Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614027090/sk3571sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614027090/sk3571Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229614027090/sk3571sup3.pdf |
CCDC reference: 1038656
In recent years, much attention has been paid to the crystal engineering of new dielectric and ferroelectric materials due to a combination of their fascinating molecular structures and their potential applications as capacitors, resonators, switchable nonlinear optical devices and light modulators (Scott & Dearaujo, 1989; Fu et al., 2008., Ye et al., 2013). In the search for potential ferroelectric materials, the quite unique Perovskite-like hybrid coordination polymers, which are assembled by the inclusion of guest species into the well-matched rigid cavities, may be promising candidates for the construction of ferroelectric materials. Upon application of an external stimulus such as temperature or pressure, the mobile guest molecules or ions can act as carriers of electric dipole moments; the order–disorder transformation and even the reorientation of the guest molecules in a perovskite-type metal–organic framework (MOF) may lead to distinctive dielectric performances at the phase transition point. Reports of dielectric properties of such MOFs, however, have been scarce. Because ligands containing diatomic CN-, multi-atomic HCOO- and N3- anions can act as monovalent end-to-end bridging ligands, they are mainly employed in the construction of perovskite-type structures. An interesting example of a well-designed MOF-based switchable dielectric, [(CH3)2NH2]2[KCo(CN)6], shows a striking increase of the dielectric constant over a large temperature range (Zhang et al., 2013). Meanwhile, a family of multiferroics based on chiral metal–formate frameworks, (NH4)[M(HCOO)3] (M = Mn, Fe, Co, and Ni), have also been discovered, which display ferroelectric orderings in the range 191–254 K and antiferromagnetic orderings in the range 8–30 K (Xu et al., 2011).
On the other hand, the anionic pseudohalide dicyanamide [dca, N(CN)2-] has been used widely because of its polydentate character and its bridging ability (Batten & Murray, 2003). Encouraged by previous works, we are interested in searching for new types of ferroelectrics among perovskite-like hybrid coordination polymers. Hence, an organic phosphine salt was used as a template for the formation of a three-dimensional anionic cube-type structure. We speculate that the reorientation of the organic cation may be the driving force for a structural phase transition. The title compound, poly[ethyltriphenylphosphonium [tri-µ2-dicyanamido-cadmium(II)]], (I), was prepared and found to crystallize as the three-dimensional anionic cadmium(II) dicyanamide network, with EtPh3P+ cations in the anionic cages.
The title compound was obtained from an aqueous solution containing ethyltriphenylphosphonium bromide, cadmium nitrate tetrahydrate and sodium dicyanamide with a 1:1:3 molar ratio. The resulting aqueous solution was kept at room temperature. Suitable colourless block-shaped single crystals were obtained by slow evaporation of the aqueous solution for several days.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene), and Uiso(H) = 1.5Ueq(C) for methyl groups or 1.2Ueq(C) otherwise. The phenyl ring involving atom C1 shows some disorder. SHELXL (Sheldrick, 2008) SIMU (SIMU 0.01 0.02 3.8 C3 C2 C4) and DFIX (DFIX 1.38 0.01 C1 C6) restraints were applied to address this issue.
The crystallographically independent unit in salt (I) is composed of a CdII cation and six halves of three anionic dicyanamide (dca) ligands, complemented by a noncoordinating ethyltriphenylphosphonium (EtPh3P+) counter-ion (Fig. 1).
The CdII atom is six-coordinated by six terminal N atoms from the anionic dca ligands, adopting a distorted octahedrally coordination geometry (Fig. 1). The Cd—N bond lengths range from 2.286 (3) to 2.369 (2) Å (Table 2) and the cis-N—Cd—N angles range from 86.73 (9) to 94.21 (10)°, which are all in good agreement with values found in other CdII complexes with a six-coordinated geometry (Biswas et al., 2006). Additionally, the CdII atoms are not coordinated linearly to the dicyanamide ligands with Cd1—N1—C21, Cd1—N3—C22 and Cd1—N7—C25 bond angles of 170.9 (3), 174.7 (3) and 151.8 (3)°, respectively. The N1—C21, N3—C22, N6—C24, N2—C21 and N4—C22 bond lengths (Table 2) indicate triple- and single-bond character, as is typical for bridging [N(CN)2]- ligands. All bond lengths and angles within the dca ligands are typical of the M—N···C—N—C···N—M bridging mode.
The anionic three-dimensional [Cd(dca)3]- network (Fig. 2a) in (I) is best described topologically. Each of the CdII atoms is connected to six neighbouring CdII atoms via six separate dca ligands (Fig. 2b). This differs from the two-dimensional anionic cadmium network of the tris-dicyanamide compound (Et4N)[Cd{N(CN)2}3]·0.75H2O (Biswas et al., 2006), where the metal atoms are connected in one direction by double M(dca)2M bridges and in the other direction by single dca bridges. Even if the difference in bridging type is ignored, the topology of this anionic lattice is also different from that in (TPnA)[M(dca)3] (M = Mn and Ni, TPnA = tetrapentylammonium), where each metal atom is connected to four neighbouring mental atoms through double µ1,5-dca bridges (edge sharing) and to two others through a single µ1,5-dca bridge (corner sharing) (Schlueter et al., 2005).
The solvent-accessible volume of the anionic network in (I) was calculated with the VOID/SOLV tool in the PLATON program package (Spek, 2015). That void space amounts to 1851 Å3, which is 69.3% of the unit-cell volume. The single anionic cage is formed by Cd—N≡C—N—C≡N units and the equatorial and apical Cd···Cd distances are 8.776 (2) and 8.923 (2) Å, respectively. It should be noted that a single anionic cage can be described as a concave hexahedron rather than a cube. At different concentrations, the dca ligands have distinct shapes in this system. Firstly, they mediate the formation of adjacent cages by sharing four CdII atoms as vertices. As shown in Fig. 3(b), to better understand the anionic cage, in our notation, the letters A, B, C and D stand for the dca ligands at the top of the left cage, while the letters A', B', C' and D' stand for the dca ligands in the bottom of the left cage. Interestingly, at the top of the cage, A and B extend outward, while C and D extend inward. At the bottom of the cage, A' and B' extend inward, and C' and D' extend outward. By contrast, the dca types in the right cage are opposite to those in the left cage. In other words, it can be regarded that the right cage can be obtained from the left by an asymmetry operation of up/down conversion of 180°. This phenomenon is different from (MePh3P)[M(dca)3] (M = Co, Mn) and (EtPh3P)[M(dca)3] (M = Co, Mn), where the cavities of the anionic [M(dca)3]- networks are constructed by one hexagonal window each from two adjoining hexagonal sheets and the six dca bridges connecting the two windows (van der Werff et al., 2001, 2004). In addition, in those compounds, the cations lie in pairs within cavities in the anionic network. As shown in Fig. 3(b), each of these cavities in (I) accommodates only one EtPh3P+ cation, but the orientations of the two cations in the adjacent cages are different, the phenyl rings of the two cations also display inter-cavity edge-to-face and vertex-to-face interactions. The P···P distance between two adjacent cages is 10.552 (3) Å.
A precise analysis of the main packing of (I) is needed to disclose the roles of the dca ligands in the formation of the three-dimensional network. As shown in Fig. 4, each of the CdII atoms is connected by four dca ligands in the [100] and [001] directions, forming a two-dimensional network. The equivalent two-dimensional network stacks up effectively and co-operatively, forming the covalently linked three-dimensional framework. This is also different from what was found in our previous work. In [(CH3)4P][Cd(NCNCN)2Cl], one type of dca molecule is involved in the formation of [Cd(dca)Cl]2 building blocks and the other links these building blocks into a three-dimensional structure (Li & Wang, 2014).
Our interest in perovskite-type metal–organic frameworks (MOFs), especially the well designed MOF-based switchable dielectrics [(CH3)2NH2]2[KCo(CN)6] and [N(CH3)4][Cd(N3)3], is based mainly on their potential applications in molecular dielectrics and ferroelectrics (Zhang et al., 2013; Du et al., 2014). The variable-temperature dielectric response, especially in the relatively high frequency range, is treated as an effective indicator of a structural phase transition (Ye et al., 2011; Fu et al., 2011; Shi et al., 2014). However, we were unable to detect any dielectric anomalies for (I) over the frequency range of 10 to 1 MHz and in the temperature range from 103 to 453 K, suggesting that there are no structural phase transitions during the cooling and heating processes. Maybe the EtPh3P+ cation is too large and can not generate prominant molecular motions, such as order–disorder transformations, rotational and orientational motions. Further phase-transition materials still need to be sought and explored.
In recent years, much attention has been paid to the crystal engineering of new dielectric and ferroelectric materials due to a combination of their fascinating molecular structures and their potential applications as capacitors, resonators, switchable nonlinear optical devices and light modulators (Scott & Dearaujo, 1989; Fu et al., 2008., Ye et al., 2013). In the search for potential ferroelectric materials, the quite unique Perovskite-like hybrid coordination polymers, which are assembled by the inclusion of guest species into the well-matched rigid cavities, may be promising candidates for the construction of ferroelectric materials. Upon application of an external stimulus such as temperature or pressure, the mobile guest molecules or ions can act as carriers of electric dipole moments; the order–disorder transformation and even the reorientation of the guest molecules in a perovskite-type metal–organic framework (MOF) may lead to distinctive dielectric performances at the phase transition point. Reports of dielectric properties of such MOFs, however, have been scarce. Because ligands containing diatomic CN-, multi-atomic HCOO- and N3- anions can act as monovalent end-to-end bridging ligands, they are mainly employed in the construction of perovskite-type structures. An interesting example of a well-designed MOF-based switchable dielectric, [(CH3)2NH2]2[KCo(CN)6], shows a striking increase of the dielectric constant over a large temperature range (Zhang et al., 2013). Meanwhile, a family of multiferroics based on chiral metal–formate frameworks, (NH4)[M(HCOO)3] (M = Mn, Fe, Co, and Ni), have also been discovered, which display ferroelectric orderings in the range 191–254 K and antiferromagnetic orderings in the range 8–30 K (Xu et al., 2011).
On the other hand, the anionic pseudohalide dicyanamide [dca, N(CN)2-] has been used widely because of its polydentate character and its bridging ability (Batten & Murray, 2003). Encouraged by previous works, we are interested in searching for new types of ferroelectrics among perovskite-like hybrid coordination polymers. Hence, an organic phosphine salt was used as a template for the formation of a three-dimensional anionic cube-type structure. We speculate that the reorientation of the organic cation may be the driving force for a structural phase transition. The title compound, poly[ethyltriphenylphosphonium [tri-µ2-dicyanamido-cadmium(II)]], (I), was prepared and found to crystallize as the three-dimensional anionic cadmium(II) dicyanamide network, with EtPh3P+ cations in the anionic cages.
The crystallographically independent unit in salt (I) is composed of a CdII cation and six halves of three anionic dicyanamide (dca) ligands, complemented by a noncoordinating ethyltriphenylphosphonium (EtPh3P+) counter-ion (Fig. 1).
The CdII atom is six-coordinated by six terminal N atoms from the anionic dca ligands, adopting a distorted octahedrally coordination geometry (Fig. 1). The Cd—N bond lengths range from 2.286 (3) to 2.369 (2) Å (Table 2) and the cis-N—Cd—N angles range from 86.73 (9) to 94.21 (10)°, which are all in good agreement with values found in other CdII complexes with a six-coordinated geometry (Biswas et al., 2006). Additionally, the CdII atoms are not coordinated linearly to the dicyanamide ligands with Cd1—N1—C21, Cd1—N3—C22 and Cd1—N7—C25 bond angles of 170.9 (3), 174.7 (3) and 151.8 (3)°, respectively. The N1—C21, N3—C22, N6—C24, N2—C21 and N4—C22 bond lengths (Table 2) indicate triple- and single-bond character, as is typical for bridging [N(CN)2]- ligands. All bond lengths and angles within the dca ligands are typical of the M—N···C—N—C···N—M bridging mode.
The anionic three-dimensional [Cd(dca)3]- network (Fig. 2a) in (I) is best described topologically. Each of the CdII atoms is connected to six neighbouring CdII atoms via six separate dca ligands (Fig. 2b). This differs from the two-dimensional anionic cadmium network of the tris-dicyanamide compound (Et4N)[Cd{N(CN)2}3]·0.75H2O (Biswas et al., 2006), where the metal atoms are connected in one direction by double M(dca)2M bridges and in the other direction by single dca bridges. Even if the difference in bridging type is ignored, the topology of this anionic lattice is also different from that in (TPnA)[M(dca)3] (M = Mn and Ni, TPnA = tetrapentylammonium), where each metal atom is connected to four neighbouring mental atoms through double µ1,5-dca bridges (edge sharing) and to two others through a single µ1,5-dca bridge (corner sharing) (Schlueter et al., 2005).
The solvent-accessible volume of the anionic network in (I) was calculated with the VOID/SOLV tool in the PLATON program package (Spek, 2015). That void space amounts to 1851 Å3, which is 69.3% of the unit-cell volume. The single anionic cage is formed by Cd—N≡C—N—C≡N units and the equatorial and apical Cd···Cd distances are 8.776 (2) and 8.923 (2) Å, respectively. It should be noted that a single anionic cage can be described as a concave hexahedron rather than a cube. At different concentrations, the dca ligands have distinct shapes in this system. Firstly, they mediate the formation of adjacent cages by sharing four CdII atoms as vertices. As shown in Fig. 3(b), to better understand the anionic cage, in our notation, the letters A, B, C and D stand for the dca ligands at the top of the left cage, while the letters A', B', C' and D' stand for the dca ligands in the bottom of the left cage. Interestingly, at the top of the cage, A and B extend outward, while C and D extend inward. At the bottom of the cage, A' and B' extend inward, and C' and D' extend outward. By contrast, the dca types in the right cage are opposite to those in the left cage. In other words, it can be regarded that the right cage can be obtained from the left by an asymmetry operation of up/down conversion of 180°. This phenomenon is different from (MePh3P)[M(dca)3] (M = Co, Mn) and (EtPh3P)[M(dca)3] (M = Co, Mn), where the cavities of the anionic [M(dca)3]- networks are constructed by one hexagonal window each from two adjoining hexagonal sheets and the six dca bridges connecting the two windows (van der Werff et al., 2001, 2004). In addition, in those compounds, the cations lie in pairs within cavities in the anionic network. As shown in Fig. 3(b), each of these cavities in (I) accommodates only one EtPh3P+ cation, but the orientations of the two cations in the adjacent cages are different, the phenyl rings of the two cations also display inter-cavity edge-to-face and vertex-to-face interactions. The P···P distance between two adjacent cages is 10.552 (3) Å.
A precise analysis of the main packing of (I) is needed to disclose the roles of the dca ligands in the formation of the three-dimensional network. As shown in Fig. 4, each of the CdII atoms is connected by four dca ligands in the [100] and [001] directions, forming a two-dimensional network. The equivalent two-dimensional network stacks up effectively and co-operatively, forming the covalently linked three-dimensional framework. This is also different from what was found in our previous work. In [(CH3)4P][Cd(NCNCN)2Cl], one type of dca molecule is involved in the formation of [Cd(dca)Cl]2 building blocks and the other links these building blocks into a three-dimensional structure (Li & Wang, 2014).
Our interest in perovskite-type metal–organic frameworks (MOFs), especially the well designed MOF-based switchable dielectrics [(CH3)2NH2]2[KCo(CN)6] and [N(CH3)4][Cd(N3)3], is based mainly on their potential applications in molecular dielectrics and ferroelectrics (Zhang et al., 2013; Du et al., 2014). The variable-temperature dielectric response, especially in the relatively high frequency range, is treated as an effective indicator of a structural phase transition (Ye et al., 2011; Fu et al., 2011; Shi et al., 2014). However, we were unable to detect any dielectric anomalies for (I) over the frequency range of 10 to 1 MHz and in the temperature range from 103 to 453 K, suggesting that there are no structural phase transitions during the cooling and heating processes. Maybe the EtPh3P+ cation is too large and can not generate prominant molecular motions, such as order–disorder transformations, rotational and orientational motions. Further phase-transition materials still need to be sought and explored.
The title compound was obtained from an aqueous solution containing ethyltriphenylphosphonium bromide, cadmium nitrate tetrahydrate and sodium dicyanamide with a 1:1:3 molar ratio. The resulting aqueous solution was kept at room temperature. Suitable colourless block-shaped single crystals were obtained by slow evaporation of the aqueous solution for several days.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene), and Uiso(H) = 1.5Ueq(C) for methyl groups or 1.2Ueq(C) otherwise. The phenyl ring involving atom C1 shows some disorder. SHELXL (Sheldrick, 2008) SIMU (SIMU 0.01 0.02 3.8 C3 C2 C4) and DFIX (DFIX 1.38 0.01 C1 C6) restraints were applied to address this issue.
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: PLATON (Spek, 2009) and SHELXL97 (Sheldrick, 2008).
(C20H20P)[Cd(C2N3)3] | F(000) = 1208 |
Mr = 601.89 | Dx = 1.497 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 17111 reflections |
a = 12.238 (2) Å | θ = 3.2–27.5° |
b = 17.073 (3) Å | µ = 0.91 mm−1 |
c = 12.782 (3) Å | T = 293 K |
β = 90.95 (3)° | Block, colourless |
V = 2670.3 (9) Å3 | 0.30 × 0.26 × 0.25 mm |
Z = 4 |
Rigaku SCXmini diffractometer | 6110 independent reflections |
Radiation source: fine-focus sealed tube | 5318 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | h = −15→14 |
Tmin = 0.761, Tmax = 0.797 | k = −20→22 |
18346 measured reflections | l = −15→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0392P)2 + 3.4753P] where P = (Fo2 + 2Fc2)/3 |
6110 reflections | (Δ/σ)max = 0.002 |
335 parameters | Δρmax = 0.60 e Å−3 |
19 restraints | Δρmin = −0.65 e Å−3 |
(C20H20P)[Cd(C2N3)3] | V = 2670.3 (9) Å3 |
Mr = 601.89 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.238 (2) Å | µ = 0.91 mm−1 |
b = 17.073 (3) Å | T = 293 K |
c = 12.782 (3) Å | 0.30 × 0.26 × 0.25 mm |
β = 90.95 (3)° |
Rigaku SCXmini diffractometer | 6110 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 5318 reflections with I > 2σ(I) |
Tmin = 0.761, Tmax = 0.797 | Rint = 0.029 |
18346 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 19 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.60 e Å−3 |
6110 reflections | Δρmin = −0.65 e Å−3 |
335 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.801258 (14) | 0.244510 (10) | 0.718461 (13) | 0.02472 (7) | |
P1 | 0.25602 (6) | 0.15254 (4) | 0.72354 (5) | 0.03389 (16) | |
N6 | 0.7625 (2) | 0.37253 (14) | 0.6568 (2) | 0.0435 (6) | |
N7 | 0.9440 (2) | 0.22471 (17) | 0.6039 (2) | 0.0463 (6) | |
N3 | 0.6839 (2) | 0.19920 (17) | 0.5834 (2) | 0.0494 (6) | |
N1 | 0.8299 (2) | 0.11808 (15) | 0.7835 (2) | 0.0465 (6) | |
N5 | 0.9245 (2) | 0.29835 (17) | 0.8402 (2) | 0.0487 (6) | |
N2 | 0.8417 (3) | −0.00781 (15) | 0.8725 (3) | 0.0654 (9) | |
N4 | 0.5542 (3) | 0.1402 (2) | 0.4603 (3) | 0.0899 (14) | |
N9 | 0.6570 (2) | 0.25909 (16) | 0.8281 (2) | 0.0502 (7) | |
N8 | 1.0041 (2) | 0.19281 (19) | 0.4285 (2) | 0.0606 (8) | |
C22 | 0.6221 (3) | 0.17521 (18) | 0.5242 (2) | 0.0449 (7) | |
C21 | 0.8310 (2) | 0.05794 (16) | 0.8215 (2) | 0.0390 (6) | |
C23 | 0.9871 (3) | 0.32318 (18) | 0.8980 (2) | 0.0455 (7) | |
C25 | 0.9770 (2) | 0.21247 (17) | 0.5223 (2) | 0.0370 (6) | |
C24 | 0.7156 (2) | 0.43040 (16) | 0.6483 (2) | 0.0354 (6) | |
C19 | 0.1466 (3) | 0.1737 (2) | 0.8110 (3) | 0.0502 (8) | |
H19A | 0.1697 | 0.2164 | 0.8563 | 0.060* | |
H19B | 0.0847 | 0.1923 | 0.7696 | 0.060* | |
C13 | 0.3678 (2) | 0.10658 (17) | 0.7919 (2) | 0.0398 (6) | |
C7 | 0.3029 (3) | 0.24403 (16) | 0.6729 (2) | 0.0385 (6) | |
C18 | 0.3938 (2) | 0.12893 (18) | 0.8931 (3) | 0.0456 (7) | |
H18 | 0.3495 | 0.1641 | 0.9283 | 0.055* | |
C1 | 0.2155 (3) | 0.08902 (17) | 0.6192 (2) | 0.0417 (7) | |
C12 | 0.4132 (3) | 0.25896 (19) | 0.6661 (3) | 0.0482 (8) | |
H12 | 0.4635 | 0.2213 | 0.6881 | 0.058* | |
C11 | 0.4495 (3) | 0.3294 (2) | 0.6270 (3) | 0.0601 (9) | |
H11 | 0.5241 | 0.3391 | 0.6234 | 0.072* | |
C20 | 0.1078 (3) | 0.1074 (3) | 0.8793 (3) | 0.0753 (12) | |
H20A | 0.0765 | 0.0669 | 0.8361 | 0.113* | |
H20B | 0.0536 | 0.1266 | 0.9264 | 0.113* | |
H20C | 0.1685 | 0.0866 | 0.9188 | 0.113* | |
C10 | 0.3777 (3) | 0.3846 (2) | 0.5937 (3) | 0.0645 (10) | |
H10 | 0.4028 | 0.4314 | 0.5658 | 0.077* | |
C14 | 0.4327 (3) | 0.0531 (3) | 0.7409 (3) | 0.0715 (12) | |
H14 | 0.4147 | 0.0370 | 0.6732 | 0.086* | |
C16 | 0.5508 (3) | 0.0464 (3) | 0.8906 (3) | 0.0705 (11) | |
H16 | 0.6129 | 0.0263 | 0.9238 | 0.085* | |
C6 | 0.2453 (3) | 0.1034 (2) | 0.5191 (3) | 0.0609 (9) | |
H6 | 0.2800 | 0.1502 | 0.5030 | 0.073* | |
C17 | 0.4865 (3) | 0.0986 (2) | 0.9420 (3) | 0.0605 (9) | |
H17 | 0.5049 | 0.1138 | 1.0099 | 0.073* | |
C8 | 0.2281 (3) | 0.3015 (2) | 0.6420 (4) | 0.0708 (12) | |
H8 | 0.1534 | 0.2934 | 0.6483 | 0.085* | |
C15 | 0.5252 (4) | 0.0234 (3) | 0.7916 (4) | 0.0853 (15) | |
H15 | 0.5696 | −0.0124 | 0.7575 | 0.102* | |
C5 | 0.2245 (4) | 0.0491 (3) | 0.4412 (3) | 0.0792 (13) | |
H5 | 0.2475 | 0.0591 | 0.3734 | 0.095* | |
C4 | 0.1716 (6) | −0.0178 (3) | 0.4621 (4) | 0.125 (2) | |
H4 | 0.1527 | −0.0527 | 0.4089 | 0.150* | |
C9 | 0.2681 (4) | 0.3713 (2) | 0.6014 (4) | 0.0847 (15) | |
H9 | 0.2191 | 0.4096 | 0.5791 | 0.102* | |
C2 | 0.1668 (7) | 0.0204 (3) | 0.6407 (4) | 0.146 (2) | |
H2 | 0.1468 | 0.0091 | 0.7089 | 0.176* | |
C3 | 0.1464 (7) | −0.0331 (4) | 0.5623 (5) | 0.162 (3) | |
H3 | 0.1146 | −0.0809 | 0.5789 | 0.195* | |
C26 | 0.5870 (3) | 0.27917 (19) | 0.8804 (2) | 0.0418 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.02464 (10) | 0.02685 (10) | 0.02272 (10) | 0.00198 (7) | 0.00177 (6) | −0.00041 (7) |
P1 | 0.0336 (3) | 0.0356 (4) | 0.0325 (4) | 0.0024 (3) | 0.0022 (3) | 0.0025 (3) |
N6 | 0.0526 (15) | 0.0296 (12) | 0.0481 (14) | 0.0018 (11) | −0.0036 (12) | 0.0009 (11) |
N7 | 0.0425 (14) | 0.0581 (16) | 0.0387 (14) | 0.0004 (12) | 0.0177 (11) | 0.0014 (12) |
N3 | 0.0467 (15) | 0.0550 (16) | 0.0460 (15) | 0.0039 (12) | −0.0153 (12) | −0.0085 (13) |
N1 | 0.0554 (16) | 0.0338 (13) | 0.0501 (15) | −0.0005 (11) | −0.0015 (12) | 0.0081 (11) |
N5 | 0.0444 (14) | 0.0553 (16) | 0.0459 (15) | 0.0077 (12) | −0.0157 (12) | −0.0133 (12) |
N2 | 0.081 (2) | 0.0313 (14) | 0.082 (2) | −0.0135 (14) | −0.0432 (18) | 0.0152 (14) |
N4 | 0.107 (3) | 0.0487 (18) | 0.111 (3) | −0.0013 (17) | −0.083 (3) | 0.0011 (18) |
N9 | 0.0447 (15) | 0.0624 (18) | 0.0440 (15) | 0.0045 (12) | 0.0196 (12) | −0.0009 (12) |
N8 | 0.0633 (18) | 0.071 (2) | 0.0488 (16) | −0.0267 (15) | 0.0301 (14) | −0.0172 (14) |
C22 | 0.0463 (17) | 0.0402 (16) | 0.0476 (17) | 0.0026 (13) | −0.0168 (14) | 0.0027 (13) |
C21 | 0.0422 (15) | 0.0320 (14) | 0.0425 (15) | −0.0033 (12) | −0.0064 (12) | −0.0017 (12) |
C23 | 0.0483 (17) | 0.0449 (17) | 0.0426 (16) | 0.0109 (14) | −0.0156 (14) | −0.0028 (13) |
C25 | 0.0316 (13) | 0.0381 (15) | 0.0416 (16) | −0.0036 (12) | 0.0093 (11) | 0.0022 (12) |
C24 | 0.0418 (15) | 0.0281 (13) | 0.0360 (14) | −0.0059 (11) | −0.0065 (11) | −0.0010 (11) |
C19 | 0.0408 (16) | 0.066 (2) | 0.0436 (17) | 0.0125 (15) | 0.0069 (13) | −0.0034 (15) |
C13 | 0.0378 (14) | 0.0387 (15) | 0.0429 (16) | 0.0075 (12) | 0.0032 (12) | 0.0097 (12) |
C7 | 0.0438 (16) | 0.0337 (14) | 0.0378 (15) | −0.0013 (11) | −0.0082 (12) | 0.0029 (11) |
C18 | 0.0419 (16) | 0.0421 (16) | 0.0527 (18) | 0.0022 (13) | −0.0064 (13) | 0.0008 (14) |
C1 | 0.0497 (17) | 0.0380 (15) | 0.0375 (15) | −0.0054 (13) | 0.0050 (13) | −0.0015 (12) |
C12 | 0.0411 (17) | 0.0491 (18) | 0.0545 (19) | −0.0011 (13) | 0.0018 (14) | 0.0110 (14) |
C11 | 0.055 (2) | 0.059 (2) | 0.066 (2) | −0.0118 (17) | 0.0011 (17) | 0.0117 (18) |
C20 | 0.055 (2) | 0.114 (4) | 0.058 (2) | −0.005 (2) | 0.0231 (18) | 0.015 (2) |
C10 | 0.080 (3) | 0.0440 (19) | 0.070 (2) | −0.0164 (18) | −0.008 (2) | 0.0114 (17) |
C14 | 0.073 (3) | 0.091 (3) | 0.050 (2) | 0.046 (2) | 0.0057 (18) | −0.001 (2) |
C16 | 0.052 (2) | 0.081 (3) | 0.079 (3) | 0.022 (2) | −0.0045 (19) | 0.024 (2) |
C6 | 0.082 (3) | 0.063 (2) | 0.0386 (17) | −0.0177 (19) | 0.0031 (17) | −0.0010 (16) |
C17 | 0.056 (2) | 0.062 (2) | 0.062 (2) | 0.0040 (17) | −0.0197 (17) | 0.0073 (18) |
C8 | 0.047 (2) | 0.051 (2) | 0.113 (3) | −0.0042 (16) | −0.030 (2) | 0.021 (2) |
C15 | 0.073 (3) | 0.108 (4) | 0.075 (3) | 0.058 (3) | 0.008 (2) | 0.005 (3) |
C5 | 0.114 (4) | 0.087 (3) | 0.0371 (19) | 0.005 (3) | 0.001 (2) | −0.010 (2) |
C4 | 0.240 (6) | 0.070 (3) | 0.065 (3) | −0.050 (4) | 0.016 (4) | −0.032 (2) |
C9 | 0.078 (3) | 0.049 (2) | 0.126 (4) | 0.003 (2) | −0.028 (3) | 0.034 (2) |
C2 | 0.275 (6) | 0.094 (3) | 0.072 (3) | −0.119 (4) | 0.058 (4) | −0.031 (3) |
C3 | 0.292 (6) | 0.095 (3) | 0.102 (4) | −0.116 (4) | 0.050 (4) | −0.037 (3) |
C26 | 0.0458 (17) | 0.0453 (16) | 0.0348 (15) | 0.0018 (13) | 0.0119 (13) | 0.0022 (13) |
Cd1—N1 | 2.338 (2) | C18—H18 | 0.9300 |
Cd1—N3 | 2.358 (3) | C1—C2 | 1.344 (5) |
Cd1—N5 | 2.337 (2) | C1—C6 | 1.358 (4) |
Cd1—N6 | 2.369 (2) | C12—C11 | 1.379 (5) |
Cd1—N7 | 2.323 (3) | C12—H12 | 0.9300 |
Cd1—N9 | 2.286 (3) | C11—C10 | 1.352 (5) |
N1—C21 | 1.135 (4) | C11—H11 | 0.9300 |
N2—C21 | 1.304 (4) | C20—H20A | 0.9600 |
N2—C24i | 1.292 (4) | C20—H20B | 0.9600 |
N3—C22 | 1.137 (4) | C20—H20C | 0.9600 |
N4—C22 | 1.301 (4) | C10—C9 | 1.365 (6) |
N4—C23ii | 1.296 (4) | C10—H10 | 0.9300 |
N5—C23 | 1.138 (4) | C14—C15 | 1.391 (5) |
N6—C24 | 1.147 (4) | C14—H14 | 0.9300 |
N7—C25 | 1.144 (4) | C16—C15 | 1.357 (6) |
N8—C25 | 1.293 (4) | C16—C17 | 1.365 (6) |
N8—C26iii | 1.287 (4) | C16—H16 | 0.9300 |
N9—C26 | 1.147 (4) | C6—C5 | 1.381 (5) |
P1—C1 | 1.783 (3) | C6—H6 | 0.9300 |
P1—C7 | 1.789 (3) | C17—H17 | 0.9300 |
P1—C13 | 1.792 (3) | C8—C9 | 1.391 (5) |
P1—C19 | 1.796 (3) | C8—H8 | 0.9300 |
C23—N4iv | 1.296 (4) | C15—H15 | 0.9300 |
C24—N2v | 1.292 (4) | C5—C4 | 1.343 (7) |
C19—C20 | 1.512 (5) | C5—H5 | 0.9300 |
C19—H19A | 0.9700 | C4—C3 | 1.348 (7) |
C19—H19B | 0.9700 | C4—H4 | 0.9300 |
C13—C18 | 1.381 (4) | C9—H9 | 0.9300 |
C13—C14 | 1.381 (4) | C2—C3 | 1.376 (6) |
C7—C12 | 1.379 (4) | C2—H2 | 0.9300 |
C7—C8 | 1.394 (4) | C3—H3 | 0.9300 |
C18—C17 | 1.386 (4) | C26—N8vi | 1.287 (4) |
N1—Cd1—N3 | 92.49 (10) | C2—C1—P1 | 119.7 (3) |
N1—Cd1—N7 | 88.86 (10) | C6—C1—P1 | 121.3 (2) |
N3—Cd1—N9 | 90.97 (11) | C7—C12—C11 | 120.3 (3) |
N5—Cd1—N7 | 89.59 (10) | C7—C12—H12 | 119.8 |
N5—Cd1—N6 | 88.98 (9) | C11—C12—H12 | 119.8 |
N6—Cd1—N9 | 87.17 (10) | C10—C11—C12 | 120.7 (4) |
C25—N7—Cd1 | 151.8 (3) | C10—C11—H11 | 119.6 |
C22—N3—Cd1 | 174.7 (3) | C12—C11—H11 | 119.6 |
C21—N1—Cd1 | 170.9 (3) | C19—C20—H20A | 109.5 |
N9—Cd1—N7 | 177.41 (10) | C19—C20—H20B | 109.5 |
N9—Cd1—N5 | 92.63 (11) | H20A—C20—H20B | 109.5 |
N9—Cd1—N1 | 89.73 (10) | C19—C20—H20C | 109.5 |
N5—Cd1—N1 | 92.01 (10) | H20A—C20—H20C | 109.5 |
N7—Cd1—N3 | 86.93 (10) | H20B—C20—H20C | 109.5 |
N5—Cd1—N3 | 174.26 (10) | C11—C10—C9 | 119.7 (3) |
N7—Cd1—N6 | 94.21 (10) | C11—C10—H10 | 120.2 |
N1—Cd1—N6 | 176.79 (9) | C9—C10—H10 | 120.2 |
N3—Cd1—N6 | 86.73 (9) | C13—C14—C15 | 119.4 (4) |
C1—P1—C7 | 110.29 (14) | C13—C14—H14 | 120.3 |
C1—P1—C13 | 107.41 (15) | C15—C14—H14 | 120.3 |
C7—P1—C13 | 108.19 (14) | C15—C16—C17 | 120.8 (3) |
C1—P1—C19 | 112.79 (16) | C15—C16—H16 | 119.6 |
C7—P1—C19 | 107.23 (16) | C17—C16—H16 | 119.6 |
C13—P1—C19 | 110.84 (15) | C1—C6—C5 | 120.6 (4) |
C24—N6—Cd1 | 157.5 (2) | C1—C6—H6 | 119.7 |
C23—N5—Cd1 | 177.8 (3) | C5—C6—H6 | 119.7 |
C24i—N2—C21 | 123.4 (3) | C16—C17—C18 | 120.1 (4) |
C23ii—N4—C22 | 123.7 (3) | C16—C17—H17 | 119.9 |
C26—N9—Cd1 | 168.9 (3) | C18—C17—H17 | 119.9 |
C26iii—N8—C25 | 124.3 (3) | C9—C8—C7 | 118.4 (4) |
N3—C22—N4 | 173.7 (3) | C9—C8—H8 | 120.8 |
N1—C21—N2 | 173.0 (3) | C7—C8—H8 | 120.8 |
N5—C23—N4iv | 173.0 (4) | C16—C15—C14 | 120.2 (4) |
N7—C25—N8 | 172.9 (3) | C16—C15—H15 | 119.9 |
N6—C24—N2v | 172.8 (3) | C14—C15—H15 | 119.9 |
C20—C19—P1 | 117.0 (3) | C4—C5—C6 | 120.7 (4) |
C20—C19—H19A | 108.1 | C4—C5—H5 | 119.7 |
P1—C19—H19A | 108.1 | C6—C5—H5 | 119.7 |
C20—C19—H19B | 108.1 | C3—C4—C5 | 118.2 (4) |
P1—C19—H19B | 108.1 | C3—C4—H4 | 120.9 |
H19A—C19—H19B | 107.3 | C5—C4—H4 | 120.9 |
C18—C13—C14 | 120.0 (3) | C10—C9—C8 | 121.4 (4) |
C18—C13—P1 | 119.9 (2) | C10—C9—H9 | 119.3 |
C14—C13—P1 | 120.0 (3) | C8—C9—H9 | 119.3 |
C12—C7—C8 | 119.4 (3) | C1—C2—C3 | 120.4 (5) |
C12—C7—P1 | 120.3 (2) | C1—C2—H2 | 119.8 |
C8—C7—P1 | 120.3 (3) | C3—C2—H2 | 119.8 |
C13—C18—C17 | 119.5 (3) | C4—C3—C2 | 121.4 (5) |
C13—C18—H18 | 120.2 | C4—C3—H3 | 119.3 |
C17—C18—H18 | 120.2 | C2—C3—H3 | 119.3 |
C2—C1—C6 | 118.5 (3) | N9—C26—N8vi | 172.3 (4) |
N9—Cd1—N6—C24 | −5.9 (6) | C7—P1—C1—C2 | −172.9 (5) |
N7—Cd1—N6—C24 | 171.9 (6) | C13—P1—C1—C2 | 69.4 (5) |
N5—Cd1—N6—C24 | −98.6 (6) | C19—P1—C1—C2 | −53.1 (5) |
N3—Cd1—N6—C24 | 85.2 (6) | C7—P1—C1—C6 | 15.8 (3) |
N5—Cd1—N7—C25 | −163.2 (5) | C13—P1—C1—C6 | −101.9 (3) |
N1—Cd1—N7—C25 | 104.8 (5) | C19—P1—C1—C6 | 135.7 (3) |
N3—Cd1—N7—C25 | 12.2 (5) | C8—C7—C12—C11 | −1.5 (5) |
N6—Cd1—N7—C25 | −74.3 (5) | P1—C7—C12—C11 | 179.9 (3) |
N5—Cd1—N9—C26 | 68.4 (15) | C7—C12—C11—C10 | −0.6 (6) |
N1—Cd1—N9—C26 | 160.4 (15) | C12—C11—C10—C9 | 1.6 (7) |
N3—Cd1—N9—C26 | −107.1 (15) | C18—C13—C14—C15 | −1.3 (6) |
N6—Cd1—N9—C26 | −20.4 (15) | P1—C13—C14—C15 | 174.0 (4) |
C1—P1—C19—C20 | 69.7 (3) | C2—C1—C6—C5 | 0.9 (7) |
C7—P1—C19—C20 | −168.7 (3) | P1—C1—C6—C5 | 172.3 (3) |
C13—P1—C19—C20 | −50.8 (3) | C15—C16—C17—C18 | −0.1 (7) |
C1—P1—C13—C18 | −159.9 (2) | C13—C18—C17—C16 | −0.7 (5) |
C7—P1—C13—C18 | 81.1 (3) | C12—C7—C8—C9 | 2.4 (6) |
C19—P1—C13—C18 | −36.2 (3) | P1—C7—C8—C9 | −179.0 (4) |
C1—P1—C13—C14 | 24.8 (3) | C17—C16—C15—C14 | 0.2 (8) |
C7—P1—C13—C14 | −94.2 (3) | C13—C14—C15—C16 | 0.5 (7) |
C19—P1—C13—C14 | 148.5 (3) | C1—C6—C5—C4 | 2.0 (8) |
C1—P1—C7—C12 | −100.8 (3) | C6—C5—C4—C3 | −4.8 (11) |
C13—P1—C7—C12 | 16.4 (3) | C11—C10—C9—C8 | −0.6 (8) |
C19—P1—C7—C12 | 136.0 (3) | C7—C8—C9—C10 | −1.4 (7) |
C1—P1—C7—C8 | 80.6 (3) | C6—C1—C2—C3 | −1.0 (11) |
C13—P1—C7—C8 | −162.2 (3) | P1—C1—C2—C3 | −172.5 (7) |
C19—P1—C7—C8 | −42.6 (3) | C5—C4—C3—C2 | 4.7 (14) |
C14—C13—C18—C17 | 1.4 (5) | C1—C2—C3—C4 | −1.9 (14) |
P1—C13—C18—C17 | −173.9 (3) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z+1/2; (v) −x+3/2, y+1/2, −z+3/2; (vi) x−1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C20H20P)[Cd(C2N3)3] |
Mr | 601.89 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 12.238 (2), 17.073 (3), 12.782 (3) |
β (°) | 90.95 (3) |
V (Å3) | 2670.3 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.91 |
Crystal size (mm) | 0.30 × 0.26 × 0.25 |
Data collection | |
Diffractometer | Rigaku SCXmini |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.761, 0.797 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18346, 6110, 5318 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.082, 0.94 |
No. of reflections | 6110 |
No. of parameters | 335 |
No. of restraints | 19 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.65 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), PLATON (Spek, 2009) and SHELXL97 (Sheldrick, 2008).
Cd1—N1 | 2.338 (2) | N3—C22 | 1.137 (4) |
Cd1—N3 | 2.358 (3) | N4—C22 | 1.301 (4) |
Cd1—N5 | 2.337 (2) | N4—C23ii | 1.296 (4) |
Cd1—N6 | 2.369 (2) | N5—C23 | 1.138 (4) |
Cd1—N7 | 2.323 (3) | N6—C24 | 1.147 (4) |
Cd1—N9 | 2.286 (3) | N7—C25 | 1.144 (4) |
N1—C21 | 1.135 (4) | N8—C25 | 1.293 (4) |
N2—C21 | 1.304 (4) | N8—C26iii | 1.287 (4) |
N2—C24i | 1.292 (4) | N9—C26 | 1.147 (4) |
N1—Cd1—N3 | 92.49 (10) | N6—Cd1—N9 | 87.17 (10) |
N1—Cd1—N7 | 88.86 (10) | C25—N7—Cd1 | 151.8 (3) |
N3—Cd1—N9 | 90.97 (11) | C22—N3—Cd1 | 174.7 (3) |
N5—Cd1—N7 | 89.59 (10) | C21—N1—Cd1 | 170.9 (3) |
N5—Cd1—N6 | 88.98 (9) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2. |