Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616006677/eg3201sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006677/eg3201Isup2.hkl |
CCDC reference: 1475140
\ The design and synthesis of nonlinear optical materials has developed rapidly owing to applications of these materials in the fields of optical switching and optical limiting (Tang et al., 2013; Corredor et al., 2007; Denk et al., 1990). In recent years, π-conjugated organic materials have received considerable interest for their high nonlinear optical properties and fast response time (Brédas et al., 1994). These organic compounds have a large variety of structures and diverse electronic properties, which give an opportunity to tune the NLO properties of these compounds. Previous works showed that the introduction of transition metal ions into π-conjugated systems can effectively enhance the NLO properties of metal complexes. For instance, very recently, Torres and co-workers reported several extended π-conjugated ruthenium–zinc–porphyrin complexes with large third-order nonlinear optical absorption coefficients and refractive indices (Torres et al., 2015). 4'-Phenyl-2,2':6',2''-terpyridine (PTP) is an important N-heterocyclic ligand involving π-conjugated systems and has been widely used in the fields of biology, chemistry and materials. Recently, a few of terpyridine transition metal complexes with different biological and chemical activities were reported in the literature (Chen et al., 2013; Huang et al., 2013; Hussain et al., 2012; Maity et al., 2011; Roy et al., 2011; Field et al., 2007). However, studies concerning the third-order NLO properties of terpyridine transition metal complexes are limited. Based on the above considerations, we designed and synthesized a binuclear terpyridine CoII complex bis(µ-4,4'-oxydibenzoato)-κ3O,O':O;κ3O:\ O,O'-bis[(4'-phenyl-2,2':6',2''-terpyridine-κ3N,\ N',N'')cobalt(II)], (1), with a 1:1 metal ion to ligand ratio by controlling the reaction conditions, and used the Z-scan technique to evaluate its NLO properties. Our results show that the nonlinear optical effect in (1) is much more pronounced than in PTP. We report here the crystal structure and third-order NLO properties of (1).
Co(CH3COO)2 (0.1 mmol, 0.018 g), 4,4'-oxybis(benzoic acid) (H2ODA; 0.1 mmol, 0.026 g) and PTP (0.2 mmol, 0.031 g) were added to a mixture of distilled water (5 ml) and ethanol (5 ml), and the pH was adjusted to 5.0 by the addition of 0.2 M NaOH. The resulting mixture was stirred for 1 h, transferred into a Parr Teflon-lined stainless steel vessel, and then sealed and heated at 423 K for 3 d, followed by rapid cooling to ambient temperature. Red block-shaped crystals were collected manually, washed with distilled water and dried in air at ambient temperature (yield 86%, based on Co). Elemental analysis calculated for C70H46Co2N6O10: C 67.31, N 6.73, H 3.71%; found: C 67.28, N 6.75, H, 3.73%.
Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were fixed geometrically and allowed to ride on their parent atom, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
To prepare the thin films, a fine powder of the sample were dispersed in ethanol using ultrasonic processing. The mixture was then spin-coated (1000 r.p.m., 30 s) onto cleaned quartz glass substrates and dried at room temperature for 2 h. The thickness of the film was measured with a thickness gauge [about 2 µm for (1)]. The nonlinear optical refraction and absorption were obtained with a linearly polarized laser light (7 ns, 10 Hz, 532 nm) generated from a mode-locked Q-switched Nd:YAG laser. The spatial profiles of the optical pulses are nearly Gaussian after being passed through a filter. The incident and transmitted pulsed energies are measured simultaneously by two energy detectors (RJP-765 Energy probes, laser precision, Laserprobe Corp), which were linked to a computer through an RS232 interface. The sample was mounted on a translation stage that was controlled by the computer to move along the z axis with respect to the focal point. An aperture of 0.5 mm radius was placed in front of the transmission detector and the transmittance was recorded as a function of the sample position on the z axis (closed-aperture Z-scan). For measuring the NLO absorption, the Z-dependent sample transmittance was taken without the aperture (open-aperture Z-scan).
Complex (1) exhibits a discrete structure with the ratio of the PTP ligand and the CoII ion being 1:1. Its asymmetric unit contains one CoII cation, one PTP ligand and one ODA2- dianion. As shown in Fig. 1, each CoII atom is situated in a distorted octahedral coordination sphere, defined by three N atoms from one PPT ligand and by three O atoms from two different ODA2- ligands. In this octahedral coordination sphere, atoms N1, N2, N3 and O3i [symmetry code: (i) -x+1, -y+1, -z] lie in the basal plane, while atoms O1 and O4i occupy the apical positions. The Co—N bond lengths (Table 2) are within the ranges reported for CoII complexes (Zhang, Zhang et al., 2015). Of the Co—O bond lengths (Table 2), Co1—O4i is much longer than the others. The cis angles subtended at the CoII atom by ligating atoms cover the range 58.69 (7)–110.16 (8)° (Table 2). Thus, the coordination geometry around the CoII atom can be described as a distorted CoO3N3 octahedron. The PTP ligand chelates the CoII atom and the ratio of metal ions and ligands is 1:1. Previous research showed that the ratio of metal ions and ligands plays an important role in the properties of the target compounds. For instance, Ma and coworker found that mononuclear terpyridine [ZnII(PTP)]·X2 (X = NO3, CH3COO, Cl and SO4) complexes with a 1:1 ratio of metal ions and ligands exhibit promising in vitro tumour-inhibiting activities (Ma et al., 2010), which are higher than that of cisplatin against the following human tumor cell lines: promyelocyticfina leukaemia (HL-60), hepatocellula rcarcinoma (Bel-7402), gastric carcinoma (BGC-823) and nasopharyngeal carcinoma (KB). However, the mononuclear terpyridine [ZnII(PTP)2]·(NO3)2 complexes with a 1:2 ratio of metal ions and ligands do not bind DNA significantly (Sinha et al., 2015). They also reported four mononuclear terpyridine [CuII(PTP)]·X2 (X = NO3 and CH3COO) complexes with a 1:1 ratio of metal ions and ligands which exhibit high catalytic activity, under mild conditions and in alkaline aqueous solution, for the aerobic oxidation of benzylic alcohols in combination with TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl radical) (Ma et al., 2014). Interestingly, the mononuclear terpyridine [CoII(PTP)2]·(NO3)2 complex with a 1:2 ratio of metal ions and ligands, can bind with the major groove of double helical DNA (Sinha et al., 2015).
In the title compound, (1), the ODA2- ligand employs mono- and bidentate carboxylate groups, adopting a µ2-coordination mode, connecting two CoII ions into a ring-like structure. The Co···Co separation within the ring is 11.76 (7) Å. There are two kinds of noncovalent interactions involved in the stabilization of the crystal lattice. In (1), the binuclear units are linked by a π–π interaction of 3.57 (3) Å between the pyridine rings of the TPP ligands and a C—H··· π interaction with distances of 3.74 (6) Å into a one-dimensional chain along the c axis. These one-dimensional chains are further connected by C—H··· π interactions, with distances of 3.68 (10) Å, into two-dimensional networks. Weak aromatic interactions have important effects on the properties and structures of compounds. Similar cases were encountered for comparable structures (Fu et al., 2015; McMurtrie & Dance, 2009). Field and co-workers (Field et al., 2012) found that [Pt(NCS)(PTP)]SbF6 is porous, with empty channels stabilized by extended π–π interactions. When the compound was exposed to vapours of acetonitrile, the gaseous molecules were sorbed without loss of single crystallinity to give the adduct [Pt(NCS)(PTP)]SbF6·CH3CN. Similarly, this compound can sorb vapours of methanol and acetone without loss of single crystallinity to form [Pt(NCS)(PTP)]SbF6·CH3OH and [Pt(NCS)(PTP)]SbF6·(CH3)2CO, respectively.
Although a few transition metal complexes and clusters with excellent third-order NLO properties have been reported, the data were obtained in solution (Zhang et al., 2007; Zhang, Liu & Lang, 2015). This is no suitable performance criterion for neat materials. In order to evaluate the third-order NLO performance of (1), films of (1) and TPP were prepared by spin coating and conducted open-aperture and closed-aperture Z-scan experiments. The open-aperture data of PTP and (1) are depicted in Figs. 3 and 4. It is obvious that PTP and (1) exhibit different third-order nonlinear optical absorption. From Fig. 3, the incident light irradiance is low in the far field, and the transmittance remains unchanged. As the sample moves towards the focal point, the incident light irradiance rises and the absorption increases. In the focus position, the absorption reaches the maximum. The open-aperture data clearly suggest the presence of reverse saturable absorption (RSA) behavior. The normalized transmittance drops to about 0.77. The corresponding third-order NLO absorptive coefficient β(MKS) is calculated to be 8.96 × 10 -7 m W-1. It can be seen from Fig. 4 that the transmittance increases as the incident light irradiance rises. The normalized transmittance reaches the maximum at the focus position, which indicates that saturation absorption occurs. The β values is calculated to be -37.3 × 10 -7 m W-1. The corresponding third-order NLO susceptibility χ(3) are calculated as 6.01 × 10 -8 e.s.u. for (1) and 1.44 × 10 -8 e.s.u. for PTP. Our results show that the third-order NLO susceptibility χ(3) of (1) is about four times that of PTP. This result is in agreement with the fact that the incorporation of transition metal atoms into π-conjugated organic systems may introduce more sublevels into the energy hierarchy, which is in favour of delocalization of the π-electron cloud. In addition, the charge-transfer nature of the metal–ligand bonds can also enhance the nonlinearity. The χ(3) values of (1) and PTP in the solid state are much larger than those of other neat materials, such as neat inorganic semiconductors (about 10 -10 e.s.u.) and conjugated polymers (Chen et al., 2014; Liu et al., 2013).
\ The design and synthesis of nonlinear optical materials has developed rapidly owing to applications of these materials in the fields of optical switching and optical limiting (Tang et al., 2013; Corredor et al., 2007; Denk et al., 1990). In recent years, π-conjugated organic materials have received considerable interest for their high nonlinear optical properties and fast response time (Brédas et al., 1994). These organic compounds have a large variety of structures and diverse electronic properties, which give an opportunity to tune the NLO properties of these compounds. Previous works showed that the introduction of transition metal ions into π-conjugated systems can effectively enhance the NLO properties of metal complexes. For instance, very recently, Torres and co-workers reported several extended π-conjugated ruthenium–zinc–porphyrin complexes with large third-order nonlinear optical absorption coefficients and refractive indices (Torres et al., 2015). 4'-Phenyl-2,2':6',2''-terpyridine (PTP) is an important N-heterocyclic ligand involving π-conjugated systems and has been widely used in the fields of biology, chemistry and materials. Recently, a few of terpyridine transition metal complexes with different biological and chemical activities were reported in the literature (Chen et al., 2013; Huang et al., 2013; Hussain et al., 2012; Maity et al., 2011; Roy et al., 2011; Field et al., 2007). However, studies concerning the third-order NLO properties of terpyridine transition metal complexes are limited. Based on the above considerations, we designed and synthesized a binuclear terpyridine CoII complex bis(µ-4,4'-oxydibenzoato)-κ3O,O':O;κ3O:\ O,O'-bis[(4'-phenyl-2,2':6',2''-terpyridine-κ3N,\ N',N'')cobalt(II)], (1), with a 1:1 metal ion to ligand ratio by controlling the reaction conditions, and used the Z-scan technique to evaluate its NLO properties. Our results show that the nonlinear optical effect in (1) is much more pronounced than in PTP. We report here the crystal structure and third-order NLO properties of (1).
To prepare the thin films, a fine powder of the sample were dispersed in ethanol using ultrasonic processing. The mixture was then spin-coated (1000 r.p.m., 30 s) onto cleaned quartz glass substrates and dried at room temperature for 2 h. The thickness of the film was measured with a thickness gauge [about 2 µm for (1)]. The nonlinear optical refraction and absorption were obtained with a linearly polarized laser light (7 ns, 10 Hz, 532 nm) generated from a mode-locked Q-switched Nd:YAG laser. The spatial profiles of the optical pulses are nearly Gaussian after being passed through a filter. The incident and transmitted pulsed energies are measured simultaneously by two energy detectors (RJP-765 Energy probes, laser precision, Laserprobe Corp), which were linked to a computer through an RS232 interface. The sample was mounted on a translation stage that was controlled by the computer to move along the z axis with respect to the focal point. An aperture of 0.5 mm radius was placed in front of the transmission detector and the transmittance was recorded as a function of the sample position on the z axis (closed-aperture Z-scan). For measuring the NLO absorption, the Z-dependent sample transmittance was taken without the aperture (open-aperture Z-scan).
Complex (1) exhibits a discrete structure with the ratio of the PTP ligand and the CoII ion being 1:1. Its asymmetric unit contains one CoII cation, one PTP ligand and one ODA2- dianion. As shown in Fig. 1, each CoII atom is situated in a distorted octahedral coordination sphere, defined by three N atoms from one PPT ligand and by three O atoms from two different ODA2- ligands. In this octahedral coordination sphere, atoms N1, N2, N3 and O3i [symmetry code: (i) -x+1, -y+1, -z] lie in the basal plane, while atoms O1 and O4i occupy the apical positions. The Co—N bond lengths (Table 2) are within the ranges reported for CoII complexes (Zhang, Zhang et al., 2015). Of the Co—O bond lengths (Table 2), Co1—O4i is much longer than the others. The cis angles subtended at the CoII atom by ligating atoms cover the range 58.69 (7)–110.16 (8)° (Table 2). Thus, the coordination geometry around the CoII atom can be described as a distorted CoO3N3 octahedron. The PTP ligand chelates the CoII atom and the ratio of metal ions and ligands is 1:1. Previous research showed that the ratio of metal ions and ligands plays an important role in the properties of the target compounds. For instance, Ma and coworker found that mononuclear terpyridine [ZnII(PTP)]·X2 (X = NO3, CH3COO, Cl and SO4) complexes with a 1:1 ratio of metal ions and ligands exhibit promising in vitro tumour-inhibiting activities (Ma et al., 2010), which are higher than that of cisplatin against the following human tumor cell lines: promyelocyticfina leukaemia (HL-60), hepatocellula rcarcinoma (Bel-7402), gastric carcinoma (BGC-823) and nasopharyngeal carcinoma (KB). However, the mononuclear terpyridine [ZnII(PTP)2]·(NO3)2 complexes with a 1:2 ratio of metal ions and ligands do not bind DNA significantly (Sinha et al., 2015). They also reported four mononuclear terpyridine [CuII(PTP)]·X2 (X = NO3 and CH3COO) complexes with a 1:1 ratio of metal ions and ligands which exhibit high catalytic activity, under mild conditions and in alkaline aqueous solution, for the aerobic oxidation of benzylic alcohols in combination with TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl radical) (Ma et al., 2014). Interestingly, the mononuclear terpyridine [CoII(PTP)2]·(NO3)2 complex with a 1:2 ratio of metal ions and ligands, can bind with the major groove of double helical DNA (Sinha et al., 2015).
In the title compound, (1), the ODA2- ligand employs mono- and bidentate carboxylate groups, adopting a µ2-coordination mode, connecting two CoII ions into a ring-like structure. The Co···Co separation within the ring is 11.76 (7) Å. There are two kinds of noncovalent interactions involved in the stabilization of the crystal lattice. In (1), the binuclear units are linked by a π–π interaction of 3.57 (3) Å between the pyridine rings of the TPP ligands and a C—H··· π interaction with distances of 3.74 (6) Å into a one-dimensional chain along the c axis. These one-dimensional chains are further connected by C—H··· π interactions, with distances of 3.68 (10) Å, into two-dimensional networks. Weak aromatic interactions have important effects on the properties and structures of compounds. Similar cases were encountered for comparable structures (Fu et al., 2015; McMurtrie & Dance, 2009). Field and co-workers (Field et al., 2012) found that [Pt(NCS)(PTP)]SbF6 is porous, with empty channels stabilized by extended π–π interactions. When the compound was exposed to vapours of acetonitrile, the gaseous molecules were sorbed without loss of single crystallinity to give the adduct [Pt(NCS)(PTP)]SbF6·CH3CN. Similarly, this compound can sorb vapours of methanol and acetone without loss of single crystallinity to form [Pt(NCS)(PTP)]SbF6·CH3OH and [Pt(NCS)(PTP)]SbF6·(CH3)2CO, respectively.
Although a few transition metal complexes and clusters with excellent third-order NLO properties have been reported, the data were obtained in solution (Zhang et al., 2007; Zhang, Liu & Lang, 2015). This is no suitable performance criterion for neat materials. In order to evaluate the third-order NLO performance of (1), films of (1) and TPP were prepared by spin coating and conducted open-aperture and closed-aperture Z-scan experiments. The open-aperture data of PTP and (1) are depicted in Figs. 3 and 4. It is obvious that PTP and (1) exhibit different third-order nonlinear optical absorption. From Fig. 3, the incident light irradiance is low in the far field, and the transmittance remains unchanged. As the sample moves towards the focal point, the incident light irradiance rises and the absorption increases. In the focus position, the absorption reaches the maximum. The open-aperture data clearly suggest the presence of reverse saturable absorption (RSA) behavior. The normalized transmittance drops to about 0.77. The corresponding third-order NLO absorptive coefficient β(MKS) is calculated to be 8.96 × 10 -7 m W-1. It can be seen from Fig. 4 that the transmittance increases as the incident light irradiance rises. The normalized transmittance reaches the maximum at the focus position, which indicates that saturation absorption occurs. The β values is calculated to be -37.3 × 10 -7 m W-1. The corresponding third-order NLO susceptibility χ(3) are calculated as 6.01 × 10 -8 e.s.u. for (1) and 1.44 × 10 -8 e.s.u. for PTP. Our results show that the third-order NLO susceptibility χ(3) of (1) is about four times that of PTP. This result is in agreement with the fact that the incorporation of transition metal atoms into π-conjugated organic systems may introduce more sublevels into the energy hierarchy, which is in favour of delocalization of the π-electron cloud. In addition, the charge-transfer nature of the metal–ligand bonds can also enhance the nonlinearity. The χ(3) values of (1) and PTP in the solid state are much larger than those of other neat materials, such as neat inorganic semiconductors (about 10 -10 e.s.u.) and conjugated polymers (Chen et al., 2014; Liu et al., 2013).
Co(CH3COO)2 (0.1 mmol, 0.018 g), 4,4'-oxybis(benzoic acid) (H2ODA; 0.1 mmol, 0.026 g) and PTP (0.2 mmol, 0.031 g) were added to a mixture of distilled water (5 ml) and ethanol (5 ml), and the pH was adjusted to 5.0 by the addition of 0.2 M NaOH. The resulting mixture was stirred for 1 h, transferred into a Parr Teflon-lined stainless steel vessel, and then sealed and heated at 423 K for 3 d, followed by rapid cooling to ambient temperature. Red block-shaped crystals were collected manually, washed with distilled water and dried in air at ambient temperature (yield 86%, based on Co). Elemental analysis calculated for C70H46Co2N6O10: C 67.31, N 6.73, H 3.71%; found: C 67.28, N 6.75, H, 3.73%.
Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were fixed geometrically and allowed to ride on their parent atom, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: Please supply data collection software; cell refinement: SAINT-Plus (Bruker, 2012); data reduction: SAINT-Plus (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
[Co2(C14H8O5)2(C21H15N3)2] | Z = 1 |
Mr = 1248.99 | F(000) = 642 |
Triclinic, P1 | Dx = 1.456 Mg m−3 |
a = 9.710 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.891 (12) Å | Cell parameters from 3954 reflections |
c = 15.546 (16) Å | θ = 2.3–28.2° |
α = 77.129 (15)° | µ = 0.65 mm−1 |
β = 74.474 (15)° | T = 296 K |
γ = 65.034 (15)° | Block, red |
V = 1425 (3) Å3 | 0.29 × 0.26 × 0.22 mm |
Bruker SMART CCD 6000 area-detector diffractometer | 5301 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
phi and ω scans | θmax = 28.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −6→12 |
Tmin = 0.66, Tmax = 0.71 | k = −8→14 |
8920 measured reflections | l = −20→19 |
6574 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.063P)2 + 0.254P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
6574 reflections | Δρmax = 0.37 e Å−3 |
397 parameters | Δρmin = −0.51 e Å−3 |
[Co2(C14H8O5)2(C21H15N3)2] | γ = 65.034 (15)° |
Mr = 1248.99 | V = 1425 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.710 (9) Å | Mo Kα radiation |
b = 10.891 (12) Å | µ = 0.65 mm−1 |
c = 15.546 (16) Å | T = 296 K |
α = 77.129 (15)° | 0.29 × 0.26 × 0.22 mm |
β = 74.474 (15)° |
Bruker SMART CCD 6000 area-detector diffractometer | 6574 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 5301 reflections with I > 2σ(I) |
Tmin = 0.66, Tmax = 0.71 | Rint = 0.016 |
8920 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.37 e Å−3 |
6574 reflections | Δρmin = −0.51 e Å−3 |
397 parameters |
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 | ||
Co1 | 0.26720 (3) | 0.74565 (3) | 0.33762 (2) | 0.03165 (10) | |
O1 | 0.27408 (16) | 0.93005 (16) | 0.28187 (10) | 0.0377 (4) | |
O2 | 0.44156 (19) | 1.0023 (2) | 0.30945 (12) | 0.0567 (5) | |
O3 | 0.7626 (2) | 0.3079 (2) | −0.22612 (12) | 0.0531 (5) | |
O4 | 0.7361 (2) | 0.4721 (2) | −0.33961 (12) | 0.0576 (5) | |
O5 | 0.8489 (2) | 0.7387 (2) | −0.04874 (14) | 0.0700 (7) | |
N1 | 0.01997 (19) | 0.81678 (18) | 0.39856 (12) | 0.0325 (4) | |
N2 | 0.26266 (18) | 0.74909 (17) | 0.47066 (11) | 0.0293 (4) | |
N3 | 0.51276 (19) | 0.64794 (18) | 0.34928 (12) | 0.0348 (4) | |
C1 | −0.0988 (2) | 0.8430 (2) | 0.35879 (16) | 0.0389 (5) | |
H1 | −0.0769 | 0.8285 | 0.2990 | 0.047* | |
C2 | −0.2540 (3) | 0.8912 (3) | 0.40368 (17) | 0.0440 (6) | |
H2 | −0.3334 | 0.9087 | 0.3743 | 0.053* | |
C3 | −0.2864 (2) | 0.9121 (3) | 0.49273 (16) | 0.0453 (6) | |
H3 | −0.3884 | 0.9436 | 0.5241 | 0.054* | |
C4 | −0.1651 (2) | 0.8856 (2) | 0.53529 (15) | 0.0381 (5) | |
H4 | −0.1850 | 0.8994 | 0.5951 | 0.046* | |
C5 | −0.0133 (2) | 0.8382 (2) | 0.48621 (13) | 0.0291 (4) | |
C6 | 0.1242 (2) | 0.8022 (2) | 0.52688 (14) | 0.0290 (4) | |
C7 | 0.1150 (2) | 0.8182 (2) | 0.61441 (14) | 0.0330 (4) | |
H7 | 0.0188 | 0.8571 | 0.6510 | 0.040* | |
C8 | 0.2515 (2) | 0.7753 (2) | 0.64794 (14) | 0.0331 (4) | |
C9 | 0.3948 (2) | 0.7180 (2) | 0.58839 (14) | 0.0355 (5) | |
H9 | 0.4875 | 0.6886 | 0.6080 | 0.043* | |
C10 | 0.3968 (2) | 0.7057 (2) | 0.50062 (14) | 0.0304 (4) | |
C11 | 0.5394 (2) | 0.6459 (2) | 0.43115 (14) | 0.0313 (4) | |
C12 | 0.6901 (2) | 0.5886 (2) | 0.44862 (16) | 0.0394 (5) | |
H12 | 0.7064 | 0.5855 | 0.5055 | 0.047* | |
C13 | 0.8155 (3) | 0.5363 (3) | 0.37925 (18) | 0.0471 (6) | |
H13 | 0.9162 | 0.5002 | 0.3892 | 0.056* | |
C14 | 0.7888 (3) | 0.5385 (3) | 0.29572 (17) | 0.0458 (6) | |
H14 | 0.8706 | 0.5032 | 0.2490 | 0.055* | |
C15 | 0.6359 (3) | 0.5952 (2) | 0.28345 (16) | 0.0434 (6) | |
H15 | 0.6177 | 0.5968 | 0.2274 | 0.052* | |
C16 | 0.2426 (3) | 0.7886 (2) | 0.74323 (15) | 0.0363 (5) | |
C17 | 0.1072 (3) | 0.8785 (3) | 0.79329 (16) | 0.0452 (6) | |
H17 | 0.0213 | 0.9301 | 0.7669 | 0.054* | |
C18 | 0.1010 (3) | 0.8907 (3) | 0.88128 (17) | 0.0528 (6) | |
H18 | 0.0112 | 0.9505 | 0.9133 | 0.063* | |
C19 | 0.2281 (4) | 0.8141 (3) | 0.92209 (18) | 0.0564 (7) | |
H19 | 0.2243 | 0.8234 | 0.9808 | 0.068* | |
C20 | 0.3594 (4) | 0.7244 (3) | 0.87454 (19) | 0.0652 (8) | |
H20 | 0.4440 | 0.6718 | 0.9019 | 0.078* | |
C21 | 0.3675 (3) | 0.7114 (3) | 0.78584 (18) | 0.0564 (7) | |
H21 | 0.4574 | 0.6503 | 0.7548 | 0.068* | |
C22 | 0.5145 (2) | 0.9015 (2) | 0.17516 (14) | 0.0343 (5) | |
C23 | 0.4721 (3) | 0.8549 (3) | 0.11340 (16) | 0.0428 (5) | |
H23 | 0.3714 | 0.8596 | 0.1228 | 0.051* | |
C24 | 0.5800 (3) | 0.8013 (3) | 0.03750 (17) | 0.0513 (6) | |
H24 | 0.5507 | 0.7718 | −0.0038 | 0.062* | |
C25 | 0.7320 (3) | 0.7924 (3) | 0.02405 (16) | 0.0450 (6) | |
C26 | 0.7752 (3) | 0.8412 (3) | 0.08355 (17) | 0.0463 (6) | |
H26 | 0.8759 | 0.8367 | 0.0738 | 0.056* | |
C27 | 0.6664 (3) | 0.8969 (3) | 0.15795 (15) | 0.0407 (5) | |
H27 | 0.6946 | 0.9316 | 0.1970 | 0.049* | |
C28 | 0.8244 (3) | 0.6613 (3) | −0.09975 (17) | 0.0498 (6) | |
C29 | 0.8011 (3) | 0.7170 (3) | −0.18676 (18) | 0.0460 (6) | |
H29 | 0.7989 | 0.8042 | −0.2095 | 0.055* | |
C30 | 0.7812 (3) | 0.6394 (2) | −0.23930 (16) | 0.0417 (5) | |
H30 | 0.7645 | 0.6758 | −0.2974 | 0.050* | |
C31 | 0.7859 (2) | 0.5096 (2) | −0.20621 (14) | 0.0353 (5) | |
C32 | 0.8131 (3) | 0.4549 (3) | −0.11914 (17) | 0.0512 (6) | |
H32 | 0.8190 | 0.3666 | −0.0968 | 0.061* | |
C33 | 0.8315 (4) | 0.5314 (3) | −0.06599 (18) | 0.0611 (8) | |
H33 | 0.8485 | 0.4951 | −0.0079 | 0.073* | |
C34 | 0.4041 (2) | 0.9490 (2) | 0.26201 (15) | 0.0351 (5) | |
C35 | 0.7602 (2) | 0.4256 (3) | −0.26118 (16) | 0.0402 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.02599 (15) | 0.03727 (18) | 0.02785 (16) | −0.00585 (12) | −0.00477 (10) | −0.01023 (12) |
O1 | 0.0292 (7) | 0.0391 (8) | 0.0395 (9) | −0.0098 (6) | −0.0040 (6) | −0.0049 (7) |
O2 | 0.0376 (9) | 0.0928 (15) | 0.0475 (10) | −0.0237 (9) | −0.0001 (7) | −0.0367 (10) |
O3 | 0.0646 (12) | 0.0598 (11) | 0.0451 (10) | −0.0327 (10) | −0.0016 (8) | −0.0200 (9) |
O4 | 0.0627 (12) | 0.0597 (12) | 0.0482 (11) | −0.0068 (9) | −0.0259 (9) | −0.0187 (9) |
O5 | 0.0627 (12) | 0.1126 (18) | 0.0617 (13) | −0.0595 (13) | 0.0269 (10) | −0.0583 (13) |
N1 | 0.0262 (8) | 0.0385 (10) | 0.0313 (9) | −0.0075 (7) | −0.0064 (7) | −0.0110 (8) |
N2 | 0.0217 (8) | 0.0316 (9) | 0.0307 (9) | −0.0040 (7) | −0.0059 (6) | −0.0078 (7) |
N3 | 0.0278 (9) | 0.0351 (10) | 0.0341 (10) | −0.0036 (7) | −0.0051 (7) | −0.0091 (8) |
C1 | 0.0316 (11) | 0.0482 (13) | 0.0361 (12) | −0.0097 (10) | −0.0106 (9) | −0.0109 (10) |
C2 | 0.0273 (10) | 0.0563 (15) | 0.0485 (14) | −0.0104 (10) | −0.0147 (9) | −0.0096 (11) |
C3 | 0.0226 (10) | 0.0616 (16) | 0.0440 (14) | −0.0072 (10) | −0.0047 (9) | −0.0125 (12) |
C4 | 0.0235 (10) | 0.0504 (13) | 0.0336 (11) | −0.0058 (9) | −0.0051 (8) | −0.0101 (10) |
C5 | 0.0229 (9) | 0.0315 (10) | 0.0293 (10) | −0.0056 (8) | −0.0052 (7) | −0.0067 (8) |
C6 | 0.0232 (9) | 0.0305 (10) | 0.0297 (10) | −0.0058 (8) | −0.0052 (7) | −0.0059 (8) |
C7 | 0.0250 (9) | 0.0396 (11) | 0.0300 (11) | −0.0072 (8) | −0.0024 (8) | −0.0100 (9) |
C8 | 0.0317 (10) | 0.0367 (11) | 0.0300 (11) | −0.0101 (9) | −0.0081 (8) | −0.0065 (9) |
C9 | 0.0272 (10) | 0.0442 (12) | 0.0336 (11) | −0.0091 (9) | −0.0088 (8) | −0.0080 (9) |
C10 | 0.0237 (9) | 0.0318 (10) | 0.0324 (11) | −0.0061 (8) | −0.0059 (8) | −0.0067 (8) |
C11 | 0.0232 (9) | 0.0318 (10) | 0.0337 (11) | −0.0056 (8) | −0.0044 (8) | −0.0054 (9) |
C12 | 0.0258 (10) | 0.0452 (13) | 0.0423 (13) | −0.0075 (9) | −0.0087 (9) | −0.0061 (10) |
C13 | 0.0246 (10) | 0.0481 (14) | 0.0569 (16) | −0.0046 (10) | −0.0049 (10) | −0.0071 (12) |
C14 | 0.0306 (11) | 0.0432 (13) | 0.0458 (14) | −0.0022 (10) | 0.0037 (9) | −0.0095 (11) |
C15 | 0.0344 (11) | 0.0455 (13) | 0.0347 (12) | −0.0017 (10) | −0.0006 (9) | −0.0100 (10) |
C16 | 0.0387 (11) | 0.0427 (12) | 0.0305 (11) | −0.0170 (10) | −0.0066 (9) | −0.0082 (9) |
C17 | 0.0402 (12) | 0.0606 (16) | 0.0367 (13) | −0.0206 (11) | −0.0030 (10) | −0.0128 (11) |
C18 | 0.0547 (15) | 0.0714 (18) | 0.0363 (13) | −0.0298 (14) | 0.0047 (11) | −0.0202 (13) |
C19 | 0.0751 (19) | 0.0717 (19) | 0.0328 (13) | −0.0365 (16) | −0.0112 (12) | −0.0092 (13) |
C20 | 0.0631 (18) | 0.086 (2) | 0.0454 (16) | −0.0162 (16) | −0.0271 (14) | −0.0119 (15) |
C21 | 0.0445 (14) | 0.0736 (19) | 0.0435 (15) | −0.0054 (13) | −0.0165 (11) | −0.0189 (13) |
C22 | 0.0322 (10) | 0.0382 (12) | 0.0311 (11) | −0.0114 (9) | −0.0055 (8) | −0.0069 (9) |
C23 | 0.0362 (11) | 0.0600 (15) | 0.0385 (13) | −0.0230 (11) | −0.0042 (9) | −0.0130 (11) |
C24 | 0.0534 (15) | 0.0784 (19) | 0.0393 (13) | −0.0386 (14) | −0.0008 (11) | −0.0241 (13) |
C25 | 0.0471 (13) | 0.0586 (15) | 0.0371 (13) | −0.0292 (12) | 0.0074 (10) | −0.0222 (11) |
C26 | 0.0373 (12) | 0.0665 (16) | 0.0451 (14) | −0.0288 (12) | 0.0035 (10) | −0.0224 (12) |
C27 | 0.0384 (12) | 0.0580 (15) | 0.0345 (12) | −0.0244 (11) | −0.0030 (9) | −0.0156 (11) |
C28 | 0.0449 (13) | 0.0741 (18) | 0.0414 (14) | −0.0319 (13) | 0.0098 (10) | −0.0323 (13) |
C29 | 0.0399 (12) | 0.0403 (13) | 0.0551 (15) | −0.0137 (10) | −0.0018 (11) | −0.0137 (11) |
C30 | 0.0380 (12) | 0.0437 (13) | 0.0378 (13) | −0.0092 (10) | −0.0073 (9) | −0.0078 (10) |
C31 | 0.0302 (10) | 0.0410 (12) | 0.0317 (11) | −0.0081 (9) | −0.0034 (8) | −0.0137 (9) |
C32 | 0.0710 (18) | 0.0534 (15) | 0.0391 (14) | −0.0334 (14) | −0.0134 (12) | −0.0026 (12) |
C33 | 0.089 (2) | 0.083 (2) | 0.0306 (13) | −0.0519 (18) | −0.0132 (13) | −0.0051 (13) |
C34 | 0.0300 (10) | 0.0383 (11) | 0.0320 (11) | −0.0064 (9) | −0.0066 (8) | −0.0081 (9) |
C35 | 0.0282 (10) | 0.0496 (14) | 0.0403 (13) | −0.0078 (9) | −0.0035 (9) | −0.0194 (11) |
Co1—O1 | 2.024 (3) | C12—C13 | 1.398 (3) |
Co1—O3i | 2.071 (2) | C13—H13 | 0.9300 |
Co1—O4i | 2.379 (3) | C13—C14 | 1.384 (4) |
Co1—N1 | 2.191 (3) | C14—H14 | 0.9300 |
Co1—N2 | 2.065 (3) | C14—C15 | 1.395 (4) |
Co1—N3 | 2.203 (3) | C15—H15 | 0.9300 |
O1—C34 | 1.309 (3) | C16—C17 | 1.414 (3) |
O2—C34 | 1.235 (3) | C16—C21 | 1.392 (3) |
O3—Co1i | 2.071 (2) | C17—H17 | 0.9300 |
O3—C35 | 1.270 (3) | C17—C18 | 1.386 (4) |
O4—Co1i | 2.379 (3) | C18—H18 | 0.9300 |
O4—C35 | 1.255 (3) | C18—C19 | 1.391 (4) |
O5—C25 | 1.399 (3) | C19—H19 | 0.9300 |
O5—C28 | 1.401 (3) | C19—C20 | 1.376 (4) |
N1—C1 | 1.349 (3) | C20—H20 | 0.9300 |
N1—C5 | 1.363 (3) | C20—C21 | 1.396 (4) |
N2—C6 | 1.359 (3) | C21—H21 | 0.9300 |
N2—C10 | 1.358 (3) | C22—C23 | 1.397 (3) |
N3—C11 | 1.359 (3) | C22—C27 | 1.408 (3) |
N3—C15 | 1.354 (3) | C22—C34 | 1.519 (3) |
C1—H1 | 0.9300 | C23—H23 | 0.9300 |
C1—C2 | 1.402 (3) | C23—C24 | 1.400 (3) |
C2—H2 | 0.9300 | C24—H24 | 0.9300 |
C2—C3 | 1.383 (4) | C24—C25 | 1.398 (4) |
C3—H3 | 0.9300 | C25—C26 | 1.389 (3) |
C3—C4 | 1.398 (3) | C26—H26 | 0.9300 |
C4—H4 | 0.9300 | C26—C27 | 1.392 (3) |
C4—C5 | 1.397 (3) | C27—H27 | 0.9300 |
C5—C6 | 1.495 (3) | C28—C29 | 1.389 (4) |
C6—C7 | 1.385 (3) | C28—C33 | 1.374 (4) |
C7—H7 | 0.9300 | C29—H29 | 0.9300 |
C7—C8 | 1.409 (3) | C29—C30 | 1.396 (4) |
C8—C9 | 1.421 (3) | C30—H30 | 0.9300 |
C8—C16 | 1.497 (3) | C30—C31 | 1.378 (4) |
C9—H9 | 0.9300 | C31—C32 | 1.399 (4) |
C9—C10 | 1.394 (3) | C31—C35 | 1.511 (3) |
C10—C11 | 1.503 (3) | C32—H32 | 0.9300 |
C11—C12 | 1.404 (3) | C32—C33 | 1.386 (4) |
C12—H12 | 0.9300 | C33—H33 | 0.9300 |
O1—Co1—O3i | 97.90 (9) | C13—C14—H14 | 120.9 |
O1—Co1—O4i | 156.25 (7) | C13—C14—C15 | 118.3 (2) |
O1—Co1—N1 | 97.66 (7) | C15—C14—H14 | 120.9 |
O1—Co1—N2 | 100.92 (8) | N3—C15—C14 | 123.2 (2) |
O1—Co1—N3 | 95.24 (7) | N3—C15—H15 | 118.4 |
O3i—Co1—O4i | 58.69 (7) | C14—C15—H15 | 118.4 |
O3i—Co1—N1 | 93.61 (9) | C17—C16—C8 | 121.3 (2) |
O3i—Co1—N3 | 110.16 (8) | C21—C16—C8 | 120.9 (2) |
N1—Co1—O4i | 88.47 (8) | C21—C16—C17 | 117.8 (2) |
N1—Co1—N3 | 151.05 (8) | C16—C17—H17 | 119.6 |
N2—Co1—O3i | 159.67 (8) | C18—C17—C16 | 120.7 (2) |
N2—Co1—O4i | 102.83 (7) | C18—C17—H17 | 119.6 |
N2—Co1—N1 | 76.37 (7) | C17—C18—H18 | 119.7 |
N2—Co1—N3 | 75.80 (7) | C17—C18—C19 | 120.6 (3) |
N3—Co1—O4i | 90.06 (8) | C19—C18—H18 | 119.7 |
C34—O1—Co1 | 121.01 (13) | C18—C19—H19 | 120.4 |
C35—O3—Co1i | 96.97 (16) | C20—C19—C18 | 119.2 (3) |
C35—O4—Co1i | 83.32 (16) | C20—C19—H19 | 120.4 |
C25—O5—C28 | 118.1 (2) | C19—C20—H20 | 119.5 |
C1—N1—Co1 | 127.44 (16) | C19—C20—C21 | 120.9 (3) |
C1—N1—C5 | 118.18 (18) | C21—C20—H20 | 119.5 |
C5—N1—Co1 | 114.37 (13) | C16—C21—C20 | 120.8 (3) |
C6—N2—Co1 | 119.35 (14) | C16—C21—H21 | 119.6 |
C10—N2—Co1 | 120.40 (14) | C20—C21—H21 | 119.6 |
C10—N2—C6 | 120.14 (19) | C23—C22—C27 | 118.6 (2) |
C11—N3—Co1 | 114.78 (13) | C23—C22—C34 | 121.7 (2) |
C15—N3—Co1 | 126.77 (16) | C27—C22—C34 | 119.69 (19) |
C15—N3—C11 | 118.42 (19) | C22—C23—H23 | 119.7 |
N1—C1—H1 | 118.6 | C22—C23—C24 | 120.5 (2) |
N1—C1—C2 | 122.8 (2) | C24—C23—H23 | 119.7 |
C2—C1—H1 | 118.6 | C23—C24—H24 | 120.1 |
C1—C2—H2 | 120.8 | C25—C24—C23 | 119.7 (2) |
C3—C2—C1 | 118.5 (2) | C25—C24—H24 | 120.1 |
C3—C2—H2 | 120.8 | C24—C25—O5 | 124.2 (2) |
C2—C3—H3 | 120.2 | C26—C25—O5 | 115.3 (2) |
C2—C3—C4 | 119.6 (2) | C26—C25—C24 | 120.5 (2) |
C4—C3—H3 | 120.2 | C25—C26—H26 | 120.3 |
C3—C4—H4 | 120.7 | C25—C26—C27 | 119.4 (2) |
C5—C4—C3 | 118.7 (2) | C27—C26—H26 | 120.3 |
C5—C4—H4 | 120.7 | C22—C27—H27 | 119.4 |
N1—C5—C4 | 122.17 (18) | C26—C27—C22 | 121.2 (2) |
N1—C5—C6 | 115.27 (17) | C26—C27—H27 | 119.4 |
C4—C5—C6 | 122.5 (2) | C29—C28—O5 | 118.1 (3) |
N2—C6—C5 | 114.14 (19) | C33—C28—O5 | 120.6 (3) |
N2—C6—C7 | 121.67 (18) | C33—C28—C29 | 121.2 (2) |
C7—C6—C5 | 124.18 (18) | C28—C29—H29 | 120.6 |
C6—C7—H7 | 120.0 | C28—C29—C30 | 118.7 (2) |
C6—C7—C8 | 119.94 (19) | C30—C29—H29 | 120.6 |
C8—C7—H7 | 120.0 | C29—C30—H30 | 119.5 |
C7—C8—C9 | 117.4 (2) | C31—C30—C29 | 120.9 (2) |
C7—C8—C16 | 120.34 (19) | C31—C30—H30 | 119.5 |
C9—C8—C16 | 122.30 (19) | C30—C31—C32 | 119.2 (2) |
C8—C9—H9 | 119.9 | C30—C31—C35 | 121.6 (2) |
C10—C9—C8 | 120.12 (19) | C32—C31—C35 | 119.2 (2) |
C10—C9—H9 | 119.9 | C31—C32—H32 | 119.8 |
N2—C10—C9 | 120.74 (18) | C33—C32—C31 | 120.4 (3) |
N2—C10—C11 | 113.56 (19) | C33—C32—H32 | 119.8 |
C9—C10—C11 | 125.69 (18) | C28—C33—C32 | 119.5 (3) |
N3—C11—C10 | 115.17 (18) | C28—C33—H33 | 120.2 |
N3—C11—C12 | 121.44 (19) | C32—C33—H33 | 120.2 |
C12—C11—C10 | 123.4 (2) | O1—C34—C22 | 117.22 (19) |
C11—C12—H12 | 120.5 | O2—C34—O1 | 124.0 (2) |
C13—C12—C11 | 119.0 (2) | O2—C34—C22 | 118.7 (2) |
C13—C12—H12 | 120.5 | O3—C35—C31 | 118.6 (2) |
C12—C13—H13 | 120.2 | O4—C35—O3 | 120.9 (2) |
C14—C13—C12 | 119.6 (2) | O4—C35—C31 | 120.4 (2) |
C14—C13—H13 | 120.2 | ||
Co1—O1—C34—O2 | −99.8 (2) | C9—C8—C16—C21 | −19.1 (4) |
Co1—O1—C34—C22 | 80.1 (2) | C9—C10—C11—N3 | −178.4 (2) |
Co1i—O3—C35—O4 | 3.3 (2) | C9—C10—C11—C12 | 3.0 (4) |
Co1i—O3—C35—C31 | −177.15 (16) | C10—N2—C6—C5 | −176.69 (18) |
Co1i—O4—C35—O3 | −2.8 (2) | C10—N2—C6—C7 | 2.2 (3) |
Co1i—O4—C35—C31 | 177.59 (19) | C10—C11—C12—C13 | −179.6 (2) |
Co1—N1—C1—C2 | −178.59 (18) | C11—N3—C15—C14 | 0.2 (4) |
Co1—N1—C5—C4 | 178.96 (17) | C11—C12—C13—C14 | −1.7 (4) |
Co1—N1—C5—C6 | −3.2 (2) | C12—C13—C14—C15 | 0.8 (4) |
Co1—N2—C6—C5 | 7.0 (2) | C13—C14—C15—N3 | 0.0 (4) |
Co1—N2—C6—C7 | −174.16 (16) | C15—N3—C11—C10 | −179.7 (2) |
Co1—N2—C10—C9 | 174.78 (16) | C15—N3—C11—C12 | −1.2 (3) |
Co1—N2—C10—C11 | −5.4 (2) | C16—C8—C9—C10 | 179.0 (2) |
Co1—N3—C11—C10 | 2.2 (2) | C16—C17—C18—C19 | −0.2 (4) |
Co1—N3—C11—C12 | −179.22 (17) | C17—C16—C21—C20 | −1.1 (4) |
Co1—N3—C15—C14 | 177.98 (19) | C17—C18—C19—C20 | −1.0 (5) |
O5—C25—C26—C27 | 179.9 (2) | C18—C19—C20—C21 | 1.2 (5) |
O5—C28—C29—C30 | 178.1 (2) | C19—C20—C21—C16 | −0.1 (5) |
O5—C28—C33—C32 | −177.4 (3) | C21—C16—C17—C18 | 1.2 (4) |
N1—C1—C2—C3 | −0.3 (4) | C22—C23—C24—C25 | 0.9 (4) |
N1—C5—C6—N2 | −2.1 (3) | C23—C22—C27—C26 | −3.1 (4) |
N1—C5—C6—C7 | 179.1 (2) | C23—C22—C34—O1 | 7.7 (3) |
N2—C6—C7—C8 | −1.8 (3) | C23—C22—C34—O2 | −172.5 (2) |
N2—C10—C11—N3 | 1.8 (3) | C23—C24—C25—O5 | 179.0 (3) |
N2—C10—C11—C12 | −176.8 (2) | C23—C24—C25—C26 | −2.5 (4) |
N3—C11—C12—C13 | 1.9 (3) | C24—C25—C26—C27 | 1.2 (4) |
C1—N1—C5—C4 | 0.1 (3) | C25—O5—C28—C29 | 109.9 (3) |
C1—N1—C5—C6 | 177.90 (19) | C25—O5—C28—C33 | −73.4 (4) |
C1—C2—C3—C4 | 0.3 (4) | C25—C26—C27—C22 | 1.6 (4) |
C2—C3—C4—C5 | −0.1 (4) | C27—C22—C23—C24 | 1.8 (4) |
C3—C4—C5—N1 | −0.1 (3) | C27—C22—C34—O1 | −168.9 (2) |
C3—C4—C5—C6 | −177.7 (2) | C27—C22—C34—O2 | 10.9 (3) |
C4—C5—C6—N2 | 175.7 (2) | C28—O5—C25—C24 | −15.2 (4) |
C4—C5—C6—C7 | −3.1 (3) | C28—O5—C25—C26 | 166.2 (3) |
C5—N1—C1—C2 | 0.1 (3) | C28—C29—C30—C31 | −0.6 (3) |
C5—C6—C7—C8 | 177.0 (2) | C29—C28—C33—C32 | −0.8 (4) |
C6—N2—C10—C9 | −1.5 (3) | C29—C30—C31—C32 | −0.8 (3) |
C6—N2—C10—C11 | 178.28 (18) | C29—C30—C31—C35 | 178.3 (2) |
C6—C7—C8—C9 | 0.7 (3) | C30—C31—C32—C33 | 1.5 (4) |
C6—C7—C8—C16 | −178.4 (2) | C30—C31—C35—O3 | −178.4 (2) |
C7—C8—C9—C10 | −0.1 (3) | C30—C31—C35—O4 | 1.1 (3) |
C7—C8—C16—C17 | −19.3 (3) | C31—C32—C33—C28 | −0.7 (4) |
C7—C8—C16—C21 | 159.9 (2) | C32—C31—C35—O3 | 0.7 (3) |
C8—C9—C10—N2 | 0.5 (3) | C32—C31—C35—O4 | −179.7 (2) |
C8—C9—C10—C11 | −179.3 (2) | C33—C28—C29—C30 | 1.5 (4) |
C8—C16—C17—C18 | −179.5 (2) | C34—C22—C23—C24 | −174.8 (2) |
C8—C16—C21—C20 | 179.7 (3) | C34—C22—C27—C26 | 173.5 (2) |
C9—C8—C16—C17 | 161.7 (2) | C35—C31—C32—C33 | −177.7 (2) |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Co2(C14H8O5)2(C21H15N3)2] |
Mr | 1248.99 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 9.710 (9), 10.891 (12), 15.546 (16) |
α, β, γ (°) | 77.129 (15), 74.474 (15), 65.034 (15) |
V (Å3) | 1425 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.65 |
Crystal size (mm) | 0.29 × 0.26 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART CCD 6000 area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.66, 0.71 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8920, 6574, 5301 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.672 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.121, 1.09 |
No. of reflections | 6574 |
No. of parameters | 397 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.51 |
Computer programs: Please supply data collection software, SAINT-Plus (Bruker, 2012), SAINT-Plus (Bruker, 2012), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009).
Co1—O1 | 2.024 (3) | Co1—N1 | 2.191 (3) |
Co1—O3i | 2.071 (2) | Co1—N2 | 2.065 (3) |
Co1—O4i | 2.379 (3) | Co1—N3 | 2.203 (3) |
O1—Co1—O3i | 97.90 (9) | N1—Co1—O4i | 88.47 (8) |
O1—Co1—O4i | 156.25 (7) | N1—Co1—N3 | 151.05 (8) |
O1—Co1—N1 | 97.66 (7) | N2—Co1—O3i | 159.67 (8) |
O1—Co1—N2 | 100.92 (8) | N2—Co1—O4i | 102.83 (7) |
O1—Co1—N3 | 95.24 (7) | N2—Co1—N1 | 76.37 (7) |
O3i—Co1—O4i | 58.69 (7) | N2—Co1—N3 | 75.80 (7) |
O3i—Co1—N1 | 93.61 (9) | N3—Co1—O4i | 90.06 (8) |
O3i—Co1—N3 | 110.16 (8) |
Symmetry code: (i) −x+1, −y+1, −z. |