catena-Poly[[[(di-2-pyridylamine-κ²N²,N^2′)­copper(II)]-μ-benzene-1,3-dicarboxyl­ato-κ³O¹,O^1′:O³] mono­hydrate], a zigzag coordination polymer with strong π–π inter­actions

The novel title coordination polymer, {[Cu(C₈H₄O₄)(C₁₀H₉N₃)]·H₂O}_n, synthesized by the slow-diffusion method, takes the form of one-dimensional zigzag chains built up of Cu^II cations linked by benzene-1,3-dicarboxyl­ate (ipht) anions. An exceptional characteristic of this structure is that it belongs to a small group of metal–organic polymers where ipht is coordinated as a bridging tridentate ligand with monodentate and chelate coordination of individual carboxyl­ate groups. The Cu^II cation has a highly distorted square-pyramidal geometry formed by three O atoms from two ipht anions and two N atoms from a di-2-pyridyl­amine (dipya) ligand. The zigzag chains, which run along the b axis, further construct a three-dimensional metal–organic framework via strong face-to-face π–π inter­actions and hydrogen bonds. A solvent water mol­ecule is linked to the different carboxyl­ate groups via hydrogen bonds. Thermogravimetric and differential scanning calorimetric analyses confirm the strong hydrogen bonding.

S1. Comment

The design and synthesis of mixed metal–organic coordination polymers are of current interest in the fields of supramolecular chemistry and crystal engineering, not only for the fascinating architectures and structural diversity of these compounds, but also for their potential applications as functional materials (Li & Wei, 2007; Cui et al., 2009; Du et al., 2009; Shyu et al., 2009; Huang et al., 2010; Liu et al., 2010). An effective approach for the synthesis of such complexes is the appropriate choice of aromatic polycarboxylate ligands as bridges with a variety of transition metal ions as nodes. During the past decade, there have been many reports of the synthesis of coordination compounds where dianions of benzene-1,3-dicarboxylic (isophthalic) acid, ipht, combined with aromatic N-containing chelating ligands have been used to assemble a wide range of coordination polymers from chains to sheets to networks (see, for example, Liu et al., 2008; Ma, Liu et al., 2010). The multi-dimensional framework structures formed by these combinations of aromatic ligands are often stabilized via noncovalent intermolecular forces – hydrogen bonds and/or π–π interactions (Zhang et al., 2003; Li & Wei, 2007; An et al., 2008; Li et al., 2009; Ma et al., 2009; Guo et al., 2010; He et al., 2010). The title compound, {[Cu(dipya)(ipht)].H₂O}_n, (I), where dipya is 2,2'-dipyridylamine, represents a new example, comprising a three-dimensional structure built up from one-dimensional zigzag polymeric chains.

In (I), Cu^II cations are surrounded by three O atoms from two COO^- groups of neighbouring ipht anions and two N atoms from dipya ligands, forming a (4+1) coordination polyhedron, which can be described as a square pyramid with a tetrahedrally distorted basal plane (Fig. 1). The dihedral angle between coordinated COO^- groups is 82.73 (8)°. The bond distances between the Cu^II cation and atoms O1, O2 and O4 (Table 1) are within the usual ranges for complexes where monodentate and chelate COO^- groups of ipht or substituted ipht are present (Li & Wei, 2007; Cui et al., 2009; Du et al., 2009; Su et al., 2009; Zeng et al., 2009; Al-Hashemi et al., 2010; Guo et al., 2010). The chelate O1—Cu1—O2 angle [56.76 (6)°] is also similar to those found in these related structures. Due to the constraints imposed by chelation, the coordination polyhedron of Cu1 is highly distorted.

As expected, the apical Cu1—O2 bond distance [2.546 (2) Å] is significantly longer than the remaining four distances in the Cu1 coordination polyhedron (Table 1). Nevertheless, according to bond-valence analysis (Wills, 2009), atom Cu1 is oversaturated (2.21 bond valence units). A short Cu1—O3 contact of 3.0229 (18) Å, which is only slightly longer than the sum of the van der Waals radii (2.92 Å; Bondi, 1964), should also be mentioned. Since the O2—Cu1—O3 angle is 160.56 (5) °, the Cu1 environment could also be described as an extremely deformed very elongated octahedron.

As usual, dipya is a chelating ligand in (I), while the ipht anions act as bridging tridentate ligands with monodentately (C18/O3/O4) and chelately (C11/O1/O2) coordinated COO^- groups, forming one-dimensional zigzag chains running along the b axis (Fig. 2). The distance between two Cu1 atoms bridged by the ipht anion is 11.7216 (5) Å, while the shortest interchain Cu1···Cu1 distance is 7.9931 (4) Å. Very similar zigzag chains are found in [Zn(ipht)(1-methylimidazole)₂]_n (Zhao, 2008a), [Co(1-ethylimidazole)₂(ipht)]_n (Zhao, 2008b), [Cu(bipy)(tbipht)]_n (bipy is 2,2'-bipyridine and tbipht is 5-tert-butylisophthalate; Li & Huang, 2008) and [Mn(bipy)(H₂O)₂(ipht)]_n.nH₂O (Ma, Hu et al., 2010). In (I), the ipht aromatic ring and entire dipya ligand are nearly perpendicular to each other [dihedral angle 82.20 (6)°]. Considering the bridging role of the ipht anion, the value of this angle is probably the main reason for the existence of the zigzag chains.

All dipya ligands in (I) are oriented approximately parallel to the (102) plane (Fig. 3). This enables stacking of the chains by face-to-face π–π interactions between neighbouring dipya ligands. Although in mixed metal–organic complexes (Rogan et al., 2006) the dihedral angle between the two pyridine rings of dipya can reach 29°, in (I) this angle is very small [7.68 (7)°] and both pyridine rings are involved in π–π interactions. The shortest distances between C atoms of neighbouring dipya ligands are 3.307 (4) for C5···C5ⁱ and 3.303 (4) Å for C6···C6ⁱ [symmetry code: (i) -x, y, 1/2 - z], confirming strong face-to-face π–π interactions (Janiak, 2000). In this way, hydrophilic and hydrophobic layers parallel to the bc plane are formed. With a few exceptions where π–π interactions with centroid-to-centroid distances of around 3.2 (Guo et al., 2010) and 3.3 Å (Zhang et al., 2003; Li et al., 2009) were found, in most reported ipht and substituted ipht complexes the π–π interactions are weaker and distances are in the range 3.5–3.9 Å (Zhang et al., 2003; Li & Wei, 2007; An et al., 2008; Ma et al., 2009; Guo et al., 2010; He et al., 2010).

In addition to π–π interactions, the zigzag chains in (I) are also interconnected via hydrogen bonding, yielding a three-dimensional metal–organic framework (Fig. 3). The hydrogen-bonding geometry is listed in Table 2. Three of the four hydrogen bonds are between the H₂O molecule and O atoms from different COO^- groups, while the fourth is between amine atom H5 from dipya and uncoordinated atom O3 from the monodentate C18/O3/O4 group (Table 2). Atom O3 acts as a double hydrogen-bond acceptor from the already mentioned atom H5 and from atom H11 of the uncoordinated water molecule. The remaining H atom (H12) of the water molecule very likely participates in two hydrogen bonds, and therefore this bond can be described as bifurcated. The D···A distance for O5—H12···O1 is longer but the angle is acceptable, which is not the case for O5—H12···O4, where the distance is suitable but a much smaller angle [127 (3)°] is found (Table 2).

Since the initial positions of the H atoms were not found in ΔF maps but were generated using a combined geometric and force-field approach (Nardelli, 1999), they can not be considered as very reliable. For a better insight into the strength of the hydrogen bonding in (I), thermogravimetric and differential scanning calorimetric (TG and DSC) analyses were performed. It was found that the TG and DSC curves of (I) are practically identical to the recently published curves of the corresponding polycrystalline complex (Rogan et al., 2011), so only dehydration will be discussed here. The dehydration is a single-step process and the mass loss of 4.5% between 396 and 450 K is attributed to the loss of the solvent H₂O molecule (calculated 4.3%). The endothermic peak in the DSC curve relating to the dehydration process gives a molar enthalpy of 50.4 kJ mol^-1, which, together with the high final dehydration temperature, indicates strong hydrogen bonding. A similar value of the dehydration molar enthalpy was recently found for an Mn^II complex {[Mn(bipy)(C₅O₅)(H₂O)].H₂O}_n (Chen et al., 2010), where the solvent H₂O molecule participates in two hydrogen bonds but with significantly shorter D···A distances (2.88–2.98 Å). At the same time, a detailed analysis of analogous terephthalate complexes (Rogan & Poleti, 2004) has shown that the mean energy of a hydrogen bond should be about 16 kJ mol^-1 or slightly above this value. Therefore, the hydrogen bonds in (I) are stronger than expected and it is evident that all three hydrogen bonds in which the solvent H₂O molecule participates really exist.

Metal–organic polymers where ipht is coordinated as a bridging tridentate ligand with monodentate and chelate COO^- groups are quite rare among numerous ipht complexes. To the best of our knowledge, in total four such transition metal complexes have been described so far (Li & Wei, 2007; Cui et al., 2009; Su et al., 2009; Al-Hashemi et al., 2010), but two of them (Su et al., 2009; Al-Hashemi et al., 2010) contain two chemically different ipht anions, i.e. one anion is not a bridging tridentate ligand. In addition, five complexes are known containing derivatives of ipht coordinating in the same mode to Cu^II (Guo et al., 2010) and Co^II (Du et al., 2009; Zeng et al., 2009) as central atoms. The predominant coordination number of the transition metal atoms in these complexes is 6.

The similarities in geometry between (I) and comparable metal–organic polymers are related to the dihedral angle between the plane of the benzene ring of the polycarboxylate ligand and the chelate or monodentate COO^- group, as well as that between the planes of the chelate and monodentate COO^- group. With one exception (Table 3), these angles do not exceed 25°. Accordingly, a general characteristic of (I) and related complexes containing ipht or its derivatives is that these kinds of ligands do not deviate very much from planarity. It seems that higher dihedral angles in several complexes (Table 3) are associated with the bulkiness of the second ligand (Al-Hashemi et al., 2010), the bulkiness of the substituent on the ipht ligand (Du et al., 2009) or the overall bulkiness of the complex unit (Guo et al., 2010). The same coordination mode of polycarboxylate ligands is presumably the main explanation for the minor deviations between the stated dihedral angles.

Related literature

For related literature, see: Al-Hashemi, Safari, Amani, Amani & Khavasi (2010); An et al. (2008); Bondi (1964); Chen et al. (2010); Cui et al. (2009); Du et al. (2009); Guo et al. (2010); He et al. (2010); Huang et al. (2010); Janiak (2000); Li & Huang (2008); Li & Wei (2007); Li et al. (2009); Liu et al. (2008, 2010); Ma et al. (2009); Ma, Hu, Chen, Wang, Zhang, Chen & Liu (2010); Ma, Liu, Wang, Li & Du (2010); Nardelli (1999); Rogan & Poleti (2004); Rogan et al. (2006, 2011); Shyu et al. (2009); Su et al. (2009); Wills (2009); Zeng et al. (2009); Zhang et al. (2003); Zhao (2008a, 2008b).

S2. Experimental

Single crystals of (I) were obtained by a modification of the slow-diffusion method. A mixture containing Cu(NO₃)₂.3H₂O (60 mg, 0.25 mmol), 2,2'-dipyridylamine (43 mg, 0.25 mmol) and H₂ipht (42 mg, 0.25 mmol) was dissolved in dimethyl sulfoxide (12 ml). The mixture was stirred for 10 min and then transferred into a small test tube. A dilute solution of Na₂ipht in H₂O (0.05 M) was then layered on top carefully and very slowly in order to minimize mixing of the solutions. The first prismatic green crystals of (I) appeared within a 24 h period, but single crystals of a suitable size were filtered off after about 10 d. The complex is stable in air and insoluble in all common solvents.

The thermal properties of (I) were examined from room temperature up to 973 K on an SDT Q600 TGA/DSC instrument (TA Instruments). The heating rate was 20 K min^-1 using less than 10 mg sample mass. The furnace atmosphere consisted of dry nitrogen at a flow rate of 100 cm³ min^-1.

S3. Refinement

C-bound H atoms and amine atom H5 of the dipya ligand were positioned geometrically and refined as riding, with restraints of C—H = 0.93 (2) and N—H = 0.86 (2) Å, and with U_iso(H) = 1.2U_eq(C,N). The initial positions of water atoms H11 and H12 were calculated using the program HYDROGEN (Nardelli, 1999) and then refined with O—H restrained to 0.85 (1) Å and U_iso(H) = 1.5U_eq(O5).

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010) and PARST (Nardelli, 1995).

Figures

	Fig. 1. Part of the polymeric zigzag chain of (I), showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 40% probability level. [Symmetry codes: (i) -x + 1/2, y - 1/2, -z + 1/2; (ii) -x + 1/2, y + 1/2, -z + 1/2.]
	Fig. 2. The zigzag chain of (I), running along the b axis.
	Fig. 3. A projection of (I) along the b axis, showing the crystal packing, π–π interactions and hydrogen bonding (dashed lines). For emphasis, solvent water molecules are shown with displacement ellipsoids (orange in the electronic version of the paper).

catena-Poly[[[(di-2-pyridylamine- κ²N²,N^2')copper(II)]-µ-benzene- 1,3-dicarboxylato-κ³O¹,O^1':O³] monohydrate]

Crystal data

[Cu(C8H4O4)(C10H9N3)]·H2O	F(000) = 1704
Mr = 416.87	Dx = 1.632 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 4359 reflections
a = 23.2351 (11) Å	θ = 3.0–28.8°
b = 11.7216 (4) Å	µ = 1.32 mm^−1
c = 13.7825 (7) Å	T = 295 K
β = 115.285 (6)°	Prismatic, green
V = 3394.1 (3) Å^3	0.29 × 0.16 × 0.10 mm
Z = 8

Data collection

Oxford Gemini-S diffractometer	3214 independent reflections
Radiation source: fine-focus sealed tube	2473 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 16.3280 pixels mm^-1	θmax = 25.7°, θmin = 3.2°
ϕ and ω scans	h = −28→27
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −13→14
Tmin = 0.700, Tmax = 0.879	l = −16→16
8071 measured reflections

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.049P)^2] where P = (Fo^2 + 2Fc^2)/3
3214 reflections	(Δ/σ)max = 0.001
250 parameters	Δρmax = 0.45 e Å^−3
2 restraints	Δρmin = −0.34 e Å^−3

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.123259 (12)	0.23927 (2)	0.19814 (2)	0.02947 (11)
O1	0.18310 (7)	0.33307 (14)	0.17023 (13)	0.0378 (4)
O2	0.13043 (8)	0.24125 (14)	0.01890 (16)	0.0476 (5)
O3	0.34074 (8)	0.70357 (15)	0.06576 (14)	0.0427 (4)
O4	0.30760 (7)	0.66024 (14)	0.18977 (13)	0.0352 (4)
O5	0.17288 (13)	0.2579 (3)	0.6570 (3)	0.0920 (10)
H11	0.170 (3)	0.262 (4)	0.5939 (18)	0.138*
H12	0.2118 (9)	0.244 (4)	0.697 (4)	0.138*
N1	0.05454 (8)	0.35484 (16)	0.15302 (15)	0.0302 (4)
N2	0.06390 (8)	0.11088 (15)	0.17010 (15)	0.0288 (4)
N3	−0.02877 (9)	0.22293 (16)	0.11721 (16)	0.0345 (5)
H5	−0.0689	0.2184	0.1003	0.041*
C1	0.07216 (12)	0.4660 (2)	0.1588 (2)	0.0393 (6)
H1	0.1148	0.4822	0.1773	0.047*
C2	0.03169 (13)	0.5539 (2)	0.1394 (2)	0.0477 (7)
H2	0.0461	0.6286	0.1442	0.057*
C3	−0.03173 (13)	0.5317 (2)	0.1121 (2)	0.0450 (7)
H3	−0.0607	0.5911	0.0986	0.054*
C4	−0.05123 (12)	0.4207 (2)	0.10525 (19)	0.0395 (6)
H4	−0.0937	0.4038	0.0873	0.047*
C5	−0.00720 (10)	0.33308 (19)	0.12533 (18)	0.0299 (5)
C6	0.00039 (10)	0.11822 (19)	0.13045 (17)	0.0290 (5)
C7	−0.03740 (12)	0.0209 (2)	0.1029 (2)	0.0380 (6)
H7	−0.0814	0.0280	0.0761	0.046*
C8	−0.01125 (13)	−0.0835 (2)	0.1145 (2)	0.0430 (6)
H8	−0.0366	−0.1485	0.0963	0.052*
C9	0.05470 (12)	−0.0920 (2)	0.1544 (2)	0.0446 (7)
H9	0.0745	−0.1628	0.1633	0.054*
C10	0.08888 (12)	0.0044 (2)	0.1794 (2)	0.0367 (6)
H10	0.1328	−0.0019	0.2051	0.044*
C11	0.16975 (10)	0.31292 (19)	0.0718 (2)	0.0322 (5)
C12	0.20251 (10)	0.38632 (18)	0.02202 (18)	0.0277 (5)
C13	0.19719 (11)	0.3640 (2)	−0.07991 (19)	0.0387 (6)
H13	0.1738	0.3015	−0.1181	0.046*
C14	0.22669 (13)	0.4348 (2)	−0.1248 (2)	0.0467 (7)
H14	0.2230	0.4199	−0.1935	0.056*
C15	0.26152 (12)	0.5271 (2)	−0.0687 (2)	0.0408 (6)
H15	0.2812	0.5743	−0.0997	0.049*
C16	0.26739 (10)	0.54976 (19)	0.03310 (18)	0.0275 (5)
C17	0.23776 (10)	0.47899 (18)	0.07762 (18)	0.0274 (5)
H17	0.2416	0.4940	0.1464	0.033*
C18	0.30793 (10)	0.64609 (19)	0.09891 (19)	0.0293 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02373 (16)	0.02800 (17)	0.03503 (17)	−0.00222 (12)	0.01096 (12)	0.00501 (12)
O1	0.0345 (9)	0.0438 (10)	0.0348 (10)	−0.0136 (8)	0.0144 (8)	0.0023 (8)
O2	0.0414 (10)	0.0436 (11)	0.0557 (12)	−0.0229 (8)	0.0187 (9)	−0.0109 (9)
O3	0.0326 (9)	0.0440 (10)	0.0522 (11)	−0.0121 (8)	0.0186 (8)	0.0028 (9)
O4	0.0295 (8)	0.0367 (9)	0.0376 (10)	−0.0077 (7)	0.0126 (7)	−0.0097 (7)
O5	0.0606 (15)	0.125 (2)	0.102 (2)	−0.0276 (15)	0.0466 (16)	−0.058 (2)
N1	0.0282 (10)	0.0271 (10)	0.0341 (11)	−0.0016 (8)	0.0122 (9)	0.0053 (8)
N2	0.0283 (10)	0.0264 (10)	0.0310 (11)	−0.0026 (8)	0.0118 (8)	0.0023 (8)
N3	0.0206 (10)	0.0359 (11)	0.0441 (12)	−0.0030 (8)	0.0111 (9)	0.0052 (9)
C1	0.0362 (14)	0.0328 (13)	0.0479 (16)	−0.0042 (11)	0.0170 (12)	0.0022 (11)
C2	0.0592 (19)	0.0274 (13)	0.0565 (18)	0.0005 (12)	0.0248 (15)	0.0048 (12)
C3	0.0449 (16)	0.0387 (15)	0.0451 (16)	0.0139 (12)	0.0133 (13)	0.0091 (12)
C4	0.0306 (13)	0.0451 (15)	0.0371 (15)	0.0072 (11)	0.0091 (11)	0.0078 (11)
C5	0.0279 (12)	0.0341 (13)	0.0257 (12)	−0.0003 (10)	0.0096 (10)	0.0051 (10)
C6	0.0292 (13)	0.0349 (13)	0.0240 (12)	−0.0059 (10)	0.0123 (10)	0.0014 (9)
C7	0.0324 (13)	0.0451 (15)	0.0349 (14)	−0.0121 (11)	0.0128 (11)	−0.0012 (11)
C8	0.0511 (17)	0.0341 (14)	0.0423 (16)	−0.0163 (12)	0.0184 (13)	−0.0068 (12)
C9	0.0513 (17)	0.0299 (13)	0.0510 (17)	−0.0013 (12)	0.0203 (14)	−0.0020 (12)
C10	0.0344 (14)	0.0317 (13)	0.0426 (15)	−0.0011 (10)	0.0153 (12)	−0.0004 (11)
C11	0.0215 (11)	0.0293 (12)	0.0429 (15)	0.0009 (10)	0.0110 (11)	0.0032 (11)
C12	0.0221 (11)	0.0288 (12)	0.0306 (12)	−0.0010 (9)	0.0099 (10)	0.0018 (10)
C13	0.0398 (14)	0.0367 (14)	0.0371 (15)	−0.0069 (11)	0.0139 (12)	−0.0097 (11)
C14	0.0602 (17)	0.0539 (17)	0.0296 (14)	−0.0111 (14)	0.0227 (13)	−0.0072 (12)
C15	0.0457 (15)	0.0424 (15)	0.0400 (16)	−0.0062 (12)	0.0237 (13)	0.0048 (12)
C16	0.0224 (11)	0.0283 (12)	0.0302 (12)	0.0001 (9)	0.0097 (9)	0.0022 (10)
C17	0.0250 (11)	0.0313 (12)	0.0256 (12)	−0.0021 (9)	0.0104 (10)	−0.0021 (9)
C18	0.0200 (11)	0.0271 (12)	0.0374 (14)	0.0032 (9)	0.0090 (10)	0.0047 (10)

Geometric parameters (Å, º)

Cu1—O4^i	1.9250 (15)	C3—C4	1.368 (4)
Cu1—O1	1.9356 (15)	C3—H3	0.9300
Cu1—N2	1.9650 (17)	C4—C5	1.391 (3)
Cu1—N1	1.9806 (18)	C4—H4	0.9300
Cu1—O2	2.546 (2)	C6—C7	1.390 (3)
Cu1—O3^i	3.0229 (18)	C7—C8	1.345 (3)
O1—C11	1.278 (3)	C7—H7	0.9300
O2—C11	1.226 (3)	C8—C9	1.393 (3)
O3—C18	1.241 (3)	C8—H8	0.9300
O3—Cu1^ii	3.0229 (18)	C9—C10	1.339 (3)
O4—C18	1.266 (3)	C9—H9	0.9300
O4—Cu1^ii	1.9250 (15)	C10—H10	0.9300
O5—H11	0.844 (10)	C11—C12	1.496 (3)
O5—H12	0.851 (10)	C12—C17	1.379 (3)
N1—C5	1.342 (3)	C12—C13	1.382 (3)
N1—C1	1.358 (3)	C13—C14	1.379 (3)
N2—C6	1.339 (3)	C13—H13	0.9300
N2—C10	1.359 (3)	C14—C15	1.374 (4)
N3—C5	1.372 (3)	C14—H14	0.9300
N3—C6	1.376 (3)	C15—C16	1.377 (3)
N3—H5	0.8600	C15—H15	0.9300
C1—C2	1.343 (3)	C16—C17	1.378 (3)
C1—H1	0.9300	C16—C18	1.502 (3)
C2—C3	1.381 (4)	C17—H17	0.9300
C2—H2	0.9300
O4^i—Cu1—O1	90.50 (7)	N1—C5—N3	120.72 (19)
O4^i—Cu1—N2	93.69 (7)	N1—C5—C4	121.5 (2)
O1—Cu1—N2	154.07 (8)	N3—C5—C4	117.8 (2)
O4^i—Cu1—N1	149.96 (8)	N2—C6—N3	120.37 (19)
O1—Cu1—N1	95.76 (7)	N2—C6—C7	121.1 (2)
N2—Cu1—N1	93.33 (8)	N3—C6—C7	118.6 (2)
O4^i—Cu1—O2	113.90 (7)	C8—C7—H7	119.5
O1—Cu1—O2	56.76 (6)	C6—C7—H7	119.5
N2—Cu1—O2	98.48 (7)	Cu1—C7—H7	137.7
N1—Cu1—O2	93.85 (7)	C7—C8—C9	118.5 (2)
O4^i—Cu1—O3^i	46.93 (6)	C7—C8—H8	120.8
O1—Cu1—O3^i	113.61 (6)	C9—C8—H8	120.8
N2—Cu1—O3^i	87.36 (6)	C10—C9—C8	118.2 (2)
N1—Cu1—O3^i	104.36 (6)	C10—C9—H9	120.9
O2—Cu1—O3^i	160.56 (5)	C8—C9—H9	120.9
H11—O5—H12	106 (5)	C9—C10—N2	124.6 (2)
C5—N1—C1	117.25 (19)	C9—C10—H10	117.7
C5—N1—Cu1	125.43 (15)	N2—C10—H10	117.7
C1—N1—Cu1	117.10 (15)	O2—C11—O1	122.6 (2)
C6—N2—C10	116.69 (19)	O2—C11—C12	121.2 (2)
C6—N2—Cu1	126.12 (15)	O1—C11—C12	116.14 (19)
C10—N2—Cu1	116.68 (15)	C17—C12—C13	119.2 (2)
C5—N3—C6	133.35 (18)	C17—C12—C11	119.7 (2)
C5—N3—H5	113.3	C13—C12—C11	121.0 (2)
C6—N3—H5	113.3	C14—C13—C12	119.8 (2)
Cu1—N3—H5	175.9	C14—C13—H13	120.1
Cu1^iii—N3—H5	49.6	C12—C13—H13	120.1
C2—C1—N1	123.8 (2)	C15—C14—C13	120.5 (2)
C2—C1—H1	118.1	C15—C14—H14	119.8
N1—C1—H1	118.1	C13—C14—H14	119.8
C1—C2—C3	119.0 (2)	C14—C15—C16	120.2 (2)
C3—C2—Cu1	106.44 (17)	C14—C15—H15	119.9
C1—C2—H2	120.5	C16—C15—H15	119.9
C3—C2—H2	120.5	C15—C16—C17	119.1 (2)
Cu1—C2—H2	133.0	C15—C16—C18	121.6 (2)
C4—C3—C2	118.8 (2)	C17—C16—C18	119.2 (2)
C4—C3—H3	120.6	C16—C17—C12	121.2 (2)
C2—C3—H3	120.6	C16—C17—H17	119.4
C3—C4—C5	119.6 (2)	C12—C17—H17	119.4
C3—C4—Cu1	102.08 (16)	O3—C18—O4	123.8 (2)
C3—C4—Cu1^iii	129.26 (17)	O3—C18—C16	120.7 (2)
C3—C4—H4	120.2	O4—C18—C16	115.37 (19)
C5—C4—H4	120.2

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H11···O3^i	0.84 (3)	2.21 (3)	3.017 (4)	159 (2)
O5—H12···O1^iv	0.85 (2)	2.51 (3)	3.346 (3)	167 (3)
O5—H12···O4^v	0.85 (2)	2.53 (4)	3.117 (4)	127 (3)
N3—H5···O3^vi	0.86	1.95	2.813 (3)	178

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