Crystal structure of poly[[(acetato-κO){μ3-N-[(pyridin-4-yl)meth­yl]pyrazine-2-carboxamidato-κ4N:N1,N2:N4]copper(II)] dihydrate]: a metal–organic framework (MOF)

Cati, D.S.; Stoeckli-Evans, H.

doi:10.1107/S1600536814011520

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Volume 70| Part 7| July 2014| Pages 23-26

https://doi.org/10.1107/S1600536814011520

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Crystal structure of poly[[(acetato-κO){μ₃-N-[(pyridin-4-yl)methyl]pyrazine-2-carboxamidato-κ⁴N:N¹,N²:N⁴]copper(II)] dihydrate]: a metal–organic framework (MOF)¹

Dilovan S. Cati ^a and Helen Stoeckli-Evans ^b ^*

^aDebiopharm International S.A., Chemin Messidor 5-7, CP 5911, 1002 Lausanne, Switzerland, and ^bInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
^*Correspondence e-mail: helen.stoeckli-evans@unine.ch

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 28 April 2014; accepted 16 May 2014; online 23 June 2014)

The title compound, [Cu(C₁₁H₉N₄O)(CH₃CO₂)]·2H₂O (CuL), is a hydrated copper acetate complex of the ligand N-[(pyridin-4-yl)methyl]pyrazine-2-carboxamide (HL). Complex CuL has a metal–organic framework (MOF) structure with a 10 (3) network topology. The ligand coordinates in a bidentate and a bis-monodentate manner, bridging three equivalent Cu^II atoms via the pyridine N atom and the second pyrazine N atom. The Cu^II atom has a fivefold coordination sphere, CuN₄O, being coordinated to three N atoms of the ligand and the acetate O atom in the equatorial plane and to the second pyrazine atom in the apical position. This gives rise to a fairly regular square-pyramidal geometry. In the crystal, the water molecules are linked to each other and to the three-dimensional framework via O—H⋯O hydrogen bonds. There are also a number of C—H⋯O hydrogen bonds present within the framework.

Keywords: crystal structure; metal-organic framework; 10 (3) network topology; copper(II); pyrazine-2-carboxamide.

CCDC reference: 1004264

1. Chemical context

The ligand N-[(pyridin-4-yl)methyl]pyrazine-2-carboxamide (HL) is one of a series of ligands which were synthesized in order to study their coordination behaviour towards first-row transition metals (Cati, 2002 ; Cati et al., 2004 ; Cati & Stoeckli-Evans, 2014 ). HL is expected to coordinate in a bidentate and possibly a monodentate manner, with eventual bridging of metal atoms to construct two- or three-dimensional networks. A excellent review on the subject of coordination polymers and network structures has been published by Batten et al. (2009 ).

2. Structural commentary

The title compound, CuL, is a copper acetate complex of the ligand N-[(pyridin-4-yl)methyl]pyrazine-2-carboxamide (HL) [Cati & Stoeckli-Evans, 2014]. In complex CuL the ligand coordinates in a bidentate and a bis-monodentate manner, so bridging three equivalent copper atoms (Fig. 1). This gives rise to the formation of a three-dimensional coordination polymer, or MOF (metal–organic framework) structure, as shown in Fig. 2. The copper⋯copper distances are 7.156 (2) Å via the bridging pyrazine ring (Cu1⋯Cu1ⁱⁱⁱ) and 7.420 (2) Å via the pyridine N atom Cu1⋯Cu1^iv; see Fig. 1). Atom Cu1 has a fivefold coordination sphere, CuN₄O, with three N atoms (N1, N3 and N4ⁱ) and the acetate O atom, O2, in the equatorial plane and the second pyrazine N atom, N2ⁱⁱ, in the apical position [Fig. 2; symmetry codes: (i) x, −y, z − $[{1\over 2}]$ ; (ii) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ]. The apical Cu1—N2 bond distance of 2.393 (3) Å is considerably longer that the Cu1–N1, Cu1—N3 and Cu1—N4 bond lengths [2.003 (8), 1.964 (9) and 1.993 (7) Å, respectively], and the Cu1—O2 bond length [1.947 (7) Å] in the equatorial plane. Bond angles O2—Cu1—N3 and N4—Cu1—N1 are 172.2 (3) and 170.6 (3)°, respectively, and this leads to a perfect square-pyramidal geometry with τ = 0.03 (τ = 0 square-pyramidal; τ = 1 trigonal-bipyramidal; Addison et al., 1984 ). The pyridine ring is inclined to the pyrazine ring by 79.6 (5)° compared to 84.33 (12)° in the free ligand (Cati & Stoeckli-Evans, 2014). The bond distances and angles are normal when compared with geometrical parameters of related copper(II) complexes in the Cambridge Structural Database (Version 5.35, last update November 2013; Allen, 2002 ), and are similar to those observed in the mononuclear copper(II) acetate complex of the analogous ligand N-[(pyridin-2-yl)methyl]pyrazine-2-carboxamide (Mohamadou et al., 2012 ). The title compound crystallizes with two solvent water molecules per asymmetric unit.

Figure 1
A view of the asymmetric unit of complex CuL, with atom labelling [symmetry codes: (i) x, −y, z − $[{1\over 2}]$ ; (ii) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (iii) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (iv) x, −y, z + $[{1\over 2}]$ ]. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
A view along the a axis of the metal–organic framework (MOF) structure of complex CuL. Solvent water molecules and H atoms have been omitted for clarity.

3. Supramolecular features

The three-dimensional network of the title MOF structure has a 10 (3) network topology (Fig. 3). It is one of the most commonly encountered 3-connected three-dimensional nets with ten-membered rings (Wells, 1984 ). It is a cubic (10,3)-a net, also known as the srs (SrSi₂) net, which is chiral [note that the Flack x parameter = −0.01 (3)]. Such structures contain fourfold helices along the three axes all of the same hand (Batten et al., 2009).

Figure 3
A view of the 10 (3) network topology of the title metal–organic framework (MOF) structure, illustrating the 3-connected three-dimensional nets with ten-membered rings.

In the crystal of CuL, the water molecules are located in the cavities of the MOF structure. They are hydrogen bonded to one another and to the ligand and acetate carbonyl O atoms (Table 1 and Fig. 4). There are also a number of C—H⋯O hydrogen bonds present within the framework (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O3ⁱ	0.84 (3)	2.13 (5)	2.908 (9)	154 (9)
O1W—H1WB⋯O3ⁱⁱⁱ	0.84 (3)	2.23 (5)	2.964 (10)	146 (8)
O2W—H2WA⋯O1W	0.86 (3)	2.11 (4)	2.951 (10)	165 (10)
O2W—H2WB⋯O1^iv	0.85 (3)	2.20 (3)	3.033 (8)	169 (10)
C2—H2⋯O2^v	0.95	2.37	2.987 (13)	123
C8—H8⋯O3^vi	0.95	2.57	3.364 (11)	141
C9—H9⋯O2W^vii	0.95	2.50	3.358 (12)	151
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (iii) x, y, z-1; (iv) x+1, y, z-1; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) x-1, y, z; (vii) $[x-1, -y, z+{\script{1\over 2}}]$ .

Figure 4
A view along the c axis of the crystal packing of complex CuL, with the hydrogen bonds involving the water molecules shown as dashed lines (see Table 1

for details; H atoms not involved in these hydrogen bonding have been omitted for clarity).

4. Database survey

A search of the Cambridge Structural Database (Version 5.35, last update November 2013; Allen, 2002) indicated that no complexes of the ligand HL have been described previously. The analogous ligand N-[(pyridin-2-yl)methyl]pyrazine-2-carboxamide has been described as well as a number of metal complexes. These include the mononuclear copper acetate complex (Mohamadou et al., 2012). Here this ligand coordinates in a tridentate manner but in a number of other complexes it coordinates in a bis-monodentate manner via the pyridine N atom and a pyrazine N atom; for example, in two polymeric mercury chloride complexes (Khavasi et al., 2010 ), and a polymeric silver tetrafluoroborate complex (Hellyer et al., 2009 ).

5. Synthesis and crystallization

The synthesis of the ligand N-[(pyridin-4-yl)methyl]pyrazine-2-carboxamide (HL) has been described elsewhere (Cati, 2002; Cati & Stoeckli-Evans, 2014). Complex CuL was prepared by adding Cu(acetate)₂·H₂O (64 mg, 0.318 mmol) to a hot solution (323 K) of HL (68 mg, 0.318 mmol) in dry methanol (25 ml). In 2 min a precipitate appeared and heating was stopped and the mixture stirred as the temperature decreased to room temperature. After 30 min the precipitate was filtered off and washed with dry methanol. It was then dissolved in a mixture of water (12 ml) and methanol (15 ml) and stirred with warming to between 313 to 323 K for 15 min. The resulting blue solution was allowed to stand at room temperature and yielded blue crystals in a few days [yield 72 mg, 61%]. Analysis for C₁₃H₁₂CuN₄O₃·2(H₂O) (M_r = 371.84). Calculated (%): C 41.99, H 4.34, N 15.07. Found: C 42.17, H 4.33, N 14.75.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The water H atoms were located in difference Fourier maps were refined with distance restraints: O—H = 0.84 (2) and H⋯H = 1.35 (2) Å with U_iso(H) = 1.5U_eq(O). The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.95 Å with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₁₁H₉N₄O)(C₂H₃O₂)]·2H₂O
M_r	371.84
Crystal system, space group	Monoclinic, Cc
Temperature (K)	153
a, b, c (Å)	7.8256 (12), 22.331 (2), 8.9976 (13)
β (°)	110.040 (16)
V (Å³)	1477.2 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.51
Crystal size (mm)	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Stoe IPDS I
Absorption correction	Multi-scan (MULscanABS in PLATON; Spek, 2009 )
T_min, T_max	0.979, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5730, 2705, 1778
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.072, 0.78
No. of reflections	2705
No. of parameters	203
No. of restraints	8
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.59
Absolute structure	Flack x determined using 665 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons & Flack, 2004 )
Absolute structure parameter	−0.01 (3)
Computer programs: EXPOSE in IPDSI, CELL and INTEGRATE in IPDSI (Stoe & Cie, 2004 ), SHELXS97 and SHELXL2013 (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1004264

Crystal structure: contains datablock CuL. DOI: https://doi.org/10.1107/S1600536814011520/hb0008sup1.cif

Structure factors: contains datablock CuL2. DOI: https://doi.org/10.1107/S1600536814011520/hb0008CuL2sup2.hkl

checkCIF report

Computing details top

Data collection: EXPOSE in IPDSI (Stoe & Cie, 2004); cell refinement: CELL in IPDSI (Stoe & Cie, 2004); data reduction: INTEGRATE in IPDSI (Stoe & Cie, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Poly[[(acetato-κO){µ₃-N-[(pyridin-4-yl)methyl]pyrazine-2-carboxamidato-κ⁴N:N¹,N²:N⁴]copper(II)] dihydrate] top

Crystal data top

[Cu(C₁₁H₉N₄O)(C₂H₃O₂)]·2H₂O	F(000) = 764
M_r = 371.84	D_x = 1.672 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2705 reflections
a = 7.8256 (12) Å	θ = 2.1–26.1°
b = 22.331 (2) Å	µ = 1.51 mm⁻¹
c = 8.9976 (13) Å	T = 153 K
β = 110.040 (16)°	Block, turquoise blue
V = 1477.2 (4) Å³	0.40 × 0.30 × 0.30 mm
Z = 4

Data collection top

Stoe IPDS I diffractometer	2705 independent reflections
Radiation source: fine-focus sealed tube	1778 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.070
φ rotation scans	θ_max = 25.9°, θ_min = 2.9°
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009)	h = −9→9
T_min = 0.979, T_max = 1.000	k = −27→26
5730 measured reflections	l = −11→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.007P)²] where P = (F_o² + 2F_c²)/3
S = 0.78	(Δ/σ)_max < 0.001
2705 reflections	Δρ_max = 0.40 e Å⁻³
203 parameters	Δρ_min = −0.59 e Å⁻³
8 restraints	Absolute structure: Flack x determined using 665 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons & Flack, 2004)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (3)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.44720 (19)	0.13211 (4)	0.83884 (18)	0.0155 (2)
O1	0.3072 (8)	0.1995 (2)	1.2004 (7)	0.0248 (16)
O2	0.5973 (10)	0.1326 (3)	0.7054 (9)	0.0169 (15)
O3	0.7386 (8)	0.0439 (3)	0.7464 (8)	0.0266 (15)
N1	0.5958 (11)	0.1988 (3)	0.9695 (9)	0.0155 (9)
N2	0.7658 (12)	0.2933 (3)	1.1646 (9)	0.0155 (9)
N3	0.3109 (12)	0.1421 (4)	0.9844 (11)	0.0155 (9)
N4	0.3255 (10)	−0.0570 (3)	1.2361 (9)	0.0155 (9)
C1	0.7378 (15)	0.2255 (5)	0.9510 (12)	0.018 (3)
H1	0.7839	0.2120	0.8720	0.022*
C2	0.8206 (16)	0.2742 (5)	1.0483 (12)	0.018 (3)
H2	0.9191	0.2940	1.0304	0.021*
C3	0.6208 (15)	0.2647 (4)	1.1831 (13)	0.015 (2)
H3	0.5771	0.2774	1.2644	0.018*
C4	0.5351 (15)	0.2174 (5)	1.0852 (11)	0.014 (2)
C5	0.3707 (11)	0.1848 (3)	1.0932 (10)	0.0146 (19)
C6	0.1512 (13)	0.1078 (4)	0.9801 (12)	0.015 (2)
H6A	0.0774	0.0987	0.8689	0.018*
H6B	0.0757	0.1320	1.0262	0.018*
C7	0.2058 (11)	0.0497 (3)	1.0721 (11)	0.0124 (17)
C8	0.1360 (11)	−0.0045 (4)	1.0059 (11)	0.020 (2)
H8	0.0425	−0.0061	0.9053	0.024*
C9	0.2044 (13)	−0.0571 (4)	1.0884 (13)	0.020 (2)
H9	0.1638	−0.0944	1.0381	0.024*
C10	0.3872 (11)	−0.0036 (3)	1.3001 (11)	0.019 (2)
H10	0.4747	−0.0028	1.4039	0.023*
C11	0.3310 (12)	0.0503 (4)	1.2239 (10)	0.016 (2)
H11	0.3775	0.0871	1.2748	0.019*
C12	0.6927 (13)	0.0907 (5)	0.6705 (13)	0.016 (2)
C13	0.7531 (12)	0.1058 (4)	0.5323 (10)	0.024 (2)
H13A	0.7724	0.0687	0.4820	0.035*
H13B	0.8669	0.1285	0.5701	0.035*
H13C	0.6591	0.1298	0.4552	0.035*
O1W	0.7662 (12)	0.0650 (3)	0.0791 (10)	0.0313 (19)
H1WA	0.764 (17)	0.042 (4)	0.151 (8)	0.047*
H1WB	0.752 (15)	0.044 (4)	−0.002 (7)	0.047*
O2W	0.9960 (9)	0.1546 (3)	0.2989 (8)	0.0358 (18)
H2WA	0.925 (10)	0.134 (4)	0.222 (8)	0.054*
H2WB	1.072 (10)	0.169 (4)	0.261 (10)	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0184 (5)	0.0119 (4)	0.0183 (5)	−0.0019 (8)	0.0092 (4)	−0.0025 (8)
O1	0.032 (4)	0.021 (3)	0.032 (4)	−0.011 (3)	0.025 (4)	−0.013 (3)
O2	0.023 (4)	0.008 (3)	0.023 (4)	0.000 (3)	0.012 (3)	−0.004 (3)
O3	0.025 (4)	0.019 (3)	0.037 (5)	0.009 (3)	0.013 (3)	0.005 (3)
N1	0.018 (2)	0.0133 (18)	0.018 (2)	−0.0018 (16)	0.009 (2)	0.0013 (17)
N2	0.018 (2)	0.0133 (18)	0.018 (2)	−0.0018 (16)	0.009 (2)	0.0013 (17)
N3	0.018 (2)	0.0133 (18)	0.018 (2)	−0.0018 (16)	0.009 (2)	0.0013 (17)
N4	0.018 (2)	0.0133 (18)	0.018 (2)	−0.0018 (16)	0.009 (2)	0.0013 (17)
C1	0.017 (6)	0.017 (5)	0.020 (6)	−0.004 (4)	0.007 (5)	−0.002 (5)
C2	0.019 (6)	0.022 (6)	0.016 (6)	−0.003 (5)	0.011 (5)	−0.001 (5)
C3	0.018 (6)	0.014 (5)	0.016 (6)	−0.005 (4)	0.012 (5)	−0.001 (4)
C4	0.023 (6)	0.010 (5)	0.012 (5)	−0.005 (4)	0.010 (5)	0.001 (4)
C5	0.015 (5)	0.016 (4)	0.014 (5)	−0.002 (3)	0.006 (4)	0.001 (4)
C6	0.013 (6)	0.010 (5)	0.021 (6)	−0.002 (4)	0.004 (5)	0.003 (4)
C7	0.011 (4)	0.009 (4)	0.018 (5)	0.002 (3)	0.006 (4)	0.006 (4)
C8	0.012 (5)	0.020 (4)	0.027 (6)	0.001 (4)	0.005 (4)	0.000 (4)
C9	0.020 (5)	0.012 (5)	0.028 (7)	−0.004 (4)	0.009 (5)	0.002 (4)
C10	0.024 (6)	0.017 (4)	0.017 (6)	0.000 (3)	0.009 (5)	0.002 (4)
C11	0.023 (5)	0.007 (4)	0.018 (5)	−0.003 (4)	0.008 (5)	−0.004 (4)
C12	0.007 (5)	0.022 (6)	0.019 (6)	0.001 (4)	0.004 (5)	0.001 (5)
C13	0.019 (5)	0.035 (5)	0.022 (6)	0.004 (4)	0.014 (5)	−0.003 (4)
O1W	0.047 (5)	0.019 (4)	0.033 (5)	−0.002 (4)	0.019 (5)	0.001 (3)
O2W	0.042 (5)	0.038 (4)	0.034 (5)	−0.007 (3)	0.022 (4)	−0.006 (3)

Geometric parameters (Å, º) top

Cu1—O2	1.947 (7)	C3—H3	0.9500
Cu1—N3	1.964 (9)	C4—C5	1.500 (13)
Cu1—N4ⁱ	1.993 (7)	C6—C7	1.520 (11)
Cu1—N1	2.003 (8)	C6—H6A	0.9900
Cu1—N2ⁱⁱ	2.393 (8)	C6—H6B	0.9900
O1—C5	1.270 (9)	C7—C8	1.376 (11)
O2—C12	1.300 (12)	C7—C11	1.382 (12)
O3—C12	1.232 (11)	C8—C9	1.395 (13)
N1—C1	1.323 (13)	C8—H8	0.9500
N1—C4	1.349 (12)	C9—H9	0.9500
N2—C2	1.330 (13)	C10—C11	1.381 (11)
N2—C3	1.360 (13)	C10—H10	0.9500
N2—Cu1ⁱⁱⁱ	2.393 (8)	C11—H11	0.9500
N3—C5	1.332 (11)	C12—C13	1.512 (12)
N3—C6	1.455 (13)	C13—H13A	0.9800
N4—C10	1.341 (10)	C13—H13B	0.9800
N4—C9	1.342 (13)	C13—H13C	0.9800
N4—Cu1^iv	1.992 (7)	O1W—H1WA	0.84 (3)
C1—C2	1.405 (14)	O1W—H1WB	0.84 (3)
C1—H1	0.9500	O2W—H2WA	0.86 (3)
C2—H2	0.9500	O2W—H2WB	0.85 (3)
C3—C4	1.393 (13)

O2—Cu1—N3	172.2 (3)	O1—C5—N3	127.8 (8)
O2—Cu1—N4ⁱ	90.7 (3)	O1—C5—C4	118.5 (8)
N3—Cu1—N4ⁱ	97.0 (3)	N3—C5—C4	113.7 (8)
O2—Cu1—N1	90.4 (3)	N3—C6—C7	110.9 (8)
N3—Cu1—N1	82.1 (4)	N3—C6—H6A	109.5
N4ⁱ—Cu1—N1	170.6 (3)	C7—C6—H6A	109.5
O2—Cu1—N2ⁱⁱ	86.5 (3)	N3—C6—H6B	109.5
N3—Cu1—N2ⁱⁱ	91.3 (3)	C7—C6—H6B	109.5
N4ⁱ—Cu1—N2ⁱⁱ	101.5 (3)	H6A—C6—H6B	108.0
N1—Cu1—N2ⁱⁱ	87.8 (2)	C8—C7—C11	118.6 (8)
C12—O2—Cu1	131.5 (6)	C8—C7—C6	121.3 (8)
C1—N1—C4	119.4 (8)	C11—C7—C6	120.1 (8)
C1—N1—Cu1	127.3 (7)	C7—C8—C9	119.2 (9)
C4—N1—Cu1	113.3 (7)	C7—C8—H8	120.4
C2—N2—C3	116.9 (9)	C9—C8—H8	120.4
C2—N2—Cu1ⁱⁱⁱ	117.4 (7)	N4—C9—C8	122.6 (9)
C3—N2—Cu1ⁱⁱⁱ	125.3 (7)	N4—C9—H9	118.7
C5—N3—C6	118.6 (9)	C8—C9—H9	118.7
C5—N3—Cu1	115.9 (6)	N4—C10—C11	123.8 (8)
C6—N3—Cu1	125.5 (7)	N4—C10—H10	118.1
C10—N4—C9	117.0 (7)	C11—C10—H10	118.1
C10—N4—Cu1^iv	120.3 (6)	C10—C11—C7	118.6 (8)
C9—N4—Cu1^iv	121.4 (6)	C10—C11—H11	120.7
N1—C1—C2	119.9 (10)	C7—C11—H11	120.7
N1—C1—H1	120.0	O3—C12—O2	124.0 (9)
C2—C1—H1	120.0	O3—C12—C13	122.0 (9)
N2—C2—C1	122.3 (10)	O2—C12—C13	113.9 (8)
N2—C2—H2	118.9	C12—C13—H13A	109.5
C1—C2—H2	118.9	C12—C13—H13B	109.5
N2—C3—C4	121.3 (10)	H13A—C13—H13B	109.5
N2—C3—H3	119.3	C12—C13—H13C	109.5
C4—C3—H3	119.3	H13A—C13—H13C	109.5
N1—C4—C3	120.1 (10)	H13B—C13—H13C	109.5
N1—C4—C5	115.0 (8)	H1WA—O1W—H1WB	107 (4)
C3—C4—C5	124.9 (9)	H2WA—O2W—H2WB	104 (4)

C4—N1—C1—C2	−2.0 (14)	N1—C4—C5—N3	0.4 (12)
Cu1—N1—C1—C2	176.4 (8)	C3—C4—C5—N3	178.4 (10)
C3—N2—C2—C1	−1.9 (15)	C5—N3—C6—C7	−95.5 (10)
Cu1ⁱⁱⁱ—N2—C2—C1	172.1 (9)	Cu1—N3—C6—C7	85.8 (10)
N1—C1—C2—N2	2.8 (17)	N3—C6—C7—C8	−128.6 (9)
C2—N2—C3—C4	0.5 (14)	N3—C6—C7—C11	49.7 (12)
Cu1ⁱⁱⁱ—N2—C3—C4	−173.0 (8)	C11—C7—C8—C9	−5.2 (12)
C1—N1—C4—C3	0.5 (14)	C6—C7—C8—C9	173.2 (8)
Cu1—N1—C4—C3	−178.0 (8)	C10—N4—C9—C8	−3.5 (12)
C1—N1—C4—C5	178.7 (9)	Cu1^iv—N4—C9—C8	−171.0 (7)
Cu1—N1—C4—C5	0.1 (11)	C7—C8—C9—N4	5.7 (13)
N2—C3—C4—N1	0.2 (16)	C9—N4—C10—C11	1.1 (11)
N2—C3—C4—C5	−177.7 (9)	Cu1^iv—N4—C10—C11	168.8 (6)
C6—N3—C5—O1	1.8 (14)	N4—C10—C11—C7	−0.9 (12)
Cu1—N3—C5—O1	−179.4 (7)	C8—C7—C11—C10	2.9 (12)
C6—N3—C5—C4	−179.5 (9)	C6—C7—C11—C10	−175.5 (8)
Cu1—N3—C5—C4	−0.7 (10)	Cu1—O2—C12—O3	−17.2 (15)
N1—C4—C5—O1	179.2 (8)	Cu1—O2—C12—C13	166.2 (7)
C3—C4—C5—O1	−2.8 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3ⁱ	0.84 (3)	2.13 (5)	2.908 (9)	154 (9)
O1W—H1WB···O3^v	0.84 (3)	2.23 (5)	2.964 (10)	146 (8)
O2W—H2WA···O1W	0.86 (3)	2.11 (4)	2.951 (10)	165 (10)
O2W—H2WB···O1^vi	0.85 (3)	2.20 (3)	3.033 (8)	169 (10)
C2—H2···O2ⁱⁱⁱ	0.95	2.37	2.987 (13)	123
C8—H8···O3^vii	0.95	2.57	3.364 (11)	141
C9—H9···O2W^viii	0.95	2.50	3.358 (12)	151

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

Footnotes

¹This work is part of the PhD thesis (University of Neuchâtel, 2002) of DSC.

Acknowledgements

This work was supported by the Swiss National Science Foundation and the University of Neuchâtel.

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