Three-dimensional organic–inorganic hybrid sodium halide perovskite: C4H12N2·NaI3 and a hydrogen-bonded supra­molecular three-dimensional network in 3C4H12N2·NaI4·3I·H2O

Chen, X.-G.; Gao, J.-X.; Hua, X.-N.; Liao, W.-Q.

doi:10.1107/S2053229618006885

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 74| Part 6| June 2018| Pages 728-733

https://doi.org/10.1107/S2053229618006885

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Three-dimensional organic–inorganic hybrid sodium halide perovskite: C₄H₁₂N₂·NaI₃ and a hydrogen-bonded supramolecular three-dimensional network in 3C₄H₁₂N₂·NaI₄·3I·H₂O

Xiao-Gang Chen,^a Ji-Xing Gao,^a Xiu-Ni Hua ^a and Wei-Qiang Liao ^a,^b ^*

^aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China, and ^bCollege of Chemistry, Nanchang University, Nanchang 330031, People's Republic of China
^*Correspondence e-mail: weiqiangliao@seu.edu.cn

Edited by H. Shepherd, University of Canterbury, England (Received 3 March 2018; accepted 4 May 2018; online 23 May 2018)

The rational selection of ligands is vitally important in the construction of new organic–inorganic hybrid three-dimensional perovskite complexes. As part of an exploration of perovskite-type materials, two new Na–I compounds based on the piperazine ligand, namely poly[piperazinediium [tri-μ-iodido-sodium]], {(C₄H₁₂N₂)[NaI₃]}_n, 1, and catena-poly[tris(piperazinediium) [[triiodidosodium]-μ-iodido] triiodide monohydrate], {(C₄H₁₂N₂)₃[NaI₄]I₃·H₂O}_n, 2, have been synthesized by adjusting the stoichiometric ratio of sodium iodide and piperazine, and were characterized by single-crystal X-ray diffraction. In the crystal structures of 1 and 2, each Na^I cation is linked to six I atoms, but the compounds show completely different configurations. In 1, the structure includes a perovskite-like array of vertex-sharing NaI₆ octahedra stretching along the direction of the three axes, and each piperazinediium dication is enclosed in the NaI₃ perovskite cage. However, in 2, each Na^I atom bridges a single I atom to form a one-dimensional linear chain, and complex intermolecular hydrogen bonds connect these one-dimensional chains into a three-dimensional supramolecular network.

Keywords: three-dimensional perovskite; organic–inorganic hybrid; sodium halides; iodide; hydrogen bonds; crystal structure.

CCDC references: 1826738; 1826739

1. Introduction

In recent decades, three-dimensional organic–inorganic hybrid perovskites have been of interest to researchers, not only for their remarkable structural variability and highly tunable properties, but also for their rich physical properties, such as superconductivity, ionic conductivity and ferroelectric related properties (Jin et al., 2009 ; Saparov & Mitzi, 2016 ; Veldhuis et al., 2016 ). Such hybrid perovskites have a simple generic formula of AMX₃ (A = organic cation, M = metal cation and X = halogen anion) and the structural characteristic of corner-sharing MX₆ octahedra. Among them, there have been a large number of reports on the halometallates of Pb^II and Sn^II ions because of their superior semiconducting properties, but related systems containing alkali metal halides are rare (Lee et al., 2003 ; Shi et al., 2017 ; Liao et al., 2016b ; Galkowski et al., 2016 ; Yang et al., 2015 ; Liao et al., 2016a ). To be precise, the first alkali metal halide perovskites, RMCl₃ (R = piperazine and M = K, Rb and Cs), were found less than ten years ago (Paton & Harrison, 2010 ). In recent years, due to the development of molecular ferroelectric materials (You et al., 2017 ; Xu et al., 2017 ; Liao et al., 2017 ), three-dimensional alkali metal halide perovskites have attracted the attention of researchers again. Just last year, Xiong and co-workers reported two high-T_c three-dimensional perovskite ferroelectric materials, i.e. [3-ammoniopyrrolidinium]·RbBr₃ and [N-methyl-1,4-diazoniabicyclo[2.2.2]octane]·RbI₃ (Pan et al., 2017 ; Zhang et al., 2017 ).

Following on from this work, we report the new three-dimensional organic–inorganic hybrid perovskite C₄H₁₂N₂·NaI₃ (1). In addition, considering that the dimensionality of three-dimensional perovskites can often be switched by alteration of the experimental conditions (e.g. CH₃NH₃·PbI₃; Jodlowski et al., 2016 ), we obtained a new compound, i.e. 3C₄H₁₂N₂·NaI₄·3I·H₂O (2) with a peculiar one-dimensional [NaI₅]⁴⁻ linear chain and a three-dimensional hydrogen-bonded supramolecular network by adjusting the stoichiometry of piperazine and sodium iodide.

2. Experimental

2.1. Synthesis and crystallization

2.1.1. Synthesis of C₄H₁₂N₂·NaI₃, (1)

An aqueous solution (20 ml) of sodium iodide (1.49 g, 10 mmol) was added dropwise to an equimolar ratio of piperazine (0.86 g, 10 mmol) in water (5 ml) with stirring. The solution was then filtered to remove insoluble impurities. Yellow block-shaped crystals of 1 suitable for X-ray diffraction were obtained by slow volatilization of the aqueous solution at 330 K after 2 d.

2.1.2. Synthesis of 3C₄H₁₂N₂·NaI₄·3I·H₂O, (2)

An aqueous solution (20 ml) of sodium iodide (0.75 g, 5 mmol) was added dropwise to an aqueous solution (5 ml) of piperazine (1.29 g, 15 mmol). The solution was stirred for 20 min and then filtered to remove insoluble impurities. Yellow needle-shaped crystals of 2 were obtained by slow volatilization of the aqueous solution at 330 K after 2 d.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to O atoms were located from difference Fourier maps and refined with an O—H distance restraint of 0.85 (1) Å. Other H atoms were placed in idealized positions and included as riding, with C—H = 0.97 Å (methylene) or N—H = 0.89 Å. U_iso(H) values were set at 1.2U_eq(C,N) for methylene and piperazinediium, and at 1.5U_eq(O) of water H atoms.

Table 1
Experimental details

	1	2
Crystal data
Chemical formula	(C₄H₁₂N₂)[NaI₃]	(C₄H₁₂N₂)₃[NaI₄]I₃·H₂O
M_r	491.85	1193.77
Crystal system, space group	Monoclinic, C2/c	Monoclinic, P2₁/n
Temperature (K)	293	293
a, b, c (Å)	9.842 (6), 9.309 (6), 12.538 (8)	12.186 (2), 22.828 (5), 12.214 (2)
β (°)	93.450 (9)	111.89 (3)
V (Å³)	1146.6 (13)	3152.7 (12)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	8.16	6.92
Crystal size (mm)	0.38 × 0.28 × 0.20	0.38 × 0.28 × 0.20

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008 )
T_min, T_max	0.080, 0.195	0.112, 0.251
No. of measured, independent and observed [I > 2σ(I)] reflections	3288, 1311, 1153	20677, 7234, 4432
R_int	0.083	0.075
(sin θ/λ)_max (Å⁻¹)	0.648	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.165, 1.03	0.085, 0.142, 1.09
No. of reflections	1311	7234
No. of parameters	48	252
No. of restraints	0	2
H-atom treatment	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.80, −1.66	1.23, −1.05
Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), SHELXL2014 (Sheldrick, 2015) and DIAMOND (Brandenburg & Putz, 2005 ).

3. Results and discussion

3.1. Structure of C₄H₁₂N₂·NaI₃, (1)

Compound 1 crystallizes in the monoclinic system (space group C2/c) and exhibits the three-dimensional perovskite framework. The asymmetry unit (Fig. 1) includes one Na^I cation located on a twofold axis, one half of a piperazinediium dication located about a centre of inversion and two iodide ions attached to the Na^I cation. As shown in Fig. 2, 1 is different from C₄H₁₂N₂·KCl₃·H₂O, due to the Na—I bond length being less than that of K—Cl (Table 2); the NaI₆ perovskite cage encloses one piperazinediium cation and prevents the entry of water molecules. In addition, the H atoms on the C and N atoms of piperazinediium form weak hydrogen bonds with the I atoms in the cage, resulting in significant octahedral tilting (Fig. 3). According to Glazer's 23 tilt system (Glazer, 1972 , 1975 ), the octahedral tilting of compound 1 should belong to the `a⁻b⁻b⁻' type. Detailed information of the C—H⋯I and N—H⋯I hydrogen bonds is given in Table 3. It can be seen from the packing diagram (Fig. 4) that the piperazinediium cations in the ab plane are arranged along the same direction; however, the piperazinediium cations along the c axis are arranged in a zigzag manner, viz. `\/\'. In summary, compound 1 has the familiar three-dimensional perovskite framework structure, where the piperazinediium cations are confined in the cavities enclosed by corner-sharing NaI₆ octahedra and stabilized by C—H⋯I and N—H⋯I hydrogen bonds.

Table 2
Selected geometric parameters (Å, °) for 1

C2—C1	1.504 (14)	Na1—I2	3.156 (2)
C2—N1ⁱ	1.532 (14)	Na1—I1	3.325 (5)
N1—C1	1.456 (13)

Na1—I1—Na1ⁱⁱ	169.12 (12)	I2—Na1—I1^v	84.40 (9)
Na1ⁱⁱⁱ—I2—Na1	180.0	I2^iv—Na1—I1^vi	84.40 (9)
N1—C1—C2	111.6 (8)	I1^vi—Na1—I1^v	100.45 (19)
I2^iv—Na1—I1	101.40 (10)	I1—Na1—I1^v	169.12 (12)
I2—Na1—I1^iv	101.40 (10)	I1^iv—Na1—I1^vi	169.12 (12)
I2^iv—Na1—I2	166.6 (3)	I1^iv—Na1—I1	86.15 (18)
I2—Na1—I1	88.41 (8)	I1^iv—Na1—I1^v	87.29 (5)
I2^iv—Na1—I1^iv	88.41 (8)	I1—Na1—I1^vi	87.29 (5)
I2^iv—Na1—I1^v	87.06 (9)	C1—C2—N1ⁱ	108.4 (9)
I2—Na1—I1^vi	87.06 (9)	C1—N1—C2ⁱ	110.2 (8)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) -x+1, -y+1, -z+1; (iv) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (vi) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 3
Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1D⋯I1ⁱ	0.97	3.12	3.937 (11)	143
C1—H1C⋯I2	0.97	3.23	3.914 (11)	129
C1—H1C⋯I1^vii	0.97	3.14	3.790 (10)	126
C2—H2B⋯I1^viii	0.97	3.17	3.930 (11)	136
C2—H2A⋯I1^iv	0.97	3.23	3.930 (13)	131
N1—H1B⋯I1ⁱ	0.89	2.80	3.628 (10)	156
N1—H1A⋯I2ⁱⁱ	0.89	3.11	3.677 (8)	123
N1—H1A⋯I1^vii	0.89	3.14	3.746 (8)	127
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (vii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (viii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
A view of the asymmetric unit in compound 1. All H atoms have been omitted for clarity. [Symmetry codes: (i) −x + 1, −y + 2, −z + 1; (ii) x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , z; (iii) −x + 1, −y + 1, −z + 1; (iv) −x + 1, y, −z + $[{1\over 2}]$ ; (v) x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , z; (vi) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

Figure 2
(a) A view of the three-dimensional perovskite cage of C₄H₁₂N₂·KCl₃·H₂O. (b) A view of the three-dimensional perovskite cage of compound 1.

Figure 3
The hydrogen bonds (dashed lines) in 1 of the C and N atoms of the piperazinediium cation with the I atoms of the NaI₆ octahedra. [Symmetry codes: (i) −x + 1, −y + 2, −z + 1; (ii) x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , z; (iv) −x + 1, y, −z + $[{1\over 2}]$ ; (vii) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (viii) x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ .]

Figure 4
A packing view of compound 1, showing the three-dimensional perovskite structure.

3.2. Structure of 3C₄H₁₂N₂·NaI₄·3I·H₂O, (2)

Compound 2 crystallizes in the monoclinic system (space group P2₁/n) but displays a one-dimensional linear chain-like geometry. The asymmetry unit contains three whole piperazinediium cations, one lattice water molecule, two dissociated iodide ions and one Na atom in a glide plane coordinated with five iodide ions. As can be seen from Fig. 5, each Na atom is coordinated by six I atoms, and two Na atoms are bridged by one I atom and extended in an infinite manner along a horizontal direction, thus presenting a one-dimensional linear chain. As shown in Table 4, the length of the Na—I bonds are within the reasonable range 3.180 (5)–3.515 (6) Å and the I—Na—I angles are in the ranges 84.32 (14)–94.56 (16) and 176.97 (18)–178.20 (17)°. It is worth noting that there are very complex hydrogen bonds in compound 2. These hydrogen bonds can be divided roughly into four types (Fig. 6): (i) piperazinediium N atoms act as donors and water O atoms act as acceptors in N—H⋯O hydrogen bonds (red dashed lines); (ii) water O atoms act as donors and I atoms in the metal halide chain act as acceptors in O—H⋯I hydrogen bonds (green dashed lines); (iii) piperazinediium N atoms act as donors and bridging I atoms act as acceptors in N—H⋯I hydrogen bonds (yellow dashed lines); (iv) piperazinediium N atoms act as donors and the free I atoms act as acceptors in N—H⋯I hydrogen bonds (blue dashed lines). Detailed information of the hydrogen bonds is given in Table 5. As shown in Fig. 7, the water H atoms form hydrogen bonds with the I atoms on the two sides of the NaI₅ chain (i.e. O1ⁱ—H1⋯I5ⁱⁱ and O1ⁱ—H2⋯I2^ix; Table 5), thus forming a two-dimensional network on the ac plane. On the other hand, the free I atoms (i.e. I6 and I7) and the bridging I atoms (i.e. I3) form N—H⋯I hydrogen bonds with the H atoms of the piperazinediium N atoms, which extends the two-dimensional network into a three-dimensional hydrogen-bonded supramolecular network (Fig. 8).

Table 4
Selected geometric parameters (Å, °) for 2

C1—N1	1.515 (14)	C9—C10	1.480 (18)
C1—C2	1.511 (18)	C10—N6	1.477 (13)
C2—N2	1.451 (16)	C11—C12	1.514 (17)
C3—N1	1.481 (14)	C11—N5	1.487 (13)
C3—C4	1.519 (16)	C12—N6	1.509 (13)
C4—N2	1.447 (17)	I1—Na1	3.419 (6)
C5—C6	1.527 (16)	I2—Na1	3.205 (5)
C5—N3	1.472 (13)	I3—Na1	3.381 (5)
C6—N4	1.452 (14)	I3—Na1ⁱ	3.456 (5)
C7—C8	1.532 (16)	I4—Na1	3.515 (6)
C7—N3	1.475 (13)	I5—Na1	3.180 (5)
C8—N4	1.486 (14)	Na1—I3ⁱⁱ	3.456 (5)
C9—N5	1.493 (14)

C10—N6—C12	111.1 (9)	I3—Na1—I1	91.38 (13)
C10—C9—N5	110.8 (10)	I5—Na1—I4	94.12 (14)
C11—N5—C9	110.5 (8)	I5—Na1—I3ⁱⁱ	92.63 (13)
C2—C1—N1	111.0 (10)	I5—Na1—I1	86.95 (13)
C3—N1—C1	109.5 (10)	I5—Na1—I3	88.73 (12)
C4—N2—C2	114.6 (12)	I5—Na1—I2	177.4 (2)
C5—N3—C7	112.7 (10)	N1—C3—C4	113.1 (10)
C6—N4—C8	111.8 (10)	N2—C4—C3	109.0 (11)
I1—Na1—I4	178.20 (17)	N2—C2—C1	108.3 (11)
I1—Na1—I3ⁱⁱ	91.40 (13)	N3—C7—C8	110.8 (10)
I2—Na1—I4	84.32 (12)	N3—C5—C6	110.7 (10)
I2—Na1—I3ⁱⁱ	89.46 (12)	N4—C8—C7	105.3 (11)
I2—Na1—I1	94.56 (14)	N4—C6—C5	106.4 (10)
I2—Na1—I3	89.12 (13)	N5—C11—C12	111.3 (10)
I3ⁱⁱ—Na1—I4	90.00 (12)	N6—C12—C11	109.0 (10)
I3—Na1—I4	87.19 (13)	N6—C10—C9	110.8 (10)
I3—Na1—I3ⁱⁱ	176.97 (18)	Na1—I3—Na1ⁱ	176.87 (7)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Table 5
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6^vi—H6B⋯I6^vi	0.89	2.99	3.626 (11)	130
N6^vi—H6A⋯O1ⁱⁱⁱ	0.89	1.97	2.856 (16)	175
N5^vi—H5B⋯O1ⁱⁱ	0.89	1.99	2.878 (15)	178
N5^vi—H5A⋯I7^xii	0.89	2.83	3.557 (10)	140
N4^v—H4B⋯I6^xiii	0.89	2.55	3.440 (12)	175
N4^v—H4A⋯I5^vii	0.89	2.99	3.663 (13)	134
N4^v—H4A⋯I1^vii	0.89	3.25	3.881 (14)	130
N3^v—H3B⋯I4^iv	0.89	3.22	3.748 (11)	121
N3^v—H3B⋯I3^ix	0.89	3.22	3.767 (12)	122
N3^v—H3B⋯I2^ix	0.89	3.04	3.610 (11)	124
N3^v—H3A⋯I7^xii	0.89	2.68	3.543 (12)	165
N2^iv—H2B⋯I2^ix	0.89	3.14	3.867 (16)	140
N2^iv—H2A⋯I3^ix	0.89	2.70	3.405 (13)	138
N1^iv—H1B⋯I6^xi	0.89	2.62	3.496 (11)	169
N1^iv—H1A⋯I7^xii	0.89	2.92	3.613 (11)	136
N1^iv—H1A⋯I1^viii	0.89	3.32	3.804 (11)	117
O1ⁱ—H2⋯I2^ix	0.85 (1)	2.68 (9)	3.471 (12)	155 (18)
O1ⁱ—H1⋯I5ⁱⁱ	0.85 (1)	2.69 (4)	3.501 (11)	161 (11)
Symmetry codes: (i) x-2, y, z; (ii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x, -y+2, -z+1; (iv) -x-1, -y+1, -z+1; (v) $[x-{\script{3\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (vi) x-2, y+1, z; (vii) $[-x-{\script{1\over 2}}]$ , $[y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (viii) $[x-{\script{3\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ix) -x-1, -y+1, -z+1; (x) $[-x-{\script{3\over 2}}, y+{\script{1\over 2}}]$ , $[-z+{\script{1\over 2}}]$ ; (xi) $[x-{\script{5\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (xii) x-2, y+1, z; (xiii) $[x-{\script{3\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 5
A view of the asymmetric unit in compound 2. All H atoms have been omitted for clarity. [Symmetry codes: (i) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (ii) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ .]

Figure 6
A partial view of the crystal packing of compound 2, showing the intermolecular N—H⋯I (blee and yellow dashed lines), N—H⋯O (red dashed lines) and O—H⋯I (green dashed lines) hydrogen bonds. All H atoms on C atoms have been omitted for clarity. [Symmetry codes: (i) x − 2, y, z; (ii) −x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iii) −x, −y + 2, −z + 1; (iv) −x − 1, −y + 1, −z + 1; (v) x − $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + $[{1\over 2}]$ ; (vi) x − 2, y + 1, z; (vii) −x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (viii) x − $[{3\over 2}]$ , −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (ix) −x − 1, −y + 1, −z + 1; (x) −x − $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (xi) x − $[{5\over 2}]$ , −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (xii) x − 2, y + 1, z; (xiii) x − $[{3\over 2}]$ , −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ .]

Figure 7
The hydrogen bonds of the O—H⋯I (green dashed lines) and N—H⋯O (red dashed lines) types in 2, showing the two-dimensional network on the ac plane.

Figure 8
A packing view of compound 2, showing the three-dimensional hydrogen-bonded network.

4. Summary

Two new organic–inorganic hybrid sodium halides have been synthesized by adjusting the stoichiometric ratio of sodium iodide and piperazine. C₄H₁₂N₂·NaI₃, 1, presents an interesting three-dimensional perovskite structure. However, compound 3C₄H₁₂N₂·NaI₄·3I·H₂O, 2, features a singular three-dimensional hydrogen-bonded network. The different structures of compounds 1 and 2 show that the stoichiometric ratio plays a key role in the synthesis of various frameworks.

Supporting information

CCDC references: 1826738; 1826739

Crystal structure: contains datablocks C2C, C, global. DOI: https://doi.org/10.1107/S2053229618006885/qp3008sup1.cif

Structure factors: contains datablock C2C. DOI: https://doi.org/10.1107/S2053229618006885/qp3008C2Csup2.hkl

Structure factors: contains datablock C. DOI: https://doi.org/10.1107/S2053229618006885/qp3008Csup3.hkl

Computing details top

For both structures, data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) for C2C; SHELXL2014/7 (Sheldrick, 2015) for C. For both structures, molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Poly[piperazinediium [tri-µ-iodido-sodium]] (C2C) top

Crystal data top

(C₄H₁₂N₂)[NaI₃]	F(000) = 880
M_r = 491.85	D_x = 2.849 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.842 (6) Å	Cell parameters from 1311 reflections
b = 9.309 (6) Å	θ = 3.0–27.4°
c = 12.538 (8) Å	µ = 8.16 mm⁻¹
β = 93.450 (9)°	T = 293 K
V = 1146.6 (13) Å³	Thick sheet, pale yellow
Z = 4	0.38 × 0.28 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	1153 reflections with I > 2σ(I)
ω scans	R_int = 0.083
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	θ_max = 27.4°, θ_min = 3.0°
T_min = 0.080, T_max = 0.195	h = −12→12
3288 measured reflections	k = −12→11
1311 independent reflections	l = −13→16

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.058	w = 1/[σ²(F_o²) + (0.0991P)² + 35.0953P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.165	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 1.80 e Å⁻³
1311 reflections	Δρ_min = −1.66 e Å⁻³
48 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015)
0 restraints	Extinction coefficient: 0.0060 (7)

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
C2	0.6137 (11)	0.9015 (13)	0.5161 (10)	0.038 (2)
H2A	0.5962	0.8325	0.4589	0.045*
H2B	0.6967	0.8737	0.5564	0.045*
N1	0.3706 (8)	0.9477 (9)	0.5305 (7)	0.0297 (17)
H1A	0.3033	0.9475	0.5748	0.036*
H1B	0.3496	0.8858	0.4780	0.036*
C1	0.4967 (10)	0.9034 (11)	0.5879 (7)	0.030 (2)
H1C	0.4850	0.8082	0.6175	0.036*
H1D	0.5173	0.9690	0.6468	0.036*
Na1	0.5000	0.5394 (8)	0.2500	0.0416 (14)
I1	0.27208 (6)	0.80033 (7)	0.26933 (5)	0.0303 (3)
I2	0.5000	0.5000	0.5000	0.0300 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.031 (5)	0.040 (5)	0.043 (6)	0.011 (4)	0.007 (4)	0.016 (5)
N1	0.022 (4)	0.032 (4)	0.035 (4)	−0.005 (3)	0.007 (3)	0.008 (3)
C1	0.039 (5)	0.034 (5)	0.018 (4)	−0.003 (4)	0.004 (3)	0.012 (4)
Na1	0.053 (4)	0.046 (4)	0.027 (3)	0.000	0.008 (3)	0.000
I1	0.0337 (4)	0.0296 (4)	0.0278 (4)	−0.0045 (2)	0.0037 (3)	−0.0039 (2)
I2	0.0287 (5)	0.0368 (5)	0.0248 (5)	−0.0031 (3)	0.0036 (3)	−0.0013 (3)

Geometric parameters (Å, º) top

C2—C1	1.504 (14)	C1—H1D	0.9700
C2—N1ⁱ	1.532 (14)	Na1—I2ⁱⁱ	3.156 (2)
C2—H2A	0.9700	Na1—I2	3.156 (2)
C2—H2B	0.9700	Na1—I1ⁱⁱ	3.325 (5)
N1—C1	1.456 (13)	Na1—I1	3.325 (5)
N1—C2ⁱ	1.532 (14)	Na1—I1ⁱⁱⁱ	3.479 (5)
N1—H1A	0.8900	Na1—I1^iv	3.479 (5)
N1—H1B	0.8900	I1—Na1^v	3.479 (5)
C1—H1C	0.9700	I2—Na1^vi	3.156 (2)

Na1—I1—Na1^v	169.12 (12)	C1—C2—N1ⁱ	108.4 (9)
Na1^vi—I2—Na1	180.0	C1—C2—H2A	110.0
N1—C1—C2	111.6 (8)	N1ⁱ—C2—H2A	110.0
I2ⁱⁱ—Na1—I1	101.40 (10)	C1—C2—H2B	110.0
I2—Na1—I1ⁱⁱ	101.40 (10)	N1ⁱ—C2—H2B	110.0
I2ⁱⁱ—Na1—I2	166.6 (3)	H2A—C2—H2B	108.4
I2—Na1—I1	88.41 (8)	C1—N1—C2ⁱ	110.2 (8)
I2ⁱⁱ—Na1—I1ⁱⁱ	88.41 (8)	C1—N1—H1A	109.6
I2ⁱⁱ—Na1—I1^iv	87.06 (9)	C2ⁱ—N1—H1A	109.6
I2—Na1—I1ⁱⁱⁱ	87.06 (9)	C1—N1—H1B	109.6
I2—Na1—I1^iv	84.40 (9)	C2ⁱ—N1—H1B	109.6
I2ⁱⁱ—Na1—I1ⁱⁱⁱ	84.40 (9)	H1A—N1—H1B	108.1
I1ⁱⁱⁱ—Na1—I1^iv	100.45 (19)	N1—C1—H1C	109.3
I1—Na1—I1^iv	169.12 (12)	C2—C1—H1C	109.3
I1ⁱⁱ—Na1—I1ⁱⁱⁱ	169.12 (12)	N1—C1—H1D	109.3
I1ⁱⁱ—Na1—I1	86.15 (18)	C2—C1—H1D	109.3
I1ⁱⁱ—Na1—I1^iv	87.29 (5)	H1C—C1—H1D	108.0
I1—Na1—I1ⁱⁱⁱ	87.29 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1D···I1ⁱ	0.97	3.12	3.937 (11)	143
C1—H1C···I2	0.97	3.23	3.914 (11)	129
C1—H1C···I1^vii	0.97	3.14	3.790 (10)	126
C2—H2B···I1^viii	0.97	3.17	3.930 (11)	136
C2—H2A···I1ⁱⁱ	0.97	3.23	3.930 (13)	131
N1—H1B···I1ⁱ	0.89	2.80	3.628 (10)	156
N1—H1A···I2^v	0.89	3.11	3.677 (8)	123
N1—H1A···I1^vii	0.89	3.14	3.746 (8)	127

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

catena-Poly[tris(piperazinediium) [µ-iodido-triiodidosodium] triiodide monohydrate] (C) top

Crystal data top

(C₄H₁₂N₂)₃[NaI₄]I₃·H₂O	F(000) = 2168
M_r = 1193.77	D_x = 2.515 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.186 (2) Å	Cell parameters from 7234 reflections
b = 22.828 (5) Å	θ = 3.0–27.5°
c = 12.214 (2) Å	µ = 6.92 mm⁻¹
β = 111.89 (3)°	T = 293 K
V = 3152.7 (12) Å³	Bar, pale yellow
Z = 4	0.38 × 0.28 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	4432 reflections with I > 2σ(I)
ω scans	R_int = 0.075
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	θ_max = 27.5°, θ_min = 3.1°
T_min = 0.112, T_max = 0.251	h = −12→15
20677 measured reflections	k = −29→29
7234 independent reflections	l = −15→15

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)] = 0.085	w = 1/[σ²(F_o²) + (0.0274P)² + 33.3838P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.142	(Δ/σ)_max = 0.024
S = 1.09	Δρ_max = 1.23 e Å⁻³
7234 reflections	Δρ_min = −1.05 e Å⁻³
252 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015)
2 restraints	Extinction coefficient: 0.0060 (7)

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.5220 (12)	0.0196 (6)	0.6547 (11)	0.056 (4)
H1C	0.5688	−0.0046	0.6232	0.068*
H1D	0.4545	0.0342	0.5889	0.068*
C2	0.5959 (12)	0.0706 (6)	0.7215 (13)	0.059 (4)
H2C	0.6662	0.0564	0.7846	0.071*
H2D	0.6203	0.0944	0.6689	0.071*
C3	0.4140 (10)	0.0205 (6)	0.7881 (11)	0.051 (4)
H3C	0.3933	−0.0026	0.8442	0.061*
H3D	0.3411	0.0335	0.7270	0.061*
C4	0.4843 (12)	0.0737 (6)	0.8507 (12)	0.060 (4)
H4C	0.4349	0.0990	0.8768	0.072*
H4D	0.5514	0.0614	0.9195	0.072*
C5	0.5148 (9)	0.5834 (5)	0.1450 (10)	0.042 (3)
H5C	0.5565	0.6192	0.1791	0.050*
H5D	0.5100	0.5809	0.0640	0.050*
C6	0.5831 (10)	0.5308 (6)	0.2146 (10)	0.048 (3)
H6C	0.5446	0.4946	0.1790	0.058*
H6D	0.6632	0.5306	0.2159	0.058*
C7	0.3947 (11)	0.5840 (6)	0.2674 (9)	0.046 (3)
H7A	0.3138	0.5823	0.2638	0.056*
H7B	0.4304	0.6197	0.3085	0.056*
C8	0.4636 (10)	0.5310 (6)	0.3357 (10)	0.051 (4)
H8A	0.4668	0.5313	0.4162	0.061*
H8B	0.4267	0.4948	0.2981	0.061*
C9	0.7130 (11)	0.2167 (6)	0.5849 (11)	0.054 (4)
H9A	0.6342	0.2104	0.5848	0.065*
H9B	0.7667	0.1902	0.6418	0.065*
C10	0.7496 (11)	0.2779 (6)	0.6197 (11)	0.052 (4)
H10A	0.6930	0.3046	0.5657	0.062*
H10B	0.7504	0.2851	0.6983	0.062*
C11	0.8322 (10)	0.2155 (6)	0.4619 (11)	0.050 (4)
H11A	0.8300	0.2085	0.3828	0.060*
H11B	0.8890	0.1887	0.5149	0.060*
C12	0.8713 (11)	0.2779 (6)	0.4977 (10)	0.048 (3)
H12A	0.9508	0.2837	0.4996	0.058*
H12B	0.8189	0.3050	0.4409	0.058*
H1	0.984 (8)	0.803 (4)	0.168 (8)	0.03 (3)*
H2	0.940 (14)	0.810 (4)	0.233 (13)	0.12 (7)*
I1	0.16282 (7)	0.35776 (4)	0.65969 (7)	0.0437 (2)
I2	0.19192 (8)	0.14533 (4)	0.64746 (8)	0.0530 (3)
I3	0.04389 (7)	0.24624 (3)	0.29429 (7)	0.0400 (2)
I4	0.41057 (7)	0.14436 (4)	0.41939 (7)	0.0459 (2)
I5	0.38048 (8)	0.35852 (4)	0.42790 (8)	0.0544 (3)
I6	0.77355 (7)	0.43764 (4)	0.52414 (7)	0.0412 (2)
I7	0.77778 (7)	0.05265 (4)	0.52459 (7)	0.0420 (2)
N1	0.4792 (9)	−0.0172 (5)	0.7341 (9)	0.055 (3)
H1A	0.4320	−0.0455	0.6923	0.066*
H1B	0.5407	−0.0337	0.7904	0.066*
N2	0.5249 (12)	0.1051 (5)	0.7700 (13)	0.096 (5)
H2A	0.5673	0.1359	0.8076	0.116*
H2B	0.4622	0.1188	0.7107	0.116*
N3	0.3948 (9)	0.5853 (5)	0.1468 (9)	0.057 (3)
H3A	0.3537	0.5548	0.1066	0.068*
H3B	0.3587	0.6178	0.1107	0.068*
N4	0.5841 (10)	0.5368 (5)	0.3333 (10)	0.072 (4)
H4A	0.6138	0.5716	0.3621	0.086*
H4B	0.6309	0.5094	0.3793	0.086*
N5	0.7133 (7)	0.2041 (4)	0.4651 (7)	0.033 (2)
H5A	0.6936	0.1668	0.4466	0.040*
H5B	0.6599	0.2265	0.4119	0.040*
N6	0.8684 (8)	0.2893 (4)	0.6183 (8)	0.042 (3)
H6A	0.9210	0.2664	0.6711	0.050*
H6B	0.8884	0.3264	0.6386	0.050*
Na1	0.2893 (5)	0.2536 (2)	0.5431 (5)	0.0628 (15)
O1	0.9568 (9)	0.7784 (5)	0.2044 (9)	0.055 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.083 (10)	0.052 (9)	0.041 (8)	−0.015 (8)	0.031 (8)	−0.003 (7)
C2	0.054 (8)	0.062 (10)	0.081 (11)	0.004 (8)	0.049 (8)	0.019 (8)
C3	0.047 (7)	0.055 (9)	0.068 (9)	−0.021 (7)	0.043 (7)	−0.032 (7)
C4	0.069 (10)	0.060 (10)	0.069 (10)	−0.010 (8)	0.047 (9)	−0.013 (8)
C5	0.037 (7)	0.048 (8)	0.045 (8)	0.001 (6)	0.021 (6)	0.002 (6)
C6	0.037 (7)	0.069 (10)	0.039 (8)	0.005 (7)	0.015 (6)	−0.015 (7)
C7	0.054 (8)	0.063 (10)	0.025 (7)	0.023 (7)	0.018 (6)	0.008 (6)
C8	0.041 (7)	0.082 (11)	0.030 (7)	0.004 (7)	0.015 (6)	−0.005 (7)
C9	0.045 (8)	0.069 (10)	0.056 (9)	−0.016 (7)	0.029 (7)	−0.012 (8)
C10	0.054 (8)	0.063 (10)	0.048 (8)	−0.019 (7)	0.030 (7)	−0.023 (7)
C11	0.048 (8)	0.057 (9)	0.058 (9)	−0.018 (7)	0.033 (7)	−0.022 (7)
C12	0.056 (8)	0.055 (9)	0.040 (8)	−0.006 (7)	0.024 (7)	−0.004 (6)
I1	0.0415 (5)	0.0397 (5)	0.0435 (5)	−0.0021 (4)	0.0084 (4)	−0.0001 (4)
I2	0.0637 (6)	0.0488 (6)	0.0507 (6)	0.0036 (5)	0.0260 (5)	−0.0005 (4)
I3	0.0472 (5)	0.0315 (4)	0.0473 (5)	0.0007 (4)	0.0247 (4)	0.0015 (4)
I4	0.0398 (5)	0.0429 (5)	0.0491 (5)	−0.0039 (4)	0.0096 (4)	0.0039 (4)
I5	0.0668 (6)	0.0471 (6)	0.0530 (6)	−0.0021 (5)	0.0268 (5)	−0.0028 (5)
I6	0.0399 (4)	0.0455 (5)	0.0373 (5)	0.0053 (4)	0.0134 (4)	0.0055 (4)
I7	0.0405 (5)	0.0433 (5)	0.0419 (5)	0.0023 (4)	0.0150 (4)	0.0036 (4)
N1	0.059 (7)	0.044 (7)	0.056 (7)	−0.007 (6)	0.015 (6)	−0.004 (6)
N2	0.104 (11)	0.034 (8)	0.149 (14)	−0.027 (8)	0.046 (11)	−0.022 (9)
N3	0.066 (7)	0.044 (7)	0.065 (8)	0.015 (6)	0.030 (6)	0.013 (6)
N4	0.065 (8)	0.077 (9)	0.060 (8)	0.032 (7)	0.008 (7)	0.015 (7)
N5	0.028 (5)	0.035 (6)	0.031 (6)	−0.007 (4)	0.004 (4)	−0.011 (4)
N6	0.043 (6)	0.037 (6)	0.051 (7)	−0.023 (5)	0.025 (5)	−0.020 (5)
Na1	0.068 (3)	0.052 (3)	0.069 (4)	−0.006 (3)	0.026 (3)	0.014 (3)
O1	0.068 (6)	0.047 (6)	0.065 (7)	−0.001 (5)	0.040 (6)	0.001 (5)

Geometric parameters (Å, º) top

C1—N1	1.515 (14)	C4—H4D	0.9700
C1—C2	1.511 (18)	C5—H5C	0.9700
C2—N2	1.451 (16)	C5—H5D	0.9700
C3—N1	1.481 (14)	C6—H6C	0.9700
C3—C4	1.519 (16)	C6—H6D	0.9700
C4—N2	1.447 (17)	C7—H7A	0.9700
C5—C6	1.527 (16)	C7—H7B	0.9700
C5—N3	1.472 (13)	C8—H8A	0.9700
C6—N4	1.452 (14)	C8—H8B	0.9700
C7—C8	1.532 (16)	C9—H9A	0.9700
C7—N3	1.475 (13)	C9—H9B	0.9700
C8—N4	1.486 (14)	C10—H10A	0.9700
C9—N5	1.493 (14)	C10—H10B	0.9700
C9—C10	1.480 (18)	C11—H11A	0.9700
C10—N6	1.477 (13)	C11—H11B	0.9700
C11—C12	1.514 (17)	C12—H12A	0.9700
C11—N5	1.487 (13)	C12—H12B	0.9700
C12—N6	1.509 (13)	N1—H1A	0.8900
I1—Na1	3.419 (6)	N1—H1B	0.8900
I2—Na1	3.205 (5)	N2—H2A	0.8900
I3—Na1	3.381 (5)	N2—H2B	0.8900
I3—Na1ⁱ	3.456 (5)	N3—H3A	0.8900
I4—Na1	3.515 (6)	N3—H3B	0.8900
I5—Na1	3.180 (5)	N4—H4A	0.8900
Na1—I3ⁱⁱ	3.456 (5)	N4—H4B	0.8900
C1—H1C	0.9700	N5—H5A	0.8900
C1—H1D	0.9700	N5—H5B	0.8900
C2—H2C	0.9700	N6—H6A	0.8900
C2—H2D	0.9700	N6—H6B	0.8900
C3—H3C	0.9700	O1—H1	0.849 (10)
C3—H3D	0.9700	O1—H2	0.850 (10)
C4—H4C	0.9700

C10—N6—C12	111.1 (9)	H6C—C6—H6D	108.6
C10—C9—N5	110.8 (10)	N3—C7—H7A	109.5
C11—N5—C9	110.5 (8)	C8—C7—H7A	109.5
C2—C1—N1	111.0 (10)	N3—C7—H7B	109.5
C3—N1—C1	109.5 (10)	C8—C7—H7B	109.5
C4—N2—C2	114.6 (12)	H7A—C7—H7B	108.1
C5—N3—C7	112.7 (10)	N4—C8—H8A	110.7
C6—N4—C8	111.8 (10)	C7—C8—H8A	110.7
I1—Na1—I4	178.20 (17)	N4—C8—H8B	110.7
I1—Na1—I3ⁱⁱ	91.40 (13)	C7—C8—H8B	110.7
I2—Na1—I4	84.32 (12)	H8A—C8—H8B	108.8
I2—Na1—I3ⁱⁱ	89.46 (12)	C10—C9—H9A	109.5
I2—Na1—I1	94.56 (14)	N5—C9—H9A	109.5
I2—Na1—I3	89.12 (13)	C10—C9—H9B	109.5
I3ⁱⁱ—Na1—I4	90.00 (12)	N5—C9—H9B	109.5
I3—Na1—I4	87.19 (13)	H9A—C9—H9B	108.1
I3—Na1—I3ⁱⁱ	176.97 (18)	N6—C10—H10A	109.5
I3—Na1—I1	91.38 (13)	C9—C10—H10A	109.5
I5—Na1—I4	94.12 (14)	N6—C10—H10B	109.5
I5—Na1—I3ⁱⁱ	92.63 (13)	C9—C10—H10B	109.5
I5—Na1—I1	86.95 (13)	H10A—C10—H10B	108.1
I5—Na1—I3	88.73 (12)	N5—C11—H11A	109.4
I5—Na1—I2	177.4 (2)	C12—C11—H11A	109.4
N1—C3—C4	113.1 (10)	N5—C11—H11B	109.4
N2—C4—C3	109.0 (11)	C12—C11—H11B	109.4
N2—C2—C1	108.3 (11)	H11A—C11—H11B	108.0
N3—C7—C8	110.8 (10)	N6—C12—H12A	109.9
N3—C5—C6	110.7 (10)	C11—C12—H12A	109.9
N4—C8—C7	105.3 (11)	N6—C12—H12B	109.9
N4—C6—C5	106.4 (10)	C11—C12—H12B	109.9
N5—C11—C12	111.3 (10)	H12A—C12—H12B	108.3
N6—C12—C11	109.0 (10)	C3—N1—H1A	109.8
N6—C10—C9	110.8 (10)	C1—N1—H1A	109.8
Na1—I3—Na1ⁱ	176.87 (7)	C3—N1—H1B	109.8
C2—C1—H1C	109.4	C1—N1—H1B	109.8
N1—C1—H1C	109.4	H1A—N1—H1B	108.2
C2—C1—H1D	109.4	C4—N2—H2A	108.6
N1—C1—H1D	109.4	C2—N2—H2A	108.6
H1C—C1—H1D	108.0	C4—N2—H2B	108.6
N2—C2—H2C	110.0	C2—N2—H2B	108.6
C1—C2—H2C	110.0	H2A—N2—H2B	107.6
N2—C2—H2D	110.0	C5—N3—H3A	109.1
C1—C2—H2D	110.0	C7—N3—H3A	109.1
H2C—C2—H2D	108.4	C5—N3—H3B	109.1
N1—C3—H3C	108.9	C7—N3—H3B	109.1
C4—C3—H3C	108.9	H3A—N3—H3B	107.8
N1—C3—H3D	108.9	C6—N4—H4A	109.3
C4—C3—H3D	108.9	C8—N4—H4A	109.3
H3C—C3—H3D	107.8	C6—N4—H4B	109.3
N2—C4—H4C	109.9	C8—N4—H4B	109.3
C3—C4—H4C	109.9	H4A—N4—H4B	107.9
N2—C4—H4D	109.9	C11—N5—H5A	109.6
C3—C4—H4D	109.9	C9—N5—H5A	109.6
H4C—C4—H4D	108.3	C11—N5—H5B	109.6
N3—C5—H5C	109.5	C9—N5—H5B	109.6
C6—C5—H5C	109.5	H5A—N5—H5B	108.1
N3—C5—H5D	109.5	C10—N6—H6A	109.4
C6—C5—H5D	109.5	C12—N6—H6A	109.4
H5C—C5—H5D	108.1	C10—N6—H6B	109.4
N4—C6—H6C	110.5	C12—N6—H6B	109.4
C5—C6—H6C	110.5	H6A—N6—H6B	108.0
N4—C6—H6D	110.5	H1—O1—H2	82 (10)
C5—C6—H6D	110.5

N1—C1—C2—N2	−57.7 (15)	C1—C2—N2—C4	60.1 (16)
N1—C3—C4—N2	53.3 (17)	C6—C5—N3—C7	54.3 (14)
N3—C5—C6—N4	−57.8 (13)	C8—C7—N3—C5	−54.8 (14)
N3—C7—C8—N4	57.5 (13)	C5—C6—N4—C8	66.0 (14)
N5—C9—C10—N6	−58.0 (14)	C7—C8—N4—C6	−65.9 (13)
N5—C11—C12—N6	56.2 (13)	C12—C11—N5—C9	−56.9 (13)
C4—C3—N1—C1	−53.5 (15)	C10—C9—N5—C11	57.2 (14)
C2—C1—N1—C3	55.7 (14)	C9—C10—N6—C12	58.3 (14)
C3—C4—N2—C2	−57.2 (16)	C11—C12—N6—C10	−56.7 (13)

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) 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
N6viⁱⁱⁱ—H6B···I6viⁱⁱⁱ	0.89	2.99	3.626 (11)	130
N6viⁱⁱⁱ—H6A···O1iii^iv	0.89	1.97	2.856 (16)	175
N5viⁱⁱⁱ—H5B···O1ii^v	0.89	1.99	2.878 (15)	178
N5viⁱⁱⁱ—H5A···I7xiiⁱⁱⁱ	0.89	2.83	3.557 (10)	140
N4v^vi—H4B···I6xiii^vii	0.89	2.55	3.440 (12)	175
N4v^vi—H4A···I5vii^viii	0.89	2.99	3.663 (13)	134
N4v^vi—H4A···I1vii^viii	0.89	3.25	3.881 (14)	130
N3v^vi—H3B···I4iv^ix	0.89	3.22	3.748 (11)	121
N3v^vi—H3B···I3ix^ix	0.89	3.22	3.767 (12)	122
N3v^vi—H3B···I2ix^ix	0.89	3.04	3.610 (11)	124
N3v^vi—H3A···I7xiiⁱⁱⁱ	0.89	2.68	3.543 (12)	165
N2iv^ix—H2B···I2ix^ix	0.89	3.14	3.867 (16)	140
N2iv^ix—H2A···I3ix^ix	0.89	2.70	3.405 (13)	138
N1iv^ix—H1B···I6xi^x	0.89	2.62	3.496 (11)	169
N1iv^ix—H1A···I7xiiⁱⁱⁱ	0.89	2.92	3.613 (11)	136
N1iv^ix—H1A···I1viii^xi	0.89	3.32	3.804 (11)	117
O1i^xii—H2···I2ix^ix	0.85 (1)	2.68 (9)	3.471 (12)	155 (18)
O1i^xii—H1···I5ii^v	0.85 (1)	2.69 (4)	3.501 (11)	161 (11)

Symmetry codes: (iii) x−2, y+1, z; (iv) −x, −y+2, −z+1; (v) −x−1/2, y+1/2, −z+1/2; (vi) x−3/2, −y+1/2, z+1/2; (vii) x−3/2, −y+3/2, z+1/2; (viii) −x−1/2, y+1/2, −z+3/2; (ix) −x−1, −y+1, −z+1; (x) x−5/2, −y+3/2, z−1/2; (xi) x−3/2, −y+1/2, z−1/2; (xii) x+2, y, z.

Acknowledgements

The authors thank the College of Chemistry and Chemical Engineering, Southeast University, China, for support.

Funding information

Funding for this research was provided by: National Natural Science Foundation of China (award No. 21703033); Natural Science Foundation of Jaingsu Province (award No. BK20170658).

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