Structure and magnetic properties of a mixed-ligand copper(II) complex

The hydro­thermal synthesis of the novel complex poly[[[mu]₂-N¹,N⁴-bis­(pyridin-3-yl)naphthalene-1,4-dicarboxamide-[kappa]²N³:N^3']([mu]₄-phthalato-[kappa]⁴O¹:O¹:O^1':O^2')copper(II)], [Cu(C₈H₄O₄)(C₂₂H₁₆N₄O₂)]_n, is described. With the phthalate ligand connecting neighbouring Cu^II cations, an infinite one-dimensional chain is formed. Adjacent one-dimensional chains are connected by the dicarboxamide ligand, forming an intriguing two-dimensional framework. The magnetic properties and thermal stability of this complex are also described.

S1. Introduction

The huge rise in the literature on metal–organic frameworks (MOFs) is due to their fascinating architectures, intriguing topologies (Luo et al., 2008; Luo et al., 2011; Liao et al., 2011; Qi et al., 2008; Xu et al., 2009) and functional properties, including gas storage, luminescence, catalysis, electronics, molecular sensing, porous or magnetic devices and nanosize materials (Luo et al., 2012 [Luo, Wang et al., 2012 OR Luo, Yuan et al., 2012 ?]; Zeng et al., 2010; PrakashaReddy & Pedireddi, 2007; Wei et al., 2006). Recently, an aspect of coordination chemistry which has flourished is the synthesis of complexes of 3d metals with primarily oxygen- and/or nitro­gen-based ligation (Winpenny, 2001, 2002; Efthymioul et al., 2006; Zhang et al., 2014), and they find applications in bioinorganic chemistry and as molecular magnetic materials. The discovery of molecular magnetism is a significant development (Mukhopadhyay et al., 2004; Sessoli, Tsai et al., 1993; Sessoli, Gatteschi et al., 1993; Christou et al., 2000; Gatteschi & Sessoli, 2003), and molecules based on Cu^II cations have proven to be a fruitful source of molecular magnetism (Adhikary & Koner, 2010).

Flexible nitro­gen-containing organic ligands are viewed as excellent candidates for the construction of MOFs, because they have multiple coordination sites and conformational freedom. Among many flexible N-donor ligands, pyridyl­amide–aromatic amide–pyridyl-type ligands are often used for the construction of intriguing structures based on the following: (i) the pyridyl and amide groups can provide potential coordination sites; (ii) the amide groups with N—H donor groups and C═O acceptor groups may result in hydrogen-bonding inter­actions, further affecting the final structures of the target complexes. According to our recent research, we consider that the N-donor ligand N¹,N⁴-bis­(pyridin-3-yl)naphthalene-1,4-dicarboxamide (L) would be an ideal precursor for the construction of diverse structures. The organic carb­oxy­lic acid ligand phthalic acid, H₂pdc, has also been well used, again for its diverse coordination modes. To the best of our knowledge, a complex of Cu^II based on L and H₂pdc has not been reported to date. As mentioned above, we have now synthesized the novel two-dimensional complex [Cu(pdc)(L)]_n, (I), hydro­thermally from CuCl₂, L, H₂pdc and NaOH.

S2. Experimental

S2.1. Synthesis and crystallization

N¹,N⁴-Bis(pyridin-3-yl)naphthalene-1,4-dicarboxamide (L) was synthesised according to literature methods (Luo, Wang et al., 2012; Luo, Yuan et al., 2012). For the preparation of complex (I), CuCl₂ (0.0269 g, 0.20 mmol), L (0.0368 g, 0.10 mmol), H₂pdc (0.0332 g, 0.20 mmol), NaOH (0.0092 g, 0.23 mmol) and H₂O (12.0 ml) were mixed in a 25 ml Teflon-lined reactor, then heated to 423 K for 4320 min. The mixture was cooled to room temperature at a rate of 3 K h^-1. Finally, blue block-shaped crystals of (I) were obtained in 79% yield (based on Cu^II cations). Analysis, calculated for C₃₈H₂₄Cu₂N₄O₁₀: C 55.47, H 2.94, N 6.81%; found: C 55.34, H 3.04, N 6.85%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms were placed in calculated positions, with C—H = 0.93 Å, and treated using a riding-model approximation, with U_iso(H) = 1.2U_eq(C). H atoms bonded to N atoms were found through residual Q peaks, and refined with N—H = 0.86 Å and U_iso(H) = 1.2U_eq(N).

S3. Results and discussion

The title complex, (I), crystallized in the monoclinic space group C2/c. As shown in Fig. 1(a), the asymmetric unit of (I) contains a Cu^II cation, a crystallographically independent anionic phthalate (pdc^2-) ligand and an N¹,N⁴-bis­(pyridin-3-yl)naphthalene-1,4-dicarboxamide (L) ligand. Each Cu^II cation is five-coordinated in a square-pyramidal geometry, and connects to four O atoms from four pdc^2- ligands [Cu—O = 1.968 (2)–2.3646 (19) Å; Table 2] and to one N atom from an L ligand [Cu—N = 1.979 (2) Å]. These bond lengths are in the normal ranges observed in the literature (Sun et al., 2012). Two Cu^II cations are connected by two pdc^2- ligands, creating a square ring in which the Cu···Cu distance is ca 3.2 Å. The other (eight-membered) ring is formed by two pdc^2- ligands connecting two Cu^II cations, with a Cu···Cu distance of ca 3.5 Å (Fig. 1b). Each pdc^2- ligand connects to four Cu^II cations, as shown in the Scheme. As the pdc^2- ligands connect to Cu^II cations, the structure is extended into an infinite one-dimensional chain along the c direction. Two neighbouring such chains are bridged by L ligands, forming a two-dimensional network in the ac plane. Each L ligand connects to two Cu^II cations with the a cis–cis configuration (see Scheme), in which cis means that the pyridyl N atom and the N atom of the amide group have the same orientation. Between the acyl­amide group and the O atoms of the pdc^2- ligand, there are N2—H1M···O3 hydrogen-bond inter­actions (Table 3) in the two-dimensional network (Fig. 2). The three-dimensional structure is formed by the ···AA··· stacking of the two-dimensional networks (Fig. 3).

Thermogravimetric analysis (TGA) of complex (I) was carried out under a nitro­gen atmosphere from 309 to 1071 K at a heating rate of 10 K min^-1. As shown in Fig. S1 in the Supporting information, complex (I) is stable when heated to 525 K, then displays a sharp weight loss around 530 K, indicating chemical decomposition. The residual after 920 K is CuCO₃.

In addition, we have investigated the DC susceptibility of (I) with crushed single-crystal samples, at 1.8–300 K under an applied field of 1000 Oe. The Cu···Cu distances between the layers are greater than 9 Å in the structure of (I), precluding the possibility of significant inter­layer exchange inter­actions. Thus, the magnetic properties of complex (I) may be adequately described by theories for low-dimensional cooperative phenomena. At 300 K, the product of molar susceptibility and temperature is equal to 0.5688 cm³ mol^-1, slightly higher than the spin-only value of 0.375 cm³ mol^-1 for one Cu^II cation (S = 1/2; g = 2.0). The temperature dependence of the molar susceptibility of (I) is shown in Fig. 4. With decreasing temperature, the molar susceptibility first increases gradually and then decreases until 1.8 K, with a broad maximum observed at 99 K, indicative of anti­ferromagnetic inter­actions. Fig. 5 shows a gradual decrease in the product of molar susceptibility and temperature with decreasing temperature, which then drops rapidly at low temperature, a sure sign of an anti­ferromagnetic ground state.

In summary, a new Cu^II coordination polymer has been prepared under hydro­thermal conditions using N¹,N⁴-bis­(pyridin-3-yl)naphthalene-1,4-dicarboxamide and phthalic acid. This study further demonstrates the aesthetic diversity of coordinative network chemistry.

Related literature

For related literature, see: Adhikary & Koner (2010); Christou et al. (2000); Efthymioul et al. (2006); Gatteschi & Sessoli (2003); Liao et al. (2011); Luo et al. (2008, 2011); Luo, Wang, Luo, Sun, Song, Li & Guo (2012); Luo, Yuan, Feng, Batten, Li, Luo, Liu, Xu, Sun, Song, Huang & Tian (2012); Mukhopadhyay et al. (2004); PrakashaReddy & Pedireddi (2007); Qi et al. (2008); Sessoli, Gatteschi, Caneschi & Novak (1993); Sessoli, Tsai, Schake, Wang, Vincent, Folting, Gatteschi, Christou & Hendrickson (1993); Sun et al. (2012); Wei et al. (2006); Winpenny (2001, 2002); Xu et al. (2009); Zeng et al. (2010); Zhang et al. (2014).

Computing details

Data collection: SMART [or APEX2?] (Bruker, 2008); cell refinement: SMART [or APEX2?] (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. (a) The coordination environment of the Cu^II centre in (I). H atoms, except for those of the acylamide group, have been omitted for clarity. [Symmetry codes: (#1) -x, -y, -z; (#2) x, -y, z - 1/2; (#3) -x, y, -z + 1/2]. (b) The Cu···Cu distances within the complex (Å).
	Fig. 2. A view of the two-dimensional structure of (I), along the b direction, showing the hydrogen-bond interactions (black dotted lines).
	Fig. 3. A view of the three-dimensional structure of (I), with different colours used to distinguish the different two-dimensional networks.
	Fig. 4. The temperature dependence of the molar susceptibility for (I), measured at 1 kOe.
	Fig. 5. The temperature dependence of the product of the molar susceptibility and temperature for (I), measured at 1 kOe

Poly[[µ₂-N¹,N⁴-bis(pyridin-3-yl)naphthalene-1,4-dicarboxamide-κ²N³:N^3'](µ₄-phthalato-κ⁴O¹:O¹:O^1':O^2')copper(II)]

Crystal data

[Cu(C8H4O4)(C22H16N4O2)]	F(000) = 1672
Mr = 823.69	Dx = 1.705 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.1034 (11) Å	Cell parameters from 3333 reflections
b = 23.9203 (17) Å	θ = 2.4–24.9°
c = 9.5545 (7) Å	µ = 1.40 mm^−1
β = 111.666 (5)°	T = 296 K
V = 3208.0 (4) Å^3	Block, blue
Z = 4	0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART [or APEXII?] CCD area-detector diffractometer	2830 independent reflections
Radiation source: fine-focus sealed tube	2329 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
ϕ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.767, Tmax = 0.787	k = −27→28
12179 measured reflections	l = −11→11

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0361P)^2 + 4.929P] where P = (Fo^2 + 2Fc^2)/3
2830 reflections	(Δ/σ)max < 0.001
248 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.39 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
C1	−0.12379 (19)	−0.00589 (12)	0.1500 (3)	0.0244 (6)
C2	−0.20394 (19)	−0.04756 (12)	0.0950 (3)	0.0253 (7)
C3	−0.2621 (2)	−0.04458 (14)	−0.0556 (4)	0.0340 (7)
H3	−0.2482	−0.0190	−0.1179	0.041*
C4	−0.3408 (2)	−0.07921 (15)	−0.1148 (4)	0.0417 (8)
H4	−0.3791	−0.0770	−0.2164	0.050*
C5	−0.3623 (2)	−0.11697 (15)	−0.0232 (4)	0.0418 (9)
H5	−0.4149	−0.1403	−0.0624	0.050*
C6	−0.3053 (2)	−0.11988 (14)	0.1265 (4)	0.0375 (8)
H6	−0.3209	−0.1450	0.1881	0.045*
C7	−0.2250 (2)	−0.08646 (13)	0.1890 (3)	0.0273 (7)
C8	−0.1625 (2)	−0.09568 (13)	0.3513 (4)	0.0325 (7)
C9	0.1591 (2)	0.14027 (13)	0.2305 (4)	0.0315 (7)
H9	0.1685	0.1152	0.3092	0.038*
C10	0.2169 (2)	0.18678 (13)	0.2566 (3)	0.0308 (7)
C11	0.2032 (2)	0.22422 (15)	0.1411 (4)	0.0393 (8)
H11	0.2405	0.2562	0.1552	0.047*
C12	0.1323 (2)	0.21287 (15)	0.0036 (4)	0.0426 (9)
H12	0.1215	0.2374	−0.0765	0.051*
C13	0.0777 (2)	0.16568 (14)	−0.0155 (4)	0.0357 (8)
H13	0.0307	0.1585	−0.1091	0.043*
C14	0.3735 (2)	0.21469 (16)	0.4379 (4)	0.0434 (9)
C15	0.4381 (2)	0.21085 (14)	0.6003 (4)	0.0350 (8)
C16	0.4692 (2)	0.25979 (15)	0.6742 (4)	0.0356 (8)
H16	0.4497	0.2935	0.6239	0.043*
C17	0.4683 (2)	0.15836 (14)	0.6733 (4)	0.0366 (8)
C18	0.4399 (3)	0.10632 (16)	0.6000 (5)	0.0500 (10)
H18	0.3996	0.1057	0.4992	0.060*
C19	0.4701 (3)	0.05750 (18)	0.6735 (5)	0.0657 (13)
H19	0.4512	0.0238	0.6227	0.079*
Cu1	0.01495 (2)	0.060300 (15)	0.07617 (4)	0.02532 (13)
H1M	0.279 (2)	0.1749 (14)	0.470 (4)	0.039 (10)*
N1	0.09071 (16)	0.12951 (10)	0.0982 (3)	0.0271 (6)
N2	0.28514 (19)	0.19269 (13)	0.4027 (3)	0.0371 (7)
O1	−0.06978 (13)	−0.00251 (8)	0.0758 (2)	0.0271 (5)
O2	−0.11949 (13)	0.02560 (8)	0.2565 (2)	0.0275 (5)
O3	−0.19611 (19)	−0.11485 (14)	0.4392 (3)	0.0667 (9)
O4	−0.07512 (14)	−0.08307 (9)	0.3837 (2)	0.0322 (5)
O5	0.3975 (2)	0.23840 (17)	0.3459 (3)	0.0934 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0213 (14)	0.0279 (16)	0.0204 (16)	0.0057 (12)	0.0033 (13)	0.0047 (13)
C2	0.0200 (14)	0.0293 (17)	0.0273 (17)	0.0007 (12)	0.0096 (13)	−0.0044 (13)
C3	0.0272 (16)	0.046 (2)	0.0275 (18)	−0.0027 (14)	0.0083 (14)	−0.0013 (15)
C4	0.0319 (18)	0.058 (2)	0.0280 (19)	−0.0051 (16)	0.0031 (16)	−0.0083 (17)
C5	0.0293 (17)	0.053 (2)	0.039 (2)	−0.0157 (16)	0.0079 (16)	−0.0134 (17)
C6	0.0345 (18)	0.040 (2)	0.038 (2)	−0.0111 (15)	0.0136 (16)	−0.0011 (16)
C7	0.0243 (15)	0.0331 (17)	0.0247 (17)	−0.0016 (13)	0.0092 (14)	−0.0044 (14)
C8	0.0352 (18)	0.0296 (18)	0.0313 (18)	−0.0036 (14)	0.0106 (15)	0.0007 (14)
C9	0.0336 (17)	0.0275 (17)	0.0305 (18)	−0.0012 (13)	0.0085 (15)	0.0037 (14)
C10	0.0277 (16)	0.0378 (19)	0.0244 (17)	−0.0034 (13)	0.0069 (14)	0.0004 (14)
C11	0.0341 (18)	0.041 (2)	0.038 (2)	−0.0090 (15)	0.0073 (17)	0.0063 (16)
C12	0.042 (2)	0.045 (2)	0.037 (2)	−0.0059 (16)	0.0104 (18)	0.0174 (17)
C13	0.0331 (18)	0.043 (2)	0.0281 (18)	−0.0020 (15)	0.0078 (15)	0.0082 (15)
C14	0.0367 (19)	0.057 (2)	0.032 (2)	−0.0148 (17)	0.0080 (17)	−0.0002 (17)
C15	0.0260 (16)	0.049 (2)	0.0300 (19)	−0.0055 (14)	0.0102 (15)	0.0031 (16)
C16	0.0296 (17)	0.042 (2)	0.0335 (18)	−0.0009 (14)	0.0094 (15)	0.0034 (15)
C17	0.0291 (17)	0.045 (2)	0.0372 (19)	−0.0035 (14)	0.0140 (15)	−0.0034 (15)
C18	0.044 (2)	0.046 (2)	0.057 (3)	−0.0076 (17)	0.0142 (19)	−0.0114 (19)
C19	0.055 (3)	0.043 (2)	0.094 (4)	−0.0078 (19)	0.023 (2)	−0.014 (2)
Cu1	0.0254 (2)	0.0258 (2)	0.0222 (2)	−0.00178 (15)	0.00572 (16)	0.00062 (16)
N1	0.0251 (13)	0.0273 (14)	0.0250 (14)	−0.0006 (10)	0.0047 (11)	−0.0012 (11)
N2	0.0321 (15)	0.0518 (19)	0.0238 (16)	−0.0139 (13)	0.0059 (13)	0.0031 (14)
O1	0.0259 (10)	0.0320 (12)	0.0254 (11)	−0.0036 (9)	0.0119 (9)	−0.0018 (9)
O2	0.0287 (11)	0.0291 (12)	0.0233 (11)	0.0012 (9)	0.0080 (9)	−0.0059 (9)
O3	0.0575 (17)	0.102 (2)	0.0376 (16)	−0.0305 (16)	0.0135 (14)	0.0172 (15)
O4	0.0287 (12)	0.0346 (12)	0.0273 (12)	0.0007 (9)	0.0034 (10)	−0.0023 (10)
O5	0.0595 (19)	0.166 (4)	0.0411 (18)	−0.060 (2)	0.0028 (15)	0.026 (2)

Geometric parameters (Å, º)

C1—O2	1.248 (3)	C13—N1	1.346 (4)
C1—O1	1.266 (3)	C13—H13	0.9300
C1—C2	1.505 (4)	C14—O5	1.209 (4)
C2—C3	1.384 (4)	C14—N2	1.356 (4)
C2—C7	1.409 (4)	C14—C15	1.500 (5)
C3—C4	1.387 (4)	C15—C16	1.358 (5)
C3—H3	0.9300	C15—C17	1.427 (5)
C4—C5	1.377 (5)	C16—C16^i	1.403 (6)
C4—H4	0.9300	C16—H16	0.9300
C5—C6	1.372 (5)	C17—C18	1.415 (5)
C5—H5	0.9300	C17—C17^i	1.424 (7)
C6—C7	1.389 (4)	C18—C19	1.352 (5)
C6—H6	0.9300	C18—H18	0.9300
C7—C8	1.504 (4)	C19—C19^i	1.406 (9)
C8—O3	1.220 (4)	C19—H19	0.9300
C8—O4	1.276 (4)	Cu1—O4^ii	1.919 (2)
C9—N1	1.329 (4)	Cu1—O2^iii	1.968 (2)
C9—C10	1.379 (4)	Cu1—O1	1.9726 (19)
C9—H9	0.9300	Cu1—N1	1.979 (2)
C10—C11	1.377 (4)	Cu1—O1^iv	2.3646 (19)
C10—N2	1.403 (4)	N2—H1M	0.81 (4)
C11—C12	1.381 (5)	O1—Cu1^iv	2.3646 (19)
C11—H11	0.9300	O2—Cu1^iii	1.968 (2)
C12—C13	1.369 (5)	O4—Cu1^v	1.919 (2)
C12—H12	0.9300
O2—C1—O1	124.6 (3)	O5—C14—N2	122.2 (3)
O2—C1—C2	118.5 (2)	O5—C14—C15	121.7 (3)
O1—C1—C2	116.7 (3)	N2—C14—C15	116.0 (3)
C3—C2—C7	119.4 (3)	C16—C15—C17	121.2 (3)
C3—C2—C1	116.7 (3)	C16—C15—C14	116.9 (3)
C7—C2—C1	123.9 (3)	C17—C15—C14	121.9 (3)
C2—C3—C4	120.9 (3)	C15—C16—C16^i	120.4 (2)
C2—C3—H3	119.6	C15—C16—H16	119.8
C4—C3—H3	119.6	C16^i—C16—H16	119.8
C5—C4—C3	120.0 (3)	C18—C17—C17^i	118.4 (2)
C5—C4—H4	120.0	C18—C17—C15	123.3 (3)
C3—C4—H4	120.0	C17^i—C17—C15	118.35 (19)
C6—C5—C4	119.5 (3)	C19—C18—C17	121.3 (4)
C6—C5—H5	120.3	C19—C18—H18	119.3
C4—C5—H5	120.3	C17—C18—H18	119.3
C5—C6—C7	122.0 (3)	C18—C19—C19^i	120.3 (3)
C5—C6—H6	119.0	C18—C19—H19	119.9
C7—C6—H6	119.0	C19^i—C19—H19	119.9
C6—C7—C2	118.2 (3)	O4^ii—Cu1—O2^iii	166.04 (9)
C6—C7—C8	118.3 (3)	O4^ii—Cu1—O1	89.11 (8)
C2—C7—C8	123.4 (3)	O2^iii—Cu1—O1	90.33 (8)
O3—C8—O4	125.3 (3)	O4^ii—Cu1—N1	92.41 (10)
O3—C8—C7	120.2 (3)	O2^iii—Cu1—N1	90.42 (9)
O4—C8—C7	114.5 (3)	O1—Cu1—N1	170.58 (9)
N1—C9—C10	123.1 (3)	O4^ii—Cu1—O1^iv	82.11 (8)
N1—C9—H9	118.4	O2^iii—Cu1—O1^iv	83.94 (8)
C10—C9—H9	118.4	O1—Cu1—O1^iv	85.84 (7)
C11—C10—C9	118.8 (3)	N1—Cu1—O1^iv	103.58 (8)
C11—C10—N2	124.8 (3)	C9—N1—C13	118.3 (3)
C9—C10—N2	116.4 (3)	C9—N1—Cu1	118.6 (2)
C10—C11—C12	118.0 (3)	C13—N1—Cu1	123.1 (2)
C10—C11—H11	121.0	C14—N2—C10	125.5 (3)
C12—C11—H11	121.0	C14—N2—H1M	113 (3)
C13—C12—C11	120.4 (3)	C10—N2—H1M	119 (3)
C13—C12—H12	119.8	C1—O1—Cu1	126.82 (19)
C11—C12—H12	119.8	C1—O1—Cu1^iv	138.66 (19)
N1—C13—C12	121.4 (3)	Cu1—O1—Cu1^iv	94.16 (7)
N1—C13—H13	119.3	C1—O2—Cu1^iii	134.53 (18)
C12—C13—H13	119.3	C8—O4—Cu1^v	127.1 (2)
O2—C1—C2—C3	122.7 (3)	C17^i—C17—C18—C19	1.4 (6)
O1—C1—C2—C3	−51.8 (4)	C15—C17—C18—C19	−179.9 (3)
O2—C1—C2—C7	−53.8 (4)	C17—C18—C19—C19^i	0.9 (7)
O1—C1—C2—C7	131.7 (3)	C10—C9—N1—C13	0.3 (4)
C7—C2—C3—C4	0.2 (4)	C10—C9—N1—Cu1	178.8 (2)
C1—C2—C3—C4	−176.5 (3)	C12—C13—N1—C9	−0.9 (5)
C2—C3—C4—C5	0.4 (5)	C12—C13—N1—Cu1	−179.3 (2)
C3—C4—C5—C6	0.1 (5)	O4^ii—Cu1—N1—C9	169.9 (2)
C4—C5—C6—C7	−1.1 (5)	O2^iii—Cu1—N1—C9	−23.8 (2)
C5—C6—C7—C2	1.7 (5)	O1—Cu1—N1—C9	70.8 (6)
C5—C6—C7—C8	−175.3 (3)	O1^iv—Cu1—N1—C9	−107.7 (2)
C3—C2—C7—C6	−1.2 (4)	O4^ii—Cu1—N1—C13	−11.7 (2)
C1—C2—C7—C6	175.3 (3)	O2^iii—Cu1—N1—C13	154.6 (2)
C3—C2—C7—C8	175.6 (3)	O1—Cu1—N1—C13	−110.8 (6)
C1—C2—C7—C8	−7.9 (4)	O1^iv—Cu1—N1—C13	70.7 (2)
C6—C7—C8—O3	−27.1 (5)	O5—C14—N2—C10	10.1 (6)
C2—C7—C8—O3	156.1 (3)	C15—C14—N2—C10	−173.3 (3)
C6—C7—C8—O4	151.5 (3)	C11—C10—N2—C14	−36.0 (5)
C2—C7—C8—O4	−25.3 (4)	C9—C10—N2—C14	145.2 (3)
N1—C9—C10—C11	0.4 (5)	O2—C1—O1—Cu1	−13.8 (4)
N1—C9—C10—N2	179.2 (3)	C2—C1—O1—Cu1	160.38 (19)
C9—C10—C11—C12	−0.6 (5)	O2—C1—O1—Cu1^iv	157.5 (2)
N2—C10—C11—C12	−179.3 (3)	C2—C1—O1—Cu1^iv	−28.4 (4)
C10—C11—C12—C13	0.1 (5)	O4^ii—Cu1—O1—C1	−103.6 (2)
C11—C12—C13—N1	0.6 (5)	O2^iii—Cu1—O1—C1	90.3 (2)
O5—C14—C15—C16	57.8 (5)	N1—Cu1—O1—C1	−4.3 (7)
N2—C14—C15—C16	−118.7 (3)	O1^iv—Cu1—O1—C1	174.2 (3)
O5—C14—C15—C17	−120.2 (4)	O4^ii—Cu1—O1—Cu1^iv	82.15 (8)
N2—C14—C15—C17	63.3 (4)	O2^iii—Cu1—O1—Cu1^iv	−83.90 (8)
C17—C15—C16—C16^i	−1.2 (5)	N1—Cu1—O1—Cu1^iv	−178.5 (5)
C14—C15—C16—C16^i	−179.3 (3)	O1^iv—Cu1—O1—Cu1^iv	0.0
C16—C15—C17—C18	−178.3 (3)	O1—C1—O2—Cu1^iii	−38.4 (4)
C14—C15—C17—C18	−0.3 (5)	C2—C1—O2—Cu1^iii	147.6 (2)
C16—C15—C17—C17^i	0.5 (5)	O3—C8—O4—Cu1^v	−28.0 (5)
C14—C15—C17—C17^i	178.4 (3)	C7—C8—O4—Cu1^v	153.4 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1M···O3^vi	0.805 (4)	2.27 (7)	3.009 (4)	151 (4)

Symmetry code: (vi) −x, −y, −z+1.