(Azido-[kappa]N)bis­(di-2-pyridylamine)­copper(II) hexa­fluoro­phosphate and (azido-[kappa]N)bis­(di-2-pyridylamine)­copper(II) chloride tetra­hydrate

The two new title complexes, [Cu(N₃)(dpyam)₂]PF₆ (dpyam is di-2-pyridylamine, C₁₀H₁₁N₃), (I), and [Cu(N₃)(dpyam)₂]Cl·4H₂O, (II), respectively, have been characterized by single-crystal X-ray diffraction. Both complexes display a distorted square-pyramidal geometry. Each Cu atom is coordinated in the basal plane by three dpyam N atoms and one azide N atom in equatorial positions, and by another N atom from the dpyam group in the apical position. In complex (I), the one-dimensional supra­molecular architecture is assembled via hydrogen-bonding inter­actions between the amine N atom and terminal azide N atoms and the F atoms of the PF₆^- anion. For complex (II), hydrogen-bonding inter­actions between the amine N atom, the Cl^- anion and water O atoms result in a two-dimensional lattice.

S1. Comment

The synthesis of pseudohalide bridged complexes continues to be a subject of much interest, and intensive investigations have taken place as a result of their diverse structures and potential applications in magnetic materials. Pseudohalide (OCN^-, SCN^-, N₃^- etc.) ligands can coordinate to transition metal atoms in different ways, for example as a terminal ligand or as a bridge (Talukder et al., 2004). One-, two- or three-dimensional supramolecular architectures assembled via intermolecular non-covalent interactions are of considerable interest for the crystal engineering of new functional solid-state materials, as well as for their fascinating structures (Gao et al., 2001). Hydrogen bonding, which combines directionality, selectivity and strength, has been noted as the most versatile organizing force for supramolecular assembly (Chen et al., 2001). We report here the two new title complexes, [Cu(dpyam)₂(N₃)]PF₆, (I), and [Cu(dpyam)₂(N₃)]Cl·(H₂O)₄, (II). The dpyam ligand has been selected primarily because it also has an N—H hydrogen-bond donor function that might produce one-, two- or three-dimensional supramolecular architectures.

The crystal structures of (I) and (II) (Figs. 1 and 2) consist of a [Cu(dpyam)₂(N₃)]⁺ cation and PF₆^- and Cl^- anions, respectively. The Cu atoms of both molecules exhibit five-coordination of the CuN₄N' chromophore (see scheme). The coordination around each Cu atom consists of three dpyam N atoms and one azido N atom in equatorial positions, and in the apical position is the other N atom from dpyam. Both complexes exhibit a slightly distorted square-pyramidal environment, the geometric τ values (Addison et al., 1984) being 0.061 for (I) and 0.148 for (II). The Cu—N distances are shown in Tables 1 and 3. The average Cu—N distances in the equatorial positions are 2.017 (1) Å for (I) and 2.009 (1) Å for (II). The axial Cu—N distances are longer, at 2.153 (2) Å for (I) and 2.169 (2) Å for (II). The Cu atoms are displaced by 0.264 (1) Å for (I) and 0.255 (1) Å for (II) from the mean basal plane towards the apical position. The dpyam ligands are not planar, with dihedral angles between the two pyridine rings of 34.4 (1) and 16.1 (1)° for (I) and 35.3 (1) and 14.6 (1)° for (II).

There are extensive hydrogen-bonding interactions in the both structures. In complex (I), the intermolecular hydrogen-bonding interactions between N—H···F and N—H···N(azido) (Table 2) produce a one-dimensional chain (Fig. 3). The crystal packing of complex (II) is stabilized by intermolecular N—H···Cl, O—H···N(azido), O—H···Cl and O—H···O hydrogen bonds (Table 4) leading to a two-dimensional supramolecular structure (Fig. 4).

The chromophores of (I) and (II) are very similar except for the four additional water molecules in the asymmetric unit of complex (II), which create a two-dimensional hydrogen-bonded network in (II).

Related literature

For related literature, see: Addison et al. (1984); Chen et al. (2001); Gao et al. (2001); Sheldrick (2000b); Talukder et al. (2004).

S2. Experimental

Complex (I) was prepared by adding a warm solution of di-2-pyridylamine (0.17 g, 1.00 mmol) in methanol (15 ml) to a hot aqueous solution (10 ml) containing Cu(CH₃COO)₂·H₂O (0.091 g, 0.5 mmol) and NaN₃ (0.065 g, 1.0 mmol). An aqueous solution (15 ml) of KPF₆ (0.184 g, 1.0 mmol) was then added, giving a clear green solution. The resulting solution was slowly evaporated at room temperature. After several days, green needle-shaped crystals of (I) were formed which were filtered off, washed with mother liquor and air-dried (yield ca 90%).

Green needle crystals of (II) were obtained by adding a warm solution of di-2-pyridylamine (0.171 g, 1.0 mmol) in methanol (15 ml) to a boiling aqueous solution (15 ml) of CuCl₂·2H₂O (0.085 g, 0.5 mmol). NaN₃ (0.130 g, 2.0 mmol) was then added to the reaction mixture. After several days, crystals of (II) were formed which were filtered off, washed with mother liquor and air-dried (yield ca 85%).

The electronic reflectance spectra of both complexes involve main peaks at 14050 and 14000 cm^-1 and lower energy shoulders at 11010 and 11110 cm^-1 for (I) and (II), respectively. These spectroscopic characteristics of the compounds are consistent with the distorted square-pyramidal geometry with a small τ value. The transitions may be assigned as the d_z² → d_x²-_y² transition for the low-energy shoulder and the d_xz ~ d_yz → d_x²-_y² transition for the high-energy peak. The strongest intensity features in the spectra of (I) and (II) appear at 2042 and 2040 cm^-1, respectively, together with sharp and medium intensity peaks at 2035 and 2034 cm^-1, respectively, attributed to ν_as(N₃). For the IR spectrum of sodium azide, a single strong peak at 2033 cm^-1 is observed. Hence, in the present compounds, the shift towards higher wavenumbers of the ν_as stretching of the azide indicates that it must be coordinated.

S3. Refinement

In (I), H atoms attached to N3 and N6 were located in a difference Fourier map and refined with a DFIX (SHELXTL; Sheldrick, 2000b) restraint of N—H = 0.86 (1) Å. The remaining H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 Å and with U_iso(H) = 1.2U_eq(C) [Please check added text]. The F atoms of the PF₆ group showed disorder; the occupancies of the disordered positions were initially refined and later fixed at 0.5.

In (II), H atoms attached to water O atoms were located in difference Fourier maps and refined with a DFIX restraint of O—H = 0.90 (1) Å. The remaining H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 Å and N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(C,N) [Please check added text].

Computing details

Data collection: SMART (Bruker, 2000) for (I); MACH3 (Enraf–Nonius, 1993) for (II). Cell refinement: SAINT (Bruker, 2000) for (I); MACH3 for (II). Data reduction: SAINT for (I); MolEN (Fair, 1990) for (II). For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2000b); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of (II), with 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. A packing diagram for (I) with hydrogen bonds (dashed lines), showing the one-dimensional structure.
	Fig. 4. A packing diagram for (II) with hydrogen bonds (dashed lines), showing the two-dimensional structure.

(I) (Azido-κN)bis(di-2-pyridylamine)copper(II) hexafluorophosphate

Crystal data

[Cu(N3)(C10H11N3)2]PF6	F(000) = 1196
Mr = 592.94	Dx = 1.683 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 20720 reflections
a = 14.1074 (8) Å	θ = 1.7–28.3°
b = 8.5839 (5) Å	µ = 1.08 mm^−1
c = 19.4144 (11) Å	T = 298 K
β = 95.635 (1)°	Needle, green
V = 2339.7 (2) Å^3	0.31 × 0.21 × 0.11 mm
Z = 4

Data collection

Siemens SMART CCD area detector diffractometer	5804 independent reflections
Radiation source: fine-focus sealed tube	4381 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000a)	h = −17→18
Tmin = 0.769, Tmax = 0.884	k = −11→11
19955 measured reflections	l = −25→25

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0547P)^2 + 0.9007P] where P = (Fo^2 + 2Fc^2)/3
5635 reflections	(Δ/σ)max < 0.001
397 parameters	Δρmax = 0.39 e Å^−3
2 restraints	Δρmin = −0.22 e Å^−3

Special details

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)
H5	0.6160 (19)	0.426 (3)	0.4399 (10)	0.054 (8)*
Cu1	0.570147 (19)	0.50403 (3)	0.236855 (13)	0.03382 (10)
P1	0.31278 (5)	0.70725 (8)	0.40283 (4)	0.04793 (18)
N1	0.59821 (14)	0.6512 (2)	0.31640 (10)	0.0370 (4)
N2	0.49990 (14)	0.3691 (2)	0.30004 (10)	0.0398 (5)
N3	0.59923 (17)	0.4481 (3)	0.39722 (11)	0.0493 (5)
N4	0.44637 (14)	0.5883 (2)	0.17416 (10)	0.0403 (5)
N5	0.57562 (14)	0.3218 (2)	0.17021 (9)	0.0366 (4)
N6	0.45768 (17)	0.4085 (3)	0.08334 (11)	0.0489 (6)
N7	0.66685 (15)	0.6195 (3)	0.18704 (10)	0.0459 (5)
N8	0.65241 (15)	0.6322 (2)	0.12557 (11)	0.0417 (5)
N9	0.6401 (2)	0.6466 (3)	0.06652 (12)	0.0696 (8)
C1	0.61004 (19)	0.8047 (3)	0.30363 (14)	0.0459 (6)
H1	0.5988	0.8396	0.2582	0.055*
C2	0.6377 (2)	0.9113 (3)	0.35414 (16)	0.0548 (7)
H2	0.6449	1.0158	0.3433	0.066*
C3	0.6545 (2)	0.8599 (4)	0.42144 (16)	0.0594 (8)
H3	0.6741	0.9294	0.4567	0.071*
C4	0.6420 (2)	0.7064 (4)	0.43577 (13)	0.0525 (7)
H4	0.6532	0.6702	0.4810	0.063*
C5	0.61236 (16)	0.6034 (3)	0.38198 (12)	0.0386 (5)
C6	0.52824 (18)	0.3515 (3)	0.36700 (12)	0.0396 (5)
C7	0.4893 (2)	0.2377 (3)	0.40724 (15)	0.0558 (7)
H7	0.5126	0.2240	0.4533	0.067*
C8	0.4172 (3)	0.1476 (3)	0.37822 (17)	0.0657 (9)
H8	0.3908	0.0709	0.4043	0.079*
C9	0.3834 (2)	0.1702 (3)	0.30987 (17)	0.0627 (8)
H9	0.3326	0.1117	0.2896	0.075*
C10	0.42589 (19)	0.2799 (3)	0.27277 (14)	0.0520 (7)
H10	0.4033	0.2945	0.2266	0.062*
C11	0.4075 (2)	0.7201 (3)	0.19623 (15)	0.0550 (7)
H11	0.4199	0.7468	0.2427	0.066*
C12	0.3510 (2)	0.8163 (4)	0.15455 (18)	0.0711 (10)
H12	0.3263	0.9072	0.1718	0.085*
C13	0.3316 (3)	0.7757 (4)	0.08626 (18)	0.0783 (11)
H13	0.2947	0.8407	0.0561	0.094*
C14	0.3665 (2)	0.6396 (4)	0.06277 (15)	0.0626 (8)
H14	0.3519	0.6087	0.0170	0.075*
C15	0.42454 (17)	0.5475 (3)	0.10858 (13)	0.0399 (5)
C16	0.52202 (18)	0.2993 (3)	0.11050 (12)	0.0415 (5)
C17	0.5308 (3)	0.1631 (4)	0.07217 (17)	0.0702 (10)
H17	0.4926	0.1480	0.0309	0.084*
C18	0.5957 (3)	0.0522 (4)	0.0954 (2)	0.0745 (10)
H18	0.6021	−0.0384	0.0700	0.089*
C19	0.6517 (2)	0.0760 (3)	0.15711 (15)	0.0538 (7)
H19	0.6962	0.0021	0.1742	0.065*
C20	0.63977 (17)	0.2098 (3)	0.19174 (13)	0.0431 (6)
H20	0.6779	0.2263	0.2330	0.052*
F1	0.2536 (6)	0.8287 (12)	0.3699 (6)	0.159 (5)	0.50
F2	0.4030 (7)	0.7743 (11)	0.3725 (4)	0.083 (3)	0.50
F3	0.3334 (9)	0.5749 (11)	0.4493 (6)	0.170 (6)	0.50
F4	0.2319 (6)	0.6336 (11)	0.4380 (6)	0.122 (4)	0.50
F5	0.3096 (10)	0.8409 (14)	0.4564 (6)	0.111 (5)	0.50
F6	0.3140 (8)	0.5686 (14)	0.3484 (6)	0.119 (4)	0.50
F1A	0.2788 (6)	0.8411 (7)	0.3458 (4)	0.112 (3)	0.50
F2A	0.4147 (7)	0.7553 (15)	0.3955 (6)	0.143 (5)	0.50
F3A	0.3863 (7)	0.5884 (10)	0.4504 (4)	0.119 (4)	0.50
F4A	0.2007 (5)	0.6689 (13)	0.4027 (6)	0.121 (4)	0.50
F5A	0.3306 (12)	0.8104 (18)	0.4700 (8)	0.115 (4)	0.50
F6A	0.3035 (9)	0.6021 (13)	0.3388 (3)	0.101 (4)	0.50
H15	0.432 (2)	0.393 (4)	0.0418 (11)	0.070 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03666 (16)	0.03901 (17)	0.02500 (15)	−0.00203 (12)	−0.00090 (11)	0.00146 (11)
P1	0.0561 (4)	0.0403 (4)	0.0471 (4)	−0.0067 (3)	0.0038 (3)	−0.0013 (3)
N1	0.0399 (11)	0.0393 (10)	0.0322 (10)	−0.0035 (8)	0.0051 (8)	−0.0002 (8)
N2	0.0436 (11)	0.0430 (11)	0.0327 (10)	−0.0064 (9)	0.0025 (8)	0.0010 (8)
N3	0.0622 (14)	0.0521 (13)	0.0309 (11)	−0.0070 (11)	−0.0086 (10)	0.0097 (10)
N4	0.0398 (11)	0.0470 (12)	0.0332 (10)	0.0068 (9)	−0.0012 (8)	0.0004 (9)
N5	0.0395 (10)	0.0392 (11)	0.0304 (10)	0.0013 (8)	−0.0009 (8)	0.0011 (8)
N6	0.0583 (14)	0.0486 (13)	0.0355 (11)	0.0068 (11)	−0.0170 (10)	−0.0065 (10)
N7	0.0477 (12)	0.0584 (14)	0.0316 (10)	−0.0094 (10)	0.0044 (9)	−0.0005 (9)
N8	0.0471 (12)	0.0403 (11)	0.0386 (12)	−0.0044 (9)	0.0088 (9)	−0.0038 (9)
N9	0.091 (2)	0.0837 (19)	0.0332 (12)	−0.0138 (16)	0.0048 (12)	0.0017 (12)
C1	0.0517 (15)	0.0410 (14)	0.0464 (14)	−0.0040 (11)	0.0117 (12)	0.0036 (11)
C2	0.0599 (17)	0.0393 (15)	0.0665 (19)	−0.0115 (12)	0.0131 (14)	−0.0090 (13)
C3	0.0585 (17)	0.0594 (18)	0.0597 (18)	−0.0146 (14)	0.0032 (14)	−0.0246 (15)
C4	0.0549 (16)	0.0672 (19)	0.0341 (13)	−0.0045 (14)	−0.0028 (11)	−0.0107 (12)
C5	0.0364 (12)	0.0464 (14)	0.0325 (11)	−0.0033 (10)	0.0007 (9)	−0.0009 (10)
C6	0.0476 (14)	0.0371 (12)	0.0346 (12)	−0.0001 (10)	0.0065 (10)	0.0012 (10)
C7	0.080 (2)	0.0448 (15)	0.0439 (15)	−0.0036 (14)	0.0130 (14)	0.0087 (12)
C8	0.091 (2)	0.0443 (16)	0.066 (2)	−0.0191 (16)	0.0293 (18)	0.0033 (14)
C9	0.0656 (19)	0.0541 (17)	0.071 (2)	−0.0248 (15)	0.0183 (16)	−0.0112 (15)
C10	0.0528 (16)	0.0573 (17)	0.0459 (15)	−0.0127 (13)	0.0054 (12)	−0.0062 (13)
C11	0.0515 (16)	0.0669 (18)	0.0451 (15)	0.0175 (14)	−0.0024 (12)	−0.0091 (13)
C12	0.069 (2)	0.066 (2)	0.074 (2)	0.0340 (17)	−0.0158 (17)	−0.0123 (16)
C13	0.086 (2)	0.071 (2)	0.070 (2)	0.0339 (19)	−0.0334 (18)	−0.0003 (17)
C14	0.073 (2)	0.0615 (18)	0.0476 (16)	0.0162 (15)	−0.0243 (14)	−0.0034 (14)
C15	0.0378 (13)	0.0421 (13)	0.0378 (13)	0.0002 (10)	−0.0061 (10)	0.0004 (10)
C16	0.0481 (14)	0.0382 (13)	0.0365 (12)	−0.0011 (11)	−0.0043 (10)	−0.0014 (10)
C17	0.089 (2)	0.0521 (17)	0.0628 (19)	0.0109 (16)	−0.0273 (17)	−0.0226 (15)
C18	0.092 (3)	0.0450 (16)	0.083 (2)	0.0129 (17)	−0.014 (2)	−0.0207 (16)
C19	0.0552 (17)	0.0435 (15)	0.0622 (18)	0.0075 (13)	0.0033 (14)	0.0047 (13)
C20	0.0408 (13)	0.0472 (14)	0.0403 (13)	0.0039 (11)	−0.0016 (10)	0.0060 (11)
F1	0.076 (4)	0.200 (9)	0.200 (10)	0.069 (5)	0.011 (5)	0.107 (7)
F2	0.103 (7)	0.069 (3)	0.086 (3)	−0.032 (4)	0.054 (4)	−0.014 (3)
F3	0.245 (13)	0.089 (5)	0.148 (7)	−0.056 (8)	−0.118 (8)	0.070 (5)
F4	0.120 (7)	0.084 (5)	0.181 (9)	−0.051 (6)	0.108 (7)	−0.036 (6)
F5	0.193 (12)	0.054 (3)	0.100 (8)	−0.041 (6)	0.085 (9)	−0.040 (4)
F6	0.094 (5)	0.080 (5)	0.192 (10)	−0.025 (4)	0.063 (5)	−0.077 (6)
F1A	0.168 (8)	0.058 (3)	0.097 (4)	−0.036 (4)	−0.049 (5)	0.035 (3)
F2A	0.031 (3)	0.129 (7)	0.265 (13)	−0.011 (3)	−0.005 (5)	−0.037 (8)
F3A	0.186 (8)	0.112 (6)	0.054 (3)	0.086 (6)	−0.011 (4)	0.009 (3)
F4A	0.049 (3)	0.090 (5)	0.222 (11)	−0.007 (3)	0.006 (4)	−0.041 (6)
F5A	0.140 (6)	0.120 (10)	0.083 (5)	0.000 (5)	−0.009 (4)	−0.052 (5)
F6A	0.169 (8)	0.097 (6)	0.037 (2)	−0.060 (5)	0.009 (3)	−0.021 (3)

Geometric parameters (Å, º)

Cu1—N1	2.0046 (19)	C1—H1	0.9300
Cu1—N7	2.009 (2)	C2—C3	1.377 (4)
Cu1—N2	2.0166 (19)	C2—H2	0.9300
Cu1—N5	2.0361 (19)	C3—C4	1.361 (4)
Cu1—N4	2.1534 (19)	C3—H3	0.9300
P1—F1	1.445 (7)	C4—C5	1.401 (3)
P1—F3	1.461 (8)	C4—H4	0.9300
P1—F2A	1.516 (9)	C6—C7	1.396 (3)
P1—F4	1.522 (6)	C7—C8	1.356 (4)
P1—F6A	1.531 (8)	C7—H7	0.9300
P1—F5	1.552 (12)	C8—C9	1.379 (5)
P1—F2	1.564 (7)	C8—H8	0.9300
P1—F5A	1.576 (14)	C9—C10	1.360 (4)
P1—F6	1.593 (10)	C9—H9	0.9300
P1—F4A	1.615 (8)	C10—H10	0.9300
P1—F1A	1.634 (7)	C11—C12	1.358 (4)
P1—F3A	1.668 (7)	C11—H11	0.9300
N1—C5	1.334 (3)	C12—C13	1.372 (4)
N1—C1	1.354 (3)	C12—H12	0.9300
N2—C6	1.331 (3)	C13—C14	1.364 (4)
N2—C10	1.360 (3)	C13—H13	0.9300
N3—C5	1.382 (3)	C14—C15	1.394 (4)
N3—C6	1.385 (3)	C14—H14	0.9300
N3—H5	0.859 (17)	C16—C17	1.398 (4)
N4—C15	1.327 (3)	C17—C18	1.365 (4)
N4—C11	1.345 (3)	C17—H17	0.9300
N5—C16	1.335 (3)	C18—C19	1.384 (4)
N5—C20	1.358 (3)	C18—H18	0.9300
N6—C16	1.374 (3)	C19—C20	1.350 (4)
N6—C15	1.389 (3)	C19—H19	0.9300
N6—H15	0.863 (18)	C20—H20	0.9300
N7—N8	1.196 (3)	F1—F1A	0.624 (14)
N8—N9	1.149 (3)	F3—F3A	0.754 (15)
C1—C2	1.369 (4)	F4—F4A	0.834 (14)
N1—Cu1—N7	88.15 (8)	C6—N3—H5	113 (2)
N1—Cu1—N2	88.00 (8)	C15—N4—C11	117.6 (2)
N7—Cu1—N2	166.76 (8)	C15—N4—Cu1	123.53 (16)
N1—Cu1—N5	163.10 (8)	C11—N4—Cu1	115.85 (16)
N7—Cu1—N5	90.18 (8)	C16—N5—C20	117.9 (2)
N2—Cu1—N5	89.82 (8)	C16—N5—Cu1	127.57 (16)
N1—Cu1—N4	108.15 (8)	C20—N5—Cu1	114.47 (15)
N7—Cu1—N4	96.51 (8)	C16—N6—C15	133.1 (2)
N2—Cu1—N4	96.73 (8)	C16—N6—H15	117 (2)
N5—Cu1—N4	88.75 (8)	C15—N6—H15	109 (2)
F1—P1—F3	154.8 (7)	N8—N7—Cu1	117.91 (17)
F1—P1—F2A	105.9 (6)	N9—N8—N7	178.6 (3)
F3—P1—F2A	97.8 (7)	N1—C1—C2	123.4 (3)
F1—P1—F4	94.1 (5)	N1—C1—H1	118.3
F3—P1—F4	60.9 (6)	C2—C1—H1	118.3
F2A—P1—F4	156.1 (7)	C1—C2—C3	118.4 (3)
F1—P1—F6A	93.8 (7)	C1—C2—H2	120.8
F3—P1—F6A	92.2 (6)	C3—C2—H2	120.8
F2A—P1—F6A	95.2 (6)	C4—C3—C2	119.3 (3)
F4—P1—F6A	96.4 (6)	C4—C3—H3	120.3
F1—P1—F5	73.1 (8)	C2—C3—H3	120.3
F3—P1—F5	100.3 (7)	C3—C4—C5	119.6 (3)
F2A—P1—F5	87.2 (7)	C3—C4—H4	120.2
F4—P1—F5	86.3 (5)	C5—C4—H4	120.2
F6A—P1—F5	166.8 (7)	N1—C5—N3	119.4 (2)
F1—P1—F2	91.4 (5)	N1—C5—C4	121.5 (2)
F3—P1—F2	113.5 (7)	N3—C5—C4	119.1 (2)
F4—P1—F2	174.1 (6)	N2—C6—N3	118.8 (2)
F6A—P1—F2	85.4 (5)	N2—C6—C7	121.9 (2)
F5—P1—F2	93.3 (5)	N3—C6—C7	119.3 (2)
F1—P1—F5A	89.9 (7)	C8—C7—C6	119.1 (3)
F3—P1—F5A	85.4 (7)	C8—C7—H7	120.4
F2A—P1—F5A	81.3 (8)	C6—C7—H7	120.4
F4—P1—F5A	85.9 (7)	C7—C8—C9	119.6 (3)
F6A—P1—F5A	175.5 (8)	C7—C8—H8	120.2
F2—P1—F5A	92.0 (7)	C9—C8—H8	120.2
F1—P1—F6	106.8 (7)	C10—C9—C8	118.6 (3)
F3—P1—F6	79.3 (7)	C10—C9—H9	120.7
F2A—P1—F6	94.0 (6)	C8—C9—H9	120.7
F4—P1—F6	92.5 (5)	N2—C10—C9	123.0 (3)
F5—P1—F6	178.7 (6)	N2—C10—H10	118.5
F2—P1—F6	87.9 (5)	C9—C10—H10	118.5
F5A—P1—F6	163.2 (8)	N4—C11—C12	123.7 (3)
F1—P1—F4A	67.9 (5)	N4—C11—H11	118.1
F3—P1—F4A	88.7 (6)	C12—C11—H11	118.1
F2A—P1—F4A	173.2 (6)	C11—C12—C13	118.1 (3)
F6A—P1—F4A	82.7 (6)	C11—C12—H12	121.0
F5—P1—F4A	93.4 (6)	C13—C12—H12	121.0
F2—P1—F4A	155.2 (5)	C14—C13—C12	119.7 (3)
F5A—P1—F4A	101.1 (7)	C14—C13—H13	120.1
F6—P1—F4A	85.4 (6)	C12—C13—H13	120.1
F3—P1—F1A	172.5 (4)	C13—C14—C15	118.8 (3)
F2A—P1—F1A	87.9 (5)	C13—C14—H14	120.6
F4—P1—F1A	114.4 (5)	C15—C14—H14	120.6
F6A—P1—F1A	82.4 (5)	N4—C15—N6	120.7 (2)
F5—P1—F1A	84.7 (6)	N4—C15—C14	121.9 (2)
F2—P1—F1A	71.5 (5)	N6—C15—C14	117.3 (2)
F5A—P1—F1A	100.2 (6)	N5—C16—N6	122.1 (2)
F6—P1—F1A	95.6 (5)	N5—C16—C17	120.7 (2)
F4A—P1—F1A	85.4 (5)	N6—C16—C17	117.2 (2)
F1—P1—F3A	170.8 (6)	C18—C17—C16	119.9 (3)
F2A—P1—F3A	71.0 (6)	C18—C17—H17	120.0
F4—P1—F3A	87.2 (5)	C16—C17—H17	120.0
F6A—P1—F3A	95.1 (5)	C17—C18—C19	119.4 (3)
F5—P1—F3A	98.0 (6)	C17—C18—H18	120.3
F2—P1—F3A	87.0 (5)	C19—C18—H18	120.3
F5A—P1—F3A	81.1 (7)	C20—C19—C18	117.9 (3)
F6—P1—F3A	82.2 (5)	C20—C19—H19	121.1
F4A—P1—F3A	115.6 (5)	C18—C19—H19	121.1
F1A—P1—F3A	158.5 (5)	C19—C20—N5	124.1 (2)
C5—N1—C1	117.7 (2)	C19—C20—H20	117.9
C5—N1—Cu1	122.74 (16)	N5—C20—H20	117.9
C1—N1—Cu1	119.40 (17)	F1A—F1—P1	96.2 (13)
C6—N2—C10	117.5 (2)	F3A—F3—P1	92.0 (13)
C6—N2—Cu1	122.75 (16)	F4A—F4—P1	80.8 (10)
C10—N2—Cu1	119.42 (17)	F1—F1A—P1	61.5 (10)
C5—N3—C6	126.4 (2)	F3—F3A—P1	61.1 (10)
C5—N3—H5	113 (2)	F4—F4A—P1	68.5 (8)
N7—Cu1—N1—C5	−133.96 (19)	C16—N6—C15—N4	−8.8 (5)
N2—Cu1—N1—C5	33.37 (19)	C16—N6—C15—C14	172.4 (3)
N5—Cu1—N1—C5	−49.4 (4)	C13—C14—C15—N4	0.2 (5)
N4—Cu1—N1—C5	129.79 (18)	C13—C14—C15—N6	179.0 (3)
N7—Cu1—N1—C1	41.32 (19)	C20—N5—C16—N6	−177.6 (2)
N2—Cu1—N1—C1	−151.35 (19)	Cu1—N5—C16—N6	4.9 (4)
N5—Cu1—N1—C1	125.9 (3)	C20—N5—C16—C17	1.1 (4)
N4—Cu1—N1—C1	−54.9 (2)	Cu1—N5—C16—C17	−176.4 (2)
N1—Cu1—N2—C6	−36.0 (2)	C15—N6—C16—N5	−7.6 (5)
N7—Cu1—N2—C6	37.2 (5)	C15—N6—C16—C17	173.7 (3)
N5—Cu1—N2—C6	127.2 (2)	N5—C16—C17—C18	−0.7 (5)
N4—Cu1—N2—C6	−144.04 (19)	N6—C16—C17—C18	178.0 (3)
N1—Cu1—N2—C10	150.6 (2)	C16—C17—C18—C19	0.3 (6)
N7—Cu1—N2—C10	−136.2 (3)	C17—C18—C19—C20	−0.3 (5)
N5—Cu1—N2—C10	−46.2 (2)	C18—C19—C20—N5	0.7 (4)
N4—Cu1—N2—C10	42.5 (2)	C16—N5—C20—C19	−1.1 (4)
N1—Cu1—N4—C15	159.72 (19)	Cu1—N5—C20—C19	176.7 (2)
N7—Cu1—N4—C15	69.5 (2)	F2A—P1—F1—F1A	37.2 (17)
N2—Cu1—N4—C15	−110.2 (2)	F4—P1—F1—F1A	−156.0 (16)
N5—Cu1—N4—C15	−20.5 (2)	F6A—P1—F1—F1A	−59.3 (16)
N1—Cu1—N4—C11	−0.2 (2)	F5—P1—F1—F1A	119.2 (16)
N7—Cu1—N4—C11	−90.4 (2)	F2—P1—F1—F1A	26.1 (16)
N2—Cu1—N4—C11	89.9 (2)	F5A—P1—F1—F1A	118.1 (17)
N5—Cu1—N4—C11	179.5 (2)	F6—P1—F1—F1A	−62.1 (16)
N1—Cu1—N5—C16	−174.6 (2)	F4A—P1—F1—F1A	−139.9 (18)
N7—Cu1—N5—C16	−90.4 (2)	F1—P1—F3—F3A	−159.4 (14)
N2—Cu1—N5—C16	102.9 (2)	F2A—P1—F3—F3A	1.2 (15)
N4—Cu1—N5—C16	6.1 (2)	F4—P1—F3—F3A	−167.2 (17)
N1—Cu1—N5—C20	7.8 (4)	F6A—P1—F3—F3A	96.8 (14)
N7—Cu1—N5—C20	92.07 (18)	F5—P1—F3—F3A	−87.4 (15)
N2—Cu1—N5—C20	−74.69 (18)	F2—P1—F3—F3A	10.9 (16)
N4—Cu1—N5—C20	−171.43 (17)	F5A—P1—F3—F3A	−79.4 (15)
N1—Cu1—N7—N8	−145.5 (2)	F6—P1—F3—F3A	93.8 (15)
N2—Cu1—N7—N8	141.3 (3)	F4A—P1—F3—F3A	179.4 (15)
N5—Cu1—N7—N8	51.3 (2)	F1—P1—F4—F4A	30.4 (14)
N4—Cu1—N7—N8	−37.5 (2)	F3—P1—F4—F4A	−153.0 (15)
C5—N1—C1—C2	1.5 (4)	F2A—P1—F4—F4A	177.6 (14)
Cu1—N1—C1—C2	−174.0 (2)	F6A—P1—F4—F4A	−63.9 (14)
N1—C1—C2—C3	0.1 (4)	F5—P1—F4—F4A	103.1 (14)
C1—C2—C3—C4	−0.8 (4)	F5A—P1—F4—F4A	120.0 (14)
C2—C3—C4—C5	0.0 (4)	F6—P1—F4—F4A	−76.7 (14)
C1—N1—C5—N3	178.8 (2)	F1A—P1—F4—F4A	20.6 (15)
Cu1—N1—C5—N3	−5.9 (3)	F3A—P1—F4—F4A	−158.7 (13)
C1—N1—C5—C4	−2.4 (3)	F2A—P1—F1A—F1	−144.4 (17)
Cu1—N1—C5—C4	172.92 (19)	F4—P1—F1A—F1	26.4 (17)
C6—N3—C5—N1	−39.0 (4)	F6A—P1—F1A—F1	120.0 (17)
C6—N3—C5—C4	142.2 (3)	F5—P1—F1A—F1	−57.0 (17)
C3—C4—C5—N1	1.7 (4)	F2—P1—F1A—F1	−152.3 (17)
C3—C4—C5—N3	−179.5 (3)	F5A—P1—F1A—F1	−63.7 (17)
C10—N2—C6—N3	−175.8 (2)	F6—P1—F1A—F1	121.8 (16)
Cu1—N2—C6—N3	10.7 (3)	F4A—P1—F1A—F1	36.8 (16)
C10—N2—C6—C7	5.0 (4)	F3A—P1—F1A—F1	−155.4 (15)
Cu1—N2—C6—C7	−168.5 (2)	F2A—P1—F3A—F3	−178.7 (16)
C5—N3—C6—N2	36.1 (4)	F4—P1—F3A—F3	11.2 (15)
C5—N3—C6—C7	−144.7 (3)	F6A—P1—F3A—F3	−85.0 (15)
N2—C6—C7—C8	−3.4 (4)	F5—P1—F3A—F3	97.0 (15)
N3—C6—C7—C8	177.4 (3)	F2—P1—F3A—F3	−170.0 (15)
C6—C7—C8—C9	−0.3 (5)	F5A—P1—F3A—F3	97.5 (15)
C7—C8—C9—C10	2.1 (5)	F6—P1—F3A—F3	−81.7 (15)
C6—N2—C10—C9	−3.1 (4)	F4A—P1—F3A—F3	−0.7 (16)
Cu1—N2—C10—C9	170.7 (2)	F1A—P1—F3A—F3	−167.1 (12)
C8—C9—C10—N2	−0.5 (5)	F1—P1—F4A—F4	−147.0 (15)
C15—N4—C11—C12	−3.1 (4)	F3—P1—F4A—F4	23.4 (14)
Cu1—N4—C11—C12	158.1 (3)	F6A—P1—F4A—F4	115.8 (14)
N4—C11—C12—C13	0.9 (5)	F5—P1—F4A—F4	−76.8 (14)
C11—C12—C13—C14	1.9 (6)	F2—P1—F4A—F4	177.7 (10)
C12—C13—C14—C15	−2.4 (6)	F5A—P1—F4A—F4	−61.7 (14)
C11—N4—C15—N6	−176.3 (2)	F6—P1—F4A—F4	102.8 (14)
Cu1—N4—C15—N6	24.1 (3)	F1A—P1—F4A—F4	−161.2 (13)
C11—N4—C15—C14	2.5 (4)	F3A—P1—F4A—F4	23.7 (15)
Cu1—N4—C15—C14	−157.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H5···F3^i	0.86 (2)	2.20 (2)	3.045 (12)	168 (2)
N3—H5···F3A^i	0.86 (2)	2.14 (2)	2.963 (8)	161 (2)
N6—H15···N9^ii	0.86 (2)	2.27 (2)	3.130 (3)	179 (3)

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

(II) (azido-κN)bis(di-2-pyridylamine)copper(II) chloride tetrahydrate

Crystal data

[Cu(N3)(C10H11N3)2]Cl·4H2O	F(000) = 1148
Mr = 555.49	Dx = 1.477 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12357 reflections
a = 7.0560 (2) Å	θ = 1.5–29.1°
b = 27.8360 (13) Å	µ = 1.03 mm^−1
c = 12.8780 (6) Å	T = 298 K
β = 99.009 (2)°	Needle, green
V = 2498.18 (18) Å^3	0.50 × 0.20 × 0.15 mm
Z = 4

Data collection

Enraf–Nonius MACH3 diffractometer	4900 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Graphite monochromator	θmax = 29.1°, θmin = 1.5°
psi–scan	h = −9→9
12357 measured reflections	k = −37→38
6685 independent reflections	l = −17→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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0828P)^2 + 0.2714P] where P = (Fo^2 + 2Fc^2)/3
6407 reflections	(Δ/σ)max = 0.012
348 parameters	Δρmax = 0.46 e Å^−3
12 restraints	Δρmin = −0.82 e Å^−3

Special details

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
Cu1	0.83631 (4)	0.147129 (10)	0.69350 (2)	0.03488 (12)
Cl1	0.92856 (15)	0.13850 (3)	0.19694 (6)	0.0656 (2)
O1	1.1787 (4)	−0.02182 (10)	0.1077 (2)	0.0707 (6)
H2W	1.176 (5)	−0.0257 (13)	0.0383 (15)	0.077 (12)*
H1W	1.079 (4)	−0.0023 (13)	0.112 (3)	0.084 (13)*
O2	0.3700 (5)	0.11480 (15)	0.2813 (3)	0.1026 (10)
H3W	0.248 (4)	0.1238 (17)	0.257 (3)	0.109 (18)*
H4W	0.355 (7)	0.102 (2)	0.344 (3)	0.15 (3)*
O3	0.8391 (4)	0.03325 (11)	0.1132 (2)	0.0790 (7)
H5W	0.731 (5)	0.0293 (17)	0.144 (4)	0.15 (2)*
H6W	0.880 (5)	0.0617 (9)	0.140 (3)	0.090 (13)*
O4	0.5012 (4)	0.02940 (12)	0.1944 (2)	0.0840 (8)
H7W	0.455 (5)	0.0566 (9)	0.217 (3)	0.085 (13)*
H8W	0.399 (5)	0.0157 (14)	0.155 (3)	0.115 (17)*
N1	0.7802 (3)	0.19488 (7)	0.80059 (15)	0.0382 (4)
N2	1.0597 (3)	0.12442 (8)	0.80080 (15)	0.0379 (4)
N3	0.9012 (3)	0.14473 (8)	0.94253 (16)	0.0427 (5)
H5	0.8672	0.1312	0.9967	0.051*
N4	1.0074 (3)	0.18866 (7)	0.59980 (15)	0.0381 (4)
N5	0.8549 (3)	0.09194 (7)	0.59587 (15)	0.0368 (4)
N6	0.9125 (3)	0.13975 (8)	0.45143 (16)	0.0414 (5)
H15	0.8812	0.1418	0.3843	0.050*
N7	0.5662 (3)	0.15840 (9)	0.62191 (19)	0.0497 (6)
N8	0.4725 (3)	0.13130 (9)	0.56518 (18)	0.0438 (5)
N9	0.3727 (4)	0.10560 (11)	0.5108 (3)	0.0723 (8)
C1	0.6881 (4)	0.23620 (10)	0.7664 (2)	0.0471 (6)
H1	0.6768	0.2438	0.6954	0.056*
C2	0.6113 (4)	0.26709 (11)	0.8311 (2)	0.0507 (7)
H2	0.5546	0.2958	0.8057	0.061*
C3	0.6208 (3)	0.25425 (11)	0.9354 (2)	0.0493 (7)
H3	0.5666	0.2741	0.9809	0.059*
C4	0.7092 (4)	0.21262 (10)	0.9720 (2)	0.0443 (6)
H4	0.7122	0.2034	1.0416	0.053*
C5	0.7955 (3)	0.18403 (9)	0.90283 (18)	0.0381 (5)
C6	1.0570 (4)	0.12463 (9)	0.90444 (18)	0.0379 (5)
C7	1.2082 (4)	0.10579 (11)	0.9764 (2)	0.0532 (7)
H7	1.2014	0.1054	1.0479	0.064*
C8	1.3650 (5)	0.08805 (13)	0.9402 (2)	0.0633 (9)
H8	1.4663	0.0752	0.9867	0.076*
C9	1.3728 (4)	0.08929 (13)	0.8334 (3)	0.0614 (8)
H9	1.4808	0.0783	0.8076	0.074*
C10	1.2192 (4)	0.10694 (11)	0.7669 (2)	0.0498 (7)
H10	1.2237	0.1070	0.6951	0.060*
C11	1.1016 (4)	0.22830 (10)	0.6400 (2)	0.0461 (6)
H11	1.1086	0.2340	0.7117	0.055*
C12	1.1876 (4)	0.26068 (11)	0.5820 (2)	0.0497 (6)
H12	1.2491	0.2878	0.6131	0.060*
C13	1.1797 (4)	0.25158 (10)	0.4756 (2)	0.0471 (6)
H13	1.2347	0.2730	0.4335	0.056*
C14	1.0906 (4)	0.21093 (10)	0.4332 (2)	0.0423 (6)
H14	1.0872	0.2040	0.3623	0.051*
C15	1.0047 (3)	0.17990 (9)	0.49744 (17)	0.0349 (5)
C16	0.8611 (3)	0.09694 (9)	0.49296 (18)	0.0361 (5)
C17	0.8115 (4)	0.05858 (10)	0.4231 (2)	0.0463 (6)
H17	0.8157	0.0625	0.3518	0.056*
C18	0.7574 (4)	0.01575 (11)	0.4597 (2)	0.0541 (7)
H18	0.7219	−0.0095	0.4136	0.065*
C19	0.7557 (4)	0.01009 (11)	0.5666 (2)	0.0543 (7)
H19	0.7219	−0.0191	0.5936	0.065*
C20	0.8049 (4)	0.04864 (10)	0.6310 (2)	0.0453 (6)
H20	0.8040	0.0449	0.7027	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0399 (2)	0.03890 (18)	0.02621 (16)	0.00206 (11)	0.00643 (12)	−0.00145 (10)
Cl1	0.0979 (7)	0.0685 (5)	0.0325 (3)	−0.0025 (4)	0.0166 (4)	0.0001 (3)
O1	0.0684 (16)	0.0788 (18)	0.0625 (15)	−0.0007 (13)	0.0022 (12)	−0.0004 (13)
O2	0.097 (2)	0.123 (3)	0.089 (2)	0.009 (2)	0.0168 (18)	−0.019 (2)
O3	0.0825 (18)	0.0784 (19)	0.0810 (18)	−0.0108 (14)	0.0286 (14)	−0.0199 (14)
O4	0.0676 (16)	0.090 (2)	0.093 (2)	−0.0054 (15)	0.0093 (14)	−0.0272 (17)
N1	0.0457 (11)	0.0385 (11)	0.0300 (10)	0.0029 (8)	0.0046 (8)	−0.0027 (8)
N2	0.0388 (11)	0.0423 (11)	0.0331 (10)	0.0029 (9)	0.0069 (8)	0.0023 (8)
N3	0.0537 (14)	0.0476 (13)	0.0289 (10)	0.0042 (9)	0.0129 (9)	0.0047 (8)
N4	0.0421 (11)	0.0419 (11)	0.0305 (9)	−0.0032 (9)	0.0062 (8)	−0.0009 (8)
N5	0.0430 (11)	0.0381 (11)	0.0293 (9)	0.0028 (8)	0.0056 (8)	−0.0009 (8)
N6	0.0536 (13)	0.0459 (12)	0.0248 (9)	−0.0014 (9)	0.0063 (9)	0.0009 (8)
N7	0.0435 (13)	0.0544 (14)	0.0492 (13)	0.0037 (10)	0.0005 (10)	−0.0094 (11)
N8	0.0380 (12)	0.0471 (12)	0.0459 (12)	0.0054 (9)	0.0054 (9)	−0.0011 (10)
N9	0.0548 (16)	0.0659 (18)	0.088 (2)	0.0039 (13)	−0.0132 (14)	−0.0245 (16)
C1	0.0544 (15)	0.0471 (15)	0.0385 (13)	0.0089 (12)	0.0031 (11)	−0.0018 (11)
C2	0.0467 (14)	0.0461 (15)	0.0569 (17)	0.0081 (12)	0.0005 (12)	−0.0095 (13)
C3	0.0347 (13)	0.0585 (17)	0.0561 (17)	−0.0021 (12)	0.0118 (11)	−0.0223 (13)
C4	0.0401 (13)	0.0569 (16)	0.0381 (13)	−0.0036 (11)	0.0132 (10)	−0.0131 (11)
C5	0.0353 (12)	0.0466 (14)	0.0328 (11)	−0.0061 (10)	0.0072 (9)	−0.0046 (10)
C6	0.0453 (13)	0.0396 (13)	0.0291 (11)	−0.0001 (10)	0.0066 (9)	0.0026 (9)
C7	0.0593 (18)	0.0630 (18)	0.0352 (13)	0.0088 (14)	0.0004 (12)	0.0096 (12)
C8	0.0564 (19)	0.073 (2)	0.0567 (18)	0.0157 (15)	−0.0036 (14)	0.0149 (15)
C9	0.0484 (17)	0.079 (2)	0.0585 (18)	0.0180 (15)	0.0125 (13)	0.0102 (16)
C10	0.0486 (15)	0.0614 (18)	0.0416 (14)	0.0087 (13)	0.0137 (12)	0.0026 (12)
C11	0.0497 (15)	0.0480 (15)	0.0401 (13)	−0.0058 (12)	0.0053 (11)	−0.0034 (11)
C12	0.0418 (14)	0.0457 (15)	0.0615 (17)	−0.0053 (11)	0.0076 (12)	−0.0004 (13)
C13	0.0369 (13)	0.0481 (15)	0.0589 (17)	0.0040 (11)	0.0160 (11)	0.0124 (12)
C14	0.0429 (14)	0.0481 (14)	0.0388 (13)	0.0036 (11)	0.0152 (10)	0.0050 (11)
C15	0.0350 (12)	0.0386 (12)	0.0319 (11)	0.0067 (9)	0.0079 (9)	0.0030 (9)
C16	0.0366 (12)	0.0410 (13)	0.0314 (11)	0.0052 (9)	0.0074 (9)	−0.0031 (9)
C17	0.0522 (15)	0.0499 (15)	0.0363 (12)	0.0002 (12)	0.0050 (11)	−0.0101 (11)
C18	0.0587 (18)	0.0482 (16)	0.0550 (17)	−0.0044 (13)	0.0072 (13)	−0.0138 (13)
C19	0.0638 (18)	0.0413 (15)	0.0589 (18)	−0.0038 (13)	0.0128 (14)	0.0016 (12)
C20	0.0524 (15)	0.0427 (14)	0.0419 (13)	0.0006 (11)	0.0105 (11)	0.0032 (11)

Geometric parameters (Å, º)

Cu1—N1	1.999 (2)	C2—C3	1.382 (4)
Cu1—N5	2.003 (2)	C2—H2	0.9300
Cu1—N7	2.007 (2)	C3—C4	1.365 (4)
Cu1—N2	2.028 (2)	C3—H3	0.9300
Cu1—N4	2.169 (2)	C4—C5	1.403 (3)
O1—H1W	0.90 (3)	C4—H4	0.9300
O1—H2W	0.90 (2)	C6—C7	1.401 (4)
O2—H3W	0.91 (3)	C7—C8	1.359 (4)
O2—H4W	0.91 (4)	C7—H7	0.9300
O3—H5W	0.92 (4)	C8—C9	1.385 (4)
O3—H6W	0.89 (3)	C8—H8	0.9300
O4—H7W	0.89 (3)	C9—C10	1.364 (4)
O4—H8W	0.90 (4)	C9—H9	0.9300
N1—C5	1.339 (3)	C10—H10	0.9300
N1—C1	1.360 (3)	C11—C12	1.371 (4)
N2—C6	1.338 (3)	C11—H11	0.9300
N2—C10	1.359 (3)	C12—C13	1.386 (4)
N3—C5	1.377 (3)	C12—H12	0.9300
N3—C6	1.389 (3)	C13—C14	1.367 (4)
N3—H5	0.8600	C13—H13	0.9300
N4—C15	1.338 (3)	C14—C15	1.398 (3)
N4—C11	1.349 (3)	C14—H14	0.9300
N5—C16	1.340 (3)	C16—C17	1.405 (3)
N5—C20	1.354 (3)	C17—C18	1.359 (4)
N6—C16	1.378 (3)	C17—H17	0.9300
N6—C15	1.380 (3)	C18—C19	1.387 (4)
N6—H15	0.8600	C18—H18	0.9300
N7—N8	1.179 (3)	C19—C20	1.368 (4)
N8—N9	1.159 (3)	C19—H19	0.9300
C1—C2	1.367 (4)	C20—H20	0.9300
C1—H1	0.9300
N1—Cu1—N5	169.35 (9)	N1—C5—C4	121.4 (2)
N1—Cu1—N7	86.36 (9)	N3—C5—C4	118.6 (2)
N5—Cu1—N7	88.99 (9)	N2—C6—N3	119.3 (2)
N1—Cu1—N2	87.37 (8)	N2—C6—C7	122.0 (2)
N5—Cu1—N2	93.91 (8)	N3—C6—C7	118.7 (2)
N7—Cu1—N2	160.47 (10)	C8—C7—C6	119.0 (3)
N1—Cu1—N4	102.54 (8)	C8—C7—H7	120.5
N5—Cu1—N4	87.86 (8)	C6—C7—H7	120.5
N7—Cu1—N4	103.42 (9)	C7—C8—C9	119.5 (3)
N2—Cu1—N4	95.99 (8)	C7—C8—H8	120.2
H2W—O1—H1W	103 (2)	C9—C8—H8	120.2
H3W—O2—H4W	100 (2)	C10—C9—C8	118.8 (3)
H5W—O3—H6W	100 (2)	C10—C9—H9	120.6
H7W—O4—H8W	104 (3)	C8—C9—H9	120.6
C5—N1—C1	118.1 (2)	N2—C10—C9	123.0 (3)
C5—N1—Cu1	122.30 (17)	N2—C10—H10	118.5
C1—N1—Cu1	118.36 (16)	C9—C10—H10	118.5
C6—N2—C10	117.6 (2)	N4—C11—C12	124.2 (3)
C6—N2—Cu1	123.19 (16)	N4—C11—H11	117.9
C10—N2—Cu1	119.15 (17)	C12—C11—H11	117.9
C5—N3—C6	127.0 (2)	C11—C12—C13	117.7 (3)
C5—N3—H5	116.5	C11—C12—H12	121.1
C6—N3—H5	116.5	C13—C12—H12	121.1
C15—N4—C11	117.2 (2)	C14—C13—C12	119.4 (2)
C15—N4—Cu1	121.87 (16)	C14—C13—H13	120.3
C11—N4—Cu1	120.39 (16)	C12—C13—H13	120.3
C16—N5—C20	118.3 (2)	C13—C14—C15	119.3 (2)
C16—N5—Cu1	123.82 (17)	C13—C14—H14	120.3
C20—N5—Cu1	115.28 (16)	C15—C14—H14	120.3
C16—N6—C15	132.0 (2)	N4—C15—N6	120.2 (2)
C16—N6—H15	114.0	N4—C15—C14	122.0 (2)
C15—N6—H15	114.0	N6—C15—C14	117.7 (2)
N8—N7—Cu1	125.8 (2)	N5—C16—N6	121.7 (2)
N9—N8—N7	176.8 (3)	N5—C16—C17	120.7 (2)
N1—C1—C2	123.3 (3)	N6—C16—C17	117.6 (2)
N1—C1—H1	118.3	C18—C17—C16	120.0 (3)
C2—C1—H1	118.3	C18—C17—H17	120.0
C1—C2—C3	117.8 (3)	C16—C17—H17	120.0
C1—C2—H2	121.1	C17—C18—C19	119.4 (3)
C3—C2—H2	121.1	C17—C18—H18	120.3
C4—C3—C2	120.3 (2)	C19—C18—H18	120.3
C4—C3—H3	119.8	C20—C19—C18	118.2 (3)
C2—C3—H3	119.8	C20—C19—H19	120.9
C3—C4—C5	118.9 (2)	C18—C19—H19	120.9
C3—C4—H4	120.6	N5—C20—C19	123.4 (2)
C5—C4—H4	120.6	N5—C20—H20	118.3
N1—C5—N3	120.0 (2)	C19—C20—H20	118.3
N5—Cu1—N1—C5	57.6 (5)	Cu1—N1—C5—C4	−162.89 (19)
N7—Cu1—N1—C5	121.9 (2)	C6—N3—C5—N1	28.0 (4)
N2—Cu1—N1—C5	−39.60 (19)	C6—N3—C5—C4	−150.5 (3)
N4—Cu1—N1—C5	−135.16 (18)	C3—C4—C5—N1	−5.1 (4)
N5—Cu1—N1—C1	−109.2 (4)	C3—C4—C5—N3	173.4 (2)
N7—Cu1—N1—C1	−44.9 (2)	C10—N2—C6—N3	176.3 (2)
N2—Cu1—N1—C1	153.6 (2)	Cu1—N2—C6—N3	−5.3 (3)
N4—Cu1—N1—C1	58.0 (2)	C10—N2—C6—C7	−2.7 (4)
N1—Cu1—N2—C6	33.0 (2)	Cu1—N2—C6—C7	175.7 (2)
N5—Cu1—N2—C6	−136.4 (2)	C5—N3—C6—N2	−35.1 (4)
N7—Cu1—N2—C6	−38.4 (4)	C5—N3—C6—C7	144.0 (3)
N4—Cu1—N2—C6	135.3 (2)	N2—C6—C7—C8	2.0 (5)
N1—Cu1—N2—C10	−148.7 (2)	N3—C6—C7—C8	−177.0 (3)
N5—Cu1—N2—C10	41.9 (2)	C6—C7—C8—C9	0.5 (5)
N7—Cu1—N2—C10	140.0 (3)	C7—C8—C9—C10	−2.2 (5)
N4—Cu1—N2—C10	−46.4 (2)	C6—N2—C10—C9	0.9 (4)
N1—Cu1—N4—C15	−149.28 (18)	Cu1—N2—C10—C9	−177.5 (3)
N5—Cu1—N4—C15	28.39 (19)	C8—C9—C10—N2	1.5 (5)
N7—Cu1—N4—C15	−60.1 (2)	C15—N4—C11—C12	2.5 (4)
N2—Cu1—N4—C15	122.10 (19)	Cu1—N4—C11—C12	−169.4 (2)
N1—Cu1—N4—C11	22.2 (2)	N4—C11—C12—C13	−1.1 (4)
N5—Cu1—N4—C11	−160.1 (2)	C11—C12—C13—C14	−1.0 (4)
N7—Cu1—N4—C11	111.4 (2)	C12—C13—C14—C15	1.6 (4)
N2—Cu1—N4—C11	−66.4 (2)	C11—N4—C15—N6	179.4 (2)
N1—Cu1—N5—C16	134.0 (4)	Cu1—N4—C15—N6	−8.9 (3)
N7—Cu1—N5—C16	69.9 (2)	C11—N4—C15—C14	−1.8 (3)
N2—Cu1—N5—C16	−129.39 (19)	Cu1—N4—C15—C14	169.93 (18)
N4—Cu1—N5—C16	−33.53 (19)	C16—N6—C15—N4	−21.4 (4)
N1—Cu1—N5—C20	−27.3 (5)	C16—N6—C15—C14	159.8 (3)
N7—Cu1—N5—C20	−91.4 (2)	C13—C14—C15—N4	−0.2 (4)
N2—Cu1—N5—C20	69.29 (19)	C13—C14—C15—N6	178.6 (2)
N4—Cu1—N5—C20	165.15 (19)	C20—N5—C16—N6	−179.4 (2)
N1—Cu1—N7—N8	−155.7 (3)	Cu1—N5—C16—N6	19.8 (3)
N5—Cu1—N7—N8	14.7 (3)	C20—N5—C16—C17	1.8 (3)
N2—Cu1—N7—N8	−84.2 (4)	Cu1—N5—C16—C17	−158.96 (19)
N4—Cu1—N7—N8	102.3 (3)	C15—N6—C16—N5	16.8 (4)
C5—N1—C1—C2	0.2 (4)	C15—N6—C16—C17	−164.4 (3)
Cu1—N1—C1—C2	167.6 (2)	N5—C16—C17—C18	−0.3 (4)
N1—C1—C2—C3	−3.1 (4)	N6—C16—C17—C18	−179.2 (3)
C1—C2—C3—C4	1.8 (4)	C16—C17—C18—C19	−1.3 (4)
C2—C3—C4—C5	2.1 (4)	C17—C18—C19—C20	1.4 (4)
C1—N1—C5—N3	−174.6 (2)	C16—N5—C20—C19	−1.7 (4)
Cu1—N1—C5—N3	18.6 (3)	Cu1—N5—C20—C19	160.7 (2)
C1—N1—C5—C4	4.0 (4)	C18—C19—C20—N5	0.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O3	0.90 (3)	1.96 (3)	2.855 (4)	172 (4)
O1—H2W···O3^i	0.90 (2)	1.95 (2)	2.847 (4)	178 (1)
O2—H3W···Cl1^ii	0.90 (3)	2.30 (3)	3.203 (4)	174 (1)
O2—H4W···N9	0.91 (4)	2.12 (4)	2.964 (5)	153 (5)
O3—H5W···O4	0.92 (4)	1.84 (4)	2.751 (4)	171 (4)
O3—H6W···Cl1	0.89 (3)	2.27 (3)	3.151 (3)	170 (3)
O4—H7W···O2	0.89 (3)	1.96 (3)	2.843 (5)	174 (3)
O4—H8W···O1^ii	0.90 (4)	1.89 (4)	2.768 (4)	164 (1)
N3—H5···Cl1^iii	0.86	2.56	3.256 (2)	139
N6—H15···Cl1	0.86	2.49	3.297 (2)	157

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