Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616005180/lf3032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616005180/lf3032Isup2.hkl |
CCDC reference: 1470880
In recent decades, the design and construction of coordination polymers (CPs) have gained much attention not only due to their fascinating structures but also due to their potential applications in many fields such as nonlinear optics, sensors, magnetism, catalysis, gas storage/separation etc. (Sezer et al., 2016; Spencer et al., 2006; Liu et al., 2010; Lin et al., 2014; Pinkowicz et al., 2015; Nagarkar et al., 2011). Moreover, polynuclear d10 metal complexes, such as CdII coordination polymers, have attracted extensive interest due to their high thermal stability and good photoluminescence and electroluminescence properties (Ford et al., 1999; Manjunatha et al., 2011). Although there are numerous factors, such as the nature of the metal ion, the structural characteristics of the ligand, the presence of solvents and counter-ions and the metal–ligand ratio, which play important roles in the construction of these CPs, the most effective way is to choose suitable N- and O-donor multidentate organic ligands (Yin et al., 2016; Zhao et al., 2015; Hopa & Cokay, 2016). Schiff base metal complexes have been used widely as catalysts for many organic reactions, such as ring-opening polymerization and oxidation (Keypour et al., 2015; Chen et al., 2006; Hung et al., 2008; Gupta & Sutar, 2008). Recently, our research group and others have reported the synthesss and structural characterization of transition metal complexes containing ONNO-, ONO- and NNO-type Schiff base ligands (Gungor & Kara, 2011, 2012; Kara, 2007, 2008a,b,c; Yahsi et al., 2011; Yahsi & Kara, 2013, 2014; Hung & Lin, 2009; Surati & Thaker, 2010; Khandar et al., 2015; Keypour et al., 2015). In view of the importance of CdII coordination polymers and in an effort to enlarge the library of such complexes, we report here the synthesis of a new dichloride-bridged one-dimensional polymeric CdII complex, namely catena-poly[bis[4-bromo-2-({[2-(pyrrolidin-1-yl)ethyl]imino}methyl)phenolato-κ3N,N',O]di-µ3-chlorido-di-µ2-chlorido-bis(methanol-κO)tricadmium(II)], (I), along with its characterization, single-crystal X-ray structure, UV and IR spectroscopic data and photoluminescence study.
A solution of 5-bromosalicylaldehyde (5-BrSal; 1 mmol) in methanol (40 ml) was added dropwise to a solution of 1-(2-aminoethyl)pyrrolidine (aep; 1 mmol) in methanol (40 ml). To the resulting yellow solution was added CdCl2 (1 mmol) in methanol (40 ml). It turned light-yellow quickly and after stirring in air for 2 h it is allowed to stay at room temperature for a few weeks. And then the colourless crystals of complex (1) were filtered off, washed with methanol and dried in air (yield 68%, 0.38 g). Analysis calculated for C28H40Br2Cd3Cl4N4O4: C 29.62, H 3.55, N 4.93%; found: C 30.01, H 3.50, N 4.98%. UV–Vis (DMSO): 330 and 390 nm.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were included in idealized positions with isotropic displacement parameters constrained to 1.5Ueq(C) for methyl H atoms and to 1.2Ueq(C,O) otherwise.
The X-ray structure analysis of (1) shows that the Schiff base ligand coordinates to the Cd2 atom in a tridentate manner using the phenolate O and the N atoms from the imine and pyrrolidine groups (Fig. 1). In complex (1), each CdII ion is six-coordinated and the environment around the Cd2 atom can be described as distorted octahedral, while that around Cd1 is octahedral, completed by four bridging chloride ligands in the equatorial plane and two axial O atoms (Fig. 2 and Table 2). The coordination spheres of the Cd1 and Cd2 atoms deviate slightly from planarity, with a Cd1—Cl1—Cd2—Cl2iii torsion angle of 19.17(s.u.?)° [symmetry code: (iii) ???]. The Cd2 atom deviates by 0.112 Å from the NCl3 coordination plane (atoms Cl2, N2, Cl1 and Cl2iii) toward the apical N1 atom, while the deviation of the Cd1 atom from the Cl4 coordination plane (atoms Cl1, Cl2iii, Cl1i and Cl2ii) is 0.0 Å. The coordination sphere around the Cd2 atom is strictly planar, with a Cd2—Cl2—Cd2iii—Cl2iii torsion angle of 0°.
The bridging chloride ligands connect metal centres to generate a one-dimensional infinite chain along the [100] direction (Fig. 3). Selected Cd—Cl and Cd···Cd distances are compared in Table 3. The intramolecular nonbonding Cd···Cd distances are comparable with the values (in the range 3.675-4.016 Å) found in previously reported chloride-bridged cadmium complexes (Park et al., 2010; Wen et al., 2011; Lu et al., 2013; Hopa et al., 2010; Chen et al., 2007). The bridging Cd—Cl bond lengths are also in good agreement within the range of values reported for the corresponding bond lengths of CdII complexes. Further analysis of the crystal packing of complex (1) reveals the existence of weak C14—H14···Cl1 and C5—H5B···C13 interactions between the chains (Fig. 4). Such interchain contacts extend the one-dimensional coordination arrays into a supramolecular layer along the (001) plane and these layers are stacked in a parallel manner along the [001] direction without any interlayer interactions. The hydrogen-bond geometry for complex (1) is given in Table 4.
The IR spectral data for complex (1) are given in Table 5. The bands in the region of 1640 cm-1 are assignable to the ν(C═N) stretches of the Schiff base ligands, suggesting that the imine N atoms coordinate to the metal atoms. The bands in the range 2835–2910 cm-1 are characteristic of aliphatic ν(C—H) vibrations and the band observed at 3010 cm-1 is attributed to the aromatic ν(C—H) vibrations of complex (1). The observed bands in the region of 634 cm-1 are assignable to the ν(C—Br) vibrations of bromosalicylideneimine ligand. Thus, the IR data are found to be in good agreement with the structural features of complex (1).
The solid-state luminescence properties of complex (1) and free 5-BrSal and aep were investigated at room temperature in the visible regions upon excitation at λex= 349 nm (Fig. 5). Free 5-BrSal shows a broad emission band at λmax = 600 nm, whereas free aep shows a broad emission band at λmax = 590 nm which may be assigned to the n → π* or π → π* electronic transition (ILCT) (Feng et al., 2014). While the free ligands are combined with CdII in compound (1), a stronger red emission band is seen at λmax = 650 nm. No emissions originating from metal-centred excited states are expected for CdII complexes, since they are difficult to oxidize or reduce due to their d10 configuration (Paira et al., 2007; Manjunatha et al., 2011). Thus, the observed emissions of complex (1) are probably contributed by the n → π* or π → π* intraligand fluorescence since a similar emission was also observed for the ligands (Che et al., 2001; Wu et al., 2006; Erkarslan et al., 2016). The observed red or blue shift of the emission maximum between the complex and the corresponding ligands was considered to mainly originate from the influence of the coordination of metal atom to the ligand (Feng et al., 2014; Song et al., 2015; Manjunatha et al., 2011). The enhancement of luminescence may be attributed to the chelation of the ligand to the central metal atom. The chelation enhances the `rigidity' of the ligand and thus reduces the loss of energy through a radiationless pathway (Chen et al., 2011; Ji et al., 2012; Zheng et al., 2001; Wang et al., 2006).
A new dichloride-bridged CdII coordination polymer, (1), has been synthesized and its crystal structure determined by single-crystal X-ray diffraction analysis. The structural analysis of (1) shows that the Schiff base ligand coordinates to the Cd2 atom in an N,N',O-tridentate manner. In complex (1), each CdII ion is six-coordinated and the environment around the Cd2 atom can be described as distorted octahedral geometry, while that around the Cd1 atom is octahedral. The intramolecular nonbonding Cd···Cd separations are 3.701(s.u.?) and 4.356(s.u.?) Å. The Cd—Cl and Cd···Cd distances for (1) are in good agreement with the values that found in other dichloride-bridged CdII complexes. The bridging chloride ligands connect metal centres to generate a one-dimensional infinite chain. Furthermore, analysis of the crystal packing of (1) reveals the existence of weak short-contact interactions between the chains. The photoluminescence studies of complex (1) indicate a red shift compared with its free ligands, and the emission intensity of (1) is stronger than that of the ligands. The luminescence properties show that the photoluminescence arose from an intraligand emission and that it is a novel potential candidate for application in optoelectronic devices.
In recent decades, the design and construction of coordination polymers (CPs) have gained much attention not only due to their fascinating structures but also due to their potential applications in many fields such as nonlinear optics, sensors, magnetism, catalysis, gas storage/separation etc. (Sezer et al., 2016; Spencer et al., 2006; Liu et al., 2010; Lin et al., 2014; Pinkowicz et al., 2015; Nagarkar et al., 2011). Moreover, polynuclear d10 metal complexes, such as CdII coordination polymers, have attracted extensive interest due to their high thermal stability and good photoluminescence and electroluminescence properties (Ford et al., 1999; Manjunatha et al., 2011). Although there are numerous factors, such as the nature of the metal ion, the structural characteristics of the ligand, the presence of solvents and counter-ions and the metal–ligand ratio, which play important roles in the construction of these CPs, the most effective way is to choose suitable N- and O-donor multidentate organic ligands (Yin et al., 2016; Zhao et al., 2015; Hopa & Cokay, 2016). Schiff base metal complexes have been used widely as catalysts for many organic reactions, such as ring-opening polymerization and oxidation (Keypour et al., 2015; Chen et al., 2006; Hung et al., 2008; Gupta & Sutar, 2008). Recently, our research group and others have reported the synthesss and structural characterization of transition metal complexes containing ONNO-, ONO- and NNO-type Schiff base ligands (Gungor & Kara, 2011, 2012; Kara, 2007, 2008a,b,c; Yahsi et al., 2011; Yahsi & Kara, 2013, 2014; Hung & Lin, 2009; Surati & Thaker, 2010; Khandar et al., 2015; Keypour et al., 2015). In view of the importance of CdII coordination polymers and in an effort to enlarge the library of such complexes, we report here the synthesis of a new dichloride-bridged one-dimensional polymeric CdII complex, namely catena-poly[bis[4-bromo-2-({[2-(pyrrolidin-1-yl)ethyl]imino}methyl)phenolato-κ3N,N',O]di-µ3-chlorido-di-µ2-chlorido-bis(methanol-κO)tricadmium(II)], (I), along with its characterization, single-crystal X-ray structure, UV and IR spectroscopic data and photoluminescence study.
The X-ray structure analysis of (1) shows that the Schiff base ligand coordinates to the Cd2 atom in a tridentate manner using the phenolate O and the N atoms from the imine and pyrrolidine groups (Fig. 1). In complex (1), each CdII ion is six-coordinated and the environment around the Cd2 atom can be described as distorted octahedral, while that around Cd1 is octahedral, completed by four bridging chloride ligands in the equatorial plane and two axial O atoms (Fig. 2 and Table 2). The coordination spheres of the Cd1 and Cd2 atoms deviate slightly from planarity, with a Cd1—Cl1—Cd2—Cl2iii torsion angle of 19.17(s.u.?)° [symmetry code: (iii) ???]. The Cd2 atom deviates by 0.112 Å from the NCl3 coordination plane (atoms Cl2, N2, Cl1 and Cl2iii) toward the apical N1 atom, while the deviation of the Cd1 atom from the Cl4 coordination plane (atoms Cl1, Cl2iii, Cl1i and Cl2ii) is 0.0 Å. The coordination sphere around the Cd2 atom is strictly planar, with a Cd2—Cl2—Cd2iii—Cl2iii torsion angle of 0°.
The bridging chloride ligands connect metal centres to generate a one-dimensional infinite chain along the [100] direction (Fig. 3). Selected Cd—Cl and Cd···Cd distances are compared in Table 3. The intramolecular nonbonding Cd···Cd distances are comparable with the values (in the range 3.675-4.016 Å) found in previously reported chloride-bridged cadmium complexes (Park et al., 2010; Wen et al., 2011; Lu et al., 2013; Hopa et al., 2010; Chen et al., 2007). The bridging Cd—Cl bond lengths are also in good agreement within the range of values reported for the corresponding bond lengths of CdII complexes. Further analysis of the crystal packing of complex (1) reveals the existence of weak C14—H14···Cl1 and C5—H5B···C13 interactions between the chains (Fig. 4). Such interchain contacts extend the one-dimensional coordination arrays into a supramolecular layer along the (001) plane and these layers are stacked in a parallel manner along the [001] direction without any interlayer interactions. The hydrogen-bond geometry for complex (1) is given in Table 4.
The IR spectral data for complex (1) are given in Table 5. The bands in the region of 1640 cm-1 are assignable to the ν(C═N) stretches of the Schiff base ligands, suggesting that the imine N atoms coordinate to the metal atoms. The bands in the range 2835–2910 cm-1 are characteristic of aliphatic ν(C—H) vibrations and the band observed at 3010 cm-1 is attributed to the aromatic ν(C—H) vibrations of complex (1). The observed bands in the region of 634 cm-1 are assignable to the ν(C—Br) vibrations of bromosalicylideneimine ligand. Thus, the IR data are found to be in good agreement with the structural features of complex (1).
The solid-state luminescence properties of complex (1) and free 5-BrSal and aep were investigated at room temperature in the visible regions upon excitation at λex= 349 nm (Fig. 5). Free 5-BrSal shows a broad emission band at λmax = 600 nm, whereas free aep shows a broad emission band at λmax = 590 nm which may be assigned to the n → π* or π → π* electronic transition (ILCT) (Feng et al., 2014). While the free ligands are combined with CdII in compound (1), a stronger red emission band is seen at λmax = 650 nm. No emissions originating from metal-centred excited states are expected for CdII complexes, since they are difficult to oxidize or reduce due to their d10 configuration (Paira et al., 2007; Manjunatha et al., 2011). Thus, the observed emissions of complex (1) are probably contributed by the n → π* or π → π* intraligand fluorescence since a similar emission was also observed for the ligands (Che et al., 2001; Wu et al., 2006; Erkarslan et al., 2016). The observed red or blue shift of the emission maximum between the complex and the corresponding ligands was considered to mainly originate from the influence of the coordination of metal atom to the ligand (Feng et al., 2014; Song et al., 2015; Manjunatha et al., 2011). The enhancement of luminescence may be attributed to the chelation of the ligand to the central metal atom. The chelation enhances the `rigidity' of the ligand and thus reduces the loss of energy through a radiationless pathway (Chen et al., 2011; Ji et al., 2012; Zheng et al., 2001; Wang et al., 2006).
A new dichloride-bridged CdII coordination polymer, (1), has been synthesized and its crystal structure determined by single-crystal X-ray diffraction analysis. The structural analysis of (1) shows that the Schiff base ligand coordinates to the Cd2 atom in an N,N',O-tridentate manner. In complex (1), each CdII ion is six-coordinated and the environment around the Cd2 atom can be described as distorted octahedral geometry, while that around the Cd1 atom is octahedral. The intramolecular nonbonding Cd···Cd separations are 3.701(s.u.?) and 4.356(s.u.?) Å. The Cd—Cl and Cd···Cd distances for (1) are in good agreement with the values that found in other dichloride-bridged CdII complexes. The bridging chloride ligands connect metal centres to generate a one-dimensional infinite chain. Furthermore, analysis of the crystal packing of (1) reveals the existence of weak short-contact interactions between the chains. The photoluminescence studies of complex (1) indicate a red shift compared with its free ligands, and the emission intensity of (1) is stronger than that of the ligands. The luminescence properties show that the photoluminescence arose from an intraligand emission and that it is a novel potential candidate for application in optoelectronic devices.
A solution of 5-bromosalicylaldehyde (5-BrSal; 1 mmol) in methanol (40 ml) was added dropwise to a solution of 1-(2-aminoethyl)pyrrolidine (aep; 1 mmol) in methanol (40 ml). To the resulting yellow solution was added CdCl2 (1 mmol) in methanol (40 ml). It turned light-yellow quickly and after stirring in air for 2 h it is allowed to stay at room temperature for a few weeks. And then the colourless crystals of complex (1) were filtered off, washed with methanol and dried in air (yield 68%, 0.38 g). Analysis calculated for C28H40Br2Cd3Cl4N4O4: C 29.62, H 3.55, N 4.93%; found: C 30.01, H 3.50, N 4.98%. UV–Vis (DMSO): 330 and 390 nm.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were included in idealized positions with isotropic displacement parameters constrained to 1.5Ueq(C) for methyl H atoms and to 1.2Ueq(C,O) otherwise.
Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007; Palatinus & van der Lee, 2008; Palatinus et al., 2012); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
[Cd3Cl4(C13H16BrN2O)2(CH4O)2] | Z = 1 |
Mr = 1135.51 | F(000) = 547.8019 |
Triclinic, P1 | Dx = 2.019 Mg m−3 |
a = 8.1048 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.3928 (6) Å | Cell parameters from 3216 reflections |
c = 11.5740 (6) Å | θ = 3.8–28.3° |
α = 100.957 (5)° | µ = 4.16 mm−1 |
β = 96.178 (4)° | T = 293 K |
γ = 99.694 (5)° | Block, colorless |
V = 933.59 (9) Å3 | 0.48 × 0.44 × 0.14 mm |
Agilent Xcalibur Eos diffractometer | 3810 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3063 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 8.0667 pixels mm-1 | θmax = 26.4°, θmin = 3.0° |
ω scans | h = −9→10 |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2014), based on expressions derived by Clark & Reid (1995)] | k = −12→12 |
Tmin = 0.258, Tmax = 0.613 | l = −13→14 |
7022 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0334P)2 + 0.0622P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3810 reflections | Δρmax = 1.44 e Å−3 |
209 parameters | Δρmin = −1.16 e Å−3 |
1 restraint | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods |
[Cd3Cl4(C13H16BrN2O)2(CH4O)2] | γ = 99.694 (5)° |
Mr = 1135.51 | V = 933.59 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.1048 (4) Å | Mo Kα radiation |
b = 10.3928 (6) Å | µ = 4.16 mm−1 |
c = 11.5740 (6) Å | T = 293 K |
α = 100.957 (5)° | 0.48 × 0.44 × 0.14 mm |
β = 96.178 (4)° |
Agilent Xcalibur Eos diffractometer | 3810 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2014), based on expressions derived by Clark & Reid (1995)] | 3063 reflections with I > 2σ(I) |
Tmin = 0.258, Tmax = 0.613 | Rint = 0.029 |
7022 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 1 restraint |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 1.44 e Å−3 |
3810 reflections | Δρmin = −1.16 e Å−3 |
209 parameters |
Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.5 | 0.5 | 0.5 | 0.02913 (13) | |
Cd2 | 0.91061 (4) | 0.66122 (3) | 0.43178 (3) | 0.03185 (12) | |
Br1 | 1.47271 (10) | 1.16649 (6) | 0.95059 (5) | 0.0753 (2) | |
Cl1 | 0.59816 (15) | 0.67965 (12) | 0.38107 (11) | 0.0418 (3) | |
Cl2 | 1.20870 (14) | 0.56760 (11) | 0.52121 (10) | 0.0354 (3) | |
O1 | 0.9191 (4) | 0.7708 (3) | 0.6176 (3) | 0.0414 (8) | |
O2 | 0.3712 (4) | 0.3379 (4) | 0.3312 (3) | 0.0435 (8) | |
H2 | 0.269 (3) | 0.311 (5) | 0.340 (5) | 0.0653 (12)* | |
N1 | 0.9900 (5) | 0.6193 (4) | 0.2375 (3) | 0.0321 (9) | |
N2 | 1.1034 (5) | 0.8462 (4) | 0.4305 (3) | 0.0342 (9) | |
C1 | 0.4434 (8) | 0.2237 (7) | 0.2930 (6) | 0.090 (3) | |
H1a | 0.366 (3) | 0.161 (2) | 0.231 (3) | 0.135 (4)* | |
H1b | 0.547 (4) | 0.2509 (10) | 0.264 (4) | 0.135 (4)* | |
H1c | 0.466 (6) | 0.182 (3) | 0.3588 (13) | 0.135 (4)* | |
C2 | 0.9993 (7) | 0.4773 (5) | 0.1929 (4) | 0.0481 (14) | |
H2a | 1.0716 (7) | 0.4695 (5) | 0.1314 (4) | 0.0577 (16)* | |
H2b | 1.0437 (7) | 0.4391 (5) | 0.2570 (4) | 0.0577 (16)* | |
C3 | 0.8219 (8) | 0.4083 (6) | 0.1440 (5) | 0.0630 (17) | |
H3a | 0.8196 (8) | 0.3382 (6) | 0.0750 (5) | 0.076 (2)* | |
H3b | 0.7678 (8) | 0.3693 (6) | 0.2034 (5) | 0.076 (2)* | |
C4 | 0.7329 (8) | 0.5169 (6) | 0.1098 (5) | 0.0654 (17) | |
H4a | 0.6967 (8) | 0.4982 (6) | 0.0247 (5) | 0.078 (2)* | |
H4b | 0.6346 (8) | 0.5226 (6) | 0.1501 (5) | 0.078 (2)* | |
C5 | 0.8611 (7) | 0.6442 (5) | 0.1482 (4) | 0.0470 (13) | |
H5a | 0.8088 (7) | 0.7169 (5) | 0.1828 (4) | 0.0564 (16)* | |
H5b | 0.9122 (7) | 0.6672 (5) | 0.0809 (4) | 0.0564 (16)* | |
C6 | 1.1536 (6) | 0.7074 (5) | 0.2503 (4) | 0.0412 (12) | |
H6a | 1.2378 (6) | 0.6730 (5) | 0.2953 (4) | 0.0495 (14)* | |
H6b | 1.1863 (6) | 0.7081 (5) | 0.1722 (4) | 0.0495 (14)* | |
C7 | 1.1515 (7) | 0.8493 (5) | 0.3126 (4) | 0.0451 (13) | |
H7a | 1.0710 (7) | 0.8862 (5) | 0.2669 (4) | 0.0541 (15)* | |
H7b | 1.2626 (7) | 0.9049 (5) | 0.3201 (4) | 0.0541 (15)* | |
C8 | 1.1941 (6) | 0.9262 (4) | 0.5196 (4) | 0.0387 (11) | |
H8 | 1.2825 (6) | 0.9870 (4) | 0.5039 (4) | 0.0464 (13)* | |
C9 | 1.1747 (6) | 0.9331 (4) | 0.6445 (4) | 0.0334 (10) | |
C10 | 1.0403 (6) | 0.8572 (4) | 0.6857 (4) | 0.0339 (11) | |
C11 | 1.0433 (7) | 0.8809 (5) | 0.8105 (4) | 0.0419 (12) | |
H11 | 0.9561 (7) | 0.8337 (5) | 0.8408 (4) | 0.0503 (14)* | |
C12 | 1.1684 (7) | 0.9701 (5) | 0.8889 (4) | 0.0473 (13) | |
H12 | 1.1665 (7) | 0.9818 (5) | 0.9704 (4) | 0.0567 (16)* | |
C13 | 1.2978 (7) | 1.0426 (5) | 0.8451 (4) | 0.0445 (13) | |
C14 | 1.2996 (7) | 1.0241 (4) | 0.7264 (4) | 0.0403 (11) | |
H14 | 1.3872 (7) | 1.0738 (4) | 0.6984 (4) | 0.0484 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0178 (3) | 0.0307 (3) | 0.0392 (3) | 0.0013 (2) | 0.00573 (19) | 0.0102 (2) |
Cd2 | 0.0250 (2) | 0.0326 (2) | 0.03467 (19) | −0.00278 (15) | 0.00705 (14) | 0.00509 (14) |
Br1 | 0.0760 (5) | 0.0579 (4) | 0.0680 (4) | −0.0194 (3) | −0.0351 (3) | 0.0085 (3) |
Cl1 | 0.0265 (7) | 0.0478 (7) | 0.0582 (7) | 0.0056 (6) | 0.0070 (5) | 0.0300 (6) |
Cl2 | 0.0202 (6) | 0.0345 (6) | 0.0543 (7) | 0.0048 (5) | 0.0072 (5) | 0.0155 (5) |
O1 | 0.0269 (19) | 0.044 (2) | 0.0426 (18) | −0.0076 (16) | 0.0107 (15) | −0.0066 (15) |
O2 | 0.031 (2) | 0.046 (2) | 0.0460 (18) | −0.0054 (18) | 0.0085 (16) | 0.0022 (16) |
N1 | 0.026 (2) | 0.035 (2) | 0.0338 (19) | 0.0055 (18) | 0.0019 (16) | 0.0062 (16) |
N2 | 0.033 (2) | 0.030 (2) | 0.038 (2) | 0.0000 (18) | 0.0068 (17) | 0.0069 (17) |
C1 | 0.053 (4) | 0.079 (5) | 0.110 (5) | −0.007 (4) | 0.032 (4) | −0.043 (4) |
C2 | 0.056 (4) | 0.042 (3) | 0.044 (3) | 0.016 (3) | 0.004 (3) | 0.001 (2) |
C3 | 0.071 (5) | 0.054 (4) | 0.055 (3) | −0.001 (3) | −0.001 (3) | 0.006 (3) |
C4 | 0.044 (4) | 0.085 (5) | 0.059 (3) | 0.010 (4) | −0.003 (3) | 0.003 (3) |
C5 | 0.047 (3) | 0.061 (4) | 0.034 (2) | 0.013 (3) | 0.001 (2) | 0.012 (2) |
C6 | 0.033 (3) | 0.053 (3) | 0.038 (3) | 0.002 (2) | 0.011 (2) | 0.011 (2) |
C7 | 0.044 (3) | 0.043 (3) | 0.046 (3) | −0.007 (3) | 0.013 (2) | 0.016 (2) |
C8 | 0.031 (3) | 0.029 (2) | 0.054 (3) | −0.002 (2) | 0.007 (2) | 0.014 (2) |
C9 | 0.028 (3) | 0.026 (2) | 0.042 (2) | 0.001 (2) | −0.003 (2) | 0.005 (2) |
C10 | 0.029 (3) | 0.028 (2) | 0.042 (3) | 0.005 (2) | 0.006 (2) | 0.002 (2) |
C11 | 0.041 (3) | 0.037 (3) | 0.045 (3) | 0.005 (2) | 0.006 (2) | 0.003 (2) |
C12 | 0.055 (4) | 0.043 (3) | 0.040 (3) | 0.007 (3) | −0.005 (2) | 0.007 (2) |
C13 | 0.043 (3) | 0.030 (3) | 0.052 (3) | −0.001 (2) | −0.014 (2) | 0.007 (2) |
C14 | 0.038 (3) | 0.027 (2) | 0.054 (3) | 0.001 (2) | 0.000 (2) | 0.014 (2) |
Cd1—Cl1i | 2.5935 (12) | N1—C5 | 1.479 (6) |
Cd1—Cl1 | 2.5935 (12) | N1—C6 | 1.455 (6) |
Cd1—Cl2ii | 2.5972 (10) | N2—C7 | 1.463 (5) |
Cd1—Cl2iii | 2.5972 (10) | N2—C8 | 1.265 (6) |
Cd1—O2 | 2.337 (3) | C2—C3 | 1.492 (8) |
Cd1—O2i | 2.337 (3) | C3—C4 | 1.528 (8) |
Cd2—Cl1 | 2.5846 (12) | C4—C5 | 1.497 (8) |
Cd2—Cl2 | 2.9140 (11) | C6—C7 | 1.517 (6) |
Cd2—Cl2ii | 2.5917 (12) | C8—C9 | 1.461 (6) |
Cd2—O1 | 2.222 (3) | C9—C10 | 1.415 (6) |
Cd2—N1 | 2.386 (3) | C9—C14 | 1.396 (6) |
Cd2—N2 | 2.268 (4) | C10—C11 | 1.415 (6) |
Br1—C13 | 1.890 (5) | C11—C12 | 1.370 (7) |
O1—C10 | 1.289 (5) | C12—C13 | 1.385 (7) |
O2—C1 | 1.427 (7) | C13—C14 | 1.352 (6) |
N1—C2 | 1.485 (6) | ||
Cl1—Cd1—Cl1i | 180.0 | Cd2—Cl2—Cd1iv | 152.28 (5) |
Cl2iii—Cd1—Cl1 | 94.52 (4) | C10—O1—Cd2 | 129.4 (3) |
Cl2ii—Cd1—Cl1i | 94.52 (4) | C1—O2—Cd1 | 120.7 (3) |
Cl2iii—Cd1—Cl1i | 85.48 (4) | C2—N1—Cd2 | 113.2 (3) |
Cl2ii—Cd1—Cl1 | 85.48 (4) | C5—N1—Cd2 | 111.3 (3) |
Cl2ii—Cd1—Cl2iii | 180.0 | C5—N1—C2 | 103.3 (4) |
O2i—Cd1—Cl1i | 94.42 (9) | C6—N1—Cd2 | 103.9 (2) |
O2i—Cd1—Cl1 | 85.58 (9) | C6—N1—C2 | 111.9 (4) |
O2—Cd1—Cl1i | 85.58 (9) | C6—N1—C5 | 113.6 (4) |
O2—Cd1—Cl1 | 94.42 (9) | C7—N2—Cd2 | 112.8 (3) |
O2—Cd1—Cl2iii | 88.81 (9) | C8—N2—Cd2 | 127.0 (3) |
O2i—Cd1—Cl2ii | 88.81 (9) | C8—N2—C7 | 118.3 (4) |
O2—Cd1—Cl2ii | 91.19 (9) | C3—C2—N1 | 105.4 (4) |
O2i—Cd1—Cl2iii | 91.19 (9) | C4—C3—C2 | 105.3 (5) |
O2i—Cd1—O2 | 180.0 | C5—C4—C3 | 105.6 (5) |
Cl2ii—Cd2—Cl1 | 85.78 (4) | C4—C5—N1 | 106.0 (4) |
Cl2—Cd2—Cl1 | 160.89 (4) | C7—C6—N1 | 112.3 (4) |
O1—Cd2—Cl1 | 90.95 (9) | C6—C7—N2 | 108.3 (4) |
O1—Cd2—Cl2 | 86.11 (9) | C9—C8—N2 | 126.9 (4) |
O1—Cd2—Cl2ii | 93.15 (9) | C10—C9—C8 | 125.0 (4) |
N1—Cd2—Cl1 | 100.64 (9) | C14—C9—C8 | 115.5 (4) |
N1—Cd2—Cl2ii | 107.56 (9) | C14—C9—C10 | 119.5 (4) |
N1—Cd2—Cl2 | 89.04 (9) | C9—C10—O1 | 124.3 (4) |
N1—Cd2—O1 | 156.81 (13) | C11—C10—O1 | 119.6 (4) |
N2—Cd2—Cl1 | 115.26 (10) | C11—C10—C9 | 116.0 (4) |
N2—Cd2—Cl2ii | 158.05 (10) | C12—C11—C10 | 123.2 (5) |
N2—Cd2—Cl2 | 82.95 (10) | C13—C12—C11 | 119.1 (5) |
N2—Cd2—O1 | 80.90 (12) | C12—C13—Br1 | 120.2 (4) |
N2—Cd2—N1 | 76.01 (12) | C14—C13—Br1 | 119.9 (4) |
Cd2—Cl1—Cd1i | 91.24 (4) | C14—C13—C12 | 119.9 (5) |
Cd2ii—Cl2—Cd1iv | 91.00 (3) | C13—C14—C9 | 122.3 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x−1, y, z; (iv) x+1, y, z. |
Cg11 is the centroid of the C9–C14 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.88 (3) | 1.78 (4) | 2.612 (5) | 165 (5) |
C14—H14···Cl1v | 0.93 | 2.87 | 3.540 (4) | 130 |
C5—H5A···C13v | 0.97 | 2.84 | 3.687 (5) | 146 |
C7—H7B···Cg11v | 0.97 | 2.84 | 3.740 (6) | 156 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (v) −x+2, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cd3Cl4(C13H16BrN2O)2(CH4O)2] |
Mr | 1135.51 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.1048 (4), 10.3928 (6), 11.5740 (6) |
α, β, γ (°) | 100.957 (5), 96.178 (4), 99.694 (5) |
V (Å3) | 933.59 (9) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 4.16 |
Crystal size (mm) | 0.48 × 0.44 × 0.14 |
Data collection | |
Diffractometer | Agilent Xcalibur Eos |
Absorption correction | Analytical [CrysAlis PRO (Agilent, 2014), based on expressions derived by Clark & Reid (1995)] |
Tmin, Tmax | 0.258, 0.613 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7022, 3810, 3063 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.082, 1.03 |
No. of reflections | 3810 |
No. of parameters | 209 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.44, −1.16 |
Computer programs: CrysAlis PRO (Agilent, 2014), SUPERFLIP (Palatinus & Chapuis, 2007; Palatinus & van der Lee, 2008; Palatinus et al., 2012), OLEX2 (Dolomanov et al., 2009).
Cd1—Cl1i | 2.5935 (12) | Cd2—Cl2 | 2.9140 (11) |
Cd1—Cl1 | 2.5935 (12) | Cd2—Cl2iii | 2.5917 (12) |
Cd1—Cl2ii | 2.5972 (10) | Cd2—O1 | 2.222 (3) |
Cd1—O2 | 2.337 (3) | Cd2—N1 | 2.386 (3) |
Cd2—Cl1 | 2.5846 (12) | Cd2—N2 | 2.268 (4) |
Cl1—Cd1—Cl1i | 180.0 | N1—Cd2—Cl2iii | 107.56 (9) |
Cl2ii—Cd1—Cl1i | 85.48 (4) | N1—Cd2—Cl2 | 89.04 (9) |
O2i—Cd1—Cl1i | 94.42 (9) | N1—Cd2—O1 | 156.81 (13) |
O2—Cd1—Cl2ii | 88.81 (9) | N2—Cd2—Cl1 | 115.26 (10) |
Cl2iii—Cd2—Cl1 | 85.78 (4) | N2—Cd2—O1 | 80.90 (12) |
Cl2—Cd2—Cl1 | 160.89 (4) | N2—Cd2—N1 | 76.01 (12) |
O1—Cd2—Cl1 | 90.95 (9) | Cd2—Cl1—Cd1i | 91.24 (4) |
O1—Cd2—Cl2 | 86.11 (9) | Cd2iii—Cl2—Cd1iv | 91.00 (3) |
O1—Cd2—Cl2iii | 93.15 (9) | Cd2—Cl2—Cd1iv | 152.28 (5) |
N1—Cd2—Cl1 | 100.64 (9) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+2, −y+1, −z+1; (iv) x+1, y, z. |
Cg11 is the centroid of the C9–C14 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.88 (3) | 1.78 (4) | 2.612 (5) | 165 (5) |
C14—H14···Cl1v | 0.930 | 2.87 | 3.540 (4) | 130 |
C5—H5A···C13v | 0.970 | 2.84 | 3.687 (5) | 146 |
C7—H7B···Cg11v | 0.970 | 2.84 | 3.740 (6) | 156 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (v) −x+2, −y+2, −z+1. |
Complex | ν(C—H) (aromatic) | ν(C—H) (aliphatic) | ν(C═N) | ν(C—O) (aromatic) | ν(C—Br) |
(1) | 3010 | 2910, 2835 | 1640 | 1308 | 634 |