Crystal structures and thermogravimetric analyses of six CuCN net­work structures with protonated N-alkyl­ethano­lamines as guest cations

Corfield, P.W.R.; Carlson, A.; Contrera, G.J.; Eisha, N.; Faisal, E.; Garcia, D.J.; Gencarelli, N.R.

doi:10.1107/S2053229625008113

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 81| Part 10| October 2025| Pages 584-595

https://doi.org/10.1107/S2053229625008113

Crystal structures and thermogravimetric analyses of six CuCN network structures with protonated N-alkylethanolamines as guest cations

Peter W. R. Corfield,^a ^* Abigail Carlson,^a Gianni J. Contrera,^a Nurul Eisha,^a Elali Faisal,^a Daniel J. Garcia ^a and Nina R. Gencarelli ^a

^aDepartment of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA
^*Correspondence e-mail: [email protected]

Edited by D. R. Turner, University of Monash, Australia (Received 25 July 2025; accepted 12 September 2025; online 24 September 2025)

The structures of six triperiodic CuCN network structures with conjugate acids of four N-alkylethanolamines as guest cations are described, namely, poly[2-hydroxyethan-1-aminium [μ₃-cyanido-di-μ₂-cyanido-dicuprate(I)]], {(C₂H₈NO)[Cu₂(CN)₃]}_n, 1, poly[bis(2-hydroxy-N-methylethan-1-aminium) [di-μ₃-cyanido-tri-μ₂-cyanido-tricuprate(I)] monohydrate], {(C₄H₁₂NO)₂[Cu₃(CN)₅]·H₂O}_n, 2, poly[tetrakis[N-(2-hydroxyethyl)ethan-1-aminium] [chloridotetra-μ₃-cyanido-penta-μ₂-cyanido-tricuprate(I)]], {(C₄H₁₂NO)₄[Cu₆(CN)₉Cl]}_n, 3, poly[tetrakis[N-(2-hydroxyethyl)ethan-1-aminium] [penta-μ₃-cyanido-hepta-μ₂-cyanido-octacuprate(I)]], {(C₄H₁₂NO)₄[Cu₈(CN)₁₂]}_n, 4, poly[2-hydroxy-N,N-diisopropylethan-1-aminium [μ₃-cyanido-μ₂-cyanido-dicuprate(I)] monohydrate], {(C₈H₂₀NO)[Cu₃(CN)₄]·H₂O}_n, 5, and poly[2-hydroxy-N,N-diisopropylethan-1-aminium [μ₃-cyanido-di-μ₂-cyanido-dicuprate(I)]], {(C₈H₂₀NO)[Cu₂(CN)₃]}_n, 6. In five of the structures (1–5), the CuCN network includes Cu atoms occurring in pairs, linked by cuprophilic interactions. Analysis with the intent of exploring the `template effect' of the cations on the CuCN network structure indicated five separate CuCN topologies. The two different crystal structures involving cations from N-ethylethanolamine have the same basic topology, whereas the two crystal structures involving cations from N,N-diisopropylethanolamine have different topologies, contrary to what might be expected from a template effect. Thermogravimetric analysis of the compounds usually shows loss of HCN(g) and the free base by 200 °C, with a CuCN(s) residue, but decomposition of one of the structures is more complex.

Keywords: crystal structure; copper cyanide; network; thermogravimetric analysis; ethanolamine; cuprophilic interaction; topology.

CCDC references: 2487534; 2487533; 2487532; 2487531; 2487530; 2487529

1. Chemical context

Copper cyanide network structures are of interest because of their fascinating variety of structures and their potentially useful physical properties (Tronic et al., 2007 ; Lim et al., 2008 ; Pike, 2012 ; Etaiw et al., 2016 ). Their luminescence properties have been noted by several investigators (for example, Dembo et al., 2010 ; Grifasi et al., 2016 ; Nicholas et al., 2019 ). This interest is ongoing, as 99 of the 705 CuCN crystal structures in the Cambridge Structural Database (CSD; Groom et al., 2016 ) were deposited in the last five years. For instance, Iwai et al. (2024 ) describe the thermal flexibility of the planar CuCN network in a triethylammonium–copper cyanide complex and the potential applications of this property, while Mishra et al. (2024 ) describe a 2D CuCN network as an example of a 2D MOF with potential use as an electrode material. Our own work has focussed on the structural aspects of CuCN networks, with previous work on mixed-valence compounds with diamines and triamines revealing neutral 1D, 2D, and 3D network structures involving a variety of topologies, as well as monomeric structures (Corfield et al., 2016 , 2018 ). More recently, we have explored the so-called template effect of guest cations on anionic triperiodic Cu^ICN networks (Corfield et al., 2022 ; Koenigsmann et al., 2020 ). Our goal is to understand how the guest–host interactions lead to the various network topologies.

2. Experimental

2.1. Syntheses

Chemicals were used as purchased from TCI or Aldrich Chemicals. In general, samples were prepared by reacting CuCN(s) with NaCN(aq) in one vessel, while dissolving the base separately in water and neutralizing with acid in a second vessel. The neutralized base was added to the CuCN/NaCN mixture with stirring, the final mixture filtered if necessary, and the solutions left to crystallize through slow evaporation at room temperature. Crystalline products usually appeared within 1–4 weeks. The course of the reactions appears to be sensitive to the initial conditions, so that many preparations did not result in suitable crystalline samples, and dark insoluble powders were often obtained.

Relevant IR stretching frequencies for 1, 2, 4–6, and two previously reported compounds are summarized in Table 1. The CN stretch for the μ₃-CN groups is systematically shifted to lower frequencies by about 25 cm⁻¹, consistent with the slight reduction in bond order expected by the coordination to three Cu atoms rather than two for the μ₂-CN groups, resulting in a slightly lower bond order due to increased back donation from filled d orbitals on the Cu atoms to empty π* orbitals on the CN groups. We do not see the expected slight increase in C—N distances for the μ₃-CN groups, however. The weighted average C—N distances and estimated standard deviations for the μ₂- and μ₃-CN groups are 1.1474 (5) and 1.1427 (7) Å, respectively, indicating, if anything, a slight reduction in bond length for the μ₃-CN groups.

Table 1
C≡N IR stretching frequencies

	Base, B	Molecular formula	Cyanides	C≡N IR stretches (cm⁻¹)
1	oen	BH·Cu₂(CN)₃	μ₂; 2 × μ₃	2082, 2111
*	meoen	BH·Cu₂(CN)₃	2 × μ₂; μ₃	2083, 2104
2	etoen	[BH]₂·Cu₃(CN)₅·H₂O	4 × μ₂; μ₃	2092, 2112
4	me₂oen	[BH]₄Cu₈(CN)₁₂	7 × μ₂; 5 × μ₃	2075, 2103
**	et₂oen	BH·Cu₂(CN)₃	2 × μ₂; μ₃	2071, 2100 2122
5	ipr₂oen	BH·Cu₃(CN)₄·H₂O	3 × μ₂; μ₃	Shoulder, 2128 (broad)
6	ipr₂oen	BH·Cu₂(CN)₃	3 × μ₂	2114
Notes: () Koenigsmann et al.* (2020). (*) Corfield et al.* (2016).

2.1.1. Preparation of 1

The data crystal was from a synthesis that used: CuCN, 10 mmol; NaCN, 20 mmol; ethanolamine, 10 mmol. Base first neutralized with 1 M HCl. Volume of the final mixture was about 30 ml. 66 mg of colorless crystals were harvested after three weeks, corresponding to a yield of 5%, based upon Cu.

2.1.2. Preparation of 2 and 3

The amounts used were: CuCN, 10 mmol; NaCN, 16 mmol; N-ethylethanolamine, 40 mmol. Base first neutralized with 6 M HCl. Volume of the final mixture was about 35 ml with a pH of 6.4. 125 mg of colorless crystals harvested after one week, with a yield of 7%, based upon Cu. A crystal of 3 was obtained during a search of this sample for a better crystal of 2. In spite of multiple attempts, we have been unable to reproduce the synthesis of 3. In a recent attempt with 5.0 mmol CuCN, 8.0 g NaCN, 8.5 mmol etoen, and 30 mmol HCl(aq), 640 mg of a white powder were produced immediately. The IR spectrum indicated both CN and protonated ligand stretches, and the TGA analysis showed a fall-off to a plateau as seen in the other complexes. The percentage (%) remaining after thermal decomposition gave a y/x value of 2.96, as discussed below, indicating a compound with possible formula etoenH·Cu₃(CN)₄, which was confirmed by CHN and Cu analyses. We are currently seeking to determine the structure from the powder X-ray diffraction data.

2.1.3. Preparation of 4

The amounts used were: CuCN, 10 mmol; NaCN, 20 mmol; dimethylethanolamine, 40 mmol. Base first neutralized with 6 M HCl. After three weeks, 107 mg of well-formed pale-yellow crystals were filtered off; yield 7%, based upon Cu.

2.1.4. Preparation of 5 and 6

The amounts used were: CuCN, 1.24 mmol; NaCN, 1.05 mmol; diisopropylethanolamine, 2.5 mmol, volume 20 ml, final pH 11.4 (no acid was added). Crystals of 6 were filtered off after three weeks and after six months; the dried-out filtrate contained 10 mg of well-formed dark-green crystals of 5 (5% yield, based upon CuCN) and some blue powder.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms on C atoms were placed in idealized positions, with distances fixed at 0.97 Å for CH₂, 0.96 Å for CH₃, and 0.98 Å for C₃H; U_iso(H) values were set at 1.5U_eq for methyl H atoms, 1.2U_eq for methylene and methine H atoms, and 1.0U_eq for the aminium H atoms, which were refined with restraints. Hydroxyl H atoms were sometimes too poorly defined for this and were constrained to reasonable positions, with O—H distances of 0.82 Å. Near the end of the refinements for each compound, CN/NC disorder was allowed for the cyanide groups and the occupancies of the two orientations were refined. If the occupancies were within 2–3 standard deviations of either 0.50 or 1.0, they were set at these values and not refined. In all structures, the μ₃-CN groups were found to have the C atom bonded to the two cuprophilic Cu atoms, and these CN groups are ordered. In many of the structure refinements, the SHELXL SHEL command was used to limit the use of higher resolution data where few intensities were above background.

Table 2
Experimental details

For all structures: Z = 4. Experiments were carried out with Mo Kα radiation using an Enraf–Nonius KappaCCD diffractometer. Absorption correction was part of the refinement model (ΔF) (DENZO; Otwinowski & Minor, 1997).

	1	2	3
Crystal data
Chemical formula	(C₂H₈NO)[Cu₂(CN)₃]	(C₄H₁₂NO)₂[Cu₃(CN)₅]·H₂O	(C₄H₁₂NO)₄[Cu₆(CN)₉Cl]
M_r	267.23	519.03	1011.45
Crystal system, space group	Monoclinic, Cc	Monoclinic, P2₁/c	Monoclinic, C2/c
Temperature (K)	300	299	299
a, b, c (Å)	14.1276 (3), 8.2049 (2), 7.8186 (2)	12.0606 (2), 21.2559 (3), 8.4115 (1)	8.2206 (1), 23.0970 (4), 20.9992 (4)
β (°)	109.263 (1)	108.1267 (7)	92.3301 (11)
V (Å³)	855.56 (4)	2049.34 (5)	3983.85 (11)
μ (mm⁻¹)	4.93	3.11	3.26
Crystal size (mm)	0.27 × 0.09 × 0.06	0.30 × 0.16 × 0.06	0.23 × 0.12 × 0.05

Data collection
T_min, T_max	0.61, 0.82	0.43, 0.52	0.60, 0.71
No. of measured, independent and observed [I > 2σ(I)] reflections	22177, 3586, 3048	65386, 5996, 4837	59964, 4566, 3558
R_int	0.045	0.043	0.055
(sin θ/λ)_max (Å⁻¹)	0.807	0.704	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.080, 1.05	0.038, 0.093, 1.05	0.038, 0.101, 1.03
No. of reflections	3586	5996	4566
No. of parameters	114	292	244
No. of restraints	4	35	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.77	0.51, −0.53	0.44, −0.52
Absolute structure	Flack x determined using 1290 quotients [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)] (Parsons et al., 2013 )	–	–
Absolute structure parameter	0.54 (3)	–	–

	4	5	6
Crystal data
Chemical formula	(C₄H₁₂NO)₄[Cu₈(CN)₁₂]	(C₈H₂₀NO)[Cu₃(CN)₄]·H₂O	(C₈H₂₀NO)[Cu₂(CN)₃]
M_r	1181.14	458.96	351.39
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/n	Monoclinic, P2₁/c
Temperature (K)	298	296	297
a, b, c (Å)	15.3810 (1), 15.9128 (2), 18.0222 (2)	11.1671 (9), 9.7754 (19), 17.1556 (5)	7.2470 (1), 13.9706 (4), 15.3264 (4)
β (°)	108.6885 (6)	105.876 (5)	92.9207 (15)
V (Å³)	4178.45 (8)	1801.3 (4)	1549.70 (6)
μ (mm⁻¹)	4.04	3.52	2.74
Crystal size (mm)	0.30 × 0.10 × 0.10	0.40 × 0.40 × 0.35	0.16 × 0.11 × 0.10

Data collection
T_min, T_max	0.65, 0.79	0.45, 0.56	0.782, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	148190, 12231, 9299	119728, 4652, 3298	42261, 3418, 2664
R_int	0.059	0.051	0.045
(sin θ/λ)_max (Å⁻¹)	0.704	0.676	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.088, 1.04	0.024, 0.072, 1.04	0.057, 0.192, 1.17
No. of reflections	12231	4652	3418
No. of parameters	594	264	248
No. of restraints	80	86	261
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −1.10	0.30, −0.35	0.56, −0.49
Computer programs: KappaCCD Server Software (Nonius, 1997 ), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), XABS2 (Parkin et al., 1995 ), ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 2012 ), and publCIF (Westrip, 2010 ).

In 1, where the base was oen, the choice between space groups C2/c and Cc was not at first clear from the reflection statistics. This is due to the CuCN network having a symmetry very close to that of C2/c, with the origin inversion center between Cu1 and Cu2. Refinements with disordered cations in the centric space group were unsatisfactory, however, and the lower symmetry was chosen. Because only the four atoms of the cation break the centric symmetry, the standard deviations of the bond distances and angles in the cation are higher than would be expected for such an overdetermined dataset and higher than those for the CN group geometries, while the H atoms of the –OH and –NH₃⁺ groups had to be refined with constraints or severe restraints. The Flack parameter indicated that the crystal was an inversion twin, which is understandable since the CuCN network is essentially centrosymmetric.

Near the end of the refinements in 2, with base etoen, we observed a 1.8 e Å⁻³ peak in the difference Fourier map near Cu1, and we modeled this as an alternative position for Cu1, Cu1B. After including this, the R factors dropped significantly, and the occupancy factors for Cu1A and Cu1B refined to 0.881 (6) and 0.111 (6), respectively, with Cu1A and Cu1B at a distance of 0.497 Å apart. While Cu1A forms a cuprophilic pair with centrosymmetrically related Cu1A′, bridged by μ₃-C1 and C1′, Cu1B is not close to Cu1B′ or to C1′, so that Cu1A is four-coordinated and Cu1B is three-coordinated. Of the two independent cations O11/C16 and O21/O26, there was considerable residual density around O21/C26, which we have modeled as a completely separate minor component of this cation, with the occupancy refining to 0.271 (5). Tight restraints on the geometry were necessary for refinements of the disordered cation.

In contrast with 2, there were no disorder issues with 3.

In 4, two of the four independent cations are disordered between two sets of atomic sites. In each case, the positions of the terminal HOCH₂– groups were modeled as fixed, while the CH₂N moieties led to alternative positions with oppositely handed gauche conformations for the O—C—C—N backbones, with concomitant shifts of the methyl groups. Site occupancies for C43A/C46A and C43B/C46B refined to 0.726 (6) and 0.274 (6), respectively, while the occupancies for C53A/C56A and C53B/C56B were both set at 0.50. Restraints on displacement parameters were set. The disordered N—H atoms were not refined, but placed in ideal positions with N—H = 0.98 Å. The DENZO (Otwinowski & Minor, 1997 ) output is missing the 100, 110, and 011 reflections, presumably due to occultation by the backstop, and the 32 $[\overline{1}]$ reflection, which apparently led to overflow.

In 5, the displacement parameters for Cu2 were so elongated that we chose to model this atom as disordered between two sites, Cu2A and Cu2B, with occupancies set at 50%, since the refined occupancies were within 1σ of this value. The CN occupancies were refined, resulting in values of 0.76 (3) for C1N1, 0.73 (3) for C2N2, and 0.69 (3) for C3N3. The other two crystallographic CN groups are disordered across centers of symmetry. The cation disorder is different from all of the other structures: our refined model has the ⁱPr₂N part fixed, while the two disorder components involve alternating positions of the N—H and N—(CH₂)₂OH bonds, with refined occupancies of 0.814 (5) and 0.186 (5). The H₂O molecule is part of the same disorder, as it is strongly hydrogen bonded to the amine H atom. The positions of the H₂O, O—H, and N—H hydrogens were refined with restraints, except for the N—H proton in the minor cation component, H14B, and the U_iso(H) values were set at 1.5U_eq for H₂O and OH, and at 1.0U_eq for the N—H protons, except for the O—H proton in the major disorder component, H11A, which was allowed to refine.

The structure refined satisfactorily to R₁(F² > 2σ) = 0.0273 and R_w = 0.0874. However, all 30 reflections where F_o² and F_c² differed by more than 3.5σ had F_o² > F_c², including 11 weak-to-moderate intensities where the difference was above 7σ. This is usually an indication of twinning, which is not expected in a monoclinic structure. However, it was noticed that roughly one-third of the unweighted reciprocal lattice points are related by reflection across the (hk $[\overline h]$ ) plane, and that the worst fitting intensities had a much stronger reflection that was related by this plane. We have assumed there was a fragment crystallite on the main crystal, related by this (hk $[\overline h]$ ) plane, with about 4.0% of the scattering. The DENZO software used to process our X-ray diffraction images would have rejected the few intensities above background of non-overlapping reflections from the fragment. With a FORTRAN program we transformed the hkl indices for the fragment crystal onto the axes of the main crystal. We found 987 overlapping pairs, assuming overlap occurred if the individual transformed and the main hkl values differed by no more than 0.08, and we corrected these observed F_o² values for overlap. With the corrected dataset, refinement converged with R₁(>2σ) = 0.0243 and R_w = 0.0708, values significantly less than for the refinement with the unmodified data.

In 6, O—H protons were refined as riding, with U_iso(H) values constrained to 1.5U_eq of their bonded O atoms. The disorder in 6 was difficult to resolve. Our model has alternative superimposed orientations for the –CH₂CH₂OH group and one of the isopropyl groups, with concomitant shifts in the other isopropyl group and N—H proton. Refinements required many restraints. The disorder may be more complex than this, but we have accepted this imperfect model because of the interest in the CuCN network, which is different from the network in 5, although the guest cation is the same.

3. Results and discussion

3.1. Structural commentary

The names and formulae of the six title compounds are given in Table 3. The structures consist of anionic CuCN networks, with guest cations composed of the conjugate acid of the ethanolamine base. We used oenH as the abbreviation for the conjugate base of 2-aminoethanol, and the same notation with the usual alkyl prefixes for the other compounds. Many of the guest cations exhibit disorder between two alternate positions. When the disorder involves a major and a minor component, rather than components with equal occupation, we have restricted discussion to the major component. All cations and their disordered components have a curved shape, with a gauche conformation around the C—C bond in the ethanolamine part, except for component A in 6, which is eclipsed, with an N—C—C—O torsion angle of 15 (4)°. Otherwise, the absolute values of the N—C—C—O torsion angles vary from 52.5 (6)° in 4 to 80.0 (5)° in 2. There may be intramolecular N—H⋯O hydrogen bonds in some cases, but the angle at H is always less than our cut-off value of 125°.

Table 3
Details of the six title compounds, with the conjugate acid indicated by addition of hydrogen to the base

	Base, with abbreviation	Asymmetric unit	Compound name
1	NH₂(CH₂)₂OH, oen	oenH·Cu₂(CN)₃	Poly[2-hydroxyethan-1-aminium [μ₃-cyanido-κ³C:C:N-di-μ₂-cyanido-κ⁴C:N-dicuprate(I)]]
2	C₂H₅NH(CH₂)₂OH, etoen	(etoenH)₂·Cu₃(CN)₅·H₂O	Poly[bis[N-(2-hydroxyethyl)ethan-1-aminium] [di-μ₃-cyanido-κ⁶C:C:N-tri-μ₂-cyanido-κ⁶C:N-tricuprate(I)] monohydrate]
3	C₂H₅NH(CH₂)₂OH, etoen	(etoenH)₂·Cu₃(CN)_4.5Cl_0.5	Poly[tetrakis[N-(2-hydroxyethyl)ethan-1-aminium] [chloridotetra-μ₃-cyanido-κ¹²C:C:N-penta-μ₂-cyanido-κ¹⁰C:N-tricuprate(I)]]
4	(CH₃)₂NH(CH₂)₂OH, me₂oen	(me₂oenH)₄·Cu₈(CN)₁₂	Poly[tetrakis[N-(2-hydroxyethyl)ethan-1-aminium] [penta-μ₃-cyanido-κ¹⁵C:C:N-hepta-μ₂-cyanido-κ¹⁴C:N-octacuprate(I)]]
5	[(CH₃)₂CH]₂N(CH₂)₂OH, ipr₂oen	ipr₂enH·Cu₃(CN)₄·H₂O	Poly[2-hydroxy-N,N-diisopropylethan-1-aminium [μ₃-cyanido-κ³C:C:N-di-μ₂-cyanido-κ⁴C:N-dicuprate(I)] monohydrate]
6	[(CH₃)₂CH]₂N(CH₂)₂OH, ipr₂oen	ipr₂oenH·Cu₂(CN)₃	Poly[2-hydroxy-N,N-diisopropylethan-1-aminium [μ₃-cyanido-κ³C:C:N-di-μ₂-cyanido-κ⁴C:N-dicuprate(I)]]

The CuCN networks for 1–5 involve at least one pair of Cu atoms linked together by a cuprophilic interaction and by one or two μ₃-CN bridges. There are no cuprophilic bonds in structure 6. Cuprophilic interactions in Cu^I compounds have been noted for some time (Hanika-Heidl et al., 2003 ; Chen et al., 2016 ) and have been reviewed recently (Harisomayajula et al., 2019 ). All of complexes 1–5 exhibit short Cu⋯Cu distances, as seen in Table 4. Stocker et al. (1999 ) noted that longer Cu⋯Cu distances are usually associated with unequal Cu—C distances to the bridging μ₃-CN groups, while for the shorter distances, at least one bridging μ₃-CN group has more equal Cu—C bond lengths, and this trend is mostly seen in the geometries in Table 4. Further discussion of the CuCN networks is given below.

Table 4
Cuprophilic geometries for compounds 1–6

	Cation, LH⁺	Cu⋯Cu (Å)	Short Cu—C (Å)	Long Cu—C (Å)
1	oenH	2.459 (1)	1.996 (6)	2.267 (6)
			2.079 (6)	2.106 (6)
2	etoenH	2.651 (4) Cu1A	1.958 (2)	2.420 (3)
			1.958 (2)	2.420 (3)
3	etoenH	2.604 (1)	1.970 (3)	2.384 (3)
			1.970 (3)	2.384 (3)
4	me₂oenH	2.472 (1)	2.113 (3)	2.174 (3)
		2.529 (1)	2.124 (3)	2.153 (3)
		2.506 (1)	2.006 (3)	2.290 (3)
			2.102 (3)	2.164 (3)
			1.997 (3)	2.172 (3)
			1.916 (3)	2.615 (3)
5	ipr₂oenH	2.654 (1) Cu2A	2.609 (1)	2.677 (1)
		2.483 (1) Cu2B	2.315 (1)	2.609 (1)

In structure 1, [oenH][Cu₂(CN)₃], the basic unit of the CuCN network is a cuprophilic pair of Cu atoms that are 2.459 (1) Å apart (Fig. 1), bridged by the C atoms of two μ₃-CN groups, with each Cu atom also bonded to two μ₂-CN groups. The μ₃-cyanide C1 atom bonds asymmetrically to the Cu atoms, while the other μ₃-cyanide forms more symmetrical bridge bonds (Table 4).

Figure 1
The asymmetric unit of 1, oenH, with displacement ellipsoids drawn at the 75% probability level. Arbitrary circles have been used for H atoms in all figures. Incomplete ellipsoids are symmetry-related atoms. The colors for all the figures are as follows: pink Cu, red O, blue N, and black C and H, with cuprophilic bonds in pink.

In 2, [etoenH]₂[Cu₃(CN)₅]·H₂O (Fig. 2), there are three independent Cu atoms in the CuCN network and two independent cations, O11/C16 and O21/C26. The structural model includes a minor component for Cu1 and for cation O21/C26. The two minor components do not seem correlated, as their occupancy factors differ significantly. Cu1A forms a cuprophilic pair with Cu1A′ at (−x, −y + 1, −z + 1), with a Cu⋯Cu distance of 2.644 (4) Å, and the μ₃-C1N1 group with its symmetry-related group forming very unsymmetrical bridges. The minor component Cu1B does not form a cuprophilic bond.

Figure 2
The asymmetric unit of 2, etoenHW, with displacement ellipsoids drawn at the 30% probability level and atoms of the minor component fainter. Incomplete ellipsoids are for symmetry-related atoms.

Structure 3, [etoenH]₂[Cu₃(CN)_4.5Cl_0.5] (Fig. 3), has the same formula as 2, except that a Cl⁻ ion lying on a twofold axis replaces what in 2 was a CN⁻ group; also one CN⁻ group lies across an inversion center, and there is no water of crystallization. In contrast to 2, no disorder in the cations or in Cu was found.

Figure 3
The asymmetric unit of 3, with displacement ellipsoids drawn at the 30% probability level. Fainter atoms are symmetry related.

Due to the complexity of structure 4, [me₂oenH]₄[Cu₈(CN)₁₂], the asymmetric unit is shown in two halves (Figs. 4 and 5). Six of the eight Cu atoms are in cuprophilic pairs, while there are four independent cations, two of them disordered.

Figure 4
The asymmetric unit of the CuCN network for 4, with displacement ellipsoids drawn at the 50% probability level.

Figure 5
The asymmetric unit cations in 4, with displacement ellipsoids drawn at the 30% probability level. The minor cation components are fainter.

In structure 5, [ipr₂oenH][Cu₃(CN)₄]·H₂O (Fig. 6), we modeled a 50:50 disorder between two different positions for Cu2. Cu2B forms a cuprophilic bond with Cu1, with C1—N1 as the sole μ₃-bridging cyanide, but Cu2A forms no cuprophilic bond. CN3 and CN5 are CN groups lying across inversion centers. The cation with its hydrogen-bonded water molecule is disordered, with a minor component that has the two isopropyl groups and the central N atom fixed, but the NH atom and the –(CH₂)₂OH moieties, with the associated water molecule, are interchanged.

Figure 6
The asymmetric unit of 5, with displacement ellipsoids drawn at the 30% probability level. The minor cation components are fainter.

In 6, [ipr₂oenH][Cu₂(CN)₃] (Fig. 7), there is no cuprophilic bond. Two CN groups are each disordered across a center of symmetry. The cation is completely disordered, with the two components in a 50:50 ratio sharing a common N14 atom.

Figure 7
The asymmetric unit of 6, with displacement ellipsoids drawn at the 30% probability level. For clarity, the two cation components are shown separately, each relative to the same CuCN unit.

3.2. Supramolecular features

The discussion here focuses on intermolecular interactions involving the guest cations, while a review of the CuCN networks is given in the next section. Table 5 summarizes the hydrogen-bonding contacts between cations, and between cations and the CuCN network, with arbitrary O/N⋯CN cut-off distances of 3.30 Å and angles at hydrogen of 125°. Possible C—H⋯X interactions and interactions involving minor components are not included. More complete listings of the hydrogen bonding in these six structures are given in the tables in the supporting information.

Table 5
Hydrogen-bonding summary (Å, °)

Cation–cation or cation–water hydrogen bonds
1	N14—H14C⋯O11(x, 1 − y, z + $[{1\over 2}]$ )	2.870 (7)	168
2	O11—H11⋯O21A	2.765 (5)	153 (7)
2	N14—H14A⋯OW(−x + 1, −y − 1, −z + 2)	2.843 (3)	168 (3)
2	N24—H24B⋯OW(−x + 1, −y − 1, −z + 2)	2.988 (5)	166
2	OW—HW1⋯O11	2.794 (3)	149 (5)
3	N24—N24A⋯O11(−x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ )	2.776 (4)	166 (3)
4	O41A—H41A⋯O51(x − 1, y, z)	2.880 (4)	164 (4)
4	N54—H54A⋯O21	2.774 (2)	145
5	N14—H14⋯OWA	2.781 (2)	165 (1)
5	OWA—HWA⋯O11A(−x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ )	2.738 (2)	157 (2)

Cation–network or water–network hydrogen bonds
1	O11—H11⋯N3(x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , z)	2.996 (7)	174 (7)
2	N14—H14B⋯C5(−x + 1, −y − 1, −z + 1)	3.216 (3)	135 (3)
2	O21A—H21A⋯N2(−x + 1, −y − 1, −z + 1)	3.152 (4)	171 (7)
2	OW—HW2⋯N4	3.210 (3)	145 (5)
2	OW—HW2⋯N5(x, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ )	3.298 (3)	140 (5)
3	N14—H14A ⋯C3	3.294 (4)	147 (3)
3	N24—H24B⋯N1(−x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ )	3.228 (4)	172 (3)
3	O21—H21⋯N4(x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ )	3.287 (4)	142 (5)
3	O11—H11⋯Cl	3.410 (3)	137 (4)
3	N14—H14⋯Cl	3.323 (3)	166 (4)
4	O21—H21⋯N7(x + 1, y, z)	3.169 (4)	170 (5)
4	N24—H24⋯C8N(−x + 1, −y + 2, −z + 1)	3.111 (3)	149 (2)
4	N34—H34⋯·N3(−x + 1, −y + 2, −z + 2)	3.276 (4)	140 (3)
4	O51—H51⋯N12(−x + 1, −y + 2, −z + 2)	2.975 (4)	171 (5)
5	O11A—H11A⋯N2	3.244 (2)	122 (1)
6	O11A—H11A⋯N1(−x + 2, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ )	3.17 (3)	148

In 1, the CN groups link the Cu atoms into 2D networks of 12-membered rings linked by perpendicular μ₂-CN groups to form the 3D structure which has elongated 12-membered rings perpendicular to the 2D networks, as shown in Figs. 8(a) and 8(b). Cations are linked into chains along the c axis by N—H⋯O hydrogen bonds to glide-related molecules. In addition, O14—H14⋯N3 hydrogen bonds link each cation to the μ₂-cyanide of the CuCN network, possibly ensuring the ordering of that CN group. N—H bonds point in the direction of both μ₃-cyanide groups, but the distances are longer than our cut-off distance of 3.30 Å.

Figure 8
(a) Projection of 1 down the b axis. (b) Part of the projection of 1, viewed at a small angle from the a-axis direction. In these, and in all packing diagrams, dashed blue lines represent cation–cation hydrogen-bonding interactions, and dashed green lines represent cation–CuCN network interactions. In part (b), the OH⋯C3N3 hydrogen bonds are shown in green, but the C3 and N3 atoms are outside the layer and are not shown.

In 2, hydrogen bonding between the water molecule and the O atoms of the two cations forms a centrosymmetric assembly of two water molecules and four cations, shown in Fig. 9. As in 1, the closest interaction with the CuCN network involves an ethanolamine OH group, O21A⋯N2, perhaps explaining the higher N-atom occupancy at that CN site. There are also amine–cyanide and water–cyanide interactions.

Figure 9
Projection of 2 along the c axis.

In 3, N—H⋯O hydrogen bonds link the two independent cations into a chain along the b axis in the crystal, as seen in Fig. 10. The closest cation–CuCN hydrogen bond is N24—H24B⋯N1(−x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ). There are also two cation–chloride interactions, included as network interactions because the Cl ions are part of the CuCN network.

Figure 10
Projection of 3 along the a axis. The orientation of the structure is similar to that for 2 in Fig. 9

The packing diagram for 4 (Fig. 11) shows that the CuCN network has a fairly simple structure, in spite of the complex asymmetric unit. In this figure, 2D CuCN puckered layers parallel to (101) are seen edge-on, and they are joined by perpendicular μ₂-CN groups. An individual CuCN layer is shown in Fig. 12. Three of the four cations form hydrogen bonds to CN groups in the CuCN network, listed in Table 5 and shown in Fig. 11. There are several other such contacts which are more distant. Between cations, O41 is a donor to O51, and N54A is a donor to O21.

Figure 11
Projection of 4 along the b axis.

Figure 12
A single puckered layer in 4.

In 5, the CuCN network is complex. The b-axis projection shown in Fig. 13 shows alternating bands of 12- and 18-membered rings extending along [101], with the cuprophilic bonds hidden due to overlap. For each disorder component of the cation, the H₂O molecule in that component forms N—H⋯OW and OW—HW⋯O11 hydrogen bonds to a cation, forming a chain of screw-related moieties along the screw axes. Also, for each disorder component, there is a hydrogen bond between the cation O—H group and a CN group in the network.

Figure 13
Projection of 5 along the b axis. Only the A component [occupancy 82.1 (1)%] is shown.

In 6, each of the two independent Cu atoms is three-coordinated, in a roughly trigonal–planar geometry. The projection along a (Fig. 14) might suggest a bidirectional honeycomb structure, but the CuCN is in fact triperiodic, as can be seen in Fig. 15. The OH group of the cation is a donor to one of the μ₂-CN groups, in the only hydrogen bond noted for this structure.

Figure 14
Projection down the a axis for 6.

Figure 15
A b-axis projection for 6.

3.3. Thermogravimetric analysis

Thermogravimetric analyses (TGA) were carried out with a TA Q500 instrument. Samples were heated at a rate of 2 °C min⁻¹ under nitrogen gas. Plots of percent weight remaining versus temperature for five of the six compounds are shown superimposed in Fig. 16. (No sample of 3 was available for this analysis.) In most cases, a smooth weight loss begins at around 100 °C and the weight levels out by 250 °C. Compound 5 held on to the base more tightly, so that the mass did not completely level out before further decomposition began. Quantitative data are listed in Table 6, where we have included data for the two structures of this type that were previously published by us. We surmise that the reduction in mass is due to loss of HCN(g) and B(g), where B is the base used, as was shown to be the case for the N-methyl derivative (Koenigsmann et al., 2020). In each case, except for compound 5, the percent loss in mass by the time the mass reaches the plateau matches what is calculated for loss of base plus HCN(g) (plus H₂O in the case of 2) within 1–2%. The reason for the anomalous results for 5 is not clear; there may have been some decomposition of the sample. The general equation for the decomposition may be written:

Table 6
Tabulation of thermogravimetric results. y/x is the ratio computed from R_exp, assuming formula (BH)_xCu_y(CN)_x + y

	Base, B	Asymmetric unit, u	Molar mass, u	Mass base + HCN, u	R_pred, % remaining	R_exp, % remaining	y/x
1	oen	BH·Cu₂(CN)₃	267.2	88.1	67.0	66.7	1.97
*	meoen	BH·Cu₂(CN)₃	281.3	102.1	63.7	64.6	2.08
2	etoen	(BH)₂·Cu₃(CN)₅·H₂O	519.1	250.3 (incl. H₂O)	51.8	51.5	–
3	etoenCl	(BH)₂·Cu₃(CN)_4.5Cl_0.5	505.8	237.5 (incl. HCl)	53.0	Not available	–
4	me₂oen	BH·Cu₂(CN)₃ ×4	295.3 ×4	116.2	60.7	59.3	1.89
**	et₂oen	BH·Cu₂(CN)₃	323.4	144.2	55.4	54.9	1.96
5	ipr₂oen	BH·Cu₃(CN)₄·H₂O	459.0	190.3 (incl. H₂O)	58.5	Not applicable	–
6	ipr₂oen	BH·Cu₂(CN)₃	351.4	172.3	51.0	52.3 (mean of 4)	2.11
Notes: () Koenigsmann et al.* (2020). (*) Corfield et al.* (2016).

Figure 16
Thermogravimetric analyses for compounds 1–6.

[BH]_x·Cu_y(CN)_x+y(s) → xB(g) + xHCN(g) + yCuCN(s)

The fraction, R, remaining after the loss of HCN and base would be the mass of CuCN(s) divided by the mass of the original reactant, [BH]_x·Cu_y(CN)_x+y(s). By algebraic manipulation, it can be shown that:

y/x = R(M_B + M_HCN)/[(1 − R)M_CuCN],

where M_B, M_HCN, and M_CuCN represent the molar masses of base B, HCN, and CuCN, respectively. The ratio y/x should be an integer or the ratio of simple integers if the sample is pure and the above equation correctly represents what happens upon thermal decomposition. One can also use this ratio to estimate the formula of a new compound, as detailed in Section 2.1. Of course, this ratio estimate does not apply if other species are present, as in compounds 2, 3, and 5. Also, the ratio R/(1 − R) magnifies any errors in the measurement of R, as can be seen in the last column of Table 6.

We have examined possible ways in which the different 3D networks could lose one or more CN groups to form the unidimensional CuCN chains seen in the structure of the CuCN residues. Table 5 shows that in all structures there is hydrogen bonding between an N—H or O—H group of the cation(s) and the CuCN network. The single exception is for one of the cations in 4. Even in this case, however, there is a weak N44—H44⋯N5 interaction with d = 3.48 Å, too long to be included in Table 5. We surmise that initial attack on the CuCN network occurs via this hydrogen bonding, leading to extraction of the CN group as HCN, concomitant with loss of the now free base. In the case of OH⋯CuCN hydrogen bonding, the free bases would be formed by rapid isomerization of the oxide moieties formed by abstraction of the OH proton. HCN abstraction would be followed by the break-up of any cuprophilic assemblies, with the μ₃-CN groups becoming μ₂-CN groups. This can be shown to lead to unidimensional chains.

3.4. CuCN networks: a topographical study

We have distinguished the triperiodic networks from each other both by consideration of the Cu atoms as nodes in a graph, and by topographical analysis of the networks carried out by ToposPro (Blatov et al., 2014 ). We simplified the analysis by replacing cuprophilic pairs of Cu atoms by a single atom at the mid-point. The disordered atom Cu1B in 2 was not included in the analysis as it is a minor component. Results are given in Table 7, where we have also included data for two structures of this same type that were previously published by us. Columns two and three repeat the formulae of compounds 1–6 for convenience, and column four gives a representation for the Cu nodes, where Cu(n) represents an n-coordinated Cu atom, and Cu₂(n) a cuprophilic pair (represented as one Cu atom at their mid-point for the ToposPro analysis), with a total of n links to CN groups. In cases where the cuprophilic pair of Cu atoms straddles an inversion center, we used the notation 1/2Cu₂(n). The next column gives the point group symbols as calculated by ToposPro. The program calculates the smallest closed rings associated with each angle in the coordination sphere around each Cu atom. There are three such rings for the trigonal planar atoms, six for four-coordinated atoms, and n(n − 1)/2 for n-coordinated atoms. The point groups give the numbers of Cu nodes in each closed ring found, with the exponents giving the number of those rings. For each Cu node, the sum of the exponents for an n-coordinated atom equals n(n − 1)/2. 12- and 18-membered rings are the most common. In the last column, we have tabulated the ring sizes for each structure, including the bridging CN groups.

Table 7
Nodes and topology of eight related CuCN network structures

	Base, B	Formula	Nodes	Point symbols at Cu atoms	Ring sizes
1	oen	BH·Cu₂(CN)₃	Cu₂(6)	4¹².6³	12, 18
*	meoen	BH·Cu₂(CN)₃	Cu₂(6)	3³.5⁹.6³	9, 15, 18
2	etoen	(BH)₂Cu₃(CN)₅·H₂O	1/2Cu₂(6) Cu(4) Cu(3)	4².6¹⁰.8³ 6⁶ 4.6²	12, 18, 24
3	etoenCl	(BH)₂Cu₃(CN)_4.5Cl_0.5	1/2Cu₂(6) Cu(4) Cu(3)	4².6¹⁰.8³ 6⁶ 4.6²	12, 18, 24
4	me₂oen	BH·Cu₂(CN)₃ ×4	Cu₂(6) Cu₂(6)	4⁷.5³.6⁵ 4⁵.5⁴.6⁵.7	12, 15, 18, 21
			Cu₂(5)	4⁵.5².6².7
			Cu(4) Cu(3)	4².5³.6 4.5²
**	et₂oen	BH·Cu₂(CN)₃	1/2Cu₂(6) Cu(3)	4².6¹⁰.8³ 4.6²	12, 18, 24
5	ipr₂oen	BH·Cu₃(CN)₄·H₂O	Cu₂(5) Cu(3)	4.6⁷.8² 4.6²	12, 18, 24
6	ipr₂oen	BH·Cu₃(CN)₄	Cu(3) Cu(3)	10³ 10³	30
Notes: () Koenigsmann et al.* (2020); (*) Corfield et al.* (2016).

The eight structures in the table show seven different sets of Cu nodes and, correspondingly, seven different sets of point symbols. There appears to be a tendency for structures with larger cations to have a greater proportion of larger rings, with larger pores in the network. Thus, the small oenH⁺ and meoenH⁺ cations are associated with single-node structures, whereas all of the other cations are associated with at least two different nodes. Structures 2 and 3 involve the same base and show the same nodes and point groups, even though they have different unit cells and space groups, and in structure 3, a chloride ion replaces just one of the CN groups of 2 and there is no hydrate. These observations are in line with what one might expect if each cation were to exert its own `template effect' on the formation of the CuCN network structure. However, results for structures 5 and 6 indicate that the template effect is perhaps more nuanced. Both structures involve the same cation, but they have a different set of Cu nodes, and radically different CuCN networks, with 6 not even showing the cuprophilic Cu pair seen in all of the other structures.

3.5. Database survey

We found no other examples of homometallic polymeric CuCN complexes involving guests from ethanolamine derivatives in the CSD (Groom et al., 2016), except for structures published by us earlier (Corfield et al., 2016, 2024 ).

Supporting information

CCDC references: 2487534; 2487533; 2487532; 2487531; 2487530; 2487529

Crystal structure: contains datablocks oenH, etoenHfinal, etoenHClfin, me2oenHx3fin, ipr2oenHWfinfin, ipr2oenHfinal, global. DOI: https://doi.org/10.1107/S2053229625008113/jx3098sup1.cif

Structure factors: contains datablock oenH. DOI: https://doi.org/10.1107/S2053229625008113/jx3098oenHsup2.hkl

Structure factors: contains datablock etoenHfinal. DOI: https://doi.org/10.1107/S2053229625008113/jx3098etoenHfinalsup3.hkl

Structure factors: contains datablock etoenHClfin. DOI: https://doi.org/10.1107/S2053229625008113/jx3098etoenHClfinsup4.hkl

Structure factors: contains datablock me2oenHx3fin. DOI: https://doi.org/10.1107/S2053229625008113/jx3098me2oenHx3finsup5.hkl

Structure factors: contains datablock ipr2oenHWfinfin. DOI: https://doi.org/10.1107/S2053229625008113/jx3098ipr2oenHWfinfinsup6.hkl

Structure factors: contains datablock ipr2oenHfinal. DOI: https://doi.org/10.1107/S2053229625008113/jx3098ipr2oenHfinalsup7.hkl

Computing details top

Poly[2-hydroxyethan-1-aminium [µ₃-cyanido-κ³C:C:N-di-µ₂-cyanido-κ⁴C:N-dicuprate(I)]] (oenH) top

Crystal data top

(C₂H₈NO)[Cu₂(CN)₃]	F(000) = 528
M_r = 267.23	D_x = 2.075 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.7107 Å
a = 14.1276 (3) Å	Cell parameters from 1338 reflections
b = 8.2049 (2) Å	θ = 1.0–30.0°
c = 7.8186 (2) Å	µ = 4.93 mm⁻¹
β = 109.263 (1)°	T = 300 K
V = 855.56 (4) Å³	Needle, white
Z = 4	0.27 × 0.09 × 0.06 mm

Data collection top

Enraf-Nonius KappaCCD diffractometer	3586 independent reflections
Radiation source: fine-focus sealed tube	3048 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 9 pixels mm^-1	θ_max = 35.0°, θ_min = 2.9°
combination of ω and φ scans	h = −22→22
Absorption correction: part of the refinement model (ΔF) (DENZO; Otwinowski & Minor, 1997)	k = −13→12
T_min = 0.61, T_max = 0.82	l = −12→12
22177 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.035	w = 1/[σ²(F_o²) + (0.034P)² + 1.570P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.080	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.54 e Å⁻³
3586 reflections	Δρ_min = −0.77 e Å⁻³
114 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
4 restraints	Extinction coefficient: 0.0113 (8)
Primary atom site location: heavy-atom method	Absolute structure: Flack x determined using 1290 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.54 (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.

Refinement. Refined as an inversion twin.

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

	x	y	z	U_iso*/U_eq
Cu1	0.00021 (3)	0.31738 (6)	−0.00157 (4)	0.02484 (15)
Cu2	0.12004 (3)	0.18154 (7)	0.26176 (5)	0.02829 (17)
C1	0.0599 (4)	0.1036 (7)	−0.0327 (8)	0.0303 (11)
N1	0.0735 (4)	−0.0093 (7)	−0.1081 (8)	0.0334 (10)
C2	0.0425 (5)	0.4002 (7)	0.2644 (8)	0.0319 (11)
N2	0.0311 (4)	0.5026 (7)	0.3530 (8)	0.0358 (10)
C3	−0.2355 (5)	0.3080 (7)	−0.1607 (9)	0.0294 (12)
N3	−0.1489 (4)	0.3062 (6)	−0.1027 (8)	0.0339 (12)
O11	0.3345 (4)	0.5769 (5)	0.1843 (6)	0.0546 (10)
H11	0.335 (5)	0.639 (6)	0.100 (7)	0.066*
C12	0.2633 (4)	0.6353 (9)	0.2610 (9)	0.0537 (14)
H12A	0.239751	0.546125	0.317871	0.081*
H12B	0.206190	0.680845	0.166878	0.081*
C13	0.3112 (8)	0.7647 (7)	0.4004 (12)	0.0502 (14)
H13A	0.327679	0.858749	0.340597	0.075*
H13B	0.263909	0.799152	0.459315	0.075*
N14	0.4031 (4)	0.7026 (6)	0.5381 (7)	0.0487 (11)
H14A	0.432308	0.782642	0.613959	0.058*
H14B	0.445189	0.665861	0.483608	0.058*
H14C	0.387300	0.621763	0.599637	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0268 (3)	0.0232 (3)	0.0236 (3)	0.0019 (3)	0.0071 (2)	0.0020 (3)
Cu2	0.0230 (3)	0.0282 (3)	0.0316 (3)	−0.0005 (3)	0.0062 (3)	0.0059 (3)
C1	0.028 (2)	0.027 (2)	0.037 (2)	−0.0013 (17)	0.0136 (18)	−0.0055 (18)
N1	0.034 (2)	0.030 (2)	0.035 (2)	0.0024 (17)	0.0086 (17)	−0.0097 (17)
C2	0.035 (2)	0.027 (2)	0.038 (2)	−0.0051 (18)	0.019 (2)	−0.0099 (19)
N2	0.036 (2)	0.036 (2)	0.036 (2)	−0.0005 (19)	0.0132 (18)	−0.0108 (19)
C3	0.024 (2)	0.029 (3)	0.033 (2)	0.0002 (18)	0.0062 (19)	0.0016 (19)
N3	0.026 (2)	0.036 (3)	0.037 (2)	0.0007 (17)	0.0069 (19)	0.0034 (19)
O11	0.077 (3)	0.049 (2)	0.0393 (19)	0.000 (2)	0.0213 (19)	0.0041 (17)
C12	0.038 (3)	0.068 (4)	0.051 (3)	−0.001 (3)	0.008 (2)	0.019 (3)
C13	0.056 (3)	0.045 (2)	0.052 (4)	0.010 (4)	0.021 (3)	0.001 (3)
N14	0.048 (3)	0.058 (3)	0.040 (2)	−0.001 (2)	0.0139 (19)	−0.008 (2)

Geometric parameters (Å, º) top

Cu1—N3	1.993 (6)	O11—C12	1.414 (8)
Cu1—C1	1.996 (6)	O11—H11	0.837 (14)
Cu1—N2ⁱ	1.998 (5)	C12—C13	1.512 (10)
Cu1—C2	2.079 (6)	C12—H12A	0.9700
Cu1—Cu2	2.4591 (5)	C12—H12B	0.9700
Cu2—C3ⁱⁱ	1.930 (6)	C13—N14	1.478 (11)
Cu2—N1ⁱⁱⁱ	1.977 (5)	C13—H13A	0.9700
Cu2—C2	2.106 (6)	C13—H13B	0.9700
Cu2—C1	2.267 (6)	N14—H14A	0.8900
C1—N1	1.148 (8)	N14—H14B	0.8900
C2—N2	1.134 (8)	N14—H14C	0.8900
C3—N3	1.157 (5)

N3—Cu1—C1	110.2 (2)	N2—C2—Cu2	144.7 (6)
N3—Cu1—N2ⁱ	102.1 (2)	Cu1—C2—Cu2	71.97 (18)
C1—Cu1—N2ⁱ	113.6 (2)	C2—N2—Cu1^v	175.7 (6)
N3—Cu1—C2	109.2 (3)	N3—C3—Cu2^vi	175.2 (5)
C1—Cu1—C2	114.6 (3)	C3—N3—Cu1	176.6 (6)
N2ⁱ—Cu1—C2	106.4 (3)	C12—O11—H11	109 (3)
N3—Cu1—Cu2	131.07 (16)	O11—C12—C13	109.4 (6)
C1—Cu1—Cu2	60.12 (17)	O11—C12—H12A	109.8
N2ⁱ—Cu1—Cu2	126.31 (16)	C13—C12—H12A	109.8
C2—Cu1—Cu2	54.52 (18)	O11—C12—H12B	109.8
C3ⁱⁱ—Cu2—N1ⁱⁱⁱ	111.5 (2)	C13—C12—H12B	109.8
C3ⁱⁱ—Cu2—C2	117.3 (2)	H12A—C12—H12B	108.2
N1ⁱⁱⁱ—Cu2—C2	110.0 (2)	N14—C13—C12	111.1 (5)
C3ⁱⁱ—Cu2—C1	109.6 (3)	N14—C13—H13A	109.4
N1ⁱⁱⁱ—Cu2—C1	104.1 (2)	C12—C13—H13A	109.4
C2—Cu2—C1	103.2 (2)	N14—C13—H13B	109.4
C3ⁱⁱ—Cu2—Cu1	127.4 (2)	C12—C13—H13B	109.4
N1ⁱⁱⁱ—Cu2—Cu1	120.06 (15)	H13A—C13—H13B	108.0
C2—Cu2—Cu1	53.51 (17)	C13—N14—H14A	109.5
C1—Cu2—Cu1	49.74 (15)	C13—N14—H14B	109.5
N1—C1—Cu1	157.1 (6)	H14A—N14—H14B	109.5
N1—C1—Cu2	132.8 (5)	C13—N14—H14C	109.5
Cu1—C1—Cu2	70.13 (18)	H14A—N14—H14C	109.5
C1—N1—Cu2^iv	169.1 (5)	H14B—N14—H14C	109.5
N2—C2—Cu1	143.3 (6)

Cu1—C1—N1—Cu2^iv	100 (3)	O11—C12—C13—N14	−55.0 (8)
Cu2—C1—N1—Cu2^iv	−82 (3)

Symmetry codes: (i) x, −y+1, z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, −y, z+1/2; (iv) x, −y, z−1/2; (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
N14—H14A···N2^vii	0.89	2.61	3.499 (8)	175
N14—H14B···N1ⁱⁱ	0.89	2.51	3.380 (8)	166
N14—H14B···O11	0.89	2.46	2.808 (6)	104
N14—H14C···O11^v	0.89	1.99	2.870 (7)	168
O11—H11···N3^viii	0.84 (1)	2.16 (2)	2.996 (7)	174 (7)

Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (v) x, −y+1, z+1/2; (vii) x+1/2, −y+3/2, z+1/2; (viii) x+1/2, y+1/2, z.

Poly[bis(2-hydroxy-N-methylethan-1-aminium) [di-µ₃-cyanido-κ⁶C:C:N-tri-µ₂-cyanido-κ⁶C:N-tricuprate(I)] monohydrate] (etoenHfinal) top

Crystal data top

(C₄H₁₂NO)₂[Cu₃(CN)₅]·H₂O	F(000) = 1056
M_r = 519.03	D_x = 1.682 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
a = 12.0606 (2) Å	Cell parameters from 6155 reflections
b = 21.2559 (3) Å	θ = 1.0–30.0°
c = 8.4115 (1) Å	µ = 3.11 mm⁻¹
β = 108.1267 (7)°	T = 299 K
V = 2049.34 (5) Å³	Plate, white
Z = 4	0.30 × 0.16 × 0.06 mm

Data collection top

Enraf-Nonius KappaCCD diffractometer	5996 independent reflections
Radiation source: fine-focus sealed tube	4837 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 9 pixels mm^-1	θ_max = 30.0°, θ_min = 2.0°
combination of ω and φ scans	h = −16→16
Absorption correction: part of the refinement model (ΔF) (DENZO; Otwinowski & Minor, 1997)	k = 0→29
T_min = 0.43, T_max = 0.52	l = 0→11
65386 measured reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: mixed
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0356P)² + 2.140P] where P = (F_o² + 2F_c²)/3
5996 reflections	(Δ/σ)_max = 0.013
292 parameters	Δρ_max = 0.51 e Å⁻³
35 restraints	Δρ_min = −0.53 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1A	0.02262 (4)	0.55471 (10)	0.44120 (6)	0.0415 (2)	0.880 (6)
Cu1B	0.0228 (4)	0.5780 (5)	0.4410 (6)	0.0415 (2)	0.120 (6)
Cu2	0.79743 (3)	0.59967 (2)	0.83898 (4)	0.04243 (9)
Cu3	0.39483 (3)	0.68215 (2)	0.52419 (4)	0.04337 (9)
C1	−0.0588 (2)	0.55421 (14)	0.6096 (3)	0.0437 (6)
N1	0.8939 (2)	0.57034 (12)	0.6995 (3)	0.0456 (5)
C2	0.1770 (2)	0.59698 (12)	0.4945 (3)	0.0435 (6)	0.61 (3)
N2	0.2616 (2)	0.62475 (11)	0.5085 (3)	0.0411 (6)	0.61 (3)
C2A	0.2616 (2)	0.62475 (11)	0.5085 (3)	0.0411 (6)	0.39 (3)
N2A	0.1770 (2)	0.59698 (12)	0.4945 (3)	0.0435 (6)	0.39 (3)
C3	0.8796 (2)	0.59195 (13)	1.0735 (3)	0.0452 (7)	0.61 (3)
N3	−0.0711 (2)	0.58078 (13)	0.2110 (3)	0.0458 (7)	0.61 (3)
C3A	−0.0711 (2)	0.58078 (13)	0.2110 (3)	0.0458 (7)	0.39 (3)
N3A	0.8796 (2)	0.59195 (13)	1.0735 (3)	0.0452 (7)	0.39 (3)
C4	0.6447 (2)	0.62659 (13)	0.7142 (3)	0.0431 (7)	0.85 (3)
N4	0.5528 (2)	0.64225 (12)	0.6358 (3)	0.0450 (6)	0.85 (3)
C4A	0.5528 (2)	0.64225 (12)	0.6358 (3)	0.0450 (6)	0.15 (3)
N4A	0.6447 (2)	0.62659 (13)	0.7142 (3)	0.0431 (7)	0.15 (3)
C5	0.3943 (2)	0.72392 (12)	0.3186 (3)	0.0393 (6)	0.76 (3)
N5	0.3912 (2)	0.75359 (11)	0.2029 (3)	0.0440 (6)	0.76 (3)
C5A	0.3912 (2)	0.75359 (11)	0.2029 (3)	0.0440 (6)	0.24 (3)
N5A	0.3943 (2)	0.72392 (12)	0.3186 (3)	0.0393 (6)	0.24 (3)
O11	0.4863 (3)	0.49759 (12)	0.8137 (3)	0.0677 (6)
H11	0.553 (3)	0.489 (3)	0.812 (9)	0.18 (3)*
C12	0.4152 (3)	0.47509 (14)	0.6560 (4)	0.0607 (8)
H12A	0.464173	0.461012	0.590815	0.091*
H12B	0.366051	0.508931	0.595231	0.091*
C13	0.3413 (3)	0.42245 (14)	0.6782 (4)	0.0523 (7)
H13A	0.285576	0.411966	0.570692	0.078*
H13B	0.297823	0.435771	0.751764	0.078*
N14	0.40999 (19)	0.36560 (11)	0.7491 (3)	0.0417 (5)
H14A	0.458 (3)	0.3770 (16)	0.845 (2)	0.064 (10)*
H14B	0.443 (3)	0.3518 (16)	0.679 (4)	0.067 (11)*
C15	0.3420 (3)	0.31272 (15)	0.7890 (4)	0.0571 (8)
H15A	0.395184	0.279095	0.841554	0.086*
H15B	0.304112	0.327186	0.868517	0.086*
C16	0.2527 (4)	0.2877 (2)	0.6391 (6)	0.0866 (13)
H16A	0.216283	0.251498	0.669557	0.130*
H16B	0.288964	0.276048	0.556799	0.130*
H16C	0.194820	0.319465	0.593799	0.130*
O21A	0.6799 (4)	0.4288 (2)	0.8059 (4)	0.0801 (12)	0.755 (5)
H21A	0.687 (6)	0.415 (3)	0.718 (5)	0.120*	0.755 (5)
C22A	0.8000 (5)	0.4387 (2)	0.9056 (6)	0.0767 (16)	0.755 (5)
H22A	0.843237	0.456861	0.837075	0.115*	0.755 (5)
H22B	0.803612	0.467590	0.996298	0.115*	0.755 (5)
C23A	0.8505 (4)	0.3795 (2)	0.9720 (6)	0.0674 (13)	0.755 (5)
H23A	0.934669	0.384111	1.012787	0.101*	0.755 (5)
H23B	0.832112	0.348803	0.882387	0.101*	0.755 (5)
N24A	0.8102 (6)	0.3553 (3)	1.1095 (8)	0.091 (3)	0.755 (5)
H24A	0.828543	0.383693	1.191213	0.109*	0.755 (5)
H24B	0.732654	0.353050	1.071655	0.109*	0.755 (5)
C25A	0.8527 (5)	0.2957 (3)	1.1815 (9)	0.090 (2)	0.755 (5)
H25A	0.846657	0.296061	1.293837	0.135*	0.755 (5)
H25B	0.797367	0.264540	1.119361	0.135*	0.755 (5)
C26A	0.9645 (6)	0.2719 (4)	1.1957 (13)	0.118 (3)	0.755 (5)
H26A	1.013250	0.274763	1.310011	0.176*	0.755 (5)
H26B	0.998354	0.296025	1.126064	0.176*	0.755 (5)
H26C	0.958093	0.228693	1.160777	0.176*	0.755 (5)
O21B	0.7386 (19)	0.4692 (11)	0.8130 (17)	0.150*	0.245 (5)
H21B	0.720079	0.434015	0.773997	0.225*	0.245 (5)
C22B	0.7332 (11)	0.4714 (6)	0.9792 (15)	0.059 (3)*	0.245 (5)
H22C	0.656578	0.458881	0.982513	0.089*	0.245 (5)
H22D	0.749998	0.513420	1.025291	0.089*	0.245 (5)
C23B	0.8215 (16)	0.4272 (8)	1.071 (2)	0.115 (8)*	0.245 (5)
H23C	0.858150	0.445099	1.181164	0.172*	0.245 (5)
H23D	0.880840	0.425513	1.015503	0.172*	0.245 (5)
N24B	0.790 (2)	0.3621 (10)	1.096 (5)	0.171 (17)*	0.245 (5)
H24C	0.775444	0.360445	1.193272	0.257*	0.245 (5)
H24D	0.723420	0.353437	1.016437	0.257*	0.245 (5)
C25B	0.872 (2)	0.3117 (10)	1.096 (3)	0.130 (9)*	0.245 (5)
H25C	0.829236	0.279088	1.020956	0.196*	0.245 (5)
H25D	0.928996	0.328457	1.046963	0.196*	0.245 (5)
C26B	0.935 (3)	0.2822 (14)	1.252 (3)	0.122 (11)*	0.245 (5)
H26D	0.985301	0.250210	1.231841	0.183*	0.245 (5)
H26E	0.981022	0.313210	1.326657	0.183*	0.245 (5)
H26F	0.880757	0.263591	1.300518	0.183*	0.245 (5)
OW	0.4347 (2)	0.61505 (12)	0.9223 (3)	0.0561 (5)
HW1	0.425 (4)	0.5798 (10)	0.883 (6)	0.103 (17)*
HW2	0.447 (5)	0.636 (2)	0.848 (5)	0.123 (19)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1A	0.03625 (17)	0.0544 (7)	0.03553 (17)	−0.0033 (2)	0.01338 (13)	0.0006 (2)
Cu1B	0.03625 (17)	0.0544 (7)	0.03553 (17)	−0.0033 (2)	0.01338 (13)	0.0006 (2)
Cu2	0.03783 (17)	0.0534 (2)	0.03503 (16)	0.00912 (14)	0.00992 (12)	0.00235 (13)
Cu3	0.04395 (18)	0.04983 (19)	0.03591 (16)	0.00321 (14)	0.01182 (13)	0.00305 (13)
C1	0.0333 (12)	0.0657 (17)	0.0311 (11)	0.0044 (11)	0.0088 (10)	−0.0001 (11)
N1	0.0405 (11)	0.0612 (14)	0.0360 (11)	0.0097 (10)	0.0130 (9)	0.0018 (10)
C2	0.0370 (13)	0.0517 (15)	0.0397 (12)	−0.0027 (11)	0.0089 (10)	−0.0011 (10)
N2	0.0393 (13)	0.0452 (13)	0.0373 (11)	−0.0023 (10)	0.0097 (9)	0.0019 (9)
C2A	0.0393 (13)	0.0452 (13)	0.0373 (11)	−0.0023 (10)	0.0097 (9)	0.0019 (9)
N2A	0.0370 (13)	0.0517 (15)	0.0397 (12)	−0.0027 (11)	0.0089 (10)	−0.0011 (10)
C3	0.0395 (13)	0.0616 (16)	0.0347 (13)	0.0099 (11)	0.0117 (10)	0.0001 (11)
N3	0.0392 (12)	0.0613 (16)	0.0363 (13)	0.0040 (11)	0.0108 (10)	0.0010 (11)
C3A	0.0392 (12)	0.0613 (16)	0.0363 (13)	0.0040 (11)	0.0108 (10)	0.0010 (11)
N3A	0.0395 (13)	0.0616 (16)	0.0347 (13)	0.0099 (11)	0.0117 (10)	0.0001 (11)
C4	0.0392 (14)	0.0551 (15)	0.0362 (12)	0.0081 (11)	0.0135 (10)	0.0018 (11)
N4	0.0392 (13)	0.0508 (14)	0.0452 (12)	0.0058 (10)	0.0134 (10)	0.0036 (10)
C4A	0.0392 (13)	0.0508 (14)	0.0452 (12)	0.0058 (10)	0.0134 (10)	0.0036 (10)
N4A	0.0392 (14)	0.0551 (15)	0.0362 (12)	0.0081 (11)	0.0135 (10)	0.0018 (11)
C5	0.0405 (12)	0.0429 (13)	0.0357 (12)	−0.0020 (10)	0.0135 (10)	−0.0001 (10)
N5	0.0489 (13)	0.0436 (13)	0.0434 (13)	0.0012 (10)	0.0202 (10)	0.0040 (10)
C5A	0.0489 (13)	0.0436 (13)	0.0434 (13)	0.0012 (10)	0.0202 (10)	0.0040 (10)
N5A	0.0405 (12)	0.0429 (13)	0.0357 (12)	−0.0020 (10)	0.0135 (10)	−0.0001 (10)
O11	0.0820 (18)	0.0541 (13)	0.0661 (15)	−0.0068 (12)	0.0217 (13)	−0.0115 (11)
C12	0.087 (2)	0.0445 (16)	0.0476 (16)	0.0067 (16)	0.0171 (16)	0.0053 (13)
C13	0.0452 (15)	0.0523 (16)	0.0537 (16)	0.0113 (13)	0.0071 (13)	0.0015 (13)
N14	0.0372 (11)	0.0451 (12)	0.0437 (12)	0.0056 (9)	0.0136 (9)	−0.0007 (10)
C15	0.0560 (18)	0.0511 (17)	0.072 (2)	0.0025 (14)	0.0313 (16)	0.0078 (15)
C16	0.070 (2)	0.067 (2)	0.117 (4)	−0.019 (2)	0.020 (2)	−0.008 (2)
O21A	0.094 (3)	0.094 (3)	0.061 (2)	0.027 (2)	0.036 (2)	0.0132 (19)
C22A	0.110 (5)	0.063 (3)	0.070 (3)	−0.003 (3)	0.048 (3)	0.006 (2)
C23A	0.066 (3)	0.077 (3)	0.067 (3)	−0.009 (2)	0.032 (2)	0.003 (2)
N24A	0.089 (4)	0.128 (5)	0.075 (3)	0.053 (4)	0.055 (3)	0.052 (3)
C25A	0.063 (3)	0.108 (5)	0.109 (5)	0.009 (3)	0.039 (3)	0.045 (4)
C26A	0.097 (5)	0.092 (5)	0.177 (9)	0.033 (4)	0.063 (6)	0.037 (5)
OW	0.0765 (15)	0.0560 (13)	0.0384 (10)	−0.0008 (11)	0.0218 (10)	0.0062 (10)

Geometric parameters (Å, º) top

Cu1A—C1	1.958 (3)	C16—H16C	0.9600
Cu1A—C2	1.989 (3)	O21A—C22A	1.446 (5)
Cu1A—N3	1.993 (3)	O21A—H21A	0.825 (10)
Cu1A—C1ⁱ	2.418 (4)	C22A—C23A	1.432 (6)
Cu1A—Cu1Aⁱ	2.650 (4)	C22A—H22A	0.9700
Cu1B—C2	1.818 (6)	C22A—H22B	0.9700
Cu1B—N3	1.914 (5)	C23A—N24A	1.479 (5)
Cu1B—C1	2.026 (6)	C23A—H23A	0.9700
Cu1B—Cu1Bⁱ	3.55 (2)	C23A—H23B	0.9700
Cu2—C4	1.902 (3)	N24A—C25A	1.428 (6)
Cu2—C3	1.920 (2)	N24A—H24A	0.8900
Cu2—N1	1.992 (2)	N24A—H24B	0.8900
Cu3—C5	1.942 (2)	C25A—C26A	1.410 (7)
Cu3—N2	1.989 (2)	C25A—H25A	0.9700
Cu3—N4	2.030 (2)	C25A—H25B	0.9700
Cu3—N5ⁱⁱ	2.042 (2)	C26A—H26A	0.9600
C1—N1ⁱⁱⁱ	1.133 (3)	C26A—H26B	0.9600
C2—N2	1.153 (3)	C26A—H26C	0.9600
C3—N3^iv	1.149 (3)	O21B—C22B	1.420 (7)
C4—N4	1.149 (3)	O21B—H21B	0.8200
C5—N5	1.150 (3)	C22B—C23B	1.450 (9)
O11—C12	1.420 (4)	C22B—H22C	0.9700
O11—H11	0.827 (10)	C22B—H22D	0.9700
C12—C13	1.478 (4)	C23B—N24B	1.467 (9)
C12—H12A	0.9700	C23B—H23C	0.9700
C12—H12B	0.9700	C23B—H23D	0.9700
C13—N14	1.481 (3)	N24B—C25B	1.458 (9)
C13—H13A	0.9700	N24B—H24C	0.8900
C13—H13B	0.9700	N24B—H24D	0.8900
N14—C15	1.490 (4)	C25B—C26B	1.440 (9)
N14—H14A	0.866 (10)	C25B—H25C	0.9700
N14—H14B	0.864 (10)	C25B—H25D	0.9700
C15—C16	1.479 (5)	C26B—H26D	0.9600
C15—H15A	0.9700	C26B—H26E	0.9600
C15—H15B	0.9700	C26B—H26F	0.9600
C16—H16A	0.9600	OW—HW1	0.814 (10)
C16—H16B	0.9600	OW—HW2	0.815 (10)

C1—Cu1A—C2	118.96 (12)	H16A—C16—H16B	109.5
C1—Cu1A—N3	116.35 (11)	C15—C16—H16C	109.5
C2—Cu1A—N3	107.55 (12)	H16A—C16—H16C	109.5
C1—Cu1A—C1ⁱ	106.32 (12)	H16B—C16—H16C	109.5
C2—Cu1A—C1ⁱ	105.35 (11)	C22A—O21A—H21A	102 (5)
N3—Cu1A—C1ⁱ	99.99 (11)	C23A—C22A—O21A	109.1 (4)
C1—Cu1A—Cu1Aⁱ	61.15 (9)	C23A—C22A—H22A	109.9
C2—Cu1A—Cu1Aⁱ	126.83 (10)	O21A—C22A—H22A	109.9
N3—Cu1A—Cu1Aⁱ	119.10 (11)	C23A—C22A—H22B	109.9
C1ⁱ—Cu1A—Cu1Aⁱ	45.17 (8)	O21A—C22A—H22B	109.9
C2—Cu1B—N3	118.8 (3)	H22A—C22A—H22B	108.3
C2—Cu1B—C1	124.4 (3)	C22A—C23A—N24A	114.1 (4)
N3—Cu1B—C1	116.8 (3)	C22A—C23A—H23A	108.7
C2—Cu1B—Cu1Bⁱ	111.9 (4)	N24A—C23A—H23A	108.7
N3—Cu1B—Cu1Bⁱ	102.5 (4)	C22A—C23A—H23B	108.7
C1—Cu1B—Cu1Bⁱ	54.6 (2)	N24A—C23A—H23B	108.7
C4—Cu2—C3	134.00 (10)	H23A—C23A—H23B	107.6
C4—Cu2—N1	114.32 (10)	C25A—N24A—C23A	118.6 (5)
C3—Cu2—N1	111.66 (10)	C25A—N24A—H24A	107.7
C5—Cu3—N2	116.28 (10)	C23A—N24A—H24A	107.7
C5—Cu3—N4	110.20 (10)	C25A—N24A—H24B	107.7
N2—Cu3—N4	113.40 (10)	C23A—N24A—H24B	107.7
C5—Cu3—N5ⁱⁱ	110.79 (10)	H24A—N24A—H24B	107.1
N2—Cu3—N5ⁱⁱ	104.91 (10)	C26A—C25A—N24A	124.2 (5)
N4—Cu3—N5ⁱⁱ	99.85 (10)	C26A—C25A—H25A	106.3
N1ⁱⁱⁱ—C1—Cu1A	162.0 (3)	N24A—C25A—H25A	106.3
N1ⁱⁱⁱ—C1—Cu1B	147.9 (4)	C26A—C25A—H25B	106.3
N1ⁱⁱⁱ—C1—Cu1Aⁱ	124.3 (2)	N24A—C25A—H25B	106.3
Cu1A—C1—Cu1Aⁱ	73.68 (12)	H25A—C25A—H25B	106.4
C1^v—N1—Cu2	174.6 (2)	C25A—C26A—H26A	109.5
N2—C2—Cu1B	160.7 (4)	C25A—C26A—H26B	109.5
N2—C2—Cu1A	172.4 (2)	H26A—C26A—H26B	109.5
C2—N2—Cu3	172.8 (2)	C25A—C26A—H26C	109.5
N3^iv—C3—Cu2	172.9 (3)	H26A—C26A—H26C	109.5
C3^vi—N3—Cu1B	169.0 (4)	H26B—C26A—H26C	109.5
C3^vi—N3—Cu1A	174.3 (2)	C22B—O21B—H21B	109.5
N4—C4—Cu2	178.5 (2)	O21B—C22B—C23B	104.7 (10)
C4—N4—Cu3	170.5 (2)	O21B—C22B—H22C	110.8
N5—C5—Cu3	173.7 (2)	C23B—C22B—H22C	110.8
C5—N5—Cu3^vii	170.8 (2)	O21B—C22B—H22D	110.8
C12—O11—H11	103 (5)	C23B—C22B—H22D	110.8
O11—C12—C13	110.5 (3)	H22C—C22B—H22D	108.9
O11—C12—H12A	109.6	C22B—C23B—N24B	120.4 (13)
C13—C12—H12A	109.6	C22B—C23B—H23C	107.2
O11—C12—H12B	109.6	N24B—C23B—H23C	107.2
C13—C12—H12B	109.6	C22B—C23B—H23D	107.2
H12A—C12—H12B	108.1	N24B—C23B—H23D	107.2
C12—C13—N14	112.7 (2)	H23C—C23B—H23D	106.8
C12—C13—H13A	109.1	C25B—N24B—C23B	119.1 (14)
N14—C13—H13A	109.1	C25B—N24B—H24C	107.6
C12—C13—H13B	109.1	C23B—N24B—H24C	107.6
N14—C13—H13B	109.1	C25B—N24B—H24D	107.5
H13A—C13—H13B	107.8	C23B—N24B—H24D	107.5
C13—N14—C15	115.4 (2)	H24C—N24B—H24D	107.0
C13—N14—H14A	106 (2)	C26B—C25B—N24B	119.0 (14)
C15—N14—H14A	105 (2)	C26B—C25B—H25C	107.6
C13—N14—H14B	109 (2)	N24B—C25B—H25C	107.6
C15—N14—H14B	108 (2)	C26B—C25B—H25D	107.6
H14A—N14—H14B	114 (3)	N24B—C25B—H25D	107.6
C16—C15—N14	112.6 (3)	H25C—C25B—H25D	107.0
C16—C15—H15A	109.1	C25B—C26B—H26D	109.5
N14—C15—H15A	109.1	C25B—C26B—H26E	109.5
C16—C15—H15B	109.1	H26D—C26B—H26E	109.5
N14—C15—H15B	109.1	C25B—C26B—H26F	109.5
H15A—C15—H15B	107.8	H26D—C26B—H26F	109.5
C15—C16—H16A	109.5	H26E—C26B—H26F	109.5
C15—C16—H16B	109.5	HW1—OW—HW2	103 (5)

N3—Cu1B—C2—N2	61.0 (12)	O21A—C22A—C23A—N24A	−73.6 (6)
C1—Cu1B—C2—N2	−118.7 (8)	C22A—C23A—N24A—C25A	178.3 (6)
Cu1Bⁱ—Cu1B—C2—N2	−179.8 (7)	C23A—N24A—C25A—C26A	32.0 (13)
O11—C12—C13—N14	−67.1 (4)	O21B—C22B—C23B—N24B	−95 (3)
C12—C13—N14—C15	174.7 (3)	C22B—C23B—N24B—C25B	145 (2)
C13—N14—C15—C16	62.7 (4)	C23B—N24B—C25B—C26B	107 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O21Ac	0.83 (1)	2.02 (4)	2.773 (5)	152 (7)
O11—H11···O21Bd	0.83 (1)	2.28 (2)	3.10 (2)	178 (7)
N14—H14A···OW^viii	0.87 (1)	1.99 (1)	2.845 (3)	168 (3)
N14—H14B···N5A^ix	0.86 (1)	2.53 (3)	3.217 (3)	137 (3)
O21Ac—H21Ac···N2^ix	0.83 (1)	2.34 (2)	3.154 (4)	171 (7)
N24Ac—H24Bc···OW^viii	0.89	2.15	2.950 (6)	150
N24Bd—H24Dd···OW^viii	0.89	2.23	2.71 (2)	114
N24Bd—H24Dd···N5^ix	0.89	2.98	3.70 (4)	139
OW—HW1···O11	0.81 (1)	2.05 (3)	2.794 (4)	152 (5)
OW—HW2···N4	0.82 (1)	2.50 (3)	3.210 (3)	147 (5)
OW—HW2···N5ⁱⁱ	0.82 (1)	2.64 (4)	3.297 (3)	139 (5)

Symmetry codes: (ii) x, −y+3/2, z+1/2; (viii) −x+1, −y+1, −z+2; (ix) −x+1, −y+1, −z+1.

Poly[tetrakis[N-(2-hydroxyethyl)ethan-1-aminium] [chloridotetra-µ₃-cyanido-κ¹²C:C:N-penta-µ₂-cyanido-κ¹⁰C:N-tricuprate(I)]] (etoenHClfin) top

Crystal data top

(C₄H₁₂NO)₄[Cu₆(CN)₉Cl]	F(000) = 2048
M_r = 1011.45	D_x = 1.686 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.7107 Å
a = 8.2206 (1) Å	Cell parameters from 4682 reflections
b = 23.0970 (4) Å	θ = 1.0–27.5°
c = 20.9992 (4) Å	µ = 3.26 mm⁻¹
β = 92.3301 (11)°	T = 299 K
V = 3983.85 (11) Å³	Plate, white
Z = 4	0.23 × 0.12 × 0.05 mm

Data collection top

Enraf-Nonius KappaCCD diffractometer	4566 independent reflections
Radiation source: fine-focus sealed tube	3558 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 1.9°
combination of ω and φ scans	h = −10→10
Absorption correction: part of the refinement model (ΔF) (DENZO; Otwinowski & Minor, 1997)	k = −29→29
T_min = 0.60, T_max = 0.71	l = −27→27
59964 measured reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: mixed
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.054P)² + 3.1P] where P = (F_o² + 2F_c²)/3
4566 reflections	(Δ/σ)_max = 0.001
244 parameters	Δρ_max = 0.44 e Å⁻³
6 restraints	Δρ_min = −0.52 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.32230 (4)	0.26251 (2)	0.05460 (2)	0.05150 (13)
Cu2	−0.17157 (4)	0.14598 (2)	0.09565 (2)	0.04871 (12)
Cu3	0.23243 (5)	0.44596 (2)	0.17644 (2)	0.05680 (13)
Cl1	0.500000	0.42004 (5)	0.250000	0.0611 (3)
C1	0.1337 (3)	0.20980 (12)	0.05269 (15)	0.0485 (7)
N1	0.0332 (3)	0.18101 (11)	0.07123 (13)	0.0521 (6)
C2	0.2599 (3)	0.37901 (12)	0.12191 (14)	0.0517 (6)	0.5
N2	0.2841 (3)	0.33606 (12)	0.09578 (13)	0.0505 (6)	0.5
C2N	0.2599 (3)	0.37901 (12)	0.12191 (14)	0.0517 (6)	0.5
N2C	0.2841 (3)	0.33606 (12)	0.09578 (13)	0.0505 (6)	0.5
C3	0.2917 (3)	0.52186 (11)	0.14366 (13)	0.0479 (6)	0.5
N3	−0.1847 (3)	0.06827 (12)	0.12526 (14)	0.0525 (7)	0.5
C3N	0.2917 (3)	0.52186 (11)	0.14366 (13)	0.0479 (6)	0.5
N3C	−0.1847 (3)	0.06827 (12)	0.12526 (14)	0.0525 (7)	0.5
C4	0.5321 (3)	0.22546 (13)	0.07547 (15)	0.0558 (7)	0.5
N4	−0.3541 (3)	0.19730 (12)	0.08410 (15)	0.0578 (7)	0.5
C4N	0.5321 (3)	0.22546 (13)	0.07547 (15)	0.0558 (7)	0.5
N4C	−0.3541 (3)	0.19730 (12)	0.08410 (15)	0.0578 (7)	0.5
C5	0.0543 (4)	0.44449 (11)	0.23336 (15)	0.0563 (7)	0.5
N5	0.0543 (4)	0.44449 (11)	0.23336 (15)	0.0563 (7)	0.5
O11	0.6026 (3)	0.45587 (11)	0.09930 (13)	0.0725 (7)
H11	0.528 (4)	0.449 (2)	0.1241 (19)	0.109*
C12	0.6416 (4)	0.41071 (16)	0.05821 (17)	0.0685 (9)
H12A	0.685982	0.426564	0.019826	0.103*
H12B	0.543723	0.389256	0.046068	0.103*
C13	0.7625 (5)	0.37104 (17)	0.0897 (2)	0.0739 (11)
H13A	0.857632	0.393086	0.103902	0.111*
H13B	0.796827	0.342595	0.058995	0.111*
N14	0.6945 (4)	0.34064 (13)	0.14525 (16)	0.0648 (7)
H14A	0.655 (5)	0.3666 (14)	0.1711 (17)	0.095 (15)*
H14B	0.614 (3)	0.3180 (11)	0.1313 (15)	0.055 (9)*
C15	0.8186 (6)	0.30640 (18)	0.1822 (2)	0.0915 (14)
H15A	0.866906	0.278198	0.154467	0.137*
H15B	0.904414	0.331983	0.198335	0.137*
C16	0.7455 (8)	0.2761 (2)	0.2364 (3)	0.127 (2)
H16A	0.828129	0.254332	0.259442	0.190*
H16B	0.699262	0.304006	0.264265	0.190*
H16C	0.661801	0.250289	0.220452	0.190*
O21	0.7012 (4)	0.03026 (14)	0.50092 (13)	0.0900 (8)
H21	0.709 (7)	0.033 (2)	0.5409 (6)	0.135*
C22	0.6089 (5)	0.07478 (17)	0.47311 (19)	0.0737 (10)
H22A	0.655511	0.111979	0.485166	0.111*
H22B	0.498485	0.073234	0.487597	0.111*
C23	0.6083 (4)	0.06775 (16)	0.40326 (18)	0.0656 (9)
H23A	0.548387	0.099491	0.383201	0.098*
H23B	0.552964	0.032002	0.391486	0.098*
N24	0.7750 (3)	0.06652 (12)	0.37951 (13)	0.0492 (6)
H24A	0.822 (4)	0.0343 (8)	0.3923 (14)	0.052 (9)*
H24B	0.819 (4)	0.0978 (10)	0.3959 (16)	0.073 (11)*
C25	0.7814 (5)	0.06789 (16)	0.30794 (17)	0.0671 (9)
H25A	0.888021	0.055089	0.295575	0.101*
H25B	0.701205	0.041215	0.289695	0.101*
C26	0.7500 (9)	0.1258 (2)	0.2824 (2)	0.133 (2)
H26A	0.755072	0.125037	0.236853	0.199*
H26B	0.643704	0.138361	0.293909	0.199*
H26C	0.830390	0.152226	0.299785	0.199*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0473 (2)	0.0425 (2)	0.0647 (3)	−0.00434 (15)	0.00268 (17)	−0.00479 (16)
Cu2	0.0458 (2)	0.0469 (2)	0.0537 (2)	−0.00440 (15)	0.00560 (15)	0.00535 (16)
Cu3	0.0589 (2)	0.0478 (2)	0.0648 (3)	0.00028 (17)	0.01603 (18)	−0.00456 (18)
Cl1	0.0663 (7)	0.0591 (7)	0.0574 (6)	0.000	−0.0025 (5)	0.000
C1	0.0419 (14)	0.0375 (14)	0.0665 (19)	0.0021 (12)	0.0071 (13)	0.0027 (13)
N1	0.0444 (13)	0.0477 (14)	0.0644 (16)	0.0006 (11)	0.0063 (11)	0.0112 (12)
C2	0.0553 (15)	0.0491 (16)	0.0508 (16)	−0.0041 (13)	0.0049 (12)	−0.0058 (13)
N2	0.0540 (15)	0.0478 (15)	0.0496 (15)	−0.0038 (12)	0.0026 (12)	−0.0036 (13)
C2N	0.0553 (15)	0.0491 (16)	0.0508 (16)	−0.0041 (13)	0.0049 (12)	−0.0058 (13)
N2C	0.0540 (15)	0.0478 (15)	0.0496 (15)	−0.0038 (12)	0.0026 (12)	−0.0036 (13)
C3	0.0491 (14)	0.0411 (15)	0.0540 (16)	0.0037 (11)	0.0106 (11)	0.0046 (12)
N3	0.0458 (14)	0.0535 (17)	0.0585 (17)	0.0047 (12)	0.0073 (12)	0.0033 (13)
C3N	0.0491 (14)	0.0411 (15)	0.0540 (16)	0.0037 (11)	0.0106 (11)	0.0046 (12)
N3C	0.0458 (14)	0.0535 (17)	0.0585 (17)	0.0047 (12)	0.0073 (12)	0.0033 (13)
C4	0.0456 (15)	0.0522 (16)	0.0689 (19)	−0.0004 (13)	−0.0052 (13)	0.0028 (14)
N4	0.0471 (16)	0.0490 (16)	0.077 (2)	−0.0047 (13)	−0.0018 (14)	0.0056 (14)
C4N	0.0456 (15)	0.0522 (16)	0.0689 (19)	−0.0004 (13)	−0.0052 (13)	0.0028 (14)
N4C	0.0471 (16)	0.0490 (16)	0.077 (2)	−0.0047 (13)	−0.0018 (14)	0.0056 (14)
C5	0.0589 (17)	0.0429 (14)	0.0686 (19)	−0.0029 (12)	0.0206 (13)	−0.0044 (13)
N5	0.0589 (17)	0.0429 (14)	0.0686 (19)	−0.0029 (12)	0.0206 (13)	−0.0044 (13)
O11	0.0771 (17)	0.0605 (14)	0.0826 (17)	−0.0035 (12)	0.0382 (13)	0.0002 (13)
C12	0.075 (2)	0.070 (2)	0.061 (2)	−0.0233 (19)	0.0166 (17)	−0.0084 (18)
C13	0.075 (2)	0.064 (2)	0.085 (3)	−0.0041 (19)	0.032 (2)	−0.014 (2)
N14	0.0713 (19)	0.0531 (17)	0.0699 (19)	−0.0036 (15)	0.0015 (15)	−0.0118 (15)
C15	0.099 (3)	0.059 (2)	0.114 (4)	0.009 (2)	−0.031 (3)	−0.013 (2)
C16	0.199 (7)	0.079 (3)	0.099 (4)	0.017 (4)	−0.035 (4)	0.001 (3)
O21	0.122 (2)	0.087 (2)	0.0610 (16)	0.0142 (18)	0.0109 (16)	0.0018 (15)
C22	0.076 (2)	0.070 (2)	0.076 (3)	0.004 (2)	0.0192 (19)	−0.014 (2)
C23	0.0500 (18)	0.070 (2)	0.077 (2)	0.0075 (16)	0.0019 (15)	−0.0076 (18)
N24	0.0469 (13)	0.0465 (14)	0.0541 (15)	−0.0038 (12)	−0.0005 (11)	0.0004 (12)
C25	0.078 (2)	0.070 (2)	0.0532 (19)	0.0007 (18)	0.0020 (16)	−0.0072 (17)
C26	0.249 (7)	0.093 (4)	0.055 (3)	0.032 (4)	−0.007 (3)	0.012 (2)

Geometric parameters (Å, º) top

Cu1—N2	1.938 (3)	N14—C15	1.485 (5)
Cu1—C4	1.959 (3)	N14—H14A	0.879 (10)
Cu1—C1	1.970 (3)	N14—H14B	0.882 (10)
Cu1—C1ⁱ	2.384 (3)	C15—C16	1.483 (7)
Cu1—Cu1ⁱ	2.6044 (8)	C15—H15A	0.9700
Cu2—N3	1.904 (3)	C15—H15B	0.9700
Cu2—N4	1.920 (3)	C16—H16A	0.9600
Cu2—N1	1.955 (2)	C16—H16B	0.9600
Cu3—C5	1.928 (3)	C16—H16C	0.9600
Cu3—C2	1.943 (3)	O21—C22	1.392 (5)
Cu3—C3	1.952 (3)	O21—H21	0.841 (10)
Cu3—Cl1ⁱⁱ	2.7031 (5)	C22—C23	1.476 (5)
Cu3—Cl1	2.7031 (5)	C22—H22A	0.9700
Cl1—Cl1ⁱⁱ	0.0000	C22—H22B	0.9700
C1—N1	1.141 (4)	C23—N24	1.477 (4)
C2—N2	1.155 (4)	C23—H23A	0.9700
C3—N3ⁱⁱⁱ	1.158 (4)	C23—H23B	0.9700
C4—N4^iv	1.147 (4)	N24—C25	1.506 (4)
C5—C5^v	1.155 (5)	N24—H24A	0.874 (10)
O11—C12	1.399 (4)	N24—H24B	0.874 (10)
O11—H11	0.835 (10)	C25—C26	1.461 (6)
C12—C13	1.487 (6)	C25—H25A	0.9700
C12—H12A	0.9700	C25—H25B	0.9700
C12—H12B	0.9700	C26—H26A	0.9600
C13—N14	1.490 (5)	C26—H26B	0.9600
C13—H13A	0.9700	C26—H26C	0.9600
C13—H13B	0.9700

N2—Cu1—C4	116.12 (12)	C15—N14—C13	112.9 (3)
N2—Cu1—C1	114.15 (12)	C15—N14—H14A	108 (3)
C4—Cu1—C1	114.80 (12)	C13—N14—H14A	109 (3)
N2—Cu1—C1ⁱ	102.72 (11)	C15—N14—H14B	110 (2)
C4—Cu1—C1ⁱ	99.36 (11)	C13—N14—H14B	109 (2)
C1—Cu1—C1ⁱ	107.22 (10)	H14A—N14—H14B	109 (4)
N2—Cu1—Cu1ⁱ	120.73 (8)	C16—C15—N14	111.2 (4)
C4—Cu1—Cu1ⁱ	117.79 (9)	C16—C15—H15A	109.4
C1—Cu1—Cu1ⁱ	60.95 (9)	N14—C15—H15A	109.4
C1ⁱ—Cu1—Cu1ⁱ	46.26 (7)	C16—C15—H15B	109.4
N3—Cu2—N4	124.65 (12)	N14—C15—H15B	109.4
N3—Cu2—N1	122.46 (11)	H15A—C15—H15B	108.0
N4—Cu2—N1	112.86 (11)	C15—C16—H16A	109.5
C5—Cu3—C2	117.43 (12)	C15—C16—H16B	109.5
C5—Cu3—C3	116.18 (11)	H16A—C16—H16B	109.5
C2—Cu3—C3	118.05 (11)	C15—C16—H16C	109.5
C5—Cu3—Cl1ⁱⁱ	105.24 (10)	H16A—C16—H16C	109.5
C2—Cu3—Cl1ⁱⁱ	92.82 (9)	H16B—C16—H16C	109.5
C3—Cu3—Cl1ⁱⁱ	101.04 (8)	C22—O21—H21	112 (4)
C5—Cu3—Cl1	105.24 (10)	O21—C22—C23	108.4 (3)
C2—Cu3—Cl1	92.82 (9)	O21—C22—H22A	110.0
C3—Cu3—Cl1	101.04 (8)	C23—C22—H22A	110.0
Cl1ⁱⁱ—Cu3—Cl1	0.00 (5)	O21—C22—H22B	110.0
Cl1ⁱⁱ—Cl1—Cu3	0 (10)	C23—C22—H22B	110.0
Cl1ⁱⁱ—Cl1—Cu3ⁱⁱ	0 (7)	H22A—C22—H22B	108.4
Cu3—Cl1—Cu3ⁱⁱ	154.40 (5)	C22—C23—N24	111.8 (3)
N1—C1—Cu1	158.9 (3)	C22—C23—H23A	109.2
N1—C1—Cu1ⁱ	128.2 (3)	N24—C23—H23A	109.2
Cu1—C1—Cu1ⁱ	72.78 (10)	C22—C23—H23B	109.2
C1—N1—Cu2	166.8 (2)	N24—C23—H23B	109.2
N2—C2—Cu3	172.0 (3)	H23A—C23—H23B	107.9
C2—N2—Cu1	177.9 (3)	C23—N24—C25	114.0 (3)
N3ⁱⁱⁱ—C3—Cu3	174.9 (2)	C23—N24—H24A	108 (2)
C3^vi—N3—Cu2	173.6 (2)	C25—N24—H24A	107 (2)
N4^iv—C4—Cu1	170.9 (3)	C23—N24—H24B	103 (2)
C4^vii—N4—Cu2	176.1 (3)	C25—N24—H24B	110 (2)
C5^v—C5—Cu3	178.5 (3)	H24A—N24—H24B	114 (3)
C12—O11—H11	116 (3)	C26—C25—N24	111.8 (3)
O11—C12—C13	110.6 (3)	C26—C25—H25A	109.2
O11—C12—H12A	109.5	N24—C25—H25A	109.2
C13—C12—H12A	109.5	C26—C25—H25B	109.2
O11—C12—H12B	109.5	N24—C25—H25B	109.2
C13—C12—H12B	109.5	H25A—C25—H25B	107.9
H12A—C12—H12B	108.1	C25—C26—H26A	109.5
C12—C13—N14	111.9 (3)	C25—C26—H26B	109.5
C12—C13—H13A	109.2	H26A—C26—H26B	109.5
N14—C13—H13A	109.2	C25—C26—H26C	109.5
C12—C13—H13B	109.2	H26A—C26—H26C	109.5
N14—C13—H13B	109.2	H26B—C26—H26C	109.5
H13A—C13—H13B	107.9

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N14—H14B···C4N	0.88 (1)	2.52 (2)	3.293 (4)	147 (3)
N14—H14A···Cl1ⁱⁱ	0.88 (1)	2.46 (2)	3.323 (3)	166 (4)
N24—H24A···O11^viii	0.87 (1)	1.92 (1)	2.776 (4)	165 (3)
N24—H24B···N1ⁱⁱ	0.87 (1)	2.36 (1)	3.227 (4)	172 (3)
O11—H11···Cl1	0.84 (1)	2.75 (3)	3.410 (3)	138 (4)
O21—H21···C3N^ix	0.84 (1)	2.57 (3)	3.287 (4)	144 (5)

Symmetry codes: (ii) −x+1, y, −z+1/2; (viii) −x+3/2, y−1/2, −z+1/2; (ix) x+1/2, −y+1/2, z+1/2.

Poly[tetrakis[N-(2-hydroxyethyl)ethan-1-aminium] [penta-µ₃-cyanido-κ¹⁵C:C:N-hepta-µ₂-cyanido-κ¹⁴C:N-octacuprate(I)]] (me2oenHx3fin) top

Crystal data top

(C₄H₁₂NO)₄[Cu₈(CN)₁₂]	F(000) = 2368
M_r = 1181.14	D_x = 1.878 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
a = 15.3810 (1) Å	Cell parameters from 12600 reflections
b = 15.9128 (2) Å	θ = 1.0–30.0°
c = 18.0222 (2) Å	µ = 4.04 mm⁻¹
β = 108.6885 (6)°	T = 298 K
V = 4178.45 (8) Å³	Block, colourless
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf-Nonius KappaCCD diffractometer	12231 independent reflections
Radiation source: fine-focus sealed tube	9299 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 9 pixels mm^-1	θ_max = 30.0°, θ_min = 2.0°
combination of ω and φ scans	h = 0→21
Absorption correction: part of the refinement model (ΔF) (DENZO; Otwinowski & Minor, 1997)	k = 0→22
T_min = 0.65, T_max = 0.79	l = −25→24
148190 measured reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: mixed
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0371P)² + 4.120P] where P = (F_o² + 2F_c²)/3
12231 reflections	(Δ/σ)_max = 0.006
594 parameters	Δρ_max = 0.96 e Å⁻³
80 restraints	Δρ_min = −1.10 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.25140 (2)	0.93661 (2)	0.44984 (2)	0.03326 (8)
Cu2	0.25902 (2)	0.84024 (2)	0.55930 (2)	0.03683 (8)
Cu3	0.51041 (2)	0.92341 (2)	0.32944 (2)	0.03172 (8)
Cu4	0.51683 (2)	0.85298 (2)	0.20549 (2)	0.03476 (8)
Cu5	0.00402 (2)	0.85811 (2)	0.67901 (2)	0.03916 (9)
Cu6	0.06445 (2)	0.80869 (2)	0.81818 (2)	0.03585 (8)
Cu7	0.37770 (2)	1.12600 (2)	1.10997 (2)	0.03633 (8)
Cu8	0.17631 (2)	1.10678 (2)	0.83592 (2)	0.03707 (9)
C1	0.32820 (18)	0.96075 (18)	0.56796 (16)	0.0346 (6)
N1	0.61703 (15)	0.99546 (14)	0.39241 (13)	0.0328 (5)
C2	0.18849 (18)	0.81631 (18)	0.43715 (17)	0.0364 (6)
N2	0.14213 (15)	0.73100 (15)	0.89498 (14)	0.0363 (5)
C3	0.54725 (18)	0.80239 (17)	0.33018 (16)	0.0338 (6)
N3	0.43210 (18)	1.23528 (16)	1.14879 (15)	0.0440 (6)
C4	0.46397 (18)	0.97668 (17)	0.21682 (16)	0.0331 (6)
N4	0.43314 (17)	1.03210 (15)	1.17614 (14)	0.0398 (5)
C5	−0.03418 (17)	0.74950 (17)	0.73470 (16)	0.0333 (6)
N5	0.08702 (16)	1.19712 (15)	0.78856 (15)	0.0384 (5)
C6	0.16122 (17)	0.83815 (16)	0.60871 (14)	0.0341 (5)	0.5
N6	0.10316 (17)	0.84106 (17)	0.63634 (15)	0.0361 (5)	0.5
C6N	0.16122 (17)	0.83815 (16)	0.60871 (14)	0.0341 (5)	0.5
N6C	0.10316 (17)	0.84106 (17)	0.63634 (15)	0.0361 (5)	0.5
C7	0.15506 (17)	1.02136 (16)	0.40304 (15)	0.0365 (5)	0.5
N7	−0.09746 (17)	0.93261 (17)	0.62932 (15)	0.0378 (6)	0.5
C7N	0.15506 (17)	1.02136 (16)	0.40304 (15)	0.0365 (5)	0.5
N7C	−0.09746 (17)	0.93261 (17)	0.62932 (15)	0.0378 (6)	0.5
C8	0.34800 (16)	0.93519 (15)	0.39824 (14)	0.0314 (5)	0.5
N8	0.40757 (17)	0.93254 (15)	0.37230 (14)	0.0316 (5)	0.5
C8N	0.34800 (16)	0.93519 (15)	0.39824 (14)	0.0314 (5)	0.5
N8C	0.40757 (17)	0.93254 (15)	0.37230 (14)	0.0316 (5)	0.5
C9	0.63747 (19)	0.86841 (16)	0.19570 (17)	0.0404 (6)	0.5
N9	0.2893 (2)	1.12173 (16)	0.80714 (18)	0.0437 (6)	0.5
C9N	0.63747 (19)	0.86841 (16)	0.19570 (17)	0.0404 (6)	0.5
N9C	0.2893 (2)	1.12173 (16)	0.80714 (18)	0.0437 (6)	0.5
C10	0.41940 (18)	0.78185 (16)	0.14249 (15)	0.0343 (7)	0.67 (3)
N10	0.35953 (16)	0.76085 (16)	0.60744 (14)	0.0349 (6)	0.67 (3)
C10A	0.35953 (16)	0.76085 (16)	0.60744 (14)	0.0349 (6)	0.33 (3)
N10A	0.41940 (18)	0.78185 (16)	0.14249 (15)	0.0343 (7)	0.33 (3)
C11	0.09483 (19)	0.92501 (18)	0.81415 (17)	0.0379 (6)
N11	0.11936 (17)	0.99322 (15)	0.81710 (15)	0.0415 (6)
C12	0.2788 (2)	1.12266 (18)	1.01507 (17)	0.0420 (8)	0.84 (3)
N12	0.2256 (2)	1.12028 (18)	0.95425 (16)	0.0507 (8)	0.84 (3)
C12N	0.2788 (2)	1.12266 (18)	1.01507 (17)	0.0420 (8)	0.16 (3)
N12C	0.2256 (2)	1.12028 (18)	0.95425 (16)	0.0507 (8)	0.16 (3)
O21	0.79074 (18)	0.92200 (17)	0.74927 (15)	0.0576 (7)
H21	0.820 (3)	0.918 (3)	0.721 (3)	0.098 (18)*
C22	0.7382 (2)	0.8473 (2)	0.74437 (18)	0.0444 (7)
H22A	0.733309	0.834738	0.795536	0.067*
H22B	0.769821	0.800845	0.729314	0.067*
C23	0.6437 (2)	0.85533 (18)	0.68616 (16)	0.0371 (6)
H23A	0.609636	0.804498	0.687893	0.056*
H23B	0.612572	0.901690	0.701850	0.056*
N24	0.64161 (15)	0.86963 (14)	0.60351 (13)	0.0306 (5)
H24	0.6653 (19)	0.9187 (19)	0.6021 (16)	0.027 (7)*
C25	0.6916 (2)	0.8052 (2)	0.57333 (19)	0.0469 (7)
H25A	0.667675	0.750484	0.578184	0.070*
H25B	0.755735	0.807084	0.603074	0.070*
H25C	0.683823	0.816319	0.519220	0.070*
C26	0.5444 (2)	0.8751 (2)	0.5506 (2)	0.0505 (8)
H26A	0.543516	0.890575	0.498921	0.076*
H26B	0.512208	0.916725	0.570314	0.076*
H26C	0.515040	0.821543	0.548766	0.076*
O31	0.5003 (3)	0.8845 (2)	1.00293 (18)	0.0964 (11)
H31	0.526 (2)	0.877 (4)	1.054 (3)	0.145*
C32	0.4087 (4)	0.9107 (3)	0.9885 (2)	0.0879 (15)
H32A	0.406768	0.958984	1.020777	0.132*
H32B	0.373173	0.865733	1.001137	0.132*
C33	0.3699 (3)	0.9330 (2)	0.9042 (2)	0.0622 (10)
H33A	0.399804	0.983472	0.894276	0.093*
H33B	0.305042	0.945099	0.891857	0.093*
N34	0.38190 (19)	0.86458 (17)	0.85187 (16)	0.0441 (6)
H34	0.440 (3)	0.862 (2)	0.866 (2)	0.050 (10)*
C35	0.3460 (3)	0.8928 (3)	0.7699 (2)	0.0697 (11)
H35A	0.371565	0.946719	0.764923	0.105*
H35B	0.362750	0.852947	0.736814	0.105*
H35C	0.280383	0.897060	0.754480	0.105*
C36	0.3453 (3)	0.7825 (3)	0.8630 (4)	0.0993 (18)
H36A	0.370176	0.766340	0.917033	0.149*
H36B	0.279626	0.785735	0.848519	0.149*
H36C	0.361992	0.741622	0.830853	0.149*
O41A	−0.0648 (2)	0.80696 (17)	0.89298 (16)	0.0695 (7)	0.725 (6)
H41A	−0.095 (3)	0.858 (2)	0.908 (3)	0.104*	0.725 (6)
C42A	−0.0461 (3)	0.7599 (3)	0.9624 (2)	0.0731 (12)	0.725 (6)
H42A	−0.092584	0.770760	0.986996	0.110*	0.725 (6)
H42B	0.013110	0.775806	0.998744	0.110*	0.725 (6)
C43A	−0.0458 (3)	0.6665 (3)	0.9423 (3)	0.0516 (13)	0.725 (6)
H43A	0.005557	0.655358	0.923532	0.077*	0.725 (6)
H43B	−0.036988	0.633699	0.989451	0.077*	0.725 (6)
N44A	−0.1319 (4)	0.6391 (5)	0.8819 (6)	0.0429 (10)	0.725 (6)
H44A	−0.136777	0.668028	0.832717	0.043*	0.725 (6)
C45A	−0.1285 (5)	0.5458 (3)	0.8688 (4)	0.0709 (18)	0.725 (6)
H45A	−0.074974	0.532550	0.854641	0.106*	0.725 (6)
H45B	−0.125876	0.516488	0.916033	0.106*	0.725 (6)
H45C	−0.182463	0.528884	0.827389	0.106*	0.725 (6)
C46A	−0.2143 (3)	0.6586 (3)	0.9036 (3)	0.0564 (14)	0.725 (6)
H46A	−0.267924	0.639777	0.862908	0.085*	0.725 (6)
H46B	−0.210472	0.630637	0.951722	0.085*	0.725 (6)
H46C	−0.218020	0.718232	0.910321	0.085*	0.725 (6)
O41B	−0.0648 (2)	0.80696 (17)	0.89298 (16)	0.0695 (7)	0.275 (6)
H41B	−0.095 (3)	0.858 (2)	0.908 (3)	0.104*	0.275 (6)
C42B	−0.0461 (3)	0.7599 (3)	0.9624 (2)	0.0731 (12)	0.275 (6)
H42C	−0.044713	0.796346	1.005868	0.110*	0.275 (6)
H42D	0.013063	0.732359	0.974178	0.110*	0.275 (6)
C43B	−0.1202 (10)	0.6960 (9)	0.9502 (9)	0.081 (4)	0.275 (6)
H43C	−0.179342	0.723990	0.935896	0.121*	0.275 (6)
H43D	−0.111971	0.665671	0.998723	0.121*	0.275 (6)
N44B	−0.1189 (11)	0.6359 (13)	0.8878 (17)	0.0429 (10)	0.275 (6)
H44B	−0.128350	0.668603	0.839780	0.043*	0.275 (6)
C45B	−0.0352 (10)	0.5843 (11)	0.8995 (12)	0.090 (6)	0.275 (6)
H45D	−0.043598	0.548422	0.854926	0.135*	0.275 (6)
H45E	0.016419	0.620574	0.905305	0.135*	0.275 (6)
H45F	−0.024416	0.550632	0.945742	0.135*	0.275 (6)
C46B	−0.2002 (10)	0.5815 (11)	0.8749 (11)	0.084 (6)	0.275 (6)
H46D	−0.202386	0.541209	0.834690	0.125*	0.275 (6)
H46E	−0.196281	0.552532	0.922628	0.125*	0.275 (6)
H46F	−0.254779	0.615256	0.859063	0.125*	0.275 (6)
O51	0.8823 (2)	0.9590 (2)	0.9539 (2)	0.0817 (9)
H51	0.847 (4)	0.9324 (14)	0.976 (3)	0.122*
C52A	0.8855 (3)	1.0454 (3)	0.9741 (2)	0.0761 (12)	0.5
H52A	0.931394	1.055683	1.024557	0.114*	0.5
H52B	0.826285	1.064644	0.975792	0.114*	0.5
C53A	0.9120 (5)	1.0902 (5)	0.9059 (4)	0.065 (2)	0.5
H53A	0.916517	1.150330	0.914947	0.098*	0.5
H53B	0.971332	1.070000	0.905374	0.098*	0.5
N54A	0.8416 (6)	1.0724 (9)	0.8292 (5)	0.0391 (14)	0.5
H54A	0.835480	1.011348	0.822696	0.039*	0.5
C55A	0.7506 (5)	1.1076 (6)	0.8252 (6)	0.073 (2)	0.5
H55A	0.732436	1.085694	0.867632	0.109*	0.5
H55B	0.754628	1.167767	0.829057	0.109*	0.5
H55C	0.705921	1.092145	0.776271	0.109*	0.5
C56A	0.8682 (6)	1.1071 (5)	0.7633 (4)	0.065 (2)	0.5
H56A	0.821261	1.094519	0.714733	0.098*	0.5
H56B	0.875396	1.166915	0.769098	0.098*	0.5
H56C	0.925096	1.082360	0.763240	0.098*	0.5
C52B	0.8855 (3)	1.0454 (3)	0.9741 (2)	0.0761 (12)	0.5
H52C	0.945919	1.067613	0.979641	0.114*	0.5
H52D	0.874878	1.051364	1.024102	0.114*	0.5
C53B	0.8134 (5)	1.0954 (4)	0.9120 (4)	0.0506 (16)	0.5
H53C	0.752522	1.076573	0.909399	0.076*	0.5
H53D	0.818725	1.154527	0.925664	0.076*	0.5
N54B	0.8269 (6)	1.0833 (9)	0.8346 (5)	0.0391 (14)	0.5
H54B	0.808469	1.025628	0.817673	0.039*	0.5
C55B	0.7650 (7)	1.1405 (5)	0.7765 (5)	0.070 (2)	0.5
H55D	0.773716	1.132743	0.726531	0.106*	0.5
H55E	0.702477	1.128201	0.772114	0.106*	0.5
H55F	0.778796	1.197644	0.793233	0.106*	0.5
C56B	0.9237 (5)	1.0937 (6)	0.8365 (5)	0.072 (2)	0.5
H56D	0.962346	1.056041	0.874545	0.109*	0.5
H56E	0.928280	1.081280	0.785784	0.109*	0.5
H56F	0.942925	1.150581	0.850470	0.109*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02960 (16)	0.03484 (18)	0.03288 (17)	−0.00048 (13)	0.00657 (13)	0.00109 (13)
Cu2	0.03222 (17)	0.0403 (2)	0.03652 (18)	0.00371 (14)	0.00902 (14)	0.00495 (15)
Cu3	0.03143 (16)	0.02791 (16)	0.03554 (17)	−0.00136 (13)	0.01032 (13)	−0.00418 (13)
Cu4	0.03394 (17)	0.03285 (18)	0.03689 (18)	−0.00503 (14)	0.01052 (14)	−0.00536 (14)
Cu5	0.03100 (17)	0.0443 (2)	0.0431 (2)	0.00982 (15)	0.01314 (15)	0.01112 (16)
Cu6	0.03610 (18)	0.02555 (16)	0.03659 (18)	−0.00252 (13)	−0.00138 (14)	0.00563 (13)
Cu7	0.03733 (18)	0.02871 (17)	0.03710 (18)	−0.00056 (14)	0.00374 (14)	0.00178 (14)
Cu8	0.03291 (17)	0.02890 (17)	0.0455 (2)	−0.00020 (13)	0.00714 (15)	0.00228 (14)
C1	0.0266 (12)	0.0380 (15)	0.0367 (14)	0.0018 (11)	0.0066 (11)	−0.0109 (12)
N1	0.0295 (11)	0.0340 (12)	0.0325 (11)	−0.0026 (9)	0.0065 (9)	−0.0043 (9)
C2	0.0272 (13)	0.0400 (15)	0.0427 (15)	−0.0031 (11)	0.0121 (12)	−0.0116 (12)
N2	0.0323 (12)	0.0351 (12)	0.0372 (12)	0.0026 (10)	0.0050 (10)	0.0078 (10)
C3	0.0327 (13)	0.0284 (14)	0.0382 (14)	0.0030 (11)	0.0084 (11)	0.0020 (11)
N3	0.0496 (15)	0.0347 (14)	0.0405 (14)	−0.0058 (11)	0.0044 (11)	0.0000 (11)
C4	0.0320 (13)	0.0286 (13)	0.0392 (14)	0.0017 (11)	0.0119 (11)	0.0045 (11)
N4	0.0490 (14)	0.0315 (13)	0.0345 (12)	0.0034 (11)	0.0072 (11)	−0.0015 (10)
C5	0.0247 (12)	0.0319 (14)	0.0416 (15)	−0.0015 (10)	0.0084 (11)	−0.0042 (11)
N5	0.0305 (11)	0.0349 (13)	0.0460 (14)	0.0015 (10)	0.0069 (10)	0.0025 (11)
C6	0.0308 (12)	0.0386 (14)	0.0335 (13)	0.0000 (10)	0.0112 (10)	0.0010 (10)
N6	0.0328 (13)	0.0393 (14)	0.0354 (13)	0.0030 (11)	0.0097 (11)	0.0033 (11)
C6N	0.0308 (12)	0.0386 (14)	0.0335 (13)	0.0000 (10)	0.0112 (10)	0.0010 (10)
N6C	0.0328 (13)	0.0393 (14)	0.0354 (13)	0.0030 (11)	0.0097 (11)	0.0033 (11)
C7	0.0338 (13)	0.0366 (14)	0.0377 (13)	0.0075 (11)	0.0095 (11)	0.0045 (11)
N7	0.0332 (13)	0.0397 (14)	0.0407 (14)	0.0077 (11)	0.0120 (11)	0.0092 (11)
C7N	0.0338 (13)	0.0366 (14)	0.0377 (13)	0.0075 (11)	0.0095 (11)	0.0045 (11)
N7C	0.0332 (13)	0.0397 (14)	0.0407 (14)	0.0077 (11)	0.0120 (11)	0.0092 (11)
C8	0.0321 (12)	0.0292 (12)	0.0346 (12)	0.0001 (10)	0.0134 (10)	0.0020 (10)
N8	0.0343 (12)	0.0276 (12)	0.0331 (12)	0.0010 (10)	0.0108 (10)	0.0001 (10)
C8N	0.0321 (12)	0.0292 (12)	0.0346 (12)	0.0001 (10)	0.0134 (10)	0.0020 (10)
N8C	0.0343 (12)	0.0276 (12)	0.0331 (12)	0.0010 (10)	0.0108 (10)	0.0001 (10)
C9	0.0434 (15)	0.0313 (13)	0.0523 (16)	−0.0011 (11)	0.0237 (13)	−0.0043 (12)
N9	0.0440 (15)	0.0293 (13)	0.0665 (19)	−0.0011 (11)	0.0298 (14)	−0.0024 (13)
C9N	0.0434 (15)	0.0313 (13)	0.0523 (16)	−0.0011 (11)	0.0237 (13)	−0.0043 (12)
N9C	0.0440 (15)	0.0293 (13)	0.0665 (19)	−0.0011 (11)	0.0298 (14)	−0.0024 (13)
C10	0.0367 (14)	0.0303 (13)	0.0359 (14)	−0.0023 (11)	0.0116 (11)	−0.0048 (10)
N10	0.0348 (13)	0.0330 (13)	0.0353 (13)	0.0042 (10)	0.0090 (10)	0.0056 (10)
C10A	0.0348 (13)	0.0330 (13)	0.0353 (13)	0.0042 (10)	0.0090 (10)	0.0056 (10)
N10A	0.0367 (14)	0.0303 (13)	0.0359 (14)	−0.0023 (11)	0.0116 (11)	−0.0048 (10)
C11	0.0384 (15)	0.0286 (14)	0.0411 (15)	−0.0034 (12)	0.0050 (12)	0.0024 (11)
N11	0.0411 (13)	0.0337 (13)	0.0468 (14)	−0.0064 (11)	0.0099 (11)	−0.0006 (11)
C12	0.0416 (16)	0.0377 (16)	0.0390 (17)	−0.0070 (12)	0.0023 (13)	0.0045 (12)
N12	0.0555 (18)	0.0492 (17)	0.0402 (16)	−0.0099 (13)	0.0053 (14)	0.0090 (12)
C12N	0.0416 (16)	0.0377 (16)	0.0390 (17)	−0.0070 (12)	0.0023 (13)	0.0045 (12)
N12C	0.0555 (18)	0.0492 (17)	0.0402 (16)	−0.0099 (13)	0.0053 (14)	0.0090 (12)
O21	0.0598 (15)	0.0696 (17)	0.0472 (14)	−0.0194 (13)	0.0224 (12)	−0.0131 (12)
C22	0.0494 (18)	0.0448 (17)	0.0360 (15)	0.0014 (14)	0.0093 (13)	0.0028 (13)
C23	0.0458 (16)	0.0347 (15)	0.0354 (14)	0.0004 (12)	0.0193 (13)	−0.0003 (11)
N24	0.0339 (11)	0.0237 (11)	0.0344 (12)	0.0015 (9)	0.0112 (9)	0.0007 (9)
C25	0.0507 (18)	0.0444 (18)	0.0522 (18)	0.0064 (14)	0.0258 (15)	−0.0075 (14)
C26	0.0406 (17)	0.0514 (19)	0.0507 (19)	0.0056 (14)	0.0024 (14)	−0.0020 (15)
O31	0.110 (3)	0.104 (3)	0.0518 (17)	0.024 (2)	−0.0068 (17)	0.0018 (18)
C32	0.126 (4)	0.095 (4)	0.049 (2)	0.038 (3)	0.035 (3)	0.010 (2)
C33	0.083 (3)	0.056 (2)	0.050 (2)	0.020 (2)	0.0229 (19)	0.0022 (17)
N34	0.0381 (14)	0.0443 (15)	0.0496 (15)	−0.0004 (12)	0.0138 (12)	−0.0036 (12)
C35	0.064 (2)	0.093 (3)	0.044 (2)	−0.017 (2)	0.0053 (17)	−0.004 (2)
C36	0.079 (3)	0.049 (2)	0.170 (6)	−0.010 (2)	0.040 (3)	0.018 (3)
O41A	0.083 (2)	0.0512 (15)	0.0697 (18)	0.0043 (14)	0.0186 (15)	0.0055 (13)
C42A	0.091 (3)	0.055 (2)	0.059 (2)	−0.018 (2)	0.004 (2)	0.0006 (19)
C43A	0.034 (2)	0.052 (3)	0.061 (3)	−0.0049 (19)	0.004 (2)	0.004 (2)
N44A	0.048 (2)	0.0382 (15)	0.043 (2)	0.0060 (16)	0.016 (2)	0.0052 (14)
C45A	0.091 (5)	0.043 (3)	0.069 (4)	0.006 (3)	0.012 (3)	−0.009 (3)
C46A	0.036 (2)	0.062 (3)	0.071 (3)	−0.001 (2)	0.016 (2)	−0.001 (3)
O41B	0.083 (2)	0.0512 (15)	0.0697 (18)	0.0043 (14)	0.0186 (15)	0.0055 (13)
C42B	0.091 (3)	0.055 (2)	0.059 (2)	−0.018 (2)	0.004 (2)	0.0006 (19)
C43B	0.075 (8)	0.093 (9)	0.074 (8)	−0.008 (7)	0.024 (7)	0.006 (7)
N44B	0.048 (2)	0.0382 (15)	0.043 (2)	0.0060 (16)	0.016 (2)	0.0052 (14)
C45B	0.053 (9)	0.090 (13)	0.142 (17)	0.019 (9)	0.051 (10)	0.010 (12)
C46B	0.053 (9)	0.099 (15)	0.101 (13)	−0.024 (9)	0.027 (9)	0.007 (11)
O51	0.093 (2)	0.0637 (19)	0.106 (2)	−0.0046 (16)	0.0558 (19)	0.0188 (17)
C52A	0.091 (3)	0.079 (3)	0.054 (2)	0.000 (2)	0.017 (2)	0.008 (2)
C53A	0.057 (4)	0.064 (5)	0.059 (5)	−0.014 (4)	−0.003 (4)	0.009 (4)
N54A	0.039 (3)	0.034 (3)	0.0458 (17)	−0.001 (2)	0.0155 (16)	−0.0022 (17)
C55A	0.046 (4)	0.088 (7)	0.074 (6)	0.012 (4)	0.007 (4)	−0.006 (5)
C56A	0.074 (5)	0.069 (5)	0.058 (5)	−0.021 (4)	0.030 (4)	0.002 (4)
C52B	0.091 (3)	0.079 (3)	0.054 (2)	0.000 (2)	0.017 (2)	0.008 (2)
C53B	0.055 (4)	0.044 (4)	0.052 (4)	0.008 (3)	0.016 (3)	−0.004 (3)
N54B	0.039 (3)	0.034 (3)	0.0458 (17)	−0.001 (2)	0.0155 (16)	−0.0022 (17)
C55B	0.091 (6)	0.058 (5)	0.043 (4)	0.008 (4)	−0.005 (4)	0.004 (4)
C56B	0.056 (4)	0.095 (7)	0.076 (6)	−0.014 (4)	0.035 (4)	0.014 (5)

Geometric parameters (Å, º) top

Cu1—C7N	1.981 (2)	C35—H35C	0.9600
Cu1—C8N	1.989 (2)	C36—H36A	0.9600
Cu1—C1	2.113 (3)	C36—H36B	0.9600
Cu1—C2	2.124 (3)	C36—H36C	0.9600
Cu1—Cu2	2.4716 (5)	O41A—C42A	1.407 (5)
Cu2—N10	1.970 (2)	O41A—H41A	1.01 (4)
Cu2—C6N	1.979 (2)	C42A—C43A	1.529 (6)
Cu2—C2	2.153 (3)	C42A—H42A	0.9700
Cu2—C1	2.174 (3)	C42A—H42B	0.9700
Cu3—N8C	1.976 (2)	C43A—N44A	1.484 (8)
Cu3—C3	2.006 (3)	C43A—H43A	0.9700
Cu3—N1	2.025 (2)	C43A—H43B	0.9700
Cu3—C4	2.102 (3)	N44A—C46A	1.474 (8)
Cu3—Cu4	2.5292 (5)	N44A—C45A	1.507 (8)
Cu4—C10	1.930 (3)	N44A—H44A	0.9800
Cu4—C9N	1.935 (3)	C45A—H45A	0.9600
Cu4—C4	2.164 (3)	C45A—H45B	0.9600
Cu4—C3	2.290 (3)	C45A—H45C	0.9600
Cu5—N6C	1.934 (3)	C46A—H46A	0.9600
Cu5—N7C	1.936 (2)	C46A—H46B	0.9600
Cu5—C5	2.172 (3)	C46A—H46C	0.9600
Cu5—Cu6	2.5059 (5)	O41B—C42B	1.407 (5)
Cu6—C11	1.916 (3)	O41B—H41B	1.01 (4)
Cu6—N2	1.952 (2)	C42B—C43B	1.490 (12)
Cu6—C5	1.997 (3)	C42B—H42C	0.9700
Cu7—C12N	1.891 (3)	C42B—H42D	0.9700
Cu7—N4	1.931 (2)	C43B—N44B	1.481 (15)
Cu7—N3	1.959 (3)	C43B—H43C	0.9700
Cu8—N9C	1.981 (3)	C43B—H43D	0.9700
Cu8—N5	1.983 (2)	N44B—C45B	1.484 (15)
Cu8—N11	1.989 (2)	N44B—C46B	1.477 (15)
Cu8—N12C	2.033 (3)	N44B—H44B	0.9800
C1—N1ⁱ	1.149 (3)	C45B—H45D	0.9600
C2—N2ⁱⁱ	1.143 (3)	C45B—H45E	0.9600
C3—N3ⁱⁱⁱ	1.144 (4)	C45B—H45F	0.9600
C4—N4^iv	1.148 (3)	C46B—H46D	0.9600
C5—N5^v	1.146 (3)	C46B—H46E	0.9600
C6N—N6C	1.154 (4)	C46B—H46F	0.9600
C8N—N8C	1.155 (3)	O51—C52B	1.418 (5)
C10—N10ⁱⁱ	1.156 (3)	O51—C52A	1.418 (5)
C11—N11	1.145 (4)	O51—H51	0.88 (4)
C12N—N12C	1.139 (4)	C52A—C53A	1.584 (8)
O21—C22	1.424 (4)	C52A—H52A	0.9700
O21—H21	0.79 (5)	C52A—H52B	0.9700
C22—C23	1.501 (4)	C53A—N54A	1.484 (9)
C22—H22A	0.9700	C53A—H53A	0.9700
C22—H22B	0.9700	C53A—H53B	0.9700
C23—N24	1.497 (3)	N54A—C56A	1.482 (8)
C23—H23A	0.9700	N54A—C55A	1.489 (8)
C23—H23B	0.9700	N54A—H54A	0.9800
N24—C25	1.486 (3)	C55A—H55A	0.9600
N24—C26	1.496 (4)	C55A—H55B	0.9600
N24—H24	0.87 (3)	C55A—H55C	0.9600
C25—H25A	0.9600	C56A—H56A	0.9600
C25—H25B	0.9600	C56A—H56B	0.9600
C25—H25C	0.9600	C56A—H56C	0.9600
C26—H26A	0.9600	C52B—C53B	1.523 (7)
C26—H26B	0.9600	C52B—H52C	0.9700
C26—H26C	0.9600	C52B—H52D	0.9700
O31—C32	1.412 (6)	C53B—N54B	1.487 (8)
O31—H31	0.88 (5)	C53B—H53C	0.9700
C32—C33	1.487 (5)	C53B—H53D	0.9700
C32—H32A	0.9700	N54B—C55B	1.480 (9)
C32—H32B	0.9700	N54B—C56B	1.487 (8)
C33—N34	1.489 (4)	N54B—H54B	0.9800
C33—H33A	0.9700	C55B—H55D	0.9600
C33—H33B	0.9700	C55B—H55E	0.9600
N34—C36	1.461 (5)	C55B—H55F	0.9600
N34—C35	1.472 (5)	C56B—H56D	0.9600
N34—H34	0.85 (4)	C56B—H56E	0.9600
C35—H35A	0.9600	C56B—H56F	0.9600
C35—H35B	0.9600

C7N—Cu1—C8N	112.18 (10)	C35—N34—C33	109.3 (3)
C7N—Cu1—C1	113.93 (11)	C36—N34—H34	109 (2)
C8N—Cu1—C1	102.29 (10)	C35—N34—H34	109 (2)
C7N—Cu1—C2	108.35 (11)	C33—N34—H34	101 (2)
C8N—Cu1—C2	108.80 (10)	N34—C35—H35A	109.5
C1—Cu1—C2	111.14 (11)	N34—C35—H35B	109.5
C7N—Cu1—Cu2	126.85 (8)	H35A—C35—H35B	109.5
C8N—Cu1—Cu2	120.97 (7)	N34—C35—H35C	109.5
C1—Cu1—Cu2	55.97 (8)	H35A—C35—H35C	109.5
C2—Cu1—Cu2	55.26 (8)	H35B—C35—H35C	109.5
N10—Cu2—C6N	113.18 (10)	N34—C36—H36A	109.5
N10—Cu2—C2	113.83 (11)	N34—C36—H36B	109.5
C6N—Cu2—C2	104.51 (10)	H36A—C36—H36B	109.5
N10—Cu2—C1	103.72 (10)	N34—C36—H36C	109.5
C6N—Cu2—C1	114.06 (10)	H36A—C36—H36C	109.5
C2—Cu2—C1	107.70 (11)	H36B—C36—H36C	109.5
N10—Cu2—Cu1	125.40 (7)	C42A—O41A—H41A	100 (2)
C6N—Cu2—Cu1	121.41 (8)	O41A—C42A—C43A	108.8 (3)
C2—Cu2—Cu1	54.15 (8)	O41A—C42A—H42A	109.9
C1—Cu2—Cu1	53.63 (7)	C43A—C42A—H42A	109.9
N8C—Cu3—C3	109.13 (11)	O41A—C42A—H42B	109.9
N8C—Cu3—N1	110.21 (9)	C43A—C42A—H42B	109.9
C3—Cu3—N1	111.32 (10)	H42A—C42A—H42B	108.3
N8C—Cu3—C4	106.31 (10)	N44A—C43A—C42A	112.9 (4)
C3—Cu3—C4	113.67 (11)	N44A—C43A—H43A	109.0
N1—Cu3—C4	106.05 (10)	C42A—C43A—H43A	109.0
N8C—Cu3—Cu4	129.84 (7)	N44A—C43A—H43B	109.0
C3—Cu3—Cu4	59.32 (8)	C42A—C43A—H43B	109.0
N1—Cu3—Cu4	119.48 (6)	H43A—C43A—H43B	107.8
C4—Cu3—Cu4	54.78 (7)	C46A—N44A—C43A	112.6 (6)
C10—Cu4—C9N	127.39 (11)	C46A—N44A—C45A	109.0 (6)
C10—Cu4—C4	110.16 (10)	C43A—N44A—C45A	109.7 (6)
C9N—Cu4—C4	107.06 (10)	C46A—N44A—H44A	108.5
C10—Cu4—C3	104.31 (11)	C43A—N44A—H44A	108.5
C9N—Cu4—C3	103.51 (11)	C45A—N44A—H44A	108.5
C4—Cu4—C3	101.07 (10)	N44A—C45A—H45A	109.5
C10—Cu4—Cu3	122.46 (8)	N44A—C45A—H45B	109.5
C9N—Cu4—Cu3	109.52 (8)	H45A—C45A—H45B	109.5
C4—Cu4—Cu3	52.52 (7)	N44A—C45A—H45C	109.5
C3—Cu4—Cu3	48.89 (7)	H45A—C45A—H45C	109.5
N6C—Cu5—N7C	121.57 (11)	H45B—C45A—H45C	109.5
N6C—Cu5—C5	115.88 (10)	N44A—C46A—H46A	109.5
N7C—Cu5—C5	113.80 (10)	N44A—C46A—H46B	109.5
N6C—Cu5—Cu6	105.49 (8)	H46A—C46A—H46B	109.5
N7C—Cu5—Cu6	129.84 (8)	N44A—C46A—H46C	109.5
C5—Cu5—Cu6	49.93 (7)	H46A—C46A—H46C	109.5
C11—Cu6—N2	122.50 (11)	H46B—C46A—H46C	109.5
C11—Cu6—C5	124.24 (12)	C42B—O41B—H41B	100 (2)
N2—Cu6—C5	112.33 (11)	O41B—C42B—C43B	107.7 (7)
C11—Cu6—Cu5	71.08 (9)	O41B—C42B—H42C	110.2
N2—Cu6—Cu5	148.74 (7)	C43B—C42B—H42C	110.2
C5—Cu6—Cu5	56.32 (8)	O41B—C42B—H42D	110.2
C12N—Cu7—N4	127.22 (12)	C43B—C42B—H42D	110.2
C12N—Cu7—N3	118.41 (12)	H42C—C42B—H42D	108.5
N4—Cu7—N3	114.37 (10)	C42B—C43B—N44B	110.8 (11)
N9C—Cu8—N5	110.19 (11)	C42B—C43B—H43C	109.5
N9C—Cu8—N11	116.10 (11)	N44B—C43B—H43C	109.5
N5—Cu8—N11	112.26 (10)	C42B—C43B—H43D	109.5
N9C—Cu8—N12C	101.46 (13)	N44B—C43B—H43D	109.5
N5—Cu8—N12C	110.42 (12)	H43C—C43B—H43D	108.1
N11—Cu8—N12C	105.70 (11)	C43B—N44B—C45B	118.1 (18)
N1ⁱ—C1—Cu1	143.0 (2)	C43B—N44B—C46B	106.3 (16)
N1ⁱ—C1—Cu2	145.5 (2)	C45B—N44B—C46B	110.5 (16)
Cu1—C1—Cu2	70.40 (8)	C43B—N44B—H44B	107.1
C1ⁱ—N1—Cu3	173.2 (2)	C45B—N44B—H44B	107.1
N2ⁱⁱ—C2—Cu1	146.2 (3)	C46B—N44B—H44B	107.1
N2ⁱⁱ—C2—Cu2	143.0 (3)	N44B—C45B—H45D	109.5
Cu1—C2—Cu2	70.59 (9)	N44B—C45B—H45E	109.5
C2^vi—N2—Cu6	176.8 (2)	H45D—C45B—H45E	109.5
N3ⁱⁱⁱ—C3—Cu3	161.2 (3)	N44B—C45B—H45F	109.5
N3ⁱⁱⁱ—C3—Cu4	127.0 (2)	H45D—C45B—H45F	109.5
Cu3—C3—Cu4	71.79 (9)	H45E—C45B—H45F	109.5
C3^vii—N3—Cu7	171.4 (3)	N44B—C46B—H46D	109.5
N4^iv—C4—Cu3	150.4 (2)	N44B—C46B—H46E	109.5
N4^iv—C4—Cu4	136.8 (2)	H46D—C46B—H46E	109.5
Cu3—C4—Cu4	72.70 (8)	N44B—C46B—H46F	109.5
C4^viii—N4—Cu7	177.6 (2)	H46D—C46B—H46F	109.5
N5^v—C5—Cu6	153.8 (3)	H46E—C46B—H46F	109.5
N5^v—C5—Cu5	132.5 (2)	C52B—O51—H51	109 (3)
Cu6—C5—Cu5	73.75 (9)	C52A—O51—H51	109 (3)
C5^ix—N5—Cu8	175.9 (2)	O51—C52A—C53A	103.4 (4)
N6C—C6N—Cu2	176.6 (2)	O51—C52A—H52A	111.1
C6N—N6C—Cu5	174.0 (2)	C53A—C52A—H52A	111.1
N7^x—C7N—Cu1	174.9 (3)	O51—C52A—H52B	111.1
C7^x—N7C—Cu5	176.0 (2)	C53A—C52A—H52B	111.1
N8C—C8N—Cu1	176.0 (2)	H52A—C52A—H52B	109.0
C8N—N8C—Cu3	177.7 (2)	N54A—C53A—C52A	110.2 (6)
N9ⁱ—C9N—Cu4	177.4 (3)	N54A—C53A—H53A	109.6
C9ⁱ—N9C—Cu8	168.0 (3)	C52A—C53A—H53A	109.6
N10ⁱⁱ—C10—Cu4	177.0 (2)	N54A—C53A—H53B	109.6
C10^vi—N10—Cu2	173.4 (2)	C52A—C53A—H53B	109.6
N11—C11—Cu6	174.2 (3)	H53A—C53A—H53B	108.1
C11—N11—Cu8	171.8 (3)	C56A—N54A—C53A	111.7 (9)
N12C—C12N—Cu7	173.2 (3)	C56A—N54A—C55A	108.5 (8)
C12N—N12C—Cu8	157.5 (3)	C53A—N54A—C55A	111.6 (8)
C22—O21—H21	109 (4)	C56A—N54A—H54A	108.3
O21—C22—C23	112.1 (3)	C53A—N54A—H54A	108.3
O21—C22—H22A	109.2	C55A—N54A—H54A	108.3
C23—C22—H22A	109.2	N54A—C55A—H55A	109.5
O21—C22—H22B	109.2	N54A—C55A—H55B	109.5
C23—C22—H22B	109.2	H55A—C55A—H55B	109.5
H22A—C22—H22B	107.9	N54A—C55A—H55C	109.5
N24—C23—C22	114.6 (2)	H55A—C55A—H55C	109.5
N24—C23—H23A	108.6	H55B—C55A—H55C	109.5
C22—C23—H23A	108.6	N54A—C56A—H56A	109.5
N24—C23—H23B	108.6	N54A—C56A—H56B	109.5
C22—C23—H23B	108.6	H56A—C56A—H56B	109.5
H23A—C23—H23B	107.6	N54A—C56A—H56C	109.5
C25—N24—C26	109.6 (2)	H56A—C56A—H56C	109.5
C25—N24—C23	114.2 (2)	H56B—C56A—H56C	109.5
C26—N24—C23	110.0 (2)	O51—C52B—C53B	111.1 (4)
C25—N24—H24	109.8 (19)	O51—C52B—H52C	109.4
C26—N24—H24	105.8 (18)	C53B—C52B—H52C	109.4
C23—N24—H24	107.0 (19)	O51—C52B—H52D	109.4
N24—C25—H25A	109.5	C53B—C52B—H52D	109.4
N24—C25—H25B	109.5	H52C—C52B—H52D	108.0
H25A—C25—H25B	109.5	N54B—C53B—C52B	109.6 (5)
N24—C25—H25C	109.5	N54B—C53B—H53C	109.8
H25A—C25—H25C	109.5	C52B—C53B—H53C	109.8
H25B—C25—H25C	109.5	N54B—C53B—H53D	109.8
N24—C26—H26A	109.5	C52B—C53B—H53D	109.8
N24—C26—H26B	109.5	H53C—C53B—H53D	108.2
H26A—C26—H26B	109.5	C55B—N54B—C53B	109.4 (8)
N24—C26—H26C	109.5	C55B—N54B—C56B	111.1 (9)
H26A—C26—H26C	109.5	C53B—N54B—C56B	113.8 (8)
H26B—C26—H26C	109.5	C55B—N54B—H54B	107.4
C32—O31—H31	109 (3)	C53B—N54B—H54B	107.4
O31—C32—C33	107.9 (4)	C56B—N54B—H54B	107.4
O31—C32—H32A	110.1	N54B—C55B—H55D	109.5
C33—C32—H32A	110.1	N54B—C55B—H55E	109.5
O31—C32—H32B	110.1	H55D—C55B—H55E	109.5
C33—C32—H32B	110.1	N54B—C55B—H55F	109.5
H32A—C32—H32B	108.4	H55D—C55B—H55F	109.5
C32—C33—N34	112.5 (3)	H55E—C55B—H55F	109.5
C32—C33—H33A	109.1	N54B—C56B—H56D	109.5
N34—C33—H33A	109.1	N54B—C56B—H56E	109.5
C32—C33—H33B	109.1	H56D—C56B—H56E	109.5
N34—C33—H33B	109.1	N54B—C56B—H56F	109.5
H33A—C33—H33B	107.8	H56D—C56B—H56F	109.5
C36—N34—C35	111.9 (3)	H56E—C56B—H56F	109.5
C36—N34—C33	115.8 (3)

O21—C22—C23—N24	62.4 (3)	O41B—C42B—C43B—N44B	63.9 (17)
C22—C23—N24—C25	55.2 (3)	C42B—C43B—N44B—C45B	61 (3)
C22—C23—N24—C26	179.0 (3)	C42B—C43B—N44B—C46B	−174.2 (15)
O31—C32—C33—N34	52.5 (6)	O51—C52A—C53A—N54A	59.9 (8)
C32—C33—N34—C36	55.3 (5)	C52A—C53A—N54A—C56A	−175.0 (8)
C32—C33—N34—C35	−177.3 (4)	C52A—C53A—N54A—C55A	63.3 (12)
O41A—C42A—C43A—N44A	−55.0 (7)	O51—C52B—C53B—N54B	−56.6 (8)
C42A—C43A—N44A—C46A	−55.2 (9)	C52B—C53B—N54B—C55B	−172.6 (8)
C42A—C43A—N44A—C45A	−176.7 (6)	C52B—C53B—N54B—C56B	−47.6 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21···N7^xi	0.79 (5)	2.39 (5)	3.169 (4)	170 (5)
N24—H24···C8Nⁱ	0.87 (3)	2.33 (3)	3.111 (3)	149 (2)
N54Ac—H54Ac···O21	0.98	1.91	2.774 (15)	145
N34—H34···N3^xii	0.85 (4)	2.58 (4)	3.276 (4)	140 (3)
O31—H31···C9N^viii	0.88 (5)	2.58 (4)	3.448 (4)	166 (5)
O41Aa—H41Aa···O51^xiii	1.01 (4)	1.90 (4)	2.880 (4)	164 (4)
N44Aa—H44Aa···N5^v	0.98	2.58	3.482 (11)	153
O51—H51···N12^xii	0.88 (4)	2.10 (5)	2.975 (4)	171 (5)

Symmetry codes: (i) −x+1, −y+2, −z+1; (v) −x, y−1/2, −z+3/2; (viii) x, y, z+1; (xi) x+1, y, z; (xii) −x+1, −y+2, −z+2; (xiii) x−1, y, z.

Poly[2-hydroxy-N,N-diisopropylethan-1-aminium [µ₃-cyanido-κ³C:C:N-di-µ₂-cyanido-κ⁴C:N-dicuprate(I)] monohydrate] (ipr2oenHWfinfin) top

Crystal data top

(C₈H₂₀NO)[Cu₃(CN)₄]·H₂O	F(000) = 928
M_r = 458.96	D_x = 1.692 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
a = 11.1671 (9) Å	Cell parameters from 21784 reflections
b = 9.7754 (19) Å	θ = 1.0–30.0°
c = 17.1556 (5) Å	µ = 3.52 mm⁻¹
β = 105.876 (5)°	T = 296 K
V = 1801.3 (4) Å³	Block, green
Z = 4	0.40 × 0.40 × 0.35 mm

Data collection top

Enraf-Nonius KappaCCD diffractometer	4652 independent reflections
Radiation source: fine-focus sealed tube	3298 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 9 pixels mm^-1	θ_max = 28.7°, θ_min = 2.0°
combination of ω and φ scans	h = −15→14
Absorption correction: part of the refinement model (ΔF) (DENZO; Otwinowski & Minor, 1997)	k = 0→13
T_min = 0.45, T_max = 0.56	l = 0→23
119728 measured reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.024	Hydrogen site location: mixed
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0398P)² + 0.180P] where P = (F_o² + 2F_c²)/3
4652 reflections	(Δ/σ)_max = 0.003
264 parameters	Δρ_max = 0.30 e Å⁻³
86 restraints	Δρ_min = −0.35 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.36808 (2)	0.18136 (3)	0.03581 (2)	0.05107 (9)
Cu2A	0.3256 (3)	0.4453 (3)	0.05283 (16)	0.0595 (5)	0.5
Cu2B	0.3414 (3)	0.4236 (3)	0.07126 (15)	0.0466 (3)	0.5
Cu3	0.47698 (2)	0.17950 (2)	0.33249 (2)	0.04308 (8)
C1	0.22233 (19)	0.2457 (2)	−0.04306 (12)	0.0497 (6)	0.69 (2)
N1	0.63311 (16)	0.2277 (2)	0.40801 (11)	0.0494 (5)	0.69 (2)
NC1	0.22233 (19)	0.2457 (2)	−0.04306 (12)	0.0497 (6)	0.31 (2)
CN1	0.63311 (16)	0.2277 (2)	0.40801 (11)	0.0494 (5)	0.31 (2)
C2	0.41155 (16)	0.2323 (2)	0.15021 (12)	0.0506 (6)	0.69 (2)
N2	0.43821 (15)	0.22166 (19)	0.21913 (11)	0.0463 (5)	0.69 (2)
NC2	0.41155 (16)	0.2323 (2)	0.15021 (12)	0.0506 (6)	0.31 (2)
CN2	0.43821 (15)	0.22166 (19)	0.21913 (11)	0.0463 (5)	0.31 (2)
C3	0.4686 (3)	0.0402 (3)	0.00814 (14)	0.0941 (10)	0.5
N3	0.4686 (3)	0.0402 (3)	0.00814 (14)	0.0941 (10)	0.5
C4	0.21014 (17)	0.5175 (2)	0.10154 (11)	0.0464 (5)	0.69 (2)
N4	0.36132 (16)	0.07536 (18)	0.37417 (10)	0.0466 (5)	0.69 (2)
NC4	0.21014 (17)	0.5175 (2)	0.10154 (11)	0.0464 (5)	0.31 (2)
CN4	0.36132 (16)	0.07536 (18)	0.37417 (10)	0.0466 (5)	0.31 (2)
CN5	0.46241 (16)	0.4818 (2)	0.01512 (11)	0.0498 (4)	0.5
NC5	0.46241 (16)	0.4818 (2)	0.01512 (11)	0.0498 (4)	0.5
O11A	0.7039 (2)	0.3316 (3)	0.2020 (3)	0.1250 (14)	0.826 (4)
H11A	0.661 (5)	0.258 (4)	0.193 (2)	0.188*	0.826 (4)
C12A	0.7531 (3)	0.3591 (5)	0.1375 (3)	0.0944 (14)	0.826 (4)
H12A	0.719080	0.444296	0.111803	0.113*	0.826 (4)
H12B	0.730507	0.286576	0.097591	0.113*	0.826 (4)
C13A	0.8908 (2)	0.3695 (3)	0.16734 (17)	0.0558 (7)	0.826 (4)
H13A	0.912400	0.428357	0.214640	0.067*	0.826 (4)
H13B	0.922333	0.411702	0.125754	0.067*	0.826 (4)
N14A	0.95517 (18)	0.2283 (2)	0.18999 (11)	0.0477 (4)	0.826 (4)
H14A	0.906 (2)	0.194 (3)	0.1863 (17)	0.032 (9)*	0.826 (4)
OWA	0.7807 (4)	0.0181 (4)	0.1765 (2)	0.1195 (14)	0.826 (4)
HWA1	0.816 (4)	−0.031 (5)	0.216 (2)	0.179*	0.826 (4)
HWA2	0.835 (3)	0.049 (6)	0.156 (3)	0.179*	0.826 (4)
O11B	0.6883 (11)	0.203 (2)	0.1067 (13)	0.151 (8)	0.174 (4)
H11B	0.620 (16)	0.172 (19)	0.077 (10)	0.227*	0.174 (4)
C12B	0.7322 (10)	0.117 (2)	0.1742 (10)	0.094 (6)	0.174 (4)
H12C	0.690125	0.029522	0.164660	0.113*	0.174 (4)
H12D	0.716175	0.158466	0.221761	0.113*	0.174 (4)
C13B	0.8677 (10)	0.0985 (13)	0.1869 (10)	0.097 (6)	0.174 (4)
H13C	0.878689	0.039209	0.144017	0.116*	0.174 (4)
H13D	0.899119	0.049145	0.237421	0.116*	0.174 (4)
N14B	0.95517 (18)	0.2283 (2)	0.18999 (11)	0.0477 (4)	0.174 (4)
H14B	0.907735	0.313348	0.176025	0.048*	0.174 (4)
OWB	0.7885 (17)	0.4440 (11)	0.1674 (7)	0.127 (7)	0.174 (4)
HWB1	0.759000	0.379000	0.136000	0.191*	0.174 (4)
HWB2	0.805000	0.507000	0.136000	0.191*	0.174 (4)
C15	1.03484 (19)	0.2263 (2)	0.27769 (13)	0.0540 (5)
H15	1.073120	0.135528	0.287967	0.065*
C16	0.9544 (3)	0.2442 (3)	0.33450 (16)	0.0873 (8)
H16A	0.890089	0.176045	0.323129	0.131*
H16B	1.004494	0.234514	0.389431	0.131*
H16C	0.917326	0.333590	0.327170	0.131*
C17	1.1391 (2)	0.3294 (3)	0.2910 (2)	0.0798 (8)
H17A	1.186830	0.312769	0.253129	0.120*
H17B	1.104769	0.419999	0.282983	0.120*
H17C	1.191937	0.320922	0.345244	0.120*
C18	1.0259 (2)	0.1912 (2)	0.12895 (14)	0.0598 (6)
H18	1.082523	0.266776	0.126770	0.072*
C19	1.1024 (3)	0.0634 (3)	0.15173 (18)	0.0815 (8)
H19A	1.145157	0.044391	0.111416	0.122*
H19B	1.162097	0.076260	0.203360	0.122*
H19C	1.048821	−0.011892	0.154955	0.122*
C20	0.9338 (4)	0.1771 (4)	0.04553 (17)	0.0989 (10)
H20A	0.886121	0.259717	0.032360	0.148*
H20B	0.978394	0.160918	0.005857	0.148*
H20C	0.878850	0.101648	0.045797	0.148*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.06060 (16)	0.04938 (16)	0.03936 (14)	0.01742 (11)	0.00711 (11)	−0.00042 (10)
Cu2A	0.0526 (8)	0.0657 (11)	0.0717 (13)	0.0056 (6)	0.0365 (9)	−0.0003 (7)
Cu2B	0.0499 (7)	0.0454 (7)	0.0515 (8)	0.0062 (4)	0.0260 (6)	0.0018 (5)
Cu3	0.04160 (13)	0.04784 (15)	0.03909 (13)	−0.00109 (9)	0.00985 (10)	0.00345 (9)
C1	0.0496 (12)	0.0539 (12)	0.0447 (11)	0.0068 (9)	0.0116 (10)	−0.0032 (9)
N1	0.0416 (10)	0.0609 (11)	0.0419 (10)	−0.0083 (8)	0.0047 (9)	0.0084 (8)
NC1	0.0496 (12)	0.0539 (12)	0.0447 (11)	0.0068 (9)	0.0116 (10)	−0.0032 (9)
CN1	0.0416 (10)	0.0609 (11)	0.0419 (10)	−0.0083 (8)	0.0047 (9)	0.0084 (8)
C2	0.0413 (9)	0.0705 (13)	0.0398 (13)	−0.0008 (9)	0.0108 (8)	0.0001 (9)
N2	0.0414 (9)	0.0589 (11)	0.0372 (11)	−0.0072 (8)	0.0087 (7)	0.0040 (8)
NC2	0.0413 (9)	0.0705 (13)	0.0398 (13)	−0.0008 (9)	0.0108 (8)	0.0001 (9)
CN2	0.0414 (9)	0.0589 (11)	0.0372 (11)	−0.0072 (8)	0.0087 (7)	0.0040 (8)
C3	0.144 (2)	0.0901 (19)	0.0473 (11)	0.0739 (17)	0.0239 (13)	0.0072 (12)
N3	0.144 (2)	0.0901 (19)	0.0473 (11)	0.0739 (17)	0.0239 (13)	0.0072 (12)
C4	0.0476 (10)	0.0443 (11)	0.0520 (11)	−0.0012 (8)	0.0215 (8)	−0.0023 (8)
N4	0.0451 (10)	0.0502 (10)	0.0458 (9)	−0.0043 (8)	0.0145 (8)	0.0034 (8)
NC4	0.0476 (10)	0.0443 (11)	0.0520 (11)	−0.0012 (8)	0.0215 (8)	−0.0023 (8)
CN4	0.0451 (10)	0.0502 (10)	0.0458 (9)	−0.0043 (8)	0.0145 (8)	0.0034 (8)
CN5	0.0485 (10)	0.0513 (11)	0.0552 (11)	−0.0013 (8)	0.0234 (8)	−0.0049 (9)
NC5	0.0485 (10)	0.0513 (11)	0.0552 (11)	−0.0013 (8)	0.0234 (8)	−0.0049 (9)
O11A	0.0552 (14)	0.124 (3)	0.205 (4)	−0.0169 (14)	0.0516 (19)	−0.039 (2)
C12A	0.055 (2)	0.085 (3)	0.119 (3)	0.0201 (19)	−0.018 (2)	−0.007 (3)
C13A	0.0516 (14)	0.0439 (15)	0.0683 (17)	0.0087 (12)	0.0100 (12)	0.0113 (13)
N14A	0.0401 (10)	0.0541 (11)	0.0498 (10)	0.0020 (9)	0.0141 (8)	0.0029 (8)
OWA	0.168 (3)	0.103 (3)	0.113 (2)	−0.085 (2)	0.080 (2)	−0.0432 (19)
O11B	0.057 (7)	0.182 (18)	0.188 (17)	0.001 (8)	−0.011 (9)	0.049 (14)
C12B	0.051 (8)	0.121 (16)	0.099 (13)	−0.039 (10)	0.003 (8)	−0.044 (13)
C13B	0.075 (10)	0.152 (17)	0.072 (10)	0.010 (11)	0.034 (8)	−0.018 (11)
N14B	0.0401 (10)	0.0541 (11)	0.0498 (10)	0.0020 (9)	0.0141 (8)	0.0029 (8)
OWB	0.172 (16)	0.111 (13)	0.104 (12)	0.005 (12)	0.046 (11)	0.041 (9)
C15	0.0574 (12)	0.0465 (11)	0.0524 (12)	0.0111 (9)	0.0052 (10)	0.0026 (9)
C16	0.124 (2)	0.086 (2)	0.0547 (15)	0.0161 (18)	0.0307 (15)	0.0037 (14)
C17	0.0639 (15)	0.0621 (16)	0.095 (2)	−0.0004 (12)	−0.0094 (14)	−0.0069 (14)
C18	0.0639 (13)	0.0595 (14)	0.0659 (14)	−0.0072 (10)	0.0347 (12)	0.0013 (10)
C19	0.0765 (16)	0.0783 (18)	0.097 (2)	0.0144 (14)	0.0372 (15)	−0.0189 (15)
C20	0.133 (3)	0.118 (3)	0.0549 (15)	0.013 (2)	0.0410 (17)	0.0107 (15)

Geometric parameters (Å, º) top

Cu1—C1	1.916 (2)	O11B—C12B	1.403 (11)
Cu1—C3	1.918 (2)	O11B—H11B	0.852 (10)
Cu1—C2	1.953 (2)	C12B—C13B	1.480 (10)
Cu1—Cu2B	2.482 (3)	C12B—H12C	0.9700
Cu1—Cu2A	2.654 (3)	C12B—H12D	0.9700
Cu2A—CN5	1.849 (4)	C13B—N14B	1.593 (10)
Cu2A—C4	1.857 (4)	C13B—H13C	0.9700
Cu2B—C4	1.918 (4)	C13B—H13D	0.9700
Cu2B—CN5	1.946 (4)	N14B—C18	1.518 (3)
Cu2B—C2	2.316 (3)	N14B—C15	1.524 (3)
Cu3—N2	1.9180 (18)	N14B—H14B	0.9800
Cu3—N1	1.9247 (18)	OWB—HWB1	0.839 (5)
Cu3—N4	1.9291 (18)	OWB—HWB2	0.870 (14)
C1—N1ⁱ	1.144 (3)	C15—C16	1.506 (3)
C2—N2	1.142 (3)	C15—C17	1.509 (3)
C3—C3ⁱⁱ	1.139 (4)	C15—H15	0.9800
C4—N4ⁱⁱⁱ	1.146 (2)	C16—H16A	0.9600
CN5—CN5^iv	1.157 (3)	C16—H16B	0.9600
O11A—C12A	1.389 (6)	C16—H16C	0.9600
O11A—H11A	0.850 (10)	C17—H17A	0.9600
C12A—C13A	1.486 (4)	C17—H17B	0.9600
C12A—H12A	0.9700	C17—H17C	0.9600
C12A—H12B	0.9700	C18—C19	1.503 (4)
C13A—N14A	1.556 (3)	C18—C20	1.523 (4)
C13A—H13A	0.9700	C18—H18	0.9800
C13A—H13B	0.9700	C19—H19A	0.9600
N14A—C18	1.518 (3)	C19—H19B	0.9600
N14A—C15	1.524 (3)	C19—H19C	0.9600
N14A—H14A	0.63 (3)	C20—H20A	0.9600
OWA—HWA1	0.839 (5)	C20—H20B	0.9600
OWA—HWA2	0.836 (5)	C20—H20C	0.9600

C1—Cu1—C3	120.18 (9)	O11B—C12B—H12D	110.1
C1—Cu1—C2	123.75 (8)	C13B—C12B—H12D	110.1
C3—Cu1—C2	115.51 (9)	H12C—C12B—H12D	108.4
C1—Cu1—Cu2B	74.00 (9)	C12B—C13B—N14B	119.9 (10)
C3—Cu1—Cu2B	149.77 (13)	C12B—C13B—H13C	107.3
C2—Cu1—Cu2B	61.58 (8)	N14B—C13B—H13C	107.3
C1—Cu1—Cu2A	67.41 (9)	C12B—C13B—H13D	107.3
C3—Cu1—Cu2A	149.40 (13)	N14B—C13B—H13D	107.3
C2—Cu1—Cu2A	69.16 (8)	H13C—C13B—H13D	106.9
CN5—Cu2A—C4	145.7 (2)	C18—N14B—C15	113.87 (17)
CN5—Cu2A—Cu1	87.67 (13)	C18—N14B—C13B	102.5 (6)
C4—Cu2A—Cu1	125.84 (16)	C15—N14B—C13B	102.1 (6)
C4—Cu2B—CN5	132.81 (15)	C18—N14B—H14B	112.5
C4—Cu2B—C2	112.90 (14)	C15—N14B—H14B	112.5
CN5—Cu2B—C2	110.86 (15)	C13B—N14B—H14B	112.5
C4—Cu2B—Cu1	132.41 (17)	HWB1—OWB—HWB2	104.6 (12)
CN5—Cu2B—Cu1	90.67 (13)	C16—C15—C17	113.4 (2)
C2—Cu2B—Cu1	47.88 (7)	C16—C15—N14B	110.31 (19)
N2—Cu3—N1	122.80 (7)	C17—C15—N14B	111.0 (2)
N2—Cu3—N4	120.06 (7)	C16—C15—N14A	110.31 (19)
N1—Cu3—N4	117.04 (7)	C17—C15—N14A	111.0 (2)
N1ⁱ—C1—Cu1	174.0 (2)	C16—C15—H15	107.3
C1^v—N1—Cu3	175.44 (18)	C17—C15—H15	107.3
N2—C2—Cu1	159.98 (19)	N14A—C15—H15	107.3
N2—C2—Cu2B	129.03 (19)	C15—C16—H16A	109.5
Cu1—C2—Cu2B	70.54 (10)	C15—C16—H16B	109.5
C2—N2—Cu3	172.63 (18)	H16A—C16—H16B	109.5
C3ⁱⁱ—C3—Cu1	177.6 (5)	C15—C16—H16C	109.5
N4ⁱⁱⁱ—C4—Cu2A	171.80 (19)	H16A—C16—H16C	109.5
N4ⁱⁱⁱ—C4—Cu2B	174.26 (19)	H16B—C16—H16C	109.5
C4^vi—N4—Cu3	177.56 (17)	C15—C17—H17A	109.5
CN5^iv—CN5—Cu2A	170.4 (3)	C15—C17—H17B	109.5
CN5^iv—CN5—Cu2B	177.1 (3)	H17A—C17—H17B	109.5
C12A—O11A—H11A	110 (2)	C15—C17—H17C	109.5
O11A—C12A—C13A	109.7 (3)	H17A—C17—H17C	109.5
O11A—C12A—H12A	109.7	H17B—C17—H17C	109.5
C13A—C12A—H12A	109.7	C19—C18—N14A	112.6 (2)
O11A—C12A—H12B	109.7	C19—C18—N14B	112.6 (2)
C13A—C12A—H12B	109.7	C19—C18—C20	111.0 (2)
H12A—C12A—H12B	108.2	N14A—C18—C20	109.0 (2)
C12A—C13A—N14A	112.9 (3)	N14B—C18—C20	109.0 (2)
C12A—C13A—H13A	109.0	C19—C18—H18	108.0
N14A—C13A—H13A	109.0	N14A—C18—H18	108.0
C12A—C13A—H13B	109.0	C20—C18—H18	108.0
N14A—C13A—H13B	109.0	C18—C19—H19A	109.5
H13A—C13A—H13B	107.8	C18—C19—H19B	109.5
C18—N14A—C15	113.87 (17)	H19A—C19—H19B	109.5
C18—N14A—C13A	109.36 (18)	C18—C19—H19C	109.5
C15—N14A—C13A	111.26 (18)	H19A—C19—H19C	109.5
C18—N14A—H14A	114 (3)	H19B—C19—H19C	109.5
C15—N14A—H14A	110 (3)	C18—C20—H20A	109.5
C13A—N14A—H14A	96 (2)	C18—C20—H20B	109.5
HWA1—OWA—HWA2	108.4 (14)	H20A—C20—H20B	109.5
C12B—O11B—H11B	110 (2)	C18—C20—H20C	109.5
O11B—C12B—C13B	107.9 (11)	H20A—C20—H20C	109.5
O11B—C12B—H12C	110.1	H20B—C20—H20C	109.5
C13B—C12B—H12C	110.1

O11A—C12A—C13A—N14A	73.5 (4)	C13A—N14A—C15—C16	63.9 (3)
C12A—C13A—N14A—C18	110.3 (3)	C18—N14A—C15—C17	61.5 (2)
C12A—C13A—N14A—C15	−123.0 (3)	C13A—N14A—C15—C17	−62.6 (2)
O11B—C12B—C13B—N14B	50 (2)	C15—N14A—C18—C19	48.5 (3)
C12B—C13B—N14B—C18	−128.2 (12)	C13A—N14A—C18—C19	173.6 (2)
C12B—C13B—N14B—C15	113.6 (12)	C15—N14A—C18—C20	172.1 (2)
C18—N14B—C15—C16	−171.9 (2)	C13A—N14A—C18—C20	−62.7 (3)
C13B—N14B—C15—C16	−62.2 (6)	C15—N14B—C18—C19	48.5 (3)
C18—N14B—C15—C17	61.5 (2)	C13B—N14B—C18—C19	−61.0 (6)
C13B—N14B—C15—C17	171.2 (5)	C15—N14B—C18—C20	172.1 (2)
C18—N14A—C15—C16	−171.9 (2)	C13B—N14B—C18—C20	62.7 (6)

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1, −y, −z; (iii) −x+1/2, y+1/2, −z+1/2; (iv) −x+1, −y+1, −z; (v) x+1/2, −y+1/2, 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
N14Ae—H14Ae···OWAe	0.63 (3)	2.19 (3)	2.797 (3)	160 (3)
N14Bf—H14Bf···OWBf	0.98	1.82	2.769 (17)	162
OWAe—HWA1e···O11Ae^vii	0.84 (1)	2.00 (3)	2.739 (5)	147 (5)
OWBf—HWB1f···O11Bf	0.84 (1)	1.90 (2)	2.69 (2)	156 (1)
OWBf—HWB2f···N1^viii	0.87 (1)	2.45 (1)	3.278 (13)	160 (1)
O11Ae—H11Ae···N2	0.85 (1)	2.67 (4)	3.243 (3)	126 (4)
O11Bf—H11Bf···N3	0.85 (1)	2.19 (6)	3.022 (18)	165 (21)

Symmetry codes: (vii) −x+3/2, y−1/2, −z+1/2; (viii) −x+3/2, y+1/2, −z+1/2.

Poly[2-hydroxy-N,N-diisopropylethan-1-aminium [µ₃-cyanido-κ³C:C:N-di-µ₂-cyanido-κ⁴C:N-dicuprate(I)]] (ipr2oenHfinal) top

Crystal data top

(C₈H₂₀NO)[Cu₂(CN)₃]	F(000) = 720
M_r = 351.39	D_x = 1.506 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.2470 (1) Å	Cell parameters from 4700 reflections
b = 13.9706 (4) Å	θ = 1.0–30.0°
c = 15.3264 (4) Å	µ = 2.74 mm⁻¹
β = 92.9207 (15)°	T = 297 K
V = 1549.70 (6) Å³	Block, colourless
Z = 4	0.16 × 0.11 × 0.10 mm

Data collection top

Enraf-Nonius KappaCCD diffractometer	3418 independent reflections
Radiation source: fine-focus sealed tube	2664 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 9 pixels mm^-1	θ_max = 27.1°, θ_min = 1.0°
combination of ω and φ scans	h = −9→9
Absorption correction: part of the refinement model (ΔF) (DENZO; Otwinowski & Minor, 1997)	k = 0→17
T_min = 0.782, T_max = 0.931	l = 0→19
42261 measured reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.192	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.081P)² + 2.770P] where P = (F_o² + 2F_c²)/3
3418 reflections	(Δ/σ)_max = 0.003
248 parameters	Δρ_max = 0.56 e Å⁻³
261 restraints	Δρ_min = −0.49 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.98754 (10)	0.10790 (5)	0.13016 (5)	0.0661 (3)
Cu2	0.73660 (11)	0.43991 (6)	0.10957 (5)	0.0749 (3)
C1	0.8205 (8)	0.3097 (4)	0.1142 (3)	0.0676 (13)	0.5
N1	0.8796 (7)	0.2337 (4)	0.1199 (3)	0.0648 (12)	0.5
C1N	0.8205 (8)	0.3097 (4)	0.1142 (3)	0.0676 (13)	0.5
N1C	0.8796 (7)	0.2337 (4)	0.1199 (3)	0.0648 (12)	0.5
C2	0.8408 (9)	0.5204 (4)	0.2019 (4)	0.0770 (15)	0.5
N2	1.0962 (8)	0.0583 (4)	0.2376 (4)	0.0733 (14)	0.5
C2N	0.8408 (9)	0.5204 (4)	0.2019 (4)	0.0770 (15)	0.5
N2C	1.0962 (8)	0.0583 (4)	0.2376 (4)	0.0733 (14)	0.5
CN3	0.9951 (8)	0.0250 (4)	0.0295 (3)	0.0699 (13)	0.5
NC3	0.9951 (8)	0.0250 (4)	0.0295 (3)	0.0699 (13)	0.5
CN4	0.5531 (10)	0.4854 (4)	0.0255 (4)	0.0886 (19)	0.5
NC4	0.5531 (10)	0.4854 (4)	0.0255 (4)	0.0886 (19)	0.5
O11A	0.772 (5)	0.8045 (18)	0.262 (2)	0.232 (13)	0.5
H11A	0.840820	0.803195	0.305866	0.348*	0.5
C12A	0.694 (4)	0.8978 (15)	0.2513 (17)	0.132 (8)	0.5
H12A	0.789920	0.946097	0.248182	0.159*	0.5
H12B	0.615691	0.913310	0.298641	0.159*	0.5
C13A	0.588 (4)	0.8889 (14)	0.1685 (15)	0.201 (12)	0.5
H13A	0.653250	0.924706	0.125552	0.241*	0.5
H13B	0.471432	0.921726	0.175341	0.241*	0.5
N14A	0.5423 (6)	0.7935 (4)	0.1290 (3)	0.0751 (13)	0.5
H14A	0.632546	0.754156	0.162633	0.090*	0.5
C15A	0.3747 (18)	0.7473 (13)	0.1538 (18)	0.157 (9)	0.5
H15A	0.362783	0.709357	0.100007	0.189*	0.5
C16A	0.390 (5)	0.661 (2)	0.211 (3)	0.141 (15)	0.5
H16A	0.268071	0.637910	0.222313	0.211*	0.5
H16B	0.456962	0.611665	0.182893	0.211*	0.5
H16C	0.453313	0.677435	0.265662	0.211*	0.5
C17A	0.1979 (17)	0.8004 (14)	0.1340 (12)	0.104 (5)	0.5
H17A	0.096062	0.763242	0.153115	0.157*	0.5
H17B	0.201857	0.860738	0.163933	0.157*	0.5
H17C	0.182400	0.811148	0.072170	0.157*	0.5
C18A	0.609 (3)	0.7781 (18)	0.0406 (11)	0.156 (10)	0.5
H18A	0.511977	0.732628	0.021878	0.187*	0.5
C19A	0.765 (3)	0.709 (2)	0.0340 (17)	0.095 (6)	0.5
H19A	0.797706	0.704733	−0.025787	0.143*	0.5
H19B	0.869860	0.731814	0.069182	0.143*	0.5
H19C	0.728645	0.647656	0.054353	0.143*	0.5
C20A	0.560 (10)	0.852 (3)	−0.0272 (16)	0.130 (12)	0.5
H20A	0.611120	0.833442	−0.081394	0.195*	0.5
H20B	0.428016	0.855954	−0.035162	0.195*	0.5
H20C	0.609270	0.912464	−0.008823	0.195*	0.5
O11B	0.370 (4)	0.643 (2)	0.182 (2)	0.159 (9)	0.5
H11B	0.324689	0.589133	0.186697	0.238*	0.5
C12B	0.239 (3)	0.7043 (16)	0.1366 (16)	0.139 (7)	0.5
H12C	0.118115	0.704760	0.161278	0.167*	0.5
H12D	0.227828	0.692736	0.074179	0.167*	0.5
C13B	0.352 (2)	0.7887 (14)	0.1609 (15)	0.136 (8)	0.5
H13C	0.361849	0.792539	0.224186	0.163*	0.5
H13D	0.286041	0.845238	0.139979	0.163*	0.5
N14B	0.5423 (6)	0.7935 (4)	0.1290 (3)	0.0751 (13)	0.5
H14B	0.597587	0.736582	0.157162	0.090*	0.5
C15B	0.6652 (18)	0.8691 (9)	0.1663 (9)	0.081 (3)	0.5
H15B	0.773336	0.874634	0.130816	0.097*	0.5
C16B	0.572 (3)	0.9661 (9)	0.1706 (16)	0.138 (7)	0.5
H16D	0.657506	1.012186	0.195281	0.207*	0.5
H16E	0.530919	0.985824	0.112786	0.207*	0.5
H16F	0.467076	0.961591	0.206461	0.207*	0.5
C17B	0.730 (5)	0.850 (2)	0.2601 (13)	0.142 (10)	0.5
H17D	0.808673	0.901227	0.280787	0.213*	0.5
H17E	0.624590	0.845985	0.295590	0.213*	0.5
H17F	0.796735	0.790766	0.263399	0.213*	0.5
C18B	0.556 (2)	0.7675 (13)	0.0342 (8)	0.083 (4)	0.5
H18B	0.464016	0.717873	0.019362	0.099*	0.5
C19B	0.740 (4)	0.732 (2)	0.0109 (18)	0.129 (10)	0.5
H19D	0.775392	0.678536	0.047423	0.194*	0.5
H19E	0.735236	0.712432	−0.049191	0.194*	0.5
H19F	0.829961	0.782278	0.019484	0.194*	0.5
C20B	0.527 (11)	0.849 (3)	−0.0283 (18)	0.148 (14)	0.5
H20D	0.409396	0.878267	−0.019538	0.222*	0.5
H20E	0.623359	0.895156	−0.018430	0.222*	0.5
H20F	0.528634	0.825310	−0.087104	0.222*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0664 (5)	0.0651 (5)	0.0667 (5)	0.0000 (3)	0.0030 (3)	0.0027 (3)
Cu2	0.0797 (5)	0.0695 (5)	0.0735 (5)	0.0078 (4)	−0.0152 (4)	−0.0021 (3)
C1	0.075 (3)	0.068 (3)	0.058 (3)	0.013 (3)	−0.013 (2)	−0.003 (2)
N1	0.076 (3)	0.066 (3)	0.052 (3)	0.006 (3)	−0.008 (2)	−0.003 (2)
C1N	0.075 (3)	0.068 (3)	0.058 (3)	0.013 (3)	−0.013 (2)	−0.003 (2)
N1C	0.076 (3)	0.066 (3)	0.052 (3)	0.006 (3)	−0.008 (2)	−0.003 (2)
C2	0.086 (4)	0.064 (3)	0.078 (4)	0.000 (3)	−0.021 (3)	−0.004 (3)
N2	0.085 (4)	0.062 (3)	0.071 (3)	0.005 (3)	−0.013 (3)	−0.001 (3)
C2N	0.086 (4)	0.064 (3)	0.078 (4)	0.000 (3)	−0.021 (3)	−0.004 (3)
N2C	0.085 (4)	0.062 (3)	0.071 (3)	0.005 (3)	−0.013 (3)	−0.001 (3)
CN3	0.086 (3)	0.057 (3)	0.066 (3)	0.001 (3)	0.000 (3)	0.004 (2)
NC3	0.086 (3)	0.057 (3)	0.066 (3)	0.001 (3)	0.000 (3)	0.004 (2)
CN4	0.107 (5)	0.059 (3)	0.095 (4)	0.016 (3)	−0.043 (3)	−0.019 (3)
NC4	0.107 (5)	0.059 (3)	0.095 (4)	0.016 (3)	−0.043 (3)	−0.019 (3)
O11A	0.20 (2)	0.189 (19)	0.30 (3)	0.047 (17)	−0.001 (19)	−0.019 (18)
C12A	0.090 (12)	0.152 (15)	0.153 (16)	−0.015 (11)	−0.017 (11)	−0.048 (13)
C13A	0.20 (2)	0.192 (15)	0.201 (18)	−0.045 (14)	−0.082 (16)	−0.079 (14)
N14A	0.065 (3)	0.088 (3)	0.073 (3)	−0.004 (2)	0.012 (2)	−0.004 (2)
C15A	0.081 (8)	0.134 (15)	0.26 (2)	−0.005 (8)	0.032 (12)	0.082 (15)
C16A	0.15 (2)	0.096 (16)	0.18 (3)	0.002 (13)	0.002 (18)	0.03 (2)
C17A	0.064 (7)	0.133 (14)	0.114 (12)	−0.005 (8)	−0.015 (7)	−0.002 (10)
C18A	0.175 (19)	0.19 (2)	0.110 (11)	0.059 (15)	0.061 (13)	0.033 (11)
C19A	0.081 (9)	0.107 (14)	0.101 (13)	−0.029 (8)	0.029 (8)	−0.011 (10)
C20A	0.12 (3)	0.17 (2)	0.095 (14)	−0.039 (18)	−0.023 (13)	0.031 (17)
O11B	0.177 (18)	0.151 (14)	0.152 (19)	−0.045 (12)	0.055 (14)	−0.016 (13)
C12B	0.101 (11)	0.174 (15)	0.144 (15)	−0.078 (10)	0.033 (10)	−0.035 (12)
C13B	0.115 (10)	0.117 (10)	0.185 (16)	−0.056 (9)	0.099 (12)	−0.095 (11)
N14B	0.065 (3)	0.088 (3)	0.073 (3)	−0.004 (2)	0.012 (2)	−0.004 (2)
C15B	0.075 (7)	0.093 (7)	0.075 (7)	−0.013 (6)	0.001 (6)	−0.018 (6)
C16B	0.174 (19)	0.066 (8)	0.179 (19)	0.006 (9)	0.055 (15)	−0.006 (10)
C17B	0.17 (3)	0.17 (3)	0.084 (10)	0.00 (2)	−0.016 (12)	−0.031 (13)
C18B	0.084 (8)	0.097 (9)	0.066 (6)	−0.053 (7)	−0.003 (5)	−0.004 (6)
C19B	0.169 (18)	0.108 (17)	0.118 (18)	−0.022 (12)	0.083 (15)	−0.029 (14)
C20B	0.13 (2)	0.18 (2)	0.127 (19)	−0.076 (14)	−0.032 (16)	0.08 (2)

Geometric parameters (Å, º) top

Cu1—N2	1.918 (6)	C19A—H19B	0.9600
Cu1—CN3	1.931 (5)	C19A—H19C	0.9600
Cu1—N1	1.928 (5)	C20A—H20A	0.9600
Cu2—CN4	1.912 (5)	C20A—H20B	0.9600
Cu2—C1	1.918 (5)	C20A—H20C	0.9600
Cu2—C2	1.930 (6)	O11B—C12B	1.436 (18)
C1—N1	1.146 (7)	O11B—H11B	0.8200
C2—N2ⁱ	1.144 (8)	C12B—C13B	1.475 (14)
CN3—CN3ⁱⁱ	1.149 (10)	C12B—H12C	0.9700
CN4—CN4ⁱⁱⁱ	1.144 (11)	C12B—H12D	0.9700
O11A—C12A	1.424 (18)	C13B—N14B	1.486 (11)
O11A—H11A	0.8200	C13B—H13C	0.9700
C12A—C13A	1.457 (15)	C13B—H13D	0.9700
C12A—H12A	0.9700	N14B—C15B	1.478 (11)
C12A—H12B	0.9700	N14B—C18B	1.506 (11)
C13A—N14A	1.494 (14)	N14B—H14B	0.9800
C13A—H13A	0.9700	C15B—C17B	1.511 (14)
C13A—H13B	0.9700	C15B—C16B	1.519 (14)
N14A—C15A	1.443 (12)	C15B—H15B	0.9800
N14A—C18A	1.477 (13)	C16B—H16D	0.9600
N14A—H14A	0.9800	C16B—H16E	0.9600
C15A—C16A	1.496 (15)	C16B—H16F	0.9600
C15A—C17A	1.498 (14)	C17B—H17D	0.9600
C15A—H15A	0.9800	C17B—H17E	0.9600
C16A—H16A	0.9600	C17B—H17F	0.9600
C16A—H16B	0.9600	C18B—C19B	1.487 (15)
C16A—H16C	0.9600	C18B—C20B	1.494 (15)
C17A—H17A	0.9600	C18B—H18B	0.9800
C17A—H17B	0.9600	C19B—H19D	0.9600
C17A—H17C	0.9600	C19B—H19E	0.9600
C18A—C19A	1.491 (14)	C19B—H19F	0.9600
C18A—C20A	1.491 (14)	C20B—H20D	0.9600
C18A—H18A	0.9800	C20B—H20E	0.9600
C19A—H19A	0.9600	C20B—H20F	0.9600

N2—Cu1—CN3	116.2 (2)	C18A—C20A—H20A	109.5
N2—Cu1—N1	123.1 (2)	C18A—C20A—H20B	109.5
CN3—Cu1—N1	120.6 (2)	H20A—C20A—H20B	109.5
CN4—Cu2—C1	123.3 (2)	C18A—C20A—H20C	109.5
CN4—Cu2—C2	122.2 (2)	H20A—C20A—H20C	109.5
C1—Cu2—C2	114.4 (2)	H20B—C20A—H20C	109.5
N1—C1—Cu2	175.9 (5)	C12B—O11B—H11B	109.5
C1—N1—Cu1	178.0 (5)	O11B—C12B—C13B	90.6 (19)
N2ⁱ—C2—Cu2	171.8 (5)	O11B—C12B—H12C	113.5
C2^iv—N2—Cu1	173.5 (5)	C13B—C12B—H12C	113.5
CN3ⁱⁱ—CN3—Cu1	177.9 (8)	O11B—C12B—H12D	113.5
CN4ⁱⁱⁱ—CN4—Cu2	178.0 (10)	C13B—C12B—H12D	113.5
C12A—O11A—H11A	109.5	H12C—C12B—H12D	110.8
O11A—C12A—C13A	102 (2)	C12B—C13B—N14B	117.8 (12)
O11A—C12A—H12A	111.4	C12B—C13B—H13C	107.9
C13A—C12A—H12A	111.4	N14B—C13B—H13C	107.9
O11A—C12A—H12B	111.4	C12B—C13B—H13D	107.8
C13A—C12A—H12B	111.4	N14B—C13B—H13D	107.8
H12A—C12A—H12B	109.2	H13C—C13B—H13D	107.2
C12A—C13A—N14A	121.7 (17)	C15B—N14B—C13B	117.0 (8)
C12A—C13A—H13A	106.9	C15B—N14B—C18B	118.5 (8)
N14A—C13A—H13A	106.9	C13B—N14B—C18B	114.5 (10)
C12A—C13A—H13B	106.9	C15B—N14B—H14B	100.6
N14A—C13A—H13B	106.9	C13B—N14B—H14B	100.6
H13A—C13A—H13B	106.7	C18B—N14B—H14B	100.6
C15A—N14A—C18A	119.7 (13)	N14B—C15B—C17B	113.2 (13)
C15A—N14A—C13A	117.6 (12)	N14B—C15B—C16B	113.1 (11)
C18A—N14A—C13A	115.2 (12)	C17B—C15B—C16B	103.5 (17)
C15A—N14A—H14A	99.2	N14B—C15B—H15B	109.0
C18A—N14A—H14A	99.2	C17B—C15B—H15B	109.0
C13A—N14A—H14A	99.2	C16B—C15B—H15B	109.0
N14A—C15A—C16A	118.6 (16)	C15B—C16B—H16D	109.5
N14A—C15A—C17A	116.6 (12)	C15B—C16B—H16E	109.5
C16A—C15A—C17A	123.7 (19)	H16D—C16B—H16E	109.5
N14A—C15A—H15A	93.4	C15B—C16B—H16F	109.5
C16A—C15A—H15A	93.4	H16D—C16B—H16F	109.5
C17A—C15A—H15A	93.4	H16E—C16B—H16F	109.5
C15A—C16A—H16A	109.5	C15B—C17B—H17D	109.5
C15A—C16A—H16B	109.5	C15B—C17B—H17E	109.5
H16A—C16A—H16B	109.5	H17D—C17B—H17E	109.5
C15A—C16A—H16C	109.5	C15B—C17B—H17F	109.5
H16A—C16A—H16C	109.5	H17D—C17B—H17F	109.5
H16B—C16A—H16C	109.5	H17E—C17B—H17F	109.5
C15A—C17A—H17A	109.5	C19B—C18B—C20B	101 (3)
C15A—C17A—H17B	109.5	C19B—C18B—N14B	114.6 (13)
H17A—C17A—H17B	109.5	C20B—C18B—N14B	114.9 (16)
C15A—C17A—H17C	109.5	C19B—C18B—H18B	108.5
H17A—C17A—H17C	109.5	C20B—C18B—H18B	108.5
H17B—C17A—H17C	109.5	N14B—C18B—H18B	108.5
N14A—C18A—C19A	116.2 (15)	C18B—C19B—H19D	109.5
N14A—C18A—C20A	117.5 (15)	C18B—C19B—H19E	109.5
C19A—C18A—C20A	123 (3)	H19D—C19B—H19E	109.5
N14A—C18A—H18A	95.7	C18B—C19B—H19F	109.5
C19A—C18A—H18A	95.7	H19D—C19B—H19F	109.5
C20A—C18A—H18A	95.7	H19E—C19B—H19F	109.5
C18A—C19A—H19A	109.5	C18B—C20B—H20D	109.5
C18A—C19A—H19B	109.5	C18B—C20B—H20E	109.5
H19A—C19A—H19B	109.5	H20D—C20B—H20E	109.5
C18A—C19A—H19C	109.5	C18B—C20B—H20F	109.5
H19A—C19A—H19C	109.5	H20D—C20B—H20F	109.5
H19B—C19A—H19C	109.5	H20E—C20B—H20F	109.5

O11A—C12A—C13A—N14A	15 (4)	O11B—C12B—C13B—N14B	62 (3)
C12A—C13A—N14A—C15A	89 (3)	C12B—C13B—N14B—C15B	−169 (2)
C12A—C13A—N14A—C18A	−122 (3)	C12B—C13B—N14B—C18B	45 (3)
C18A—N14A—C15A—C16A	103 (3)	C13B—N14B—C15B—C17B	72 (2)
C13A—N14A—C15A—C16A	−109 (3)	C18B—N14B—C15B—C17B	−144.2 (19)
C18A—N14A—C15A—C17A	−89 (2)	C13B—N14B—C15B—C16B	−45.3 (19)
C13A—N14A—C15A—C17A	60 (3)	C18B—N14B—C15B—C16B	98.5 (16)
C15A—N14A—C18A—C19A	−102 (2)	C15B—N14B—C18B—C19B	60 (2)
C13A—N14A—C18A—C19A	109 (2)	C13B—N14B—C18B—C19B	−155 (2)
C15A—N14A—C18A—C20A	97 (4)	C15B—N14B—C18B—C20B	−57 (4)
C13A—N14A—C18A—C20A	−53 (4)	C13B—N14B—C18B—C20B	88 (4)

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, −y, −z; (iii) −x+1, −y+1, −z; (iv) −x+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
O11A—H11A···N1ⁱ	0.82	2.47	3.19 (3)	147
N14A—H14A···O11A	0.98	1.91	2.57 (3)	122

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

C≡N IR stretching frequencies top

	Base, B	Molecular formula	Cyanides	C≡N IR stretches (cm^-1)
1	oen	BH.Cu₂(CN)₃	µ₂; 2 × µ₃	2082, 2111
*	meoen	BH.Cu₂(CN)₃	2 × µ₂; µ₃	2083, 2104
2	etoen	[BH]₂.Cu₃(CN)₅.H₂O	4 × µ₂; µ₃	2092, 2112
4	me₂oen	[BH]₄Cu₈(CN)₁₂	7 × µ₂; 5 × µ₃	2075, 2103
**	et₂oen	BH.Cu₂(CN)₃	2 × µ₂; µ₃	2071, 2100 2122
5	ipr₂oen	BH.Cu₃(CN)₄.H₂O	3 × µ₂; µ₃	Shoulder, 2128 (broad)
6	ipr₂oen	BH.Cu₂(CN)₃	3 × µ₂	2114

Notes: (*) Koenigsmann et al. (2020). (**) Corfield et al. (2016).

Details of the six title compounds. Conjugate acid indicated by addition of hydrogen to the base top

	Base, with abbreviation	Asymmetric unit	Compound name
1	NH₂(CH₂)₂OH, oen	oenH.Cu₂(CN)₃	Poly[2-hydroxyethan-1-aminium [µ₃-cyanido-κ³C:C:N-di-µ₂-cyanido-κ⁴C:N-dicuprate(I)]]
2	C₂H₅NH(CH₂)₂OH, etoen	(etoenH)₂.Cu₃(CN)₅.H₂O	Poly[bis[N-(2-hydroxyethyl)ethan-1-aminium] [di-µ₃-cyanido-κ⁶C:C:N-tri-µ₂-cyanido-κ⁶C:N-tricuprate(I)] monohydrate]
3	C₂H₅NH(CH₂)₂OH, etoen	(etoenH)₂.Cu₃(CN)_4.5Cl_0.5	Poly[tetrakis[N-(2-hydroxyethyl)ethan-1-aminium] [chloridotetra-µ₃-cyanido-κ¹²C:C:N-penta-µ₂-cyanido-κ¹⁰C:N-tricuprate(I)]]
4	(CH₃)₂NH(CH₂)₂OH, me₂oen	(me₂oenH)₄.Cu₈(CN)₁₂	Poly[tetra[N-(2-hydroxyethyl)ethan-1-aminium] [penta-µ₃-cyanido-κ¹⁵C:C:N-hepta-µ₂-cyanido-κ¹⁴C:N-octacuprate(I)]]
5	((CH₃)₂CH)₂N(CH₂)₂OH ipr₂oen	ipr₂enH.Cu₃(CN)₄.H₂O	Poly[2-hydroxy-N,N-diisopropylethan-1-aminium [µ₃-cyanido-κ³C:C:N-di-µ₂-cyanido-κ⁴C:N-dicuprate(I)] monohydrate]
6	((CH₃)₂CH)₂N(CH₂)₂OH ipr₂oen	ipr₂oenH.Cu₂(CN)₃	Poly[2-hydroxy-N,N-diisopropylethan-1-aminium [µ₃-cyanido-κ³C:C:N-di-µ₂-cyanido-κ⁴C:N-dicuprate(I)]]

Cuprophilic geometries for compounds 1–6 top

	Cation, LH⁺	Cu···Cu (Å)	Short Cu—C (Å)	Long Cu—C (Å)
1	oenH	2.459 (1)	1.996 (6)	2.267 (6)
			2.079 (6)	2.106 (6)
2	etoenH	2.651 (4) Cu1A	1.958 (2)	2.420 (3)
			1.958 (2)	2.420 (3)
3	etoenH	2.604 (1)	1.970 (3)	2.384 (3)
			1.970 (3)	2.384 (3)
4	me₂oenH	2.472 (1)	2.113 (3)	2.174 (3)
		2.529 (1)	2.124 (3)	2.153 (3)
		2.506 (1)	2.006 (3)	2.290 (3)
			2.102 (3)	2.164 (3)
			1.997 (3)	2.172 (3)
			1.916 (3)	2.615 (3)
5	ipr₂oenH	2.654 (1) Cu2A	2.609 (1)	2.677 (1)
		2.483 (1) Cu2B	2.315 (1)	2.609 (1)

Hydrogen-bonding summary top

Cation–cation or cation–water hydrogen bonds
1	N14—H14C···O11(x, 1-y, 1/2+z)	2.870 (7)	168
2	O11—H11···O21A	2.765 (5)	153 (7)
2	N14—H14A···OW(-x+1, -y-1, -z+2)	2.843 (3)	168 (3)
2	N24—H24B···OW(-x+1, -y-1, -z+2)	2.988 (5)	166
2	OW—HW1···O11	2.794 (3)	149 (5)
3	N24—N24A···O11(-x+3/2, y-1/2, -z+1/2)	2.776 (4)	166 (3)
4	O41A—H41A···O51(x-1, y, z)	2.880 (4)	164 (4)
4	N54—H54A···O21	2.774 (2)	145
5	N14—H14···OWA	2.781 (2)	165 (1)
5	OWA—HWA···O11A(-x+3/2, y-1/2, -z+1/2)	2.738(20	157 (2)

Cation–network or water–network hydrogen bonds
1	O11—H11···N3(x+1/2, y+1/2, z)	2.996 (7)	174 (7)
2	N14—H14B···C5(-x+1, -y-1, -z+1)	3.216 (3)	135 (3)
2	O21A—H21A···N2(-x+1, -y-1, -z+1)	3.152 (4)	171 (7)
2	OW—HW2···N4	3.210 (3)	145 (5)
2	OW—HW2···N5(x, -y+3/2, z+1/2)	3.298 (3)	140 (5)
3	N14—H14A ···C3	3.294 (4)	147 (3)
3	N24—H24B···N1(-x+3/2, y-1/2, -z+1/2)	3.228 (4)	172 (3)
3	O21—H21···N4(x+1/2, -y+1/2, z+1/2)	3.287 (4)	142 (5)
3	O11—H11···Cl	3.410 (3)	137 (4)
3	N14—H14···Cl	3.323 (3)	166 (4)
4	O21—H21···N7(x+1, y, z)	3.1694)	170 (5)
4	N24—H24···C8N(-x+1, -y+2, -z+1)	3.111 (3)	149 (2)
4	N34—H34···.N3(-x+1, -y+2, -z+2)	3.276 (4)	140 (3)
4	O51—H51···N12(-x+1, -y+2, -z+2)	2.975 (4)	171 (5)
5	O11A—H11A···N2	3.244 (2)	122 (1)
6	O11A—H11A···N1(-x+2, y+1/2, -z+1/2)	3.17 (3)	148

Tabulation of thermogravimetric results. y/x is the ratio computed from R_exp, assuming formula (BH)_xCu_y(CN)_x₊_y top

	Base, B	Asymmetric unit, u	Molar mass, u	Mass base + HCN, u	R_pred, % remaining	R_exp, % remaining	y/x
1	oen	BH.Cu₂(CN)₃	267.2	88.1	67.0	66.7	1.97
*	meoen	BH.Cu₂(CN)₃	281.3	102.1	63.7	64.6	2.08
2	etoen	(BH)₂.Cu₃(CN)₅.H₂O	519.1	250.3 (incl. H₂O)	51.8	51.5	–
3	etoenCl	(BH)₂.Cu₃(CN)_4.5Cl_0.5	505.8	237.5 (incl. HCl)	53.0	Not available	–
4	me₂oen	BH.Cu₂(CN)₃ ×4	295.3 ×4	116.2	60.7	59.3	1.89
**	et₂oen	BH.Cu₂(CN)₃	323.4	144.2	55.4	54.9	1.96
5	ipr₂oen	BH.Cu₃(CN)₄.H₂O	459.0	190.3 (incl. H₂O)	58.5	Not applicable	–
6	ipr₂oen	BH.Cu₂(CN)₃	351.4	172.3	51.0	52.3 (mean of 4)	2.11

Notes: (*) Koenigsmann et al. (2020). (**) Corfield et al. (2016).

Nodes and topology of eight related CuCN network structures top

	Base, B	Formula	Nodes	Point symbols at Cu atoms	Ring sizes
1	oen	BH.Cu₂(CN)₃	Cu₂(6)	4¹².6³	12,18
*	meoen	BH.Cu₂(CN)₃	Cu₂(6)	3³.5⁹.6³	9,15,18
2	etoen	(BH)₂Cu₃(CN)₅.H₂O	1/2Cu₂(6) Cu(4) Cu(3)	4².6¹⁰.8³ 6⁶ 4.6²	12,18,24
3	etoenCl	(BH)₂Cu₃(CN)_4.5Cl_0.5	1/2Cu₂(6) Cu(4) Cu(3)	4².6¹⁰.8³ 6⁶ 4.6²	12,18,24
4	me₂oen	BH.Cu₂(CN)₃ ×4	Cu₂(6) Cu₂(6) Cu₂(5) Cu(4) Cu(3)	4⁷.5³.6⁵ 4⁵.5⁴.6⁵.7 4⁵.5².6².7 4².5³.6. 4.5²	12,15,18, 21
**	et₂oen	BH.Cu₂(CN)₃	1/2Cu₂(6) Cu(3)	4².6¹⁰.8³ 4.6²	12,18,24
5	ipr₂oen	BH.Cu₃(CN)₄.H₂O	Cu₂(5) Cu(3)	4.6⁷.8² 4.6²	12,18,24
6	ipr₂oen	BH.Cu₃(CN)₄	Cu(3) Cu(3)	10³ 10³	30

Notes: (*) Koenigsmann et al. (2020). (**) Corfield et al. (2016).

Tabulation of thermogravimetric results top

	Base, B	Asymmetric unit, u	Molar mass, u	Mass base + HCN, u	Predicted % mass remaining	Experimental % mass remaining
1	oen	BH.Cu₂(CN)₃	267.2	89.1	67.0	66.7
*	meoen	BH.Cu₂(CN)₃	281.3	102.1	63.7	64.6
2	etoen	(BH)₂.Cu₃(CN)₅.H₂O	519.1	250.3 (incl. H₂O)	51.8	51.5
3	etoenCl	(BH)₂.Cu₃(CN)_4.5Cl_0.5	505.8	237.5 (incl. HCl)	53.0	Not avail.
4	me₂oen	BH.Cu₂(CN)₃ ×4	295.3 ×4	116.2	60.7	59.3
**	et₂oen	BH.Cu₂(CN)₃	323.4	144.2	55.4	54.9
5	ipr₂oen	BH.Cu₃(CN)₄.H₂O	459.0	190.3 (incl.H₂O)	58.5	Not applicable
6	ipr₂oen	BH.Cu₂(CN)₃	351.4	172.3	51.0	52.3 (mean of 4)

Notes: (*) Koenigsmann et al. (2020). (**) Corfield et al. (2016).

Acknowledgements

We thank the Department of Chemistry and Biochemistry for continuing support of this research and acknowledge the assistance of Fordham students Christina Sheedy and Ayah Ozturk.

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