Poly[[[μ3-3-(2-carboxyl­atophen­yl)propionato][μ2-N,N′-(ethane-1,2-di­yl)bis­(pyridine-4-carbox­amide)]copper(II)] monohydrate], a layered coordination polymer with (4,4) topology

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

doi:10.1107/S241431462300679X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 8| August 2023| x230679

https://doi.org/10.1107/S241431462300679X

Open

access

Poly[[[μ₃-3-(2-carboxylatophenyl)propionato][μ₂-N,N′-(ethane-1,2-diyl)bis(pyridine-4-carboxamide)]copper(II)] monohydrate], a layered coordination polymer with (4,4) topology

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 S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 9 June 2023; accepted 3 August 2023; online 10 August 2023)

In the title compound, {[Cu(C₁₀H₈O₄)(C₁₄H₁₄N₄O₂)]·H₂O}_n, the Cu^II cations are coordinated in a square-pyramidal fashion, with trans pyridyl-N donor atoms from two N-(2-(pyridin-3-ylamino)ethyl)isonicotinamide (pein) ligands in the basal plane. The other three coordination sites are taken up by carboxylate O-atom donors from three different 3-(2-carboxyphenyl)propionate (cpp) ligands. The central ethylenediamine segments of the pein ligands are disordered equally over two sets of positions. {Cu₂O₂} rhomboid clusters are connected into [Cu(cpp)(pein)]_n (4,4) coordination polymer grids by the full span of the cpp and pein ligands. Individual layer motifs stack in an AAA pattern along the a axis by means of interlayer hydrogen-bonding interactions.

Keywords: crystal structure; coordination polymer; layer; copper.

CCDC reference: 1979280

Structure description

The title compound was isolated during an exploratory synthetic effort aiming to produce a copper coordination polymer containing both 3-(2-carboxyphenyl)propionate (cpp) and N-(2-(pyridin-3-ylamino)ethyl)nicotinamide (pein) ligands. Our group has previously reported a chiral cobalt camphorate pein-containing coordination polymer that manifests a twofold parallel interpenetrated looped layer topology (Przybyla et al., 2019 ).

The asymmetric unit of the title compound contains a divalent copper atom, a fully deprotonated cpp ligand, a pein ligand, and a water molecule of crystallization. The central ethylenediamine segments of the pein ligands are disordered equally over two sets of positions. The copper atoms in the title compound display an [N₂O₃] square pyramidal coordination environment (Fig. 1), with trans pyridyl-N donor atoms from two pein ligands in the basal plane. The other two trans basal-plane sites are taken up by a shorter-arm carboxylate O-atom donor from a cpp ligand and a longer-arm carboxylate O atom donor from another cpp ligand; the apical site shows an elongated bond to the copper atom and is filled by a longer-arm carboxylate O-atom donor belonging to a third cpp ligand. The trigonality factor τ is 0.289 (Addison et al., 1984 ), indicating a significant distortion from idealized square-pyramidal geometry. Relevant bond lengths and angles within the coordination environment in the title complex are listed in Table 1.

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.9754 (18)	Cu1—N1	2.010 (2)
Cu1—O4ⁱ	2.4322 (19)	Cu1—N4ⁱⁱⁱ	2.033 (2)
Cu1—O4ⁱⁱ	2.0007 (18)

O1—Cu1—O4ⁱⁱ	156.66 (8)	O4ⁱⁱ—Cu1—N1	92.95 (8)
O1—Cu1—O4ⁱ	126.81 (7)	O4ⁱⁱ—Cu1—N4ⁱⁱⁱ	91.12 (8)
O1—Cu1—N1	91.16 (8)	N1—Cu1—O4ⁱ	87.84 (8)
O1—Cu1—N4ⁱⁱⁱ	86.83 (8)	N1—Cu1—N4ⁱⁱⁱ	173.98 (9)
O4ⁱⁱ—Cu1—O4ⁱ	76.33 (8)	N4ⁱⁱⁱ—Cu1—O4ⁱ	88.83 (8)
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 1
Coordination environment in the title compound with full ligand set. Displacement ellipsoids are drawn at the 50% probability level. Only one of the disordered components in pein is shown. Color code: Cu, dark blue; O, red; N, light blue; C, black; H, pink. Symmetry codes are as listed in Table 1

The cpp ligand in the title complex exhibits an exotridentate binding mode in which the longer carboxylate arm bridges two Cu^II atoms while the shorter carboxylate group acts as a monodentate donor to a single Cu^II atom. A single carboxylate oxygen donor atom from the longer cpp terminus bridges two copper atoms, connecting to a basal site on one and an apical site on the other. Pairs of these interactions construct {Cu₂O₂} rhomboid dimeric units with a Cu⋯Cu distance of 3.50 (1) Å and internal angles of 103.67 (7)° (Cu—O—Cu) and 76.33 (8)° (O—Cu—O). The full span of the cpp ligands connects the {Cu₂O₂} dimeric units into [Cu₂(cpp)₂]_n coordination polymer chains that are oriented parallel to the b axis (Fig. 2). The chains are pillared into [Cu(cpp)(pein)]_n coordination polymer layers arranged parallel to (101) (Fig. 3) by pairs of pein ligands that span a Cu⋯Cu distance of 17.64 (1) Å. The pairs of pein ligands interact via π–π stacking between their pyridyl rings (approximate distance between centroids: 3.6 Å).

Figure 2
[Cu₂(cpp)₂]_n coordination polymer chain in the title compound, featuring [Cu₂(O)₂] rhomboid clusters.

Figure 3
[Cu(cpp)(pein)]_n coordination polymer layer in the title compound, with [Cu₂(cpp)₂]_n coordination polymer chains drawn in red.

Supramolecular interactions are present in the crystal structure. Individual [Cu(cpp)(pein)]_n coordination polymer layers stack in an AAA pattern along the a-axis direction (Blatov et al., 2014 ; Fig. 4) by means of interlayer hydrogen-bonding donation between pein N—H groups and bound shorter-arm cpp carboxylate-O atoms. Isolated water molecules of crystallization are located in small pockets in the interlamellar regions, held to the coordination polymer layers by hydrogen-bonding donation to pein C=O groups. 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—H2B⋯O1^iv	0.88	2.12	2.959 (3)	160
N3B—H3BA⋯O1W^v	0.88	1.99	2.836 (5)	160
O1W—H1WA⋯O5	0.87	1.92	2.781 (3)	172
Symmetry codes: (iv) ; (v) .

Figure 4
AAA stacking of [Cu(cpp)(pein)]_n coordination polymer layers along the aaxis. O atoms belonging to unligated water molecules of crystallization are depicted as orange spheres.

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)isonicotinamide (pein, 100 mg, 0.37 mmol) and 0.75 ml of a 1.0 M NaOH solution were placed into 10 ml of distilled water 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. Blue crystals of the title complex were obtained in 77% yield.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Atoms C17, C18 and N3 in the pein ligand are disordered over two sites (labeled A and B), and were refined with site occupancies fixed to 1/2. This part was refined with free coordinates, with no restraints applied to the geometry or to displacement parameters.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu(C₁₀H₈O₄)(C₁₄H₁₄N₄O₂)]·H₂O
M_r	544.01
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	9.1138 (8), 9.4045 (8), 14.4758 (13)
α, β, γ (°)	97.300 (1), 94.045 (1), 114.149 (1)
V (Å³)	1112.63 (17)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.04
Crystal size (mm)	0.15 × 0.13 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.676, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	18015, 4077, 3323
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.092, 1.05
No. of reflections	4077
No. of parameters	355
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.30
Computer programs: COSMO (Bruker, 2009 ), SAINT (Bruker, 2013 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), CrystalMaker X (Palmer, 2020 ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1979280

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S241431462300679X/bh4076sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431462300679X/bh4076Isup2.hkl

checkCIF report

Computing details top

Data collection: COSMO v1.61 (Bruker, 2009); cell refinement: SAINT v8.34a (Bruker, 2013); data reduction: SAINT v8.34a (Bruker, 2013); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: CrystalMaker X (Palmer, 2020); software used to prepare material for publication: Olex2 1.3-ac4 (Dolomanov et al., 2009).

Poly[[[µ₃-3-(2-carboxylatophenyl)propionato][µ₂-N,N'-(ethane-1,2-diyl)bis(pyridine-4-carboxamide)]copper(II)] monohydrate] top

Crystal data top

[Cu(C₁₀H₈O₄)(C₁₄H₁₄N₄O₂)]·H₂O	Z = 2
M_r = 544.01	F(000) = 562
Triclinic, P1	D_x = 1.624 Mg m⁻³
a = 9.1138 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4045 (8) Å	Cell parameters from 6936 reflections
c = 14.4758 (13) Å	θ = 2.4–25.3°
α = 97.300 (1)°	µ = 1.04 mm⁻¹
β = 94.045 (1)°	T = 173 K
γ = 114.149 (1)°	Block, blue
V = 1112.63 (17) Å³	0.15 × 0.13 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	3323 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.055
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 25.4°, θ_min = 1.4°
T_min = 0.676, T_max = 0.745	h = −10→10
18015 measured reflections	k = −11→11
4077 independent reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: mixed
wR(F²) = 0.092	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0352P)² + 0.9143P] where P = (F_o² + 2F_c²)/3
4077 reflections	(Δ/σ)_max < 0.001
355 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³
0 constraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.86606 (4)	0.03522 (4)	0.42367 (2)	0.01990 (12)
O1	0.7782 (2)	0.1460 (2)	0.34432 (13)	0.0228 (4)
O2	0.9787 (2)	0.3862 (2)	0.39173 (14)	0.0293 (5)
O3	0.6356 (2)	0.7371 (2)	0.38655 (14)	0.0266 (5)
O4	0.8764 (2)	0.8502 (2)	0.47353 (12)	0.0184 (4)
O5	0.6664 (3)	0.3509 (3)	0.83105 (16)	0.0496 (7)
O6	0.1264 (3)	−0.1854 (3)	1.01159 (17)	0.0508 (7)
N1	0.7650 (3)	0.0919 (3)	0.53328 (16)	0.0192 (5)
N2	0.4476 (3)	0.1163 (3)	0.80295 (17)	0.0337 (7)
H2A	0.402136	0.029931	0.760226	0.040*	0.5
H2B	0.386529	0.023682	0.768121	0.040*	0.5
N4	−0.0154 (3)	0.0023 (3)	1.31488 (15)	0.0192 (5)
C1	0.7449 (3)	0.7266 (3)	0.43646 (18)	0.0179 (6)
C2	0.7338 (3)	0.5698 (3)	0.45840 (19)	0.0209 (6)
H2C	0.706902	0.561637	0.523154	0.025*
H2D	0.841825	0.568788	0.456932	0.025*
C3	0.6088 (3)	0.4244 (3)	0.39172 (19)	0.0234 (6)
H3A	0.597505	0.328278	0.417405	0.028*
H3B	0.502207	0.429417	0.388582	0.028*
C4	0.6538 (3)	0.4107 (3)	0.29341 (19)	0.0212 (6)
C5	0.5820 (4)	0.4578 (3)	0.2218 (2)	0.0283 (7)
H5	0.501563	0.494530	0.234762	0.034*
C6	0.6262 (4)	0.4517 (4)	0.1325 (2)	0.0329 (8)
H6	0.574460	0.482262	0.084503	0.039*
C7	0.7452 (4)	0.4016 (4)	0.1125 (2)	0.0345 (8)
H7	0.777813	0.400657	0.051600	0.041*
C8	0.8165 (4)	0.3526 (3)	0.1821 (2)	0.0284 (7)
H8	0.897859	0.317403	0.168642	0.034*
C9	0.7700 (3)	0.3546 (3)	0.27152 (19)	0.0214 (6)
C10	0.8508 (3)	0.2954 (3)	0.34283 (19)	0.0213 (6)
C11	0.8071 (4)	0.2444 (3)	0.5709 (2)	0.0241 (6)
H11	0.879640	0.325033	0.541595	0.029*
C12	0.7493 (4)	0.2880 (3)	0.6497 (2)	0.0258 (7)
H12	0.782433	0.396716	0.674135	0.031*
C13	0.6430 (3)	0.1733 (3)	0.69311 (19)	0.0229 (6)
C14	0.5999 (3)	0.0165 (4)	0.6550 (2)	0.0257 (7)
H14	0.528086	−0.066012	0.683360	0.031*
C15	0.6620 (3)	−0.0186 (3)	0.5757 (2)	0.0246 (7)
H15	0.629962	−0.126675	0.549909	0.030*
C16	0.5861 (4)	0.2215 (4)	0.7822 (2)	0.0294 (7)
C17A	0.3515 (11)	0.1133 (11)	0.8843 (7)	0.023 (2)	0.5
H17A	0.354723	0.219492	0.903713	0.028*	0.5
H17B	0.236819	0.037467	0.864359	0.028*	0.5
C18A	0.4206 (8)	0.0660 (8)	0.9653 (4)	0.0310 (15)	0.5
H18A	0.408005	−0.043997	0.947555	0.037*	0.5
H18B	0.537985	0.135696	0.981143	0.037*	0.5
N3A	0.3389 (7)	0.0770 (6)	1.0475 (4)	0.0291 (12)	0.5
H3AA	0.384594	0.160658	1.092118	0.035*	0.5
C17B	0.4120 (11)	0.1782 (10)	0.8929 (7)	0.022 (2)	0.5
H17C	0.372090	0.260031	0.885677	0.026*	0.5
H17D	0.508849	0.223066	0.941254	0.026*	0.5
C18B	0.2807 (8)	0.0313 (7)	0.9173 (4)	0.0205 (13)	0.5
H18C	0.183417	−0.006668	0.869700	0.025*	0.5
H18D	0.319387	−0.053069	0.915379	0.025*	0.5
N3B	0.2361 (7)	0.0618 (6)	1.0108 (3)	0.0214 (11)	0.5
H3BA	0.249314	0.157652	1.034990	0.026*	0.5
C19	0.1776 (5)	−0.0527 (4)	1.0571 (2)	0.0455 (10)
C20	0.1198 (4)	−0.0256 (4)	1.1499 (2)	0.0271 (7)
C21	0.1590 (4)	0.1213 (4)	1.2039 (2)	0.0307 (7)
H21	0.232813	0.214883	1.185214	0.037*
C22	0.0903 (4)	0.1301 (3)	1.28488 (19)	0.0238 (7)
H22	0.118846	0.231415	1.321265	0.029*
C23	−0.0487 (4)	−0.1394 (3)	1.2646 (2)	0.0239 (6)
H23	−0.119759	−0.231360	1.286046	0.029*
C24	0.0158 (4)	−0.1577 (4)	1.1828 (2)	0.0270 (7)
H24	−0.011059	−0.260576	1.149137	0.032*
O1W	0.7821 (3)	0.6433 (3)	0.94803 (19)	0.0512 (7)
H1WA	0.755433	0.552414	0.912263	0.077*
H1WB	0.886751	0.680825	0.962743	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0247 (2)	0.0197 (2)	0.01987 (19)	0.01197 (16)	0.00789 (14)	0.00749 (14)
O1	0.0260 (11)	0.0171 (10)	0.0282 (11)	0.0103 (9)	0.0042 (9)	0.0092 (8)
O2	0.0286 (12)	0.0252 (12)	0.0287 (12)	0.0069 (10)	−0.0062 (10)	0.0066 (9)
O3	0.0277 (12)	0.0248 (11)	0.0287 (11)	0.0142 (10)	−0.0027 (9)	0.0019 (9)
O4	0.0243 (11)	0.0144 (10)	0.0183 (10)	0.0092 (9)	0.0055 (8)	0.0048 (8)
O5	0.0671 (18)	0.0453 (16)	0.0350 (14)	0.0308 (14)	−0.0041 (13)	−0.0166 (12)
O6	0.0678 (18)	0.0453 (16)	0.0375 (14)	0.0246 (14)	0.0194 (13)	−0.0083 (12)
N1	0.0186 (12)	0.0189 (12)	0.0234 (12)	0.0099 (10)	0.0047 (10)	0.0070 (10)
N2	0.0466 (18)	0.0524 (18)	0.0169 (13)	0.0338 (16)	0.0121 (12)	0.0081 (12)
N4	0.0248 (13)	0.0222 (13)	0.0134 (11)	0.0118 (11)	0.0031 (10)	0.0057 (10)
C1	0.0218 (15)	0.0186 (15)	0.0151 (13)	0.0097 (13)	0.0099 (12)	0.0008 (11)
C2	0.0268 (16)	0.0185 (15)	0.0173 (14)	0.0089 (13)	0.0052 (12)	0.0037 (11)
C3	0.0240 (16)	0.0179 (15)	0.0278 (16)	0.0081 (13)	0.0046 (13)	0.0040 (12)
C4	0.0254 (16)	0.0118 (14)	0.0219 (15)	0.0051 (12)	−0.0033 (12)	0.0003 (11)
C5	0.0335 (18)	0.0210 (16)	0.0301 (17)	0.0147 (14)	−0.0056 (14)	−0.0014 (13)
C6	0.048 (2)	0.0299 (18)	0.0230 (16)	0.0217 (16)	−0.0094 (15)	0.0008 (13)
C7	0.057 (2)	0.0334 (19)	0.0167 (15)	0.0239 (17)	0.0008 (15)	0.0025 (13)
C8	0.0403 (19)	0.0265 (17)	0.0241 (16)	0.0204 (15)	0.0053 (14)	0.0014 (13)
C9	0.0264 (16)	0.0131 (14)	0.0225 (15)	0.0070 (12)	−0.0006 (12)	0.0028 (11)
C10	0.0246 (16)	0.0221 (16)	0.0211 (15)	0.0125 (13)	0.0065 (12)	0.0058 (12)
C11	0.0254 (16)	0.0182 (15)	0.0288 (16)	0.0087 (13)	0.0038 (13)	0.0069 (12)
C12	0.0333 (18)	0.0176 (15)	0.0268 (16)	0.0123 (14)	0.0002 (13)	0.0008 (12)
C13	0.0209 (15)	0.0269 (16)	0.0212 (15)	0.0131 (13)	−0.0033 (12)	−0.0022 (12)
C14	0.0218 (16)	0.0247 (16)	0.0286 (16)	0.0074 (13)	0.0092 (13)	0.0034 (13)
C15	0.0269 (17)	0.0163 (15)	0.0295 (16)	0.0077 (13)	0.0113 (13)	0.0003 (12)
C16	0.041 (2)	0.0350 (19)	0.0181 (15)	0.0245 (16)	−0.0038 (14)	−0.0023 (14)
C17A	0.026 (6)	0.025 (6)	0.023 (4)	0.012 (4)	0.013 (5)	0.008 (5)
C18A	0.039 (4)	0.037 (4)	0.021 (3)	0.016 (3)	0.015 (3)	0.011 (3)
N3A	0.039 (4)	0.026 (3)	0.018 (3)	0.008 (3)	0.016 (3)	0.003 (2)
C17B	0.029 (6)	0.019 (5)	0.015 (4)	0.006 (4)	0.014 (4)	0.005 (4)
C18B	0.026 (4)	0.021 (3)	0.013 (3)	0.009 (3)	0.005 (3)	−0.001 (3)
N3B	0.028 (3)	0.018 (3)	0.017 (3)	0.009 (2)	0.007 (2)	−0.002 (2)
C19	0.092 (3)	0.031 (2)	0.0285 (18)	0.035 (2)	0.0304 (19)	0.0125 (16)
C20	0.0428 (19)	0.0262 (17)	0.0186 (15)	0.0191 (15)	0.0103 (14)	0.0064 (13)
C21	0.042 (2)	0.0238 (17)	0.0277 (17)	0.0118 (15)	0.0160 (14)	0.0089 (13)
C22	0.0327 (17)	0.0210 (16)	0.0183 (14)	0.0113 (14)	0.0082 (13)	0.0031 (12)
C23	0.0295 (17)	0.0205 (16)	0.0232 (15)	0.0106 (13)	0.0080 (13)	0.0068 (12)
C24	0.0387 (19)	0.0215 (16)	0.0211 (15)	0.0141 (14)	0.0043 (13)	−0.0003 (12)
O1W	0.0749 (19)	0.0262 (13)	0.0500 (16)	0.0187 (13)	0.0156 (15)	0.0033 (12)

Geometric parameters (Å, º) top

Cu1—O1	1.9754 (18)	C9—C10	1.515 (4)
Cu1—O4ⁱ	2.4322 (19)	C11—H11	0.9500
Cu1—O4ⁱⁱ	2.0007 (18)	C11—C12	1.375 (4)
Cu1—N1	2.010 (2)	C12—H12	0.9500
Cu1—N4ⁱⁱⁱ	2.033 (2)	C12—C13	1.378 (4)
O1—C10	1.289 (3)	C13—C14	1.386 (4)
O2—C10	1.227 (3)	C13—C16	1.508 (4)
O3—C1	1.234 (3)	C14—H14	0.9500
O4—C1	1.298 (3)	C14—C15	1.377 (4)
O5—C16	1.223 (4)	C15—H15	0.9500
O6—C19	1.217 (4)	C17A—H17A	0.9900
N1—C11	1.350 (3)	C17A—H17B	0.9900
N1—C15	1.336 (3)	C17A—C18A	1.493 (11)
N2—H2A	0.8800	C18A—H18A	0.9900
N2—H2B	0.8800	C18A—H18B	0.9900
N2—C16	1.331 (4)	C18A—N3A	1.462 (7)
N2—C17A	1.512 (10)	N3A—H3AA	0.8800
N2—C17B	1.470 (10)	N3A—C19	1.507 (7)
N4—C22	1.343 (4)	C17B—H17C	0.9900
N4—C23	1.338 (4)	C17B—H17D	0.9900
C1—C2	1.512 (4)	C17B—C18B	1.515 (8)
C2—H2C	0.9900	C18B—H18C	0.9900
C2—H2D	0.9900	C18B—H18D	0.9900
C2—C3	1.528 (4)	C18B—N3B	1.467 (7)
C3—H3A	0.9900	N3B—H3BA	0.8800
C3—H3B	0.9900	N3B—C19	1.288 (6)
C3—C4	1.513 (4)	C19—C20	1.506 (4)
C4—C5	1.399 (4)	C20—C21	1.389 (4)
C4—C9	1.400 (4)	C20—C24	1.386 (4)
C5—H5	0.9500	C21—H21	0.9500
C5—C6	1.382 (4)	C21—C22	1.376 (4)
C6—H6	0.9500	C22—H22	0.9500
C6—C7	1.382 (4)	C23—H23	0.9500
C7—H7	0.9500	C23—C24	1.381 (4)
C7—C8	1.386 (4)	C24—H24	0.9500
C8—H8	0.9500	O1W—H1WA	0.8703
C8—C9	1.390 (4)	O1W—H1WB	0.8701

O1—Cu1—O4ⁱⁱ	156.66 (8)	C11—C12—C13	119.8 (3)
O1—Cu1—O4ⁱ	126.81 (7)	C13—C12—H12	120.1
O1—Cu1—N1	91.16 (8)	C12—C13—C14	117.7 (3)
O1—Cu1—N4ⁱⁱⁱ	86.83 (8)	C12—C13—C16	119.6 (3)
O4ⁱⁱ—Cu1—O4ⁱ	76.33 (8)	C14—C13—C16	122.6 (3)
O4ⁱⁱ—Cu1—N1	92.95 (8)	C13—C14—H14	120.3
O4ⁱⁱ—Cu1—N4ⁱⁱⁱ	91.12 (8)	C15—C14—C13	119.5 (3)
N1—Cu1—O4ⁱ	87.84 (8)	C15—C14—H14	120.3
N1—Cu1—N4ⁱⁱⁱ	173.98 (9)	N1—C15—C14	123.1 (3)
N4ⁱⁱⁱ—Cu1—O4ⁱ	88.83 (8)	N1—C15—H15	118.4
C10—O1—Cu1	123.27 (18)	C14—C15—H15	118.4
Cu1^iv—O4—Cu1ⁱ	103.67 (7)	O5—C16—N2	123.6 (3)
C1—O4—Cu1ⁱ	149.19 (17)	O5—C16—C13	120.2 (3)
C1—O4—Cu1^iv	107.15 (16)	N2—C16—C13	116.3 (3)
C11—N1—Cu1	121.00 (18)	N2—C17A—H17A	109.6
C15—N1—Cu1	121.71 (19)	N2—C17A—H17B	109.6
C15—N1—C11	117.2 (2)	H17A—C17A—H17B	108.1
C16—N2—H2A	113.1	C18A—C17A—N2	110.2 (7)
C16—N2—H2B	125.2	C18A—C17A—H17A	109.6
C16—N2—C17A	133.7 (4)	C18A—C17A—H17B	109.6
C16—N2—C17B	109.7 (4)	C17A—C18A—H18A	109.5
C17A—N2—H2A	113.1	C17A—C18A—H18B	109.5
C17B—N2—H2B	125.2	H18A—C18A—H18B	108.0
C22—N4—Cu1^v	118.58 (18)	N3A—C18A—C17A	110.9 (6)
C23—N4—Cu1^v	123.67 (19)	N3A—C18A—H18A	109.5
C23—N4—C22	117.4 (2)	N3A—C18A—H18B	109.5
O3—C1—O4	121.8 (3)	C18A—N3A—H3AA	119.5
O3—C1—C2	122.2 (3)	C18A—N3A—C19	121.1 (5)
O4—C1—C2	116.0 (2)	C19—N3A—H3AA	119.5
C1—C2—H2C	108.5	N2—C17B—H17C	111.4
C1—C2—H2D	108.5	N2—C17B—H17D	111.4
C1—C2—C3	114.9 (2)	N2—C17B—C18B	102.1 (5)
H2C—C2—H2D	107.5	H17C—C17B—H17D	109.2
C3—C2—H2C	108.5	C18B—C17B—H17C	111.4
C3—C2—H2D	108.5	C18B—C17B—H17D	111.4
C2—C3—H3A	109.0	C17B—C18B—H18C	109.2
C2—C3—H3B	109.0	C17B—C18B—H18D	109.2
H3A—C3—H3B	107.8	H18C—C18B—H18D	107.9
C4—C3—C2	113.0 (2)	N3B—C18B—C17B	111.9 (6)
C4—C3—H3A	109.0	N3B—C18B—H18C	109.2
C4—C3—H3B	109.0	N3B—C18B—H18D	109.2
C5—C4—C3	120.3 (3)	C18B—N3B—H3BA	120.3
C5—C4—C9	118.0 (3)	C19—N3B—C18B	119.5 (4)
C9—C4—C3	121.7 (2)	C19—N3B—H3BA	120.3
C4—C5—H5	119.5	O6—C19—N3A	122.6 (3)
C6—C5—C4	121.1 (3)	O6—C19—N3B	116.0 (4)
C6—C5—H5	119.5	O6—C19—C20	120.3 (3)
C5—C6—H6	119.8	N3B—C19—C20	119.9 (3)
C7—C6—C5	120.5 (3)	C20—C19—N3A	113.0 (3)
C7—C6—H6	119.8	C21—C20—C19	125.3 (3)
C6—C7—H7	120.3	C24—C20—C19	117.3 (3)
C6—C7—C8	119.4 (3)	C24—C20—C21	117.4 (3)
C8—C7—H7	120.3	C20—C21—H21	120.3
C7—C8—H8	119.7	C22—C21—C20	119.5 (3)
C7—C8—C9	120.6 (3)	C22—C21—H21	120.3
C9—C8—H8	119.7	N4—C22—C21	123.1 (3)
C4—C9—C10	122.3 (2)	N4—C22—H22	118.4
C8—C9—C4	120.5 (3)	C21—C22—H22	118.4
C8—C9—C10	117.2 (3)	N4—C23—H23	118.6
O1—C10—C9	114.9 (2)	N4—C23—C24	122.8 (3)
O2—C10—O1	124.7 (3)	C24—C23—H23	118.6
O2—C10—C9	120.3 (2)	C20—C24—H24	120.1
N1—C11—H11	118.6	C23—C24—C20	119.8 (3)
N1—C11—C12	122.8 (3)	C23—C24—H24	120.1
C12—C11—H11	118.6	H1WA—O1W—H1WB	104.5
C11—C12—H12	120.1

Cu1—O1—C10—O2	−2.2 (4)	C9—C4—C5—C6	−1.0 (4)
Cu1—O1—C10—C9	175.31 (17)	C11—N1—C15—C14	−0.7 (4)
Cu1^iv—O4—C1—O3	−5.1 (3)	C11—C12—C13—C14	0.6 (4)
Cu1ⁱ—O4—C1—O3	175.11 (19)	C11—C12—C13—C16	177.1 (3)
Cu1^iv—O4—C1—C2	175.05 (17)	C12—C13—C14—C15	−0.8 (4)
Cu1ⁱ—O4—C1—C2	−4.7 (4)	C12—C13—C16—O5	−22.3 (4)
Cu1—N1—C11—C12	−175.4 (2)	C12—C13—C16—N2	158.0 (3)
Cu1—N1—C15—C14	175.1 (2)	C13—C14—C15—N1	0.9 (5)
Cu1^v—N4—C22—C21	−170.4 (2)	C14—C13—C16—O5	154.0 (3)
Cu1^v—N4—C23—C24	170.2 (2)	C14—C13—C16—N2	−25.7 (4)
O3—C1—C2—C3	18.7 (4)	C15—N1—C11—C12	0.4 (4)
O4—C1—C2—C3	−161.5 (2)	C16—N2—C17A—C18A	−81.7 (8)
O6—C19—C20—C21	−174.4 (4)	C16—N2—C17B—C18B	−165.6 (5)
O6—C19—C20—C24	3.9 (5)	C16—C13—C14—C15	−177.2 (3)
N1—C11—C12—C13	−0.4 (5)	C17A—N2—C16—O5	−1.9 (7)
N2—C17A—C18A—N3A	174.7 (5)	C17A—N2—C16—C13	177.9 (6)
N2—C17B—C18B—N3B	174.4 (5)	C17A—C18A—N3A—C19	81.0 (7)
N4—C23—C24—C20	0.0 (5)	C18A—N3A—C19—O6	18.2 (8)
C1—C2—C3—C4	67.9 (3)	C18A—N3A—C19—C20	175.4 (5)
C2—C3—C4—C5	−100.4 (3)	N3A—C19—C20—C21	27.8 (5)
C2—C3—C4—C9	78.2 (3)	N3A—C19—C20—C24	−153.9 (4)
C3—C4—C5—C6	177.5 (3)	C17B—N2—C16—O5	−1.8 (6)
C3—C4—C9—C8	−175.9 (3)	C17B—N2—C16—C13	178.0 (5)
C3—C4—C9—C10	3.6 (4)	C17B—C18B—N3B—C19	−153.6 (7)
C4—C5—C6—C7	−1.3 (5)	C18B—N3B—C19—O6	−17.3 (8)
C4—C9—C10—O1	90.8 (3)	C18B—N3B—C19—C20	−175.4 (4)
C4—C9—C10—O2	−91.5 (3)	N3B—C19—C20—C21	−17.2 (6)
C5—C4—C9—C8	2.6 (4)	N3B—C19—C20—C24	161.1 (4)
C5—C4—C9—C10	−177.8 (3)	C19—C20—C21—C22	176.2 (3)
C5—C6—C7—C8	2.0 (5)	C19—C20—C24—C23	−176.1 (3)
C6—C7—C8—C9	−0.4 (5)	C20—C21—C22—N4	−0.3 (5)
C7—C8—C9—C4	−1.9 (4)	C21—C20—C24—C23	2.3 (5)
C7—C8—C9—C10	178.5 (3)	C22—N4—C23—C24	−2.5 (4)
C8—C9—C10—O1	−89.6 (3)	C23—N4—C22—C21	2.7 (4)
C8—C9—C10—O2	88.1 (3)	C24—C20—C21—C22	−2.2 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1^vi	0.88	2.12	2.959 (3)	160
N3B—H3BA···O1W^vii	0.88	1.99	2.836 (5)	160
O1W—H1WA···O5	0.87	1.92	2.781 (3)	172

Symmetry codes: (vi) −x+1, −y, −z+1; (vii) −x+1, −y+1, −z+2.

Funding information

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

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
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 (2013). 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
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). Crystal Maker X. Crystal Maker Software, Begbroke, England. Google Scholar
Przybyla, J. J., Ezenyilimba, F. C. & LaDuca, R. L. (2019). Inorg. Chim. Acta, 498, 119087. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals 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.