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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): m1055–m1056.
Published online 2010 August 4. doi:  10.1107/S1600536810030436
PMCID: PMC3008109

Aqua­(2,2′-bipyridine-κ2 N,N′)(3,5-dinitro­benzoato-κO 1)copper(II) tetra­hydro­furan monosolvate

Abstract

The title complex, [Cu(C7H3N2O6)2(C10H8N2)(H2O)]·C4H8O, features a penta­coordinate CuII atom bound by two monodentate carboxyl­ate ligands, a bidentate 2,2′-bipyridine mol­ecule [dihedral angle between pyridine rings = 5.0 (2)°] and a water mol­ecule. The resulting N2O3 donor set defines a distorted square-pyramidal geometry with the coordinated water mol­ecule in the apical position. In the crystal, the presence of O—Hw(...)Oc (w = water and c = carbon­yl) hydrogen bonding leads to the formation of a supra­molecular chain propagating along the c axis, which associates into a double chain via C—H(...) O and π–π contacts between pyridyl rings [centroid–centroid distance = 3.527 (3) Å]. The solvent mol­ecules, which are disordered over two orientations in a 0.678 (11):0.322 (11) ratio, occupy voids defined by the complex mol­ecules and are held in place via C—H(...)O inter­actions.

Related literature

For background to the study of copper carboxyl­ates, see: Ozair et al. (2010 [triangle]). For the preparation, see: Fountain & Hatfield (1965 [triangle]). For additional geometric analysis, see: Addison et al. (1984 [triangle]).

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Object name is e-66-m1055-scheme1.jpg

Experimental

Crystal data

  • [Cu(C7H3N2O6)2(C10H8N2)(H2O)]·C4H8O
  • M r = 732.08
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1055-efi1.jpg
  • a = 19.6424 (7) Å
  • b = 23.2687 (8) Å
  • c = 6.5897 (2) Å
  • V = 3011.84 (17) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.81 mm−1
  • T = 100 K
  • 0.26 × 0.07 × 0.07 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.865, T max = 1.000
  • 25602 measured reflections
  • 6223 independent reflections
  • 5759 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.060
  • wR(F 2) = 0.134
  • S = 1.28
  • 6223 reflections
  • 444 parameters
  • 14 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.50 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 2809 Friedel pairs
  • Flack parameter: 0.02 (2)

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810030436/hb5590sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030436/hb5590Isup2.hkl

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

Acknowledgments

The authors thank the Ministry of Higher Education, Malaysia, for the research grant FP046/2008 C, and they are also grateful to the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

The title complex solvate, (I), was characterized as part of on-going structural studies of copper carboxylates and their adducts (Ozair et al., 2010).

The crystallographic asymmetric unit of (I) comprises a copper(II) complex and a solvent tetrahydrofuran (thf) molecule of crystallization in a 1:1 ratio. The molecular structure of the complex in (I) is illustrated in Fig. 1 and selected geometric parameters are collected in Table 1. The Cu atom is penta-coordinate, being coordinated by two O atoms derived from two monodentate carboxylate ligand, two N atoms of the chelating 2,2'-bipyridine ligand, and an O atom derived from the coordinated water molecule. The resulting N2O3 donor set defines a square pyramidal geometry as indicated by the value of τ = 0.16 which compares to τ = 0 for an ideal square pyramid and τ = 1.0 for an ideal trigonal bipyramid (Addison et al., 1984). In this description, the coordinated water molecule occupies the apical position and each carboxylate-O atom is trans to a pyridine-N atom, Table 2. The four donor atoms defining the square plane have deviations from the least-squares plane through them of -0.089 (2), 0.090 (2), -0.097 (2), and 0.096 (2) Å for atoms O1, O7, N5, and N6, respectively; the r.m.s. deviation for the four atoms is 0.093 Å. The Cu atom lies 0.176 (2) Å out of the square plane in the direction of the O1w atom. Distortions from the ideal geometry are due to the restricted bite distance of the 2,2'-bipyridine ligand [N5–Cu–N6 = 79.95 (18) °] and to the relatively close approach of the carbonyl-O2, O8 atoms. However, the Cu···O2, O4 separations of 2.942 (4) and 3.007 (4) Å, respectively, are not considered to represent significant bonding interactions. Under these circumstances, the disparity in the C–Ocarboxylate and C–Ocarbonyl bond distances, Table 1, is not as great as might be anticipated for formal C–Ocarboxylate and C═Ocarbonyl bonds. This is due to i) the weak interaction formed by the carbonyl-O atoms with the Cu atom, and ii) the pivotal role the carbonyl-O atoms play in the supramolecular association operating in the crystal structure (see below). Each of the carbonyl-O2,O8 atoms lies to the same side of the square plane around the Cu atom and in the opposite direction to the coordinated water molecule. The dihedral angle formed between the two carboxylate aromatic rings is 82.1 (2) °, indicating that they are almost orthogonal to each other. Within the carboxylate ligands, each carboxylate group is effectively co-planar with the aromatic ring to which it is bound, with the C1–O1,O2 carboxylate having the greater twist as seen in the O1–C1–C2–C3 torsion angle of 10.0 (7) °. By contrast, one nitro group in each carboxylate ligand, i.e. containing N1 and N4, is significantly twisted out of the plane of the aromatic ring to which it is connected [the O3–N1–C4–C3 and O11–N4–C13–C12 torsion angles are -162.7 (5) and 157.4 (5) °, respectively]. The chelating 2,2'-bipyridine ligand is almost planar with the dihedral angle between the two pyridine rings being 5.0 (2) °; the small twist in the molecule is seen in the N5–C19–C20–N6 torsion angle of -2.6 (7) °.

The most prominent interactions operating in the crystal structure of (I) are O–H···O contacts occurring between the hydrogen atoms of the coordinated water molecule and the carbonyl-O atoms of a translationally related molecule; Table 2. As illustrated in Fig. 2, the water-bound hydrogen atoms effectively form a bridge between the adjacent carbonyl atoms resulting in a ten-membered {···HOH···OCOCuOCO} synthon. The result of this hydrogen bonding is the formation of a supramolecular chain along the c axis. Each supramolecular chain is connected into a double chain along c with helical topology via C–H···O contacts whereby two bipyridine-H atoms form interactions with a carbonyl-O of the second chain, and a third bipyridine-H atom forms a C–H···O contact with a nitro-O within the chain, Fig. 3 and Table 2. This arrangement brings into close proximity the 2,2'-bipyridine molecules which interdigitate, Fig. 3, allowing for the formation of π–π interactions [ring centroid(N6,C20–C24)···ring centroid(N6,C20–C24)i = 3.527 (3) Å for i: -x + 1/2, y, z - 1/2]. The double chains pack in the ac plane to form layers that stack along the b axis, Fig. 4. Within each layer, there are voids and these are occupied by the solvent thf molecules which are held in place by C–H···O interactions, Table 2 and Fig. 4. Interactions between layers are primarily of the type C–H···O as detailed in Table 2.

Experimental

Copper(II) acetate monohydrate (Merck; 1.995 g, 0.01 mol) and 3,5-dinitrobenzoic acid (Merck, 4.24 g, 0.02 mol) were reacted in an 1:2 molar ratio hot ethanol (60 ml) for 30 minutes following a literature precedent (Fountain & Hatfield, 1965). The resulting blue powder, [Cu2(3,5-(NO2)2C6H3COO)4], was isolated in 23% yield and reacted with 2,2'-bipyridine (mole ratio = 1:1) in THF (15 ml) at room temperature. Blue-green prisms of (I) formed when the solvent was allowed to slowly evaporate off at room temperature after 2 days.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Uequiv(C). The water-bound H-atoms were located in a difference Fourier map but were were refined with a distance restraints of O–H = 0.84±0.01 Å and H···H = 1.39±0.05 Å, and with Uiso(H) = 1.5Ueq(O). The complex was found to crystallize as a 1:1 tetrahydrofuran (thf) solvate. The solvent thf molecule was found to be disordered and resolved over two distinct orientations via fractional refinement. The major component of the disorder, with a site occupancy factor = 0.678 (11), was refined with anisotropic displacement parameters but, the non-hydrogen atoms comprising the minor component were refined isotropically. Finally, the distance restraints C–O = 1.40±0.01 Å and C—C = 1.50±0.01 Å were applied to the disordered atoms. While there is an indication of pseudo C-centring (excluding the disordered atoms), there are no counterparts for atoms O3 and O11.

Figures

Fig. 1.
The molecular structure of (I) showing displacement ellipsoids at the 50% probability level. The disordered thf molecule is not illustrated.
Fig. 2.
A portion of the supramolecular chain aligned along the c axis found in the crystal structure of (I) mediated by O–H···O hydrogen bonding (orange dashed lines). Colour code: Cu, orange; O, red; N, blue; C, grey; and H, ...
Fig. 3.
Double chain with helical topology in (I) mediated by O–H···O and C–H···O contacts shown as orange and blue dashed lines, respectively. Colour code: Cu, orange; O, red; N, blue; C, grey; ...
Fig. 4.
View of the unit-cell contents of (I) viewed in projection down the c axis. The double chains form layers in the ac plane which have large voids that are occupied by the solvent thf molecules; only the major component of the disordered molecules are shown. ...

Crystal data

[Cu(C7H3N2O6)2(C10H8N2)(H2O)]·C4H8OF(000) = 1500
Mr = 732.08Dx = 1.614 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 7872 reflections
a = 19.6424 (7) Åθ = 2.6–28.0°
b = 23.2687 (8) ŵ = 0.81 mm1
c = 6.5897 (2) ÅT = 100 K
V = 3011.84 (17) Å3Prism, green
Z = 40.26 × 0.07 × 0.07 mm

Data collection

Bruker SMART APEX CCD diffractometer6223 independent reflections
Radiation source: fine-focus sealed tube5759 reflections with I > 2σ(I)
graphiteRint = 0.035
ω scansθmax = 26.5°, θmin = 0.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −24→23
Tmin = 0.865, Tmax = 1.000k = −29→29
25602 measured reflectionsl = −8→8

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.060H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.134w = 1/[σ2(Fo2) + (0.0125P)2 + 10.1609P] where P = (Fo2 + 2Fc2)/3
S = 1.28(Δ/σ)max < 0.001
6223 reflectionsΔρmax = 0.50 e Å3
444 parametersΔρmin = −0.50 e Å3
14 restraintsAbsolute structure: Flack (1983), 2809 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.02 (2)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)

xyzUiso*/UeqOcc. (<1)
Cu0.42505 (3)0.74892 (3)0.81422 (13)0.01710 (13)
O10.48462 (18)0.68415 (15)0.8897 (5)0.0203 (8)
O20.43340 (18)0.68207 (18)1.1923 (6)0.0276 (9)
O30.7080 (2)0.59152 (17)0.8280 (8)0.0349 (10)
O40.7241 (2)0.51293 (17)0.9989 (6)0.0277 (9)
O50.5108 (2)0.5410 (2)1.6840 (6)0.0362 (11)
O60.6025 (2)0.4906 (2)1.6345 (8)0.0475 (13)
O70.49031 (18)0.80342 (17)0.9272 (6)0.0223 (8)
O80.41911 (19)0.8246 (2)1.1836 (6)0.0313 (10)
O90.4959 (2)0.95628 (19)1.7149 (7)0.0326 (10)
O100.5952 (2)0.9953 (2)1.6972 (8)0.0447 (13)
O110.7198 (2)0.88618 (18)0.9376 (7)0.0344 (10)
O120.73480 (19)0.96655 (16)1.0991 (7)0.0300 (10)
O1W0.4763 (3)0.7479 (2)0.5176 (6)0.0417 (11)
H2W0.450 (3)0.774 (2)0.478 (11)0.063*
H1W0.478 (4)0.723 (2)0.426 (8)0.063*
N10.6927 (2)0.5575 (2)0.9613 (7)0.0232 (10)
N20.5602 (3)0.5278 (2)1.5819 (8)0.0303 (11)
N30.5503 (2)0.9650 (2)1.6327 (7)0.0240 (10)
N40.7016 (2)0.92304 (18)1.0584 (8)0.0209 (10)
N50.3550 (2)0.80942 (19)0.7545 (6)0.0169 (9)
N60.3428 (2)0.6991 (2)0.7701 (6)0.0198 (10)
C10.4777 (2)0.6669 (2)1.0699 (8)0.0192 (11)
C20.5301 (3)0.6231 (2)1.1368 (8)0.0180 (11)
C30.5867 (3)0.6110 (2)1.0177 (8)0.0173 (10)
H30.59340.62960.89110.021*
C40.6333 (2)0.5706 (2)1.0894 (8)0.0175 (10)
C50.6267 (3)0.5431 (2)1.2735 (8)0.0199 (12)
H50.65930.51591.31960.024*
C60.5703 (3)0.5571 (2)1.3865 (8)0.0243 (12)
C70.5218 (3)0.5960 (2)1.3246 (10)0.0248 (11)
H70.48360.60431.40770.030*
C80.4735 (3)0.8296 (2)1.0928 (8)0.0225 (11)
C90.5270 (3)0.8696 (2)1.1773 (8)0.0210 (11)
C100.5142 (3)0.8988 (2)1.3576 (8)0.0181 (11)
H100.47210.89371.42600.022*
C110.5628 (3)0.9350 (2)1.4367 (9)0.0219 (11)
C120.6256 (3)0.9422 (2)1.3450 (8)0.0178 (11)
H120.65990.96541.40480.021*
C130.6362 (3)0.9144 (2)1.1637 (9)0.0205 (11)
C140.5891 (2)0.8771 (2)1.0798 (8)0.0178 (10)
H140.59890.85700.95790.021*
C150.3682 (3)0.8653 (2)0.7354 (8)0.0257 (12)
H150.41390.87840.74200.031*
C160.3158 (4)0.9047 (3)0.7059 (9)0.0345 (15)
H160.32600.94440.69150.041*
C170.2505 (4)0.8867 (3)0.6977 (9)0.0320 (14)
H170.21470.91360.67920.038*
C180.2362 (3)0.8287 (3)0.7166 (8)0.0252 (12)
H180.19060.81520.71290.030*
C190.2910 (3)0.7905 (2)0.7414 (7)0.0161 (10)
C200.2837 (3)0.7281 (2)0.7550 (7)0.0187 (11)
C210.2213 (3)0.6990 (3)0.7491 (8)0.0256 (12)
H210.17970.71970.74110.031*
C220.2212 (3)0.6388 (3)0.7554 (8)0.0289 (13)
H220.17950.61820.75260.035*
C230.2816 (3)0.6102 (3)0.7655 (8)0.0292 (13)
H230.28260.56940.76750.035*
C240.3417 (3)0.6415 (3)0.7727 (7)0.0259 (13)
H240.38360.62130.77990.031*
O1S0.6126 (3)0.6981 (3)0.5879 (10)0.0375 (19)*0.678 (11)
C1S0.6344 (5)0.7402 (3)0.7275 (13)0.029 (2)*0.678 (11)
H1S10.67340.72590.80830.035*0.678 (11)
H1S20.59700.75070.82110.035*0.678 (11)
C2S0.6551 (5)0.7910 (4)0.6005 (15)0.039 (2)*0.678 (11)
H2S10.61530.81550.56820.047*0.678 (11)
H2S20.68980.81450.67110.047*0.678 (11)
C4S0.6573 (6)0.7039 (5)0.4224 (18)0.059 (3)*0.678 (11)
H4S10.63310.69440.29500.070*0.678 (11)
H4S20.69580.67670.43770.070*0.678 (11)
C3S0.6839 (6)0.7640 (4)0.4117 (17)0.053 (3)*0.678 (11)
H3S10.66750.78390.28820.064*0.678 (11)
H3S20.73430.76470.41320.064*0.678 (11)
O2S0.6819 (9)0.7085 (7)0.296 (3)0.070 (6)*0.322 (11)
C5S0.6454 (10)0.7603 (7)0.299 (3)0.041 (5)*0.322 (11)
H5S10.59930.75370.24290.049*0.322 (11)
H5S20.66860.78880.21150.049*0.322 (11)
C8S0.6827 (10)0.6886 (8)0.496 (2)0.032 (5)*0.322 (11)
H8S10.73010.68740.54650.038*0.322 (11)
H8S20.66380.64920.50130.038*0.322 (11)
C7S0.6406 (14)0.7281 (9)0.626 (4)0.058 (7)*0.322 (11)
H7S10.59400.71280.64420.069*0.322 (11)
H7S20.66180.73330.76120.069*0.322 (11)
C6S0.6395 (15)0.7838 (9)0.511 (3)0.058 (7)*0.322 (11)
H6S10.67850.80880.54620.070*0.322 (11)
H6S20.59630.80510.53100.070*0.322 (11)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu0.0121 (2)0.0260 (3)0.0132 (2)0.0013 (3)−0.0011 (3)−0.0022 (3)
O10.0154 (18)0.0217 (19)0.024 (2)0.0063 (15)−0.0003 (14)−0.0014 (15)
O20.0168 (19)0.040 (2)0.026 (2)0.0046 (17)−0.0002 (16)−0.0089 (18)
O30.031 (2)0.035 (2)0.039 (2)0.0110 (17)0.013 (2)0.012 (2)
O40.027 (2)0.022 (2)0.034 (2)0.0091 (17)−0.0020 (18)−0.0005 (17)
O50.039 (2)0.043 (3)0.026 (2)−0.012 (2)0.007 (2)0.0052 (19)
O60.037 (3)0.054 (3)0.051 (3)0.001 (2)−0.006 (2)0.032 (3)
O70.0161 (18)0.030 (2)0.021 (2)0.0004 (16)−0.0012 (15)−0.0019 (17)
O80.0181 (19)0.054 (3)0.022 (2)−0.0079 (19)0.0015 (17)−0.0053 (19)
O90.029 (2)0.037 (2)0.031 (2)−0.0051 (19)0.0120 (19)−0.0090 (19)
O100.024 (2)0.059 (3)0.051 (3)−0.013 (2)0.009 (2)−0.029 (3)
O110.024 (2)0.029 (2)0.050 (3)−0.0030 (18)0.016 (2)−0.010 (2)
O120.023 (2)0.0222 (19)0.045 (3)−0.0030 (16)0.0079 (19)−0.0043 (19)
O1W0.063 (3)0.041 (3)0.021 (2)0.009 (3)0.016 (2)−0.002 (2)
N10.019 (2)0.023 (2)0.027 (2)0.0073 (19)−0.0023 (19)−0.003 (2)
N20.028 (3)0.039 (3)0.024 (3)−0.011 (2)0.000 (2)0.007 (2)
N30.019 (2)0.028 (3)0.025 (2)0.001 (2)0.004 (2)−0.006 (2)
N40.0121 (19)0.016 (2)0.035 (3)0.0009 (17)0.0024 (19)−0.001 (2)
N50.018 (2)0.022 (2)0.010 (2)0.0017 (17)−0.0014 (16)0.0017 (17)
N60.017 (2)0.030 (2)0.012 (2)0.0038 (18)−0.0020 (17)0.0009 (17)
C10.014 (2)0.026 (3)0.017 (3)−0.001 (2)−0.001 (2)−0.009 (2)
C20.019 (2)0.019 (3)0.017 (3)−0.002 (2)0.001 (2)−0.007 (2)
C30.019 (2)0.016 (2)0.017 (2)−0.004 (2)−0.004 (2)−0.009 (2)
C40.014 (2)0.016 (2)0.022 (3)−0.0012 (19)0.000 (2)−0.007 (2)
C50.023 (3)0.011 (2)0.026 (3)−0.0038 (19)−0.008 (2)−0.004 (2)
C60.024 (3)0.030 (3)0.019 (2)−0.008 (2)−0.003 (2)0.005 (2)
C70.022 (2)0.034 (3)0.018 (3)−0.005 (2)0.000 (3)−0.003 (3)
C80.018 (3)0.033 (3)0.017 (3)−0.001 (2)−0.005 (2)0.002 (2)
C90.013 (2)0.032 (3)0.018 (3)0.001 (2)−0.002 (2)0.010 (2)
C100.014 (2)0.020 (2)0.020 (3)0.000 (2)0.001 (2)0.001 (2)
C110.016 (2)0.027 (3)0.023 (3)0.002 (2)−0.001 (2)−0.004 (2)
C120.015 (2)0.017 (2)0.021 (3)0.0021 (18)−0.001 (2)−0.001 (2)
C130.016 (2)0.016 (2)0.030 (3)0.001 (2)0.000 (2)0.011 (2)
C140.018 (2)0.017 (2)0.018 (2)0.006 (2)−0.002 (2)0.005 (2)
C150.036 (3)0.023 (3)0.018 (2)−0.002 (2)−0.006 (2)−0.001 (2)
C160.058 (4)0.023 (3)0.022 (3)0.013 (3)−0.009 (3)0.004 (2)
C170.045 (4)0.034 (3)0.017 (3)0.024 (3)−0.010 (3)−0.003 (2)
C180.022 (3)0.042 (3)0.011 (2)0.012 (2)−0.005 (2)−0.005 (2)
C190.020 (3)0.023 (3)0.006 (2)0.006 (2)−0.0025 (19)−0.003 (2)
C200.014 (2)0.032 (3)0.010 (2)0.002 (2)0.0001 (18)−0.008 (2)
C210.021 (3)0.047 (3)0.010 (2)−0.008 (3)−0.001 (2)−0.009 (2)
C220.032 (3)0.040 (3)0.014 (3)−0.015 (3)−0.004 (2)−0.003 (2)
C230.045 (3)0.029 (3)0.014 (3)−0.013 (3)−0.003 (2)0.000 (2)
C240.024 (3)0.040 (3)0.013 (3)0.000 (2)0.000 (2)−0.005 (2)

Geometric parameters (Å, °)

Cu—O71.951 (4)C13—C141.384 (7)
Cu—O11.972 (4)C14—H140.9500
Cu—N52.007 (4)C15—C161.392 (8)
Cu—N62.010 (4)C15—H150.9500
Cu—O1W2.198 (4)C16—C171.351 (10)
C1—O11.261 (6)C16—H160.9500
C1—O21.238 (6)C17—C181.382 (8)
O3—N11.220 (6)C17—H170.9500
O4—N11.231 (6)C18—C191.406 (7)
O5—N21.221 (7)C18—H180.9500
O6—N21.248 (7)C19—C201.461 (8)
C8—O71.293 (7)C20—C211.402 (7)
C8—O81.230 (6)C21—C221.400 (8)
O9—N31.214 (6)C21—H210.9500
O10—N31.207 (6)C22—C231.363 (9)
O11—N41.224 (6)C22—H220.9500
O12—N41.234 (6)C23—C241.387 (8)
O1W—H2W0.84 (5)C23—H230.9500
O1W—H1W0.84 (5)C24—H240.9500
N1—C41.473 (6)O1S—C4S1.406 (8)
N2—C61.470 (7)O1S—C1S1.410 (8)
N3—C111.489 (7)C1S—C2S1.505 (8)
N4—C131.473 (7)C1S—H1S10.9900
N5—C151.331 (7)C1S—H1S20.9900
N5—C191.336 (6)C2S—C3S1.504 (9)
N6—C241.340 (7)C2S—H2S10.9900
N6—C201.346 (6)C2S—H2S20.9900
C1—C21.514 (7)C4S—C3S1.496 (9)
C2—C31.389 (7)C4S—H4S10.9900
C2—C71.399 (8)C4S—H4S20.9900
C3—C41.394 (7)C3S—H3S10.9900
C3—H30.9500C3S—H3S20.9900
C4—C51.378 (7)O2S—C8S1.397 (10)
C5—C61.374 (8)O2S—C5S1.401 (10)
C5—H50.9500C5S—C6S1.503 (10)
C6—C71.376 (8)C5S—H5S10.9900
C7—H70.9500C5S—H5S20.9900
C8—C91.511 (7)C8S—C7S1.506 (10)
C9—C101.392 (7)C8S—H8S10.9900
C9—C141.388 (7)C8S—H8S20.9900
C10—C111.375 (7)C7S—C6S1.503 (10)
C10—H100.9500C7S—H7S10.9900
C11—C121.383 (7)C7S—H7S20.9900
C12—C131.376 (8)C6S—H6S10.9900
C12—H120.9500C6S—H6S20.9900
O7—Cu—O190.62 (16)C17—C16—C15120.2 (6)
O7—Cu—N593.96 (16)C17—C16—H16119.9
O1—Cu—N5172.85 (17)C15—C16—H16119.9
O7—Cu—N6163.43 (16)C16—C17—C18119.5 (5)
O1—Cu—N694.15 (17)C16—C17—H17120.3
N5—Cu—N679.95 (18)C18—C17—H17120.3
O7—Cu—O1W92.59 (18)C17—C18—C19118.2 (5)
O1—Cu—O1W86.83 (17)C17—C18—H18120.9
N5—Cu—O1W98.43 (18)C19—C18—H18120.9
N6—Cu—O1W103.51 (19)N5—C19—C18121.3 (5)
C1—O1—Cu114.6 (3)N5—C19—C20114.5 (4)
C8—O7—Cu117.4 (3)C18—C19—C20124.2 (5)
Cu—O1W—H2W89 (6)N6—C20—C21120.9 (5)
Cu—O1W—H1W132 (6)N6—C20—C19114.8 (5)
H2W—O1W—H1W108 (5)C21—C20—C19124.3 (5)
O3—N1—O4124.7 (5)C22—C21—C20118.9 (5)
O3—N1—C4118.2 (4)C22—C21—H21120.5
O4—N1—C4117.1 (5)C20—C21—H21120.5
O5—N2—O6123.4 (5)C23—C22—C21119.3 (5)
O5—N2—C6118.2 (5)C23—C22—H22120.4
O6—N2—C6118.4 (5)C21—C22—H22120.4
O10—N3—O9125.7 (5)C22—C23—C24119.0 (5)
O10—N3—C11117.3 (4)C22—C23—H23120.5
O9—N3—C11117.0 (5)C24—C23—H23120.5
O11—N4—O12124.2 (4)N6—C24—C23122.6 (5)
O11—N4—C13117.7 (4)N6—C24—H24118.7
O12—N4—C13118.1 (4)C23—C24—H24118.7
C15—N5—C19119.9 (5)C4S—O1S—C1S104.5 (8)
C15—N5—Cu124.8 (4)O1S—C1S—C2S105.4 (7)
C19—N5—Cu115.2 (3)O1S—C1S—H1S1110.7
C24—N6—C20119.2 (5)C2S—C1S—H1S1110.7
C24—N6—Cu126.0 (4)O1S—C1S—H1S2110.7
C20—N6—Cu114.5 (4)C2S—C1S—H1S2110.7
O2—C1—O1126.8 (5)H1S1—C1S—H1S2108.8
O2—C1—C2118.7 (5)C3S—C2S—C1S103.5 (8)
O1—C1—C2114.5 (4)C3S—C2S—H2S1111.1
C3—C2—C7120.0 (5)C1S—C2S—H2S1111.1
C3—C2—C1121.1 (5)C3S—C2S—H2S2111.1
C7—C2—C1118.9 (5)C1S—C2S—H2S2111.1
C2—C3—C4118.1 (5)H2S1—C2S—H2S2109.0
C2—C3—H3120.9O1S—C4S—C3S110.2 (9)
C4—C3—H3120.9O1S—C4S—H4S1109.6
C5—C4—C3123.3 (5)C3S—C4S—H4S1109.6
C5—C4—N1118.9 (5)O1S—C4S—H4S2109.6
C3—C4—N1117.8 (5)C3S—C4S—H4S2109.6
C6—C5—C4116.3 (5)H4S1—C4S—H4S2108.1
C6—C5—H5121.9C4S—C3S—C2S102.7 (8)
C4—C5—H5121.9C4S—C3S—H3S1111.2
C7—C6—C5123.6 (5)C2S—C3S—H3S1111.2
C7—C6—N2118.2 (5)C4S—C3S—H3S2111.2
C5—C6—N2118.2 (5)C2S—C3S—H3S2111.2
C6—C7—C2118.7 (5)H3S1—C3S—H3S2109.1
C6—C7—H7120.7C8S—O2S—C5S106.1 (17)
C2—C7—H7120.7O2S—C5S—C6S111.5 (18)
O8—C8—O7126.0 (5)O2S—C5S—H5S1109.3
O8—C8—C9119.0 (5)C6S—C5S—H5S1109.3
O7—C8—C9115.1 (5)O2S—C5S—H5S2109.3
C10—C9—C14119.5 (5)C6S—C5S—H5S2109.3
C10—C9—C8119.3 (5)H5S1—C5S—H5S2108.0
C14—C9—C8121.1 (5)O2S—C8S—C7S109.3 (17)
C11—C10—C9119.8 (5)O2S—C8S—H8S1109.8
C11—C10—H10120.1C7S—C8S—H8S1109.8
C9—C10—H10120.1O2S—C8S—H8S2109.8
C10—C11—C12121.8 (5)C7S—C8S—H8S2109.8
C10—C11—N3120.0 (5)H8S1—C8S—H8S2108.3
C12—C11—N3118.0 (5)C6S—C7S—C8S104.2 (18)
C13—C12—C11117.2 (5)C6S—C7S—H7S1110.9
C13—C12—H12121.4C8S—C7S—H7S1110.9
C11—C12—H12121.4C6S—C7S—H7S2110.9
C12—C13—C14122.7 (5)C8S—C7S—H7S2110.9
C12—C13—N4118.5 (5)H7S1—C7S—H7S2108.9
C14—C13—N4118.8 (5)C7S—C6S—C5S98.9 (18)
C13—C14—C9118.7 (5)C7S—C6S—H6S1112.0
C13—C14—H14120.6C5S—C6S—H6S1112.0
C9—C14—H14120.6C7S—C6S—H6S2112.0
N5—C15—C16120.9 (6)C5S—C6S—H6S2112.0
N5—C15—H15119.6H6S1—C6S—H6S2109.7
C16—C15—H15119.6
O7—Cu—O1—C184.5 (4)C14—C9—C10—C110.5 (7)
N5—Cu—O1—C1−45.3 (15)C8—C9—C10—C11179.5 (5)
N6—Cu—O1—C1−79.6 (4)C9—C10—C11—C12−2.0 (8)
O1W—Cu—O1—C1177.1 (4)C9—C10—C11—N3−178.2 (5)
O1—Cu—O7—C8−109.3 (4)O10—N3—C11—C10178.4 (5)
N5—Cu—O7—C865.2 (4)O9—N3—C11—C10−0.7 (8)
N6—Cu—O7—C8−2.4 (8)O10—N3—C11—C122.1 (8)
O1W—Cu—O7—C8163.8 (4)O9—N3—C11—C12−177.0 (5)
O7—Cu—N5—C1520.9 (4)C10—C11—C12—C134.0 (8)
O1—Cu—N5—C15150.5 (12)N3—C11—C12—C13−179.8 (5)
N6—Cu—N5—C15−174.7 (5)C11—C12—C13—C14−4.6 (8)
O1W—Cu—N5—C15−72.3 (5)C11—C12—C13—N4177.6 (5)
O7—Cu—N5—C19−156.7 (3)O11—N4—C13—C12157.4 (5)
O1—Cu—N5—C19−27.0 (15)O12—N4—C13—C12−21.8 (7)
N6—Cu—N5—C197.8 (3)O11—N4—C13—C14−20.5 (7)
O1W—Cu—N5—C19110.1 (4)O12—N4—C13—C14160.3 (5)
O7—Cu—N6—C24−113.5 (6)C12—C13—C14—C93.3 (8)
O1—Cu—N6—C24−7.2 (4)N4—C13—C14—C9−178.9 (4)
N5—Cu—N6—C24176.9 (4)C10—C9—C14—C13−1.1 (7)
O1W—Cu—N6—C2480.6 (4)C8—C9—C14—C13179.9 (5)
O7—Cu—N6—C2060.4 (8)C19—N5—C15—C161.3 (8)
O1—Cu—N6—C20166.7 (3)Cu—N5—C15—C16−176.1 (4)
N5—Cu—N6—C20−9.2 (3)N5—C15—C16—C170.5 (9)
O1W—Cu—N6—C20−105.5 (4)C15—C16—C17—C18−0.7 (9)
Cu—O1—C1—O28.5 (7)C16—C17—C18—C19−0.7 (9)
Cu—O1—C1—C2−171.8 (3)C15—N5—C19—C18−2.9 (7)
O2—C1—C2—C3−170.3 (5)Cu—N5—C19—C18174.8 (4)
O1—C1—C2—C310.0 (7)C15—N5—C19—C20177.1 (4)
O2—C1—C2—C77.8 (7)Cu—N5—C19—C20−5.2 (5)
O1—C1—C2—C7−172.0 (5)C17—C18—C19—N52.6 (8)
C7—C2—C3—C41.3 (7)C17—C18—C19—C20−177.4 (5)
C1—C2—C3—C4179.3 (4)C24—N6—C20—C212.3 (7)
C2—C3—C4—C5−1.2 (7)Cu—N6—C20—C21−172.1 (4)
C2—C3—C4—N1179.3 (4)C24—N6—C20—C19−176.6 (4)
O3—N1—C4—C5−161.2 (5)Cu—N6—C20—C199.1 (5)
O4—N1—C4—C517.8 (7)N5—C19—C20—N6−2.6 (7)
O3—N1—C4—C318.3 (7)C18—C19—C20—N6177.4 (4)
O4—N1—C4—C3−162.7 (5)N5—C19—C20—C21178.6 (4)
C3—C4—C5—C60.4 (7)C18—C19—C20—C21−1.4 (8)
N1—C4—C5—C6179.9 (4)N6—C20—C21—C22−1.2 (8)
C4—C5—C6—C70.3 (8)C19—C20—C21—C22177.5 (5)
C4—C5—C6—N2178.6 (5)C20—C21—C22—C23−0.5 (8)
O5—N2—C6—C7−2.9 (8)C21—C22—C23—C241.1 (8)
O6—N2—C6—C7176.9 (5)C20—N6—C24—C23−1.7 (7)
O5—N2—C6—C5178.7 (5)Cu—N6—C24—C23172.0 (4)
O6—N2—C6—C5−1.5 (8)C22—C23—C24—N60.0 (8)
C5—C6—C7—C2−0.2 (8)C4S—O1S—C1S—C2S37.4 (10)
N2—C6—C7—C2−178.5 (5)O1S—C1S—C2S—C3S−34.0 (10)
C3—C2—C7—C6−0.6 (8)C1S—O1S—C4S—C3S−26.8 (13)
C1—C2—C7—C6−178.7 (5)O1S—C4S—C3S—C2S5.2 (14)
Cu—O7—C8—O8−2.2 (8)C1S—C2S—C3S—C4S16.9 (12)
Cu—O7—C8—C9177.9 (3)C8S—O2S—C5S—C6S17 (2)
O8—C8—C9—C101.5 (8)C5S—O2S—C8S—C7S4(2)
O7—C8—C9—C10−178.6 (5)O2S—C8S—C7S—C6S−23 (3)
O8—C8—C9—C14−179.6 (5)C8S—C7S—C6S—C5S30 (3)
O7—C8—C9—C140.3 (7)O2S—C5S—C6S—C7S−30 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1w—H1w···O2i0.84 (5)2.01 (6)2.766 (6)150 (7)
O1w—H2w···O8i0.84 (5)2.35 (7)3.048 (6)141 (6)
C18—H18···O8ii0.952.173.060 (7)155
C21—H21···O2ii0.952.413.087 (7)128
C15—H15···O9i0.952.433.285 (7)150
C1s—H1s2···O70.992.533.451 (10)155
C3—H3···O1s0.952.583.520 (8)169
C2s—H2s2···O110.992.493.385 (11)150
C5—H5···O4iii0.952.583.360 (7)140
C12—H12···O12iii0.952.433.263 (7)146
C16—H16···O12iv0.952.473.234 (8)138

Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, y, z−1/2; (iii) −x+3/2, y, z+1/2; (iv) −x+1, −y+2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5590).

References

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