In the benzene and phenol solvates of (
S)-4-{3-[2-(dimethylamino)ethyl]-1
H-indol-5-ylmethyl}oxazolidin-2-one,
viz. C
16H
21N
3O
2·C
6H
6, (I), and C
16H
21N
3O
2·C
6H
5OH, (II), the host molecule has three linked residues, namely a planar indole ring system, an ethylamine side chain and an oxazolidinone system. It has comparable features to that of sumatriptan, although the side-chain orientations of (I) and (II) differ from those of sumatriptan. Both (I) and (II) have host-guest-type structures. The host molecule in (I) and (II) has an L-shaped form, with the oxazolidinone ring occupying the base and the remainder of the molecule forming the upright section. In (I), each benzene guest molecule is surrounded by four host molecules, and these molecules are linked by a combination of N-H
N, N-H
O and C-H
O hydrogen bonds into chains of edge-fused
R44(33) rings. In (II), two independent molecules are present in the asymmetric unit, with similar conformations. The heterocyclic components are connected through N-H
N, N-H
O and C-H
O interactions to form chains of edge-fused
R64(38) rings, from which the phenol guest molecules are pendent, linked by O-H
O hydrogen bonds. The structures are further stabilized by extensive C-H
interactions.
Supporting information
CCDC references: 655546; 655547
Crystals of the title compounds were grown from benzene [for (I)] and phenol
[for (II)] solutions by slow evaporation of zolmitriptan (1:1).
H atoms attached to N and O atoms were located in a difference density map and
refined isotropically. All other H atoms were placed in geometrycally
idealized positions and allowed to ride on their parent atoms, with C—H
distances in the range 0.93–0.98 Å, and with
Uiso(H)=1.5Ueq(C) for methyl H atoms and 1.2Ueq(C)
for all other H atoms. In the compound (I), the geometries of the atoms
(C17—C22) were restrained, where distances were set to a target value of
1.39 Å. Distance restraints were also applied to the H atoms of the hydroxy
groups in the compound (II). In the absence of significant anomalous
scattering effects, Friedel pairs were merged. The absolute configuration of
zolmitriptan was known in advance.
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
(I) (
S)-4-{3-[2-(dimethylamino)ethyl]-1
H-indol-5-
ylmethyl}oxazolidin-2-one benzene solvate
top
Crystal data top
C16H21N3O2·C6H6 | Dx = 1.178 Mg m−3 |
Mr = 365.47 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 8329 reflections |
a = 8.6938 (5) Å | θ = 2.6–27.2° |
b = 12.1331 (7) Å | µ = 0.08 mm−1 |
c = 19.5321 (12) Å | T = 273 K |
V = 2060.3 (2) Å3 | Needles, colourless |
Z = 4 | 0.22 × 0.17 × 0.15 mm |
F(000) = 784 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 1995 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −10→10 |
15000 measured reflections | k = −14→14 |
2097 independent reflections | l = −23→23 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.29 | w = 1/[σ2(Fo2) + (0.0599P)2 + 0.1882P] where P = (Fo2 + 2Fc2)/3 |
2097 reflections | (Δ/σ)max < 0.001 |
254 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C16H21N3O2·C6H6 | V = 2060.3 (2) Å3 |
Mr = 365.47 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.6938 (5) Å | µ = 0.08 mm−1 |
b = 12.1331 (7) Å | T = 273 K |
c = 19.5321 (12) Å | 0.22 × 0.17 × 0.15 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 1995 reflections with I > 2σ(I) |
15000 measured reflections | Rint = 0.020 |
2097 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.29 | Δρmax = 0.24 e Å−3 |
2097 reflections | Δρmin = −0.20 e Å−3 |
254 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.6871 (3) | 0.46682 (18) | 0.58334 (11) | 0.0476 (5) | |
H1 | 0.7631 | 0.4265 | 0.6056 | 0.057* | |
C2 | 0.6908 (3) | 0.49690 (18) | 0.51596 (10) | 0.0429 (5) | |
C3 | 0.5517 (2) | 0.55737 (17) | 0.50370 (10) | 0.0391 (5) | |
C4 | 0.4911 (2) | 0.61075 (18) | 0.44644 (10) | 0.0408 (5) | |
H4 | 0.5430 | 0.6074 | 0.4049 | 0.049* | |
C5 | 0.3553 (3) | 0.66813 (18) | 0.45102 (11) | 0.0435 (5) | |
C6 | 0.2758 (3) | 0.6704 (2) | 0.51412 (12) | 0.0513 (6) | |
H6 | 0.1837 | 0.7090 | 0.5172 | 0.062* | |
C7 | 0.3313 (3) | 0.6170 (2) | 0.57126 (11) | 0.0502 (6) | |
H7 | 0.2773 | 0.6183 | 0.6124 | 0.060* | |
C8 | 0.4704 (3) | 0.56099 (18) | 0.56572 (10) | 0.0423 (5) | |
C9 | 0.8104 (3) | 0.4744 (2) | 0.46281 (12) | 0.0562 (6) | |
H9A | 0.8388 | 0.5435 | 0.4412 | 0.067* | |
H9B | 0.7663 | 0.4272 | 0.4279 | 0.067* | |
C10 | 0.9545 (3) | 0.42004 (19) | 0.49074 (11) | 0.0446 (5) | |
H10A | 1.0015 | 0.4688 | 0.5241 | 0.053* | |
H10B | 0.9258 | 0.3527 | 0.5142 | 0.053* | |
C11 | 1.2098 (3) | 0.3574 (2) | 0.46999 (15) | 0.0636 (7) | |
H11A | 1.2468 | 0.4138 | 0.5003 | 0.095* | |
H11B | 1.2854 | 0.3433 | 0.4353 | 0.095* | |
H11C | 1.1910 | 0.2911 | 0.4955 | 0.095* | |
C12 | 1.0116 (3) | 0.3079 (2) | 0.39179 (15) | 0.0649 (7) | |
H12A | 1.0937 | 0.2847 | 0.3622 | 0.097* | |
H12B | 0.9285 | 0.3363 | 0.3647 | 0.097* | |
H12C | 0.9760 | 0.2461 | 0.4181 | 0.097* | |
C13 | 0.2944 (3) | 0.72946 (19) | 0.38947 (12) | 0.0506 (5) | |
H13A | 0.3665 | 0.7201 | 0.3520 | 0.061* | |
H13B | 0.2909 | 0.8074 | 0.4004 | 0.061* | |
C14 | 0.1368 (3) | 0.69437 (18) | 0.36509 (12) | 0.0474 (5) | |
H14 | 0.0596 | 0.7106 | 0.4003 | 0.057* | |
C15 | 0.0920 (4) | 0.7500 (2) | 0.29724 (13) | 0.0603 (7) | |
H15A | −0.0038 | 0.7902 | 0.3022 | 0.072* | |
H15B | 0.1715 | 0.8010 | 0.2827 | 0.072* | |
C16 | 0.0922 (3) | 0.5648 (2) | 0.28072 (11) | 0.0494 (5) | |
N1 | 0.5545 (2) | 0.50487 (16) | 0.61341 (10) | 0.0482 (5) | |
N2 | 1.0674 (2) | 0.39388 (15) | 0.43797 (10) | 0.0452 (4) | |
N3 | 0.1285 (3) | 0.57960 (16) | 0.34577 (10) | 0.0535 (5) | |
O1 | 0.0754 (2) | 0.66264 (14) | 0.24893 (8) | 0.0610 (5) | |
O2 | 0.0758 (3) | 0.47902 (15) | 0.24963 (9) | 0.0706 (6) | |
H1N | 0.521 (3) | 0.498 (2) | 0.6582 (15) | 0.059 (7)* | |
H3N | 0.120 (3) | 0.528 (2) | 0.3747 (14) | 0.058 (8)* | |
C17 | 0.3679 (9) | 0.2540 (6) | 0.2754 (4) | 0.158 (3) | |
H17 | 0.3114 | 0.3183 | 0.2692 | 0.190* | |
C18 | 0.4968 (10) | 0.2524 (6) | 0.3174 (4) | 0.179 (3) | |
H18 | 0.5272 | 0.3161 | 0.3402 | 0.215* | |
C19 | 0.5801 (7) | 0.1556 (8) | 0.3253 (3) | 0.158 (3) | |
H19 | 0.6678 | 0.1544 | 0.3525 | 0.190* | |
C20 | 0.5313 (7) | 0.0608 (6) | 0.2920 (3) | 0.153 (3) | |
H20 | 0.5881 | −0.0035 | 0.2978 | 0.184* | |
C21 | 0.4018 (8) | 0.0571 (5) | 0.2505 (3) | 0.148 (2) | |
H21 | 0.3686 | −0.0073 | 0.2294 | 0.177* | |
C22 | 0.3256 (6) | 0.1569 (7) | 0.2428 (3) | 0.148 (3) | |
H22 | 0.2406 | 0.1588 | 0.2140 | 0.177* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0544 (13) | 0.0471 (12) | 0.0414 (10) | 0.0043 (10) | −0.0049 (10) | 0.0035 (9) |
C2 | 0.0455 (11) | 0.0441 (11) | 0.0392 (10) | 0.0015 (10) | −0.0012 (9) | −0.0005 (9) |
C3 | 0.0406 (10) | 0.0399 (10) | 0.0367 (10) | −0.0043 (9) | −0.0003 (8) | −0.0040 (8) |
C4 | 0.0421 (10) | 0.0454 (11) | 0.0350 (10) | −0.0035 (9) | −0.0022 (9) | −0.0015 (9) |
C5 | 0.0446 (11) | 0.0421 (11) | 0.0439 (11) | −0.0042 (9) | −0.0062 (9) | −0.0053 (9) |
C6 | 0.0452 (12) | 0.0549 (13) | 0.0539 (13) | 0.0061 (11) | −0.0023 (11) | −0.0125 (11) |
C7 | 0.0493 (12) | 0.0598 (13) | 0.0416 (11) | −0.0006 (11) | 0.0069 (10) | −0.0109 (10) |
C8 | 0.0475 (11) | 0.0443 (11) | 0.0351 (10) | −0.0053 (10) | −0.0004 (9) | −0.0038 (9) |
C9 | 0.0533 (13) | 0.0717 (16) | 0.0437 (11) | 0.0155 (12) | 0.0031 (11) | 0.0064 (11) |
C10 | 0.0457 (11) | 0.0452 (11) | 0.0428 (11) | 0.0030 (10) | −0.0023 (9) | 0.0011 (9) |
C11 | 0.0470 (13) | 0.0700 (16) | 0.0738 (17) | 0.0131 (13) | −0.0032 (13) | 0.0006 (14) |
C12 | 0.0664 (16) | 0.0591 (14) | 0.0692 (15) | 0.0031 (13) | 0.0010 (14) | −0.0193 (13) |
C13 | 0.0522 (12) | 0.0423 (11) | 0.0572 (13) | 0.0021 (10) | −0.0093 (11) | 0.0015 (10) |
C14 | 0.0502 (12) | 0.0431 (11) | 0.0489 (12) | 0.0088 (10) | −0.0082 (10) | −0.0043 (10) |
C15 | 0.0708 (16) | 0.0484 (13) | 0.0615 (14) | 0.0064 (13) | −0.0201 (14) | 0.0024 (11) |
C16 | 0.0567 (13) | 0.0507 (12) | 0.0408 (11) | −0.0005 (11) | −0.0086 (10) | 0.0008 (10) |
N1 | 0.0570 (11) | 0.0543 (10) | 0.0332 (9) | −0.0006 (10) | 0.0033 (9) | 0.0023 (8) |
N2 | 0.0446 (10) | 0.0428 (9) | 0.0481 (10) | 0.0034 (8) | 0.0003 (8) | −0.0009 (8) |
N3 | 0.0786 (14) | 0.0428 (10) | 0.0392 (10) | −0.0066 (10) | −0.0131 (10) | 0.0046 (8) |
O1 | 0.0813 (12) | 0.0579 (10) | 0.0437 (9) | 0.0075 (9) | −0.0162 (9) | 0.0069 (8) |
O2 | 0.1059 (16) | 0.0572 (10) | 0.0487 (9) | −0.0042 (11) | −0.0198 (11) | −0.0082 (8) |
C17 | 0.158 (6) | 0.150 (6) | 0.166 (6) | 0.050 (5) | 0.084 (5) | 0.054 (5) |
C18 | 0.191 (8) | 0.198 (8) | 0.147 (6) | −0.050 (7) | 0.086 (6) | 0.013 (6) |
C19 | 0.097 (3) | 0.296 (10) | 0.081 (3) | −0.006 (6) | 0.025 (3) | 0.024 (5) |
C20 | 0.133 (5) | 0.230 (8) | 0.097 (3) | 0.082 (5) | 0.040 (3) | 0.049 (4) |
C21 | 0.158 (6) | 0.179 (6) | 0.105 (4) | 0.015 (5) | 0.049 (4) | 0.017 (4) |
C22 | 0.083 (3) | 0.255 (8) | 0.105 (4) | 0.037 (5) | 0.035 (3) | 0.064 (5) |
Geometric parameters (Å, º) top
C1—C2 | 1.366 (3) | C12—H12B | 0.9600 |
C1—N1 | 1.374 (3) | C12—H12C | 0.9600 |
C1—H1 | 0.9300 | C13—C14 | 1.512 (3) |
C2—C3 | 1.435 (3) | C13—H13A | 0.9700 |
C2—C9 | 1.494 (3) | C13—H13B | 0.9700 |
C3—C4 | 1.396 (3) | C14—N3 | 1.445 (3) |
C3—C8 | 1.403 (3) | C14—C15 | 1.537 (3) |
C4—C5 | 1.373 (3) | C14—H14 | 0.9800 |
C4—H4 | 0.9300 | C15—O1 | 1.427 (3) |
C5—C6 | 1.413 (3) | C15—H15A | 0.9700 |
C5—C13 | 1.510 (3) | C15—H15B | 0.9700 |
C6—C7 | 1.378 (3) | C16—O2 | 1.213 (3) |
C6—H6 | 0.9300 | C16—N3 | 1.321 (3) |
C7—C8 | 1.391 (3) | C16—O1 | 1.348 (3) |
C7—H7 | 0.9300 | N1—H1N | 0.93 (3) |
C8—N1 | 1.366 (3) | N3—H3N | 0.84 (3) |
C9—C10 | 1.518 (3) | C17—C22 | 1.388 (11) |
C9—H9A | 0.9700 | C17—C18 | 1.389 (11) |
C9—H9B | 0.9700 | C17—H17 | 0.9300 |
C10—N2 | 1.458 (3) | C18—C19 | 1.388 (12) |
C10—H10A | 0.9700 | C18—H18 | 0.9300 |
C10—H10B | 0.9700 | C19—C20 | 1.388 (11) |
C11—N2 | 1.456 (3) | C19—H19 | 0.9300 |
C11—H11A | 0.9600 | C20—C21 | 1.388 (9) |
C11—H11B | 0.9600 | C20—H20 | 0.9300 |
C11—H11C | 0.9600 | C21—C22 | 1.388 (10) |
C12—N2 | 1.462 (3) | C21—H21 | 0.9300 |
C12—H12A | 0.9600 | C22—H22 | 0.9300 |
| | | |
C2—C1—N1 | 110.0 (2) | C5—C13—H13A | 108.4 |
C2—C1—H1 | 125.0 | C14—C13—H13A | 108.4 |
N1—C1—H1 | 125.0 | C5—C13—H13B | 108.4 |
C1—C2—C3 | 106.1 (2) | C14—C13—H13B | 108.4 |
C1—C2—C9 | 129.6 (2) | H13A—C13—H13B | 107.5 |
C3—C2—C9 | 124.32 (19) | N3—C14—C13 | 113.5 (2) |
C4—C3—C8 | 119.15 (19) | N3—C14—C15 | 100.69 (18) |
C4—C3—C2 | 133.58 (19) | C13—C14—C15 | 112.2 (2) |
C8—C3—C2 | 107.25 (18) | N3—C14—H14 | 110.0 |
C5—C4—C3 | 120.50 (19) | C13—C14—H14 | 110.0 |
C5—C4—H4 | 119.8 | C15—C14—H14 | 110.0 |
C3—C4—H4 | 119.8 | O1—C15—C14 | 105.64 (18) |
C4—C5—C6 | 119.2 (2) | O1—C15—H15A | 110.6 |
C4—C5—C13 | 120.0 (2) | C14—C15—H15A | 110.6 |
C6—C5—C13 | 120.9 (2) | O1—C15—H15B | 110.6 |
C7—C6—C5 | 121.7 (2) | C14—C15—H15B | 110.6 |
C7—C6—H6 | 119.1 | H15A—C15—H15B | 108.7 |
C5—C6—H6 | 119.1 | O2—C16—N3 | 128.8 (2) |
C6—C7—C8 | 118.1 (2) | O2—C16—O1 | 120.80 (19) |
C6—C7—H7 | 121.0 | N3—C16—O1 | 110.4 (2) |
C8—C7—H7 | 121.0 | C8—N1—C1 | 108.97 (18) |
N1—C8—C7 | 131.0 (2) | C8—N1—H1N | 121.4 (17) |
N1—C8—C3 | 107.67 (19) | C1—N1—H1N | 129.6 (17) |
C7—C8—C3 | 121.4 (2) | C11—N2—C10 | 109.56 (19) |
C2—C9—C10 | 113.83 (19) | C11—N2—C12 | 109.3 (2) |
C2—C9—H9A | 108.8 | C10—N2—C12 | 111.6 (2) |
C10—C9—H9A | 108.8 | C16—N3—C14 | 113.2 (2) |
C2—C9—H9B | 108.8 | C16—N3—H3N | 121.6 (18) |
C10—C9—H9B | 108.8 | C14—N3—H3N | 122.7 (17) |
H9A—C9—H9B | 107.7 | C16—O1—C15 | 109.81 (17) |
N2—C10—C9 | 113.35 (18) | C22—C17—C18 | 118.2 (7) |
N2—C10—H10A | 108.9 | C22—C17—H17 | 120.9 |
C9—C10—H10A | 108.9 | C18—C17—H17 | 120.9 |
N2—C10—H10B | 108.9 | C19—C18—C17 | 119.9 (7) |
C9—C10—H10B | 108.9 | C19—C18—H18 | 120.1 |
H10A—C10—H10B | 107.7 | C17—C18—H18 | 120.1 |
N2—C11—H11A | 109.5 | C20—C19—C18 | 119.3 (6) |
N2—C11—H11B | 109.5 | C20—C19—H19 | 120.3 |
H11A—C11—H11B | 109.5 | C18—C19—H19 | 120.3 |
N2—C11—H11C | 109.5 | C19—C20—C21 | 123.2 (6) |
H11A—C11—H11C | 109.5 | C19—C20—H20 | 118.4 |
H11B—C11—H11C | 109.5 | C21—C20—H20 | 118.4 |
N2—C12—H12A | 109.5 | C20—C21—C22 | 114.9 (5) |
N2—C12—H12B | 109.5 | C20—C21—H21 | 122.5 |
H12A—C12—H12B | 109.5 | C22—C21—H21 | 122.5 |
N2—C12—H12C | 109.5 | C21—C22—C17 | 124.4 (6) |
H12A—C12—H12C | 109.5 | C21—C22—H22 | 117.8 |
H12B—C12—H12C | 109.5 | C17—C22—H22 | 117.8 |
C5—C13—C14 | 115.5 (2) | | |
| | | |
N1—C1—C2—C3 | 0.0 (3) | C6—C5—C13—C14 | −60.3 (3) |
N1—C1—C2—C9 | −179.8 (2) | C5—C13—C14—N3 | −59.4 (3) |
C1—C2—C3—C4 | 178.4 (2) | C5—C13—C14—C15 | −172.7 (2) |
C9—C2—C3—C4 | −1.7 (4) | N3—C14—C15—O1 | −3.8 (3) |
C1—C2—C3—C8 | 0.3 (2) | C13—C14—C15—O1 | 117.2 (2) |
C9—C2—C3—C8 | −179.9 (2) | C7—C8—N1—C1 | −178.0 (2) |
C8—C3—C4—C5 | 1.4 (3) | C3—C8—N1—C1 | 0.5 (2) |
C2—C3—C4—C5 | −176.5 (2) | C2—C1—N1—C8 | −0.3 (3) |
C3—C4—C5—C6 | −1.4 (3) | C9—C10—N2—C11 | 171.7 (2) |
C3—C4—C5—C13 | 177.4 (2) | C9—C10—N2—C12 | −67.2 (3) |
C4—C5—C6—C7 | 0.3 (3) | O2—C16—N3—C14 | −179.6 (3) |
C13—C5—C6—C7 | −178.6 (2) | O1—C16—N3—C14 | 1.2 (3) |
C5—C6—C7—C8 | 0.8 (4) | C13—C14—N3—C16 | −118.4 (2) |
C6—C7—C8—N1 | 177.5 (2) | C15—C14—N3—C16 | 1.7 (3) |
C6—C7—C8—C3 | −0.8 (3) | O2—C16—O1—C15 | 176.8 (3) |
C4—C3—C8—N1 | −178.94 (18) | N3—C16—O1—C15 | −3.9 (3) |
C2—C3—C8—N1 | −0.5 (2) | C14—C15—O1—C16 | 4.8 (3) |
C4—C3—C8—C7 | −0.3 (3) | C22—C17—C18—C19 | 0.6 (9) |
C2—C3—C8—C7 | 178.16 (19) | C17—C18—C19—C20 | −1.4 (9) |
C1—C2—C9—C10 | −6.7 (4) | C18—C19—C20—C21 | 0.2 (9) |
C3—C2—C9—C10 | 173.5 (2) | C19—C20—C21—C22 | 1.7 (7) |
C2—C9—C10—N2 | 177.3 (2) | C20—C21—C22—C17 | −2.5 (8) |
C4—C5—C13—C14 | 120.8 (2) | C18—C17—C22—C21 | 1.4 (9) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.93 (3) | 1.99 (3) | 2.898 (3) | 165 (2) |
N3—H3N···N2ii | 0.84 (3) | 2.10 (3) | 2.933 (3) | 171 (3) |
C15—H15A···O2iii | 0.97 | 2.58 | 3.269 (3) | 128 |
C1—H1···Cg1iv | 0.93 | 2.88 | 3.768 | 159 |
C11—H11A···Cg2v | 0.96 | 2.83 | 3.658 | 145 |
C13—H13B···Cg3vi | 0.96 | 2.87 | 3.699 | 144 |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) x−1, y, z; (iii) −x, y+1/2, −z+1/2; (iv) −x, y+1/2, −z+3/2; (v) x+1, y, z; (vi) −x−1, y−1/2, −z+3/2. |
(II) (
S)-4-{3-[2-(dimethylamino)ethyl]-1
H-indol-5-
ylmethyl}oxazolidin-2-one phenol solvate
top
Crystal data top
C16H21N3O2·C6H6O | F(000) = 816 |
Mr = 381.47 | Dx = 1.218 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7618 (13) Å | Cell parameters from 9402 reflections |
b = 19.506 (3) Å | θ = 2.6–27.7° |
c = 12.1767 (18) Å | µ = 0.08 mm−1 |
β = 91.399 (2)° | T = 293 K |
V = 2080.5 (5) Å3 | Prism, colourless |
Z = 4 | 0.22 × 0.18 × 0.16 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3521 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
Graphite monochromator | θmax = 25.0°, θmin = 1.7° |
ω scans | h = −10→10 |
19466 measured reflections | k = −23→23 |
3780 independent reflections | l = −14→14 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0829P)2 + 0.257P] where P = (Fo2 + 2Fc2)/3 |
3780 reflections | (Δ/σ)max < 0.001 |
530 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
C16H21N3O2·C6H6O | V = 2080.5 (5) Å3 |
Mr = 381.47 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.7618 (13) Å | µ = 0.08 mm−1 |
b = 19.506 (3) Å | T = 293 K |
c = 12.1767 (18) Å | 0.22 × 0.18 × 0.16 mm |
β = 91.399 (2)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3521 reflections with I > 2σ(I) |
19466 measured reflections | Rint = 0.036 |
3780 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | Δρmax = 0.23 e Å−3 |
3780 reflections | Δρmin = −0.17 e Å−3 |
530 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.0667 (4) | 0.85185 (18) | 1.0309 (3) | 0.0466 (7) | |
H1A | −0.0063 | 0.8294 | 1.0717 | 0.056* | |
C1B | 0.5595 (4) | 1.01868 (18) | 0.4661 (3) | 0.0493 (8) | |
H1D | 0.4831 | 1.0410 | 0.4255 | 0.059* | |
C2A | 0.0615 (4) | 0.92011 (17) | 1.0021 (3) | 0.0431 (7) | |
C2B | 0.5549 (4) | 0.95126 (17) | 0.4978 (3) | 0.0439 (7) | |
C3A | 0.1966 (3) | 0.93233 (16) | 0.9404 (3) | 0.0387 (7) | |
C3B | 0.6963 (4) | 0.93904 (16) | 0.5581 (3) | 0.0393 (7) | |
C4A | 0.2546 (3) | 0.99029 (16) | 0.8885 (3) | 0.0412 (7) | |
H4A | 0.2040 | 1.0320 | 0.8939 | 0.049* | |
C4B | 0.7561 (3) | 0.88108 (16) | 0.6115 (3) | 0.0407 (7) | |
H4D | 0.7028 | 0.8399 | 0.6094 | 0.049* | |
C5A | 0.3881 (4) | 0.98585 (18) | 0.8288 (3) | 0.0441 (7) | |
C5B | 0.8956 (4) | 0.88561 (17) | 0.6674 (3) | 0.0421 (7) | |
C6A | 0.4642 (4) | 0.9224 (2) | 0.8240 (3) | 0.0515 (8) | |
H6A | 0.5529 | 0.9194 | 0.7838 | 0.062* | |
C6B | 0.9761 (4) | 0.94829 (19) | 0.6674 (3) | 0.0524 (8) | |
H6D | 1.0700 | 0.9509 | 0.7044 | 0.063* | |
C7A | 0.4129 (4) | 0.86466 (18) | 0.8762 (3) | 0.0479 (8) | |
H7A | 0.4664 | 0.8236 | 0.8731 | 0.057* | |
C7B | 0.9201 (4) | 1.00561 (18) | 0.6143 (3) | 0.0521 (8) | |
H7D | 0.9750 | 1.0464 | 0.6147 | 0.063* | |
C8A | 0.2763 (4) | 0.86987 (16) | 0.9345 (3) | 0.0405 (7) | |
C8B | 0.7783 (4) | 1.00080 (17) | 0.5596 (3) | 0.0428 (7) | |
C9A | −0.0567 (4) | 0.97266 (19) | 1.0273 (4) | 0.0547 (9) | |
H9A | −0.0839 | 0.9972 | 0.9604 | 0.066* | |
H9B | −0.0131 | 1.0055 | 1.0790 | 0.066* | |
C9B | 0.4344 (4) | 0.8987 (2) | 0.4779 (4) | 0.0589 (10) | |
H9D | 0.4064 | 0.8793 | 0.5480 | 0.071* | |
H9E | 0.4764 | 0.8620 | 0.4342 | 0.071* | |
C10A | −0.2002 (4) | 0.94285 (17) | 1.0751 (3) | 0.0437 (7) | |
H10A | −0.2457 | 0.9111 | 1.0225 | 0.052* | |
H10B | −0.1726 | 0.9171 | 1.1408 | 0.052* | |
C10B | 0.2911 (4) | 0.92560 (18) | 0.4199 (3) | 0.0454 (7) | |
H10D | 0.2439 | 0.9595 | 0.4664 | 0.054* | |
H10E | 0.3198 | 0.9483 | 0.3526 | 0.054* | |
C11A | −0.4536 (4) | 0.9613 (2) | 1.1369 (4) | 0.0640 (10) | |
H11A | −0.4315 | 0.9324 | 1.1990 | 0.096* | |
H11B | −0.4942 | 0.9341 | 1.0773 | 0.096* | |
H11C | −0.5273 | 0.9954 | 1.1567 | 0.096* | |
C11B | 0.0370 (4) | 0.9042 (2) | 0.3530 (4) | 0.0622 (10) | |
H11D | 0.0559 | 0.9289 | 0.2864 | 0.093* | |
H11E | 0.0008 | 0.9354 | 0.4075 | 0.093* | |
H11F | −0.0386 | 0.8695 | 0.3388 | 0.093* | |
C12A | −0.2576 (5) | 1.0397 (2) | 1.1928 (4) | 0.0650 (11) | |
H12A | −0.2300 | 1.0122 | 1.2556 | 0.097* | |
H12B | −0.3360 | 1.0715 | 1.2121 | 0.097* | |
H12C | −0.1697 | 1.0644 | 1.1689 | 0.097* | |
C12B | 0.2342 (5) | 0.8254 (2) | 0.3093 (3) | 0.0639 (10) | |
H12D | 0.2648 | 0.8512 | 0.2464 | 0.096* | |
H12E | 0.1543 | 0.7941 | 0.2879 | 0.096* | |
H12F | 0.3200 | 0.8001 | 0.3384 | 0.096* | |
C13A | 0.4443 (4) | 1.0485 (2) | 0.7684 (3) | 0.0508 (8) | |
H13A | 0.3747 | 1.0861 | 0.7813 | 0.061* | |
H13B | 0.4410 | 1.0388 | 0.6902 | 0.061* | |
C13B | 0.9572 (4) | 0.82348 (19) | 0.7282 (3) | 0.0487 (8) | |
H13D | 0.8829 | 0.7868 | 0.7212 | 0.058* | |
H13E | 0.9677 | 0.8348 | 0.8056 | 0.058* | |
C14A | 0.6050 (4) | 1.07125 (19) | 0.8011 (3) | 0.0472 (8) | |
H14A | 0.6793 | 1.0360 | 0.7816 | 0.057* | |
C14B | 1.1098 (4) | 0.79737 (18) | 0.6889 (3) | 0.0452 (7) | |
H14D | 1.1899 | 0.8311 | 0.7056 | 0.054* | |
C15A | 0.6449 (5) | 1.1397 (2) | 0.7469 (3) | 0.0594 (10) | |
H15A | 0.7369 | 1.1353 | 0.7048 | 0.071* | |
H15B | 0.5623 | 1.1547 | 0.6982 | 0.071* | |
C15B | 1.1535 (5) | 0.7272 (2) | 0.7406 (3) | 0.0597 (10) | |
H15D | 1.2528 | 0.7297 | 0.7774 | 0.072* | |
H15E | 1.0785 | 0.7132 | 0.7935 | 0.072* | |
C16A | 0.6575 (4) | 1.15411 (19) | 0.9320 (3) | 0.0506 (8) | |
C16B | 1.1330 (4) | 0.71385 (19) | 0.5553 (3) | 0.0463 (8) | |
N1A | 0.1952 (3) | 0.82185 (15) | 0.9906 (2) | 0.0472 (6) | |
N1B | 0.6936 (3) | 1.04863 (16) | 0.5032 (3) | 0.0502 (7) | |
N2A | −0.3146 (3) | 0.99488 (15) | 1.1032 (2) | 0.0460 (6) | |
N2B | 0.1789 (3) | 0.87200 (15) | 0.3930 (2) | 0.0446 (6) | |
N3A | 0.6217 (4) | 1.08869 (16) | 0.9149 (3) | 0.0533 (7) | |
N3B | 1.1100 (4) | 0.78010 (16) | 0.5736 (3) | 0.0493 (7) | |
O1A | 0.6677 (3) | 1.18744 (14) | 0.8353 (2) | 0.0632 (7) | |
O1B | 1.1564 (3) | 0.68024 (13) | 0.6507 (2) | 0.0578 (6) | |
O2A | 0.6812 (4) | 1.18399 (15) | 1.0185 (2) | 0.0699 (8) | |
O2B | 1.1336 (3) | 0.68342 (14) | 0.4678 (2) | 0.0613 (7) | |
H1BN | 0.729 (4) | 1.088 (2) | 0.495 (3) | 0.045 (10)* | |
H3AN | 0.619 (4) | 1.064 (2) | 0.971 (3) | 0.041 (9)* | |
H3BN | 1.116 (4) | 0.805 (2) | 0.523 (3) | 0.049 (11)* | |
H5D | 0.965 (4) | 0.718 (6) | 0.381 (7) | 0.18 (4)* | |
C17A | 0.6548 (6) | 0.6835 (3) | 0.5820 (5) | 0.0780 (13) | |
C18A | 0.5648 (6) | 0.6927 (3) | 0.6690 (6) | 0.0929 (17) | |
H18A | 0.4812 | 0.7219 | 0.6626 | 0.111* | |
C19A | 0.5929 (8) | 0.6608 (4) | 0.7638 (6) | 0.1009 (19) | |
H19A | 0.5303 | 0.6693 | 0.8229 | 0.121* | |
C20A | 0.7112 (10) | 0.6161 (4) | 0.7766 (6) | 0.116 (3) | |
H20A | 0.7276 | 0.5928 | 0.8424 | 0.140* | |
C21A | 0.8080 (7) | 0.6061 (3) | 0.6877 (7) | 0.0985 (18) | |
H21A | 0.8915 | 0.5769 | 0.6952 | 0.118* | |
C22A | 0.7799 (6) | 0.6390 (3) | 0.5906 (5) | 0.0838 (16) | |
H22A | 0.8427 | 0.6321 | 0.5311 | 0.101* | |
O3A | 0.6220 (5) | 0.7193 (3) | 0.4878 (4) | 0.1084 (13) | |
H3A | 0.696 (7) | 0.699 (4) | 0.454 (6) | 0.15 (3)* | |
H1AN | 0.229 (5) | 0.779 (3) | 0.999 (3) | 0.059 (11)* | |
C17B | 0.8462 (6) | 0.7203 (3) | 0.2452 (4) | 0.0779 (14) | |
C18B | 0.9362 (6) | 0.6839 (3) | 0.1762 (5) | 0.0828 (14) | |
H18D | 1.0215 | 0.6604 | 0.2031 | 0.099* | |
C19B | 0.8975 (11) | 0.6828 (4) | 0.0649 (6) | 0.118 (3) | |
H19D | 0.9560 | 0.6567 | 0.0178 | 0.141* | |
C20B | 0.7751 (14) | 0.7191 (5) | 0.0226 (7) | 0.131 (3) | |
H20D | 0.7543 | 0.7213 | −0.0525 | 0.157* | |
C21B | 0.6877 (10) | 0.7509 (5) | 0.0944 (7) | 0.119 (3) | |
H21D | 0.5997 | 0.7724 | 0.0675 | 0.143* | |
C22B | 0.7178 (6) | 0.7543 (3) | 0.2041 (6) | 0.0931 (17) | |
H22D | 0.6546 | 0.7787 | 0.2503 | 0.112* | |
O3B | 0.8729 (5) | 0.7252 (3) | 0.3554 (3) | 0.1074 (14) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.0513 (18) | 0.0367 (17) | 0.0520 (18) | −0.0027 (14) | 0.0037 (14) | 0.0036 (14) |
C1B | 0.0497 (18) | 0.0390 (17) | 0.059 (2) | 0.0066 (15) | −0.0005 (15) | 0.0034 (15) |
C2A | 0.0428 (16) | 0.0351 (16) | 0.0514 (18) | −0.0018 (13) | 0.0031 (13) | 0.0003 (14) |
C2B | 0.0415 (16) | 0.0368 (17) | 0.0531 (18) | 0.0028 (14) | −0.0028 (13) | 0.0032 (14) |
C3A | 0.0371 (14) | 0.0335 (16) | 0.0453 (16) | −0.0017 (12) | −0.0038 (12) | −0.0036 (12) |
C3B | 0.0372 (15) | 0.0352 (16) | 0.0455 (16) | 0.0007 (12) | 0.0027 (12) | −0.0046 (13) |
C4A | 0.0378 (15) | 0.0323 (15) | 0.0532 (18) | 0.0008 (13) | −0.0021 (13) | −0.0035 (13) |
C4B | 0.0383 (15) | 0.0340 (15) | 0.0499 (17) | 0.0018 (13) | −0.0001 (12) | −0.0040 (13) |
C5A | 0.0430 (16) | 0.0423 (17) | 0.0468 (17) | −0.0090 (14) | −0.0054 (13) | −0.0038 (14) |
C5B | 0.0396 (15) | 0.0416 (17) | 0.0451 (16) | 0.0066 (13) | −0.0001 (12) | −0.0076 (13) |
C6A | 0.0392 (16) | 0.056 (2) | 0.060 (2) | −0.0018 (15) | 0.0048 (14) | −0.0125 (17) |
C6B | 0.0402 (16) | 0.0503 (19) | 0.066 (2) | 0.0039 (15) | −0.0094 (15) | −0.0126 (17) |
C7A | 0.0413 (16) | 0.0401 (17) | 0.062 (2) | 0.0054 (14) | −0.0026 (14) | −0.0108 (15) |
C7B | 0.0460 (18) | 0.0388 (18) | 0.071 (2) | −0.0076 (14) | −0.0007 (16) | −0.0113 (16) |
C8A | 0.0397 (15) | 0.0337 (16) | 0.0477 (17) | 0.0005 (12) | −0.0064 (12) | −0.0040 (13) |
C8B | 0.0420 (16) | 0.0350 (16) | 0.0515 (18) | 0.0009 (13) | 0.0051 (13) | −0.0048 (14) |
C9A | 0.0502 (19) | 0.0365 (17) | 0.078 (2) | 0.0023 (15) | 0.0132 (17) | 0.0056 (17) |
C9B | 0.052 (2) | 0.0397 (19) | 0.084 (3) | −0.0022 (16) | −0.0170 (18) | 0.0108 (18) |
C10A | 0.0408 (16) | 0.0374 (16) | 0.0530 (18) | 0.0026 (13) | 0.0027 (13) | 0.0000 (14) |
C10B | 0.0394 (16) | 0.0390 (17) | 0.0575 (19) | 0.0015 (14) | −0.0039 (14) | 0.0024 (15) |
C11A | 0.0456 (19) | 0.071 (3) | 0.075 (3) | −0.0014 (18) | 0.0088 (17) | −0.001 (2) |
C11B | 0.0446 (18) | 0.065 (2) | 0.076 (3) | 0.0008 (17) | −0.0137 (17) | 0.005 (2) |
C12A | 0.060 (2) | 0.067 (3) | 0.068 (2) | 0.008 (2) | −0.0006 (18) | −0.022 (2) |
C12B | 0.065 (2) | 0.067 (3) | 0.060 (2) | −0.005 (2) | 0.0022 (18) | −0.017 (2) |
C13A | 0.0451 (17) | 0.056 (2) | 0.0510 (18) | −0.0103 (16) | −0.0011 (14) | 0.0045 (16) |
C13B | 0.0494 (18) | 0.052 (2) | 0.0443 (17) | 0.0064 (16) | −0.0015 (13) | −0.0006 (15) |
C14A | 0.0431 (16) | 0.0470 (19) | 0.0518 (19) | −0.0042 (14) | 0.0093 (13) | −0.0014 (15) |
C14B | 0.0418 (16) | 0.0458 (18) | 0.0476 (17) | 0.0057 (14) | −0.0073 (13) | −0.0002 (14) |
C15A | 0.060 (2) | 0.064 (2) | 0.054 (2) | −0.0215 (19) | 0.0047 (17) | 0.0057 (18) |
C15B | 0.060 (2) | 0.069 (3) | 0.050 (2) | 0.0205 (19) | −0.0041 (16) | 0.0091 (18) |
C16A | 0.055 (2) | 0.0455 (19) | 0.0516 (19) | −0.0083 (16) | 0.0026 (15) | −0.0003 (16) |
C16B | 0.0413 (17) | 0.0418 (18) | 0.056 (2) | 0.0040 (14) | 0.0044 (14) | 0.0005 (16) |
N1A | 0.0522 (16) | 0.0297 (14) | 0.0595 (17) | 0.0024 (12) | −0.0007 (13) | 0.0026 (12) |
N1B | 0.0520 (16) | 0.0302 (14) | 0.0683 (19) | −0.0049 (13) | −0.0006 (14) | 0.0017 (13) |
N2A | 0.0410 (14) | 0.0454 (15) | 0.0517 (16) | 0.0038 (12) | 0.0014 (11) | −0.0009 (13) |
N2B | 0.0417 (14) | 0.0419 (14) | 0.0498 (15) | −0.0011 (12) | −0.0033 (11) | −0.0004 (12) |
N3A | 0.0687 (19) | 0.0372 (15) | 0.0538 (18) | −0.0147 (14) | −0.0052 (14) | 0.0060 (14) |
N3B | 0.0638 (18) | 0.0389 (16) | 0.0452 (16) | 0.0130 (13) | 0.0036 (13) | 0.0063 (13) |
O1A | 0.0855 (19) | 0.0425 (14) | 0.0622 (15) | −0.0198 (13) | 0.0116 (13) | 0.0054 (12) |
O1B | 0.0633 (15) | 0.0448 (14) | 0.0650 (15) | 0.0120 (12) | −0.0047 (12) | 0.0089 (12) |
O2A | 0.100 (2) | 0.0470 (15) | 0.0622 (16) | −0.0200 (16) | 0.0032 (14) | −0.0077 (13) |
O2B | 0.0745 (17) | 0.0497 (14) | 0.0600 (15) | 0.0085 (13) | 0.0062 (12) | −0.0078 (13) |
C17A | 0.072 (3) | 0.071 (3) | 0.092 (3) | −0.022 (3) | 0.013 (2) | −0.017 (3) |
C18A | 0.072 (3) | 0.094 (4) | 0.114 (4) | −0.030 (3) | 0.019 (3) | −0.027 (4) |
C19A | 0.097 (4) | 0.108 (5) | 0.099 (4) | −0.033 (4) | 0.019 (3) | −0.024 (4) |
C20A | 0.138 (6) | 0.110 (5) | 0.100 (4) | −0.065 (5) | −0.018 (4) | 0.004 (4) |
C21A | 0.081 (3) | 0.076 (3) | 0.139 (5) | −0.024 (3) | −0.001 (3) | −0.003 (4) |
C22A | 0.069 (3) | 0.074 (3) | 0.110 (4) | −0.024 (3) | 0.023 (3) | −0.020 (3) |
O3A | 0.088 (3) | 0.113 (4) | 0.124 (4) | 0.010 (3) | 0.009 (2) | 0.001 (3) |
C17B | 0.078 (3) | 0.085 (3) | 0.070 (3) | −0.027 (3) | −0.011 (2) | 0.019 (3) |
C18B | 0.067 (3) | 0.079 (3) | 0.101 (4) | −0.018 (3) | −0.006 (2) | 0.012 (3) |
C19B | 0.166 (7) | 0.095 (5) | 0.091 (4) | −0.051 (5) | 0.006 (4) | −0.014 (4) |
C20B | 0.177 (8) | 0.120 (6) | 0.093 (5) | −0.069 (6) | −0.053 (5) | 0.012 (5) |
C21B | 0.115 (5) | 0.120 (6) | 0.119 (6) | −0.051 (5) | −0.056 (4) | 0.051 (5) |
C22B | 0.064 (3) | 0.090 (4) | 0.125 (5) | −0.014 (3) | −0.013 (3) | 0.028 (3) |
O3B | 0.078 (2) | 0.166 (4) | 0.078 (2) | −0.006 (3) | −0.0009 (18) | 0.013 (3) |
Geometric parameters (Å, º) top
C1A—N1A | 1.370 (5) | C12B—H12D | 0.9600 |
C1A—C2A | 1.377 (5) | C12B—H12E | 0.9600 |
C1A—H1A | 0.9300 | C12B—H12F | 0.9600 |
C1B—C2B | 1.371 (5) | C13A—C14A | 1.520 (5) |
C1B—N1B | 1.379 (5) | C13A—H13A | 0.9700 |
C1B—H1D | 0.9300 | C13A—H13B | 0.9700 |
C2A—C3A | 1.438 (5) | C13B—C14B | 1.519 (5) |
C2A—C9A | 1.494 (5) | C13B—H13D | 0.9700 |
C2B—C3B | 1.445 (5) | C13B—H13E | 0.9700 |
C2B—C9B | 1.488 (5) | C14A—N3A | 1.432 (5) |
C3A—C4A | 1.397 (5) | C14A—C15A | 1.533 (5) |
C3A—C8A | 1.407 (4) | C14A—H14A | 0.9800 |
C3B—C4B | 1.399 (5) | C14B—N3B | 1.444 (5) |
C3B—C8B | 1.402 (5) | C14B—C15B | 1.550 (5) |
C4A—C5A | 1.395 (5) | C14B—H14D | 0.9800 |
C4A—H4A | 0.9300 | C15A—O1A | 1.434 (5) |
C4B—C5B | 1.388 (5) | C15A—H15A | 0.9700 |
C4B—H4D | 0.9300 | C15A—H15B | 0.9700 |
C5A—C6A | 1.408 (5) | C15B—O1B | 1.429 (5) |
C5A—C13A | 1.514 (5) | C15B—H15D | 0.9700 |
C5B—C6B | 1.412 (5) | C15B—H15E | 0.9700 |
C5B—C13B | 1.513 (5) | C16A—O2A | 1.217 (5) |
C6A—C7A | 1.374 (5) | C16A—N3A | 1.329 (5) |
C6A—H6A | 0.9300 | C16A—O1A | 1.350 (4) |
C6B—C7B | 1.376 (5) | C16B—O2B | 1.220 (4) |
C6B—H6D | 0.9300 | C16B—N3B | 1.327 (5) |
C7A—C8A | 1.410 (5) | C16B—O1B | 1.345 (4) |
C7A—H7A | 0.9300 | N1A—H1AN | 0.89 (5) |
C7B—C8B | 1.398 (5) | N1B—H1BN | 0.83 (4) |
C7B—H7D | 0.9300 | N3A—H3AN | 0.84 (4) |
C8A—N1A | 1.368 (5) | N3B—H3BN | 0.79 (4) |
C8B—N1B | 1.367 (5) | C17A—C18A | 1.348 (8) |
C9A—C10A | 1.515 (5) | C17A—O3A | 1.366 (7) |
C9A—H9A | 0.9700 | C17A—C22A | 1.400 (8) |
C9A—H9B | 0.9700 | C18A—C19A | 1.329 (10) |
C9B—C10B | 1.519 (5) | C18A—H18A | 0.9300 |
C9B—H9D | 0.9700 | C19A—C20A | 1.360 (11) |
C9B—H9E | 0.9700 | C19A—H19A | 0.9300 |
C10A—N2A | 1.473 (4) | C20A—C21A | 1.405 (11) |
C10A—H10A | 0.9700 | C20A—H20A | 0.9300 |
C10A—H10B | 0.9700 | C21A—C22A | 1.364 (9) |
C10B—N2B | 1.467 (4) | C21A—H21A | 0.9300 |
C10B—H10D | 0.9700 | C22A—H22A | 0.9300 |
C10B—H10E | 0.9700 | O3A—H3A | 0.87 (6) |
C11A—N2A | 1.451 (5) | C17B—O3B | 1.360 (6) |
C11A—H11A | 0.9600 | C17B—C18B | 1.365 (8) |
C11A—H11B | 0.9600 | C17B—C22B | 1.389 (8) |
C11A—H11C | 0.9600 | C18B—C19B | 1.389 (9) |
C11B—N2B | 1.465 (5) | C18B—H18D | 0.9300 |
C11B—H11D | 0.9600 | C19B—C20B | 1.375 (13) |
C11B—H11E | 0.9600 | C19B—H19D | 0.9300 |
C11B—H11F | 0.9600 | C20B—C21B | 1.329 (14) |
C12A—N2A | 1.476 (5) | C20B—H20D | 0.9300 |
C12A—H12A | 0.9600 | C21B—C22B | 1.357 (10) |
C12A—H12B | 0.9600 | C21B—H21D | 0.9300 |
C12A—H12C | 0.9600 | C22B—H22D | 0.9300 |
C12B—N2B | 1.458 (5) | O3B—H5D | 0.87 (5) |
| | | |
N1A—C1A—C2A | 110.2 (3) | C14A—C13A—H13A | 108.6 |
N1A—C1A—H1A | 124.9 | C5A—C13A—H13B | 108.6 |
C2A—C1A—H1A | 124.9 | C14A—C13A—H13B | 108.6 |
C2B—C1B—N1B | 110.2 (3) | H13A—C13A—H13B | 107.5 |
C2B—C1B—H1D | 124.9 | C5B—C13B—C14B | 114.9 (3) |
N1B—C1B—H1D | 124.9 | C5B—C13B—H13D | 108.6 |
C1A—C2A—C3A | 105.7 (3) | C14B—C13B—H13D | 108.6 |
C1A—C2A—C9A | 129.1 (3) | C5B—C13B—H13E | 108.6 |
C3A—C2A—C9A | 125.3 (3) | C14B—C13B—H13E | 108.6 |
C1B—C2B—C3B | 105.7 (3) | H13D—C13B—H13E | 107.5 |
C1B—C2B—C9B | 129.9 (3) | N3A—C14A—C13A | 113.3 (3) |
C3B—C2B—C9B | 124.4 (3) | N3A—C14A—C15A | 101.0 (3) |
C4A—C3A—C8A | 119.4 (3) | C13A—C14A—C15A | 111.2 (3) |
C4A—C3A—C2A | 133.2 (3) | N3A—C14A—H14A | 110.3 |
C8A—C3A—C2A | 107.4 (3) | C13A—C14A—H14A | 110.3 |
C4B—C3B—C8B | 120.2 (3) | C15A—C14A—H14A | 110.3 |
C4B—C3B—C2B | 132.5 (3) | N3B—C14B—C13B | 114.0 (3) |
C8B—C3B—C2B | 107.3 (3) | N3B—C14B—C15B | 100.5 (3) |
C5A—C4A—C3A | 120.3 (3) | C13B—C14B—C15B | 112.2 (3) |
C5A—C4A—H4A | 119.8 | N3B—C14B—H14D | 109.9 |
C3A—C4A—H4A | 119.8 | C13B—C14B—H14D | 109.9 |
C5B—C4B—C3B | 119.5 (3) | C15B—C14B—H14D | 109.9 |
C5B—C4B—H4D | 120.3 | O1A—C15A—C14A | 105.8 (3) |
C3B—C4B—H4D | 120.3 | O1A—C15A—H15A | 110.6 |
C4A—C5A—C6A | 118.7 (3) | C14A—C15A—H15A | 110.6 |
C4A—C5A—C13A | 119.4 (3) | O1A—C15A—H15B | 110.6 |
C6A—C5A—C13A | 121.9 (3) | C14A—C15A—H15B | 110.6 |
C4B—C5B—C6B | 119.3 (3) | H15A—C15A—H15B | 108.7 |
C4B—C5B—C13B | 119.2 (3) | O1B—C15B—C14B | 105.3 (3) |
C6B—C5B—C13B | 121.5 (3) | O1B—C15B—H15D | 110.7 |
C7A—C6A—C5A | 122.7 (3) | C14B—C15B—H15D | 110.7 |
C7A—C6A—H6A | 118.6 | O1B—C15B—H15E | 110.7 |
C5A—C6A—H6A | 118.6 | C14B—C15B—H15E | 110.7 |
C7B—C6B—C5B | 122.1 (3) | H15D—C15B—H15E | 108.8 |
C7B—C6B—H6D | 119.0 | O2A—C16A—N3A | 129.1 (4) |
C5B—C6B—H6D | 119.0 | O2A—C16A—O1A | 120.7 (3) |
C6A—C7A—C8A | 117.7 (3) | N3A—C16A—O1A | 110.2 (3) |
C6A—C7A—H7A | 121.1 | O2B—C16B—N3B | 128.6 (3) |
C8A—C7A—H7A | 121.1 | O2B—C16B—O1B | 120.9 (3) |
C6B—C7B—C8B | 118.2 (3) | N3B—C16B—O1B | 110.5 (3) |
C6B—C7B—H7D | 120.9 | C1A—N1A—C8A | 109.1 (3) |
C8B—C7B—H7D | 120.9 | C1A—N1A—H1AN | 129 (3) |
N1A—C8A—C3A | 107.6 (3) | C8A—N1A—H1AN | 122 (3) |
N1A—C8A—C7A | 131.2 (3) | C8B—N1B—C1B | 108.9 (3) |
C3A—C8A—C7A | 121.1 (3) | C8B—N1B—H1BN | 119 (3) |
N1B—C8B—C7B | 131.2 (3) | C1B—N1B—H1BN | 132 (3) |
N1B—C8B—C3B | 108.0 (3) | C11A—N2A—C10A | 109.6 (3) |
C7B—C8B—C3B | 120.8 (3) | C11A—N2A—C12A | 109.2 (3) |
C2A—C9A—C10A | 113.7 (3) | C10A—N2A—C12A | 111.1 (3) |
C2A—C9A—H9A | 108.8 | C12B—N2B—C11B | 109.2 (3) |
C10A—C9A—H9A | 108.8 | C12B—N2B—C10B | 111.6 (3) |
C2A—C9A—H9B | 108.8 | C11B—N2B—C10B | 109.1 (3) |
C10A—C9A—H9B | 108.8 | C16A—N3A—C14A | 113.5 (3) |
H9A—C9A—H9B | 107.7 | C16A—N3A—H3AN | 117 (3) |
C2B—C9B—C10B | 114.4 (3) | C14A—N3A—H3AN | 130 (3) |
C2B—C9B—H9D | 108.7 | C16B—N3B—C14B | 113.2 (3) |
C10B—C9B—H9D | 108.7 | C16B—N3B—H3BN | 117 (3) |
C2B—C9B—H9E | 108.7 | C14B—N3B—H3BN | 128 (3) |
C10B—C9B—H9E | 108.7 | C16A—O1A—C15A | 109.3 (3) |
H9D—C9B—H9E | 107.6 | C16B—O1B—C15B | 110.1 (3) |
N2A—C10A—C9A | 113.6 (3) | C18A—C17A—O3A | 118.5 (6) |
N2A—C10A—H10A | 108.8 | C18A—C17A—C22A | 119.7 (6) |
C9A—C10A—H10A | 108.8 | O3A—C17A—C22A | 121.8 (5) |
N2A—C10A—H10B | 108.8 | C19A—C18A—C17A | 121.4 (7) |
C9A—C10A—H10B | 108.8 | C19A—C18A—H18A | 119.3 |
H10A—C10A—H10B | 107.7 | C17A—C18A—H18A | 119.3 |
N2B—C10B—C9B | 113.5 (3) | C18A—C19A—C20A | 121.6 (6) |
N2B—C10B—H10D | 108.9 | C18A—C19A—H19A | 119.2 |
C9B—C10B—H10D | 108.9 | C20A—C19A—H19A | 119.2 |
N2B—C10B—H10E | 108.9 | C19A—C20A—C21A | 118.3 (7) |
C9B—C10B—H10E | 108.9 | C19A—C20A—H20A | 120.8 |
H10D—C10B—H10E | 107.7 | C21A—C20A—H20A | 120.8 |
N2A—C11A—H11A | 109.5 | C22A—C21A—C20A | 120.2 (7) |
N2A—C11A—H11B | 109.5 | C22A—C21A—H21A | 119.9 |
H11A—C11A—H11B | 109.5 | C20A—C21A—H21A | 119.9 |
N2A—C11A—H11C | 109.5 | C21A—C22A—C17A | 118.8 (6) |
H11A—C11A—H11C | 109.5 | C21A—C22A—H22A | 120.6 |
H11B—C11A—H11C | 109.5 | C17A—C22A—H22A | 120.6 |
N2B—C11B—H11D | 109.5 | C17A—O3A—H3A | 91 (6) |
N2B—C11B—H11E | 109.5 | O3B—C17B—C18B | 123.8 (5) |
H11D—C11B—H11E | 109.5 | O3B—C17B—C22B | 116.1 (6) |
N2B—C11B—H11F | 109.5 | C18B—C17B—C22B | 120.1 (5) |
H11D—C11B—H11F | 109.5 | C17B—C18B—C19B | 118.5 (6) |
H11E—C11B—H11F | 109.5 | C17B—C18B—H18D | 120.7 |
N2A—C12A—H12A | 109.5 | C19B—C18B—H18D | 120.7 |
N2A—C12A—H12B | 109.5 | C20B—C19B—C18B | 121.8 (8) |
H12A—C12A—H12B | 109.5 | C20B—C19B—H19D | 119.1 |
N2A—C12A—H12C | 109.5 | C18B—C19B—H19D | 119.1 |
H12A—C12A—H12C | 109.5 | C21B—C20B—C19B | 116.8 (7) |
H12B—C12A—H12C | 109.5 | C21B—C20B—H20D | 121.6 |
N2B—C12B—H12D | 109.5 | C19B—C20B—H20D | 121.6 |
N2B—C12B—H12E | 109.5 | C20B—C21B—C22B | 124.6 (8) |
H12D—C12B—H12E | 109.5 | C20B—C21B—H21D | 117.7 |
N2B—C12B—H12F | 109.5 | C22B—C21B—H21D | 117.7 |
H12D—C12B—H12F | 109.5 | C21B—C22B—C17B | 117.9 (7) |
H12E—C12B—H12F | 109.5 | C21B—C22B—H22D | 121.1 |
C5A—C13A—C14A | 114.8 (3) | C17B—C22B—H22D | 121.1 |
C5A—C13A—H13A | 108.6 | C17B—O3B—H5D | 118 (7) |
| | | |
N1A—C1A—C2A—C3A | −0.2 (4) | C5A—C13A—C14A—N3A | −60.0 (4) |
N1A—C1A—C2A—C9A | 179.8 (4) | C5A—C13A—C14A—C15A | −172.9 (3) |
N1B—C1B—C2B—C3B | −0.2 (4) | C5B—C13B—C14B—N3B | −57.0 (4) |
N1B—C1B—C2B—C9B | 179.6 (4) | C5B—C13B—C14B—C15B | −170.5 (3) |
C1A—C2A—C3A—C4A | 179.2 (3) | N3A—C14A—C15A—O1A | −4.0 (4) |
C9A—C2A—C3A—C4A | −0.8 (6) | C13A—C14A—C15A—O1A | 116.5 (3) |
C1A—C2A—C3A—C8A | 0.5 (4) | N3B—C14B—C15B—O1B | −5.7 (4) |
C9A—C2A—C3A—C8A | −179.5 (3) | C13B—C14B—C15B—O1B | 115.8 (3) |
C1B—C2B—C3B—C4B | 179.0 (4) | C2A—C1A—N1A—C8A | −0.1 (4) |
C9B—C2B—C3B—C4B | −0.7 (6) | C3A—C8A—N1A—C1A | 0.4 (4) |
C1B—C2B—C3B—C8B | 0.2 (4) | C7A—C8A—N1A—C1A | −178.2 (3) |
C9B—C2B—C3B—C8B | −179.5 (3) | C7B—C8B—N1B—C1B | −178.7 (4) |
C8A—C3A—C4A—C5A | 1.8 (5) | C3B—C8B—N1B—C1B | 0.1 (4) |
C2A—C3A—C4A—C5A | −176.8 (3) | C2B—C1B—N1B—C8B | 0.0 (4) |
C8B—C3B—C4B—C5B | 1.2 (5) | C9A—C10A—N2A—C11A | 173.9 (3) |
C2B—C3B—C4B—C5B | −177.5 (3) | C9A—C10A—N2A—C12A | −65.3 (4) |
C3A—C4A—C5A—C6A | −1.3 (5) | C9B—C10B—N2B—C12B | −67.8 (4) |
C3A—C4A—C5A—C13A | 176.9 (3) | C9B—C10B—N2B—C11B | 171.5 (3) |
C3B—C4B—C5B—C6B | −1.4 (5) | O2A—C16A—N3A—C14A | −178.8 (4) |
C3B—C4B—C5B—C13B | 177.9 (3) | O1A—C16A—N3A—C14A | 0.4 (5) |
C4A—C5A—C6A—C7A | −0.4 (5) | C13A—C14A—N3A—C16A | −116.6 (4) |
C13A—C5A—C6A—C7A | −178.5 (3) | C15A—C14A—N3A—C16A | 2.4 (4) |
C4B—C5B—C6B—C7B | 0.6 (5) | O2B—C16B—N3B—C14B | 177.0 (3) |
C13B—C5B—C6B—C7B | −178.7 (3) | O1B—C16B—N3B—C14B | −2.5 (4) |
C5A—C6A—C7A—C8A | 1.5 (5) | C13B—C14B—N3B—C16B | −115.2 (3) |
C5B—C6B—C7B—C8B | 0.4 (5) | C15B—C14B—N3B—C16B | 5.1 (4) |
C4A—C3A—C8A—N1A | −179.5 (3) | O2A—C16A—O1A—C15A | 176.1 (4) |
C2A—C3A—C8A—N1A | −0.6 (4) | N3A—C16A—O1A—C15A | −3.2 (4) |
C4A—C3A—C8A—C7A | −0.7 (5) | C14A—C15A—O1A—C16A | 4.6 (4) |
C2A—C3A—C8A—C7A | 178.2 (3) | O2B—C16B—O1B—C15B | 178.7 (3) |
C6A—C7A—C8A—N1A | 177.5 (3) | N3B—C16B—O1B—C15B | −1.7 (4) |
C6A—C7A—C8A—C3A | −1.0 (5) | C14B—C15B—O1B—C16B | 4.8 (4) |
C6B—C7B—C8B—N1B | 178.2 (4) | O3A—C17A—C18A—C19A | −178.2 (5) |
C6B—C7B—C8B—C3B | −0.6 (5) | C22A—C17A—C18A—C19A | 0.7 (8) |
C4B—C3B—C8B—N1B | −179.2 (3) | C17A—C18A—C19A—C20A | −1.8 (9) |
C2B—C3B—C8B—N1B | −0.2 (4) | C18A—C19A—C20A—C21A | 2.4 (9) |
C4B—C3B—C8B—C7B | −0.2 (5) | C19A—C20A—C21A—C22A | −2.0 (9) |
C2B—C3B—C8B—C7B | 178.8 (3) | C20A—C21A—C22A—C17A | 0.9 (8) |
C1A—C2A—C9A—C10A | −10.7 (6) | C18A—C17A—C22A—C21A | −0.3 (7) |
C3A—C2A—C9A—C10A | 169.3 (3) | O3A—C17A—C22A—C21A | 178.6 (5) |
C1B—C2B—C9B—C10B | −4.2 (6) | O3B—C17B—C18B—C19B | −179.9 (5) |
C3B—C2B—C9B—C10B | 175.5 (3) | C22B—C17B—C18B—C19B | 1.0 (8) |
C2A—C9A—C10A—N2A | 178.2 (3) | C17B—C18B—C19B—C20B | 2.3 (9) |
C2B—C9B—C10B—N2B | 175.3 (3) | C18B—C19B—C20B—C21B | −5.3 (11) |
C4A—C5A—C13A—C14A | 122.3 (4) | C19B—C20B—C21B—C22B | 5.4 (12) |
C6A—C5A—C13A—C14A | −59.6 (5) | C20B—C21B—C22B—C17B | −2.2 (10) |
C4B—C5B—C13B—C14B | 119.6 (3) | O3B—C17B—C22B—C21B | 179.7 (5) |
C6B—C5B—C13B—C14B | −61.2 (4) | C18B—C17B—C22B—C21B | −1.1 (8) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1BN···O2Bi | 0.83 (4) | 2.26 (4) | 3.050 (4) | 159 (4) |
N3A—H3AN···N2Aii | 0.84 (4) | 2.17 (4) | 2.975 (4) | 162 (3) |
N3B—H3BN···N2Bii | 0.79 (4) | 2.14 (5) | 2.912 (4) | 169 (4) |
N1A—H1AN···O2Aiii | 0.89 (5) | 2.02 (5) | 2.902 (4) | 166 (4) |
C15A—H15A···O2Bi | 0.97 | 2.59 | 3.403 (5) | 142 |
O3A—H3A···O3B | 0.87 (6) | 2.05 (7) | 2.760 (6) | 137 (9) |
O3B—H5D···O2B | 0.87 (5) | 1.92 (4) | 2.758 (5) | 162 (10) |
C1A—H1A···Cg1iv | 0.93 | 2.81 | 3.683 | 156 |
C1B—H1D···Cg2v | 0.93 | 2.86 | 3.747 | 160 |
C11A—H11C···Cg3ii | 0.96 | 2.80 | 3.648 | 148 |
C11B—H11F···Cg3ii | 0.96 | 2.92 | 3.733 | 143 |
C13B—H13D···Cg4vi | 0.97 | 2.81 | 3.666 | 148 |
Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+2; (iv) x+1, y, z−1; (v) −x+1, y−1/2, −z+1; (vi) x−1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C16H21N3O2·C6H6 | C16H21N3O2·C6H6O |
Mr | 365.47 | 381.47 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21 |
Temperature (K) | 273 | 293 |
a, b, c (Å) | 8.6938 (5), 12.1331 (7), 19.5321 (12) | 8.7618 (13), 19.506 (3), 12.1767 (18) |
α, β, γ (°) | 90, 90, 90 | 90, 91.399 (2), 90 |
V (Å3) | 2060.3 (2) | 2080.5 (5) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.22 × 0.17 × 0.15 | 0.22 × 0.18 × 0.16 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15000, 2097, 1995 | 19466, 3780, 3521 |
Rint | 0.020 | 0.036 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.113, 1.29 | 0.047, 0.137, 1.19 |
No. of reflections | 2097 | 3780 |
No. of parameters | 254 | 530 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.20 | 0.23, −0.17 |
Selected geometric parameters (Å, º) for (I) topC1—N1 | 1.374 (3) | C14—N3 | 1.445 (3) |
C8—N1 | 1.366 (3) | C16—O2 | 1.213 (3) |
C10—N2 | 1.458 (3) | C16—N3 | 1.321 (3) |
C12—N2 | 1.462 (3) | C16—O1 | 1.348 (3) |
| | | |
N3—C14—C13 | 113.5 (2) | C11—N2—C10 | 109.56 (19) |
O2—C16—O1 | 120.80 (19) | C11—N2—C12 | 109.3 (2) |
C8—N1—C1 | 108.97 (18) | | |
| | | |
C13—C5—C6—C7 | −178.6 (2) | C4—C5—C13—C14 | 120.8 (2) |
C1—C2—C9—C10 | −6.7 (4) | C13—C14—C15—O1 | 117.2 (2) |
C2—C9—C10—N2 | 177.3 (2) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.93 (3) | 1.99 (3) | 2.898 (3) | 165 (2) |
N3—H3N···N2ii | 0.84 (3) | 2.10 (3) | 2.933 (3) | 171 (3) |
C15—H15A···O2iii | 0.97 | 2.58 | 3.269 (3) | 127.9 |
C1—H1···Cg1iv | 0.93 | 2.88 | 3.768 | 159 |
C11—H11A···Cg2v | 0.96 | 2.83 | 3.658 | 145 |
C13—H13B···Cg3vi | 0.96 | 2.87 | 3.699 | 144 |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) x−1, y, z; (iii) −x, y+1/2, −z+1/2; (iv) −x, y+1/2, −z+3/2; (v) x+1, y, z; (vi) −x−1, y−1/2, −z+3/2. |
Selected geometric parameters (Å, º) for (II) topC1A—N1A | 1.370 (5) | C14A—N3A | 1.432 (5) |
C1B—N1B | 1.379 (5) | C14B—N3B | 1.444 (5) |
C8A—N1A | 1.368 (5) | C16A—O2A | 1.217 (5) |
C8B—N1B | 1.367 (5) | C16A—N3A | 1.329 (5) |
C10A—N2A | 1.473 (4) | C16A—O1A | 1.350 (4) |
C10B—N2B | 1.467 (4) | C16B—O2B | 1.220 (4) |
C12A—N2A | 1.476 (5) | C16B—N3B | 1.327 (5) |
C12B—N2B | 1.458 (5) | C16B—O1B | 1.345 (4) |
| | | |
N3A—C14A—C13A | 113.3 (3) | C8B—N1B—C1B | 108.9 (3) |
N3B—C14B—C13B | 114.0 (3) | C11A—N2A—C10A | 109.6 (3) |
O2A—C16A—O1A | 120.7 (3) | C11A—N2A—C12A | 109.2 (3) |
O2B—C16B—O1B | 120.9 (3) | C12B—N2B—C11B | 109.2 (3) |
C1A—N1A—C8A | 109.1 (3) | C11B—N2B—C10B | 109.1 (3) |
| | | |
C13A—C5A—C6A—C7A | −178.5 (3) | C2B—C9B—C10B—N2B | 175.3 (3) |
C13B—C5B—C6B—C7B | −178.7 (3) | C4A—C5A—C13A—C14A | 122.3 (4) |
C1A—C2A—C9A—C10A | −10.7 (6) | C13A—C14A—C15A—O1A | 116.5 (3) |
C1B—C2B—C9B—C10B | −4.2 (6) | C13B—C14B—C15B—O1B | 115.8 (3) |
C2A—C9A—C10A—N2A | 178.2 (3) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1BN···O2Bi | 0.83 (4) | 2.26 (4) | 3.050 (4) | 159 (4) |
N3A—H3AN···N2Aii | 0.84 (4) | 2.17 (4) | 2.975 (4) | 162 (3) |
N3B—H3BN···N2Bii | 0.79 (4) | 2.14 (5) | 2.912 (4) | 169 (4) |
N1A—H1AN···O2Aiii | 0.89 (5) | 2.02 (5) | 2.902 (4) | 166 (4) |
C15A—H15A···O2Bi | 0.97 | 2.59 | 3.403 (5) | 141.6 |
O3A—H3A···O3B | 0.87 (6) | 2.05 (7) | 2.760 (6) | 137 (9) |
O3B—H5D···O2B | 0.87 (5) | 1.92 (4) | 2.758 (5) | 162 (10) |
C1A—H1A···Cg1iv | 0.93 | 2.81 | 3.683 | 156 |
C1B—H1D···Cg2v | 0.93 | 2.86 | 3.747 | 160 |
C11A—H11C···Cg3ii | 0.96 | 2.80 | 3.648 | 148 |
C11B—H11F···Cg3ii | 0.96 | 2.92 | 3.733 | 143 |
C13B—H13D···Cg4vi | 0.97 | 2.81 | 3.666 | 148 |
Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+2; (iv) x+1, y, z−1; (v) −x+1, y−1/2, −z+1; (vi) x−1, y, z. |
Zolmitriptan is an effective drug for the treatment of migraine headaches, which are believed to result from dilation of the blood vessels in the brain. The structure and its mechanism of action are comparable to that of sumatriptan (Ravikumar et al., 2004). We have previously published the crystal structure of zolmitriptan (Ravikumar et al., 2007) and its chloroform solvate (Sridhar et al., 2007). In an attempt to understand the effect on drug polymorphism in the light of host–guest structural mechanisms, we crystallized two inclusion compounds and their crystal structures are presented here.
The molecule of zolmitriptan consists of three linked residues, viz. a planar indole ring system, an ethylamine side chain and an oxazolidinone unit. Compound (I) contains molecules of zolmitriptan (host) and benzene (guest) (Fig. 1). Compound (II) consists of two independent molecules (A and B) of zolmitriptan (host) and phenol (guest) (1:1) in the asymmetric unit (Fig. 2). In both structures, the host molecule aquires an L-shaped conformation, with the oxazolidinone ring occupying the base and the rest of the molecule forming the upright section. In contrast, some relatively large conformational differences [in compounds (I) and (II) {unclear whether (I) and (II) are different from each other AND from the parent, or if (I) and (II) are similar to each other but both are different from the parent}] are observed in both the side chains, when compared with the parent (pure) zolmitriptan and its chloroform solvate. Interestingly, the indole ring system remains planar in all the structures. Another noteworthy point is that the oxazolidinone ring in the present structures is almost planar, unlike in the parent molecule and its chloroform solvate, where the ring takes a twist conformation. Furthermore, the orientation of the oxazolidinone side chain is synclinical with respect to the indole ring system in (I) and (II) (Tables 1 and 3), whereas, in pure zolmitriptan, the value deviates significantly [C4—C5—C13—C14 = 95.6 (3)°]. The ethylamine side chain of the host molecule has an extended conformation in both compounds (I) and (II). This can be seen clearly in terms of their C2—C9—C10—N2 torsion angle (Tables 1 and 3). In (I), with respect to the indole ring system, the planes of the ethylamine and the oxazolidinone ring, make dihedral angles of 53.7 (1) and 64.4 (1)°, respectively [54.0 (1) and 64.8 (1) for molecule A of (II), and 54.0 (1) and 62.8 (1)° for molecule B]. Similarly, the dihedral angle between the planes of the oxazolidinone ring and the ethylamine moiety is 74.4 (1)° (75.9 (1) and 74.4 (1)° respectively for compound (II)). Again, these values are predominantly different from the pure zolmitriptan (30.0 (1)°). This significant conformational change could be attributed to the guest molecules present in the respective compounds. An overlay fitting of the indole ring system of compounds (I) and (II) along with pure zolmitriptan and its chloroform solvate is shown in Fig. 3.
In both the structures, oxazolidinone atom N3 acts as a hydrogen-bond donor to ethylamine atom N2 (Tables 2 and 4), so forming continuous screw-symmetric helical chains of C11 type (Bernstein et al., 1995) along the a axis (Figs. 4 and 5). In (I), these chains are further connected into R44(33) rings through N—H···O and C—H···O hydrogen bonds along the c axis, forming a supramolecular network (Fig. 4). The guest benzene molecules are involved in C—H···π interactions with the indole ring system of the host molecules (Table 2). In (II), within the asymmetric unit, atom O3A of the guest phenol molecule A acts as a hydrogen-bond donor, via H3A, to hydroxy atom O3B of phenol molecule B, and the pendent guest molecules are linked to the ketone atom O2B of the host molecule B via atom H3C (Table 4). In (II), these A and B chains are further interconnected via N—H···O and C—H···O interactions. The combination of these two independent molecules (A and B) then generates two-dimensional edge-fused R46 (38) rings. This two-dimensional supramolecular network is further strengthened by extensive C—H···π interactions (Table 4). The centroids of the guest molecules (C17–C22 of A/B) lie 2.81 and 2.86 Å, respectively, from the H atoms of the pyrrole rings of the indole ring systems (H1A and H1D). These values agree well with those expected for typical C—H···π interactions (Guo et al., 2005; Huang et al., 2001), demonstrating C—H···π interactions in the inclusion compound. The C—H···π interaction in (I) and (II) are rather weak; however, they play a significant role in maintaining the conformational changes in the host molecules.
In conclusion, zolmitriptan produces inclusion compounds when it crystallizes from chloroform (Sridhar et al., 2007), benzene and phenol (the present work), whereas crystallization from methanol (Ravikumar et al., 2007), which presumably is not a preferred guest, does not produce an inclusion compound.