407 (14)	−0.0220 (10)
O7	0.087 (2)	0.102 (2)	0.0321 (13)	−0.0295 (19)	−0.0035 (13)	−0.0103 (14)
O8	0.196 (4)	0.0305 (12)	0.081 (2)	−0.0135 (18)	−0.063 (3)	−0.0098 (13)
N3	0.0394 (12)	0.0306 (10)	0.0282 (10)	0.0005 (9)	−0.0132 (9)	−0.0071 (8)
N4	0.0412 (12)	0.0265 (10)	0.0281 (10)	−0.0033 (9)	−0.0118 (9)	−0.0049 (8)
N1A	0.045 (3)	0.067 (4)	0.041 (3)	0.010 (3)	−0.021 (2)	−0.012 (3)
N2A	0.0391 (12)	0.0295 (10)	0.0329 (11)	−0.0004 (9)	−0.0170 (10)	−0.0089 (8)
C1A	0.071 (7)	0.060 (5)	0.066 (7)	0.001 (6)	−0.044 (6)	0.001 (5)
C2A	0.075 (6)	0.034 (3)	0.056 (5)	−0.002 (4)	−0.043 (5)	−0.002 (3)
C3A	0.067 (12)	0.036 (4)	0.064 (13)	−0.007 (8)	−0.046 (10)	0.001 (7)
C4A	0.058 (5)	0.028 (3)	0.047 (5)	−0.003 (3)	−0.027 (4)	−0.004 (3)
C5A	0.036 (4)	0.028 (3)	0.041 (3)	−0.001 (2)	−0.015 (3)	−0.007 (2)
N1B	0.121 (10)	0.091 (9)	0.078 (6)	−0.045 (8)	−0.055 (7)	0.004 (6)
N2B	0.0391 (12)	0.0295 (10)	0.0329 (11)	−0.0004 (9)	−0.0170 (10)	−0.0089 (8)
C1B	0.059 (6)	0.064 (5)	0.042 (5)	−0.002 (5)	−0.028 (5)	−0.002 (4)
C2B	0.063 (7)	0.075 (7)	0.056 (6)	0.023 (5)	−0.032 (5)	−0.027 (5)
C3B	0.043 (7)	0.044 (10)	0.031 (4)	0.006 (6)	−0.012 (4)	−0.011 (5)
C4B	0.038 (5)	0.035 (4)	0.033 (4)	0.005 (3)	−0.010 (3)	−0.010 (3)
C5B	0.026 (3)	0.026 (3)	0.023 (3)	−0.005 (2)	−0.006 (2)	−0.004 (2)
C6	0.0450 (16)	0.0310 (12)	0.0350 (13)	−0.0041 (11)	−0.0129 (12)	−0.0103 (10)
C7	0.0483 (17)	0.0404 (14)	0.0386 (15)	−0.0012 (12)	−0.0190 (13)	−0.0125 (12)
C8	0.0525 (19)	0.062 (2)	0.0389 (16)	0.0045 (15)	−0.0232 (14)	−0.0202 (14)
C9	0.056 (2)	0.0589 (19)	0.0358 (15)	0.0147 (16)	−0.0249 (15)	−0.0103 (14)
C10	0.0463 (16)	0.0387 (14)	0.0300 (13)	0.0054 (12)	−0.0138 (12)	−0.0007 (11)
C11	0.069 (2)	0.0369 (15)	0.0435 (17)	0.0038 (15)	−0.0216 (17)	0.0069 (13)
C12	0.076 (3)	0.0269 (13)	0.0524 (19)	−0.0041 (14)	−0.0192 (18)	0.0036 (13)
C13	0.0493 (17)	0.0271 (12)	0.0393 (15)	−0.0041 (11)	−0.0077 (13)	−0.0040 (11)
C14	0.061 (2)	0.0315 (14)	0.059 (2)	−0.0095 (14)	−0.0126 (17)	−0.0143 (14)
C15	0.061 (2)	0.0450 (16)	0.0485 (18)	−0.0100 (15)	−0.0185 (16)	−0.0198 (14)
C16	0.0506 (17)	0.0389 (14)	0.0357 (14)	−0.0042 (12)	−0.0167 (13)	−0.0115 (11)
C17	0.0329 (13)	0.0271 (11)	0.0277 (11)	−0.0024 (9)	−0.0057 (10)	−0.0041 (9)
C18	0.0344 (13)	0.0298 (11)	0.0261 (11)	0.0014 (10)	−0.0090 (10)	−0.0048 (9)
O9	0.079 (3)	0.172 (5)	0.126 (4)	0.014 (3)	−0.040 (3)	−0.060 (3)
O10	0.0671 (17)	0.0685 (17)	0.0555 (15)	−0.0091 (13)	−0.0349 (14)	−0.0068 (13)

Geometric parameters (Å, º) top

Cu1—O1	1.940 (2)	N1B—H1B2	0.8900
Cu1—N2B	2.001 (2)	N1B—H1B3	0.8900
Cu1—N2A	2.001 (2)	N2B—C5B	1.464 (6)
Cu1—N3	2.008 (2)	N2B—H2BC	0.8900
Cu1—N4	2.023 (2)	N2B—H2BD	0.8900
Cu1—O3	2.282 (2)	C1B—C2B	1.700 (17)
V1—O3	1.631 (2)	C1B—H1BA	0.9700
V1—O5	1.643 (2)	C1B—H1BB	0.9700
V1—O4	1.788 (2)	C2B—C3B	1.50 (4)
V1—O6	1.796 (2)	C2B—H2BA	0.9700
V2—O8	1.624 (3)	C2B—H2BB	0.9700
V2—O7	1.636 (3)	C3B—C4B	1.54 (3)
V2—O6	1.792 (3)	C3B—H3BA	0.9700
V2—O4ⁱ	1.8090 (19)	C3B—H3BB	0.9700
O1—C6	1.272 (3)	C4B—C5B	1.520 (12)
O2—C6	1.224 (4)	C4B—H4BA	0.9700
N3—C7	1.323 (4)	C4B—H4BB	0.9700
N3—C18	1.353 (3)	C5B—C6	1.570 (6)
N4—C16	1.325 (4)	C5B—H5BA	0.9800
N4—C17	1.358 (3)	C7—C8	1.402 (4)
N1A—C1A	1.499 (15)	C7—H7A	0.9300
N1A—H1A1	0.8900	C8—C9	1.361 (5)
N1A—H1A2	0.8900	C8—H8A	0.9300
N1A—H1A3	0.8900	C9—C10	1.408 (5)
N2A—C5A	1.476 (7)	C9—H9A	0.9300
N2A—H2AC	0.8900	C10—C18	1.402 (4)
N2A—H2AD	0.8900	C10—C11	1.433 (5)
C1A—C2A	1.506 (14)	C11—C12	1.355 (6)
C1A—H1AA	0.9700	C11—H11A	0.9300
C1A—H1AB	0.9700	C12—C13	1.428 (5)
C2A—C3A	1.52 (3)	C12—H12A	0.9300
C2A—H2AA	0.9700	C13—C17	1.403 (4)
C2A—H2AB	0.9700	C13—C14	1.409 (5)
C3A—C4A	1.51 (3)	C14—C15	1.362 (5)
C3A—H3AA	0.9700	C14—H14A	0.9300
C3A—H3AB	0.9700	C15—C16	1.404 (4)
C4A—C5A	1.516 (11)	C15—H15A	0.9300
C4A—H4AA	0.9700	C16—H16A	0.9300
C4A—H4AB	0.9700	C17—C18	1.430 (4)
C5A—C6	1.526 (7)	O9—H91	0.8356
C5A—H5AA	0.9800	O9—H92	0.8396
N1B—C1B	1.383 (16)	O10—H101	0.8369
N1B—H1B1	0.8900	O10—H102	0.8367

O1—Cu1—N2B	83.94 (9)	H1B1—N1B—H1B3	109.5
O1—Cu1—N2A	83.94 (9)	H1B2—N1B—H1B3	109.5
O1—Cu1—N3	90.65 (9)	C5B—N2B—Cu1	109.4 (3)
N2B—Cu1—N3	172.79 (10)	C5B—N2B—H2BC	109.8
N2A—Cu1—N3	172.79 (10)	Cu1—N2B—H2BC	109.8
O1—Cu1—N4	157.13 (10)	C5B—N2B—H2BD	109.8
N2B—Cu1—N4	101.14 (9)	Cu1—N2B—H2BD	109.8
N2A—Cu1—N4	101.14 (9)	H2BC—N2B—H2BD	108.3
N3—Cu1—N4	82.07 (9)	N1B—C1B—C2B	92.3 (11)
O1—Cu1—O3	101.31 (9)	N1B—C1B—H1BA	113.2
N2B—Cu1—O3	92.76 (9)	C2B—C1B—H1BA	113.2
N2A—Cu1—O3	92.76 (9)	N1B—C1B—H1BB	113.2
N3—Cu1—O3	92.97 (9)	C2B—C1B—H1BB	113.2
N4—Cu1—O3	100.70 (9)	H1BA—C1B—H1BB	110.6
O3—V1—O5	108.89 (13)	C3B—C2B—C1B	103.3 (12)
O3—V1—O4	107.83 (10)	C3B—C2B—H2BA	111.1
O5—V1—O4	112.78 (13)	C1B—C2B—H2BA	111.1
O3—V1—O6	109.91 (12)	C3B—C2B—H2BB	111.1
O5—V1—O6	108.72 (15)	C1B—C2B—H2BB	111.1
O4—V1—O6	108.68 (10)	H2BA—C2B—H2BB	109.1
O8—V2—O7	111.8 (2)	C2B—C3B—C4B	113.4 (17)
O8—V2—O6	108.32 (17)	C2B—C3B—H3BA	108.9
O7—V2—O6	109.89 (14)	C4B—C3B—H3BA	108.9
O8—V2—O4ⁱ	109.20 (14)	C2B—C3B—H3BB	108.9
O7—V2—O4ⁱ	107.28 (13)	C4B—C3B—H3BB	108.9
O6—V2—O4ⁱ	110.39 (12)	H3BA—C3B—H3BB	107.7
C6—O1—Cu1	115.86 (18)	C5B—C4B—C3B	111.3 (13)
V1—O3—Cu1	134.84 (12)	C5B—C4B—H4BA	109.4
V1—O4—V2ⁱ	129.04 (12)	C3B—C4B—H4BA	109.4
V2—O6—V1	129.23 (14)	C5B—C4B—H4BB	109.4
C7—N3—C18	119.0 (2)	C3B—C4B—H4BB	109.4
C7—N3—Cu1	128.5 (2)	H4BA—C4B—H4BB	108.0
C18—N3—Cu1	112.50 (17)	N2B—C5B—C4B	113.6 (7)
C16—N4—C17	118.0 (2)	N2B—C5B—C6	107.7 (4)
C16—N4—Cu1	130.04 (19)	C4B—C5B—C6	112.0 (6)
C17—N4—Cu1	111.87 (18)	N2B—C5B—H5BA	107.8
C1A—N1A—H1A1	109.5	C4B—C5B—H5BA	107.8
C1A—N1A—H1A2	109.5	C6—C5B—H5BA	107.8
H1A1—N1A—H1A2	109.5	O2—C6—O1	124.2 (3)
C1A—N1A—H1A3	109.5	O2—C6—C5A	116.7 (3)
H1A1—N1A—H1A3	109.5	O1—C6—C5A	117.7 (3)
H1A2—N1A—H1A3	109.5	O2—C6—C5B	122.0 (3)
C5A—N2A—Cu1	109.5 (3)	O1—C6—C5B	112.5 (3)
C5A—N2A—H2AC	109.8	N3—C7—C8	121.5 (3)
Cu1—N2A—H2AC	109.8	N3—C7—H7A	119.3
C5A—N2A—H2AD	109.8	C8—C7—H7A	119.3
Cu1—N2A—H2AD	109.8	C9—C8—C7	120.2 (3)
H2AC—N2A—H2AD	108.2	C9—C8—H8A	119.9
N1A—C1A—C2A	119.4 (8)	C7—C8—H8A	119.9
N1A—C1A—H1AA	107.5	C8—C9—C10	119.4 (3)
C2A—C1A—H1AA	107.5	C8—C9—H9A	120.3
N1A—C1A—H1AB	107.5	C10—C9—H9A	120.3
C2A—C1A—H1AB	107.5	C18—C10—C9	116.9 (3)
H1AA—C1A—H1AB	107.0	C18—C10—C11	118.8 (3)
C3A—C2A—C1A	113.4 (13)	C9—C10—C11	124.3 (3)
C3A—C2A—H2AA	108.9	C12—C11—C10	120.7 (3)
C1A—C2A—H2AA	108.9	C12—C11—H11A	119.7
C3A—C2A—H2AB	108.9	C10—C11—H11A	119.7
C1A—C2A—H2AB	108.9	C11—C12—C13	121.7 (3)
H2AA—C2A—H2AB	107.7	C11—C12—H12A	119.2
C2A—C3A—C4A	114.1 (19)	C13—C12—H12A	119.2
C2A—C3A—H3AA	108.7	C17—C13—C14	116.8 (3)
C4A—C3A—H3AA	108.7	C17—C13—C12	118.7 (3)
C2A—C3A—H3AB	108.7	C14—C13—C12	124.5 (3)
C4A—C3A—H3AB	108.7	C15—C14—C13	119.6 (3)
H3AA—C3A—H3AB	107.6	C15—C14—H14A	120.2
C5A—C4A—C3A	113.7 (13)	C13—C14—H14A	120.2
C5A—C4A—H4AA	108.8	C14—C15—C16	119.8 (3)
C3A—C4A—H4AA	108.8	C14—C15—H15A	120.1
C5A—C4A—H4AB	108.8	C16—C15—H15A	120.1
C3A—C4A—H4AB	108.8	N4—C16—C15	122.4 (3)
H4AA—C4A—H4AB	107.7	N4—C16—H16A	118.8
N2A—C5A—C4A	115.8 (7)	C15—C16—H16A	118.8
N2A—C5A—C6	109.4 (4)	N4—C17—C13	123.5 (3)
C4A—C5A—C6	111.9 (6)	N4—C17—C18	116.6 (2)
N2A—C5A—H5AA	106.4	C13—C17—C18	119.9 (2)
C4A—C5A—H5AA	106.4	N3—C18—C10	123.0 (3)
C6—C5A—H5AA	106.4	N3—C18—C17	116.7 (2)
C1B—N1B—H1B1	109.5	C10—C18—C17	120.3 (2)
C1B—N1B—H1B2	109.5	H91—O9—H92	100.7
H1B1—N1B—H1B2	109.5	H101—O10—H102	104.1
C1B—N1B—H1B3	109.5

O5—V1—O3—Cu1	162.47 (18)	C18—N3—C7—C8	0.0 (5)
O4—V1—O3—Cu1	39.8 (2)	Cu1—N3—C7—C8	178.5 (2)
O6—V1—O3—Cu1	−78.53 (19)	N3—C7—C8—C9	−1.1 (5)
O3—V1—O4—V2ⁱ	174.60 (15)	C7—C8—C9—C10	0.8 (5)
O5—V1—O4—V2ⁱ	54.3 (2)	C8—C9—C10—C18	0.4 (5)
O6—V1—O4—V2ⁱ	−66.30 (19)	C8—C9—C10—C11	178.0 (3)
O8—V2—O6—V1	−160.5 (2)	C18—C10—C11—C12	−0.8 (5)
O7—V2—O6—V1	−38.2 (2)	C9—C10—C11—C12	−178.4 (4)
O4ⁱ—V2—O6—V1	80.0 (2)	C10—C11—C12—C13	1.1 (6)
O3—V1—O6—V2	95.4 (2)	C11—C12—C13—C17	−0.8 (6)
O5—V1—O6—V2	−145.5 (2)	C11—C12—C13—C14	178.9 (4)
O4—V1—O6—V2	−22.4 (2)	C17—C13—C14—C15	0.4 (5)
N1A—C1A—C2A—C3A	−35 (2)	C12—C13—C14—C15	−179.2 (4)
C1A—C2A—C3A—C4A	−173.0 (13)	C13—C14—C15—C16	−0.3 (6)
C2A—C3A—C4A—C5A	178.6 (12)	C17—N4—C16—C15	0.5 (5)
Cu1—N2A—C5A—C4A	146.8 (6)	Cu1—N4—C16—C15	−176.5 (2)
Cu1—N2A—C5A—C6	19.2 (6)	C14—C15—C16—N4	−0.2 (5)
C3A—C4A—C5A—N2A	57.7 (16)	C16—N4—C17—C13	−0.4 (4)
C3A—C4A—C5A—C6	−176.0 (11)	Cu1—N4—C17—C13	177.1 (2)
N1B—C1B—C2B—C3B	115.6 (18)	C16—N4—C17—C18	179.2 (3)
C1B—C2B—C3B—C4B	171.0 (15)	Cu1—N4—C17—C18	−3.3 (3)
C2B—C3B—C4B—C5B	−172.6 (14)	C14—C13—C17—N4	−0.1 (5)
Cu1—N2B—C5B—C4B	−151.4 (6)	C12—C13—C17—N4	179.6 (3)
Cu1—N2B—C5B—C6	−26.8 (6)	C14—C13—C17—C18	−179.6 (3)
C3B—C4B—C5B—N2B	−67.3 (16)	C12—C13—C17—C18	0.1 (4)
C3B—C4B—C5B—C6	170.4 (13)	C7—N3—C18—C10	1.3 (4)
Cu1—O1—C6—O2	164.7 (3)	Cu1—N3—C18—C10	−177.4 (2)
Cu1—O1—C6—C5A	−1.3 (5)	C7—N3—C18—C17	−178.1 (3)
Cu1—O1—C6—C5B	−28.3 (4)	Cu1—N3—C18—C17	3.2 (3)
N2A—C5A—C6—O2	−179.6 (4)	C9—C10—C18—N3	−1.5 (4)
C4A—C5A—C6—O2	50.7 (10)	C11—C10—C18—N3	−179.3 (3)
N2A—C5A—C6—O1	−12.5 (8)	C9—C10—C18—C17	177.9 (3)
C4A—C5A—C6—O1	−142.2 (7)	C11—C10—C18—C17	0.2 (4)
N2B—C5B—C6—O2	−156.2 (4)	N4—C17—C18—N3	0.1 (4)
C4B—C5B—C6—O2	−30.6 (9)	C13—C17—C18—N3	179.7 (3)
N2B—C5B—C6—O1	36.5 (6)	N4—C17—C18—C10	−179.3 (3)
C4B—C5B—C6—O1	162.1 (6)	C13—C17—C18—C10	0.2 (4)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A1···O5ⁱ	0.89	2.09	2.794 (7)	136
N1A—H1A2···O7ⁱⁱ	0.89	2.49	2.958 (7)	114
N1A—H1A2···O10ⁱⁱⁱ	0.89	2.21	2.979 (7)	145
N1A—H1A3···O5^iv	0.89	1.89	2.769 (8)	169
N2A—H2AC···O4	0.89	2.25	3.094 (3)	159
N2A—H2AD···O10^v	0.89	2.22	3.077 (3)	163
C1A—H1AA···O9ⁱⁱ	0.97	2.56	3.157 (11)	120
C5A—H5AA···O1^v	0.98	2.44	3.390 (10)	163
N1B—H1B1···O5^iv	0.89	2.60	3.090 (10)	115
N2B—H2BC···O4	0.89	2.48	3.094 (3)	127
N2B—H2BC···O7	0.89	2.39	3.127 (4)	141
N2B—H2BD···O10^v	0.89	2.23	3.077 (3)	159
C1B—H1BB···O6ⁱ	0.97	2.37	3.326 (13)	167
C5B—H5BA···O4	0.98	2.39	3.140 (8)	133
C8—H8A···O4^vi	0.93	2.51	3.412 (4)	162
C16—H16A···O7	0.93	2.31	3.097 (4)	143
O9—H91···O8	0.84	2.00	2.780 (6)	155
O9—H92···O8^vii	0.84	2.21	2.861 (6)	135
O10—H101···O5^vi	0.84	2.09	2.837 (4)	148
O10—H102···O2	0.84	2.07	2.811 (4)	147

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z; (iii) x, y, z−1; (iv) x−1, y, z; (v) −x, −y+1, −z+1; (vi) −x+1, −y+1, −z+1; (vii) −x+1, −y, −z.

Funding information

Funding for this research was provided by Consejo Nacional de Ciencia y Tecnología (Award No. 268178, Infraestructura). ESL is thankful to CONACyT (Mexico) for the PhD Fellowship (support No. 293256).

References

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