research communications
p-tolyl-1H-imidazol-1-yl]acetate
of ethyl 2-[2-(4-methylbenzoyl)-5-aDepartment of Physics, University College of Engineering Nagercoil, Anna University, Nagercoil 629 004, India, and bMedicinal Chemistry Division, Indian Institute of Integrative Medicine (IIIM) and Academy of Scientific and Innovative Research (AcSIR-IIIM), Jammu 180 001, India
*Correspondence e-mail: athi81s@yahoo.co.in
In the title compound, C22H22N2O3, the plane of the five-membered ring is oriented at dihedral angles of 45.4 (1) and 52.5 (1)° to the phenyl rings. Furthermore, this ring makes an angle of 85.2 (2)° with the plane of the ethyl acetate substituent. The molecular structure is affected by an intramolecular C—H⋯O hydrogen bond between an H atom from the p-tolyl group and the carbonyl O atom of the acetate. The methyl group of the ethyl acetate residue is disordered over two sites with equal occupancies. The features intermolecular C—H⋯O and C—H⋯N interactions. One of the C—H⋯O hydrogen bonds forms a C(5) chain motif extending along the a axis. In addition, C—H⋯N contacts form inversion dimers with R22(12) ring motifs, linking the imidazole ring system to the benzene ring of the p-tolyl substituent.
Keywords: crystal structure; imidazole derivative; new synthesis; 2-(4-methoxyphenyl)-2-oxoacetaldehyde; glycine methyl ester hydrochloride.
CCDC reference: 1452746
1. Chemical context
Imidazole and its derivatives have numerous pharmaceutical applications including uses as antifungal (Shingalapur et al. 2009), antimicrobial (Sharma et al. 2009), anti-inflammatory (Puratchikody et al. 2007), analgesic (Achar et al. 2010), antitubercular (Pandey et al. 2009), antidepressant (Hadizadeh et al. 2008), antileishmanial (Bhandari et al. 2009) and anticancer agents (Ozkay et al. 2010). We are interested in the synthesis of active pharmaceutical ingredients (APIs) based on imidazoles and we report here the synthesis and of the title imidazole derivative.
2. Structural commentary
The molecular structure of the title compound is shown in Fig. 1. The C—N bond lengths within the imidazole ring are 1.373 (3) Å (C10—N2), 1.372 (3) Å (C8—N2), 1.349 (3) Å (C9—N1) and 1.329 (3) Å (C10—N1). These bond distances are shorter than the single-bond length (1.443 Å) and longer than the accepted double-bond length (1.269 Å) due to electron delocalization in the central imidazole ring. The phenyl rings and the plane of the imidazole ring are inclined at angles of 45.4 (1)° (with the C12–C17 ring) and 52.5 (1)° (with the C2–C7 ring). The phenyl rings are oriented to each other with a dihedral angle of 88.1 (1)°. Further, the imidazole ring is inclined at an angle of 85.2 (2)° to the best-fit plane through atoms C19, C20, O3, C21 and C22 of the ethyl acetate substituent. The molecular structure is also influenced by the formation of an intramolecular C6—H6⋯O2 hydrogen bond, Table 1, which generates an S(8) ring motif (Bernstein et al., 1995).
3. Supramolecular features
The N-bound methylene group of the side chain is connected with the carbonyl oxygen of an adjacent molecule through a C19—H19A⋯O2 hydrogen bond, forming a linear C(5) chain motif along the a axis, Table 1 and Fig. 2. The phenyl and imidazole rings are linked through inversion-dimer formation involving C4—H4⋯N1 hydrogen bonds that generate R22(12) ring motifs. A second inversion dimer to an adjacent molecule results from C1—H1⋯O2 contacts, forming ring R22(22) [OK?] rings, Fig. 3.
4. Database survey
The Cambridge Structural Database (Groom & Allen, 2014) reveals only five structures of imidazole derivatives with a CH2COOCH2CH3 substituent on nitrogen (Cai et al., 2014; Bahnous et al., 2013; Zaprutko et al., 2012). Imidazoles with benzoyl substituents are slightly more common with eight occurrences (Xue et al., 2014; Nagaraj et al., 2012; Samanta et al., 2013), while the structures of only six p-tolyl-substituted imidazoles are found (Bu et al., 1996; Fridman et al., 2006, 2009). These searches also reveal the unique nature of the molecule reported here.
5. Synthesis and crystallization
The title compound was synthesized from a mixture of 2-(4-methoxyphenyl)-2-oxoacetaldehyde (1 mmol), glycine methyl ester hydrochloride (1 mmol) and selenium dioxide (1 mmol) in a basic environment in acetonitrile at 373 K. Crystals suitable for X-ray investigation were obtained by solvent evaporation from the resulting solution in 33% yield.
6. Refinement
Crystal data, data collection and structure . All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 −0.97 Å and Uiso(H) = 1.2–1.5Ueq(parent C atom). The methyl group C22 of the side chain is disordered over two positions, each with a site-occupancy factor of 0.5. The atomic displacement parameters of these two C atoms are restrained to be equivalent and the C21—C22 and C21—C22′ bond distances were restrained during the using DFIX commands.
details are summarized in Table 2Supporting information
CCDC reference: 1452746
10.1107/S2056989016002504/sj5493sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016002504/sj5493Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016002504/sj5493Isup3.cml
Imidazoles are fundamental components of many biological molecules. Imidazole and its derivatives have numerous pharmaceutical applications including uses as antifungal (Shingalapur et al. 2009), antimicrobial (Sharma et al. 2009), anti-inflammatory (Puratchikody et al. 2007), analgesic (Achar et al. 2010), antitubercular (Pandey et al. 2009), antidepressant (Hadizadeh et al. 2008), antileishmanial (Bhandari et al. 2009) and anticancer agents (Ozkay et al. 2010). We are interested in the synthesis of active pharmaceutical ingredients (APIs) based on imidazoles and we report here the synthesis and
of the title imidazole derivative.The molecular structure of the title compound is shown in Fig. 1. The C—N bond lengths within the imidazole ring are 1.373 (3) Å (C10—N2), 1.372 (3) Å (C8—N2), 1.349 (3) Å (C9—N1) and 1.329 (3) Å (C10—N1). These bond distances are shorter than the single-bond length (1.443 Å) and longer than the accepted double-bond length (1.269 Å) due to electron delocalization in the central imidazole ring. The phenyl rings and the plane of the imidazole ring are inclined at angles of 45.4 (1)° (with the C12/C17 ring) and 52.5 (1)° (with the C2/C7 ring). The phenyl rings are oriented to each other with a dihedral angle of 88.1 (1)°. Further, the imidazole ring is inclined at an angle of 85.2 (2)° to the best-fit plane through atoms C19, C20, O3, C21 and C22 of the ethyl acetate substituent. The molecular structure is also influenced by the formation of an intramolecular C6—H6···O2 hydrogen bond, which generates an S(8) ring motif (Bernstein et al., 1995).
The N-bound methylene group of the side chain is connected with the carbonyl oxygen of an adjacent molecule through a C19—H19A···O2 hydrogen bond, forming a linear C(5) chain motif along the a axis, Fig. 2. The phenyl and imidazole rings are linked through inversion-dimer formation involving C4—H4···N1 hydrogen bonds that generate R22(12) ring motifs. A second inversion dimer to an adjacent molecule results from C1—H1···O2 contacts, forming ring R22(22) rings, Fig. 3.
The Cambridge Structural Database (Groom & Allen, 2014) reveals only five structures of imidazole derivatives with a CH2COOCh2CH3 substituent on nitrogen (Cai et al., 2014; Bahnous et al., 2013; Zaprutko et al., 2012). Imidazoles with benzoyl substituents are slightly more common with eight occurrences (Xue et al., 2014; Nagaraj et al., 2012; Samanta et al., 2013), while the structures of only six p-tolyl-substituted imidazoles are found (Bu et al., 1996; Fridman et al., 2006, 2009). These searches also reveal the unique nature of the molecule reported here.
The title compound was synthesized from a mixture of 2-(4-methoxyphenyl)-2-oxoacetaldehyde (1 mmol), glycine methyl ester hydrochloride (1 mmol) and selenium dioxide (1 mmol) in a basic environment in acetonitrile at 373 K. Crystals suitable for X-ray investigation were obtained from the resulting solution in 33% yield.
Crystal data, data collection and structure
details are summarized in Table 2. A l l H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 − 0.97 Å and Uiso(H) = 1.2–1.5Ueq(parent C atom). The methyl group C22 of the side chain is disordered over two positions, each with a site-occupancy factor of 0.5. The atomic displacement parameters of these two C atoms are restrained to be equivalent and the C21—C22 and C21—C22' bond distances were restrained during the using DFIX commands.Imidazoles are fundamental components of many biological molecules. Imidazole and its derivatives have numerous pharmaceutical applications including uses as antifungal (Shingalapur et al. 2009), antimicrobial (Sharma et al. 2009), anti-inflammatory (Puratchikody et al. 2007), analgesic (Achar et al. 2010), antitubercular (Pandey et al. 2009), antidepressant (Hadizadeh et al. 2008), antileishmanial (Bhandari et al. 2009) and anticancer agents (Ozkay et al. 2010). We are interested in the synthesis of active pharmaceutical ingredients (APIs) based on imidazoles and we report here the synthesis and
of the title imidazole derivative.The molecular structure of the title compound is shown in Fig. 1. The C—N bond lengths within the imidazole ring are 1.373 (3) Å (C10—N2), 1.372 (3) Å (C8—N2), 1.349 (3) Å (C9—N1) and 1.329 (3) Å (C10—N1). These bond distances are shorter than the single-bond length (1.443 Å) and longer than the accepted double-bond length (1.269 Å) due to electron delocalization in the central imidazole ring. The phenyl rings and the plane of the imidazole ring are inclined at angles of 45.4 (1)° (with the C12/C17 ring) and 52.5 (1)° (with the C2/C7 ring). The phenyl rings are oriented to each other with a dihedral angle of 88.1 (1)°. Further, the imidazole ring is inclined at an angle of 85.2 (2)° to the best-fit plane through atoms C19, C20, O3, C21 and C22 of the ethyl acetate substituent. The molecular structure is also influenced by the formation of an intramolecular C6—H6···O2 hydrogen bond, which generates an S(8) ring motif (Bernstein et al., 1995).
The N-bound methylene group of the side chain is connected with the carbonyl oxygen of an adjacent molecule through a C19—H19A···O2 hydrogen bond, forming a linear C(5) chain motif along the a axis, Fig. 2. The phenyl and imidazole rings are linked through inversion-dimer formation involving C4—H4···N1 hydrogen bonds that generate R22(12) ring motifs. A second inversion dimer to an adjacent molecule results from C1—H1···O2 contacts, forming ring R22(22) rings, Fig. 3.
The Cambridge Structural Database (Groom & Allen, 2014) reveals only five structures of imidazole derivatives with a CH2COOCh2CH3 substituent on nitrogen (Cai et al., 2014; Bahnous et al., 2013; Zaprutko et al., 2012). Imidazoles with benzoyl substituents are slightly more common with eight occurrences (Xue et al., 2014; Nagaraj et al., 2012; Samanta et al., 2013), while the structures of only six p-tolyl-substituted imidazoles are found (Bu et al., 1996; Fridman et al., 2006, 2009). These searches also reveal the unique nature of the molecule reported here.
The title compound was synthesized from a mixture of 2-(4-methoxyphenyl)-2-oxoacetaldehyde (1 mmol), glycine methyl ester hydrochloride (1 mmol) and selenium dioxide (1 mmol) in a basic environment in acetonitrile at 373 K. Crystals suitable for X-ray investigation were obtained from the resulting solution in 33% yield.
detailsCrystal data, data collection and structure
details are summarized in Table 2. A l l H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 − 0.97 Å and Uiso(H) = 1.2–1.5Ueq(parent C atom). The methyl group C22 of the side chain is disordered over two positions, each with a site-occupancy factor of 0.5. The atomic displacement parameters of these two C atoms are restrained to be equivalent and the C21—C22 and C21—C22' bond distances were restrained during the using DFIX commands.Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008); program(s) used to refine structure: SHELXTL/PC (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and 50% probability displacement ellipsoids. The methyl group (C22) of the side chain is disordered over two positions each with 0.5 occupancy. | |
Fig. 2. Linear C(5) chains formed by a C—H···O intermolecular interaction extending along the a axis of the unit cell | |
Fig. 3. Inversion dimers with R22(12) and R22(22) ring motifs resulting from C—H···N and C—H···O hydrogen bonds. |
C22H22N2O3 | Z = 2 |
Mr = 362.41 | F(000) = 384 |
Triclinic, P1 | Dx = 1.239 Mg m−3 |
a = 5.0968 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.8189 (15) Å | Cell parameters from 2986 reflections |
c = 14.6993 (17) Å | θ = 2.1–24.4° |
α = 71.484 (5)° | µ = 0.08 mm−1 |
β = 84.018 (5)° | T = 293 K |
γ = 82.531 (5)° | Block, colourless |
V = 971.20 (18) Å3 | 0.21 × 0.19 × 0.16 mm |
Bruker SMART APEX CCD area-detector diffractometer | Rint = 0.055 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.5° |
ω scans | h = −6→6 |
18453 measured reflections | k = −16→16 |
3405 independent reflections | l = −17→17 |
2354 reflections with I > 2σ(I) |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.168 | w = 1/[σ2(Fo2) + (0.0636P)2 + 0.5608P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.002 |
3405 reflections | Δρmax = 0.52 e Å−3 |
251 parameters | Δρmin = −0.30 e Å−3 |
C22H22N2O3 | γ = 82.531 (5)° |
Mr = 362.41 | V = 971.20 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.0968 (5) Å | Mo Kα radiation |
b = 13.8189 (15) Å | µ = 0.08 mm−1 |
c = 14.6993 (17) Å | T = 293 K |
α = 71.484 (5)° | 0.21 × 0.19 × 0.16 mm |
β = 84.018 (5)° |
Bruker SMART APEX CCD area-detector diffractometer | 2354 reflections with I > 2σ(I) |
18453 measured reflections | Rint = 0.055 |
3405 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | 2 restraints |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.52 e Å−3 |
3405 reflections | Δρmin = −0.30 e Å−3 |
251 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | −0.6633 (7) | 0.3819 (3) | 0.6826 (2) | 0.0754 (9) | |
H1A | −0.6105 | 0.4476 | 0.6779 | 0.113* | |
H1B | −0.6498 | 0.3372 | 0.7474 | 0.113* | |
H1C | −0.8433 | 0.3901 | 0.6655 | 0.113* | |
C2 | −0.4852 (5) | 0.3362 (2) | 0.61545 (19) | 0.0530 (7) | |
C3 | −0.5093 (5) | 0.2386 (2) | 0.6123 (2) | 0.0568 (7) | |
H3 | −0.6403 | 0.2015 | 0.6517 | 0.068* | |
C4 | −0.3441 (5) | 0.19537 (19) | 0.55220 (19) | 0.0501 (6) | |
H4 | −0.3636 | 0.1293 | 0.5524 | 0.060* | |
C5 | −0.1486 (5) | 0.24912 (17) | 0.49132 (17) | 0.0426 (6) | |
C6 | −0.1244 (5) | 0.34725 (19) | 0.4938 (2) | 0.0536 (7) | |
H6 | 0.0048 | 0.3851 | 0.4539 | 0.064* | |
C7 | −0.2906 (5) | 0.3891 (2) | 0.5551 (2) | 0.0573 (7) | |
H7 | −0.2705 | 0.4548 | 0.5557 | 0.069* | |
C8 | 0.0360 (5) | 0.19884 (17) | 0.43313 (17) | 0.0419 (6) | |
C9 | 0.1875 (5) | 0.10614 (18) | 0.46091 (18) | 0.0466 (6) | |
H9 | 0.1835 | 0.0613 | 0.5233 | 0.056* | |
C10 | 0.2885 (5) | 0.16918 (17) | 0.31157 (17) | 0.0428 (6) | |
C11 | 0.4033 (5) | 0.1806 (2) | 0.21394 (19) | 0.0539 (7) | |
C12 | 0.6016 (5) | 0.0980 (2) | 0.19780 (17) | 0.0480 (6) | |
C17 | 0.8022 (5) | 0.0507 (2) | 0.25858 (19) | 0.0514 (7) | |
H17 | 0.8186 | 0.0717 | 0.3117 | 0.062* | |
C16 | 0.9772 (6) | −0.0268 (2) | 0.2414 (2) | 0.0614 (8) | |
H16 | 1.1136 | −0.0560 | 0.2821 | 0.074* | |
C15 | 0.9556 (6) | −0.0622 (2) | 0.1653 (2) | 0.0629 (8) | |
C14 | 0.7592 (7) | −0.0130 (3) | 0.1034 (2) | 0.0777 (10) | |
H14 | 0.7426 | −0.0345 | 0.0505 | 0.093* | |
C13 | 0.5874 (6) | 0.0671 (3) | 0.1182 (2) | 0.0709 (9) | |
H13 | 0.4612 | 0.1004 | 0.0742 | 0.085* | |
C18 | 1.1384 (8) | −0.1519 (3) | 0.1513 (3) | 0.0990 (13) | |
H18A | 1.0844 | −0.1703 | 0.0988 | 0.149* | |
H18B | 1.1306 | −0.2092 | 0.2089 | 0.149* | |
H18C | 1.3167 | −0.1334 | 0.1372 | 0.149* | |
C19 | −0.0310 (5) | 0.33098 (18) | 0.27136 (18) | 0.0488 (6) | |
H19A | −0.1902 | 0.3538 | 0.3044 | 0.059* | |
H19B | −0.0836 | 0.3150 | 0.2167 | 0.059* | |
C20 | 0.1464 (5) | 0.41606 (19) | 0.23635 (19) | 0.0510 (7) | |
C21 | 0.2175 (8) | 0.5710 (2) | 0.1156 (2) | 0.0923 (12) | |
H21A | 0.4038 | 0.5456 | 0.1198 | 0.111* | |
H21B | 0.1794 | 0.6196 | 0.1517 | 0.111* | |
C22 | 0.161 (3) | 0.6255 (15) | 0.0101 (4) | 0.119 (4) | 0.5 |
H22A | 0.2473 | 0.5850 | −0.0289 | 0.179* | 0.5 |
H22B | 0.2273 | 0.6915 | −0.0105 | 0.179* | 0.5 |
H22C | −0.0267 | 0.6340 | 0.0036 | 0.179* | 0.5 |
C22' | 0.047 (3) | 0.6433 (15) | 0.0364 (5) | 0.119 (4) | 0.5 |
H22D | 0.0075 | 0.6068 | −0.0055 | 0.179* | 0.5 |
H22E | 0.1418 | 0.7005 | 0.0001 | 0.179* | 0.5 |
H22F | −0.1156 | 0.6677 | 0.0651 | 0.179* | 0.5 |
N1 | 0.3431 (4) | 0.08765 (14) | 0.38698 (14) | 0.0464 (5) | |
N2 | 0.1006 (4) | 0.23871 (14) | 0.33651 (14) | 0.0434 (5) | |
O1 | 0.3314 (5) | 0.25504 (18) | 0.14648 (15) | 0.0913 (8) | |
O2 | 0.3358 (4) | 0.42182 (16) | 0.27496 (17) | 0.0774 (7) | |
O3 | 0.0563 (4) | 0.48554 (13) | 0.15783 (13) | 0.0663 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.077 (2) | 0.081 (2) | 0.077 (2) | 0.0039 (17) | −0.0022 (17) | −0.0423 (18) |
C2 | 0.0517 (15) | 0.0546 (16) | 0.0558 (16) | 0.0006 (13) | −0.0118 (13) | −0.0211 (13) |
C3 | 0.0558 (16) | 0.0555 (17) | 0.0601 (17) | −0.0134 (13) | 0.0026 (13) | −0.0185 (14) |
C4 | 0.0553 (15) | 0.0386 (13) | 0.0585 (16) | −0.0095 (12) | −0.0050 (13) | −0.0155 (12) |
C5 | 0.0453 (13) | 0.0361 (12) | 0.0458 (14) | −0.0031 (10) | −0.0120 (11) | −0.0094 (11) |
C6 | 0.0531 (15) | 0.0392 (14) | 0.0681 (18) | −0.0111 (12) | −0.0003 (13) | −0.0149 (13) |
C7 | 0.0617 (17) | 0.0408 (14) | 0.0759 (19) | −0.0036 (13) | −0.0105 (15) | −0.0259 (14) |
C8 | 0.0475 (14) | 0.0331 (12) | 0.0450 (14) | −0.0075 (10) | −0.0073 (11) | −0.0092 (11) |
C9 | 0.0595 (16) | 0.0362 (13) | 0.0405 (14) | −0.0052 (11) | −0.0059 (12) | −0.0060 (11) |
C10 | 0.0459 (14) | 0.0346 (12) | 0.0447 (14) | −0.0027 (10) | −0.0072 (11) | −0.0071 (11) |
C11 | 0.0557 (16) | 0.0496 (15) | 0.0467 (15) | −0.0009 (12) | −0.0049 (12) | −0.0025 (12) |
C12 | 0.0499 (15) | 0.0515 (15) | 0.0401 (14) | −0.0078 (12) | −0.0016 (11) | −0.0099 (11) |
C17 | 0.0535 (15) | 0.0524 (15) | 0.0478 (15) | −0.0058 (13) | −0.0060 (12) | −0.0136 (12) |
C16 | 0.0600 (17) | 0.0582 (17) | 0.0561 (17) | 0.0031 (14) | −0.0026 (13) | −0.0077 (14) |
C15 | 0.0662 (19) | 0.0526 (17) | 0.0669 (19) | −0.0124 (14) | 0.0146 (15) | −0.0175 (15) |
C14 | 0.074 (2) | 0.109 (3) | 0.070 (2) | −0.016 (2) | 0.0051 (17) | −0.055 (2) |
C13 | 0.0578 (18) | 0.106 (3) | 0.0529 (17) | 0.0029 (17) | −0.0105 (14) | −0.0325 (17) |
C18 | 0.116 (3) | 0.063 (2) | 0.112 (3) | −0.003 (2) | 0.032 (2) | −0.032 (2) |
C19 | 0.0471 (14) | 0.0397 (13) | 0.0500 (15) | 0.0019 (11) | −0.0091 (11) | −0.0010 (11) |
C20 | 0.0540 (16) | 0.0381 (14) | 0.0522 (15) | 0.0030 (12) | −0.0057 (13) | −0.0041 (12) |
C21 | 0.133 (3) | 0.0462 (18) | 0.085 (2) | −0.0256 (19) | −0.012 (2) | 0.0059 (17) |
C22 | 0.199 (13) | 0.099 (7) | 0.050 (4) | −0.063 (7) | 0.004 (6) | 0.004 (6) |
C22' | 0.199 (13) | 0.099 (7) | 0.050 (4) | −0.063 (7) | 0.004 (6) | 0.004 (6) |
N1 | 0.0566 (13) | 0.0345 (11) | 0.0443 (12) | −0.0018 (9) | −0.0086 (10) | −0.0061 (9) |
N2 | 0.0462 (11) | 0.0331 (10) | 0.0448 (12) | −0.0018 (9) | −0.0081 (9) | −0.0029 (9) |
O1 | 0.1031 (18) | 0.0828 (16) | 0.0517 (12) | 0.0282 (14) | 0.0041 (12) | 0.0128 (11) |
O2 | 0.0675 (13) | 0.0612 (13) | 0.0934 (16) | −0.0175 (11) | −0.0261 (12) | 0.0010 (11) |
O3 | 0.0886 (14) | 0.0412 (10) | 0.0577 (12) | −0.0074 (10) | −0.0135 (10) | 0.0037 (9) |
C1—C2 | 1.503 (4) | C16—C15 | 1.375 (4) |
C1—H1A | 0.9600 | C16—H16 | 0.9300 |
C1—H1B | 0.9600 | C15—C14 | 1.383 (4) |
C1—H1C | 0.9600 | C15—C18 | 1.506 (4) |
C2—C7 | 1.377 (4) | C14—C13 | 1.379 (4) |
C2—C3 | 1.386 (4) | C14—H14 | 0.9300 |
C3—C4 | 1.377 (4) | C13—H13 | 0.9300 |
C3—H3 | 0.9300 | C18—H18A | 0.9600 |
C4—C5 | 1.389 (3) | C18—H18B | 0.9600 |
C4—H4 | 0.9300 | C18—H18C | 0.9600 |
C5—C6 | 1.390 (3) | C19—N2 | 1.459 (3) |
C5—C8 | 1.463 (3) | C19—C20 | 1.503 (4) |
C6—C7 | 1.381 (4) | C19—H19A | 0.9700 |
C6—H6 | 0.9300 | C19—H19B | 0.9700 |
C7—H7 | 0.9300 | C20—O2 | 1.193 (3) |
C8—C9 | 1.371 (3) | C20—O3 | 1.325 (3) |
C8—N2 | 1.372 (3) | C21—O3 | 1.462 (4) |
C9—N1 | 1.349 (3) | C21—C22 | 1.534 (2) |
C9—H9 | 0.9300 | C21—C22' | 1.535 (2) |
C10—N1 | 1.329 (3) | C21—H21A | 0.9700 |
C10—N2 | 1.373 (3) | C21—H21B | 0.9700 |
C10—C11 | 1.460 (4) | C22—H22A | 0.9600 |
C11—O1 | 1.227 (3) | C22—H22B | 0.9600 |
C11—C12 | 1.484 (4) | C22—H22C | 0.9600 |
C12—C13 | 1.379 (4) | C22'—H22D | 0.9600 |
C12—C17 | 1.384 (3) | C22'—H22E | 0.9600 |
C17—C16 | 1.373 (4) | C22'—H22F | 0.9600 |
C17—H17 | 0.9300 | ||
C2—C1—H1A | 109.5 | C14—C15—C18 | 121.8 (3) |
C2—C1—H1B | 109.5 | C13—C14—C15 | 121.5 (3) |
H1A—C1—H1B | 109.5 | C13—C14—H14 | 119.2 |
C2—C1—H1C | 109.5 | C15—C14—H14 | 119.2 |
H1A—C1—H1C | 109.5 | C12—C13—C14 | 120.4 (3) |
H1B—C1—H1C | 109.5 | C12—C13—H13 | 119.8 |
C7—C2—C3 | 117.3 (3) | C14—C13—H13 | 119.8 |
C7—C2—C1 | 121.5 (3) | C15—C18—H18A | 109.5 |
C3—C2—C1 | 121.2 (3) | C15—C18—H18B | 109.5 |
C4—C3—C2 | 121.6 (3) | H18A—C18—H18B | 109.5 |
C4—C3—H3 | 119.2 | C15—C18—H18C | 109.5 |
C2—C3—H3 | 119.2 | H18A—C18—H18C | 109.5 |
C3—C4—C5 | 120.8 (2) | H18B—C18—H18C | 109.5 |
C3—C4—H4 | 119.6 | N2—C19—C20 | 111.7 (2) |
C5—C4—H4 | 119.6 | N2—C19—H19A | 109.3 |
C4—C5—C6 | 117.8 (2) | C20—C19—H19A | 109.3 |
C4—C5—C8 | 119.7 (2) | N2—C19—H19B | 109.3 |
C6—C5—C8 | 122.3 (2) | C20—C19—H19B | 109.3 |
C7—C6—C5 | 120.5 (2) | H19A—C19—H19B | 107.9 |
C7—C6—H6 | 119.7 | O2—C20—O3 | 124.9 (2) |
C5—C6—H6 | 119.7 | O2—C20—C19 | 125.1 (2) |
C2—C7—C6 | 121.9 (2) | O3—C20—C19 | 109.9 (2) |
C2—C7—H7 | 119.1 | O3—C21—C22 | 111.1 (9) |
C6—C7—H7 | 119.1 | O3—C21—C22' | 102.4 (9) |
C9—C8—N2 | 104.8 (2) | O3—C21—H21A | 109.4 |
C9—C8—C5 | 129.3 (2) | C22—C21—H21A | 109.4 |
N2—C8—C5 | 125.8 (2) | O3—C21—H21B | 109.4 |
N1—C9—C8 | 112.0 (2) | C22—C21—H21B | 109.4 |
N1—C9—H9 | 124.0 | H21A—C21—H21B | 108.0 |
C8—C9—H9 | 124.0 | C21—C22—H22A | 109.5 |
N1—C10—N2 | 111.2 (2) | C21—C22—H22B | 109.5 |
N1—C10—C11 | 124.2 (2) | H22A—C22—H22B | 109.5 |
N2—C10—C11 | 124.5 (2) | C21—C22—H22C | 109.5 |
O1—C11—C10 | 120.8 (2) | H22A—C22—H22C | 109.5 |
O1—C11—C12 | 120.8 (2) | H22B—C22—H22C | 109.5 |
C10—C11—C12 | 118.3 (2) | C21—C22'—H22D | 109.5 |
C13—C12—C17 | 118.2 (3) | C21—C22'—H22E | 109.5 |
C13—C12—C11 | 118.7 (2) | H22D—C22'—H22E | 109.5 |
C17—C12—C11 | 123.2 (2) | C21—C22'—H22F | 109.5 |
C16—C17—C12 | 120.8 (3) | H22D—C22'—H22F | 109.5 |
C16—C17—H17 | 119.6 | H22E—C22'—H22F | 109.5 |
C12—C17—H17 | 119.6 | C10—N1—C9 | 105.0 (2) |
C17—C16—C15 | 121.5 (3) | C8—N2—C10 | 106.94 (18) |
C17—C16—H16 | 119.2 | C8—N2—C19 | 125.8 (2) |
C15—C16—H16 | 119.2 | C10—N2—C19 | 126.8 (2) |
C16—C15—C14 | 117.4 (3) | C20—O3—C21 | 114.8 (2) |
C16—C15—C18 | 120.8 (3) | ||
C7—C2—C3—C4 | 0.7 (4) | C17—C16—C15—C14 | 3.4 (4) |
C1—C2—C3—C4 | −178.8 (3) | C17—C16—C15—C18 | −176.0 (3) |
C2—C3—C4—C5 | −0.9 (4) | C16—C15—C14—C13 | −1.4 (5) |
C3—C4—C5—C6 | 0.6 (4) | C18—C15—C14—C13 | 178.0 (3) |
C3—C4—C5—C8 | 175.8 (2) | C17—C12—C13—C14 | 3.8 (4) |
C4—C5—C6—C7 | 0.0 (4) | C11—C12—C13—C14 | −176.6 (3) |
C8—C5—C6—C7 | −175.1 (2) | C15—C14—C13—C12 | −2.3 (5) |
C3—C2—C7—C6 | −0.2 (4) | N2—C19—C20—O2 | −20.6 (4) |
C1—C2—C7—C6 | 179.4 (3) | N2—C19—C20—O3 | 161.4 (2) |
C5—C6—C7—C2 | −0.2 (4) | N2—C10—N1—C9 | −0.2 (3) |
C4—C5—C8—C9 | −51.0 (4) | C11—C10—N1—C9 | −177.1 (2) |
C6—C5—C8—C9 | 124.0 (3) | C8—C9—N1—C10 | −0.3 (3) |
C4—C5—C8—N2 | 131.5 (3) | C9—C8—N2—C10 | −0.7 (3) |
C6—C5—C8—N2 | −53.5 (4) | C5—C8—N2—C10 | 177.3 (2) |
N2—C8—C9—N1 | 0.7 (3) | C9—C8—N2—C19 | 172.2 (2) |
C5—C8—C9—N1 | −177.2 (2) | C5—C8—N2—C19 | −9.8 (4) |
N1—C10—C11—O1 | 175.3 (3) | N1—C10—N2—C8 | 0.6 (3) |
N2—C10—C11—O1 | −1.2 (4) | C11—C10—N2—C8 | 177.5 (2) |
N1—C10—C11—C12 | −2.5 (4) | N1—C10—N2—C19 | −172.3 (2) |
N2—C10—C11—C12 | −179.0 (2) | C11—C10—N2—C19 | 4.7 (4) |
O1—C11—C12—C13 | −39.9 (4) | C20—C19—N2—C8 | 111.7 (3) |
C10—C11—C12—C13 | 137.9 (3) | C20—C19—N2—C10 | −76.8 (3) |
O1—C11—C12—C17 | 139.7 (3) | O2—C20—O3—C21 | 3.5 (4) |
C10—C11—C12—C17 | −42.6 (4) | C19—C20—O3—C21 | −178.5 (2) |
C13—C12—C17—C16 | −1.8 (4) | C22—C21—O3—C20 | 160.0 (6) |
C11—C12—C17—C16 | 178.6 (2) | C22'—C21—O3—C20 | −172.9 (6) |
C12—C17—C16—C15 | −1.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O2 | 0.93 | 2.91 | 3.723 (4) | 147 |
C1—H1A···O2i | 0.96 | 2.71 | 3.605 (4) | 155 |
C4—H4···N1ii | 0.93 | 2.83 | 3.724 (3) | 161 |
C19—H19A···O2iii | 0.97 | 2.51 | 3.309 (3) | 140 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z+1; (iii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O2 | 0.93 | 2.91 | 3.723 (4) | 146.7 |
C1—H1A···O2i | 0.96 | 2.71 | 3.605 (4) | 155.3 |
C4—H4···N1ii | 0.93 | 2.83 | 3.724 (3) | 160.5 |
C19—H19A···O2iii | 0.97 | 2.51 | 3.309 (3) | 140.1 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z+1; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C22H22N2O3 |
Mr | 362.41 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 5.0968 (5), 13.8189 (15), 14.6993 (17) |
α, β, γ (°) | 71.484 (5), 84.018 (5), 82.531 (5) |
V (Å3) | 971.20 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.21 × 0.19 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18453, 3405, 2354 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.168, 1.07 |
No. of reflections | 3405 |
No. of parameters | 251 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.30 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL/PC (Sheldrick, 2008), PLATON (Spek, 2009).
Acknowledgements
SA and SSK thank the Department of Science and Technology, New Delhi, for financial support of this work through the Fasttrack Young Scientist scheme.
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