Related literature   {#sec1}
====================

For the biological activity of clioquinol, see: Di Vaira *et al.* (2004[@bb4]). For the use of clioquinol in the treatment of Alzheimer's disease, see: Bareggi & Cornelli (2012[@bb1]). For crystal structures of copper(II) complexes with 8-hy­droxy­quinoline (8-HQ) derivatives and the metal in a five-coordinate environment, see: Deraeve *et al.* (2008[@bb3]). For \[Cu(8-HQ)~2~(H~2~O)~2~\] with six-coordinate Cu(II), see: Okabe & Saishu (2001[@bb9]). For copper(II), zinc(II) and iron(III) crystalline complexes with 8-HQ, see: Palenik (1964[@bb10]); Najafi *et al.* (2011[@bb8]); Jian *et al.* (2001[@bb5]). For EPR studies performed on a putative \[Cu(8-HQ)~2~(pyri­dine)\] complex, see: Marov *et al.* (1975[@bb7], 1978[@bb6]).

Experimental   {#sec2}
==============

Crystal data   {#sec2.1}
--------------

\[Cu(C~9~H~6~NO)~2~(C~5~H~5~N)\]·H~2~O*M* *~r~* = 448.95Orthorhombic,*a* = 8.9129 (4) Å*b* = 13.9987 (7) Å*c* = 32.2568 (16) Å*V* = 4024.6 (3) Å^3^*Z* = 8Mo *K*α radiationμ = 1.12 mm^−1^*T* = 296 K0.21 × 0.11 × 0.08 mm

Data collection   {#sec2.2}
-----------------

Bruker APEXII CCD diffractometerAbsorption correction: multi-scan (*SADABS*; Bruker, 2002[@bb2]) *T* ~min~ = 0.800, *T* ~max~ = 0.91615390 measured reflections3542 independent reflections2301 reflections with *I* \> 2σ(*I*)*R* ~int~ = 0.050

Refinement   {#sec2.3}
------------

*R*\[*F* ^2^ \> 2σ(*F* ^2^)\] = 0.038*wR*(*F* ^2^) = 0.093*S* = 1.013542 reflections279 parametersH atoms treated by a mixture of independent and constrained refinementΔρ~max~ = 0.24 e Å^−3^Δρ~min~ = −0.27 e Å^−3^

 {#d5e610}

Data collection: *APEX2* (Bruker, 2002[@bb2]); cell refinement: *SAINT* (Bruker, 2002[@bb2]); data reduction: *SAINT*; program(s) used to solve structure: *SHELXS97* (Sheldrick, 2008[@bb11]); program(s) used to refine structure: *SHELXL97* (Sheldrick, 2015[@bb12]); molecular graphics: *SHELXTL* (Sheldrick, 2008[@bb11]); software used to prepare material for publication: *SHELXTL* and *publCIF* (Westrip, 2010[@bb13]).

Supplementary Material
======================

Crystal structure: contains datablock(s) I. DOI: [10.1107/S2056989015001279/jj2192sup1.cif](http://dx.doi.org/10.1107/S2056989015001279/jj2192sup1.cif)

Structure factors: contains datablock(s) I. DOI: [10.1107/S2056989015001279/jj2192Isup2.hkl](http://dx.doi.org/10.1107/S2056989015001279/jj2192Isup2.hkl)

###### 

Click here for additional data file.

Supporting information file. DOI: [10.1107/S2056989015001279/jj2192Isup3.cdx](http://dx.doi.org/10.1107/S2056989015001279/jj2192Isup3.cdx)

###### 

Click here for additional data file.

9 6 2 5 4 2 . DOI: [10.1107/S2056989015001279/jj2192fig1.tif](http://dx.doi.org/10.1107/S2056989015001279/jj2192fig1.tif)

ORTEP drawing of \[Cu(C~9~H~6~NO)~2~(C~5~H~4~N\]·H~2~O. Displacement ellipsoids were drawn at the 50% probability level. The hydrogen atoms have been omitted for clarity.

###### 

Click here for additional data file.

9 6 2 5 4 2 a b . DOI: [10.1107/S2056989015001279/jj2192fig2.tif](http://dx.doi.org/10.1107/S2056989015001279/jj2192fig2.tif)

A portion of the mol­ecular packing for \[Cu(C~9~H~6~NO)~2~(C~5~H~4~N\]·H~2~O viewed along the *a* axis. Dashed lines indicate O---H⋯O hydrogen bonds between water hydrogen atoms and hy­droxy­quinoline oxygen atoms forming continuous chains along the *b* axis. Displacement ellipsoids were drawn at the 5% probability level. Hydrogen atoms not involved in hydrogen bonds have been omitted for clarity.

CCDC reference: [1044628](http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=1044628)

Additional supporting information: [crystallographic information](http://scripts.iucr.org/cgi-bin/sendsupfiles?jj2192&file=jj2192sup0.html&mime=text/html); [3D view](http://scripts.iucr.org/cgi-bin/sendcif?jj2192sup1&Qmime=cif); [checkCIF report](http://scripts.iucr.org/cgi-bin/paper?jj2192&checkcif=yes)

Supporting information for this paper is available from the IUCr electronic archives (Reference: [JJ2192](http://scripts.iucr.org/cgi-bin/sendsup?jj2192)).

This work was funded by the Department of Chemistry and Biochemistry at Worcester Polytechnic Institute.

S1. Comment {#d1e22}
===========

Clioquinol is a 8-hy­droxy­quinoline (8-HQ) derivative that has been used for the treatment of Alzheimer\'s disease (Bareggi & Cornelli, 2012). The coordination chemistry of clioquinol plays a critical role in its biological activity (Di Vaira *et al.*, 2004). Copper(II), zinc(II) and iron(III) readily form crystalline complexes with 8-HQ and its derivatives (Palenik, 1964; Najafi, 2011; Jian *et al.*, 2001). Two bidentate ligands chelate a single metal ion in the square planar \[Cu(8---HQ)~2~\] cupric complex (Palenik, 1964) that is structurally analogous to \[Cu(clioquinol)~2~\] (Di Vaira *et al.*, 2004). Very few X-ray structures of five-coordinate cooper(II) complexes with 8-HQ derivatives have been reported (Deraeve *et al.*, 2008); however, a 6-coordinate complexe of \[Cu(8---HQ)~2~(H~2~O)~2~\] has been structurally characterized (Okabe & Saishu, 2001). EPR studies were performed on a putative \[Cu(8---HQ)~2~(pyridine)\] complex nearly 40 years ago (Marov *et al.*, 1975; Marov *et al.*, 1978).

The reaction of \[Cu(OAc)~2~\]·H~2~O with 8-hy­droxy­quinoline yields the well known \[Cu(C~9~H~6~NO)~2~\] moiety where each 8-hy­droxy­quionline group serves as a bidentate chelator coordinated through the oxygen and nitro­gen atoms. When recrystallized from a mixture of pyridine and H~2~O, the title complex is isolated. Herein, we report the crystal structure of \[Cu(C~9~H~6~NO)~2~(C~5~H~4~N\]·H~2~O, the first confirmation that the 5-coordinate complex can exist in the solid state. The pyridine ligand forms dihedral angles with the two quinolin-2-olate ligands of 79.5 (5)° and 88.0 (1)°, while the dihedral angle between the quinoline groups of 9.0 (3)° indicates near planarity. The Cu---N bond appears to be weak as the crystals readily decompose as they dry, presumably due to loss of the pyridine ligand.

S2. Experimental {#d1e114}
================

\[Cu(OAc)~2~\]·H~2~O (0.258 g, 1.29 mmol) and 8-hy­droxy­quinoline (0.375 g, 2.58 mol) were separately dissolved in minimal qu­anti­ties of acetic acid (ca. 2.5 mL). Upon mixing the solutions, a light green precipitate (0.486 g) formed immediately. The precipitate was isolated by filtration and dissolved in pyridine. Green blocks of \[Cu(C~9~H~6~NO)~2~(C~5~H~4~N\]·H~2~O were isolated by slow evaporation in a diffusion chamber containing water and subsequentally used for crystal structure analysis.

S3. Refinement {#d1e153}
==============

H18 and H19 were located by a difference map and refined isotropically. All of the remaining H atoms were placed in calculated positions and refined using a riding model with atom--H lengths of 0.93 Å (CH). Isotropic displacement parameters for these atoms were set to 1.2 (CH) times U~eq~ of the parent atom.

Figures
=======

![ORTEP drawing of \[Cu(C9H6NO)2(C5H4N\]·H2O. Displacement ellipsoids were drawn at the 50% probability level. The hydrogen atoms have been omitted for clarity.](e-71-00m38-fig1){#Fap1}

![A portion of the molecular packing for \[Cu(C9H6NO)2(C5H4N\]·H2O viewed along the a axis. Dashed lines indicate O---H···O hydrogen bonds between water hydrogen atoms and hydroxyquinoline oxygen atoms forming continuous chains along the b axis. Displacement ellipsoids were drawn at the 5% probability level. Hydrogen atoms not involved in hydrogen bonds have been omitted for clarity.](e-71-00m38-fig2){#Fap2}

Crystal data {#tablewrapcrystaldatalong}
============

  ---------------------------------------- ---------------------------------------
  \[Cu(C~9~H~6~NO)~2~(C~5~H~5~N)\]·H~2~O   *F*(000) = 1848
  *M~r~* = 448.95                          *D*~x~ = 1.482 Mg m^−3^
  Orthorhombic, *Pbca*                     Mo *K*α radiation, λ = 0.71073 Å
  Hall symbol: -P 2ac 2ab                  Cell parameters from 2855 reflections
  *a* = 8.9129 (4) Å                       θ = 2.6--25.1°
  *b* = 13.9987 (7) Å                      µ = 1.12 mm^−1^
  *c* = 32.2568 (16) Å                     *T* = 296 K
  *V* = 4024.6 (3) Å^3^                    Block, green
  *Z* = 8                                  0.21 × 0.11 × 0.08 mm
  ---------------------------------------- ---------------------------------------

Data collection {#tablewrapdatacollectionlong}
===============

  ------------------------------------------------------------ --------------------------------------
  Bruker APEXII CCD diffractometer                             3542 independent reflections
  Radiation source: fine-focus sealed tube                     2301 reflections with *I* \> 2σ(*I*)
  Graphite monochromator                                       *R*~int~ = 0.050
  Detector resolution: 10.00 pixels mm^-1^                     θ~max~ = 25.0°, θ~min~ = 2.6°
  φ and ω scans                                                *h* = −10→9
  Absorption correction: multi-scan (*SADABS*; Bruker, 2002)   *k* = −14→16
  *T*~min~ = 0.800, *T*~max~ = 0.916                           *l* = −27→38
  15390 measured reflections                                   
  ------------------------------------------------------------ --------------------------------------

Refinement {#tablewraprefinementdatalong}
==========

  ------------------------------------- -------------------------------------------------------------------------------------------------
  Refinement on *F*^2^                  Primary atom site location: structure-invariant direct methods
  Least-squares matrix: full            Secondary atom site location: difference Fourier map
  *R*\[*F*^2^ \> 2σ(*F*^2^)\] = 0.038   Hydrogen site location: inferred from neighbouring sites
  *wR*(*F*^2^) = 0.093                  H atoms treated by a mixture of independent and constrained refinement
  *S* = 1.01                            *w* = 1/\[σ^2^(*F*~o~^2^) + (0.0441*P*)^2^ + 0.2191*P*\] where *P* = (*F*~o~^2^ + 2*F*~c~^2^)/3
  3542 reflections                      (Δ/σ)~max~ = 0.001
  279 parameters                        Δρ~max~ = 0.24 e Å^−3^
  0 restraints                          Δρ~min~ = −0.27 e Å^−3^
  ------------------------------------- -------------------------------------------------------------------------------------------------

Special details {#specialdetails}
===============

  -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
  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 *F*^2^ against ALL reflections. The weighted *R*-factor *wR* and goodness of fit *S* are based on *F*^2^, conventional *R*-factors *R* are based on *F*, with *F* set to zero for negative *F*^2^. The threshold expression of *F*^2^ \> σ(*F*^2^) is used only for calculating *R*-factors(gt) *etc*. and is not relevant to the choice of reflections for refinement. *R*-factors based on *F*^2^ 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 (Å^2^) {#tablewrapcoords}
==================================================================================================

  ----- ------------- -------------- --------------- -------------------- --
        *x*           *y*            *z*             *U*~iso~\*/*U*~eq~   
  Cu1   0.16872 (4)   0.91228 (3)    0.376062 (11)   0.03289 (14)         
  O1    0.0393 (2)    0.81502 (16)   0.39962 (6)     0.0436 (6)           
  O2    0.2691 (2)    1.02164 (15)   0.35011 (6)     0.0415 (6)           
  N1    0.1945 (3)    0.9539 (2)     0.43529 (8)     0.0393 (7)           
  N2    0.0918 (3)    0.88951 (18)   0.31826 (8)     0.0346 (6)           
  N3    0.3873 (3)    0.82435 (19)   0.37496 (8)     0.0362 (6)           
  C1    0.2740 (4)    1.0222 (3)     0.45151 (10)    0.0498 (9)           
  H1    0.3242        1.0640         0.4339          0.060\*              
  C2    0.2872 (4)    1.0353 (3)     0.49500 (11)    0.0630 (11)          
  H6    0.3453        1.0847         0.5057          0.076\*              
  C3    0.2132 (4)    0.9742 (3)     0.52092 (11)    0.0573 (10)          
  H2    0.2213        0.9815         0.5495          0.069\*              
  C4    0.1255 (4)    0.9008 (3)     0.50465 (10)    0.0438 (9)           
  C5    0.0420 (4)    0.8341 (3)     0.52762 (11)    0.0592 (11)          
  H5    0.0434        0.8369         0.5564          0.071\*              
  C6    −0.0403 (5)   0.7661 (3)     0.50858 (12)    0.0646 (12)          
  H4    −0.0964       0.7241         0.5246          0.078\*              
  C7    −0.0436 (4)   0.7570 (3)     0.46570 (11)    0.0524 (10)          
  H3    −0.1001       0.7086         0.4537          0.063\*              
  C8    0.0358 (4)    0.8188 (2)     0.44086 (9)     0.0383 (8)           
  C9    0.1197 (4)    0.8923 (2)     0.46062 (10)    0.0360 (8)           
  C10   0.0008 (4)    0.8235 (2)     0.30402 (10)    0.0429 (9)           
  H7    −0.0425       0.7807         0.3225          0.051\*              
  C11   −0.0332 (4)   0.8157 (3)     0.26144 (11)    0.0534 (10)          
  H12   −0.0974       0.7680         0.2521          0.064\*              
  C12   0.0284 (4)    0.8783 (3)     0.23423 (11)    0.0505 (10)          
  H11   0.0063        0.8733         0.2061          0.061\*              
  C13   0.1255 (4)    0.9507 (2)     0.24823 (9)     0.0385 (8)           
  C14   0.1537 (3)    0.9534 (2)     0.29164 (9)     0.0340 (8)           
  C15   0.2494 (4)    1.0239 (2)     0.30931 (9)     0.0335 (8)           
  C16   0.3130 (4)    1.0896 (2)     0.28342 (11)    0.0495 (9)           
  H10   0.3749        1.1369         0.2943          0.059\*              
  C17   0.2858 (5)    1.0865 (3)     0.24070 (11)    0.0569 (11)          
  H9    0.3312        1.1317         0.2237          0.068\*              
  C18   0.1952 (4)    1.0196 (3)     0.22332 (10)    0.0542 (10)          
  H8    0.1794        1.0196         0.1948          0.065\*              
  C19   0.3876 (4)    0.7353 (2)     0.36165 (10)    0.0418 (9)           
  H17   0.2954        0.7070         0.3560          0.050\*              
  C20   0.5146 (4)    0.6814 (3)     0.35556 (10)    0.0475 (9)           
  H16   0.5084        0.6191         0.3457          0.057\*              
  C21   0.6507 (4)    0.7222 (3)     0.36438 (10)    0.0512 (10)          
  H15   0.7393        0.6881         0.3607          0.061\*              
  C22   0.6536 (4)    0.8152 (3)     0.37883 (10)    0.0515 (9)           
  H14   0.7441        0.8448         0.3852          0.062\*              
  C23   0.5208 (4)    0.8629 (3)     0.38358 (10)    0.0433 (9)           
  H13   0.5236        0.9254         0.3933          0.052\*              
  O3    −0.0217 (4)   0.6211 (2)     0.37607 (10)    0.0597 (8)           
  H19   0.006 (4)     0.671 (3)      0.3806 (12)     0.058 (15)\*         
  H18   0.054 (5)     0.595 (3)      0.3664 (13)     0.083 (17)\*         
  ----- ------------- -------------- --------------- -------------------- --

Atomic displacement parameters (Å^2^) {#tablewrapadps}
=====================================

  ----- ------------- ------------- ------------- --------------- -------------- ---------------
        *U*^11^       *U*^22^       *U*^33^       *U*^12^         *U*^13^        *U*^23^
  Cu1   0.0354 (2)    0.0357 (2)    0.0275 (2)    −0.00361 (19)   0.00111 (18)   −0.00006 (17)
  O1    0.0458 (14)   0.0499 (14)   0.0351 (12)   −0.0102 (12)    0.0018 (11)    0.0002 (11)
  O2    0.0508 (14)   0.0390 (13)   0.0348 (12)   −0.0096 (12)    0.0002 (11)    0.0031 (10)
  N1    0.0405 (17)   0.0416 (17)   0.0357 (14)   −0.0023 (15)    0.0023 (13)    −0.0040 (13)
  N2    0.0335 (16)   0.0333 (16)   0.0369 (15)   0.0002 (14)     −0.0009 (13)   −0.0004 (12)
  N3    0.0314 (16)   0.0397 (16)   0.0374 (14)   0.0014 (13)     0.0003 (13)    −0.0009 (13)
  C1    0.055 (2)     0.051 (2)     0.044 (2)     −0.006 (2)      0.0066 (19)    −0.0045 (18)
  C2    0.063 (3)     0.069 (3)     0.058 (2)     −0.008 (2)      −0.010 (2)     −0.022 (2)
  C3    0.064 (3)     0.069 (3)     0.039 (2)     0.006 (2)       −0.005 (2)     −0.009 (2)
  C4    0.045 (2)     0.055 (2)     0.0315 (17)   0.0112 (19)     0.0017 (16)    −0.0007 (17)
  C5    0.068 (3)     0.077 (3)     0.0323 (19)   0.012 (2)       0.006 (2)      0.012 (2)
  C6    0.075 (3)     0.069 (3)     0.049 (2)     −0.007 (2)      0.016 (2)      0.015 (2)
  C7    0.053 (3)     0.054 (3)     0.050 (2)     −0.0042 (19)    0.009 (2)      0.0111 (18)
  C8    0.035 (2)     0.046 (2)     0.0330 (17)   0.0102 (18)     0.0003 (15)    0.0004 (16)
  C9    0.0291 (19)   0.043 (2)     0.0363 (17)   0.0119 (16)     0.0047 (15)    0.0055 (15)
  C10   0.039 (2)     0.041 (2)     0.049 (2)     −0.0005 (19)    −0.0002 (17)   0.0042 (17)
  C11   0.050 (2)     0.050 (2)     0.060 (2)     −0.001 (2)      −0.018 (2)     −0.012 (2)
  C12   0.056 (3)     0.061 (3)     0.0341 (18)   0.009 (2)       −0.0086 (19)   −0.0006 (18)
  C13   0.041 (2)     0.0435 (19)   0.0304 (16)   0.0115 (18)     −0.0014 (16)   0.0001 (16)
  C14   0.034 (2)     0.0360 (18)   0.0324 (16)   0.0095 (17)     0.0033 (15)    −0.0001 (15)
  C15   0.037 (2)     0.0334 (18)   0.0302 (16)   0.0038 (16)     0.0040 (16)    −0.0008 (15)
  C16   0.057 (2)     0.039 (2)     0.053 (2)     −0.0053 (19)    0.0119 (19)    0.0004 (17)
  C17   0.071 (3)     0.054 (2)     0.046 (2)     0.003 (2)       0.015 (2)      0.0144 (19)
  C18   0.063 (3)     0.063 (3)     0.0360 (19)   0.012 (2)       0.0049 (19)    0.0081 (19)
  C19   0.033 (2)     0.050 (2)     0.0422 (19)   −0.0021 (19)    −0.0001 (15)   −0.0027 (17)
  C20   0.045 (2)     0.044 (2)     0.053 (2)     0.005 (2)       0.0072 (19)    −0.0028 (17)
  C21   0.039 (2)     0.063 (3)     0.051 (2)     0.012 (2)       0.0079 (18)    0.0066 (19)
  C22   0.034 (2)     0.073 (3)     0.048 (2)     −0.003 (2)      −0.0066 (18)   0.005 (2)
  C23   0.042 (2)     0.043 (2)     0.045 (2)     −0.0025 (19)    −0.0031 (17)   −0.0039 (16)
  O3    0.0487 (19)   0.0478 (19)   0.083 (2)     0.0065 (16)     0.0051 (17)    −0.0096 (17)
  ----- ------------- ------------- ------------- --------------- -------------- ---------------

Geometric parameters (Å, º) {#tablewrapgeomlong}
===========================

  --------------------- ------------- ----------------------- ------------
  Cu1---O1              1.940 (2)     C8---C9                 1.422 (4)
  Cu1---O2              1.961 (2)     C10---C11               1.411 (4)
  Cu1---N2              2.012 (3)     C10---H7                0.9300
  Cu1---N1              2.011 (3)     C11---C12               1.356 (5)
  Cu1---N3              2.305 (3)     C11---H12               0.9300
  O1---C8               1.332 (3)     C12---C13               1.408 (5)
  O2---C15              1.328 (3)     C12---H11               0.9300
  N1---C1               1.299 (4)     C13---C18               1.401 (5)
  N1---C9               1.363 (4)     C13---C14               1.423 (4)
  N2---C10              1.312 (4)     C14---C15               1.424 (4)
  N2---C14              1.357 (4)     C15---C16               1.366 (4)
  N3---C19              1.318 (4)     C16---C17               1.400 (5)
  N3---C23              1.336 (4)     C16---H10               0.9300
  C1---C2               1.420 (4)     C17---C18               1.357 (5)
  C1---H1               0.9300        C17---H9                0.9300
  C2---C3               1.366 (5)     C18---H8                0.9300
  C2---H6               0.9300        C19---C20               1.375 (4)
  C3---C4               1.393 (5)     C19---H17               0.9300
  C3---H2               0.9300        C20---C21               1.371 (4)
  C4---C5               1.405 (5)     C20---H16               0.9300
  C4---C9               1.426 (4)     C21---C22               1.383 (5)
  C5---C6               1.349 (5)     C21---H15               0.9300
  C5---H5               0.9300        C22---C23               1.367 (4)
  C6---C7               1.389 (5)     C22---H14               0.9300
  C6---H4               0.9300        C23---H13               0.9300
  C7---C8               1.375 (4)     O3---H19                0.76 (4)
  C7---H3               0.9300        O3---H18                0.83 (5)
                                                              
  O1---Cu1---O2         170.64 (9)    N1---C9---C4            121.8 (3)
  O1---Cu1---N2         92.81 (10)    C8---C9---C4            121.7 (3)
  O2---Cu1---N2         83.32 (9)     N2---C10---C11          121.8 (3)
  O1---Cu1---N1         84.23 (10)    N2---C10---H7           119.1
  O2---Cu1---N1         97.30 (10)    C11---C10---H7          119.1
  N2---Cu1---N1         164.89 (11)   C12---C11---C10         119.6 (3)
  O1---Cu1---N3         97.70 (9)     C12---C11---H12         120.2
  O2---Cu1---N3         91.41 (9)     C10---C11---H12         120.2
  N2---Cu1---N3         100.91 (10)   C11---C12---C13         120.4 (3)
  N1---Cu1---N3         94.18 (10)    C11---C12---H11         119.8
  C8---O1---Cu1         112.2 (2)     C13---C12---H11         119.8
  C15---O2---Cu1        112.42 (19)   C18---C13---C12         125.8 (3)
  C1---N1---C9          119.4 (3)     C18---C13---C14         117.9 (3)
  C1---N1---Cu1         131.2 (2)     C12---C13---C14         116.3 (3)
  C9---N1---Cu1         109.3 (2)     N2---C14---C15          116.6 (3)
  C10---N2---C14        119.6 (3)     N2---C14---C13          122.2 (3)
  C10---N2---Cu1        130.3 (2)     C15---C14---C13         121.2 (3)
  C14---N2---Cu1        110.1 (2)     O2---C15---C16          124.6 (3)
  C19---N3---C23        116.6 (3)     O2---C15---C14          117.3 (3)
  C19---N3---Cu1        120.8 (2)     C16---C15---C14         118.1 (3)
  C23---N3---Cu1        122.3 (2)     C15---C16---C17         120.6 (3)
  N1---C1---C2          122.6 (4)     C15---C16---H10         119.7
  N1---C1---H1          118.7         C17---C16---H10         119.7
  C2---C1---H1          118.7         C18---C17---C16         122.1 (3)
  C3---C2---C1          118.9 (4)     C18---C17---H9          119.0
  C3---C2---H6          120.6         C16---C17---H9          119.0
  C1---C2---H6          120.6         C17---C18---C13         120.1 (3)
  C2---C3---C4          120.1 (3)     C17---C18---H8          119.9
  C2---C3---H2          119.9         C13---C18---H8          119.9
  C4---C3---H2          119.9         N3---C19---C20          124.5 (3)
  C3---C4---C5          126.0 (3)     N3---C19---H17          117.7
  C3---C4---C9          117.2 (3)     C20---C19---H17         117.7
  C5---C4---C9          116.8 (3)     C21---C20---C19         118.1 (3)
  C6---C5---C4          121.1 (3)     C21---C20---H16         121.0
  C6---C5---H5          119.5         C19---C20---H16         121.0
  C4---C5---H5          119.5         C20---C21---C22         118.6 (3)
  C5---C6---C7          122.0 (4)     C20---C21---H15         120.7
  C5---C6---H4          119.0         C22---C21---H15         120.7
  C7---C6---H4          119.0         C23---C22---C21         118.8 (3)
  C8---C7---C6          120.8 (4)     C23---C22---H14         120.6
  C8---C7---H3          119.6         C21---C22---H14         120.6
  C6---C7---H3          119.6         N3---C23---C22          123.4 (3)
  O1---C8---C7          124.7 (3)     N3---C23---H13          118.3
  O1---C8---C9          117.7 (3)     C22---C23---H13         118.3
  C7---C8---C9          117.7 (3)     H19---O3---H18          102 (4)
  N1---C9---C8          116.5 (3)                             
                                                              
  N2---Cu1---O1---C8    −168.2 (2)    Cu1---N1---C9---C8      −3.6 (3)
  N1---Cu1---O1---C8    −3.1 (2)      C1---N1---C9---C4       0.3 (5)
  N3---Cu1---O1---C8    90.4 (2)      Cu1---N1---C9---C4      176.2 (2)
  N2---Cu1---O2---C15   −4.6 (2)      O1---C8---C9---N1       1.2 (4)
  N1---Cu1---O2---C15   −169.4 (2)    C7---C8---C9---N1       −178.5 (3)
  N3---Cu1---O2---C15   96.2 (2)      O1---C8---C9---C4       −178.6 (3)
  O1---Cu1---N1---C1    178.9 (3)     C7---C8---C9---C4       1.7 (5)
  O2---Cu1---N1---C1    −10.4 (3)     C3---C4---C9---N1       −1.0 (5)
  N2---Cu1---N1---C1    −101.8 (5)    C5---C4---C9---N1       179.0 (3)
  N3---Cu1---N1---C1    81.6 (3)      C3---C4---C9---C8       178.8 (3)
  O1---Cu1---N1---C9    3.6 (2)       C5---C4---C9---C8       −1.2 (5)
  O2---Cu1---N1---C9    174.3 (2)     C14---N2---C10---C11    1.1 (5)
  N2---Cu1---N1---C9    82.9 (5)      Cu1---N2---C10---C11    −176.0 (2)
  N3---Cu1---N1---C9    −93.7 (2)     N2---C10---C11---C12    −0.5 (5)
  O1---Cu1---N2---C10   −7.0 (3)      C10---C11---C12---C13   −0.1 (5)
  O2---Cu1---N2---C10   −178.4 (3)    C11---C12---C13---C18   −179.6 (3)
  N1---Cu1---N2---C10   −85.2 (5)     C11---C12---C13---C14   0.1 (5)
  N3---Cu1---N2---C10   91.4 (3)      C10---N2---C14---C15    179.1 (3)
  O1---Cu1---N2---C14   175.7 (2)     Cu1---N2---C14---C15    −3.3 (3)
  O2---Cu1---N2---C14   4.3 (2)       C10---N2---C14---C13    −1.1 (4)
  N1---Cu1---N2---C14   97.5 (5)      Cu1---N2---C14---C13    176.5 (2)
  N3---Cu1---N2---C14   −85.9 (2)     C18---C13---C14---N2    −179.8 (3)
  O1---Cu1---N3---C19   44.9 (2)      C12---C13---C14---N2    0.5 (5)
  O2---Cu1---N3---C19   −133.0 (2)    C18---C13---C14---C15   0.1 (5)
  N2---Cu1---N3---C19   −49.5 (3)     C12---C13---C14---C15   −179.6 (3)
  N1---Cu1---N3---C19   129.6 (2)     Cu1---O2---C15---C16    −176.7 (3)
  O1---Cu1---N3---C23   −142.0 (2)    Cu1---O2---C15---C14    4.2 (3)
  O2---Cu1---N3---C23   40.1 (2)      N2---C14---C15---O2     −0.5 (4)
  N2---Cu1---N3---C23   123.6 (2)     C13---C14---C15---O2    179.7 (3)
  N1---Cu1---N3---C23   −57.3 (2)     N2---C14---C15---C16    −179.7 (3)
  C9---N1---C1---C2     0.3 (5)       C13---C14---C15---C16   0.5 (5)
  Cu1---N1---C1---C2    −174.5 (3)    O2---C15---C16---C17    −179.9 (3)
  N1---C1---C2---C3     −0.3 (6)      C14---C15---C16---C17   −0.8 (5)
  C1---C2---C3---C4     −0.5 (6)      C15---C16---C17---C18   0.6 (6)
  C2---C3---C4---C5     −178.9 (4)    C16---C17---C18---C13   0.0 (6)
  C2---C3---C4---C9     1.1 (5)       C12---C13---C18---C17   179.4 (3)
  C3---C4---C5---C6     179.5 (4)     C14---C13---C18---C17   −0.3 (5)
  C9---C4---C5---C6     −0.5 (5)      C23---N3---C19---C20    −1.1 (5)
  C4---C5---C6---C7     1.7 (6)       Cu1---N3---C19---C20    172.4 (2)
  C5---C6---C7---C8     −1.1 (6)      N3---C19---C20---C21    0.9 (5)
  Cu1---O1---C8---C7    −178.3 (3)    C19---C20---C21---C22   −0.1 (5)
  Cu1---O1---C8---C9    2.0 (3)       C20---C21---C22---C23   −0.3 (5)
  C6---C7---C8---O1     179.8 (3)     C19---N3---C23---C22    0.7 (5)
  C6---C7---C8---C9     −0.5 (5)      Cu1---N3---C23---C22    −172.7 (2)
  C1---N1---C9---C8     −179.5 (3)    C21---C22---C23---N3    0.0 (5)
  --------------------- ------------- ----------------------- ------------

Hydrogen-bond geometry (Å, º) {#tablewraphbondslong}
=============================

  ------------------ ---------- ---------- ----------- ---------------
  *D*---H···*A*      *D*---H    H···*A*    *D*···*A*   *D*---H···*A*
  O3---H18···O2^i^   0.83 (5)   1.95 (5)   2.776 (4)   173 (4)
  O3---H19···O1      0.76 (4)   2.13 (4)   2.871 (4)   168 (4)
  ------------------ ---------- ---------- ----------- ---------------

Symmetry code: (i) −*x*+1/2, *y*−1/2, *z*.

###### Selected geometric parameters (, )

  ------- ----------
  Cu1O1   1.940(2)
  Cu1O2   1.961(2)
  Cu1N2   2.012(3)
  Cu1N1   2.011(3)
  Cu1N3   2.305(3)
  ------- ----------

  --------- ------------
  O1Cu1N2   92.81(10)
  O2Cu1N2   83.32(9)
  O1Cu1N1   84.23(10)
  O2Cu1N1   97.30(10)
  O1Cu1N3   97.70(9)
  O2Cu1N3   91.41(9)
  N2Cu1N3   100.91(10)
  N1Cu1N3   94.18(10)
  --------- ------------

###### Hydrogen-bond geometry (, )

  *D*H*A*      *D*H      H*A*      *D* *A*    *D*H*A*
  ------------ --------- --------- ---------- ---------
  O3H18O2^i^   0.83(5)   1.95(5)   2.776(4)   173(4)
  O3H19O1      0.76(4)   2.13(4)   2.871(4)   168(4)

Symmetry code: (i) .
