research communications
A [Cu3(μ3-O)]–pyrazolate metallacycle with terminal nitrate ligands exhibiting symmetry 3
aDepartment of Chemistry, University of Puerto Rico – Rio Piedras, San Juan 00936, Puerto Rico, USA
*Correspondence e-mail: logesh.mathivathanan@fiu.edu
The trinuclear triangular cuprate anion of the title compound, tris[bis(triphenylphosphoranylidene)ammonium] tris(μ2-4-chloropyrazolato-κ2N:N′)-μ3-oxido-tris[(nitrato-κ2O,O′)cuprate(II)] nitrate monohydrate, (C36H30P2N)[Cu3(C3H2ClN2)3(NO3)3O]NO3·H2O, has symmetry 3., with the μ3-O atom located on the threefold rotation axis. The distorted square-pyramidal coordination sphere of the CuII atom is completed by two N atoms of trans-bridging pyrazolate groups and a chelating nitrate anion. The complex anion is slightly bent, with the nitrate and pyrazolate groups occupying positions above and below the Cu3 plane, respectively. In the crystal, weak O—H⋯O and C—H⋯O hydrogen bonds, as well as π–π interactions, are present.
CCDC reference: 1458061
1. Chemical context
Trinuclear copper complexes with a triangular arrangement of the copper(II) cations are of importance in terms of their magnetic and redox properties (Rivera-Carrillo et al., 2008). Moreover, Cu3(μ3-O/OH) moieties make up the active sites of several multicopper oxidase enzymes (Solomon et al., 2014). Pyrazolate anions as ligands are of bidentate chelating nature and are able to bind to the the CuII cations in suitable angles to form triangular complexes (Halcrow, 2009; Viciano-Chumillas et al., 2010).
Nitrato and pyrazolato ligands are commonly studied ligands in CuII coordination chemistry. Simple CuII nitrate complexes are aplenty in the literature and have been studied in detail with respect to their part in the nitrogen cycle. Triangular trinuclear CuII complexes with terminal nitrate ligands, however, are scarcer (Alsalme et al., 2014). Nitrates, being good hydrogen-bonding acceptors, are able to form Cu3(μ3-OH) complexes, with hydrogen bonds to the μ3-OH group and to ancilliary ligands and water molecules.
In this communication we describe the accidental synthesis and the structure of a trinuclear Cu–pyrazolato complex, viz. (PPN)3[Cu3(μ3-O)(μ-4-Clpz)3(NO3)3](NO3)·H2O, where PPN = bis(triphenylphosphoranylidene)ammonium; 4-Cl-pz = 4-chloropyrazolate. A related Cu3-pyrazolato complex was reported by Angaridis et al. (2002).
2. Structural commentary
The nine-membered metallacycle Cu3N6 in the cuprate anion (Fig. 1) is strung together by a μ3-O group located at the center of the triangle (point group symmetry of the complete molecule 3.), forming an almost planar Cu3(μ3-O)-core, where the μ3-O atom O1 is located 0.122 (7) Å above the Cu3 plane. The distorted square-pyramidal geometry of the CuII atom is completed by the two N atoms of symmetry-related trans-bridging pyrazolato ligands, and a terminal nitrato ligand that is bound to the metal in a chelating fashion (Table 1). The complex is slightly bent with the nitrate and pyrazolato groups occupying positions above and below the Cu3 plane, respectively. The Cl atom of the pyrazole anion is located approximately 1.28 Å below the Cu3 plane. The non-coordinating nitrate counter-anion is located about a special position with the nitrogen atom on the threefold rotation axis.
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The triphenylphosphene groups in the PPN cation are staggered around the central N atom [P—N—P angle 139.5 (2)°] and show bond lengths and angles characteristic for this unit (Beckett et al., 2010).
3. Supramolecular features
The interstitial water O atom is also located on a threefold rotation axis which consequently results in disordered H atoms of this moiety. Although these H atoms could not be located, three O⋯O distances to the chelating nitrate anions of 3.367 (6) Å point to weak O—H⋯O hydrogen bonds in the structure. This nitrate O atom is additionally involved in weak non-classical hydrogen-bonding interactions with one of the C–H groups of the PPN cation (Table 2). The latter shows also π–π interactions [3.902 (7) Å] with one of the pyrazolate rings, leading to an overall three-dimensional network. The packing of the molecular units is shown in Fig. 2.
4. Synthesis and crystallization
4-Cl-pz and the hexanuclear Cu6-pyrazolato complex (PPN)[{Cu3(μ3-O)(μ-4-Cl-pz)3}2(μ-3,5-Ph2pz)3], were synthesized by published procedures (Maresca et al., 1997; Mezei et al., 2007). (NH4)2Ce(NO3)6 (2 eq.) was dissolved in 5 ml of acetonitrile and was layered over a CH2Cl2 solution of the hexanuclear copper(II) complex (1 eq.). Slow mixing of the reactants and solvent evaporation over a few weeks yielded dark-blue crystals of the title compound.
5. Refinement
Crystal data, data collection and structure . The C-bound H atoms were placed geometrically, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The isolated water solvent O atom, O1W, was refined isotropically. H atoms bound to the water oxygen atom could not be placed satisfactorily with agreeable occupancy as O1W resides on a threefold rotation axis, resulting in crystallographically disordered H atoms. These H atoms were not modelled but are included in the formula of the title compound.
details are summarized in Table 3Supporting information
CCDC reference: 1458061
https://doi.org/10.1107/S2056989016003741/wm4004sup1.cif
contains datablock I. DOI:Supporting information file. DOI: https://doi.org/10.1107/S2056989016003741/wm4004Isup3.cdx
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016003741/wm4004Isup4.hkl
Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).(C36H30P2N)[Cu3(C3H2ClN2)3(NO3)3O]NO3·H2O | Dx = 1.407 Mg m−3 |
Mr = 2390.85 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 9882 reflections |
a = 23.038 (2) Å | θ = 2.3–26.0° |
c = 18.4214 (17) Å | µ = 0.79 mm−1 |
V = 8466.9 (17) Å3 | T = 296 K |
Z = 3 | Polygon, blue |
F(000) = 3687 | 0.23 × 0.14 × 0.13 mm |
Bruker APEXII CCD diffractometer | 7675 independent reflections |
Radiation source: sealed tube | 6428 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
φ and ω scans | θmax = 26.4°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −28→28 |
Tmin = 0.840, Tmax = 0.905 | k = −28→28 |
30414 measured reflections | l = −22→22 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.034 | w = 1/[σ2(Fo2) + (0.0468P)2 + 0.1352P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.088 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.41 e Å−3 |
7675 reflections | Δρmin = −0.29 e Å−3 |
468 parameters | Absolute structure: Flack x determined using 2750 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
1 restraint | Absolute structure parameter: 0.004 (5) |
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. |
x | y | z | Uiso*/Ueq | ||
O1W | 0.0000 | 1.0000 | 0.3698 (7) | 0.141 (4)* | |
Cu1 | 0.57819 (3) | 0.31688 (3) | 0.88140 (3) | 0.04893 (15) | |
O1 | 0.6667 | 0.3333 | 0.8748 (4) | 0.0691 (18) | |
O2 | 0.48058 (17) | 0.29648 (18) | 0.8736 (2) | 0.0619 (9) | |
N1 | 0.54504 (18) | 0.22155 (19) | 0.8997 (2) | 0.0504 (9) | |
N2 | 0.61014 (18) | 0.41208 (18) | 0.8960 (2) | 0.0493 (9) | |
N3 | 0.4670 (2) | 0.28251 (19) | 0.8087 (3) | 0.0582 (10) | |
C1 | 0.4851 (2) | 0.1710 (2) | 0.9186 (3) | 0.0590 (12) | |
H1 | 0.4465 | 0.1738 | 0.9249 | 0.071* | |
C2 | 0.4893 (3) | 0.1144 (2) | 0.9272 (3) | 0.0570 (12) | |
C3 | 0.5783 (3) | 0.4455 (3) | 0.9126 (3) | 0.0582 (12) | |
H3 | 0.5321 | 0.4274 | 0.9141 | 0.070* | |
Cl1 | 0.42537 (8) | 0.03570 (7) | 0.95132 (10) | 0.0859 (5) | |
O3 | 0.5141 (2) | 0.2937 (2) | 0.7664 (2) | 0.0753 (10) | |
O4 | 0.4095 (2) | 0.2572 (3) | 0.7874 (3) | 0.1105 (17) | |
P1 | 0.81315 (5) | 0.23893 (5) | 0.23155 (5) | 0.0379 (2) | |
P2 | 0.78221 (5) | 0.16748 (5) | 0.37198 (5) | 0.0392 (2) | |
N4 | 0.78666 (18) | 0.21790 (18) | 0.31150 (18) | 0.0461 (8) | |
C4 | 0.7627 (2) | 0.1937 (2) | 0.4558 (2) | 0.0440 (10) | |
C5 | 0.7353 (2) | 0.2344 (2) | 0.4544 (2) | 0.0487 (11) | |
H5 | 0.7293 | 0.2500 | 0.4101 | 0.058* | |
C6 | 0.7165 (3) | 0.2526 (3) | 0.5183 (3) | 0.0625 (13) | |
H6 | 0.6978 | 0.2803 | 0.5167 | 0.075* | |
C7 | 0.7254 (3) | 0.2299 (3) | 0.5829 (3) | 0.0754 (17) | |
H7 | 0.7129 | 0.2424 | 0.6256 | 0.090* | |
C8 | 0.7527 (3) | 0.1887 (3) | 0.5860 (3) | 0.0788 (17) | |
H8 | 0.7584 | 0.1732 | 0.6305 | 0.095* | |
C9 | 0.7717 (3) | 0.1703 (3) | 0.5224 (3) | 0.0615 (13) | |
H9 | 0.7904 | 0.1427 | 0.5242 | 0.074* | |
C10 | 0.8593 (2) | 0.1669 (2) | 0.3837 (2) | 0.0463 (10) | |
C11 | 0.9135 (2) | 0.2251 (3) | 0.4090 (3) | 0.0610 (12) | |
H11 | 0.9081 | 0.2606 | 0.4241 | 0.073* | |
C12 | 0.9761 (3) | 0.2304 (4) | 0.4120 (3) | 0.0801 (18) | |
H12 | 1.0128 | 0.2696 | 0.4289 | 0.096* | |
C13 | 0.9836 (3) | 0.1783 (4) | 0.3899 (3) | 0.0796 (18) | |
H13 | 1.0257 | 0.1819 | 0.3922 | 0.095* | |
C14 | 0.9302 (3) | 0.1205 (4) | 0.3645 (4) | 0.0833 (18) | |
H14 | 0.9363 | 0.0855 | 0.3490 | 0.100* | |
C15 | 0.8679 (3) | 0.1139 (3) | 0.3617 (3) | 0.0629 (13) | |
H15 | 0.8315 | 0.0743 | 0.3451 | 0.075* | |
C16 | 0.7162 (2) | 0.0829 (2) | 0.3546 (2) | 0.0467 (10) | |
C17 | 0.6790 (2) | 0.0681 (3) | 0.2917 (3) | 0.0569 (12) | |
H17 | 0.6875 | 0.1021 | 0.2589 | 0.068* | |
C18 | 0.6291 (3) | 0.0032 (3) | 0.2771 (3) | 0.0732 (15) | |
H18 | 0.6053 | −0.0064 | 0.2338 | 0.088* | |
C19 | 0.6146 (3) | −0.0466 (3) | 0.3259 (4) | 0.0771 (17) | |
H19 | 0.5810 | −0.0902 | 0.3158 | 0.093* | |
C20 | 0.6493 (3) | −0.0327 (3) | 0.3896 (4) | 0.0807 (18) | |
H20 | 0.6381 | −0.0665 | 0.4236 | 0.097* | |
C21 | 0.7012 (3) | 0.0315 (3) | 0.4039 (3) | 0.0737 (16) | |
H21 | 0.7260 | 0.0403 | 0.4465 | 0.088* | |
C22 | 0.8529 (2) | 0.1956 (2) | 0.1928 (2) | 0.0414 (9) | |
C23 | 0.8160 (2) | 0.1331 (2) | 0.1628 (3) | 0.0532 (11) | |
H23 | 0.7698 | 0.1141 | 0.1578 | 0.064* | |
C24 | 0.8467 (3) | 0.0979 (3) | 0.1398 (3) | 0.0678 (14) | |
H24 | 0.8214 | 0.0559 | 0.1185 | 0.081* | |
C25 | 0.9149 (3) | 0.1251 (3) | 0.1483 (3) | 0.0666 (14) | |
H25 | 0.9355 | 0.1010 | 0.1339 | 0.080* | |
C26 | 0.9520 (3) | 0.1870 (3) | 0.1778 (3) | 0.0630 (13) | |
H26 | 0.9980 | 0.2055 | 0.1828 | 0.076* | |
C27 | 0.9219 (2) | 0.2228 (2) | 0.2003 (3) | 0.0505 (10) | |
H27 | 0.9477 | 0.2652 | 0.2204 | 0.061* | |
C28 | 0.7444 (2) | 0.2268 (2) | 0.1749 (2) | 0.0415 (9) | |
C29 | 0.6909 (2) | 0.2287 (2) | 0.2075 (3) | 0.0526 (11) | |
H29 | 0.6902 | 0.2334 | 0.2575 | 0.063* | |
C30 | 0.6394 (2) | 0.2237 (3) | 0.1659 (3) | 0.0674 (14) | |
H30 | 0.6037 | 0.2250 | 0.1880 | 0.081* | |
C31 | 0.6397 (3) | 0.2167 (3) | 0.0916 (3) | 0.0738 (16) | |
H31 | 0.6048 | 0.2140 | 0.0636 | 0.089* | |
C32 | 0.6910 (3) | 0.2138 (3) | 0.0599 (3) | 0.0698 (15) | |
H32 | 0.6906 | 0.2081 | 0.0098 | 0.084* | |
C33 | 0.7439 (3) | 0.2192 (3) | 0.1000 (2) | 0.0578 (12) | |
H33 | 0.7791 | 0.2176 | 0.0772 | 0.069* | |
C34 | 0.8736 (2) | 0.3267 (2) | 0.2287 (3) | 0.0468 (10) | |
C35 | 0.8897 (3) | 0.3652 (3) | 0.2894 (4) | 0.0845 (19) | |
H35 | 0.8686 | 0.3462 | 0.3331 | 0.101* | |
C36 | 0.9372 (5) | 0.4322 (3) | 0.2866 (5) | 0.123 (3) | |
H36 | 0.9495 | 0.4580 | 0.3287 | 0.147* | |
C37 | 0.9664 (4) | 0.4611 (3) | 0.2211 (5) | 0.106 (3) | |
H37 | 0.9980 | 0.5065 | 0.2190 | 0.127* | |
C38 | 0.9497 (3) | 0.4245 (3) | 0.1612 (4) | 0.0813 (18) | |
H38 | 0.9697 | 0.4445 | 0.1173 | 0.098* | |
C39 | 0.9028 (3) | 0.3568 (2) | 0.1633 (3) | 0.0632 (13) | |
H39 | 0.8908 | 0.3316 | 0.1208 | 0.076* | |
N5 | 0.6667 | 0.3333 | 0.3566 (5) | 0.069 (2) | |
O5 | 0.6275 (3) | 0.2721 (2) | 0.3545 (3) | 0.1083 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0436 (3) | 0.0458 (3) | 0.0582 (3) | 0.0230 (3) | 0.0029 (3) | 0.0017 (3) |
O1 | 0.044 (2) | 0.044 (2) | 0.119 (6) | 0.0220 (10) | 0.000 | 0.000 |
O2 | 0.058 (2) | 0.069 (2) | 0.065 (2) | 0.0356 (18) | 0.0048 (17) | −0.0040 (18) |
N1 | 0.044 (2) | 0.046 (2) | 0.060 (2) | 0.0217 (18) | 0.0012 (17) | −0.0010 (17) |
N2 | 0.049 (2) | 0.048 (2) | 0.054 (2) | 0.0268 (19) | 0.0061 (17) | 0.0045 (17) |
N3 | 0.054 (3) | 0.048 (2) | 0.073 (3) | 0.025 (2) | −0.011 (2) | 0.007 (2) |
C1 | 0.047 (3) | 0.053 (3) | 0.069 (3) | 0.019 (2) | 0.005 (2) | −0.002 (2) |
C2 | 0.059 (3) | 0.045 (3) | 0.051 (3) | 0.014 (2) | −0.001 (2) | 0.005 (2) |
C3 | 0.060 (3) | 0.061 (3) | 0.062 (3) | 0.037 (3) | 0.011 (2) | 0.014 (2) |
Cl1 | 0.0748 (10) | 0.0513 (8) | 0.0996 (11) | 0.0075 (7) | 0.0071 (8) | 0.0112 (7) |
O3 | 0.084 (3) | 0.078 (3) | 0.064 (2) | 0.040 (2) | 0.008 (2) | 0.0030 (19) |
O4 | 0.068 (3) | 0.129 (4) | 0.118 (4) | 0.037 (3) | −0.030 (3) | 0.004 (3) |
P1 | 0.0386 (6) | 0.0401 (6) | 0.0386 (5) | 0.0224 (5) | 0.0019 (4) | 0.0017 (4) |
P2 | 0.0378 (5) | 0.0423 (6) | 0.0376 (5) | 0.0200 (5) | −0.0016 (4) | 0.0010 (4) |
N4 | 0.053 (2) | 0.055 (2) | 0.0393 (18) | 0.0341 (19) | 0.0026 (16) | 0.0058 (16) |
C4 | 0.038 (2) | 0.044 (2) | 0.040 (2) | 0.0136 (19) | −0.0028 (17) | −0.0008 (18) |
C5 | 0.046 (2) | 0.050 (3) | 0.046 (3) | 0.021 (2) | 0.0003 (19) | −0.0051 (19) |
C6 | 0.055 (3) | 0.063 (3) | 0.064 (3) | 0.025 (3) | 0.010 (2) | −0.008 (3) |
C7 | 0.068 (4) | 0.094 (4) | 0.054 (3) | 0.033 (3) | 0.009 (3) | −0.020 (3) |
C8 | 0.083 (4) | 0.100 (5) | 0.036 (3) | 0.033 (4) | 0.001 (2) | 0.007 (3) |
C9 | 0.071 (3) | 0.076 (3) | 0.043 (3) | 0.041 (3) | −0.003 (2) | 0.003 (2) |
C10 | 0.041 (2) | 0.057 (3) | 0.044 (2) | 0.027 (2) | 0.0013 (18) | 0.008 (2) |
C11 | 0.048 (3) | 0.065 (3) | 0.066 (3) | 0.026 (3) | −0.007 (2) | −0.005 (3) |
C12 | 0.042 (3) | 0.103 (5) | 0.078 (4) | 0.023 (3) | −0.008 (3) | 0.005 (3) |
C13 | 0.057 (4) | 0.120 (6) | 0.077 (4) | 0.056 (4) | 0.006 (3) | 0.027 (4) |
C14 | 0.081 (4) | 0.098 (5) | 0.099 (5) | 0.066 (4) | 0.006 (4) | 0.009 (4) |
C15 | 0.059 (3) | 0.061 (3) | 0.080 (3) | 0.038 (3) | 0.004 (3) | 0.008 (3) |
C16 | 0.040 (2) | 0.046 (2) | 0.054 (3) | 0.022 (2) | 0.0006 (19) | 0.000 (2) |
C17 | 0.048 (3) | 0.059 (3) | 0.056 (3) | 0.022 (2) | −0.009 (2) | −0.003 (2) |
C18 | 0.055 (3) | 0.079 (4) | 0.071 (3) | 0.023 (3) | −0.013 (3) | −0.020 (3) |
C19 | 0.051 (3) | 0.055 (3) | 0.105 (5) | 0.011 (3) | −0.001 (3) | −0.022 (3) |
C20 | 0.073 (4) | 0.048 (3) | 0.103 (5) | 0.017 (3) | −0.004 (3) | 0.009 (3) |
C21 | 0.069 (3) | 0.055 (3) | 0.077 (4) | 0.016 (3) | −0.015 (3) | 0.011 (3) |
C22 | 0.041 (2) | 0.046 (2) | 0.042 (2) | 0.026 (2) | 0.0018 (17) | 0.0011 (18) |
C23 | 0.044 (2) | 0.046 (3) | 0.067 (3) | 0.021 (2) | 0.002 (2) | −0.006 (2) |
C24 | 0.067 (3) | 0.050 (3) | 0.090 (4) | 0.032 (3) | 0.005 (3) | −0.016 (3) |
C25 | 0.069 (4) | 0.063 (3) | 0.087 (4) | 0.047 (3) | 0.020 (3) | 0.005 (3) |
C26 | 0.045 (3) | 0.068 (3) | 0.085 (4) | 0.035 (3) | 0.012 (2) | 0.008 (3) |
C27 | 0.042 (2) | 0.047 (3) | 0.065 (3) | 0.025 (2) | 0.002 (2) | −0.001 (2) |
C28 | 0.044 (2) | 0.042 (2) | 0.043 (2) | 0.0243 (19) | 0.0007 (17) | 0.0019 (17) |
C29 | 0.053 (3) | 0.062 (3) | 0.052 (3) | 0.036 (2) | 0.002 (2) | 0.000 (2) |
C30 | 0.049 (3) | 0.077 (4) | 0.086 (4) | 0.038 (3) | −0.006 (3) | −0.004 (3) |
C31 | 0.069 (4) | 0.079 (4) | 0.082 (4) | 0.044 (3) | −0.026 (3) | −0.001 (3) |
C32 | 0.080 (4) | 0.088 (4) | 0.049 (3) | 0.047 (3) | −0.013 (3) | 0.004 (3) |
C33 | 0.064 (3) | 0.076 (3) | 0.045 (3) | 0.043 (3) | 0.001 (2) | 0.006 (2) |
C34 | 0.046 (2) | 0.038 (2) | 0.059 (3) | 0.023 (2) | 0.004 (2) | −0.0018 (19) |
C35 | 0.089 (4) | 0.055 (3) | 0.077 (4) | 0.011 (3) | 0.013 (3) | −0.009 (3) |
C36 | 0.157 (8) | 0.054 (4) | 0.106 (6) | 0.015 (4) | 0.015 (5) | −0.025 (4) |
C37 | 0.084 (5) | 0.045 (3) | 0.166 (8) | 0.015 (3) | 0.029 (5) | 0.000 (4) |
C38 | 0.074 (4) | 0.055 (3) | 0.118 (5) | 0.035 (3) | 0.035 (4) | 0.021 (4) |
C39 | 0.064 (3) | 0.049 (3) | 0.074 (3) | 0.026 (3) | 0.017 (3) | 0.009 (2) |
N5 | 0.065 (3) | 0.065 (3) | 0.077 (5) | 0.0327 (16) | 0.000 | 0.000 |
O5 | 0.090 (3) | 0.074 (3) | 0.150 (5) | 0.032 (3) | 0.020 (3) | 0.000 (3) |
Cu1—O1 | 1.8816 (7) | C10—C15 | 1.393 (7) |
Cu1—N2 | 1.952 (4) | C11—C12 | 1.385 (8) |
Cu1—N1 | 1.960 (4) | C12—C13 | 1.360 (9) |
Cu1—O2 | 2.059 (3) | C13—C14 | 1.366 (9) |
Cu1—O3 | 2.483 (4) | C14—C15 | 1.367 (8) |
O1—Cu1i | 1.8816 (7) | C16—C17 | 1.379 (6) |
O1—Cu1ii | 1.8816 (7) | C16—C21 | 1.391 (7) |
O2—N3 | 1.237 (5) | C17—C18 | 1.382 (7) |
N1—C1 | 1.334 (6) | C18—C19 | 1.362 (9) |
N1—N2i | 1.345 (5) | C19—C20 | 1.365 (9) |
N2—C3 | 1.337 (6) | C20—C21 | 1.386 (8) |
N2—N1ii | 1.345 (5) | C22—C23 | 1.371 (6) |
N3—O4 | 1.215 (6) | C22—C27 | 1.393 (6) |
N3—O3 | 1.253 (6) | C23—C24 | 1.382 (7) |
C1—C2 | 1.364 (7) | C24—C25 | 1.379 (8) |
C2—C3i | 1.368 (7) | C25—C26 | 1.356 (8) |
C2—Cl1 | 1.727 (5) | C26—C27 | 1.381 (6) |
C3—C2ii | 1.368 (7) | C28—C33 | 1.389 (6) |
P1—N4 | 1.575 (4) | C28—C29 | 1.391 (6) |
P1—C34 | 1.794 (4) | C29—C30 | 1.368 (7) |
P1—C28 | 1.799 (4) | C30—C31 | 1.379 (8) |
P1—C22 | 1.805 (4) | C31—C32 | 1.350 (8) |
P2—N4 | 1.576 (4) | C32—C33 | 1.378 (7) |
P2—C10 | 1.795 (4) | C34—C35 | 1.358 (7) |
P2—C4 | 1.795 (4) | C34—C39 | 1.386 (7) |
P2—C16 | 1.802 (4) | C35—C36 | 1.376 (9) |
C4—C5 | 1.366 (6) | C36—C37 | 1.379 (11) |
C4—C9 | 1.397 (6) | C37—C38 | 1.323 (10) |
C5—C6 | 1.391 (7) | C38—C39 | 1.384 (8) |
C6—C7 | 1.356 (8) | N5—O5i | 1.238 (5) |
C7—C8 | 1.379 (9) | N5—O5 | 1.238 (5) |
C8—C9 | 1.388 (8) | N5—O5ii | 1.238 (5) |
C10—C11 | 1.378 (7) | ||
O1—Cu1—N2 | 91.18 (12) | C8—C9—C4 | 119.5 (5) |
O1—Cu1—N1 | 90.73 (12) | C11—C10—C15 | 119.6 (4) |
N2—Cu1—N1 | 162.20 (16) | C11—C10—P2 | 117.0 (4) |
O1—Cu1—O2 | 172.2 (2) | C15—C10—P2 | 123.2 (4) |
N2—Cu1—O2 | 91.22 (15) | C10—C11—C12 | 119.8 (5) |
N1—Cu1—O2 | 89.25 (14) | C13—C12—C11 | 119.8 (6) |
Cu1—O1—Cu1i | 119.59 (5) | C12—C13—C14 | 120.8 (5) |
Cu1—O1—Cu1ii | 119.59 (5) | C13—C14—C15 | 120.4 (6) |
Cu1i—O1—Cu1ii | 119.59 (5) | C14—C15—C10 | 119.6 (6) |
N3—O2—Cu1 | 103.4 (3) | C17—C16—C21 | 118.6 (4) |
C1—N1—N2i | 108.1 (4) | C17—C16—P2 | 120.0 (4) |
C1—N1—Cu1 | 132.6 (3) | C21—C16—P2 | 121.4 (4) |
N2i—N1—Cu1 | 119.3 (3) | C16—C17—C18 | 120.6 (5) |
C3—N2—N1ii | 108.3 (4) | C19—C18—C17 | 120.3 (5) |
C3—N2—Cu1 | 132.1 (3) | C18—C19—C20 | 120.1 (5) |
N1ii—N2—Cu1 | 118.9 (3) | C19—C20—C21 | 120.4 (6) |
O4—N3—O2 | 120.7 (5) | C20—C21—C16 | 119.9 (5) |
O4—N3—O3 | 121.5 (5) | C23—C22—C27 | 118.8 (4) |
O2—N3—O3 | 117.9 (4) | C23—C22—P1 | 121.4 (3) |
N1—C1—C2 | 109.1 (4) | C27—C22—P1 | 119.4 (3) |
C1—C2—C3i | 105.8 (4) | C22—C23—C24 | 120.6 (4) |
C1—C2—Cl1 | 127.0 (4) | C25—C24—C23 | 120.0 (5) |
C3i—C2—Cl1 | 127.2 (4) | C26—C25—C24 | 119.9 (5) |
N2—C3—C2ii | 108.6 (4) | C25—C26—C27 | 120.6 (5) |
N4—P1—C34 | 109.7 (2) | C26—C27—C22 | 120.1 (5) |
N4—P1—C28 | 108.61 (19) | C33—C28—C29 | 118.8 (4) |
C34—P1—C28 | 106.6 (2) | C33—C28—P1 | 123.1 (3) |
N4—P1—C22 | 115.14 (19) | C29—C28—P1 | 118.1 (3) |
C34—P1—C22 | 106.8 (2) | C30—C29—C28 | 120.1 (5) |
C28—P1—C22 | 109.62 (19) | C29—C30—C31 | 120.6 (5) |
N4—P2—C10 | 113.0 (2) | C32—C31—C30 | 119.5 (5) |
N4—P2—C4 | 107.2 (2) | C31—C32—C33 | 121.3 (5) |
C10—P2—C4 | 108.3 (2) | C32—C33—C28 | 119.7 (5) |
N4—P2—C16 | 112.4 (2) | C35—C34—C39 | 118.9 (5) |
C10—P2—C16 | 108.4 (2) | C35—C34—P1 | 121.2 (4) |
C4—P2—C16 | 107.4 (2) | C39—C34—P1 | 119.9 (4) |
P1—N4—P2 | 139.5 (2) | C34—C35—C36 | 120.4 (6) |
C5—C4—C9 | 119.3 (4) | C35—C36—C37 | 119.7 (7) |
C5—C4—P2 | 119.6 (3) | C38—C37—C36 | 120.5 (6) |
C9—C4—P2 | 121.0 (4) | C37—C38—C39 | 120.6 (6) |
C4—C5—C6 | 120.8 (5) | C38—C39—C34 | 119.8 (5) |
C7—C6—C5 | 119.7 (5) | O5i—N5—O5 | 119.91 (5) |
C6—C7—C8 | 120.7 (5) | O5i—N5—O5ii | 119.90 (6) |
C7—C8—C9 | 119.8 (5) | O5—N5—O5ii | 119.91 (5) |
Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O3iii | 0.93 | 2.53 | 3.410 (11) | 157 |
Symmetry code: (iii) −x+y+4/3, −x+2/3, z−1/3. |
Footnotes
‡Present address: Department of Chemistry and Biochemistry, Florida International University, 11200 SW 8th Street, Miami, FL 33199, USA.
Acknowledgements
RC thanks NSF–CREST at UPR–Mayaguez for an undergraduate research fellowship. LM thanks NSF–IFN for a graduate student fellowship.
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