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research communications
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]
aInstitut für Anorganische Chemie, Universität Kiel, Max-Eyth.-Str. 2, 24118 Kiel, Germany
*Correspondence e-mail: cnaether@ac.uni-kiel.de
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 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.
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 CuI, 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 CdII 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 CdII cations are linked by μ-1,1-bridging chloride anions into chains, in which each two CdII 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 (Δmcalc. = 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 and Cmmm but the clearly shows that the present and 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 4e (mm2) (Fig. 1). In both compounds, the CdII 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 CdII 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 + |
![]() | 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].
|
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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 Immm (Yi et al., 2002
).
In this context it is noted that three compounds containing diamagnetic ZnII 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 CuII cations, CuCl2(pyridazine) (JEFFOS) and CuBr2(pyridazine) (JEFFUY) (Thomas & Ramanan, 2016) have been, reported, but most compounds are found with CuI 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 . The C-bound hydrogen atoms were positioned with idealized geometry and refined with Uiso(H) = 1.2Ueq(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 with half of the b-axis, Cmmm is suggested. The structure can easily be solved in this but the 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.
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Supporting information
https://doi.org/10.1107/S2056989023002001/hb8056sup1.cif
contains datablocks 1, 2. DOI: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
For both structures, data collection: CrysAlis PRO 1.171.42.67a (Rigaku OD, 2022); cell
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).[CdBr2(C4H4N2)] | Dx = 3.143 Mg m−3 |
Mr = 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 |
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 | Rint = 0.039 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 33.3°, θmin = 3.1° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022) | k = −11→11 |
Tmin = 0.582, Tmax = 1.000 | l = −19→20 |
6952 measured reflections |
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(Fo2) + (0.0315P)2 + 0.191P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max < 0.001 |
769 reflections | Δρmax = 1.07 e Å−3 |
29 parameters | Δρmin = −0.52 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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 |
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. |
[CdI2(C4H4N2)] | Dx = 3.484 Mg m−3 |
Mr = 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 |
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 | Rint = 0.037 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 33.4°, θmin = 2.9° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (CrysalisPro; Rigaku OD, 2022) | k = −12→12 |
Tmin = 0.382, Tmax = 1.000 | l = −20→19 |
7478 measured reflections |
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(Fo2) + (0.0233P)2 + 0.8677P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.046 | (Δ/σ)max = 0.001 |
S = 1.18 | Δρmax = 0.78 e Å−3 |
889 reflections | Δρmin = −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 |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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 |
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.
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