research communications
trans-dichlorido(1,4,8,11-tetraazaundecane-κ4N)chromium(III) perchlorate determined from synchrotron data
ofaPohang Accelerator Laboratory, POSTECH, Pohang 37673, Republic of Korea, and bDepartment of Chemistry, Andong National University, Andong 36729, Republic of Korea
*Correspondence e-mail: jhchoi@anu.ac.kr
The structure of the title complex, [CrCl2(2,3,2-tet)]ClO4 (2,3,2-tet is 1,4,8,11-tetraazaundecane, C7H20N4), has been determined from synchrotron data. The CrIII ion is coordinated by the four N atoms of the 1,4,8,11-tetraazaundecane ligand in the equatorial plane and two chloride ions in an axial arrangement, displaying a slightly distorted octahedral coordination environment. The two H atoms of the secondary are grouped on the same side of the equatorial N4 plane (meso-RS conformation). The Cr—N bond lengths range from 2.069 (2) to 2.084 (2) Å, while the mean Cr—Cl bond length is 2.325 (2) Å. The is stabilized by intermolecular hydrogen-bonding interactions between the primary and secondary amine groups of the 2,3,2-tet ligands, the Cl ligands and the O atoms of the perchlorate counter-anion, forming corrugated layers parallel to (010).
Keywords: crystal structure; 1,4,8,11-tetraazaundecane; chloride ligand; trans–meso (RS) conformation; chromium(III) complex; hydrogen bonding; synchrotron radiation.
CCDC reference: 1454582
1. Chemical context
Geometric and conformational et al., 2008a,b). Two conformations of meso-RS or racemic-RR/SS isomers with respect to the orientation of the secondary amine hydrogen atoms in the trans isomer are also possible (Fig. 1). The two hydrogen atoms of the conformers may be on the same side (RS) of the equatorial N4 plane or on opposite sides (RR/SS) of this plane.
in chromium(III) complexes of linear flexible tetradentate ligands is an interesting field because it has played an important role in extending the concept of stereochemistry. The 1,4,8,11-tetraazaundecane ligand (2,3,2-tet) is a structural isomer of 1,4,7,11-tetraazaundecane (2,2,3-tet). These two ligands have four nitrogen atoms as donor groups and can adopt three different configurations in chromium(III) complexes with two additional Cl ligands (ChoiThe different symmetries of transition metal complexes allow the determination of their stereochemistry from electronic absorption and infrared spectra. Indeed, infrared and electronic spectroscopic properties often are useful in determining the geometric isomers of chromium(III) complexes with linear tetradentate ligands (House & Garner; 1966; Kutal & Adamson, 1973; House & Yang, 1983; Kirk & Fernando, 1994). However, it should be noted that the geometric assignments based on spectroscopic studies alone are less conclusive. Both trans and cis isomers of [CrCl2(2,3,2-tet)]ClO4 have been isolated (House & Yang, 1983; Kirk & Fernando, 1994). Whereas the and spectroscopic properties of the cis-β-dichloridochromium(III) complexes containing the 2,3,2-tet ligand were reported (Choi et al., 2008b), the trans isomers with any anion have so far not been structurally characterized. The orientation of the secondary amine hydrogen atoms in the metal complexes is also highly relevant for medical application and likely to be a major factor in determining the antiviral activity (Ronconi & Sadler, 2007; Ross et al., 2012). In order to confirm the orientation of the secondary N—H hydrogen atoms of the Cr(III) complex with 2,3,2-tet and additional Cl ligands, we report the structure of the title compound, trans-[CrCl2(2,3,2-tet)]ClO4, (I), in this communication.
2. Structural commentary
Fig. 2 displays the molecular components of compound (I). In the distorted octahedral complex chromium(III) cation, the four N atoms of the 2,3,2-tet ligand occupy the equatorial sites and the two chlorine atoms coordinate axially to the metal. The two hydrogen atoms of the secondary amine groups are grouped on the same side (meso-RS type) of the equatorial N4 plane. Such a conformation is consistent with those of trans-[CrF2(2,3,2-tet)]ClO4 (Bang & Pedersen, 1978) and trans-[Cr(NCS)2(2,3,2-tet)]NCS (Mäcke et al., 1982). The meso-RS conformation may be compared with rac-RR/SS types of trans-[CrF2(2,2,3-tet)]ClO4 (Choi & Moon, 2014) and trans-[CrF(3,2,3-tet)(H2O)](ClO4)2·H2O (Choi & Lee, 2008).
The Cr—N bond lengths to the 2,3,2-tet ligand are in the range 2.069 (2) to 2.084 (2) Å, in good agreement with those observed in the related structures of trans-[CrF2(2,3,2-tet)]ClO4 (Bang & Pedersen, 1978), trans-[Cr(NCS)2(2,3,2-tet)]NCS (Mäcke et al., 1982), trans-[CrF2(2,2,3-tet)]ClO4 (Choi & Moon, 2014), cis-β-[Cr(ox)(2,3,2-tet)]I (ox = oxalate; Kukina et al., 1990) and cis-β-[Cr(N3)2(2,2,3-tet)]Br (Choi et al., 2011). The two Cr—Cl distances in (I) average to 2.325 (2) Å and are close to the values found in cis-β-[CrCl2(2,3,2-tet)]ClO4 (Choi et al., 2008b) and cis-β-[CrCl2(2,2,3-tet)]ClO4 (Choi et al., 2008a). The Cr1A—N1A and Cr1A—N4A bond lengths to the primary amine N atoms are slightly longer than the Cr1A—N2A and Cr1A—N3A bond lengths to the secondary amine N atoms. It is interesting to note that the Cr—N bond lengths to the primary amine N atoms in cis-β-[CrCl2(2,3,2-tet)]ClO4 (Choi et al., 2008b) are slightly shorter than those to the secondary amine N atoms. Two five-membered and one six-membered chelate rings of the 2,3,2-tet ligand are present in the structure of (I). They adopt gauche and stable chair conformations, respectively. The bond angles of the five- and six-membered chelate rings around the chromium(III) atom are 83.72 (9) and 93.40 (9)°, respectively. The other N—C and C—C bond lengths and Cr—N—C, N—C—C and C—C—C angles are normal for a 2,3,2-tet ligand in a gauche or chair conformation. The tetrahedral ClO4− counter anion is distorted due to its involvement in hydrogen-bonding interactions.
3. Supramolecular features
In the crystal, molecules are stacked along [010]. An N—H⋯Cl hydrogen bond (N2A⋯Cl1A) links neighboring cations into rows parallel to [100] while a series of N—H⋯O contacts connect the cations to neighboring anions (Table 1). An extensive array of these contacts generates a two-dimensional network extending parallel to (010) (Figs. 3 and 4).
4. Database survey
A search in the Cambridge Structural Database (Version 5.36, last update May 2015; Groom & Allen, 2014) shows that there are four reports for CrIII complexes with a [CrL2(2,3,2-tet)]+ unit. The crystal structures of trans-[CrF2(2,3,2-tet)]ClO4 (Bang & Pedersen, 1978), trans-[Cr(NCS)2(2,3,2-tet)]NCS (Mäcke et al., 1982), cis-β-[Cr(ox)(2,3,2-tet)]I (Kukina et al., 1990), cis-β-[CrCl2(2,3,2-tet)]ClO4 (Choi et al., 2008b) have been reported previously. However, no structures of complexes of trans-[CrCl2(2,3,2-tet)]+ with any anions have been deposited.
5. Synthesis and crystallization
The free ligand 1,4,8,11-tetraazaundecane was purchased from Strem Chemical Company, USA. All other chemicals were reagent grade materials and were used without further purification. Compound (I) was prepared by a literature method (Kirk & Fernando, 1994). The crude perchlorate salt (0.35 g) was dissolved in 20 mL of 0.1 M HCl at 333 K. The filtrate was added to 5 mL of 60% HClO4. The resulting solution was left for slow evaporation at room temperature. Green block-like crystals suitable for X-ray structural analysis were isolated after one week. The crystals were washed with small amounts of 2-propanol and dried in air before collecting the synchrotron data.
6. Refinement
Crystal data, data collection and structure . The H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.98 Å (C—H2), and N—H distances of 0.90 Å and 0.99 Å (secondary amine and primary amine H atoms, respectively), with Uiso(H) values of 1.2Ueq of the parent atoms.
details are summarized in Table 2
|
Supporting information
CCDC reference: 1454582
10.1107/S2056989016002978/wm5269sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016002978/wm5269Isup2.hkl
Geometric and conformational
in chromium(III) complexes of linear flexible tetradentate ligands is an interesting field because it has played an important role in extending the concept of stereochemistry. The 1,4,8,11-tetraazaundecane ligand (2,3,2-tet) is a structural isomer of 1,4,7,11-tetraazaundecane (2,2,3-tet). The latter ligand has four nitrogen atoms as donor groups and can adopt three different configurations in chromium(III) complexes with two additional Cl ligands (Choi et al., 2008a,b). Two conformations of meso-RS or racemic-RR/SS isomers with respect to the orientation of the secondary amine hydrogen atoms in the trans isomer are also possible (Fig. 1). The two hydrogen atoms of the conformers may be on the same side (RS) of the equatorial N4 plane or on opposite sides (RR/SS) of this plane.The different symmetries of transition metal complexes allow the determination of their stereochemistry from electronic absorption and infrared spectra. Indeed, infrared and electronic spectroscopic properties often are useful in determining the geometric isomers of chromium(III) complexes with linear tetradentate ligands (House & Garner; 1966; Kutal & Adamson, 1973; House & Yang, 1983; Kirk & Fernando, 1994). However, it should be noted that the geometric assignments based on spectroscopic studies alone are less conclusive. Both trans and cis isomers of [CrCl2(2,3,2-tet)]ClO4 have been isolated (House & Yang, 1983; Kirk & Fernando, 1994). Whereas the β-dichloridochromium(III) complexes containing the 2,3,2-tet ligand were reported (Choi et al., 2008b), the trans isomers with any anion have so far not been structurally characterized. The orientation of the secondary amine hydrogen atoms in the metal complexes is also highly relevant for medical application and likely to be a major factor in determining the antiviral activity (Ronconi & Sadler, 2007; Ross et al., 2012). In order to confirm the orientation of the secondary N—H hydrogen atoms of the Cr(III) complex with 2,3,2-tet and additional Cl ligands, we report the structure of the title compound, trans-[CrCl2(2,3,2-tet)]ClO4, (I), in this communication.
and spectroscopic properties of the cis-Fig. 2 displays the molecular components of compound (I). In the distorted octahedral complex chromium(III) cation, the four N atoms of the 2,3,2-tet ligand occupy the equatorial sites and the two chlorine atoms coordinate axially to the metal. The two hydrogen atoms of the secondary amine groups are grouped on the same side (meso-RS type) of the equatorial N4 plane. Such a conformation is consistent with those of trans-[CrF2(2,3,2-tet)]ClO4 (Bang & Pedersen, 1978) and trans-[Cr(NCS)2(2,3,2-tet)]NCS (Mäcke et al., 1982). The meso-RS conformation may be compared with rac-RR/SS types of trans-[CrF2(2,2,3-tet)]ClO4 (Choi & Moon, 2014) and trans-[CrF(3,2,3-tet)(H2O)](ClO4)2· H2O (Choi & Lee, 2008).
The Cr—N bond lengths to the 2,3,2-tet ligand are in the range 2.069 (2) to 2.084 (2) Å, in good agreement with those observed in the related structures of trans-[CrF2(2,3,2-tet)]ClO4 (Bang & Pedersen, 1978), trans-[Cr(NCS)2(2,3,2-tet)]NCS (Mäcke et al., 1982), trans-[CrF2(2,2,3-tet)]ClO4 (Choi & Moon, 2014), cis-β-[Cr(ox)(2,3,2-tet)]I (ox = oxalate; Kukina et al., 1990) and cis-β-[Cr(N3)2(2,2,3-tet)]Br (Choi et al., 2011). The two Cr—Cl distances in (I) average to 2.325 (2) Å and are close to the values found in cis-β-[CrCl2(2,3,2-tet)]ClO4 (Choi et al., 2008b) and cis-β-[CrCl2(2,2,3-tet)]ClO4 (Choi et al., 2008a). The Cr1A—N1A and Cr1A—N4A bond lengths to the primary amine N atoms are slightly longer than the Cr1A—N2A and Cr1A—N3A bond lengths to the secondary amine N atoms. It is interesting to note that the Cr—N bond lengths to the primary amine N atoms in cis-β-[CrCl2(2,3,2-tet)]ClO4 (Choi et al., 2008a) are slightly shorter than those to the secondary amine N atoms. Two five-membered and one six-membered chelate rings of the 2,3,2-tet ligand are present in the structure of (I). They adopt gauche and stable chair conformations, respectively. The bond angles of the five- and six-membered chelate rings around the chromium(III) atom are 83.72 (9) and 93.40 (9)°, respectively. The other N—C and C—C bond lengths and Cr—N—C, N—C—C and C—C—C angles are normal for a 2,3,2-tet ligand in gauche or chair conformations. The tetrahedral ClO4− counter anion is distorted due to its involvement in hydrogen-bonding interactions.
In the crystal, molecules are stacked along [010]. An N—H···Cl hydrogen bond (N2A···Cl1A) links neighboring cations into rows parallel to [100] while a series of N—H···O contacts connect the cations to neighboring anions (Table 1). An extensive array of these contacts generates a two-dimensional network extending parallel to (010) (Figs. 3 and 4).
A search in the Cambridge Structural Database (Version 5.36, last update February 2015; Groom & Allen, 2014) shows that there are four reports for CrIII complexes with a [CrL2(2,3,2-tet)]+ unit. The crystal structures of trans-[CrF2(2,3,2-tet)]ClO4 (Bang & Pedersen, 1978), trans-[Cr(NCS)2(2,3,2-tet)]NCS (Mäcke et al., 1982), cis-β-[Cr(ox)(2,3,2-tet)]I (Kukina et al., 1990), cis-β-[CrCl2(2,3,2-tet)]ClO4 (Choi et al., 2008b) have been reported previously. However, no structures of complexes of trans-[CrCl2(2,3,2-tet)]+ with any anions have been deposited.
The free ligand 1,4,8,11-tetraazaundecane was purchased from Strem Chemical Company, USA. All other chemicals were reagent grade materials and were used without further purification. Compound (I) was prepared by a literature method (Kirk & Fernando, 1994). The crude perchlorate salt (0.35 g) was dissolved in 20 ml of 0.1 M HCl at 333 K. The filtrate was added to 5 ml of 60% HClO4. The resulting solution was left for slow evaporation at room temperature. Green block-like crystals suitable for X-ray structural analysis were isolated after one week. The crystals were washed with small amounts of 2-propanol and dried in air before collecting the synchrotron data.
Crystal data, data collection and structure
details are summarized in Table 2. The H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.98 Å (C—H2), and N—H distances of 0.90 Å and 0.99 Å (secondary amine and primary amine H atoms, respectively), with Uiso(H) values of 1.2Ueq of the parent atoms.Geometric and conformational
in chromium(III) complexes of linear flexible tetradentate ligands is an interesting field because it has played an important role in extending the concept of stereochemistry. The 1,4,8,11-tetraazaundecane ligand (2,3,2-tet) is a structural isomer of 1,4,7,11-tetraazaundecane (2,2,3-tet). The latter ligand has four nitrogen atoms as donor groups and can adopt three different configurations in chromium(III) complexes with two additional Cl ligands (Choi et al., 2008a,b). Two conformations of meso-RS or racemic-RR/SS isomers with respect to the orientation of the secondary amine hydrogen atoms in the trans isomer are also possible (Fig. 1). The two hydrogen atoms of the conformers may be on the same side (RS) of the equatorial N4 plane or on opposite sides (RR/SS) of this plane.The different symmetries of transition metal complexes allow the determination of their stereochemistry from electronic absorption and infrared spectra. Indeed, infrared and electronic spectroscopic properties often are useful in determining the geometric isomers of chromium(III) complexes with linear tetradentate ligands (House & Garner; 1966; Kutal & Adamson, 1973; House & Yang, 1983; Kirk & Fernando, 1994). However, it should be noted that the geometric assignments based on spectroscopic studies alone are less conclusive. Both trans and cis isomers of [CrCl2(2,3,2-tet)]ClO4 have been isolated (House & Yang, 1983; Kirk & Fernando, 1994). Whereas the β-dichloridochromium(III) complexes containing the 2,3,2-tet ligand were reported (Choi et al., 2008b), the trans isomers with any anion have so far not been structurally characterized. The orientation of the secondary amine hydrogen atoms in the metal complexes is also highly relevant for medical application and likely to be a major factor in determining the antiviral activity (Ronconi & Sadler, 2007; Ross et al., 2012). In order to confirm the orientation of the secondary N—H hydrogen atoms of the Cr(III) complex with 2,3,2-tet and additional Cl ligands, we report the structure of the title compound, trans-[CrCl2(2,3,2-tet)]ClO4, (I), in this communication.
and spectroscopic properties of the cis-Fig. 2 displays the molecular components of compound (I). In the distorted octahedral complex chromium(III) cation, the four N atoms of the 2,3,2-tet ligand occupy the equatorial sites and the two chlorine atoms coordinate axially to the metal. The two hydrogen atoms of the secondary amine groups are grouped on the same side (meso-RS type) of the equatorial N4 plane. Such a conformation is consistent with those of trans-[CrF2(2,3,2-tet)]ClO4 (Bang & Pedersen, 1978) and trans-[Cr(NCS)2(2,3,2-tet)]NCS (Mäcke et al., 1982). The meso-RS conformation may be compared with rac-RR/SS types of trans-[CrF2(2,2,3-tet)]ClO4 (Choi & Moon, 2014) and trans-[CrF(3,2,3-tet)(H2O)](ClO4)2· H2O (Choi & Lee, 2008).
The Cr—N bond lengths to the 2,3,2-tet ligand are in the range 2.069 (2) to 2.084 (2) Å, in good agreement with those observed in the related structures of trans-[CrF2(2,3,2-tet)]ClO4 (Bang & Pedersen, 1978), trans-[Cr(NCS)2(2,3,2-tet)]NCS (Mäcke et al., 1982), trans-[CrF2(2,2,3-tet)]ClO4 (Choi & Moon, 2014), cis-β-[Cr(ox)(2,3,2-tet)]I (ox = oxalate; Kukina et al., 1990) and cis-β-[Cr(N3)2(2,2,3-tet)]Br (Choi et al., 2011). The two Cr—Cl distances in (I) average to 2.325 (2) Å and are close to the values found in cis-β-[CrCl2(2,3,2-tet)]ClO4 (Choi et al., 2008b) and cis-β-[CrCl2(2,2,3-tet)]ClO4 (Choi et al., 2008a). The Cr1A—N1A and Cr1A—N4A bond lengths to the primary amine N atoms are slightly longer than the Cr1A—N2A and Cr1A—N3A bond lengths to the secondary amine N atoms. It is interesting to note that the Cr—N bond lengths to the primary amine N atoms in cis-β-[CrCl2(2,3,2-tet)]ClO4 (Choi et al., 2008a) are slightly shorter than those to the secondary amine N atoms. Two five-membered and one six-membered chelate rings of the 2,3,2-tet ligand are present in the structure of (I). They adopt gauche and stable chair conformations, respectively. The bond angles of the five- and six-membered chelate rings around the chromium(III) atom are 83.72 (9) and 93.40 (9)°, respectively. The other N—C and C—C bond lengths and Cr—N—C, N—C—C and C—C—C angles are normal for a 2,3,2-tet ligand in gauche or chair conformations. The tetrahedral ClO4− counter anion is distorted due to its involvement in hydrogen-bonding interactions.
In the crystal, molecules are stacked along [010]. An N—H···Cl hydrogen bond (N2A···Cl1A) links neighboring cations into rows parallel to [100] while a series of N—H···O contacts connect the cations to neighboring anions (Table 1). An extensive array of these contacts generates a two-dimensional network extending parallel to (010) (Figs. 3 and 4).
A search in the Cambridge Structural Database (Version 5.36, last update February 2015; Groom & Allen, 2014) shows that there are four reports for CrIII complexes with a [CrL2(2,3,2-tet)]+ unit. The crystal structures of trans-[CrF2(2,3,2-tet)]ClO4 (Bang & Pedersen, 1978), trans-[Cr(NCS)2(2,3,2-tet)]NCS (Mäcke et al., 1982), cis-β-[Cr(ox)(2,3,2-tet)]I (Kukina et al., 1990), cis-β-[CrCl2(2,3,2-tet)]ClO4 (Choi et al., 2008b) have been reported previously. However, no structures of complexes of trans-[CrCl2(2,3,2-tet)]+ with any anions have been deposited.
The free ligand 1,4,8,11-tetraazaundecane was purchased from Strem Chemical Company, USA. All other chemicals were reagent grade materials and were used without further purification. Compound (I) was prepared by a literature method (Kirk & Fernando, 1994). The crude perchlorate salt (0.35 g) was dissolved in 20 ml of 0.1 M HCl at 333 K. The filtrate was added to 5 ml of 60% HClO4. The resulting solution was left for slow evaporation at room temperature. Green block-like crystals suitable for X-ray structural analysis were isolated after one week. The crystals were washed with small amounts of 2-propanol and dried in air before collecting the synchrotron data.
detailsCrystal data, data collection and structure
details are summarized in Table 2. The H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.98 Å (C—H2), and N—H distances of 0.90 Å and 0.99 Å (secondary amine and primary amine H atoms, respectively), with Uiso(H) values of 1.2Ueq of the parent atoms.Data collection: PAL BL2D-SMDC Program (Shin et al., 2016); cell
HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: DIAMOND (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. Schematic representation of the 2,3,2-tet and 2,2,3-tet ligands, and two possible conformational isomers of trans-[CrCl2(2,3,2-tet)]+. | |
Fig. 2. The structures of the molecular components of complex (I), drawn with displacement ellipsoids at the 30% probability level. | |
Fig. 3. The crystal packing of complex (I) viewed perpendicular to (010). Dashed lines represent N—H···O (pink) and N—H···Cl (green) hydrogen-bonding interactions, respectively. | |
Fig. 4. The crystal packing of complex (I) viewed along [100]. The colour code is as in Fig. 3. |
[CrCl2(C7H20N4)]ClO4 | F(000) = 394 |
Mr = 382.62 | Dx = 1.691 Mg m−3 |
Monoclinic, Pn | Synchrotron radiation, λ = 0.620 Å |
a = 6.4730 (13) Å | Cell parameters from 22325 reflections |
b = 11.449 (2) Å | θ = 0.4–33.6° |
c = 10.385 (2) Å | µ = 0.89 mm−1 |
β = 102.42 (3)° | T = 243 K |
V = 751.6 (3) Å3 | Block, green |
Z = 2 | 0.13 × 0.13 × 0.05 mm |
ADSC Q210 CCD area-detector diffractometer | 4214 reflections with I > 2σ(I) |
Radiation source: PLSII 2D bending magnet | Rint = 0.023 |
ω scan | θmax = 26.0°, θmin = 2.3° |
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997) | h = −9→9 |
Tmin = 0.893, Tmax = 0.958 | k = −16→16 |
7831 measured reflections | l = −14→14 |
4422 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.025 | w = 1/[σ2(Fo2) + (0.0435P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.066 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.39 e Å−3 |
4422 reflections | Δρmin = −0.62 e Å−3 |
172 parameters | Absolute structure: Flack x determined using 2004 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
2 restraints | Absolute structure parameter: 0.038 (9) |
[CrCl2(C7H20N4)]ClO4 | V = 751.6 (3) Å3 |
Mr = 382.62 | Z = 2 |
Monoclinic, Pn | Synchrotron radiation, λ = 0.620 Å |
a = 6.4730 (13) Å | µ = 0.89 mm−1 |
b = 11.449 (2) Å | T = 243 K |
c = 10.385 (2) Å | 0.13 × 0.13 × 0.05 mm |
β = 102.42 (3)° |
ADSC Q210 CCD area-detector diffractometer | 4422 independent reflections |
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997) | 4214 reflections with I > 2σ(I) |
Tmin = 0.893, Tmax = 0.958 | Rint = 0.023 |
7831 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.066 | Δρmax = 0.39 e Å−3 |
S = 1.07 | Δρmin = −0.62 e Å−3 |
4422 reflections | Absolute structure: Flack x determined using 2004 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
172 parameters | Absolute structure parameter: 0.038 (9) |
2 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Cr1A | 0.49958 (5) | 0.29857 (3) | 0.49729 (4) | 0.01583 (8) | |
Cl1A | 0.79710 (9) | 0.18290 (6) | 0.56558 (7) | 0.02827 (14) | |
Cl2A | 0.20419 (9) | 0.41841 (5) | 0.43425 (6) | 0.02410 (12) | |
N1A | 0.5655 (3) | 0.3816 (2) | 0.6797 (2) | 0.0241 (4) | |
H1A1 | 0.6982 | 0.3651 | 0.7229 | 0.029* | |
H1A2 | 0.5535 | 0.4595 | 0.6690 | 0.029* | |
N2A | 0.3179 (3) | 0.18908 (17) | 0.5865 (2) | 0.0199 (4) | |
H2A | 0.1708 | 0.2180 | 0.5598 | 0.024* | |
N3A | 0.4222 (3) | 0.21127 (19) | 0.3180 (2) | 0.0234 (4) | |
H3A | 0.2837 | 0.2426 | 0.2713 | 0.028* | |
N4A | 0.6689 (3) | 0.4076 (2) | 0.3968 (2) | 0.0249 (4) | |
H4A1 | 0.6368 | 0.4828 | 0.4087 | 0.030* | |
H4A2 | 0.8087 | 0.3978 | 0.4278 | 0.030* | |
C1A | 0.4110 (5) | 0.3385 (3) | 0.7556 (3) | 0.0296 (6) | |
H1A3 | 0.2754 | 0.3789 | 0.7270 | 0.036* | |
H1A4 | 0.4636 | 0.3533 | 0.8499 | 0.036* | |
C2A | 0.3824 (5) | 0.2085 (3) | 0.7308 (3) | 0.0284 (5) | |
H2A1 | 0.5152 | 0.1675 | 0.7664 | 0.034* | |
H2A2 | 0.2736 | 0.1783 | 0.7746 | 0.034* | |
C3A | 0.3107 (4) | 0.0636 (2) | 0.5507 (3) | 0.0284 (5) | |
H3A1 | 0.2128 | 0.0230 | 0.5955 | 0.034* | |
H3A2 | 0.4515 | 0.0293 | 0.5812 | 0.034* | |
C4A | 0.2396 (5) | 0.0455 (3) | 0.4025 (3) | 0.0335 (6) | |
H4A3 | 0.2074 | −0.0375 | 0.3859 | 0.040* | |
H4A4 | 0.1081 | 0.0892 | 0.3713 | 0.040* | |
C5A | 0.3975 (5) | 0.0824 (2) | 0.3219 (3) | 0.0326 (6) | |
H5A1 | 0.5351 | 0.0471 | 0.3597 | 0.039* | |
H5A2 | 0.3510 | 0.0531 | 0.2317 | 0.039* | |
C6A | 0.5783 (5) | 0.2472 (3) | 0.2397 (3) | 0.0333 (6) | |
H6A1 | 0.5258 | 0.2269 | 0.1467 | 0.040* | |
H6A2 | 0.7126 | 0.2064 | 0.2716 | 0.040* | |
C7A | 0.6117 (5) | 0.3775 (3) | 0.2536 (3) | 0.0352 (6) | |
H7A1 | 0.7254 | 0.4016 | 0.2104 | 0.042* | |
H7A2 | 0.4821 | 0.4187 | 0.2113 | 0.042* | |
Cl1B | 0.50722 (11) | 0.72486 (5) | 0.49469 (7) | 0.02745 (12) | |
O1B | 0.5868 (6) | 0.6499 (3) | 0.6047 (3) | 0.0654 (10) | |
O2B | 0.5109 (4) | 0.6627 (3) | 0.3746 (3) | 0.0463 (6) | |
O3B | 0.2904 (5) | 0.7539 (3) | 0.4912 (3) | 0.0582 (7) | |
O4B | 0.6361 (5) | 0.8276 (2) | 0.5033 (3) | 0.0490 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr1A | 0.01154 (13) | 0.01462 (14) | 0.01988 (14) | 0.00061 (12) | 0.00019 (10) | −0.00054 (13) |
Cl1A | 0.0156 (2) | 0.0267 (3) | 0.0401 (3) | 0.0062 (2) | 0.0006 (2) | 0.0027 (2) |
Cl2A | 0.0175 (2) | 0.0225 (3) | 0.0308 (3) | 0.00531 (19) | 0.00184 (18) | 0.0056 (2) |
N1A | 0.0234 (9) | 0.0212 (10) | 0.0244 (9) | 0.0001 (8) | −0.0019 (7) | −0.0040 (8) |
N2A | 0.0163 (8) | 0.0153 (9) | 0.0270 (10) | −0.0001 (7) | 0.0018 (7) | 0.0032 (7) |
N3A | 0.0242 (10) | 0.0211 (10) | 0.0237 (10) | −0.0005 (8) | 0.0024 (8) | −0.0044 (8) |
N4A | 0.0186 (9) | 0.0227 (11) | 0.0337 (11) | −0.0008 (7) | 0.0063 (8) | 0.0026 (8) |
C1A | 0.0364 (14) | 0.0305 (15) | 0.0222 (11) | 0.0035 (11) | 0.0071 (10) | −0.0034 (10) |
C2A | 0.0369 (15) | 0.0236 (13) | 0.0248 (12) | 0.0033 (10) | 0.0072 (10) | 0.0056 (9) |
C3A | 0.0293 (12) | 0.0156 (11) | 0.0388 (13) | −0.0013 (9) | 0.0037 (10) | 0.0025 (10) |
C4A | 0.0333 (14) | 0.0204 (12) | 0.0422 (15) | −0.0079 (10) | −0.0023 (11) | −0.0055 (11) |
C5A | 0.0386 (15) | 0.0210 (13) | 0.0358 (13) | −0.0006 (10) | 0.0025 (11) | −0.0097 (10) |
C6A | 0.0362 (15) | 0.0376 (18) | 0.0283 (13) | 0.0012 (12) | 0.0118 (11) | −0.0037 (12) |
C7A | 0.0369 (15) | 0.0399 (18) | 0.0316 (13) | −0.0016 (13) | 0.0133 (11) | 0.0052 (12) |
Cl1B | 0.0312 (3) | 0.0245 (3) | 0.0255 (2) | 0.0024 (3) | 0.00349 (19) | 0.0028 (3) |
O1B | 0.077 (2) | 0.0510 (16) | 0.0495 (15) | −0.0175 (15) | −0.0279 (14) | 0.0247 (13) |
O2B | 0.0544 (16) | 0.0478 (14) | 0.0396 (12) | −0.0064 (12) | 0.0165 (11) | −0.0106 (10) |
O3B | 0.0421 (14) | 0.063 (2) | 0.075 (2) | 0.0116 (13) | 0.0243 (13) | 0.0017 (16) |
O4B | 0.0587 (17) | 0.0279 (12) | 0.0574 (15) | −0.0124 (11) | 0.0060 (12) | 0.0005 (10) |
Cr1A—N2A | 2.069 (2) | C1A—H1A4 | 0.9800 |
Cr1A—N3A | 2.078 (2) | C2A—H2A1 | 0.9800 |
Cr1A—N1A | 2.080 (2) | C2A—H2A2 | 0.9800 |
Cr1A—N4A | 2.084 (2) | C3A—C4A | 1.523 (4) |
Cr1A—Cl1A | 2.3191 (8) | C3A—H3A1 | 0.9800 |
Cr1A—Cl2A | 2.3300 (8) | C3A—H3A2 | 0.9800 |
N1A—C1A | 1.484 (4) | C4A—C5A | 1.514 (4) |
N1A—H1A1 | 0.9000 | C4A—H4A3 | 0.9800 |
N1A—H1A2 | 0.9000 | C4A—H4A4 | 0.9800 |
N2A—C3A | 1.482 (3) | C5A—H5A1 | 0.9800 |
N2A—C2A | 1.483 (4) | C5A—H5A2 | 0.9800 |
N2A—H2A | 0.9900 | C6A—C7A | 1.510 (5) |
N3A—C5A | 1.485 (3) | C6A—H6A1 | 0.9800 |
N3A—C6A | 1.485 (4) | C6A—H6A2 | 0.9800 |
N3A—H3A | 0.9900 | C7A—H7A1 | 0.9800 |
N4A—C7A | 1.493 (4) | C7A—H7A2 | 0.9800 |
N4A—H4A1 | 0.9000 | Cl1B—O1B | 1.433 (3) |
N4A—H4A2 | 0.9000 | Cl1B—O4B | 1.434 (2) |
C1A—C2A | 1.514 (4) | Cl1B—O3B | 1.435 (3) |
C1A—H1A3 | 0.9800 | Cl1B—O2B | 1.441 (3) |
N2A—Cr1A—N3A | 93.40 (9) | H1A3—C1A—H1A4 | 108.4 |
N2A—Cr1A—N1A | 83.91 (9) | N2A—C2A—C1A | 108.5 (2) |
N3A—Cr1A—N1A | 177.24 (9) | N2A—C2A—H2A1 | 110.0 |
N2A—Cr1A—N4A | 176.52 (9) | C1A—C2A—H2A1 | 110.0 |
N3A—Cr1A—N4A | 83.72 (9) | N2A—C2A—H2A2 | 110.0 |
N1A—Cr1A—N4A | 98.95 (9) | C1A—C2A—H2A2 | 110.0 |
N2A—Cr1A—Cl1A | 91.81 (6) | H2A1—C2A—H2A2 | 108.4 |
N3A—Cr1A—Cl1A | 91.36 (7) | N2A—C3A—C4A | 111.8 (2) |
N1A—Cr1A—Cl1A | 89.33 (7) | N2A—C3A—H3A1 | 109.3 |
N4A—Cr1A—Cl1A | 90.21 (7) | C4A—C3A—H3A1 | 109.3 |
N2A—Cr1A—Cl2A | 88.37 (6) | N2A—C3A—H3A2 | 109.3 |
N3A—Cr1A—Cl2A | 90.36 (7) | C4A—C3A—H3A2 | 109.3 |
N1A—Cr1A—Cl2A | 88.97 (7) | H3A1—C3A—H3A2 | 107.9 |
N4A—Cr1A—Cl2A | 89.69 (7) | C5A—C4A—C3A | 115.3 (2) |
Cl1A—Cr1A—Cl2A | 178.26 (3) | C5A—C4A—H4A3 | 108.5 |
C1A—N1A—Cr1A | 107.58 (16) | C3A—C4A—H4A3 | 108.5 |
C1A—N1A—H1A1 | 110.2 | C5A—C4A—H4A4 | 108.5 |
Cr1A—N1A—H1A1 | 110.2 | C3A—C4A—H4A4 | 108.5 |
C1A—N1A—H1A2 | 110.2 | H4A3—C4A—H4A4 | 107.5 |
Cr1A—N1A—H1A2 | 110.2 | N3A—C5A—C4A | 112.5 (2) |
H1A1—N1A—H1A2 | 108.5 | N3A—C5A—H5A1 | 109.1 |
C3A—N2A—C2A | 112.7 (2) | C4A—C5A—H5A1 | 109.1 |
C3A—N2A—Cr1A | 117.73 (18) | N3A—C5A—H5A2 | 109.1 |
C2A—N2A—Cr1A | 107.34 (16) | C4A—C5A—H5A2 | 109.1 |
C3A—N2A—H2A | 106.1 | H5A1—C5A—H5A2 | 107.8 |
C2A—N2A—H2A | 106.1 | N3A—C6A—C7A | 108.8 (2) |
Cr1A—N2A—H2A | 106.1 | N3A—C6A—H6A1 | 109.9 |
C5A—N3A—C6A | 112.4 (2) | C7A—C6A—H6A1 | 109.9 |
C5A—N3A—Cr1A | 117.36 (17) | N3A—C6A—H6A2 | 109.9 |
C6A—N3A—Cr1A | 107.22 (17) | C7A—C6A—H6A2 | 109.9 |
C5A—N3A—H3A | 106.4 | H6A1—C6A—H6A2 | 108.3 |
C6A—N3A—H3A | 106.4 | N4A—C7A—C6A | 108.8 (2) |
Cr1A—N3A—H3A | 106.4 | N4A—C7A—H7A1 | 109.9 |
C7A—N4A—Cr1A | 108.43 (17) | C6A—C7A—H7A1 | 109.9 |
C7A—N4A—H4A1 | 110.0 | N4A—C7A—H7A2 | 109.9 |
Cr1A—N4A—H4A1 | 110.0 | C6A—C7A—H7A2 | 109.9 |
C7A—N4A—H4A2 | 110.0 | H7A1—C7A—H7A2 | 108.3 |
Cr1A—N4A—H4A2 | 110.0 | O1B—Cl1B—O4B | 109.70 (17) |
H4A1—N4A—H4A2 | 108.4 | O1B—Cl1B—O3B | 109.9 (2) |
N1A—C1A—C2A | 108.0 (2) | O4B—Cl1B—O3B | 111.3 (2) |
N1A—C1A—H1A3 | 110.1 | O1B—Cl1B—O2B | 108.91 (19) |
C2A—C1A—H1A3 | 110.1 | O4B—Cl1B—O2B | 109.98 (17) |
N1A—C1A—H1A4 | 110.1 | O3B—Cl1B—O2B | 106.93 (19) |
C2A—C1A—H1A4 | 110.1 | ||
Cr1A—N1A—C1A—C2A | 40.4 (2) | C6A—N3A—C5A—C4A | 179.6 (2) |
C3A—N2A—C2A—C1A | 173.1 (2) | Cr1A—N3A—C5A—C4A | 54.6 (3) |
Cr1A—N2A—C2A—C1A | 41.9 (3) | C3A—C4A—C5A—N3A | −70.3 (3) |
N1A—C1A—C2A—N2A | −55.7 (3) | C5A—N3A—C6A—C7A | −173.7 (2) |
C2A—N2A—C3A—C4A | 178.8 (2) | Cr1A—N3A—C6A—C7A | −43.3 (3) |
Cr1A—N2A—C3A—C4A | −55.5 (3) | Cr1A—N4A—C7A—C6A | −36.0 (3) |
N2A—C3A—C4A—C5A | 70.5 (3) | N3A—C6A—C7A—N4A | 53.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A1···O2Bi | 0.90 | 2.30 | 3.187 (4) | 167 |
N1A—H1A2···O1B | 0.90 | 2.30 | 3.180 (4) | 164 |
N2A—H2A···Cl1Aii | 0.99 | 2.47 | 3.332 (2) | 146 |
N3A—H3A···O1Biii | 0.99 | 2.28 | 3.174 (4) | 150 |
N4A—H4A1···O2B | 0.90 | 2.21 | 3.086 (4) | 163 |
N4A—H4A2···Cl2Aiv | 0.90 | 2.56 | 3.405 (2) | 157 |
Symmetry codes: (i) x+1/2, −y+1, z+1/2; (ii) x−1, y, z; (iii) x−1/2, −y+1, z−1/2; (iv) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A1···O2Bi | 0.90 | 2.30 | 3.187 (4) | 167.0 |
N1A—H1A2···O1B | 0.90 | 2.30 | 3.180 (4) | 164.3 |
N2A—H2A···Cl1Aii | 0.99 | 2.47 | 3.332 (2) | 146.0 |
N3A—H3A···O1Biii | 0.99 | 2.28 | 3.174 (4) | 150.2 |
N4A—H4A1···O2B | 0.90 | 2.21 | 3.086 (4) | 162.7 |
N4A—H4A2···Cl2Aiv | 0.90 | 2.56 | 3.405 (2) | 157.2 |
Symmetry codes: (i) x+1/2, −y+1, z+1/2; (ii) x−1, y, z; (iii) x−1/2, −y+1, z−1/2; (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [CrCl2(C7H20N4)]ClO4 |
Mr | 382.62 |
Crystal system, space group | Monoclinic, Pn |
Temperature (K) | 243 |
a, b, c (Å) | 6.4730 (13), 11.449 (2), 10.385 (2) |
β (°) | 102.42 (3) |
V (Å3) | 751.6 (3) |
Z | 2 |
Radiation type | Synchrotron, λ = 0.620 Å |
µ (mm−1) | 0.89 |
Crystal size (mm) | 0.13 × 0.13 × 0.05 |
Data collection | |
Diffractometer | ADSC Q210 CCD area-detector |
Absorption correction | Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.893, 0.958 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7831, 4422, 4214 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.707 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.066, 1.07 |
No. of reflections | 4422 |
No. of parameters | 172 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.62 |
Absolute structure | Flack x determined using 2004 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | 0.038 (9) |
Computer programs: PAL BL2D-SMDC Program (Shin et al., 2016), HKL3000sm (Otwinowski & Minor, 1997), SHELXT (Sheldrick, 2015a), SHELXL2014/7 (Sheldrick, 2015b), DIAMOND (Putz & Brandenburg, 2014), publCIF (Westrip, 2010).
Acknowledgements
This work was supported by a grant from 2016 Research Funds of Andong National University. The X-ray crystallography experiment at the PLS-II BL2D-SMC beamline was supported in part by MSIP and POSTECH.
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