Syntheses, crystal structures and thermal properties of catena-poly[cadmium(II)-di-μ-bromido-μ-pyridazine-κ2N1:N2] and catena-poly[cadmium(II)-di-μ-iodido-μ-pyridazine-κ2N1:N2]

Näther, C.; Jess, I.

doi:10.1107/S2056989023002001

research communications

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ISSN: 2056-9890

Volume 79| Part 4| April 2023| Pages 302-307

https://doi.org/10.1107/S2056989023002001

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Syntheses, crystal structures and thermal properties of catena-poly[cadmium(II)-di-μ-bromido-μ-pyridazine-κ²N¹:N²] and catena-poly[cadmium(II)-di-μ-iodido-μ-pyridazine-κ²N¹:N²]

Christian Näther ^a ^* and Inke Jess ^a

^aInstitut für Anorganische Chemie, Universität Kiel, Max-Eyth.-Str. 2, 24118 Kiel, Germany
^*Correspondence e-mail: cnaether@ac.uni-kiel.de

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 27 February 2023; accepted 2 March 2023; online 10 March 2023)

The reactions of cadmium bromide and cadmium iodide with pyridazine (C₄H₄N₂) in ethanol under solvothermal conditions led to the formation of crystals of [CdBr₂(pyridazine)]_n (1) and [CdI₂(pyridazine)]_n (2), which were characterized by single-crystal X-ray diffraction. The asymmetric units of both compounds consist of a cadmium cation located on the intersection point of a twofold screw axis and a mirror plane (2/m), a halide anion that is located on a mirror plane and a pyridazine ligand, with all atoms occupying Wyckoff position 4e (mm2). These compounds are isotypic and consist of cadmium cations that are octahedrally coordinated by four halide anions and two pyridazine ligands and are linked into [100] chains by pairs of μ-1,1-bridging halide anions and bridging pyridazine ligands. In the crystals, the pyridazine ligands of neighboring chains are stacked onto each other, indicating π–π interactions. Larger amounts of pure samples can also be obtained by stirring at room-temperature, as proven by powder X-ray diffraction. Measurements using thermogravimetry and differential thermoanalysis (TG-DTA) reveal that upon heating all the pyridiazine ligands are removed in one step, which leads to the formation of CdBr₂ or CdI₂.

Keywords: synthesis; crystal structure; cadmium halide coordination polymer; chain compound; thermal properties.

CCDC references: 2245994; 2245993

1. Chemical context

Coordination polymers based on transition-metal halides show a versatile structural behavior and can form networks of different dimensionalities (Peng et al., 2010 ). This is especially valid for compounds based on Cu^I, which show different CuX substructures (X = Cl, Br, I) such as, for example, dimeric units, chains or layers that can be additionally connected by bridging neutral coligands (Peng et al., 2010). These compounds are of additional interest because of their luminescence behavior (Gibbons et al., 2017 ; Mensah et al., 2022 ). For one particular metal halide and coligand, compounds of different stoichiometry are frequently observed. In most cases they were synthesized in the liquid state, but in some cases the coligand-deficient phases cannot be obtained from solution or are obtained only as mixtures with coligand-rich phases.

We have been interested in the structural properties of such compounds for several years and have found that upon heating most of the coligand-rich compounds lose their coligands stepwise and transform into new coligand-deficient compounds that show condensed copper-halide networks (Näther & Jess, 2004 ; Näther et al., 2001 , 2007 ). The advantage of this method is the fact that this reaction is irreversible, and that the new compounds are obtained in quantitative yields. Moreover, in some cases, metastable polymorphs or isomers can also be obtained (Näther et al., 2007) and this method can also be used for the synthesis of new coordination polymers with other bridging anionic ligands such as, for example, thio- or selenocyanates (Werner et al., 2015 ; Wriedt & Näther, 2010 ).

We subsequently found that transition-metal halide compounds with twofold positively charged cations such as Cd^II that also show a pronounced structural variability can be obtained by this route (Näther et al., 2017 ; Jess et al., 2020 ). In most cases, discrete CdX₂ complexes are observed (Ghanbari et al., 2017 ; Liu, 2011 ), but these units can also condense into dinuclear (Santra et al., 2016 ; Xie et al., 2003 ) and tetranuclear units (Zhu, 2011 ) or polymers (Nezhadali Baghan et al., 2021 ; Satoh et al., 2001 ), where the latter can be further linked by the coligands into layers (Hu et al., 2009 ; Marchetti et al., 2011 ).

In this context, we have reported on CdX₂ coordination polymers with 2-chloro and 2-methylpyrazine with the composition CdX₂(L)₂ with X = Cl, Br, I and L = 2-chloro or 2-methylpyrazine). These compounds consists of CdX₂ chains in which the Cd cations are linked by two pairs of μ-1,1-bridging halide anions (Näther et al., 2017). Surprisingly, upon heating, the compounds with 2-chloropyrazine lose all the coligands in one single step, whereas decomposition of the 2-methylpyrazine compounds leads to the formation of compounds with the composition CdX₂(2-methylpyrazine), in which the CDX₂ chains are linked into layers by the 2-methylpyrazine ligands. These compounds can also be obtained if the discrete complex CdI₂(2-methylpyrazine)₂(H₂O) is thermally decomposed. In further work we investigated similar compounds with 2-cyanopyrazine as coligand, where we observed a different thermal reactivity as a function of the nature of the halide anions (Jess et al., 2020).

In the course of our investigations we also became interested in compounds with pyridazine as coligand. A search in the CCDC database revealed that several transition-metal halide coordination compounds with this ligand have already been reported in the literature (see Database survey). With cadmium, one compound with the composition CdCl₂(pyridazine) is reported, in which the Cd^II cations are linked by μ-1,1-bridging chloride anions into chains, in which each two Cd^II cations are additionally connected by the pyridazine ligands (Pazderski et al., 2004a ). As this compound is isotypic to many other MX₂(pyridazine) coordination compounds, one can assume that this structure represents a very stable arrangement. On the other hand, compounds with this composition have also been reported with ZnX₂. In contrast to the bromide and iodide compounds, the chloride analog crystallizes in three different modifications, which indicates that the structural behavior also depends on the nature of the halide anion (Bhosekar et al., 2006a ,b ; Pazderski et al., 2004b ; Bhosekar et al., 2007 ). Moreover, even if in the majority of compounds Nezhadali acts as a bridging ligands, some examples have been reported in which this ligand is coordinated to metal cations with only one of the two N atoms, thereby forming discrete complexes, which also include transition-metal halide complexes (Handy et al., 2017 ; Boeckmann et al., 2011 ; Laramée & Hanan, 2014 ; Yang, 2017 ; Harvey et al., 2004 ).

Based on all these findings, we reacted CdBr₂ and CdI₂ in different molar ratios with pyridazine in several solvents to investigate whether compounds with a different ratio between CdX₂ and pyridazine can be prepared, which also might include pyridazine-rich discrete complexes that upon heating might transform into new compounds with a more condensed network. However, independent of the reaction conditions and the stoichiometric ratio, we always obtained the same crystalline phases, as proven by powder X-ray diffraction (PXRD). Crystals of both compounds were obtained at elevated temperatures and structure analysis proves that compounds with the composition CdBr₂(pyridazine) (1) and CdI₂(pyridazine) (2) were obtained. Comparison of the experimental PXRD patterns with those calculated from the results of the structure determinations, prove that both compounds were obtained as pure phases (Figs. S1 and S2). Measurements using thermogravimetry and differential thermoanalysis reveal that both compounds decompose in one step, which is accompanied with an endothermic event in the DTA curve (Figs. S3 and S4). The experimental mass losses of 22.9% for 1 and 18.1% for 2 are in good agreement with those calculated for the removal of one pyridazine ligand (Δm_calc. = 22.7% for 1 and 17.9% for 2), indicating that CdBr₂ and CdI₂, respectively, have formed.

In this context, it is noted that the formation of a more pyridazine-deficient compound with a more condensed network is not expected, because for M²⁺ cations, the network should be negatively charged. This is impossible in this case, but it is noted that one compound with CdCl₂ and a more condensed metal–halide network is reported in the literature (Jin et al., 2014 ).

2. Structural commentary

The reaction of cadmium dibromide or cadmium diiodide with pyridazine leads to the formation of crystals of CdBr₂(pyridazine) (1) and CdI₂(pyridazine) (2). Both compounds are isotypic to their CdCl₂ analog already reported in the literature (Pazderski et al., 2004a). In this context, it is noted that for compound 2 a pseudo-translation along the crystallographic b-axis is detected, leading to half of the unit cell and space group Cmmm but the refinement clearly shows that the present unit cell and space group is correct (see Refinement). Both compounds are also isotypic to a number of other metal–halide coordination polymers, indicating that this is a very stable arrangement (see Database survey).

The asymmetric units of compound 1 and 2 consist of a cadmium cation located on the intersection point of a twofold screw axis and a mirror plane (Wyckoff site 4c, symmetry 2/m), as well as a bromide or iodide anion lying on a mirror plane (Wyckoff site 8h) and a pyridazine ligand, with all atoms located on Wyckoff position 4e (mm2) (Fig. 1). In both compounds, the Cd^II cations are octahedrally in a trans-CdX₄N₂ arrangement, coordinated by four halide anions and two pyridazine ligands, and are linked by pairs of μ-1,1-bridging halide anions into chains that propagate in the crystallographic a-axis direction (Fig. 2). The pyridazine ligands also act as bridging ligands, connecting two neighboring Cd^II cations (Fig. 2). Within the chains, all of the pyridazine ligands are coplanar. (Fig. 2).

Figure 1
The metal atom polyhedra in 1 (left) and 2 (right) with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes for the generation of equivalent atoms: (i) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) −x + 1, −y + $[{1\over 2}]$ , z; (iii) x − $[{1\over 2}]$ , y, −z + $[{1\over 2}]$ .

Figure 2
Fragment of a [100] polymeric chain in the crystal structure of 1.

The Cd—N bond lengths to the pyridazine ligand are slightly longer in the iodide compound 2 compared to compound 1, which might be traced back to some crowding of the bulky iodide anion. In agreement, this distance is the shortest in the corresponding chloride compound (Pazderski et al., 2004a) reported in the literature (Tables 1 and 2). The N—Cd—Br and N—Cd—I bond angles are comparable, which is also valid for that in the chloride compound (Pazderski et al., 2004a). As expected, the intrachain Cd⋯Cd distance increases from Cl [Cd⋯Cd = 3.5280 (5) Å], to Br [Cd⋯Cd = 3.6270 (3) Å] to I [Cd⋯Cd = 3.7870 (3) Å].

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

Cd1—Br1	2.7581 (2)	Cd1—N1	2.385 (2)

Br1ⁱ—Cd1—Br1ⁱⁱ	95.243 (9)	N1ⁱ—Cd1—Br1ⁱⁱ	91.08 (4)
Br1ⁱ—Cd1—Br1ⁱⁱⁱ	84.757 (9)	N1—Cd1—Br1	88.92 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

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

Cd1—I1	2.9555 (1)	Cd1—N1	2.4216 (19)

I1ⁱ—Cd1—I1ⁱⁱ	93.237 (5)	N1ⁱ—Cd1—I1ⁱⁱ	91.56 (4)
I1ⁱ—Cd1—I1ⁱⁱⁱ	86.763 (5)	N1—Cd1—I1	88.44 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

3. Supramolecular features

In the crystal structures of 1 and 2, the chains extend in the crystallographic a-axis direction (Fig. 2). Neighboring chains are arranged in such a way that the pyridazine ligands are perfectly stacked onto each other into columns that propagate along the crystallographic b-axis direction (Fig. 3). The angle between two neighboring pyridazine ligands is 180° in both compounds, which is also valid for the chloride analog (Pazderski et al., 2004a). The distance between the centroids of adjacent pyridazine rings is 3.724 Å for the chloride, 3.8623 (1) Å (slippage = 0.095 Å) for the bromide and 4.1551 (1) Å (0.226 Å) for the iodide, consistent with π–π interactions (Fig. 4), although they must be weak for the iodide. There are no directional intermolecular interactions such as intermolecular C—H⋯X hydrogen bonding. As mentioned above, this structure type is common for the majority of transition-metal pyridazine coordination compounds with such a metal-to-pyridazine ratio, indicating that π–π interactions might also be responsible for this obviously very stable arrangement.

Figure 3
Arrangement of the chains in the crystal structure of 1 in a view along the crystallographic b-axis direction.

Figure 4
Arrangement of neighboring pyridazine rings in 1 showing π–π stacking interactions.

4. Database survey

A search in the CCDC database (version 5.43, last update November 2022; Groom et al., 2016 ) revealed that some compounds with the general composition MX₂(pyridazine) (M = transition metal and X = halide anion) have already been reported in the literature. The compounds with NiCl₂ (CSD refcode POPCIG) and NiBr₂ (POPCOM) were structurally characterized by Rietveld refinements using laboratory X-ray powder diffraction data and are isotypic to the title compounds (Masciocchi et al., 1994 ). In this contribution, the compounds with Mn, Fe, Co, Cu and Zn with chloride and bromide as anions were also synthesized, and their lattice parameters determined from their powder patterns, indicating that the compounds with Mn, Fe and Co are isotypic to the Ni compound, which is not the case for the compounds with Cu and Zn (Masciocchi et al., 1994). The compounds MCl₂(pyridazine) with Mn (LANJEQ) and Fe (LANJAM) were later determined by single-crystal X-ray diffraction, which definitely proves that they crystallize in space group Immm (Yi et al., 2002 ).

In this context it is noted that three compounds containing diamagnetic Zn^II cations have been reported, which consist of discrete complexes with a tetrahedral coordination, viz. ZnI₂(pyridazine)₂ (MENSUU; Bhosekar et al., 2006a), ZnBr₂(pyridazine)₂ (VEMBEV; Bhosekar et al., 2006b) and three modifications of CuCl₂(pyridazine)₂ (YAFYOU, YAFYOU01, YAFYOU02 and YAFYOU03; Pazderski et al., 2004b and Bhosekar et al., 2007). Surprisingly, none of the different forms are isotypic to the chloride and bromide compounds reported by Masciocchi et al. (1994) based on XRPD patterns.

With Cu^II cations, CuCl₂(pyridazine) (JEFFOS) and CuBr₂(pyridazine) (JEFFUY) (Thomas & Ramanan, 2016 ) have been, reported, but most compounds are found with Cu^I cations, including CuI(pyridazine) [CAQXAT (Kromp & Sheldrick, 1999 ) and CAQXAT01 (Thomas & Ramanan, 2016)], CuBr(pyridazine) [CAQXEX (Kromp & Sheldrick, 1999), CAQXEX01 and 02 (Thomas & Ramanan, 2016)], Cu₂I₂(pyridazine) (CAQXIB; Kromp & Sheldrick, 1999), Cu₂Cl₂(pyridazine) [CAQXOH (Kromp & Sheldrick, 1999) and CAQXOH01 and 02 (Thomas & Ramanan, 2016)], two modifications of CuCl(pyridazine) [EKINOB and EKINUH (Näther and Jess, 2003 ) and EKINUH01 (Thomas & Ramanan, 2016)], Cu₂Br₂(pyridazine) [EKIPAP (Näther & Jess, 2003) and EKIPAP01 (Thomas & Ramanan, 2016)].

5. Synthesis and crystallization

Synthesis

CdBr₂, CdI₂ and pyridazine were purchased from Sigma-Aldrich. All chemicals were used without further purification.

Colorless single crystals of compound 1 and 2 were obtained by the reaction of 0.500 mmol of CdBr₂ or 0.500 mmol of CdI₂ with 0.500 mmol of pyridazine in 1 ml of ethanol. The reaction mixtures were sealed in glass tubes and heated at 388 K for 1 d and finally cooled down to room temperature.

Larger amounts of a microcrystalline powder of 1 and 2 were obtained stirring the same amount of reactants in ethanol or water at room temperature for 1 d. For the IR spectra of 1 and 2 see Figs. S5 and S6.

Experimental details

The IR spectra were measured using an ATI Mattson Genesis Series FTIR Spectrometer, control software: WINFIRST, from ATI Mattson. The PXRD measurements were performed with Cu Kα₁ radiation (λ = 1.540598 Å) using a Stoe Transmission Powder Diffraction System (STADI P) equipped with a MYTHEN 1K detector and a Johansson-type Ge(111) monochromator. Thermogravimetry and differential thermoanalysis (TG-DTA) measurements were performed in a dynamic nitrogen atmosphere in Al₂O₃ crucibles using a STA-PT 1000 thermobalance from Linseis. The instrument was calibrated using standard reference materials.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The C-bound hydrogen atoms were positioned with idealized geometry and refined with U_iso(H) = 1.2U_eq(C). For compound 2, PLATON (Spek, 2020 ) suggested a pseudo-translation along the b-axis with a fit of 80%. If the structure is determined in a unit cell with half of the b-axis, space group Cmmm is suggested. The structure can easily be solved in this space group but the refinement leads to only very poor reliability factors (R1 = 11.5%). Moreover, in this case, disorder of the nitrogen atoms of the pyridazine ring is observed, because the N atoms of the pyridazine rings of neighboring chains are superimposed.

Table 3
Experimental details

	1	2
Crystal data
Chemical formula	[CdBr₂(C₄H₄N₂)]	[CdI₂(C₄H₄N₂)]
M_r	352.31	446.29
Crystal system, space group	Orthorhombic, Imma	Orthorhombic, Imma
Temperature (K)	293	293
a, b, c (Å)	7.2540 (2), 7.7223 (2), 13.2910 (4)	7.5740 (2), 8.2979 (2), 13.5363 (4)
V (Å³)	744.53 (4)	850.73 (4)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	13.58	9.75
Crystal size (mm)	0.08 × 0.06 × 0.04	0.12 × 0.03 × 0.02

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction.]$ )
T_min, T_max	0.582, 1.000	0.382, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6952, 769, 684	7478, 889, 857
R_int	0.039	0.037
(sin θ/λ)_max (Å⁻¹)	0.772	0.774

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.057, 1.16	0.016, 0.046, 1.18
No. of reflections	769	889
No. of parameters	29	30
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.07, −0.52	0.78, −0.56
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction.]$ ), SHELXT2014/4 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2245994; 2245993

Crystal structure: contains datablocks 1, 2. DOI: https://doi.org/10.1107/S2056989023002001/hb8056sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989023002001/hb80561sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989023002001/hb80562sup3.hkl

Figure S1. Experimental (top) and calculated PXRD pattern (bottom) of compound 1. DOI: https://doi.org/10.1107/S2056989023002001/hb8056sup4.png

Figure S2. Experimental (top) and calculated PXRD pattern (bottom) of compound 2. DOI: https://doi.org/10.1107/S2056989023002001/hb8056sup5.png

Figure S3. DTG (top), TG (middle) and DTA curve (bottom) for compound 1. DOI: https://doi.org/10.1107/S2056989023002001/hb8056sup6.png

Figure S4. DTG (top), TG (middle) and DTA curve (bottom) for compound 2. DOI: https://doi.org/10.1107/S2056989023002001/hb8056sup7.png

Figure S5. IR spectrum for compound 1. The wave numbers of the most intense vibrations are given. DOI: https://doi.org/10.1107/S2056989023002001/hb8056sup8.png

Figure S6. IR spectrum for compound 2. The wave numbers of the most intense vibrations are given. DOI: https://doi.org/10.1107/S2056989023002001/hb8056sup9.png

checkCIF report

Computing details top

For both structures, data collection: CrysAlis PRO 1.171.42.67a (Rigaku OD, 2022); cell refinement: CrysAlis PRO 1.171.42.67a (Rigaku OD, 2022); data reduction: CrysAlis PRO 1.171.42.67a (Rigaku OD, 2022); program(s) used to solve structure: SHELXT2014/4 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

catena-Poly[cadmium(II)-di-µ-bromido-µ-pyridazine-κ²N¹:N²] (1) top

Crystal data top

[CdBr₂(C₄H₄N₂)]	D_x = 3.143 Mg m⁻³
M_r = 352.31	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Imma	Cell parameters from 4638 reflections
a = 7.2540 (2) Å	θ = 3.0–33.2°
b = 7.7223 (2) Å	µ = 13.58 mm⁻¹
c = 13.2910 (4) Å	T = 293 K
V = 744.53 (4) Å³	Block, colourless
Z = 4	0.08 × 0.06 × 0.04 mm
F(000) = 640

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	769 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	684 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.039
Detector resolution: 10.0000 pixels mm^-1	θ_max = 33.3°, θ_min = 3.1°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −11→11
T_min = 0.582, T_max = 1.000	l = −19→20
6952 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.020	H-atom parameters constrained
wR(F²) = 0.057	w = 1/[σ²(F_o²) + (0.0315P)² + 0.191P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max < 0.001
769 reflections	Δρ_max = 1.07 e Å⁻³
29 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints

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
Cd1	0.250000	0.250000	0.250000	0.02829 (10)
Br1	0.500000	0.49073 (3)	0.18013 (2)	0.03175 (10)
N1	0.4072 (3)	0.250000	0.40756 (16)	0.0294 (4)
C1	0.3181 (4)	0.250000	0.4947 (2)	0.0365 (6)
H1	0.189944	0.250000	0.493718	0.044*
C2	0.4065 (4)	0.250000	0.5870 (2)	0.0369 (6)
H2	0.340042	0.250000	0.646880	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01738 (14)	0.04001 (17)	0.02748 (15)	0.000	−0.00137 (9)	0.000
Br1	0.02359 (15)	0.03169 (16)	0.03996 (18)	0.000	0.000	0.00394 (10)
N1	0.0203 (10)	0.0403 (11)	0.0276 (11)	0.000	0.0005 (9)	0.000
C1	0.0216 (13)	0.0565 (18)	0.0313 (13)	0.000	0.0041 (12)	0.000
C2	0.0317 (14)	0.0527 (16)	0.0262 (12)	0.000	0.0042 (12)	0.000

Geometric parameters (Å, º) top

Cd1—Br1	2.7581 (2)	N1—N1ⁱⁱ	1.346 (4)
Cd1—Br1ⁱ	2.7581 (2)	N1—C1	1.326 (4)
Cd1—Br1ⁱⁱ	2.7581 (2)	C1—H1	0.9300
Cd1—Br1ⁱⁱⁱ	2.7581 (2)	C1—C2	1.385 (4)
Cd1—N1	2.385 (2)	C2—C2ⁱⁱ	1.357 (6)
Cd1—N1ⁱⁱⁱ	2.385 (2)	C2—H2	0.9300

Br1—Cd1—Br1ⁱⁱⁱ	180.0	N1ⁱⁱⁱ—Cd1—Br1ⁱ	88.92 (4)
Br1ⁱⁱⁱ—Cd1—Br1ⁱⁱ	95.243 (9)	N1—Cd1—N1ⁱⁱⁱ	180.0
Br1ⁱⁱ—Cd1—Br1ⁱ	180.0	Cd1—Br1—Cd1ⁱⁱ	82.223 (7)
Br1ⁱⁱⁱ—Cd1—Br1ⁱ	84.757 (9)	N1ⁱⁱ—N1—Cd1	118.58 (5)
Br1—Cd1—Br1ⁱ	95.244 (9)	C1—N1—Cd1	122.26 (19)
Br1—Cd1—Br1ⁱⁱ	84.756 (9)	C1—N1—N1ⁱⁱ	119.16 (16)
N1ⁱⁱⁱ—Cd1—Br1ⁱⁱ	91.08 (4)	N1—C1—H1	118.4
N1—Cd1—Br1	88.92 (4)	N1—C1—C2	123.3 (3)
N1—Cd1—Br1ⁱⁱⁱ	91.08 (4)	C2—C1—H1	118.4
N1ⁱⁱⁱ—Cd1—Br1ⁱⁱⁱ	88.92 (4)	C1—C2—H2	121.2
N1—Cd1—Br1ⁱ	91.08 (4)	C2ⁱⁱ—C2—C1	117.57 (17)
N1—Cd1—Br1ⁱⁱ	88.92 (4)	C2ⁱⁱ—C2—H2	121.2
N1ⁱⁱⁱ—Cd1—Br1	91.08 (4)

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

catena-Poly[cadmium(II)-di-µ-iodido-µ-pyridazine-κ²N¹:N²] (2) top

Crystal data top

[CdI₂(C₄H₄N₂)]	D_x = 3.484 Mg m⁻³
M_r = 446.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Imma	Cell parameters from 6483 reflections
a = 7.5740 (2) Å	θ = 2.9–33.4°
b = 8.2979 (2) Å	µ = 9.75 mm⁻¹
c = 13.5363 (4) Å	T = 293 K
V = 850.73 (4) Å³	Needle, colourless
Z = 4	0.12 × 0.03 × 0.02 mm
F(000) = 784

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	889 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	857 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.037
Detector resolution: 10.0000 pixels mm^-1	θ_max = 33.4°, θ_min = 2.9°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysalisPro; Rigaku OD, 2022)	k = −12→12
T_min = 0.382, T_max = 1.000	l = −20→19
7478 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.016	w = 1/[σ²(F_o²) + (0.0233P)² + 0.8677P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.046	(Δ/σ)_max = 0.001
S = 1.18	Δρ_max = 0.78 e Å⁻³
889 reflections	Δρ_min = −0.56 e Å⁻³
30 parameters	Extinction correction: SHELXL2016/6 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00206 (14)
Primary atom site location: dual

Special details top

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

	x	y	z	U_iso*/U_eq
Cd1	0.250000	0.250000	0.250000	0.02666 (8)
I1	0.500000	0.49464 (2)	0.17507 (2)	0.02931 (8)
N1	0.4115 (3)	0.250000	0.40441 (14)	0.0272 (4)
C1	0.3246 (4)	0.250000	0.48983 (19)	0.0354 (6)
H1	0.201820	0.250000	0.488661	0.042*
C2	0.4099 (4)	0.250000	0.5807 (2)	0.0377 (6)
H2	0.346328	0.250000	0.639534	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01738 (12)	0.03918 (15)	0.02342 (12)	0.000	−0.00147 (7)	0.000
I1	0.02338 (10)	0.02851 (11)	0.03603 (12)	0.000	0.000	0.00422 (5)
N1	0.0194 (9)	0.0420 (11)	0.0203 (8)	0.000	−0.0006 (7)	0.000
C1	0.0224 (11)	0.0607 (19)	0.0230 (10)	0.000	0.0017 (9)	0.000
C2	0.0303 (13)	0.0615 (18)	0.0212 (10)	0.000	0.0031 (10)	0.000

Geometric parameters (Å, º) top

Cd1—I1	2.9555 (1)	N1—N1ⁱⁱ	1.341 (4)
Cd1—I1ⁱ	2.9555 (1)	N1—C1	1.330 (3)
Cd1—I1ⁱⁱ	2.9555 (1)	C1—H1	0.9300
Cd1—I1ⁱⁱⁱ	2.9555 (1)	C1—C2	1.390 (4)
Cd1—N1	2.4216 (19)	C2—C2ⁱⁱ	1.366 (6)
Cd1—N1ⁱⁱⁱ	2.4216 (19)	C2—H2	0.9300

I1ⁱⁱⁱ—Cd1—I1	180.0	N1ⁱⁱⁱ—Cd1—I1	91.56 (4)
I1ⁱⁱⁱ—Cd1—I1ⁱⁱ	93.237 (5)	N1—Cd1—N1ⁱⁱⁱ	180.0
I1ⁱⁱⁱ—Cd1—I1ⁱ	86.763 (5)	Cd1—I1—Cd1ⁱⁱ	79.683 (4)
I1ⁱ—Cd1—I1ⁱⁱ	180.0	N1ⁱⁱ—N1—Cd1	120.33 (5)
I1ⁱⁱ—Cd1—I1	86.763 (5)	C1—N1—Cd1	120.03 (18)
I1ⁱ—Cd1—I1	93.237 (5)	C1—N1—N1ⁱⁱ	119.64 (16)
N1ⁱⁱⁱ—Cd1—I1ⁱⁱ	91.56 (4)	N1—C1—H1	118.7
N1—Cd1—I1ⁱⁱⁱ	91.56 (4)	N1—C1—C2	122.7 (3)
N1—Cd1—I1ⁱ	91.56 (4)	C2—C1—H1	118.7
N1ⁱⁱⁱ—Cd1—I1ⁱ	88.44 (4)	C1—C2—H2	121.2
N1—Cd1—I1	88.44 (4)	C2ⁱⁱ—C2—C1	117.69 (17)
N1—Cd1—I1ⁱⁱ	88.44 (4)	C2ⁱⁱ—C2—H2	121.2
N1ⁱⁱⁱ—Cd1—I1ⁱⁱⁱ	88.44 (4)

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

Acknowledgements

Financial support by the State of Schleswig-Holstein is gratefully acknowledged.

References

Bhosekar, G., Jess, I., Havlas, Z. & Näther, C. (2007). Cryst. Growth Des. 7, 2627–2634. Web of Science CSD CrossRef CAS Google Scholar
Bhosekar, G., Jess, I. & Näther, C. (2006a). Acta Cryst. E62, m2073–m2074. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bhosekar, G., Jess, I. & Näther, C. (2006b). Acta Cryst. E62, m1859–m1860. Web of Science CSD CrossRef IUCr Journals Google Scholar
Boeckmann, J., Jess, I., Reinert, T. & Näther, C. (2011). Eur. J. Inorg. Chem. pp. 5502–5511. Web of Science CSD CrossRef Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Ghanbari Niyaky, S., Montazerozohori, M., Masoudiasl, A. & White, J. M. (2017). J. Mol. Struct. 1131, 201–211. Web of Science CSD CrossRef CAS Google Scholar
Gibbons, S. K., Hughes, R. P., Glueck, D. S., Royappa, A. T., Rheingold, A. L., Arthur, R. B., Nicholas, A. D. & Patterson, H. H. (2017). Inorg. Chem. 56, 12809–12820. Web of Science CSD CrossRef CAS PubMed Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Handy, J. V., Ayala, G. & Pike, R. D. (2017). Inorg. Chim. Acta, 456, 64–75. Web of Science CSD CrossRef CAS Google Scholar
Harvey, B. G., Arif, A. M. & Ernst, R. D. (2004). Polyhedron, 23, 2725–2731. Web of Science CSD CrossRef CAS Google Scholar
Hu, J. J., Jin, C. M., Sun, T. Q. & Mei, T. F. Z. (2009). Z. Anorg. Allg. Chem. 635, 2579–2584. CAS Google Scholar
Jess, I., Neumann, T., Terraschke, H., Gallo, G., Dinnebier, R. E. & Näther, C. (2020). Z. Anorg. Allg. Chem. 646, 1046–1054. Web of Science CSD CrossRef CAS Google Scholar
Jin, Y., Yu, C., Wang, W. X., Li, S. C. & Zhang, W. (2014). Inorg. Chim. Acta, 413, 97–101. Web of Science CSD CrossRef CAS Google Scholar
Kromp, T. & Sheldrick, W. S. (1999). Z. Naturforsch. 54, 1175–1180. CrossRef CAS Google Scholar
Laramée, B. & Hanan, G. S. (2014). Acta Cryst. E70, m17. CSD CrossRef IUCr Journals Google Scholar
Liu, D. (2011). Acta Cryst. E67, m1407. Web of Science CSD CrossRef IUCr Journals Google Scholar
Marchetti, F., Masciocchi, N., Albisetti, A. F., Pettinari, C. & Pettinari, R. (2011). Inorg. Chim. Acta, 373, 32–39. Web of Science CSD CrossRef CAS Google Scholar
Masciocchi, N., Cairati, O., Carlucci, L., Ciani, G., Mezza, G. & Sironi, A. (1994). J. Chem. Soc. Dalton Trans. pp. 3009–3015. CSD CrossRef Web of Science Google Scholar
Mensah, A., Shao, J. J., Ni, J. L., Li, G. J., Wang, F. M. & Chen, L. Z. (2022). Front. Chem. 9, 816363. https://doi.org/10.3389/fchem.2021.816363 Google Scholar
Näther, C., Bhosekar, G. & Jess, I. (2007). Inorg. Chem. 46, 8079–8087. Web of Science PubMed Google Scholar
Näther, C. & Jess, I. (2004). Eur. J. Inorg. Chem. pp. 2868–2876. Google Scholar
Näther, C., Jess, I. & Greve, J. (2001). Polyhedron, 20, 1017–1022. Web of Science CrossRef CAS Google Scholar
Näther, C. & Jess, I. (2003). Inorg. Chem. 42, 2968–2976. Web of Science PubMed Google Scholar
Näther, C., Jess, I., Germann, L. S., Dinnebier, R. E., Braun, M. & Terraschke, H. (2017). Eur. J. Inorg. Chem. pp. 1245–1255. Google Scholar
Nezhadali Baghan, Z., Salimi, A., Eshtiagh-Hosseini, H. & Oliver, A. G. (2021). CrystEngComm, 23, 6276–6290. Web of Science CSD CrossRef CAS Google Scholar
Pazderski, L., Szłyk, E., Wojtczak, A., Kozerski, L., Sitkowski, J. & Kamieński, B. (2004a). J. Mol. Struct. 697, 143–149. Web of Science CSD CrossRef CAS Google Scholar
Pazderski, L., Szłyk, E., Wojtczak, A., Kozerski, L. & Sitkowski, J. (2004b). Acta Cryst. E60, m1270–m1272. Web of Science CSD CrossRef IUCr Journals Google Scholar
Peng, R., Li, M. & Li, D. (2010). Coord. Chem. Rev. 254, 1–18. Web of Science CrossRef CAS Google Scholar
Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction. Google Scholar
Santra, A., Mondal, G., Acharjya, M., Bera, P., Panja, A., Mandal, T. K., Mitra, P. & Bera, P. (2016). Polyhedron, 113, 5–15. Web of Science CSD CrossRef CAS Google Scholar
Satoh, K., Suzuki, T. & Sawada, K. (2001). Monatsh. Chem. 132, 1145–1155. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Thomas, J. & Ramanan, A. (2016). J. Chem. Sci. 128, 1687–1694. Web of Science CSD CrossRef CAS Google Scholar
Werner, J., Runčevski, T., Dinnebier, R. E., Ebbinghaus, S. G., Suckert, S. & Näther, C. (2015). Eur. J. Inorg. Chem. 2015, 3236–3245. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wriedt, M. & Näther, C. (2010). Chem. Commun. 46, 4707–4709. Web of Science CSD CrossRef CAS Google Scholar
Xie, Y. S., Liu, X. T., Yang, J. X., Jiang, H., Liu, Q. L., Du, C. X. & Zhu, Y. (2003). Collect. Czech. Chem. Commun. 68, 2139–2149. Web of Science CSD CrossRef CAS Google Scholar
Yang, J. (2017). J. Coord. Chem. 70, 3749–3758. Web of Science CSD CrossRef CAS Google Scholar
Yi, T., Chang, H. C. & Kitagawa, S. (2002). Mol. Cryst. Liq. Cryst. 376, 283–288. CrossRef CAS Google Scholar
Zhu, R.-Q. (2011). Acta Cryst. E67, m1416. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 79| Part 4| April 2023| Pages 302-307

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