Poly[[bis­[μ4-3-(2-carboxyl­atophen­yl)propionato]{N-[2-(pyridine-3-amido)­eth­yl]nicotinamide}­dicopper(II)] penta­hydrate]

Gaskin, G.J.; LaDuca, R.L.

doi:10.1107/S2414314623006223

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 7| July 2023| x230622

https://doi.org/10.1107/S2414314623006223

Open

access

Poly[[bis[μ₄-3-(2-carboxylatophenyl)propionato]{N-[2-(pyridine-3-amido)ethyl]nicotinamide}dicopper(II)] pentahydrate]

Gabrielle J. Gaskin ^a and Robert L. LaDuca ^a ^*

^aE-35 Holmes Hall, Michigan State University, Lyman Briggs College, 919 E. Shaw Lane, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

Edited by M. Zeller, Purdue University, USA (Received 7 June 2023; accepted 15 July 2023; online 22 July 2023)

In the title compound, {[Cu₂(C₁₀H₈O₄)₂(C₁₄H₁₄N₄O₂)]·5H₂O}_n, the Cu^II cations are coordinated in a square-pyramidal fashion, with four 3-(2-carboxyphenyl)propionate (cpp) carboxylate O-atom donors in the basal plane, along with an N-atom donor from a N-[2-(pyridin-3-ylamino)ethyl]nicotinamide (pen) ligand in the apical position. [Cu₂(cpp)₂]_n coordination polymer layer motifs with embedded {Cu₂(OCO)₄} paddlewheel clusters are thereby constructed. These layer motifs are connected into a three-dimensional [Cu₂(cpp)₂(pen)]_n coordination polymer network by tethering pen ligands. Treating the {Cu₂(OCO)₄ paddelwheel clusters as 6-connected nodes reveals an underlying cross-pillared self-penetrated rob network with 4⁸6⁶8 topology. The water molecules of crystallization are held to the coordination polymer network by N—H⋯O and O—H⋯O hydrogen-bonding patterns.

Keywords: crystal structure; copper(II); self-penetration; coordination polymer.

CCDC reference: 1979279

Structure description

The title compound was isolated during an exploratory synthetic effort aiming to produce a copper coordination polymer containing both 3-(2-carboxyphenyl)propionic (cpp) and N-(2-(pyridin-3-ylamino)ethyl)nicotinamide (pen) ligands. The pen ligand has to date seldom been used in coordination polymer chemistry (Wang et al., 2013 ). Our group has previously reported a racemic cobalt camphorate pen-containing coordination polymer with 4¹²6³ pcu topology (Przybyla et al., 2019 )

The asymmetric unit of the title compound contains a divalent copper atom, a fully deprotonated cpp ligand, half of a pen ligand whose central ethylene moiety is sited over a crystallographic inversion center (Wyckoff special position a), two water molecules of crystallization located on general positions, and one water molecule of crystallization best refined at half occupancy and disordered about a crystallographic twofold rotation axis (Wyckoff special position e). The copper atoms in the title compound display a {CuNO₄} square-pyramidal coordination environment (Fig. 1), with a pyridyl nitrogen donor atom from a pen ligand located in the elongated apical position. Carboxylate oxygen atom donors from four different cpp ligands occupy the basal plane, with the two `longer-arm' ethyl-carboxylate group oxygen atoms in trans position to each other, and the two `shorter-arm' benzoate carboxylate group oxygen atoms in the other two positions, also trans to each other. Bond lengths and angles within the coordination environment in the title compound are listed in Table 1.

Table 1
Selected geometric parameters (Å, °)

Cu1—O2	1.965 (5)	Cu1—O5ⁱⁱⁱ	1.975 (5)
Cu1—O3ⁱ	1.967 (5)	Cu1—N1	2.172 (6)
Cu1—O4ⁱⁱ	1.991 (5)

O2—Cu1—O3ⁱ	168.9 (2)	O3ⁱ—Cu1—O5ⁱⁱⁱ	87.1 (2)
O2—Cu1—O4ⁱⁱ	90.1 (2)	O3ⁱ—Cu1—N1	97.5 (2)
O2—Cu1—O5ⁱⁱⁱ	91.5 (2)	O4ⁱⁱ—Cu1—N1	87.0 (2)
O2—Cu1—N1	93.6 (2)	O5ⁱⁱⁱ—Cu1—O4ⁱⁱ	168.0 (2)
O3ⁱ—Cu1—O4ⁱⁱ	89.0 (2)	O5ⁱⁱⁱ—Cu1—N1	104.8 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
Coordination environment in the title compound with full ligand set and complete {Cu₂(OCO)₄} paddlewheel cluster. Water molecules of crystallization are shown. Displacement ellipsoids are drawn at the 50% probability level. Color code: Cu, dark blue; O in ligands, red; O in water molecules of crystallization, orange; N, light blue; C, black; H, pink. Symmetry codes are as listed in Table 1

The cpp ligands in the title compound connect four copper atoms in an exotetradentate pattern in which each carboxylate oxygen atom binds only to one copper atom. Via four cpp carboxylate groups – two from the longer-arm cpp termini and two from the shorter-arm cpp termini – {Cu₂(OCO)₄} paddlewheel dimeric units are formed (Fig. 1). These have a through-space Cu⋯Cu internuclear distance of 2.620 (1) Å, and their centroids are located on crystallographic inversion centers (Wyckoff special position d). Each of these dimeric units connects to four others through the full span of the cpp ligands thereby forming [Cu₂(cpp)₂]_n coordination polymer layers arranged parallel to the bc crystal planes (Fig. 2). Parallel [Cu₂(cpp)₂]_n coordination polymer layers are pillared into a three-dimensional [Cu₂(cpp)₂(pen)]_n coordination polymer network (Fig. 3) by anti-conformation ebn ligands that span a Cu⋯Cu distance of 14.87 (1) Å. The nearest internuclear distance between adjacent [Cu₂(cpp)₂]_n layers is 12.08 (1) Å, which is too short to be spanned directly by the pen ligands given their conformational constraints. As a result, the three-dimensional [Cu₂(cpp)₂(pen)]_n network is formed by cross-pillaring of the pen tethers, thereby precluding a much more common straight-pillared 4¹²6³ pcu topology. Treating each {Cu₂(OCO)₄} paddlewheel dimeric unit as a 6-connected node results in an uncommon self-penetrated, cross-pillared rob network with 4⁸6⁶8 topology when analyzed using the TOPOS software (Blatov et al., 2014 ) (Fig. 4). Discrete D(3) short water molecule chains (Infantes & Motherwell, 2002 ) positioned along the c-axis crystal direction occupy incipient channels comprising 21.8% of the unit cell volume according to PLATON (Spek, 2020 ).

Figure 2
[Cu₂(cpp)₂]_n coordination polymer layer in the title compound, featuring {Cu₂(OCO)₄} paddlewheel clusters. Water molecules of crystallization have been omitted.

Figure 3
[Cu₂(cpp)₂(pen)]_n coordination polymer network in the title compound, with [Cu₂(cpp)₂]_n layers drawn in red

Figure 4
Schematic perspective of the 4⁸6⁶8 rob cross-pillared self-penetrated topology in the title compound. The spheres represent the centroids of the 6-connected {Cu₂(OCO)₄} paddlewheel clusters. The [Cu₂(cpp)₂]_n layers are drawn in red, with the cross-pillaring pen ligands drawn in blue.

The co-crystallized water molecules are held to the coordination polymer framework by hydrogen-bonding acceptance from the pen N—H groups, and hydrogen-bonding donation to each other. Details regarding the hydrogen bonding in the title compound are listed in Table 2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1W	0.87 (2)	2.03 (4)	2.844 (10)	155 (8)
C5—H5⋯O2	0.95	2.50	3.099 (9)	121
C6—H6⋯O3^iv	0.95	2.48	3.332 (9)	149
O1W—H1WA⋯O2W	0.85 (2)	2.00 (11)	2.698 (13)	139 (15)
O1W—H1WB⋯O3W	0.85 (2)	2.10 (2)	2.79 (2)	139 (5)
O2W—H2WA⋯O5ⁱⁱⁱ	0.85 (2)	2.09 (2)	2.909 (10)	162 (7)
O2W—H2WB⋯O1^v	0.85 (2)	2.06 (2)	2.816 (9)	147 (5)
O3W—H3WA⋯O1ⁱⁱ	0.84 (2)	2.10 (2)	2.917 (19)	162 (9)
O3W—H3WB⋯O1^vi	0.84 (2)	2.10 (2)	2.848 (19)	147 (6)
Symmetry codes: (ii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x, -y+1, z-{\script{1\over 2}}]$ ; (vi) .

Synthesis and crystallization

Cu(NO₃)₂^.2.5 H₂O (87 mg, 0.37 mmol), 3-(2-carboxyphenyl)propionic acid (cppH₂) (73 mg, 0.37 mmol), N-(2-(pyridin-3-ylamino)ethyl)nicotinamide (pen) (100 mg, 0.37 mmol) and 0.75 ml of a 1.0 M NaOH solution were placed into 10 ml distilled H₂O in a Teflon-lined acid digestion bomb. The bomb was sealed and heated in an oven at 373 K for 48 h, and then cooled slowly to 273 K. Green crystals of the title complex were obtained in 43% yield.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The O3W position disordered across an inversion center was treated with a PART −1 command. Water H atom positions are refined, but suitably restrained with 0.84 (2) Å target values for O—H bonds, 1.36 (2) Å target values for H⋯H distances, and suitable DFIX commands for hydrogen-bonding H⋯O distances (with EQIV commands added as needed). The amine H-atom position was allowed to refine with an N—H distance restraint of 0.88 (2) Å.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₀H₈O₄)₂(C₁₄H₁₄N₄O₂)]·5H₂O
M_r	871.78
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	27.558 (10), 14.873 (5), 9.146 (3)
β (°)	98.396 (4)
V (Å³)	3709 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.22
Crystal size (mm)	0.28 × 0.16 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.560, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	14392, 3393, 2011
R_int	0.120
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.230, 1.02
No. of reflections	3393
No. of parameters	274
No. of restraints	15
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.68, −0.61
Computer programs: COSMO (Bruker, 2009 ), SAINT (Bruker, 2014 ), SHELXT2018/2 (Sheldrick, 2015 ), SHELXL2018/3 (Sheldrick, 2015), CrystalMaker X (Palmer, 2020 ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1979279

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006223/zl4055sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006223/zl4055Isup3.hkl

checkCIF report

Computing details top

Data collection: COSMO V1.61 Bruker, 2009); cell refinement: SAINT v8.34A (Bruker, 2014); data reduction: SAINT v8.34A (Bruker, 2014); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: CrystalMaker X (Palmer, 2020); software used to prepare material for publication: Olex2 1.3-ac4 (Dolomanov et al., 2009).

Poly[[bis[µ₄-3-(2-carboxylatophenyl)propionato]{N-[2-(pyridine-3-amido)ethyl]nicotinamide}dicopper(II)] pentahydrate] top

Crystal data top

[Cu₂(C₁₀H₈O₄)₂(C₁₄H₁₄N₄O₂)]·5H₂O	F(000) = 1800
M_r = 871.78	D_x = 1.561 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.558 (10) Å	Cell parameters from 2345 reflections
b = 14.873 (5) Å	θ = 2.6–24.4°
c = 9.146 (3) Å	µ = 1.22 mm⁻¹
β = 98.396 (4)°	T = 173 K
V = 3709 (2) Å³	Block, green
Z = 4	0.28 × 0.16 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	2011 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.120
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 25.4°, θ_min = 1.5°
T_min = 0.560, T_max = 0.745	h = −33→33
14392 measured reflections	k = −17→17
3393 independent reflections	l = −11→11

Refinement top

Refinement on F²	15 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.079	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.230	w = 1/[σ²(F_o²) + (0.1316P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3393 reflections	Δρ_max = 1.68 e Å⁻³
274 parameters	Δρ_min = −0.61 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.28340 (3)	0.31333 (5)	0.51554 (10)	0.0264 (3)
O1	0.4310 (2)	0.6336 (4)	0.8536 (6)	0.0531 (16)
O2	0.2511 (2)	0.3449 (3)	0.3163 (6)	0.0394 (14)
O3	0.19296 (19)	0.2383 (3)	0.2891 (5)	0.0327 (13)
O4	0.23078 (19)	0.6236 (3)	0.1031 (6)	0.0369 (13)
O5	0.17254 (18)	0.7279 (3)	0.0656 (6)	0.0352 (13)
N1	0.3245 (2)	0.4382 (4)	0.5434 (7)	0.0282 (14)
N2	0.4359 (3)	0.4863 (5)	0.9037 (8)	0.0406 (17)
H2	0.435 (3)	0.432 (3)	0.868 (9)	0.049*
C1	0.4759 (3)	0.4959 (6)	1.0262 (9)	0.044 (2)
H1A	0.476383	0.442866	1.091850	0.053*
H1B	0.470134	0.549866	1.084528	0.053*
C2	0.4170 (3)	0.5543 (5)	0.8263 (9)	0.037 (2)
C3	0.3778 (3)	0.5378 (5)	0.7005 (8)	0.0319 (18)
C4	0.3592 (3)	0.4538 (5)	0.6571 (8)	0.0281 (17)
H4	0.372276	0.403411	0.713309	0.034*
C5	0.3067 (2)	0.5096 (4)	0.4656 (7)	0.0219 (15)
H5	0.281838	0.499813	0.383485	0.026*
C6	0.3218 (3)	0.5968 (5)	0.4963 (9)	0.0368 (19)
H6	0.308207	0.645667	0.437001	0.044*
C7	0.3571 (3)	0.6102 (5)	0.6154 (9)	0.039 (2)
H7	0.367833	0.669622	0.640970	0.047*
C8	0.2140 (3)	0.3066 (5)	0.2454 (8)	0.0268 (16)
C9	0.1944 (3)	0.3433 (4)	0.0944 (8)	0.0283 (17)
H9A	0.160390	0.321624	0.065279	0.034*
H9B	0.214539	0.320015	0.021644	0.034*
C10	0.1947 (3)	0.4467 (4)	0.0900 (8)	0.0278 (17)
H10A	0.227492	0.467709	0.135551	0.033*
H10B	0.190022	0.465789	−0.014842	0.033*
C11	0.1564 (3)	0.4942 (5)	0.1665 (7)	0.0254 (16)
C12	0.1229 (3)	0.4454 (5)	0.2329 (8)	0.0333 (18)
H12	0.125034	0.381659	0.232085	0.040*
C13	0.0869 (3)	0.4842 (6)	0.2995 (10)	0.045 (2)
H13	0.065171	0.448100	0.346293	0.054*
C14	0.0824 (3)	0.5796 (6)	0.2977 (10)	0.045 (2)
H14	0.056980	0.608167	0.340443	0.054*
C15	0.1155 (3)	0.6296 (5)	0.2330 (8)	0.0349 (19)
H15	0.112726	0.693235	0.230924	0.042*
C16	0.1529 (3)	0.5884 (5)	0.1704 (8)	0.0299 (17)
C17	0.1880 (3)	0.6497 (5)	0.1074 (8)	0.0286 (17)
O1W	0.4372 (5)	0.2956 (5)	0.8813 (11)	0.120 (4)
H1WA	0.449 (6)	0.275 (9)	0.807 (10)	0.181*
H1WB	0.445 (5)	0.259 (4)	0.951 (7)	0.181*
O2W	0.4262 (3)	0.2494 (5)	0.5930 (8)	0.088 (3)
H2WA	0.3977 (19)	0.232 (7)	0.557 (11)	0.133*
H2WB	0.438 (2)	0.273 (6)	0.522 (9)	0.133*
O3W	0.4849 (7)	0.2581 (12)	1.166 (2)	0.111 (6)	0.5
H3WA	0.464 (4)	0.281 (12)	1.21 (2)	0.167*	0.5
H3WB	0.501 (2)	0.300 (9)	1.134 (16)	0.167*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0419 (6)	0.0104 (5)	0.0247 (5)	−0.0009 (4)	−0.0023 (4)	0.0007 (4)
O1	0.063 (4)	0.049 (4)	0.043 (4)	−0.012 (3)	−0.006 (3)	−0.012 (3)
O2	0.052 (4)	0.026 (3)	0.036 (3)	−0.011 (3)	−0.011 (3)	0.006 (2)
O3	0.047 (3)	0.020 (3)	0.026 (3)	−0.005 (2)	−0.010 (2)	0.003 (2)
O4	0.040 (3)	0.017 (3)	0.055 (4)	−0.003 (2)	0.011 (3)	0.004 (2)
O5	0.042 (3)	0.022 (3)	0.041 (3)	0.001 (2)	0.005 (3)	0.008 (2)
N1	0.045 (4)	0.010 (3)	0.029 (3)	−0.001 (3)	0.005 (3)	0.001 (3)
N2	0.046 (4)	0.036 (4)	0.038 (4)	−0.004 (3)	0.000 (3)	0.003 (3)
C1	0.043 (5)	0.048 (6)	0.039 (5)	−0.004 (4)	0.000 (4)	0.001 (4)
C2	0.046 (5)	0.034 (5)	0.031 (5)	−0.013 (4)	0.009 (4)	0.001 (4)
C3	0.039 (5)	0.026 (4)	0.029 (4)	−0.011 (3)	−0.001 (3)	0.000 (3)
C4	0.037 (4)	0.024 (4)	0.021 (4)	0.002 (3)	−0.004 (3)	0.007 (3)
C5	0.025 (4)	0.022 (4)	0.020 (4)	−0.001 (3)	0.006 (3)	0.000 (3)
C6	0.049 (5)	0.019 (4)	0.043 (5)	0.000 (3)	0.009 (4)	0.006 (4)
C7	0.054 (5)	0.020 (4)	0.043 (5)	−0.009 (4)	0.006 (4)	−0.007 (4)
C8	0.041 (4)	0.015 (4)	0.024 (4)	0.001 (3)	0.000 (3)	0.001 (3)
C9	0.053 (5)	0.011 (3)	0.019 (4)	−0.001 (3)	−0.003 (3)	−0.004 (3)
C10	0.048 (5)	0.012 (4)	0.022 (4)	−0.002 (3)	0.001 (3)	0.000 (3)
C11	0.036 (4)	0.018 (4)	0.020 (4)	−0.003 (3)	−0.004 (3)	0.004 (3)
C12	0.046 (5)	0.024 (4)	0.029 (4)	−0.002 (3)	0.002 (4)	0.006 (3)
C13	0.051 (5)	0.035 (5)	0.048 (6)	−0.007 (4)	0.007 (4)	0.010 (4)
C14	0.039 (5)	0.050 (6)	0.048 (5)	0.004 (4)	0.011 (4)	0.001 (4)
C15	0.047 (5)	0.028 (4)	0.029 (4)	0.002 (4)	0.003 (4)	−0.005 (3)
C16	0.037 (4)	0.024 (4)	0.026 (4)	−0.002 (3)	−0.002 (3)	0.009 (3)
C17	0.041 (5)	0.013 (4)	0.028 (4)	−0.004 (3)	−0.004 (3)	−0.002 (3)
O1W	0.219 (12)	0.049 (5)	0.081 (7)	0.003 (6)	−0.018 (8)	−0.001 (5)
O2W	0.125 (7)	0.055 (5)	0.079 (6)	−0.016 (5)	−0.009 (5)	0.009 (4)
O3W	0.129 (17)	0.087 (13)	0.116 (16)	−0.012 (12)	0.015 (13)	0.014 (11)

Geometric parameters (Å, º) top

Cu1—Cu1ⁱ	2.6201 (18)	C6—C7	1.365 (11)
Cu1—O2	1.965 (5)	C7—H7	0.9500
Cu1—O3ⁱ	1.967 (5)	C8—C9	1.510 (9)
Cu1—O4ⁱⁱ	1.991 (5)	C9—H9A	0.9900
Cu1—O5ⁱⁱⁱ	1.975 (5)	C9—H9B	0.9900
Cu1—N1	2.172 (6)	C9—C10	1.538 (9)
O1—C2	1.255 (9)	C10—H10A	0.9900
O2—C8	1.263 (9)	C10—H10B	0.9900
O3—C8	1.263 (8)	C10—C11	1.522 (10)
O4—C17	1.247 (8)	C11—C12	1.383 (10)
O5—C17	1.278 (8)	C11—C16	1.405 (10)
N1—C4	1.325 (9)	C12—H12	0.9500
N1—C5	1.332 (8)	C12—C13	1.366 (11)
N2—H2	0.87 (2)	C13—H13	0.9500
N2—C1	1.460 (10)	C13—C14	1.424 (12)
N2—C2	1.299 (10)	C14—H14	0.9500
C1—C1^iv	1.480 (16)	C14—C15	1.376 (11)
C1—H1A	0.9900	C15—H15	0.9500
C1—H1B	0.9900	C15—C16	1.393 (10)
C2—C3	1.479 (11)	C16—C17	1.505 (10)
C3—C4	1.387 (10)	O1W—H1WA	0.85 (2)
C3—C7	1.400 (11)	O1W—H1WB	0.85 (2)
C4—H4	0.9500	O2W—H2WA	0.846 (18)
C5—H5	0.9500	O2W—H2WB	0.85 (2)
C5—C6	1.379 (10)	O3W—H3WA	0.84 (2)
C6—H6	0.9500	O3W—H3WB	0.84 (2)

O2—Cu1—Cu1ⁱ	81.66 (15)	C7—C6—C5	117.3 (7)
O2—Cu1—O3ⁱ	168.9 (2)	C7—C6—H6	121.3
O2—Cu1—O4ⁱⁱ	90.1 (2)	C3—C7—H7	119.5
O2—Cu1—O5ⁱⁱⁱ	91.5 (2)	C6—C7—C3	121.1 (7)
O2—Cu1—N1	93.6 (2)	C6—C7—H7	119.5
O3ⁱ—Cu1—Cu1ⁱ	87.24 (15)	O2—C8—O3	125.1 (7)
O3ⁱ—Cu1—O4ⁱⁱ	89.0 (2)	O2—C8—C9	117.5 (6)
O3ⁱ—Cu1—O5ⁱⁱⁱ	87.1 (2)	O3—C8—C9	117.4 (6)
O3ⁱ—Cu1—N1	97.5 (2)	C8—C9—H9A	109.1
O4ⁱⁱ—Cu1—Cu1ⁱ	80.87 (16)	C8—C9—H9B	109.1
O4ⁱⁱ—Cu1—N1	87.0 (2)	C8—C9—C10	112.6 (6)
O5ⁱⁱⁱ—Cu1—Cu1ⁱ	87.57 (15)	H9A—C9—H9B	107.8
O5ⁱⁱⁱ—Cu1—O4ⁱⁱ	168.0 (2)	C10—C9—H9A	109.1
O5ⁱⁱⁱ—Cu1—N1	104.8 (2)	C10—C9—H9B	109.1
N1—Cu1—Cu1ⁱ	166.94 (17)	C9—C10—H10A	108.2
C8—O2—Cu1	126.3 (5)	C9—C10—H10B	108.2
C8—O3—Cu1ⁱ	119.7 (5)	H10A—C10—H10B	107.3
C17—O4—Cu1^v	127.8 (5)	C11—C10—C9	116.5 (6)
C17—O5—Cu1^vi	120.0 (5)	C11—C10—H10A	108.2
C4—N1—Cu1	123.1 (5)	C11—C10—H10B	108.2
C4—N1—C5	116.6 (6)	C12—C11—C10	120.6 (6)
C5—N1—Cu1	118.2 (5)	C12—C11—C16	117.4 (7)
C1—N2—H2	111 (6)	C16—C11—C10	121.9 (6)
C2—N2—H2	122 (6)	C11—C12—H12	118.3
C2—N2—C1	122.7 (7)	C13—C12—C11	123.3 (7)
N2—C1—C1^iv	111.9 (9)	C13—C12—H12	118.3
N2—C1—H1A	109.2	C12—C13—H13	120.6
N2—C1—H1B	109.2	C12—C13—C14	118.9 (8)
C1^iv—C1—H1A	109.2	C14—C13—H13	120.6
C1^iv—C1—H1B	109.2	C13—C14—H14	120.6
H1A—C1—H1B	107.9	C15—C14—C13	118.8 (8)
O1—C2—N2	122.4 (8)	C15—C14—H14	120.6
O1—C2—C3	118.7 (7)	C14—C15—H15	119.4
N2—C2—C3	119.0 (7)	C14—C15—C16	121.1 (8)
C4—C3—C2	124.7 (7)	C16—C15—H15	119.4
C4—C3—C7	115.5 (7)	C11—C16—C17	123.0 (7)
C7—C3—C2	119.8 (7)	C15—C16—C11	120.4 (7)
N1—C4—C3	125.2 (7)	C15—C16—C17	116.6 (7)
N1—C4—H4	117.4	O4—C17—O5	123.4 (7)
C3—C4—H4	117.4	O4—C17—C16	119.1 (6)
N1—C5—H5	117.9	O5—C17—C16	117.4 (7)
N1—C5—C6	124.3 (7)	H1WA—O1W—H1WB	107 (3)
C6—C5—H5	117.9	H2WA—O2W—H2WB	106 (3)
C5—C6—H6	121.3	H3WA—O3W—H3WB	108 (4)

Cu1—O2—C8—O3	−3.5 (11)	C4—C3—C7—C6	−1.4 (12)
Cu1—O2—C8—C9	178.6 (5)	C5—N1—C4—C3	0.2 (11)
Cu1ⁱ—O3—C8—O2	2.1 (10)	C5—C6—C7—C3	1.4 (12)
Cu1ⁱ—O3—C8—C9	179.9 (5)	C7—C3—C4—N1	0.6 (11)
Cu1^v—O4—C17—O5	−6.6 (11)	C8—C9—C10—C11	−72.9 (8)
Cu1^v—O4—C17—C16	175.9 (5)	C9—C10—C11—C12	−1.4 (10)
Cu1^vi—O5—C17—O4	1.6 (10)	C9—C10—C11—C16	179.9 (6)
Cu1^vi—O5—C17—C16	179.1 (5)	C10—C11—C12—C13	−178.1 (7)
Cu1—N1—C4—C3	−163.0 (6)	C10—C11—C16—C15	175.8 (7)
Cu1—N1—C5—C6	163.9 (6)	C10—C11—C16—C17	−3.5 (11)
O1—C2—C3—C4	179.3 (8)	C11—C12—C13—C14	1.8 (13)
O1—C2—C3—C7	−0.3 (12)	C11—C16—C17—O4	−28.2 (11)
O2—C8—C9—C10	−40.7 (10)	C11—C16—C17—O5	154.2 (7)
O3—C8—C9—C10	141.3 (7)	C12—C11—C16—C15	−3.0 (11)
N1—C5—C6—C7	−0.7 (11)	C12—C11—C16—C17	177.7 (7)
N2—C2—C3—C4	−0.1 (12)	C12—C13—C14—C15	−2.0 (13)
N2—C2—C3—C7	−179.7 (7)	C13—C14—C15—C16	−0.2 (12)
C1—N2—C2—O1	−1.8 (13)	C14—C15—C16—C11	2.7 (12)
C1—N2—C2—C3	177.7 (7)	C14—C15—C16—C17	−177.9 (7)
C2—N2—C1—C1^iv	−80.0 (12)	C15—C16—C17—O4	152.4 (7)
C2—C3—C4—N1	−179.0 (7)	C15—C16—C17—O5	−25.2 (10)
C2—C3—C7—C6	178.3 (7)	C16—C11—C12—C13	0.7 (11)
C4—N1—C5—C6	−0.1 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1W	0.87 (2)	2.03 (4)	2.844 (10)	155 (8)
C5—H5···O2	0.95	2.50	3.099 (9)	121
C6—H6···O3^vi	0.95	2.48	3.332 (9)	149
O1W—H1WA···O2W	0.85 (2)	2.00 (11)	2.698 (13)	139 (15)
O1W—H1WB···O3W	0.85 (2)	2.10 (2)	2.79 (2)	139 (5)
O2W—H2WA···O5ⁱⁱⁱ	0.85 (2)	2.09 (2)	2.909 (10)	162 (7)
O2W—H2WB···O1^v	0.85 (2)	2.06 (2)	2.816 (9)	147 (5)
O3W—H3WA···O1ⁱⁱ	0.84 (2)	2.10 (2)	2.917 (19)	162 (9)
O3W—H3WB···O1^iv	0.84 (2)	2.10 (2)	2.848 (19)	147 (6)

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

Funding information

Funding for this work was provided by the Lyman Briggs College of Science at Michigan State University.

References

Blatov, V. A., Shevchenko, A. P. & Proserpio, D. M. (2014). Cryst. Growth Des. 14, 3576–3586. Web of Science CrossRef CAS Google Scholar
Bruker (2009). COSMO. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2014). APEX2 and SAINT.. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Infantes, L. & Motherwell, S. (2002). CrystEngComm, 4, 454–461. Web of Science CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Palmer, D. (2020). CrystalMaker X. CrystalMaker Software, Begbroke, England. Google Scholar
Przybyla, J. J., Ezenyilimba, F. C. & LaDuca, R. L. (2019). Inorg. Chim. Acta, 498, 119087. CrossRef Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Wang, X., Luan, J., Lin, H., Lu, Q., Xu, C. & Liu, G. (2013). Dalton Trans. 42, 8375–8366. CrossRef CAS PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.