Crystal structure and Hirshfeld surface analysis of chiral catena-poly[l-histidinediium [[diiodido­cuprate(I)]-μ-iodido] monohydrate]

Sirenko, V.Y.; Ovdenko, V.N.; Potaskalov, V.A.; Apostu, M.-O.; Gural'skiy, I.A.

doi:10.1107/S2056989025010023

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ISSN: 2056-9890

Volume 81| Part 12| December 2025| Pages 1158-1163

https://doi.org/10.1107/S2056989025010023

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Crystal structure and Hirshfeld surface analysis of chiral catena-poly[L-histidinediium [[diiodidocuprate(I)]-μ-iodido] monohydrate]

Valerii Y. Sirenko,^a ^* Valeriia N. Ovdenko,^a Vadim A. Potaskalov,^b Mircea-Odin Apostu ^c and Il'ya A. Gural'skiy ^a

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska St. 64/13, Kyiv 01601, Ukraine, ^bDepartment of General and Inorganic Chemistry, National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute", Beresteiskyi Pr. 37, 03056 Kyiv, Ukraine, and ^cDepartment of Chemistry, Faculty of Chemistry, Al. I. Cuza University of Iasi, Carol I Blvd. 11, Iasi 700506, Romania
^*Correspondence e-mail: [email protected]

Edited by S.-L. Zheng, Harvard University, USA (Received 20 October 2025; accepted 10 November 2025; online 18 November 2025)

The title compound, {(C₆H₁₁N₃O₂)[CuI₃]·H₂O}_n or (L-HisH₂)CuI₃·H₂O (1), is a chiral organic–inorganic compound that crystallizes in the monoclinic P2₁ space group. The asymmetric unit of 1 consists of one diprotonated L-histidinium cation {4-[(2S)-2-azaniumyl-2-carboxyethyl]-1H-imidazol-3-ium}, one Cu⁺ cation, three iodide anions, and one co-crystallized water molecule. The Cu⁺ cations is four-coordinated by iodide anions forming a [CuI₄] unit. Structural analysis of the [CuI₄] unit using the Baur, τ₄, and τ₄′ indices reveals its slight deviation from ideal tetrahedral geometry. Two iodide anions from each [CuI₄] unit bridge adjacent Cu⁺ centers, forming chiral left-handed helical [CuI₃]_n²ⁿ⁻ polymeric chains. The biprotonated L-histidinium cations balance their negative charge and form N—H⋯I, O—H⋯I, and weak C—H⋯I hydrogen bonds with the [CuI₃]_n²ⁿ⁻ chains. According to the Hirshfeld surface analysis, the main contributions to the crystal packing arise from H⋯I and H⋯O contacts, while C⋯I and N⋯I interactions indicate the presence of I⋯π contacts. The compound reported here represents the first example of a chiral A₂CuX₃-type metal halide, which shows potential for second-harmonic generation, polarized blue-light emission, and other non-linear optical applications.

Keywords: crystal structure; distortion indices; L-histidine; chirality; helical; Hirshfeld surface analysis; materials; one-dimensional halides; copper(I); amino acids; iodides; A₂CuX₃-type compounds.

CCDC reference: 2501923

1. Chemical context

Recently, copper(I) halide materials have attracted significant interest because of their promising properties for applications in optoelectronics and radiation scintillators (Popy et al., 2024 ; Kirakci et al., 2017 ; Banerjee & Saparov, 2023 ; Chen et al., 2025 ; Du et al., 2023 ; Zhang et al., 2024 ). Copper(I) halide-based materials exhibit high photoluminescence quantum yields, tunable crystal structures, and, thanks to their structural and chemical diversity, feature adjustable band gaps and photophysical properties (Banerjee & Saparov, 2023). Their tunable photoluminescence wavelengths are especially important for next-generation lighting devices (Banerjee & Saparov, 2023). Compared to the extensively studied lead-halide materials, copper-based halides also have the advantage of lower toxicity.

Copper(I) halides reported so far, with both inorganic and organic counter-ions, typically form zero-dimensional or one-dimensional structures, such as Rb₂CuBr₃ (Creason et al., 2020 ), (Bmpip)₂Cu₂Br₄ (where Bmpip = 1-butyl-1-methylpiperidinium; Xu et al., 2022 ), and PPh₄CuBr₂ (Xu et al., 2022) and 1D-(Npipz)₂Cu₂I₆ (where Npipz = 1-butyl-1-methylpiperidinium; Carignan et al., 2024 ). These compounds have become known as highly efficient blue-light emitters, up-conversion materials, and scintillators with large light yields, mainly because of efficient recombination pathways involving self-trapped excitons (STE).

Recently, one-dimensional copper(I) halides with the general formula A₂CuX₃ have become more studied. These materials, made up of [CuX₃]_n²ⁿ⁻ chains formed through corner-sharing [CuX₄] tetrahedra, exhibit decent photoluminescence quantum yields and often excellent scintillation performance. Although such materials are still relatively rare, these one-dimensional copper(I) halides show halide-tunable luminescence in the lower-wavelength visible range, emitting blue, purple, and cyan light - an attractive feature for lighting and display applications (Carignan et al., 2024; Du et al., 2023; Zhang et al., 2024).

Introducing chirality into these systems could enhance their functionality, enabling polarized light emission in the visible range and expanding their potential for nonlinear optical applications. Chiral α-amino acids, particularly L-histidine, have been shown to act as effective structure-directing agents in the synthesis of chiral metal halides, including hybrid perovskite materials (Sirenko et al., 2024 , 2023 ). L-Histidine is particularly notable because it can adopt two protonation states, existing as either the mono or diprotonated L-histidinium.

In this paper we report a new chiral low-dimensional copper(I) iodide hybrid material obtained using the reaction between L-histidine and copper(I) iodide in concentrated hydroiodic acid. A detailed structural characterization and a Hirshfeld surface analysis were carried out for the resulting compound, (L-HisH₂)CuI₃·H₂O (1).

2. Structural commentary

The title compound crystallizes in the monoclinic space group P2₁. The asymmetric unit of 1 contains one L-histidinium cation, one Cu⁺ cation, three iodide anions and a co-crystallized water molecule (Fig. 1). Each Cu⁺ cation coordinated by four iodide ligands adopts a tetrahedral coordination geometry (Fig. 1). In each [CuI₄] tetrahedron, two iodide atoms bridge neighboring Cu^I centers, while the other two are terminal, interacting only with Cu^I and forming hydrogen bonds with the L-histidinium cations and co-crystallized water molecules (Fig. 1). The Cu—I bond lengths in the [CuI₄] coordination tetrahedra range from 2.62 to 2.72 Å (Table 1), which is similar to values observed in other A₂CuI₃-type compounds reported to date (Zhang et al., 2024; Carignan et al., 2024; Du et al., 2023). The I—Cu—I bond angles in the [CuI₄] tetrahedra range from 106.19 to 113.21°, deviating from the ideal tetrahedral value of ∼109.5° and demonstrating a smaller angle deviation compared to the previously reported compounds (Zhang et al., 2024; Carignan et al., 2024; Du et al., 2023). In 1, the Cu—I bonds with the terminal iodides (∼2.63 Å) are shorter than those with the bridging μ-iodides (∼2.71 Å), consistent with previously reported A₂CuI₃ compounds (Zhang et al., 2024; Carignan et al., 2024; Du et al., 2023). The Cu—μ-I—Cu bridging angle between adjacent tetrahedra is 125.79 (3)°, notably larger than the ∼108° observed in other A₂CuI₃ compounds (Zhang et al., 2024; Carignan et al., 2024; Du et al., 2023).

Table 1
Selected geometric parameters (Å, °)

I1—Cu1ⁱ	2.7063 (13)	I2—Cu1	2.6225 (12)
I1—Cu1	2.7216 (13)	I3—Cu1	2.6433 (11)

Cu1ⁱ—I1—Cu1	125.80 (3)	I2—Cu1—I3	106.19 (4)
I1ⁱⁱ—Cu1—I1	109.20 (4)	I3—Cu1—I1ⁱⁱ	110.75 (4)
I2—Cu1—I1	107.70 (4)	I3—Cu1—I1	113.21 (5)
I2—Cu1—I1ⁱⁱ	109.68 (5)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+1]$ .

Figure 1
Representation of the building units in the crystal structure of 1, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius. [Symmetry codes: (i) −x, $[{1\over 2}]$ + y, 1 − z].

A convenient way to describe distortions in coordination polyhedra is by using distortion indices. Several indices have been introduced in the literature, particularly for metal–oxygen tetrahedra. Baur proposed the following distortion indices for metal–oxide tetrahedra (Baur, 1970 ):

DI(AX) = Σ⁴_i=1 | (A – X)_i – <A – X> | / (4 < A – X >),

DI(XAX) = Σ⁶_i=1 | (X – A – X)_i – < X – A – X > | / (6 < X – A – X >)

and

DI(XX) = Σ⁶_i=1 | (X⋯X)_i – < X⋯X > | / (6 < X⋯X >).

Here, DI(AX), DI(XX) and DI(XAX) represent the bond-length distortion parameter (BLDP), edge-length distortion parameter (ELDP) and bond-angle distortion parameter (BADP), respectively, which together provide a complete description of the distortion of coordination tetrahedra. Although these indices were originally developed for ionic metal–oxygen systems, they can also be applied to tetrahedra with Cu—I bonds, which have partial covalent character. The calculated values for compound 1 are DI(AX) = 0.0152, DI(XAX) = 0.01608, and DI(XX) = 0.01615 (Table 2). Among A₂CuI₃-type compounds, 1 shows the highest DI(AX) value, whereas its DI(XAX) and DI(XX) values are the lowest reported for this family. Additionally, the parameter τ₄ which was developed for four-coordinated structures, is often used to describe deviations from ideal tetrahedral geometry (Yang et al., 2007 ). For square planar structures, τ₄ = 0, whereas for tetrahedral structures, τ₄ = 1:

Table 2
Selected octahedral distortion parameters

	L-HisH₂[CuI₃]·H₂O^a	1D-(Npipz)₂Cu₂I₆^b	[1,2-PDA]CuI₃^c	[1,3-PDA]CuI₃^d
DI(AX)	0.0152	0.00941	0.00927	0.02204
DI(XAX)	0.01608	0.04301	0.02587	0.03077
DI(XX)	0.01615	0.03742	0.01557	0.01237
τ₄	0.965	0.937	0.941	0.931
τ₄′	0.957	0.934	0.935	0.914
(a) The title compound (1); (b) Carignan et al. (2024); (c) Du et al. (2023); (d) Zhang et al. (2024).

τ₄ = [360° – (α + β)] / [360° – 2θ],

where β is the largest and α is the second-largest bond angle (β > α) in a four-coordinate geometry, and θ = arccos(–1/3) ≈ 109.5° is the ideal tetrahedral angle.

This parameter was later refined to more effectively distinguish between four-coordinate complexes that have significantly different geometries but similar τ₄ values. The revised parameter, τ₄′ (Okuniewski et al., 2015 ), provides values comparable to τ₄ but offers improved discrimination among the examined structures (τ₄′ > τ₄):

τ₄′ = [(β – α) / (360° – θ)] + [(180° – β) / (180° – θ)]

(α, β and θ as before). For 1, τ₄ and τ₄′ are 0.965 and 0.957, respectively, indicating a slight distortion of the [CuI₄] tetrahedra relative to the ideal geometry (τ₄ = τ₄′ = 1) (Table 2). These values are the highest reported among related one-dimensional copper(I) halides, suggesting that the [CuI₄] tetrahedra in 1 are the least distorted within this family (Table 2).

The [CuI₄] coordination polyhedra participate in both μ₂-bridging coordination (Cu—μ-I—Cu) and hydrogen bonding with the L-histidinium cations, forming infinite [CuI₃]_n²ⁿ⁻ polymeric chains that propagate along the [010] direction (Fig. 2). Interestingly, the [CuI₃]_n²ⁿ⁻ chains (point group 2) exhibit left-handed helical chirality, suggesting a structure-directing role of the chiral L-histidinium cations in the formation of these helical chains (Fig. 2c). Moreover, the Cu⋯Cu distance of 4.83 Å between adjacent tetrahedra is the largest reported among compounds featuring one-dimensional chains of corner-sharing [CuI₄] tetrahedra (Zhang et al., 2024; Carignan et al., 2024; Du et al., 2023).

Figure 2
Crystal packing of 1 viewed along (a) the [100] and (b) the [010] directions, and (c) side view of a fragment of the crystal structure showing an inorganic chain with left-handed helical chirality.

3. Supramolecular features

The L-histidinium cations and co-crystallized water molecules interact with the one-dimensional helical chains of corner-sharing [CuI₄] tetrahedra through a network of N—H⋯I and O—H⋯I hydrogen bonds, along with weak C—H⋯I contacts (Fig. 3, Table 3). In 1, the L-histidinium cation is doubly protonated at both the imidazolium ring and the amino group, which enables the formation of the A₂CuX₃-type structure. The protonated amino group participates in N—H⋯I hydrogen bonding with two adjacent [CuI₃]_n²⁻ chains. Specifically, two hydrogen bonds, N3_(a)—H3B_(a)⋯I2ⁱⁱ and N3_(a)—H3C_(a)⋯I2 [subscript (a) denotes the amino group], connect the L-histidinium cation to one chain, while N3_(a)—H3A_(a)⋯I3ⁱⁱⁱ links it to a second chain (Fig. 3). The protonated imidazolium ring contributes to linking neighboring [CuI₃]_n²ⁿ⁻ chains via N1_(i)—H1B_(i)⋯I1ⁱⁱⁱ hydrogen bonds [where (i) denotes the imidazolium ring] (Table 3, Fig. 3). The carboxyl group of the L-histidinium cation and the co-crystallized water molecules further consolidate the organic—inorganic framework through hydrogen-bonding interactions. In particular, the hydroxyl group of the carboxyl participates in O1_(c)—H1A_(c)⋯O3_(w)ⁱ hydrogen bonding with the co-crystallized water molecules (Fig. 3), where (w) denotes co-crystallized water and (c) denotes the carboxyl group. The co-crystallized water molecule participates in O3_(w)ⁱ—H3Eⁱ⋯I2ⁱ and O3_(w)ⁱ—H3Dⁱ⋯I3ⁱⁱ hydrogen bonding with two inorganic chains (Fig. 3, Table 3). The L-histidinium cations interact with each other through an N2_(i)—H2A_(i)⋯O2_(c)^vi hydrogen bond (Fig. 3), which links the imidazolium N—H group of one cation to the carbonyl oxygen of the carboxyl group of another cation.

Table 3
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3D⋯I3ⁱⁱⁱ	0.86	3.02	3.768 (8)	146
O3—H3E⋯I2	0.82	3.12	3.938 (7)	177
O1—H1A⋯O3^iv	0.82	1.81	2.605 (10)	162
N3—H3A⋯I3ⁱⁱ	0.89	2.69	3.571 (8)	169
N3—H3B⋯I2^v	0.89	2.75	3.601 (8)	160
N3—H3C⋯I2	0.89	2.79	3.596 (7)	152
N1—H1B⋯I1ⁱⁱ	0.86	2.81	3.516 (7)	141
N2—H2A⋯O2^vi	0.86	1.97	2.804 (9)	163
C4—H4A⋯I2^vii	0.97	2.88	3.716 (9)	146
Symmetry codes: (ii) $[-x, y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+2]$ ; (iv) ; (v) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (vi) $[-x, y-{\script{1\over 2}}, -z]$ ; (vii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ .

Figure 3
Side views of a fragment of the crystal structure of 1, illustrating the hydrogen-bonding scheme of the L-histidinium cation (dotted lines). [Symmetry codes: (i) x, y, −z + 1; (ii) −x + 1, y + $[{1\over 2}]$ , −z + 1; (iii) −x, y + $[{1\over 2}]$ , −z + 1; (iv) −x + 1, y − $[{1\over 2}]$ , −z + 1; (v) −x + 1, y, z; (vi) −x, $[{1\over 2}]$ + y, −z].

Furthermore, the secondary CH₂ group of the aliphatic backbone of L-histidinium also participate in weak C4—H4A⋯I2^iv (Fig. 3) contacts, further reinforcing the cohesion between the organic and inorganic components of 1. As previously established, C—H⋯B (where B denotes the hydrogen bond acceptor) hydrogen bonding can be considered when (r C⋯B) – [r_vdW(B) + r C—H] < 1.00 Å, where r C—H is the average C—H bond length, and r_vdW(B) is the van der Waals radius of the hydrogen-bond acceptor (Harmon et al., 1992 ). For the weak C2—H2⋯I3ⁱ contacts (Fig. 3) involving the imidazolium ring, the (r C⋯B) – [r_vdW(B) + r C—H] difference is 0.91 Å with a bond angle of 157°, which lies within the expected range for such interactions. For C4—H4A⋯I2^iv weak contact (Fig. 3) (secondary CH₂ group), the difference is 0.686 Å with a bond angle of 145°, indicating weak hydrogen bonding. Moreover, the imidazolium moiety of L-histidinium participates in an I⋯π interaction (Fig. 4) with the I3 atom of [CuI₄] unit, with centroid⋯I3ⁱ and centroid⋯I3ⁱⁱ distances of of 4.056 (4) and 3.697 (4) Å, respectively, and an I3ⁱ⋯centroid⋯I3ⁱⁱ angle of 155.36 (12)°, which falls within the range previously reported for I⋯π interactions (Prasanna & Guru Row, 2000 ). Concave red regions on the Hirshfeld surface mapped with the shape-index function (Fig. 4b,c) further indicate the presence of I⋯π interactions in the compound.

Figure 4
(a) Side views of a fragment of the crystal structure of 1, illustrating I⋯π interactions (green dashed line). (b), (c) The Hirshfeld surface mapped with the shape-index function highlights I⋯π interactions between I3ⁱ and I3ⁱⁱ atoms and the imidazolium ring. [Symmetry codes: (i) −x, y − $[{1\over 2}]$ , 1 − z; (ii) −x, y + $[{1\over 2}]$ , −z + 1].

4. Hirshfeld surface analysis

The Hirshfeld surface and the corresponding two-dimensional fingerprint plots were generated for the fragment containing the L-histidinium cation and the co-crystallized water molecule using CrystalExplorer 21.5 (Spackman et al., 2021 ) with standard resolution for the three-dimensional d_norm surfaces (Figs. 5 and 6). The red spots on the Hirshfeld surface are attributed to hydrogen bonds and weak C—H⋯I contacts between this fragment and both the [CuI₃]_n²ⁿ⁻ anionic chains and other L-histidinium cations (only hydrogen bonds) (Fig. 5). The associated fingerprint plots (Fig. 6) confirm that hydrogen bonding dominates the crystal packing of 1. The analysis shows that H⋯I interactions are predominant (Fig. 6b), accounting for approximately 33% of the total Hirshfeld surface. These correspond to N—H⋯I and O—H⋯I hydrogen bonds, as well as the weaker C—H⋯I contacts that link the organic and inorganic components. H⋯O contacts are the second most significant, contributing approximately 25% (Fig. 6c) to the Hirshfeld surface, and arise from O—H⋯O and N—H⋯O hydrogen bonds. The contribution of C⋯I and N⋯I contacts (less than 5%) to the Hirshfeld surface indicates the presence of I⋯π interactions (Fig. 6d and 6e), which further consolidate the crystal packing of 1.

Figure 5
(a)–(c) Representation of the Hirshfeld surface of the L-histidinium cation in 1 along different crystallographic directions, with the d_norm function plotted onto the surface to highlight various interactions. The subscripts indicate different functional groups: (a) = NH₃⁺; (c) = COOH; (i) = imidazolium ring; (w) = co-crystallized water molecule; (CH₂) = methylene group.

Figure 6
Two-dimensional fingerprint plots from a Hirshfeld surface analysis of 1 showing: (a) all contacts; (b) H⋯I/I⋯H (33.0%); (c) H⋯O/O⋯H (24.6%); (d) C⋯I/I⋯C (3.4%); (e) N⋯I/I⋯N (2.7%).

5. Database survey

A search of the Cambridge Structure Database (CSD version 6.00, last update August 2025; Groom et al., 2016 ) revealed 614 structures for the [CuI₄] moiety. Most similar to the title compound, namely complexes containing one-dimensional [CuI₃]_n²ⁿ⁻ chains of corner-shared tetrahedra, are catena-[1-methylpiperazine-1,4-diium (μ-iodo)diiodocopper] (BOKLEW; Carignan et al., 2024), catena-[propane-1,2-diammonium (μ-iodo)bis(iodo)dicopper(I)] (FOSMAF; Zhang et al., 2024), and catena-[propane-1,3-bis(ammonium) (μ-iodo)-bis(iodo)copper(I)] (MISJAD; Du et al., 2023).

6. Synthesis and crystallization

L-histidine (20 mg, 0.129 mmol) and copper(I) iodide (25 mg, 0.131 mmol) were dissolved in 600 µL of concentrated HI (57%) and 25 µL of H₃PO₂. The resulting mixture was left to evaporate, and after 2 weeks, colorless, plate-like crystals of the (L-HisH₂)CuI₃·H₂O compound were obtained. These crystals were placed under crystallographic oil until further single crystal X-ray diffraction measurements.

7. Refinement details

Crystal data, data collection, and structure refinement details are summarized in Table 4. All H atoms were placed geometrically and refined as riding, with C—H = 0.98 Å and U_iso(H) = 1.2U_eq(C) for ternary CH; C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for secondary CH₂; N—H = 0.86 Å and U_iso(H) = 1.2U_eq(N) for aromatic NH; C—H = 0.93 Å and U_iso(H) = 1.5U_eq(C) for aromatic CH groups; O—H = 0.86 Å and U_iso(H) = 1.5U_eq(O) for water molecules. Amino H atoms were positioned geometrically and allowed to ride on N atoms and rotate around the C—N bond, with N—H = 0.89 Å and U_iso(H) = 1.5U_eq(N) for NH₃ groups. Carboxylate H atoms were positioned geometrically and allowed to ride on O atoms and rotate around the O—C bond, O_(c)—H = 0.82 Å (c = carboxylate) and U_iso(H) = 1.5U_eq(O) for the O_(c)—H groups of carboxylate.

Table 4
Experimental details

Crystal data
Chemical formula	(C₆H₁₁N₃O₂)[CuI₃]·H₂O
M_r	619.43
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	299
a, b, c (Å)	8.5704 (3), 7.5748 (2), 12.3860 (4)
β (°)	109.113 (3)
V (Å³)	759.76 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	7.53
Crystal size (mm)	0.18 × 0.15 × 0.12

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2024 )
T_min, T_max	0.398, 0.517
No. of measured, independent and observed [I > 2σ(I)] reflections	10397, 3728, 3615
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.710

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.073, 1.05
No. of reflections	3728
No. of parameters	147
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.98, −0.86
Absolute structure	Flack x determined using 1510 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013 )
Absolute structure parameter	−0.03 (4)
Computer programs: CrysAlis PRO (Rigaku OD, 2024), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2501923

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025010023/oi2028sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025010023/oi2028Isup2.hkl

checkCIF report

Computing details top

catena-Poly[4-[(2S)-2-azaniumyl-2-carboxyethyl]-1H-imidazol-3-ium [[diiodidocuprate(I)]-µ-iodido] monohydrate] top

Crystal data top

(C₆H₁₁N₃O₂)[CuI₃]·H₂O	F(000) = 564
M_r = 619.43	D_x = 2.708 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 8.5704 (3) Å	Cell parameters from 8127 reflections
b = 7.5748 (2) Å	θ = 2.6–30.0°
c = 12.3860 (4) Å	µ = 7.53 mm⁻¹
β = 109.113 (3)°	T = 299 K
V = 759.76 (4) Å³	Plate, clear intense colourless
Z = 2	0.18 × 0.15 × 0.12 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3728 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	3615 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.025
Detector resolution: 10.0000 pixels mm^-1	θ_max = 30.3°, θ_min = 2.5°
ω scans	h = −11→11
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2024)	k = −10→10
T_min = 0.398, T_max = 0.517	l = −15→17
10397 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.029	w = 1/[σ²(F_o²) + (0.0449P)² + 0.2675P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.073	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.98 e Å⁻³
3728 reflections	Δρ_min = −0.86 e Å⁻³
147 parameters	Absolute structure: Flack x determined using 1510 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.03 (4)
Primary atom site location: dual

Special details top

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

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

	x	y	z	U_iso*/U_eq
I1	0.13680 (5)	0.06749 (6)	0.50811 (4)	0.03160 (12)
I2	0.40061 (6)	0.55289 (7)	0.62736 (4)	0.03880 (13)
I3	0.13407 (6)	0.34038 (8)	0.82833 (4)	0.03910 (14)
Cu1	0.13059 (14)	0.37960 (17)	0.61550 (9)	0.0467 (3)
C1	−0.1623 (11)	0.3476 (15)	0.1876 (8)	0.049 (2)
H1	−0.265910	0.333504	0.195383	0.059*
C5	0.3636 (9)	0.5864 (13)	0.3020 (6)	0.0395 (17)
H5	0.477608	0.580101	0.354083	0.047*
C4	0.2814 (11)	0.4064 (12)	0.3052 (8)	0.045 (2)
H4A	0.346960	0.315430	0.285442	0.054*
H4B	0.284618	0.384334	0.383101	0.054*
C3	0.1048 (10)	0.3873 (10)	0.2276 (6)	0.0340 (15)
C2	0.0371 (12)	0.3698 (14)	0.1142 (7)	0.047 (2)
H2	0.092239	0.372943	0.060802	0.057*
O3	0.5032 (10)	0.6129 (13)	0.9593 (6)	0.071 (2)
H3D	0.580076	0.691853	0.978808	0.107*
H3E	0.481288	0.605276	0.889629	0.107*
O2	0.3119 (9)	0.7716 (9)	0.1368 (5)	0.0524 (16)
O1	0.4420 (10)	0.5140 (11)	0.1428 (6)	0.0608 (19)
H1A	0.439416	0.541704	0.078238	0.091*
N3	0.2782 (10)	0.7316 (10)	0.3429 (6)	0.0433 (16)
H3A	0.177322	0.746996	0.293110	0.065*
H3B	0.335656	0.831167	0.349050	0.065*
H3C	0.270935	0.702959	0.410742	0.065*
C6	0.3693 (10)	0.6362 (13)	0.1839 (7)	0.0416 (18)
N1	−0.0242 (9)	0.3721 (10)	0.2707 (5)	0.0410 (15)
H1B	−0.014808	0.377986	0.341854	0.049*
N2	−0.1306 (9)	0.3461 (11)	0.0917 (5)	0.0479 (17)
H2A	−0.202496	0.332496	0.024939	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0338 (2)	0.0288 (2)	0.0311 (2)	−0.00231 (19)	0.00916 (16)	−0.00163 (18)
I2	0.0332 (2)	0.0415 (3)	0.0409 (3)	−0.0090 (2)	0.01095 (18)	−0.0002 (2)
I3	0.0453 (3)	0.0436 (3)	0.0279 (2)	−0.0090 (2)	0.01119 (18)	−0.0014 (2)
Cu1	0.0450 (6)	0.0545 (6)	0.0418 (5)	−0.0078 (5)	0.0160 (4)	0.0006 (5)
C1	0.044 (4)	0.053 (5)	0.050 (5)	−0.007 (4)	0.012 (4)	0.009 (5)
C5	0.029 (3)	0.050 (5)	0.037 (4)	0.008 (3)	0.007 (3)	0.005 (4)
C4	0.042 (4)	0.044 (5)	0.048 (5)	0.013 (3)	0.013 (4)	0.014 (4)
C3	0.041 (4)	0.027 (3)	0.032 (4)	0.003 (3)	0.010 (3)	0.001 (3)
C2	0.063 (6)	0.049 (5)	0.032 (4)	0.006 (4)	0.019 (4)	−0.002 (4)
O3	0.078 (5)	0.088 (6)	0.051 (4)	−0.022 (4)	0.026 (4)	−0.006 (4)
O2	0.064 (4)	0.056 (4)	0.036 (3)	0.015 (3)	0.013 (3)	0.009 (3)
O1	0.065 (4)	0.072 (5)	0.055 (4)	0.019 (4)	0.033 (3)	0.012 (3)
N3	0.047 (4)	0.046 (4)	0.038 (4)	0.004 (3)	0.015 (3)	0.002 (3)
C6	0.036 (4)	0.049 (5)	0.036 (4)	−0.001 (3)	0.006 (3)	0.001 (3)
N1	0.049 (4)	0.046 (4)	0.029 (3)	0.008 (3)	0.014 (3)	0.006 (3)
N2	0.054 (4)	0.044 (4)	0.035 (3)	0.001 (4)	−0.001 (3)	−0.003 (3)

Geometric parameters (Å, º) top

I1—Cu1ⁱ	2.7063 (13)	C3—C2	1.339 (11)
I1—Cu1	2.7216 (13)	C3—N1	1.381 (10)
I2—Cu1	2.6225 (12)	C2—H2	0.9300
I3—Cu1	2.6433 (11)	C2—N2	1.383 (12)
C1—H1	0.9300	O3—H3D	0.8634
C1—N1	1.303 (11)	O3—H3E	0.8224
C1—N2	1.303 (11)	O2—C6	1.202 (12)
C5—H5	0.9800	O1—H1A	0.8200
C5—C4	1.542 (13)	O1—C6	1.308 (12)
C5—N3	1.498 (11)	N3—H3A	0.8900
C5—C6	1.527 (11)	N3—H3B	0.8900
C4—H4A	0.9700	N3—H3C	0.8900
C4—H4B	0.9700	N1—H1B	0.8600
C4—C3	1.511 (12)	N2—H2A	0.8600

Cu1ⁱ—I1—Cu1	125.80 (3)	C2—C3—N1	105.7 (7)
I1ⁱⁱ—Cu1—I1	109.20 (4)	N1—C3—C4	121.6 (7)
I2—Cu1—I1	107.70 (4)	C3—C2—H2	126.6
I2—Cu1—I1ⁱⁱ	109.68 (5)	C3—C2—N2	106.8 (7)
I2—Cu1—I3	106.19 (4)	N2—C2—H2	126.6
I3—Cu1—I1ⁱⁱ	110.75 (4)	H3D—O3—H3E	103.6
I3—Cu1—I1	113.21 (5)	C6—O1—H1A	109.5
N1—C1—H1	125.8	C5—N3—H3A	109.5
N2—C1—H1	125.8	C5—N3—H3B	109.5
N2—C1—N1	108.3 (8)	C5—N3—H3C	109.5
C4—C5—H5	107.8	H3A—N3—H3B	109.5
N3—C5—H5	107.8	H3A—N3—H3C	109.5
N3—C5—C4	111.2 (7)	H3B—N3—H3C	109.5
N3—C5—C6	108.4 (7)	O2—C6—C5	122.6 (8)
C6—C5—H5	107.8	O2—C6—O1	125.9 (8)
C6—C5—C4	113.7 (7)	O1—C6—C5	111.5 (8)
C5—C4—H4A	108.3	C1—N1—C3	110.0 (7)
C5—C4—H4B	108.3	C1—N1—H1B	125.0
H4A—C4—H4B	107.4	C3—N1—H1B	125.0
C3—C4—C5	116.0 (7)	C1—N2—C2	109.2 (7)
C3—C4—H4A	108.3	C1—N2—H2A	125.4
C3—C4—H4B	108.3	C2—N2—H2A	125.4
C2—C3—C4	132.6 (8)

C5—C4—C3—C2	73.1 (12)	N3—C5—C4—C3	63.6 (9)
C5—C4—C3—N1	−111.8 (9)	N3—C5—C6—O2	−0.1 (11)
C4—C5—C6—O2	124.1 (9)	N3—C5—C6—O1	−179.7 (8)
C4—C5—C6—O1	−55.5 (10)	C6—C5—C4—C3	−59.0 (10)
C4—C3—C2—N2	176.1 (8)	N1—C1—N2—C2	0.4 (13)
C4—C3—N1—C1	−176.5 (8)	N1—C3—C2—N2	0.5 (10)
C3—C2—N2—C1	−0.6 (12)	N2—C1—N1—C3	−0.1 (12)
C2—C3—N1—C1	−0.3 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3D···I3ⁱⁱⁱ	0.86	3.02	3.768 (8)	146
O3—H3E···I2	0.82	3.12	3.938 (7)	177
O1—H1A···O3^iv	0.82	1.81	2.605 (10)	162
N3—H3A···I3ⁱⁱ	0.89	2.69	3.571 (8)	169
N3—H3B···I2^v	0.89	2.75	3.601 (8)	160
N3—H3C···I2	0.89	2.79	3.596 (7)	152
N1—H1B···I1ⁱⁱ	0.86	2.81	3.516 (7)	141
N2—H2A···O2^vi	0.86	1.97	2.804 (9)	163
C4—H4A···I2^vii	0.97	2.88	3.716 (9)	146

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

Selected octahedral distortion parameters top

	L-HisH₂[CuI₃]·H₂O^a	1D-(Npipz)₂Cu₂I₆^b	[1,2-PDA]CuI₃^c	[1,3-PDA]CuI₃^d
DI(AX)	0.0152	0.00941	0.00927	0.02204
DI(XAX)	0.01608	0.04301	0.02587	0.03077
DI(XX)	0.01615	0.03742	0.01557	0.01237
τ₄	0.965	0.937	0.941	0.931
τ₄^'	0.957	0.934	0.935	0.914

(a) The title compound (1); (b) Carignan et al. (2024); (c) Du et al. (2023); (d) Zhang et al. (2024).

Acknowledgements

The authors are grateful to the FAIRE programme provided by the Cambridge Crystallographic Data Centre (CCDC) for the opportunity to use the Cambridge Structural Database (CSD) and associated software. VYS acknowledges the II European Chemistry School for Ukrainians.

Funding information

Funding for this research was provided by: Ministry of Education and Science of Ukraine (grant No. 24BF037-01M).

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