A polymeric ladder complex: catena-poly­[[[μ-4,4′-bipyridyl-bis­[aqua(p-amino­benzoato)copper(II)]]-di-μ-4,4′-bipyridyl] dinitrate tetrahydrate]

The title polymeric ladder complex, {[Cu₂(C₇H₆NO₂)₂(C₁₀H₈N₂)₃(H₂O)₂](NO₃)₂·4H₂O}_n, has been synthesized and spectroscopically characterized. The polymeric nature of the compound involves two non-equivalent 4,4′-bipyridyl ligands acting as almost orthogonal bridges joining the metal coordination Jahn–Teller-distorted octahedra, and forming ladders packed under the influence of hydrogen bonds involving the uncoordinated amino group of the p-amino­­benzoate ligand, the NO₃⁻ anion and the water mol­ecules.

S1. Comment

The application of metal atoms as key elements in the self-assembly of arrays has emerged as an area of great interest over the past a few years (Fujita, 1998; Leininger et al., 2000). A series of one-, two- and three-dimensional frameworks with novel topologies and potential properties have been obtained by binding metal ions of specific coordination geometry with rigid or flexible bridging ligands, such as 4,4'-bipyridine (Tong et al., 2000; Lu et al., 1998; Yaghi et al., 1997), 1,3,5-benzenetricarboxylic acid (Plater et al., 1999), pyrazine (Carlucci et al., 1995), carboxyl-4-pyridine (MacGillivray et al., 1998), terephthalate (Lo et al., 2000), 1,2-bis(4-pyridyl)ethylene (Carlucci et al., 1999a; Jung et al., 1998), 1,4-bis(4-pyridyl)butadiyne (Blake et al., 1997), 1,2-bis(4-pyridyl)ethane (Carlucci et al., 2000), 1,2-bis(4-pyridyl)ethyne (Carlucci et al., 1999b), 3,6-bis(pyridin-3-yl)-1,2,4,5-tetrazine (Withersby et al., 1999), N,N'-p-phenylenedimethylene-bis(pyridin-4-one) (Goodgame et al., 1995) and 2,4,6-tris(4-pyridyl)-1,3,5-triazine (Fujita et al., 1998). Although many of these complex structures were obtained by chance to a certain extent, many polymers with specifically designed topologies have also been documented (Lehn & Rigault, 1998; Fujita et al., 1995; Noro et al., 2000). Recently, a systematic attempt has been made to determine the relationship between the molar ratio and the type of metal ions and ligands. The main focus of interest is on their remarkable structures and the self-assembly processes which have led to them (Beissel et al., 1996).

Recently, we have undertaken a series of investigations into metal-directed self-assembly, with the principal aim of obtaining supramolecular compounds or ordered coordination polymers. From this, a rigid organic ligand, p-aminobenzoate, has been chosen as a building block to react with transition metal ions and a series of coordination polymers with different topological structures have been generated. Here, we report the title polymeric ladder complex, (I), where the amino group of the p-aminobenzoate is uncoordinated. \sch

The present X-ray crystal structure analysis indicate that complex (I) is made up of a molecular ladder formed by the metal complex, nitrate anions and lattice water molecules. As illustrated in Fig.1, the coordination geometry around each Cu^II atom is Jahn-Teller distorted octahedral, where atoms O1W and O1, from an aqua ligand and the carboxyl group of the p-aminobenzoate, respectively, occupy the axial positions, and atom O2, from the carboxyl group of the p-aminobenzoate, atom N1, from one 4,4'-bipyridyl (4,4'-bipy) moiety, and atoms N2 and N3A from two different 4,4'-bipy ligands comprise the equatorial plane. Selected bond distances and angles are given in Table 1.

It is noted that the p-aminobenzoate acts as a bidentate chelating ligand in (I) (coordinated via the anionic carboxylate group), forming the lateral arm of the molecular ladders, with the amino group uncoordinated. Two 4,4'-bipy ligands and one p-aminobenzoate group form a T-shaped unit, producing a molecular ladder which extends along the whole crystal through the µ₂-4,4'-bipy bridge (Fig. 2). The dihedral angle between the two pyridyl rings of the 4,4'-bipy ligand along the rail of the ladder is 27.5 (1)°, and that between the pyridyl ring of the 4,4'-bipy on the rung and the phenyl ring of the p-aminobenzoate is 16.9 (1)°. It is notable that the lateral arms of each molecular ladder are threaded into the [Cu₄(4,4'-bipy)₄] squares of adjacent molecular ladders, and each [Cu₄(4,4'-bipy)₄] square includes two aromatic rings belonging to two p-aminobenzoate groups of adjacent molecular ladders, which penetrate along the opposite direction and are parallel to each other. In addition, there are hydrogen-bonding interactions between the amino H atom of the p-aminobenzoate and the O atom of one nitrate anion (Table 2).

This structural pattern is similar to that recently reported by Chen and co-workers (Tong et al., 2000), where they used p-hydroxybenzoic anions as building blocks that acted as the corresponding arms. In their case, the coordination geometry of the Cu^II atoms is also described as distorted octahedral, where two O atoms from an asymmetrically chelating carboxyl group of a p-hydroxybenzoic anion have analogous M—O lengths [Cu—O 1.992 (2) and 2.466 (3) Å] to those in (I). Moreover, the hydroxyl group of the p-hydroxybenzoic anion is also uncoordinated but is involved in different hydrogen-bonding interactions, namely with one O atom of a nitrate anion, compared with the amino group in (I).

S2. Experimental

To a stirred solution of Cu(NO₃)₂·4H₂O (0.260 g, 1.0 mmol) in methanol (10 ml), 4,4'-bipy (0.156 g, 1.0 mmol) and sodium p-aminobenzoate (0.157 g, 1.0 mmol) in methanol (15 ml) were added. The mixture was refluxed for 2 h and the precipitate was filtered out and dried in vacuo (yield: 81%). Analysis calculated for C₂₂H₂₄N₅O₈Cu: C 47.57, H 4.32, N 12.61; found: C 47.52, H 4.22, N 12.69%. Spectroscopic analysis: IR (KBr diffuse reflectance, ν, cm⁻¹): 3386, 1686, 1610, 1540, 1018.

S3. Refinement

The H-atom coordinates of three water molecules were located using the HYDROGEN program (Nardelli, 1999). The positions of all the other H atoms were fixed geometrically with distances as follows: C—H 0.96, N—H 0.86 and O—H 0.85 Å. One O atom of the p-aminobenzoate [O2 and O2'] and one N atom of the 4,4'-bipy [N3 and N3'] were found to be disordered over two sites, with occupancies of 0.60 (9) and 0.40 (9).

Computing details

Data collection: SMART (Bruker 2000; cell refinement: SMART; data reduction: SAINT (Bruker 2000); program(s) used to solve structure: SHELXTL (Bruker 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A perspective view of the crystal packing of (I). For clarity, labels are given only for the hydrogen-bond contacts.

catena-poly[[[µ-4,4'-bipyridyl-bis[aqua(p-aminobenzoato)copper(II)]]- di-µ-4,4'-bipyridyl] dinitrate tetrahydrate]

Crystal data

[Cu2(C7H6NO2)2(C10H8N2)3(H2O)2](NO3)2·4H2O	F(000) = 1136
Mr = 1100.00	Dx = 1.517 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6531 reflections
a = 11.102 (2) Å	θ = 2.5–27.1°
b = 15.478 (3) Å	µ = 0.96 mm^−1
c = 14.493 (3) Å	T = 293 K
β = 104.75 (1)°	Prism, dark blue
V = 2408.4 (8) Å^3	0.40 × 0.25 × 0.25 mm
Z = 2

Data collection

Bruker CCD area-detector diffractometer	4245 independent reflections
Radiation source: fine-focus sealed tube	3623 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→12
Tmin = 0.749, Tmax = 0.786	k = −11→18
12286 measured reflections	l = −16→17

Refinement

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) = 0.112	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0737P)^2 + 0.2627P] where P = (Fo^2 + 2Fc^2)/3
4245 reflections	(Δ/σ)max = 0.001
344 parameters	Δρmax = 0.57 e Å^−3
224 restraints	Δρmin = −0.44 e Å^−3

Special details

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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

treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.36484 (2)	0.667134 (18)	0.36424 (2)	0.02940 (14)
N1	0.40037 (18)	0.79010 (14)	0.41604 (15)	0.0338 (5)
N2	0.54381 (19)	0.66043 (13)	0.35766 (16)	0.0317 (5)
N4	0.0959 (3)	0.4040 (2)	−0.1358 (2)	0.0862 (11)
H4A	0.0562	0.4291	−0.1875	0.129*
H4B	0.1082	0.3491	−0.1352	0.129*
C1	0.5897 (2)	0.71620 (18)	0.3052 (2)	0.0406 (6)
H1A	0.5360	0.7565	0.2687	0.049*
C2	0.7120 (2)	0.71690 (18)	0.30263 (19)	0.0398 (6)
H2A	0.7397	0.7571	0.2650	0.048*
C3	0.7949 (2)	0.65770 (16)	0.35608 (18)	0.0325 (6)
C4	0.7458 (2)	0.59686 (18)	0.4069 (2)	0.0399 (6)
H4C	0.7965	0.5539	0.4412	0.048*
C5	0.6215 (2)	0.60054 (17)	0.4062 (2)	0.0393 (6)
H5A	0.5904	0.5596	0.4410	0.047*
C6	1.1104 (2)	0.73851 (17)	0.3481 (2)	0.0399 (6)
H6A	1.1452	0.7908	0.3365	0.048*
C7	0.9854 (2)	0.73754 (17)	0.3452 (2)	0.0405 (6)
H7A	0.9391	0.7883	0.3334	0.049*
C8	0.9290 (2)	0.66079 (15)	0.35982 (18)	0.0311 (6)
C9	1.0038 (2)	0.58769 (17)	0.37665 (19)	0.0350 (6)
H9A	0.9702	0.5346	0.3869	0.042*
C10	1.1274 (2)	0.59420 (17)	0.37808 (18)	0.0348 (6)
H10A	1.1773	0.5451	0.3877	0.042*
C11	0.3775 (2)	0.85868 (19)	0.3589 (2)	0.0419 (6)
H11A	0.3350	0.8504	0.2954	0.050*
C12	0.4134 (3)	0.94107 (18)	0.3890 (2)	0.0435 (7)
H12A	0.3937	0.9870	0.3465	0.052*
C13	0.4789 (2)	0.95583 (15)	0.48246 (19)	0.0347 (6)
C14	0.5018 (3)	0.88477 (18)	0.5412 (2)	0.0508 (7)
H14A	0.5446	0.8913	0.6049	0.061*
C15	0.4619 (3)	0.80381 (19)	0.5066 (2)	0.0481 (7)
H15A	0.4785	0.7570	0.5481	0.058*
C16	0.2883 (2)	0.60181 (17)	0.19554 (19)	0.0332 (6)
C17	0.2362 (2)	0.54891 (17)	0.11075 (18)	0.0369 (6)
C18	0.1680 (3)	0.58704 (19)	0.02700 (19)	0.0447 (7)
H18A	0.1541	0.6463	0.0256	0.054*
C19	0.1206 (3)	0.5393 (2)	−0.0535 (2)	0.0538 (8)
H19A	0.0751	0.5666	−0.1086	0.065*
C20	0.1394 (3)	0.4514 (2)	−0.0542 (2)	0.0523 (8)
C21	0.2066 (3)	0.4121 (2)	0.0292 (2)	0.0519 (7)
H21A	0.2198	0.3528	0.0303	0.062*
C22	0.2537 (3)	0.45996 (18)	0.1101 (2)	0.0433 (6)
H22A	0.2980	0.4324	0.1654	0.052*
O1W	0.39536 (16)	0.60068 (11)	0.50857 (12)	0.0403 (4)
H1WA	0.3564	0.6094	0.5512	0.048*
H1WB	0.4671	0.5813	0.5361	0.060*
O2W	0.61186 (19)	0.60017 (14)	0.64589 (15)	0.0586 (6)
H2WA	0.6665	0.6354	0.6369	0.088*
H2WB	0.6498	0.5581	0.6785	0.088*
O3W	0.2325 (2)	0.84117 (15)	0.10996 (19)	0.0689 (7)
H3WA	0.2474	0.7905	0.1326	0.103*
H3WB	0.1559	0.8517	0.1048	0.103*
N5	0.9057 (4)	0.6701 (3)	0.6221 (3)	0.0984 (14)
O1	0.29386 (19)	0.68251 (12)	0.19048 (14)	0.0463 (5)
O3	0.8057 (3)	0.7051 (2)	0.6158 (3)	0.1035 (10)
O4	0.9769 (4)	0.7096 (4)	0.5868 (3)	0.1600 (19)
O5	0.9308 (6)	0.6045 (3)	0.6581 (5)	0.225 (3)
O2	0.335 (2)	0.568 (2)	0.267 (2)	0.023 (3)	0.40 (9)
N3	1.179 (4)	0.675 (2)	0.365 (4)	0.028 (3)	0.40 (9)
N3'	1.185 (3)	0.6641 (18)	0.364 (2)	0.028 (2)	0.60 (9)
O2'	0.323 (2)	0.5627 (12)	0.2834 (17)	0.028 (2)	0.60 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02103 (19)	0.0276 (2)	0.0402 (2)	−0.00316 (11)	0.00908 (14)	−0.00619 (12)
N1	0.0281 (10)	0.0295 (11)	0.0446 (12)	−0.0042 (9)	0.0109 (9)	−0.0072 (9)
N2	0.0239 (10)	0.0298 (12)	0.0423 (12)	−0.0024 (8)	0.0100 (9)	−0.0028 (9)
N4	0.120 (3)	0.085 (2)	0.0427 (16)	−0.008 (2)	−0.0003 (17)	−0.0228 (15)
C1	0.0295 (13)	0.0436 (16)	0.0483 (15)	0.0049 (11)	0.0091 (11)	0.0103 (12)
C2	0.0304 (13)	0.0433 (16)	0.0484 (15)	0.0008 (11)	0.0146 (12)	0.0107 (12)
C3	0.0266 (13)	0.0346 (14)	0.0372 (13)	−0.0012 (10)	0.0098 (11)	−0.0042 (10)
C4	0.0302 (13)	0.0375 (15)	0.0544 (16)	0.0047 (11)	0.0151 (12)	0.0105 (12)
C5	0.0331 (13)	0.0320 (14)	0.0562 (16)	−0.0010 (11)	0.0180 (12)	0.0069 (12)
C6	0.0315 (13)	0.0280 (14)	0.0613 (17)	−0.0034 (11)	0.0140 (12)	−0.0012 (12)
C7	0.0295 (13)	0.0291 (14)	0.0641 (17)	0.0013 (11)	0.0141 (12)	−0.0006 (12)
C8	0.0254 (12)	0.0358 (14)	0.0326 (13)	−0.0015 (10)	0.0088 (10)	−0.0031 (10)
C9	0.0294 (13)	0.0310 (14)	0.0458 (14)	−0.0026 (10)	0.0115 (11)	0.0018 (11)
C10	0.0281 (12)	0.0326 (14)	0.0440 (14)	0.0009 (11)	0.0097 (11)	0.0002 (11)
C11	0.0394 (15)	0.0354 (15)	0.0463 (16)	−0.0067 (12)	0.0025 (12)	−0.0060 (12)
C12	0.0475 (16)	0.0320 (15)	0.0466 (15)	−0.0073 (12)	0.0039 (13)	−0.0015 (12)
C13	0.0328 (13)	0.0287 (14)	0.0443 (14)	−0.0063 (10)	0.0127 (11)	−0.0063 (11)
C14	0.0702 (19)	0.0358 (16)	0.0409 (15)	−0.0140 (14)	0.0041 (14)	−0.0068 (12)
C15	0.0627 (18)	0.0330 (15)	0.0461 (16)	−0.0088 (13)	0.0090 (14)	−0.0034 (12)
C16	0.0278 (12)	0.0374 (15)	0.0356 (15)	−0.0009 (11)	0.0102 (11)	−0.0006 (11)
C17	0.0350 (13)	0.0389 (15)	0.0373 (13)	−0.0049 (11)	0.0105 (11)	−0.0016 (11)
C18	0.0458 (15)	0.0461 (17)	0.0412 (15)	−0.0015 (13)	0.0090 (12)	0.0008 (12)
C19	0.0552 (18)	0.064 (2)	0.0372 (15)	−0.0038 (15)	0.0034 (13)	0.0041 (14)
C20	0.0586 (18)	0.062 (2)	0.0364 (15)	−0.0104 (15)	0.0127 (14)	−0.0115 (14)
C21	0.0618 (19)	0.0444 (17)	0.0492 (17)	−0.0047 (14)	0.0139 (15)	−0.0095 (13)
C22	0.0485 (16)	0.0442 (16)	0.0365 (14)	−0.0025 (13)	0.0095 (12)	−0.0015 (12)
O1W	0.0373 (10)	0.0417 (11)	0.0414 (10)	0.0009 (8)	0.0092 (8)	0.0041 (8)
O2W	0.0536 (12)	0.0482 (13)	0.0634 (14)	0.0001 (10)	−0.0048 (11)	0.0083 (10)
O3W	0.0637 (16)	0.0642 (16)	0.0809 (17)	0.0021 (11)	0.0221 (13)	0.0246 (12)
N5	0.079 (3)	0.107 (3)	0.116 (3)	−0.020 (2)	0.038 (2)	−0.067 (3)
O1	0.0520 (12)	0.0373 (12)	0.0479 (11)	−0.0028 (9)	0.0099 (9)	0.0006 (9)
O3	0.105 (2)	0.103 (2)	0.120 (3)	−0.027 (2)	0.060 (2)	−0.027 (2)
O4	0.083 (3)	0.274 (6)	0.132 (3)	−0.009 (3)	0.043 (2)	0.014 (4)
O5	0.214 (5)	0.045 (2)	0.363 (8)	0.024 (3)	−0.026 (5)	−0.025 (3)
O2	0.024 (4)	0.028 (4)	0.024 (6)	−0.006 (3)	0.019 (4)	−0.003 (4)
N3	0.023 (5)	0.024 (6)	0.040 (4)	−0.003 (5)	0.011 (4)	−0.005 (5)
N3'	0.023 (3)	0.025 (5)	0.037 (3)	0.004 (3)	0.008 (2)	−0.005 (4)
O2'	0.029 (4)	0.035 (3)	0.024 (5)	−0.004 (3)	0.014 (3)	0.004 (3)

Geometric parameters (Å, º)

Cu1—O2'	1.98 (2)	C11—C12	1.374 (4)
Cu1—N3'^i	2.00 (3)	C11—H11A	0.9300
Cu1—N2	2.016 (2)	C12—C13	1.383 (4)
Cu1—N1	2.047 (2)	C12—H12A	0.9300
Cu1—O2	2.05 (3)	C13—C14	1.374 (4)
Cu1—N3^i	2.07 (4)	C13—C13^ii	1.492 (5)
Cu1—O1W	2.2776 (18)	C14—C15	1.380 (4)
N1—C11	1.330 (4)	C14—H14A	0.9300
N1—C15	1.333 (4)	C15—H15A	0.9300
N2—C1	1.334 (3)	C16—O2	1.16 (3)
N2—C5	1.338 (3)	C16—O1	1.254 (3)
N4—C20	1.370 (4)	C16—O2'	1.37 (2)
N4—H4A	0.8600	C16—C17	1.467 (4)
N4—H4B	0.8600	C17—C18	1.388 (4)
C1—C2	1.368 (3)	C17—C22	1.391 (4)
C1—H1A	0.9300	C18—C19	1.368 (4)
C2—C3	1.387 (4)	C18—H18A	0.9300
C2—H2A	0.9300	C19—C20	1.378 (5)
C3—C4	1.390 (4)	C19—H19A	0.9300
C3—C8	1.476 (4)	C20—C21	1.388 (4)
C4—C5	1.378 (4)	C21—C22	1.373 (4)
C4—H4C	0.9300	C21—H21A	0.9300
C5—H5A	0.9300	C22—H22A	0.9300
C6—N3	1.23 (3)	O1W—H1WA	0.8498
C6—C7	1.377 (3)	O1W—H1WB	0.8501
C6—N3'	1.40 (3)	O2W—H2WA	0.8498
C6—H6A	0.9300	O2W—H2WB	0.8501
C7—C8	1.384 (4)	O3W—H3WA	0.8503
C7—H7A	0.9300	O3W—H3WB	0.8500
C8—C9	1.388 (3)	N5—O5	1.143 (6)
C9—C10	1.371 (3)	N5—O4	1.211 (6)
C9—H9A	0.9300	N5—O3	1.219 (5)
C10—N3'	1.30 (3)	N3—Cu1^iii	2.07 (3)
C10—N3	1.41 (4)	N3'—Cu1^iii	2.00 (3)
C10—H10A	0.9300
O2'—Cu1—N3'^i	84.0 (15)	N3'—C10—N3	6 (2)
O2'—Cu1—N2	90.9 (8)	C9—C10—N3	120.2 (13)
N3'^i—Cu1—N2	174.9 (9)	N3'—C10—H10A	114.1
O2'—Cu1—N1	165.9 (7)	C9—C10—H10A	119.9
N3'^i—Cu1—N1	97.0 (8)	N3—C10—H10A	119.9
N2—Cu1—N1	88.00 (8)	N1—C11—C12	123.3 (3)
O2'—Cu1—O2	8.5 (9)	N1—C11—H11A	118.3
N3'^i—Cu1—O2	89.7 (13)	C12—C11—H11A	118.3
N2—Cu1—O2	85.3 (7)	C11—C12—C13	120.1 (3)
N1—Cu1—O2	158.4 (10)	C11—C12—H12A	119.9
O2'—Cu1—N3^i	88.1 (13)	C13—C12—H12A	119.9
N3'^i—Cu1—N3^i	4.7 (15)	C14—C13—C12	116.3 (2)
N2—Cu1—N3^i	177.6 (14)	C14—C13—C13^ii	122.0 (3)
N1—Cu1—N3^i	92.4 (9)	C12—C13—C13^ii	121.7 (3)
O2—Cu1—N3^i	93.5 (10)	C13—C14—C15	120.7 (3)
O2'—Cu1—O1W	97.6 (7)	C13—C14—H14A	119.7
N3'^i—Cu1—O1W	84.6 (9)	C15—C14—H14A	119.7
N2—Cu1—O1W	95.87 (8)	N1—C15—C14	122.6 (3)
N1—Cu1—O1W	96.51 (8)	N1—C15—H15A	118.7
O2—Cu1—O1W	104.6 (10)	C14—C15—H15A	118.7
N3^i—Cu1—O1W	86.4 (14)	O2—C16—O1	119.0 (14)
C11—N1—C15	117.0 (2)	O2—C16—O2'	10.2 (17)
C11—N1—Cu1	121.67 (18)	O1—C16—O2'	119.2 (8)
C15—N1—Cu1	120.77 (19)	O2—C16—C17	119.2 (13)
C1—N2—C5	117.3 (2)	O1—C16—C17	121.4 (2)
C1—N2—Cu1	121.17 (17)	O2'—C16—C17	119.2 (8)
C5—N2—Cu1	121.51 (17)	C18—C17—C22	117.5 (3)
C20—N4—H4A	120.0	C18—C17—C16	120.4 (2)
C20—N4—H4B	120.0	C22—C17—C16	122.1 (2)
H4A—N4—H4B	120.0	C19—C18—C17	121.5 (3)
N2—C1—C2	123.1 (2)	C19—C18—H18A	119.3
N2—C1—H1A	118.4	C17—C18—H18A	119.3
C2—C1—H1A	118.4	C18—C19—C20	120.9 (3)
C1—C2—C3	120.1 (2)	C18—C19—H19A	119.6
C1—C2—H2A	120.0	C20—C19—H19A	119.6
C3—C2—H2A	120.0	N4—C20—C19	120.9 (3)
C2—C3—C4	116.7 (2)	N4—C20—C21	120.7 (3)
C2—C3—C8	121.2 (2)	C19—C20—C21	118.3 (3)
C4—C3—C8	122.0 (2)	C22—C21—C20	120.8 (3)
C5—C4—C3	119.7 (2)	C22—C21—H21A	119.6
C5—C4—H4C	120.2	C20—C21—H21A	119.6
C3—C4—H4C	120.2	C21—C22—C17	121.1 (3)
N2—C5—C4	122.9 (2)	C21—C22—H22A	119.5
N2—C5—H5A	118.5	C17—C22—H22A	119.5
C4—C5—H5A	118.5	Cu1—O1W—H1WA	127.7
N3—C6—C7	124 (2)	Cu1—O1W—H1WB	119.6
N3—C6—N3'	3 (3)	H1WA—O1W—H1WB	107.7
C7—C6—N3'	122.8 (12)	H2WA—O2W—H2WB	107.7
N3—C6—H6A	117.8	H3WA—O3W—H3WB	107.7
C7—C6—H6A	117.8	O5—N5—O4	122.2 (6)
N3'—C6—H6A	119.4	O5—N5—O3	122.7 (6)
C6—C7—C8	119.8 (2)	O4—N5—O3	115.1 (6)
C6—C7—H7A	120.1	C16—O2—Cu1	103.5 (19)
C8—C7—H7A	120.1	C6—N3—C10	119 (3)
C7—C8—C9	116.9 (2)	C6—N3—Cu1^iii	128 (3)
C7—C8—C3	120.9 (2)	C10—N3—Cu1^iii	112.8 (17)
C9—C8—C3	122.2 (2)	C10—N3'—C6	115 (2)
C10—C9—C8	119.6 (2)	C10—N3'—Cu1^iii	123.3 (18)
C10—C9—H9A	120.2	C6—N3'—Cu1^iii	121.8 (17)
C8—C9—H9A	120.2	C16—O2'—Cu1	99.0 (10)
N3'—C10—C9	126.0 (13)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O3^iv	0.86	2.41	3.255 (5)	166
N4—H4B···O4^iv	0.86	2.53	3.240 (7)	141
O1W—H1WB···O2W	0.85	1.97	2.702 (3)	143
O1W—H1WA···O3W^v	0.85	1.95	2.755 (3)	158
O2W—H2WA···O3	0.85	1.97	2.817 (4)	173
O2W—H2WB···O2^vi	0.85	2.09	2.89 (4)	155
O3W—H3WB···O4^vii	0.85	2.16	2.881 (5)	143

Symmetry codes: (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+3/2, z+1/2; (vi) −x+1, −y+1, −z+1; (vii) x−1, −y+3/2, z−1/2.