organic compounds
3′,6′-Bis(diethylamino)-2-(prop-2-ynyl)spiro[isoindoline-1,9′-xanthen]-3-one
aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and bDepartment of Organic Chemistry, University of Madras, Maraimalai Campus, Chennai 600 025, India
*Correspondence e-mail: aspandian59@gmail.com
In the title compound, C31H33N3O2, the spiropyrrolidine ring has a twisted conformation on the Cspiro—N bond, whereas the tetrahydropyran ring adopts a sofa confirmation. The spiro joined fragments are almost orthogonal, with a dihedral angle of 89.1 (2)° between the mean planes of the pyrrolidine and tetrahydropyran rings. In the diethylamine group, the ethanamine portion is disordered over the two positions, with a refined occupancy ratio of 0.73 (1):0.27 (1). In the crystal, molecules are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers with an R22(10) ring motif. The dimers are linked by further C—H⋯O hydrogen bonds, forming slabs parallel to (100).
Keywords: crystal structure; xanthen; spirolactam; rhodamine B; isoindoline; hydrogen bonding.
CCDC reference: 1478907
Structure description
Rhodamine-based dyes, known for their excellent spectroscopic properties having a large molar extinction coefficient and high fluorescence et al., 2007), have found applications in the study of complex biological systems and environmental analysis as molecular probes. Rhodamine B derivatives are known to have excellent photophysical properties, such as long absorption and emission wavelengths elongated to the visible region. They have therefore been extensively used as fluorescent chemosensors for heavy and transition metal ions, such as copper(II) (Zhang et al., 2007) and mercury(II) (Soh et al., 2007) chemical sensors.
(WuThe main skeleton of the title compound is formed by a xanthene ring and a spirolactam ring, as illustrated in Fig. 1. The spiro pyrrolidine ring (C13/C14/C19/C20/N1) adopts a twisted confirmation on the C13—N1 bond [puckering parameters: q2 = 0.068 (3) Å and φ2 = 198 (2)°]. The six-membered tetrahydropyran ring (C1/C6/O1/C7/C12/C13) of the xanthene ring system adopts a sofa confirmation [puckering parameters: Q = 0.261 (2) Å, Θ = 80.3 (7)° and φ = 184.5 (6)°]. The pyrrolidine ring mean plane is orthogonal to the mean plane of the tetrahydropyran ring with a dihedral angle of 89.1 (2)°. The dihedral angle between the benzene rings in the xanthene fragment is 17.3 (1)°.
In the crystal, molecules are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers with an R22(10) ring motif (Table 1 and Fig. 2). The dimers are linked by further C—H⋯O hydrogen bonds, forming slabs parallel to the bc plane (Table 1 and Fig. 3).
Synthesis and crystallization
To a solution of rhodamine B (5.76 g, 12 mmol) in anhydrous dichloromethane (20 ml) was added sequentially 2-(1H-benzotriazol-1-yl-1,1,3,3-tetramethyluronium hexafluorophosphate (5.45 g, 14.4 mmol), propargylamine (0.925 ml, 14.4 mmol) and triethylamine (2.5 ml, 14.4 mmol). The reaction mixture was stirred at room temperature overnight until TLC indicated the disappearance of the starting products. The reaction mixture was diluted with dichloromethane (200 ml) and then washed with brine. The organic layer was dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The crude residue was purified by flash on silica gel (hexane:EtOAc, 4:1) to yield the title compound as a pale-pink solid. Pink block-like crystals were obtained by slow evaporation of a solution in chloroform/ethanol/acetonitrile in a (2:1:1) ratio.
Refinement
Crystal data, data collection and structure . In the diethylamine group, one of the NCH2CH3 group of atoms is disordered over the two positions (N2/N2′, C30/C30′ and C31/C31′), with a refined occupancy ratio of 0.73 (1):0.27 (1).
details are summarized in Table 2Structural data
CCDC reference: 1478907
10.1107/S2414314616007720/su4041sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616007720/su4041Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616007720/su4041Isup3.cml
To a solution of rhodamine B (5.76 g, 12 mmol) in anhydrous dichloromethane (20 ml) was added sequentially 2-(1H-benzotriazol-1-yl-1,1,3,3-tetramethyluronium hexafluorophosphate (5.45 g, 14.4 mmol), propargylamine (0.925 ml, 14.4 mmol) and triethylamine (2.5 ml, 14.4 mmol). The reaction mixture was stirred at room temperature overnight until TLC indicated the disappearance of the starting products. The reaction mixture was diluted with dichloromethane (200 ml) and then washed with brine. The organic layer was dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The crude residue was purified by flash
on silica gel (hexane:EtOAc, 4:1) to yield the title compound as a pale-pink solid. Pink block-like crystals were obtained by slow evaporation of a solution in chloroform/ethanol/acetonitrile in a (2:1:1) ratio.Crystal data, data collection and structure
details are summarized in Table 2. In the diethylamine group, one of the NCH2CH3 group of atoms is disordered over the two positions (N2/N2', C30/C30' and C31/C31'), with a refined occupancy ratio of 0.73 (1):0.27 (1).Rhodamine-based dyes, known for their excellent spectroscopic properties having a large molar extinction coefficient and high fluorescence
(Wu et al., 2007), have found applications in the study of complex biological systems and environmental analysis as molecular probes. Rhodamine B derivatives are known to have excellent photophysical properties, such as long absorption and emission wavelengths elongated to the visible region. They have therefore been extensively used as fluorescent chemosensors for heavy and transition metal ions, such as copper(II) (Zhang et al., 2007) and mercury(II) (Soh et al., 2007) chemical sensors.The main skeleton of the title compound is formed by a xanthene ring and a spirolactam ring, as illustrated in Fig. 1. The spiro pyrrolidine ring (C13/C14/C19/C20/N1) adopts a twisted confirmation on the C13—N1 bond [puckering parameters: q2 = 0.068 (3) Å and φ2 = 198 (2)°]. The six-membered tetrahydropyran ring (C1/C6/O1/C7/C12/C13) of the xanthene ring system adopts a sofa confirmation [puckering parameters: Q = 0.261 (2) Å, Θ = 80.3 (7)° and φ = 184.5 (6)°]. The pyrrolidine ring mean plane is orthogonal to the mean plane of the tetrahydropyran ring with a dihedral angle of 89.1 (2)°. The dihedral angle between the benzene rings in the xanthene fragment is 17.3 (1)°.
In the crystal, molecules are linked by pairs of C—H···O hydrogen bonds, forming inversion dimers with an R22(10) ring motif (Table 1 and Fig. 2). The dimers are linked by further C—H···O hydrogen bonds, forming slabs parallel to the bc plane (Table 1 and Fig. 3).
Data collection: APEX2 (Bruker, 2004); cell
APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. A partial view of the crystal packing of the title compound, showing the formation of hydrogen-bonded dimers (dashed lines; see Table 1). The minor components of the disordered atoms and H atoms not involved in hydrogen bonding have been omitted for clarity. | |
Fig. 3. A view along the c axis of the crystal packing of the title compound. The hydrogen bonds (see Table 1) are shown as dashed lines. The minor components of the disordered atoms and H atoms not involved in hydrogen bonding have been omitted for clarity. |
C31H33N3O2 | F(000) = 1024 |
Mr = 479.60 | Dx = 1.205 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.0701 (8) Å | Cell parameters from 3350 reflections |
b = 16.2611 (7) Å | θ = 2.3–25.0° |
c = 9.0801 (4) Å | µ = 0.08 mm−1 |
β = 97.645 (2)° | T = 293 K |
V = 2644.4 (2) Å3 | Block, pink |
Z = 4 | 0.35 × 0.25 × 0.20 mm |
Bruker Kappa APEXII CCD diffractometer | 3350 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
ω and φ scan | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −21→21 |
Tmin = 0.977, Tmax = 0.985 | k = −19→19 |
40635 measured reflections | l = −10→10 |
4654 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.0474P)2 + 2.114P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
4654 reflections | Δρmax = 0.38 e Å−3 |
354 parameters | Δρmin = −0.18 e Å−3 |
72 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0061 (8) |
C31H33N3O2 | V = 2644.4 (2) Å3 |
Mr = 479.60 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.0701 (8) Å | µ = 0.08 mm−1 |
b = 16.2611 (7) Å | T = 293 K |
c = 9.0801 (4) Å | 0.35 × 0.25 × 0.20 mm |
β = 97.645 (2)° |
Bruker Kappa APEXII CCD diffractometer | 4654 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 3350 reflections with I > 2σ(I) |
Tmin = 0.977, Tmax = 0.985 | Rint = 0.037 |
40635 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 72 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.38 e Å−3 |
4654 reflections | Δρmin = −0.18 e Å−3 |
354 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 | Occ. (<1) | |
C1 | 0.29699 (12) | 0.55506 (14) | 0.4059 (3) | 0.0400 (5) | |
C2 | 0.35508 (15) | 0.60419 (16) | 0.3708 (3) | 0.0540 (7) | |
H2 | 0.3987 | 0.5790 | 0.3497 | 0.065* | |
C3 | 0.35069 (15) | 0.68822 (16) | 0.3658 (4) | 0.0601 (8) | |
H3 | 0.3911 | 0.7185 | 0.3417 | 0.072* | |
C4 | 0.28656 (15) | 0.72918 (16) | 0.3964 (3) | 0.0566 (7) | |
C5 | 0.22779 (15) | 0.68068 (16) | 0.4334 (3) | 0.0555 (7) | |
H5 | 0.1844 | 0.7056 | 0.4561 | 0.067* | |
C6 | 0.23396 (13) | 0.59608 (15) | 0.4363 (3) | 0.0436 (6) | |
C7 | 0.17976 (13) | 0.47332 (14) | 0.5134 (3) | 0.0412 (6) | |
C8 | 0.12177 (13) | 0.44161 (15) | 0.5811 (3) | 0.0447 (6) | |
H8 | 0.0807 | 0.4744 | 0.5917 | 0.054* | |
C9 | 0.12425 (13) | 0.36132 (14) | 0.6335 (3) | 0.0410 (6) | |
C10 | 0.18786 (13) | 0.31512 (15) | 0.6149 (3) | 0.0442 (6) | |
H10 | 0.1923 | 0.2616 | 0.6513 | 0.053* | |
C11 | 0.24385 (13) | 0.34752 (14) | 0.5440 (3) | 0.0426 (6) | |
H11 | 0.2847 | 0.3147 | 0.5314 | 0.051* | |
C12 | 0.24146 (12) | 0.42754 (14) | 0.4904 (3) | 0.0373 (5) | |
C13 | 0.29979 (12) | 0.46205 (14) | 0.4032 (3) | 0.0391 (5) | |
C14 | 0.29140 (13) | 0.43066 (14) | 0.2440 (3) | 0.0401 (5) | |
C15 | 0.23015 (15) | 0.43577 (16) | 0.1353 (3) | 0.0492 (6) | |
H15 | 0.1854 | 0.4588 | 0.1553 | 0.059* | |
C16 | 0.23772 (17) | 0.40540 (17) | −0.0046 (3) | 0.0585 (7) | |
H16 | 0.1972 | 0.4077 | −0.0793 | 0.070* | |
C17 | 0.30422 (17) | 0.37172 (18) | −0.0353 (3) | 0.0604 (8) | |
H17 | 0.3079 | 0.3523 | −0.1304 | 0.072* | |
C18 | 0.36521 (16) | 0.36645 (17) | 0.0729 (3) | 0.0553 (7) | |
H18 | 0.4100 | 0.3439 | 0.0526 | 0.066* | |
C19 | 0.35730 (14) | 0.39608 (15) | 0.2131 (3) | 0.0436 (6) | |
C20 | 0.41227 (14) | 0.39862 (14) | 0.3487 (3) | 0.0431 (6) | |
C21 | 0.41217 (14) | 0.44670 (16) | 0.6068 (3) | 0.0476 (6) | |
H21A | 0.4547 | 0.4827 | 0.6024 | 0.057* | |
H21B | 0.3776 | 0.4748 | 0.6626 | 0.057* | |
C22 | 0.43761 (14) | 0.37143 (17) | 0.6847 (3) | 0.0484 (6) | |
C23 | 0.45786 (16) | 0.3112 (2) | 0.7474 (3) | 0.0624 (8) | |
H23 | 0.4740 | 0.2632 | 0.7974 | 0.075* | |
N1 | 0.37558 (10) | 0.43172 (12) | 0.4563 (2) | 0.0412 (5) | |
N3 | 0.06666 (12) | 0.32915 (14) | 0.7002 (3) | 0.0552 (6) | |
O1 | 0.17142 (9) | 0.55466 (10) | 0.4709 (2) | 0.0564 (5) | |
O2 | 0.47756 (10) | 0.37691 (12) | 0.3659 (2) | 0.0570 (5) | |
C25 | 0.07600 (17) | 0.25489 (18) | 0.7890 (3) | 0.0618 (8) | |
H25A | 0.0476 | 0.2605 | 0.8719 | 0.074* | |
H25B | 0.1282 | 0.2497 | 0.8296 | 0.074* | |
C26 | −0.00442 (16) | 0.3710 (2) | 0.6930 (4) | 0.0693 (9) | |
H26A | −0.0432 | 0.3302 | 0.6979 | 0.083* | |
H26B | −0.0147 | 0.3985 | 0.5977 | 0.083* | |
C24 | 0.0522 (2) | 0.1779 (2) | 0.7072 (5) | 0.0911 (11) | |
H24A | 0.0601 | 0.1319 | 0.7735 | 0.137* | |
H24B | 0.0001 | 0.1816 | 0.6689 | 0.137* | |
H24C | 0.0809 | 0.1708 | 0.6264 | 0.137* | |
C27 | −0.0086 (2) | 0.4336 (3) | 0.8147 (5) | 0.1045 (14) | |
H27A | −0.0571 | 0.4585 | 0.8025 | 0.157* | |
H27B | 0.0001 | 0.4068 | 0.9097 | 0.157* | |
H27C | 0.0287 | 0.4751 | 0.8094 | 0.157* | |
C28 | 0.3992 (3) | 0.8913 (3) | 0.4442 (5) | 0.1125 (14) | |
H28A | 0.4341 | 0.9241 | 0.3987 | 0.169* | |
H28C | 0.3791 | 0.9233 | 0.5185 | 0.169* | |
H28B | 0.4243 | 0.8439 | 0.4898 | 0.169* | |
C29 | 0.33793 (18) | 0.86470 (19) | 0.3299 (4) | 0.0703 (9) | |
H29A | 0.3124 | 0.9123 | 0.2829 | 0.084* | |
H29B | 0.3577 | 0.8326 | 0.2541 | 0.084* | |
N2 | 0.2856 (5) | 0.8146 (6) | 0.4037 (10) | 0.073 (2) | 0.730 (10) |
C30 | 0.2286 (3) | 0.8579 (3) | 0.4703 (8) | 0.0714 (17) | 0.730 (10) |
H30A | 0.2492 | 0.9091 | 0.5123 | 0.086* | 0.730 (10) |
H30B | 0.2143 | 0.8249 | 0.5510 | 0.086* | 0.730 (10) |
C31 | 0.1602 (4) | 0.8765 (4) | 0.3633 (8) | 0.106 (2) | 0.730 (10) |
H31A | 0.1246 | 0.9051 | 0.4141 | 0.159* | 0.730 (10) |
H31B | 0.1736 | 0.9102 | 0.2842 | 0.159* | 0.730 (10) |
H31C | 0.1386 | 0.8260 | 0.3229 | 0.159* | 0.730 (10) |
N2' | 0.2711 (11) | 0.8100 (15) | 0.358 (3) | 0.060 (4) | 0.270 (10) |
C30' | 0.1995 (10) | 0.8497 (8) | 0.3683 (19) | 0.075 (4) | 0.270 (10) |
H30C | 0.1595 | 0.8178 | 0.3140 | 0.090* | 0.270 (10) |
H30D | 0.1990 | 0.9042 | 0.3247 | 0.090* | 0.270 (10) |
C31' | 0.1881 (12) | 0.8558 (10) | 0.5277 (18) | 0.103 (6) | 0.270 (10) |
H31D | 0.1411 | 0.8819 | 0.5349 | 0.155* | 0.270 (10) |
H31E | 0.1883 | 0.8017 | 0.5700 | 0.155* | 0.270 (10) |
H31F | 0.2277 | 0.8878 | 0.5807 | 0.155* | 0.270 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0367 (12) | 0.0351 (12) | 0.0485 (14) | 0.0002 (10) | 0.0066 (10) | −0.0021 (10) |
C2 | 0.0440 (14) | 0.0443 (15) | 0.0771 (19) | 0.0025 (12) | 0.0201 (13) | −0.0055 (13) |
C3 | 0.0462 (15) | 0.0426 (15) | 0.095 (2) | −0.0087 (12) | 0.0213 (15) | −0.0040 (15) |
C4 | 0.0509 (16) | 0.0399 (15) | 0.082 (2) | 0.0005 (12) | 0.0181 (14) | 0.0014 (13) |
C5 | 0.0472 (15) | 0.0407 (14) | 0.083 (2) | 0.0081 (12) | 0.0231 (14) | 0.0074 (13) |
C6 | 0.0385 (13) | 0.0383 (13) | 0.0549 (15) | 0.0005 (10) | 0.0099 (11) | 0.0055 (11) |
C7 | 0.0387 (13) | 0.0362 (13) | 0.0477 (14) | 0.0025 (10) | 0.0020 (11) | 0.0062 (10) |
C8 | 0.0381 (13) | 0.0429 (14) | 0.0531 (15) | 0.0056 (11) | 0.0060 (11) | 0.0072 (11) |
C9 | 0.0395 (13) | 0.0414 (13) | 0.0407 (13) | −0.0027 (10) | −0.0002 (10) | 0.0037 (10) |
C10 | 0.0488 (14) | 0.0335 (12) | 0.0478 (14) | −0.0011 (11) | −0.0027 (11) | 0.0041 (10) |
C11 | 0.0393 (13) | 0.0370 (13) | 0.0500 (14) | 0.0041 (10) | 0.0000 (11) | −0.0038 (11) |
C12 | 0.0359 (12) | 0.0340 (12) | 0.0413 (13) | 0.0011 (10) | 0.0028 (10) | −0.0009 (10) |
C13 | 0.0350 (12) | 0.0368 (12) | 0.0444 (13) | 0.0030 (10) | 0.0015 (10) | −0.0033 (10) |
C14 | 0.0455 (13) | 0.0321 (12) | 0.0421 (13) | −0.0043 (10) | 0.0037 (11) | −0.0002 (10) |
C15 | 0.0496 (15) | 0.0467 (15) | 0.0494 (15) | −0.0010 (12) | −0.0004 (12) | 0.0014 (12) |
C16 | 0.0691 (19) | 0.0565 (17) | 0.0453 (15) | −0.0097 (14) | −0.0091 (14) | 0.0007 (13) |
C17 | 0.074 (2) | 0.0657 (19) | 0.0413 (15) | −0.0093 (15) | 0.0080 (14) | −0.0076 (13) |
C18 | 0.0602 (17) | 0.0582 (17) | 0.0492 (15) | −0.0023 (13) | 0.0140 (13) | −0.0089 (13) |
C19 | 0.0466 (14) | 0.0420 (13) | 0.0423 (13) | −0.0018 (11) | 0.0060 (11) | −0.0044 (11) |
C20 | 0.0422 (14) | 0.0370 (13) | 0.0504 (15) | 0.0006 (11) | 0.0071 (11) | −0.0039 (11) |
C21 | 0.0460 (14) | 0.0484 (15) | 0.0467 (14) | −0.0021 (12) | −0.0004 (11) | −0.0091 (12) |
C22 | 0.0442 (14) | 0.0555 (17) | 0.0448 (14) | −0.0026 (12) | 0.0034 (11) | −0.0019 (13) |
C23 | 0.0612 (18) | 0.065 (2) | 0.0599 (18) | 0.0009 (15) | 0.0045 (14) | 0.0101 (15) |
N1 | 0.0384 (11) | 0.0424 (11) | 0.0419 (11) | 0.0032 (9) | 0.0020 (9) | −0.0066 (9) |
N3 | 0.0489 (13) | 0.0508 (13) | 0.0665 (15) | 0.0008 (10) | 0.0108 (11) | 0.0190 (11) |
O1 | 0.0408 (10) | 0.0399 (10) | 0.0914 (14) | 0.0083 (8) | 0.0200 (9) | 0.0207 (9) |
O2 | 0.0406 (10) | 0.0644 (12) | 0.0661 (12) | 0.0049 (9) | 0.0072 (9) | −0.0151 (10) |
C25 | 0.0676 (19) | 0.0595 (18) | 0.0589 (17) | −0.0004 (14) | 0.0114 (14) | 0.0160 (14) |
C26 | 0.0486 (16) | 0.071 (2) | 0.090 (2) | −0.0004 (14) | 0.0149 (16) | 0.0262 (18) |
C24 | 0.100 (3) | 0.061 (2) | 0.110 (3) | −0.0123 (19) | 0.003 (2) | 0.009 (2) |
C27 | 0.111 (3) | 0.096 (3) | 0.117 (3) | 0.032 (2) | 0.052 (3) | 0.021 (3) |
C28 | 0.122 (4) | 0.107 (3) | 0.105 (3) | −0.018 (3) | −0.001 (3) | −0.003 (3) |
C29 | 0.075 (2) | 0.0487 (17) | 0.088 (2) | −0.0019 (15) | 0.0143 (18) | 0.0119 (16) |
N2 | 0.067 (4) | 0.039 (2) | 0.116 (6) | 0.001 (3) | 0.026 (4) | −0.004 (3) |
C30 | 0.078 (4) | 0.043 (2) | 0.098 (4) | 0.001 (2) | 0.029 (3) | −0.003 (3) |
C31 | 0.071 (4) | 0.092 (4) | 0.156 (6) | 0.024 (3) | 0.019 (4) | 0.034 (4) |
N2' | 0.053 (7) | 0.034 (6) | 0.100 (10) | −0.004 (5) | 0.033 (7) | 0.021 (7) |
C30' | 0.072 (8) | 0.040 (6) | 0.112 (9) | −0.011 (6) | 0.011 (8) | 0.015 (7) |
C31' | 0.112 (12) | 0.074 (9) | 0.136 (13) | −0.003 (8) | 0.060 (11) | −0.016 (9) |
C1—C6 | 1.379 (3) | C21—N1 | 1.457 (3) |
C1—C2 | 1.390 (3) | C21—H21A | 0.9700 |
C1—C13 | 1.514 (3) | C21—H21B | 0.9700 |
C2—C3 | 1.369 (4) | C22—C23 | 1.167 (4) |
C2—H2 | 0.9300 | C23—H23 | 0.9300 |
C3—C4 | 1.396 (4) | N3—C26 | 1.447 (4) |
C3—H3 | 0.9300 | N3—C25 | 1.449 (3) |
C4—N2' | 1.38 (2) | C25—C24 | 1.489 (4) |
C4—N2 | 1.391 (10) | C25—H25A | 0.9700 |
C4—C5 | 1.399 (4) | C25—H25B | 0.9700 |
C5—C6 | 1.380 (3) | C26—C27 | 1.512 (5) |
C5—H5 | 0.9300 | C26—H26A | 0.9700 |
C6—O1 | 1.387 (3) | C26—H26B | 0.9700 |
C7—C12 | 1.379 (3) | C24—H24A | 0.9600 |
C7—O1 | 1.380 (3) | C24—H24B | 0.9600 |
C7—C8 | 1.383 (3) | C24—H24C | 0.9600 |
C8—C9 | 1.388 (3) | C27—H27A | 0.9600 |
C8—H8 | 0.9300 | C27—H27B | 0.9600 |
C9—N3 | 1.375 (3) | C27—H27C | 0.9600 |
C9—C10 | 1.402 (3) | C28—C29 | 1.478 (5) |
C10—C11 | 1.375 (3) | C28—H28A | 0.9600 |
C10—H10 | 0.9300 | C28—H28C | 0.9600 |
C11—C12 | 1.388 (3) | C28—H28B | 0.9600 |
C11—H11 | 0.9300 | C29—N2 | 1.474 (10) |
C12—C13 | 1.508 (3) | C29—N2' | 1.55 (2) |
C13—N1 | 1.475 (3) | C29—H29A | 0.9700 |
C13—C14 | 1.521 (3) | C29—H29B | 0.9700 |
C14—C19 | 1.379 (3) | N2—C30 | 1.446 (8) |
C14—C15 | 1.384 (3) | C30—C31 | 1.497 (8) |
C15—C16 | 1.386 (4) | C30—H30A | 0.9700 |
C15—H15 | 0.9300 | C30—H30B | 0.9700 |
C16—C17 | 1.382 (4) | C31—H31A | 0.9600 |
C16—H16 | 0.9300 | C31—H31B | 0.9600 |
C17—C18 | 1.378 (4) | C31—H31C | 0.9600 |
C17—H17 | 0.9300 | N2'—C30' | 1.459 (15) |
C18—C19 | 1.386 (3) | C30'—C31' | 1.492 (15) |
C18—H18 | 0.9300 | C30'—H30C | 0.9700 |
C19—C20 | 1.476 (3) | C30'—H30D | 0.9700 |
C20—O2 | 1.221 (3) | C31'—H31D | 0.9600 |
C20—N1 | 1.362 (3) | C31'—H31E | 0.9600 |
C21—C22 | 1.457 (4) | C31'—H31F | 0.9600 |
C6—C1—C2 | 115.9 (2) | C20—N1—C13 | 114.64 (19) |
C6—C1—C13 | 121.1 (2) | C21—N1—C13 | 122.43 (19) |
C2—C1—C13 | 122.9 (2) | C9—N3—C26 | 121.4 (2) |
C3—C2—C1 | 122.6 (2) | C9—N3—C25 | 121.5 (2) |
C3—C2—H2 | 118.7 | C26—N3—C25 | 117.0 (2) |
C1—C2—H2 | 118.7 | C7—O1—C6 | 117.82 (18) |
C2—C3—C4 | 121.0 (2) | N3—C25—C24 | 114.7 (3) |
C2—C3—H3 | 119.5 | N3—C25—H25A | 108.6 |
C4—C3—H3 | 119.5 | C24—C25—H25A | 108.6 |
N2'—C4—C3 | 123.4 (8) | N3—C25—H25B | 108.6 |
N2—C4—C3 | 120.1 (4) | C24—C25—H25B | 108.6 |
N2'—C4—C5 | 117.6 (8) | H25A—C25—H25B | 107.6 |
N2—C4—C5 | 122.5 (4) | N3—C26—C27 | 114.4 (3) |
C3—C4—C5 | 117.1 (2) | N3—C26—H26A | 108.7 |
C6—C5—C4 | 120.3 (2) | C27—C26—H26A | 108.7 |
C6—C5—H5 | 119.8 | N3—C26—H26B | 108.7 |
C4—C5—H5 | 119.8 | C27—C26—H26B | 108.7 |
C1—C6—C5 | 123.0 (2) | H26A—C26—H26B | 107.6 |
C1—C6—O1 | 122.0 (2) | C25—C24—H24A | 109.5 |
C5—C6—O1 | 115.0 (2) | C25—C24—H24B | 109.5 |
C12—C7—O1 | 122.3 (2) | H24A—C24—H24B | 109.5 |
C12—C7—C8 | 122.8 (2) | C25—C24—H24C | 109.5 |
O1—C7—C8 | 114.9 (2) | H24A—C24—H24C | 109.5 |
C7—C8—C9 | 120.7 (2) | H24B—C24—H24C | 109.5 |
C7—C8—H8 | 119.6 | C26—C27—H27A | 109.5 |
C9—C8—H8 | 119.6 | C26—C27—H27B | 109.5 |
N3—C9—C8 | 121.1 (2) | H27A—C27—H27B | 109.5 |
N3—C9—C10 | 122.0 (2) | C26—C27—H27C | 109.5 |
C8—C9—C10 | 116.9 (2) | H27A—C27—H27C | 109.5 |
C11—C10—C9 | 121.2 (2) | H27B—C27—H27C | 109.5 |
C11—C10—H10 | 119.4 | C29—C28—H28A | 109.5 |
C9—C10—H10 | 119.4 | C29—C28—H28C | 109.5 |
C10—C11—C12 | 122.2 (2) | H28A—C28—H28C | 109.5 |
C10—C11—H11 | 118.9 | C29—C28—H28B | 109.5 |
C12—C11—H11 | 118.9 | H28A—C28—H28B | 109.5 |
C7—C12—C11 | 116.2 (2) | H28C—C28—H28B | 109.5 |
C7—C12—C13 | 120.9 (2) | N2—C29—C28 | 108.0 (5) |
C11—C12—C13 | 122.8 (2) | C28—C29—N2' | 125.4 (10) |
N1—C13—C12 | 112.79 (19) | N2—C29—H29A | 110.1 |
N1—C13—C1 | 111.12 (18) | C28—C29—H29A | 110.1 |
C12—C13—C1 | 109.62 (19) | N2—C29—H29B | 110.1 |
N1—C13—C14 | 99.74 (18) | C28—C29—H29B | 110.1 |
C12—C13—C14 | 112.69 (19) | H29A—C29—H29B | 108.4 |
C1—C13—C14 | 110.59 (19) | C4—N2—C30 | 121.3 (7) |
C19—C14—C15 | 120.6 (2) | C4—N2—C29 | 121.2 (6) |
C19—C14—C13 | 110.5 (2) | C30—N2—C29 | 117.2 (7) |
C15—C14—C13 | 128.8 (2) | N2—C30—C31 | 113.6 (8) |
C14—C15—C16 | 117.7 (3) | N2—C30—H30A | 108.9 |
C14—C15—H15 | 121.1 | C31—C30—H30A | 108.9 |
C16—C15—H15 | 121.1 | N2—C30—H30B | 108.9 |
C17—C16—C15 | 121.3 (3) | C31—C30—H30B | 108.9 |
C17—C16—H16 | 119.3 | H30A—C30—H30B | 107.7 |
C15—C16—H16 | 119.3 | C30—C31—H31A | 109.5 |
C18—C17—C16 | 121.0 (3) | C30—C31—H31B | 109.5 |
C18—C17—H17 | 119.5 | H31A—C31—H31B | 109.5 |
C16—C17—H17 | 119.5 | C30—C31—H31C | 109.5 |
C17—C18—C19 | 117.6 (3) | H31A—C31—H31C | 109.5 |
C17—C18—H18 | 121.2 | H31B—C31—H31C | 109.5 |
C19—C18—H18 | 121.2 | C4—N2'—C30' | 123.9 (15) |
C14—C19—C18 | 121.7 (2) | C4—N2'—C29 | 117.0 (12) |
C14—C19—C20 | 108.8 (2) | C30'—N2'—C29 | 118.2 (16) |
C18—C19—C20 | 129.5 (2) | N2'—C30'—C31' | 109 (2) |
O2—C20—N1 | 125.2 (2) | N2'—C30'—H30C | 109.9 |
O2—C20—C19 | 129.1 (2) | C31'—C30'—H30C | 109.9 |
N1—C20—C19 | 105.8 (2) | N2'—C30'—H30D | 109.9 |
C22—C21—N1 | 112.9 (2) | C31'—C30'—H30D | 109.9 |
C22—C21—H21A | 109.0 | H30C—C30'—H30D | 108.3 |
N1—C21—H21A | 109.0 | C30'—C31'—H31D | 109.5 |
C22—C21—H21B | 109.0 | C30'—C31'—H31E | 109.5 |
N1—C21—H21B | 109.0 | H31D—C31'—H31E | 109.5 |
H21A—C21—H21B | 107.8 | C30'—C31'—H31F | 109.5 |
C23—C22—C21 | 179.8 (3) | H31D—C31'—H31F | 109.5 |
C22—C23—H23 | 180.0 | H31E—C31'—H31F | 109.5 |
C20—N1—C21 | 122.4 (2) | ||
C6—C1—C2—C3 | −0.1 (4) | C15—C14—C19—C18 | 1.0 (4) |
C13—C1—C2—C3 | 176.5 (3) | C13—C14—C19—C18 | −176.9 (2) |
C1—C2—C3—C4 | 0.0 (5) | C15—C14—C19—C20 | −179.8 (2) |
C2—C3—C4—N2' | −163.3 (13) | C13—C14—C19—C20 | 2.4 (3) |
C2—C3—C4—N2 | 174.3 (5) | C17—C18—C19—C14 | −0.8 (4) |
C2—C3—C4—C5 | 0.6 (5) | C17—C18—C19—C20 | −179.9 (3) |
N2'—C4—C5—C6 | 163.9 (12) | C14—C19—C20—O2 | −177.1 (3) |
N2—C4—C5—C6 | −174.6 (5) | C18—C19—C20—O2 | 2.0 (5) |
C3—C4—C5—C6 | −1.0 (4) | C14—C19—C20—N1 | 2.4 (3) |
C2—C1—C6—C5 | −0.3 (4) | C18—C19—C20—N1 | −178.5 (3) |
C13—C1—C6—C5 | −177.0 (2) | O2—C20—N1—C21 | 1.4 (4) |
C2—C1—C6—O1 | 179.0 (2) | C19—C20—N1—C21 | −178.1 (2) |
C13—C1—C6—O1 | 2.3 (4) | O2—C20—N1—C13 | 173.0 (2) |
C4—C5—C6—C1 | 0.9 (4) | C19—C20—N1—C13 | −6.6 (3) |
C4—C5—C6—O1 | −178.5 (3) | C22—C21—N1—C20 | −63.7 (3) |
C12—C7—C8—C9 | 1.8 (4) | C22—C21—N1—C13 | 125.4 (2) |
O1—C7—C8—C9 | −178.0 (2) | C12—C13—N1—C20 | 127.4 (2) |
C7—C8—C9—N3 | −179.6 (2) | C1—C13—N1—C20 | −109.1 (2) |
C7—C8—C9—C10 | 0.3 (4) | C14—C13—N1—C20 | 7.6 (2) |
N3—C9—C10—C11 | 178.0 (2) | C12—C13—N1—C21 | −61.1 (3) |
C8—C9—C10—C11 | −1.9 (3) | C1—C13—N1—C21 | 62.5 (3) |
C9—C10—C11—C12 | 1.5 (4) | C14—C13—N1—C21 | 179.1 (2) |
O1—C7—C12—C11 | 177.6 (2) | C8—C9—N3—C26 | 12.2 (4) |
C8—C7—C12—C11 | −2.2 (4) | C10—C9—N3—C26 | −167.7 (3) |
O1—C7—C12—C13 | −6.2 (4) | C8—C9—N3—C25 | −163.6 (2) |
C8—C7—C12—C13 | 174.1 (2) | C10—C9—N3—C25 | 16.5 (4) |
C10—C11—C12—C7 | 0.5 (3) | C12—C7—O1—C6 | −15.2 (3) |
C10—C11—C12—C13 | −175.7 (2) | C8—C7—O1—C6 | 164.6 (2) |
C7—C12—C13—N1 | 147.4 (2) | C1—C6—O1—C7 | 17.1 (4) |
C11—C12—C13—N1 | −36.6 (3) | C5—C6—O1—C7 | −163.6 (2) |
C7—C12—C13—C1 | 23.0 (3) | C9—N3—C25—C24 | −95.0 (3) |
C11—C12—C13—C1 | −161.0 (2) | C26—N3—C25—C24 | 89.1 (4) |
C7—C12—C13—C14 | −100.6 (2) | C9—N3—C26—C27 | −87.4 (3) |
C11—C12—C13—C14 | 75.4 (3) | C25—N3—C26—C27 | 88.6 (3) |
C6—C1—C13—N1 | −146.5 (2) | C3—C4—N2—C30 | −164.4 (6) |
C2—C1—C13—N1 | 37.1 (3) | C5—C4—N2—C30 | 9.0 (11) |
C6—C1—C13—C12 | −21.1 (3) | C3—C4—N2—C29 | 22.2 (10) |
C2—C1—C13—C12 | 162.4 (2) | C5—C4—N2—C29 | −164.5 (5) |
C6—C1—C13—C14 | 103.7 (3) | C28—C29—N2—C4 | −100.9 (7) |
C2—C1—C13—C14 | −72.7 (3) | C28—C29—N2—C30 | 85.4 (8) |
N1—C13—C14—C19 | −5.7 (2) | C4—N2—C30—C31 | −88.3 (9) |
C12—C13—C14—C19 | −125.6 (2) | C29—N2—C30—C31 | 85.3 (7) |
C1—C13—C14—C19 | 111.4 (2) | C3—C4—N2'—C30' | 170.0 (16) |
N1—C13—C14—C15 | 176.7 (2) | C5—C4—N2'—C30' | 6 (3) |
C12—C13—C14—C15 | 56.8 (3) | C3—C4—N2'—C29 | −21 (2) |
C1—C13—C14—C15 | −66.2 (3) | C5—C4—N2'—C29 | 175.3 (11) |
C19—C14—C15—C16 | −0.3 (4) | C28—C29—N2'—C4 | −68 (2) |
C13—C14—C15—C16 | 177.1 (2) | C28—C29—N2'—C30' | 101.3 (18) |
C14—C15—C16—C17 | −0.5 (4) | C4—N2'—C30'—C31' | 67 (3) |
C15—C16—C17—C18 | 0.6 (4) | C29—N2'—C30'—C31' | −102.4 (18) |
C16—C17—C18—C19 | 0.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21A···O2i | 0.97 | 2.59 | 3.483 (3) | 153 |
C23—H23···O2ii | 0.93 | 2.36 | 3.246 (4) | 159 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21A···O2i | 0.97 | 2.59 | 3.483 (3) | 153 |
C23—H23···O2ii | 0.93 | 2.36 | 3.246 (4) | 159 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C31H33N3O2 |
Mr | 479.60 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 18.0701 (8), 16.2611 (7), 9.0801 (4) |
β (°) | 97.645 (2) |
V (Å3) | 2644.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.35 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.977, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 40635, 4654, 3350 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.153, 1.09 |
No. of reflections | 4654 |
No. of parameters | 354 |
No. of restraints | 72 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.18 |
Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).
Acknowledgements
The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.
References
Bruker (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Soh, J. H., Swamy, K. M. K., Kim, S. K., Kim, S., Lee, S. H. & Yoon, J. (2007). Tetrahedron Lett. 48, 5966–5969. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, D., Huang, W., Duan, C. Y., Lin, Z. H. & Meng, Q. J. (2007). Inorg. Chem. 46, 1538–1540. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, X., Shiraishi, Y. & Hirai, T. (2007). Org. Lett. 9, 5039–5042. Web of Science CrossRef PubMed CAS Google Scholar
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