Bis(5-hy­droxy­isophthalato-κO1)bis­[4-(pyridine-3-carboxamido-κN3)pyridinium]copper(II) tetra­hydrate

O'Donovan, M.E.; LaDuca, R.L.

doi:10.1107/S1600536813030675

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page m663

doi:10.1107/S1600536813030675

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Bis(5-hydroxyisophthalato-κO¹)bis[4-(pyridine-3-carboxamido-κN³)pyridinium]copper(II) tetrahydrate

Megan E. O'Donovan ^a and Robert L. LaDuca ^a ^*

^aLyman Briggs College, Department of Chemistry, Michigan State University, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

(Received 7 November 2013; accepted 8 November 2013; online 16 November 2013)

In the title compound, [Cu(C₁₁H₁₀N₃O)₂(C₈H₄O₅)₂]·4H₂O, the Cu^II ion, located on a crystallographic inversion center, is coordinated in a square-planar environment by two trans-O atoms belonging to two monodentate 5-hydroxyisophthalate (hip) dianions and two trans nicotinamide pyridyl N-donor atoms from monodentate protonated pendant N-(pyridin-4-yl)nicotinamide (4-pnaH) ligands. The protonated 4-pyridylamine groups engage in N—H⁺⋯O⁻ hydrogen-bond donation to unligated hip O atoms to construct supramolecular chain motifs parallel to [100]. Water molecules of crystallization, situated between the chains, engage in O—H⋯O hydrogen bonding to form supramolecular layers and the overall three-dimensional network structure.

CCDC reference: 970839

Related literature

For the preparation of 4-pyridylnicotinamide, see: Gardner et al. (1954 ). For the preparation of other dicarboxylate coordination polymers containing 4-pyridylnicotinamide, see: Kumar (2009 ); Wilson et al. (2013 )

Experimental

Crystal data

[Cu(C₁₁H₁₀N₃O)₂(C₈H₄O₅)₂]·4H₂O
M_r = 896.27
Monoclinic, P 2₁ /c
a = 16.402 (2) Å
b = 7.7699 (10) Å
c = 16.403 (2) Å
β = 115.466 (1)°
V = 1887.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.67 mm⁻¹
T = 173 K
0.50 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.686, T_max = 0.745
15084 measured reflections
3483 independent reflections
3122 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.076
S = 1.07
3483 reflections
288 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4ⁱ	0.87	1.85	2.7164 (18)	170
O1W—H1WB⋯O3ⁱⁱ	0.87	1.92	2.775 (2)	169
O2W—H2WA⋯O2	0.87	1.97	2.814 (2)	163
O2W—H2WB⋯O2ⁱⁱⁱ	0.87	1.94	2.8049 (18)	177
O5—H5⋯O1W	0.84	1.81	2.6384 (18)	168
N2—H2⋯O2W^iv	0.88	2.00	2.823 (2)	156
N3—H3⋯O3^v	0.91 (3)	1.69 (3)	2.582 (2)	166 (2)
Symmetry codes: (i) -x, -y, -z; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) -x, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: CrystalMaker (Palmer, 2007 ); software used to prepare material for publication: OLEX2.

Supporting information

CCDC reference: 970839

Crystal structure: contains datablocks I, p21c. DOI: 10.1107/S1600536813030675/hg5361sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813030675/hg5361Isup2.hkl

checkCIF report

Comment top

In comparison to divalent metal coordination polymers containing rigid rod dipyridine ligands such as 4,4'-bipyridine, related phases containing the kinked and hydrogen-bonding capable dipodal ligand 4-pyridylnicotinamide (4-pna) are less widely reported (Kumar, 2009; Wilson et al., 2013). The title compound was obtained in attempt at preparing a coordination polymer, as purple crystals through the hydrothermal reaction of copper nitrate, 5-hydroxyisophthalic acid (H2hip), and 4-pna in the presence of aqueous base.

The asymmetric unit of the title compound, which exists as a simple coordination complex [Cu(hip)₂(4-pnaH)₂]·4H₂O, contains a divalent copper atom on a crystallographic inversion center, a 4-pnaH ligand protonated at its unligated 4-pyridylamine terminus, a doubly deprotonated hip ligand, and two water molecules of crystallization. The copper atom is square planar coordinated (Fig. 1) by two trans O atoms belonging to two monodentate 5-hydroxyisophthalate (hip) dianions and two trans nicotinamide pyridyl N-donor atoms from 4-pnaH ligands.

Neighboring [Cu(hip)₂(4-pnaH)₂] coordination complexes are connected into supramolecular chains parallel to [1 0 0] by charge-separated N—H⁺···O^- hydrogen bonding between the protonated termini of the 4-pnaH ligands and unligated hip oxygen atoms (Fig. 2). These chains aggregate into undulating supramolecular layers (Fig. 3) by means of O—H···O hydrogen bonding mediated by the water molecules of crystallization. The main interchain aggregation mechanism involves O—H···O hydrogen bonding from water molecules (O2W) to unbound hip oxygen atoms (O2) belonging to the ligated monodentate carboxylate groups (Fig. 4). These water molecules also accept N—H···O hydrogen bonding from the central amide functional group of the 4-pnaH ligands. The aggregation of the supramolecular layers into the full three-dimensional crystal structure of the title compound is accomplished by O—H···O hydrogen bonding patterns. The hydroxyl group of the hip ligands in one layer donates hydrogen bonds to the water molecules of crystallization (O1W), which in turn serve as hydrogen bonding donors to unligated hip oxygen atoms in a neighboring layer (Fig. 5).

Related literature top

For the preparation of 4-pyridylnicotinamide, see: Gardner et al. (1954). For the preparation of other dicarboxylate coordination polymers containing 4-pyridylnicotinamide, see: Kumar (2009); Wilson et al. (2013)

Experimental top

Copper(II) nitrate hydrate and 5-hydroxyisophthalic acid were obtained commercially. 4-Pyridylnicotinamide (4-pna) was prepared via a published procedure (Gardner et al., 1954). A mixture of copper nitrate hydrate (65 mg, 0.28 mmol), 5-hydroxyisophthalic acid (51 mg, 0.28 mmol), 4-pna (55 mg, 0.28 mmol) and 10.0 g water (550 mmol), along with 0.5 mL of 1.0 M NaOH solution was placed into a 23 ml Teflon-lined Parr acid digestion bomb, which was then heated under autogenous pressure at 373 K for 48 h. Purple blocks of the title compound were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2007); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. A complete molecule of the title compound, showing 50% probability ellipsoids, and atom numbering scheme. Hydrogen atom positions are shown as grey sticks. Color codes: dark blue Cu, red O, light blue N, black C. Symmetry code: (i) -x + 1, -y + 1, -z + 1.
	Fig. 2. A single supramolecular chain in the title compound. N—H⁺···O^- hydrogen bonding is shown as dashed lines.
	Fig. 3. Aggregation of supramolecular chains in the title compound, mediated by water molecules of crystallization (orange spheres). O—H···O hydrogen bonding is shown as dashed lines.
	Fig. 4. Layer of supramolecular chains in the title compound. O—H···O hydrogen bonding is shown as dashed lines.
	Fig. 5. Stacking of supramolecular layers within the title compound.

Bis(5-hydroxyisophthalato-κO¹)bis[4-(pyridine-3-carboxamido-κN³)pyridinium]copper(II) tetrahydrate top

Crystal data top

[Cu(C₁₁H₁₀N₃O)₂(C₈H₄O₅)₂]·4H₂O	F(000) = 926
M_r = 896.27	D_x = 1.577 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.402 (2) Å	Cell parameters from 9855 reflections
b = 7.7699 (10) Å	θ = 2.5–25.4°
c = 16.403 (2) Å	µ = 0.67 mm⁻¹
β = 115.466 (1)°	T = 173 K
V = 1887.3 (4) Å³	Block, purple
Z = 2	0.50 × 0.20 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	3483 independent reflections
Radiation source: fine-focus sealed tube	3122 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 25.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −19→19
T_min = 0.686, T_max = 0.745	k = −9→9
15084 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0359P)² + 1.2489P] where P = (F_o² + 2F_c²)/3
3483 reflections	(Δ/σ)_max < 0.001
288 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Cu(C₁₁H₁₀N₃O)₂(C₈H₄O₅)₂]·4H₂O	V = 1887.3 (4) Å³
M_r = 896.27	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.402 (2) Å	µ = 0.67 mm⁻¹
b = 7.7699 (10) Å	T = 173 K
c = 16.403 (2) Å	0.50 × 0.20 × 0.18 mm
β = 115.466 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3483 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	3122 reflections with I > 2σ(I)
T_min = 0.686, T_max = 0.745	R_int = 0.025
15084 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.26 e Å⁻³
3483 reflections	Δρ_min = −0.42 e Å⁻³
288 parameters

Special details top

Experimental. SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0479 before and 0.0373 after correction. The Ratio of minimum to maximum transmission is 0.9208. The λ/2 correction factor is 0.0015.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.5000	0.5000	0.01401 (10)
O1	0.39722 (8)	0.39435 (15)	0.40222 (8)	0.0194 (3)
O1W	0.14145 (9)	−0.00460 (18)	−0.10490 (9)	0.0275 (3)
H1WA	0.0933	−0.0485	−0.1035	0.041*
H1WB	0.1260	0.0626	−0.1516	0.041*
O2	0.46616 (8)	0.48157 (16)	0.31902 (9)	0.0228 (3)
O2W	0.40905 (9)	0.7846 (2)	0.21591 (10)	0.0321 (3)
H2WA	0.4346	0.6894	0.2425	0.048*
H2WB	0.4483	0.8481	0.2072	0.048*
O3	0.07175 (9)	0.2777 (2)	0.25064 (10)	0.0376 (4)
O4	0.01886 (9)	0.13283 (19)	0.12102 (9)	0.0304 (3)
O5	0.27672 (8)	0.14834 (18)	0.02882 (8)	0.0255 (3)
H5	0.2295	0.1022	−0.0096	0.038*
O6	0.15526 (9)	0.9500 (2)	0.45393 (9)	0.0310 (3)
N1	0.42685 (9)	0.71203 (18)	0.47758 (9)	0.0162 (3)
N2	0.23450 (10)	0.7950 (2)	0.58285 (10)	0.0209 (3)
H2	0.2868	0.7446	0.6140	0.025*
N3	0.05618 (10)	0.7640 (2)	0.69925 (11)	0.0243 (3)
H3	0.0179 (18)	0.754 (3)	0.7256 (17)	0.049 (7)*
C1	0.43854 (12)	0.8397 (2)	0.42900 (11)	0.0195 (4)
H1	0.4862	0.8312	0.4109	0.023*
C2	0.38399 (13)	0.9829 (2)	0.40438 (13)	0.0241 (4)
H2A	0.3935	1.0713	0.3694	0.029*
C3	0.31522 (13)	0.9966 (2)	0.43120 (13)	0.0227 (4)
H3A	0.2769	1.0947	0.4152	0.027*
C4	0.30281 (11)	0.8649 (2)	0.48184 (11)	0.0184 (4)
C5	0.35943 (11)	0.7231 (2)	0.50298 (11)	0.0174 (3)
H5A	0.3503	0.6312	0.5363	0.021*
C6	0.22328 (12)	0.8746 (2)	0.50426 (12)	0.0212 (4)
C7	0.02556 (12)	0.8174 (3)	0.61421 (13)	0.0272 (4)
H7	−0.0363	0.8480	0.5824	0.033*
C8	0.08076 (12)	0.8293 (3)	0.57121 (13)	0.0255 (4)
H8	0.0576	0.8666	0.5102	0.031*
C9	0.17144 (12)	0.7858 (2)	0.61853 (12)	0.0196 (4)
C10	0.20149 (12)	0.7265 (3)	0.70722 (12)	0.0246 (4)
H10	0.2627	0.6932	0.7407	0.029*
C11	0.14239 (13)	0.7166 (3)	0.74539 (13)	0.0272 (4)
H11	0.1627	0.6755	0.8055	0.033*
C12	0.32288 (11)	0.3368 (2)	0.24693 (11)	0.0165 (3)
C13	0.24036 (11)	0.3152 (2)	0.25072 (11)	0.0167 (3)
H13	0.2332	0.3524	0.3024	0.020*
C14	0.16865 (11)	0.2397 (2)	0.17922 (11)	0.0174 (4)
C15	0.17939 (11)	0.1822 (2)	0.10391 (11)	0.0183 (4)
H15	0.1306	0.1283	0.0554	0.022*
C16	0.26192 (12)	0.2041 (2)	0.10003 (11)	0.0183 (4)
C17	0.33334 (11)	0.2836 (2)	0.17084 (12)	0.0187 (4)
H17	0.3891	0.3015	0.1674	0.022*
C18	0.07858 (12)	0.2138 (2)	0.18280 (12)	0.0218 (4)
C19	0.40097 (11)	0.4108 (2)	0.32675 (11)	0.0167 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01290 (16)	0.01534 (16)	0.01324 (16)	0.00149 (11)	0.00510 (12)	−0.00120 (10)
O1	0.0185 (6)	0.0214 (6)	0.0162 (6)	−0.0007 (5)	0.0053 (5)	−0.0027 (5)
O1W	0.0196 (7)	0.0403 (9)	0.0210 (7)	−0.0074 (6)	0.0074 (6)	−0.0019 (6)
O2	0.0155 (6)	0.0255 (7)	0.0267 (7)	−0.0033 (5)	0.0084 (5)	−0.0035 (5)
O2W	0.0195 (7)	0.0429 (9)	0.0321 (8)	−0.0053 (6)	0.0096 (6)	0.0088 (7)
O3	0.0245 (7)	0.0638 (10)	0.0321 (8)	−0.0103 (7)	0.0193 (7)	−0.0163 (7)
O4	0.0189 (7)	0.0450 (9)	0.0263 (7)	−0.0103 (6)	0.0088 (6)	−0.0057 (6)
O5	0.0225 (7)	0.0359 (8)	0.0209 (7)	−0.0062 (6)	0.0119 (6)	−0.0104 (6)
O6	0.0217 (7)	0.0413 (8)	0.0309 (8)	0.0147 (6)	0.0121 (6)	0.0113 (6)
N1	0.0156 (7)	0.0166 (7)	0.0149 (7)	−0.0006 (6)	0.0051 (6)	−0.0022 (5)
N2	0.0148 (7)	0.0278 (8)	0.0207 (8)	0.0068 (6)	0.0081 (6)	0.0018 (6)
N3	0.0181 (8)	0.0325 (9)	0.0260 (8)	−0.0007 (7)	0.0130 (7)	−0.0050 (7)
C1	0.0183 (9)	0.0224 (9)	0.0188 (9)	−0.0021 (7)	0.0090 (7)	−0.0018 (7)
C2	0.0288 (10)	0.0189 (9)	0.0270 (10)	−0.0012 (8)	0.0142 (8)	0.0041 (7)
C3	0.0239 (10)	0.0178 (9)	0.0246 (10)	0.0050 (7)	0.0086 (8)	0.0019 (7)
C4	0.0170 (8)	0.0206 (9)	0.0167 (8)	0.0014 (7)	0.0062 (7)	−0.0017 (7)
C5	0.0172 (8)	0.0190 (8)	0.0164 (8)	0.0001 (7)	0.0076 (7)	0.0002 (7)
C6	0.0180 (9)	0.0222 (9)	0.0231 (9)	0.0029 (7)	0.0086 (8)	−0.0013 (7)
C7	0.0149 (9)	0.0362 (11)	0.0288 (10)	0.0041 (8)	0.0079 (8)	−0.0011 (8)
C8	0.0188 (9)	0.0342 (11)	0.0224 (9)	0.0045 (8)	0.0078 (8)	0.0017 (8)
C9	0.0171 (9)	0.0205 (9)	0.0218 (9)	0.0008 (7)	0.0091 (7)	−0.0057 (7)
C10	0.0153 (9)	0.0350 (11)	0.0218 (9)	0.0032 (8)	0.0064 (8)	0.0005 (8)
C11	0.0211 (9)	0.0399 (12)	0.0207 (9)	0.0012 (8)	0.0089 (8)	−0.0003 (8)
C12	0.0171 (8)	0.0146 (8)	0.0169 (8)	0.0008 (7)	0.0064 (7)	0.0014 (7)
C13	0.0178 (8)	0.0181 (8)	0.0143 (8)	0.0020 (7)	0.0069 (7)	0.0009 (7)
C14	0.0161 (8)	0.0180 (8)	0.0183 (8)	0.0003 (7)	0.0077 (7)	0.0034 (7)
C15	0.0165 (8)	0.0205 (9)	0.0151 (8)	−0.0018 (7)	0.0040 (7)	−0.0008 (7)
C16	0.0214 (9)	0.0192 (9)	0.0158 (8)	0.0008 (7)	0.0093 (7)	−0.0004 (7)
C17	0.0154 (8)	0.0203 (9)	0.0216 (9)	0.0004 (7)	0.0091 (7)	0.0009 (7)
C18	0.0178 (9)	0.0282 (10)	0.0199 (9)	−0.0003 (8)	0.0085 (8)	0.0031 (7)
C19	0.0146 (8)	0.0130 (8)	0.0207 (9)	0.0036 (7)	0.0058 (7)	−0.0017 (7)

Geometric parameters (Å, º) top

Cu1—O1	1.9399 (12)	C2—C3	1.380 (3)
Cu1—O1ⁱ	1.9399 (12)	C3—H3A	0.9500
Cu1—N1ⁱ	1.9772 (14)	C3—C4	1.387 (3)
Cu1—N1	1.9773 (14)	C4—C5	1.386 (2)
O1—C19	1.272 (2)	C4—C6	1.502 (2)
O1W—H1WA	0.8701	C5—H5A	0.9500
O1W—H1WB	0.8701	C7—H7	0.9500
O2—C19	1.256 (2)	C7—C8	1.369 (3)
O2W—H2WA	0.8698	C8—H8	0.9500
O2W—H2WB	0.8700	C8—C9	1.392 (2)
O3—C18	1.267 (2)	C9—C10	1.398 (3)
O4—C18	1.236 (2)	C10—H10	0.9500
O5—H5	0.8400	C10—C11	1.364 (3)
O5—C16	1.362 (2)	C11—H11	0.9500
O6—C6	1.216 (2)	C12—C13	1.392 (2)
N1—C1	1.337 (2)	C12—C17	1.394 (2)
N1—C5	1.342 (2)	C12—C19	1.498 (2)
N2—H2	0.8800	C13—H13	0.9500
N2—C6	1.369 (2)	C13—C14	1.385 (2)
N2—C9	1.392 (2)	C14—C15	1.394 (2)
N3—H3	0.91 (3)	C14—C18	1.517 (2)
N3—C7	1.330 (3)	C15—H15	0.9500
N3—C11	1.337 (2)	C15—C16	1.393 (2)
C1—H1	0.9500	C16—C17	1.390 (2)
C1—C2	1.375 (3)	C17—H17	0.9500
C2—H2A	0.9500

O1—Cu1—O1ⁱ	180.0	N3—C7—C8	121.77 (17)
O1ⁱ—Cu1—N1ⁱ	87.52 (5)	C8—C7—H7	119.1
O1—Cu1—N1ⁱ	92.48 (5)	C7—C8—H8	120.6
O1ⁱ—Cu1—N1	92.48 (5)	C7—C8—C9	118.76 (18)
O1—Cu1—N1	87.52 (5)	C9—C8—H8	120.6
N1ⁱ—Cu1—N1	180.00 (7)	N2—C9—C10	117.46 (15)
C19—O1—Cu1	111.94 (11)	C8—C9—N2	124.21 (16)
H1WA—O1W—H1WB	109.5	C8—C9—C10	118.32 (16)
H2WA—O2W—H2WB	109.5	C9—C10—H10	120.2
C16—O5—H5	109.5	C11—C10—C9	119.61 (17)
C1—N1—Cu1	119.87 (11)	C11—C10—H10	120.2
C1—N1—C5	119.10 (15)	N3—C11—C10	120.81 (18)
C5—N1—Cu1	120.71 (11)	N3—C11—H11	119.6
C6—N2—H2	116.7	C10—C11—H11	119.6
C6—N2—C9	126.57 (15)	C13—C12—C17	120.07 (16)
C9—N2—H2	116.7	C13—C12—C19	119.32 (15)
C7—N3—H3	120.0 (16)	C17—C12—C19	120.56 (15)
C7—N3—C11	120.68 (17)	C12—C13—H13	120.0
C11—N3—H3	119.3 (16)	C14—C13—C12	120.09 (15)
N1—C1—H1	118.9	C14—C13—H13	120.0
N1—C1—C2	122.24 (16)	C13—C14—C15	120.09 (16)
C2—C1—H1	118.9	C13—C14—C18	120.67 (15)
C1—C2—H2A	120.5	C15—C14—C18	119.21 (16)
C1—C2—C3	119.10 (17)	C14—C15—H15	120.1
C3—C2—H2A	120.5	C16—C15—C14	119.81 (16)
C2—C3—H3A	120.5	C16—C15—H15	120.1
C2—C3—C4	119.02 (16)	O5—C16—C15	122.39 (16)
C4—C3—H3A	120.5	O5—C16—C17	117.44 (15)
C3—C4—C6	118.46 (16)	C17—C16—C15	120.16 (15)
C5—C4—C3	118.77 (16)	C12—C17—H17	120.1
C5—C4—C6	122.53 (16)	C16—C17—C12	119.74 (16)
N1—C5—C4	121.75 (16)	C16—C17—H17	120.1
N1—C5—H5A	119.1	O3—C18—C14	115.95 (16)
C4—C5—H5A	119.1	O4—C18—O3	125.54 (16)
O6—C6—N2	124.73 (16)	O4—C18—C14	118.50 (16)
O6—C6—C4	119.88 (16)	O1—C19—C12	115.53 (15)
N2—C6—C4	115.40 (15)	O2—C19—O1	122.79 (15)
N3—C7—H7	119.1	O2—C19—C12	121.66 (15)

Cu1—O1—C19—O2	2.7 (2)	C7—N3—C11—C10	1.9 (3)
Cu1—O1—C19—C12	−178.48 (11)	C7—C8—C9—N2	−179.01 (18)
Cu1—N1—C1—C2	173.90 (14)	C7—C8—C9—C10	2.0 (3)
Cu1—N1—C5—C4	−174.92 (13)	C8—C9—C10—C11	−1.5 (3)
O1—Cu1—N1—C1	−99.24 (13)	C9—N2—C6—O6	0.2 (3)
O1ⁱ—Cu1—N1—C1	80.76 (13)	C9—N2—C6—C4	179.90 (16)
O1—Cu1—N1—C5	74.23 (13)	C9—C10—C11—N3	−0.4 (3)
O1ⁱ—Cu1—N1—C5	−105.77 (13)	C11—N3—C7—C8	−1.3 (3)
O5—C16—C17—C12	−177.43 (15)	C12—C13—C14—C15	1.1 (3)
N1—Cu1—O1—C19	91.90 (11)	C12—C13—C14—C18	179.40 (15)
N1ⁱ—Cu1—O1—C19	−88.10 (11)	C13—C12—C17—C16	−2.0 (3)
N1—C1—C2—C3	0.5 (3)	C13—C12—C19—O1	23.5 (2)
N2—C9—C10—C11	179.44 (18)	C13—C12—C19—O2	−157.68 (16)
N3—C7—C8—C9	−0.6 (3)	C13—C14—C15—C16	−1.3 (3)
C1—N1—C5—C4	−1.4 (2)	C13—C14—C18—O3	5.6 (3)
C1—C2—C3—C4	−0.3 (3)	C13—C14—C18—O4	−173.92 (17)
C2—C3—C4—C5	−0.7 (3)	C14—C15—C16—O5	179.04 (16)
C2—C3—C4—C6	−175.17 (16)	C14—C15—C16—C17	−0.2 (3)
C3—C4—C5—N1	1.6 (3)	C15—C14—C18—O3	−176.14 (17)
C3—C4—C6—O6	28.3 (3)	C15—C14—C18—O4	4.4 (3)
C3—C4—C6—N2	−151.50 (17)	C15—C16—C17—C12	1.9 (3)
C5—N1—C1—C2	0.3 (3)	C17—C12—C13—C14	0.5 (2)
C5—C4—C6—O6	−146.00 (19)	C17—C12—C19—O1	−154.05 (15)
C5—C4—C6—N2	34.2 (2)	C17—C12—C19—O2	24.8 (2)
C6—N2—C9—C8	12.5 (3)	C18—C14—C15—C16	−179.57 (16)
C6—N2—C9—C10	−168.55 (18)	C19—C12—C13—C14	−177.03 (15)
C6—C4—C5—N1	175.84 (15)	C19—C12—C17—C16	175.49 (15)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4ⁱⁱ	0.87	1.85	2.7164 (18)	170
O1W—H1WB···O3ⁱⁱⁱ	0.87	1.92	2.775 (2)	169
O2W—H2WA···O2	0.87	1.97	2.814 (2)	163
O2W—H2WB···O2^iv	0.87	1.94	2.8049 (18)	177
O5—H5···O1W	0.84	1.81	2.6384 (18)	168
N2—H2···O2W^v	0.88	2.00	2.823 (2)	156
N3—H3···O3^vi	0.91 (3)	1.69 (3)	2.582 (2)	166 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4ⁱ	0.87	1.85	2.7164 (18)	170.4
O1W—H1WB···O3ⁱⁱ	0.87	1.92	2.775 (2)	168.5
O2W—H2WA···O2	0.87	1.97	2.814 (2)	162.5
O2W—H2WB···O2ⁱⁱⁱ	0.87	1.94	2.8049 (18)	176.5
O5—H5···O1W	0.84	1.81	2.6384 (18)	168.4
N2—H2···O2W^iv	0.88	2.00	2.823 (2)	156.1
N3—H3···O3^v	0.91 (3)	1.69 (3)	2.582 (2)	166 (2)

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

Acknowledgements

We gratefully acknowledge Michigan State University for funding this work. We thank Dr A. Lifeson for helpful assistance.

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