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The structures of two potential anti-human immunodeficiency virus type 1 (HIV-1) non-nucleoside reverse transcriptase inhibitors (NNRTI), namely 1-benzyl-5-oxo-2-phenyl­pyrrolidine-2-carbox­amide, C18H18N2O2, (III), and 2-(4-isopropoxy­phenyl)-5-oxo-1-(4-tolyl)­pyrrolidine-2-carbo­nitrile, C21H22N2O2, (IV), have been investigated by X-ray diffraction, confirming the butterfly-like conformation of both compounds. The pyrrolidine ring is in an envelope conformation in (III) and a half-chair conformation in (IV). Two intermolecular N—H...O hydrogen bonds are present in the crystal structure of (III), with N...O distances of 2.995 (2) and 2.927 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102009241/gg1112sup1.cif
Contains datablocks global, III, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009241/gg1112IIIsup2.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009241/gg1112IVsup3.hkl
Contains datablock IV

CCDC references: 192978; 192979

Comment top

In the last few years, interest in non-nucleoside reverse transcriptase inhibitors (NNRTIs) has expanded, primarily because of their anti-HIV-1 activity. One of the best representatives of this class of compounds is loviride, (I) (Pauvels et al., 1993). The common structural feature of these compounds is their butterfly-like conformation, and the molecular structure consists of a hydrophilic (`body') and two hydrophobic (`wing') moieties. According to the literature, the anti-HIV-1 activity of the compounds depends on the conformational rigidity and on the orientation of the wings relative to the body (De Clercq, 1996).

The inclusion of a pyrrolidine ring into the structure of loviride might increase the conformational rigidity. For this reason, a new method of synthesis of 1,2-substituted derivatives of 5-oxo-2-pyrrolidine carboxylic acid, (II), has been developed (Martirosyan et al., 2000). Using this method, 1-benzyl-5-oxo-2-phenylpyrrolidine-2-carboxamide, (III), and 2-(4-isopropoxyphenyl)-5-oxo-1-(4-tolyl)pyrrolidine-2-carbonitrile, (IV), were synthesized as racemic mixtures, since (III) and (IV) contain structural fragments from loviride, (I). \sch

Views of molecules (III) and (IV), with the atomic numbering schemes, are depicted in Figs. 1 and 2, respectively. In the crystal structure of (III), two neighbouring asymmetric molecules of (III) are related by an inversion centre and connected into a dimer via double hydrogen bonding through the amide groups (Fig. 3). Just one of H atoms of the amide (H8A) of each molecule takes part in this double hydrogen bonding, leading to the formation of dimers with graph set R22(8). The dimers are connected into a chain through hydrogen bonding between the other H atom of the amide (H8B) and the O atom (O22) of the carbonyl group of the pyrrolidine ring (Fig. 3). The geometry of the hydrogen bonds is listed in Table 1. A weaker interaction, C5—H5A···O7, is also present; details are also given in Table 1.

In contrast with (III), compound (IV) does not have active H atoms such as NH2, and for this reason, no strong hydrogen bonding is observed in the crystal structure, apart from two C—H···N/O interactions involving atoms N7 and O8. Nevertheless, (IV) also crystallizes in a centrosymmetric space group.

As mentioned previously, the anti-HIV-1 activity of the compounds under investigation depends on the orientational relationship between the wings and the body of the butterfly-like structures. These relationships may be described by the dihedral angles between the aryl groups (wing planes W1 and W2 in the Scheme) and the pyrrolidine ring (part of the body, plane B in the Scheme). The dihedral angles W1/W2, B/W1 and B/W2 are 62.62 (8), 79.27 (6) and 68.45 (9)°, respectively, for (III), and 73.85 (13), 87.90 (13) and 73.06 (13)°, respectively, for (IV).

In the structures of (III) and (IV), the conformation of the pyrrolidine ring is markedly different, having an envelope conformation in (III) and a half-chair conformation in (IV). This difference in conformation may play an essential role in the orientation of the wings and body.

Experimental top

The title compounds were synthesized as described by Martirosyan et al. (2000). Recrystallization from ethanol afforded colourless crystals suitable for X-ray analysis.

Refinement top

Both molecules (III) and (IV) crystallized in the monoclinic system. The space groups determined from the systematic absences were both P21/c. The positional and isotropic displacement parameters of all H atoms were refined independently, apart from the methyl H atoms on C15, C24 and C25 in (IV), which were treated as riding, with C—H = 0.96 Å. Is this added text OK?

Computing details top

For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1988); cell refinement: SETANG in CAD-4 Software; data reduction: local program; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (III) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
[Figure 2] Fig. 2. A view of (IV) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
[Figure 3] Fig. 3. The connection of molecules of (III) into dimers and chains [symmetry codes: (i) 1 + x, 1/2 - y, z - 1/2; (ii) -x, 1/2 + y, 3/2 - z; (iii) -1 - x, 1 - y, 1 - z].
(III) 1-benzyl-5-oxo-2-phenylpyrrolidine-2-carboxamide top
Crystal data top
C18H18N2O2F(000) = 624
Mr = 294.34Dx = 1.289 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 11.959 (2) Åθ = 14.3–15.9°
b = 10.303 (2) ŵ = 0.09 mm1
c = 21.489 (4) ÅT = 293 K
β = 145.05 (3)°Prism, colourless
V = 1516.7 (12) Å30.25 × 0.15 × 0.10 mm
Z = 4
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.025
Radiation source: fine-focus sealed tubeθmax = 30.0°, θmin = 1.9°
Graphite monochromatorh = 016
ω/2θ scansk = 014
4601 measured reflectionsl = 3017
4411 independent reflections3 standard reflections every 60 min
2559 reflections with I > 2σ(I) intensity decay: variation +1.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048All H-atom parameters refined
wR(F2) = 0.121 w = 1/[σ2(Fo2) + (0.0453P)2 + 0.4186P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
4411 reflectionsΔρmax = 0.20 e Å3
272 parametersΔρmin = 0.16 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraintsExtinction coefficient: 0.0150 (17)
Primary atom site location: structure-invariant direct methods
Crystal data top
C18H18N2O2V = 1516.7 (12) Å3
Mr = 294.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.959 (2) ŵ = 0.09 mm1
b = 10.303 (2) ÅT = 293 K
c = 21.489 (4) Å0.25 × 0.15 × 0.10 mm
β = 145.05 (3)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.025
4601 measured reflections3 standard reflections every 60 min
4411 independent reflections intensity decay: variation +1.0%
2559 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.121All H-atom parameters refined
S = 1.01Δρmax = 0.20 e Å3
4411 reflectionsΔρmin = 0.16 e Å3
272 parameters
Special details top

Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 9.7401(0.0072)x + 5.8400(0.0067)y + 15.8704(0.0131)z = 15.0765(0.0089)

* 0.0016 (0.0011) C16 * -0.0023 (0.0012) C17 * 0.0022 (0.0013) C18 * -0.0013 (0.0014) C19 * 0.0007 (0.0013) C20 * -0.0008 (0.0012) C21

Rms deviation of fitted atoms = 0.0016

-1.9925(0.0082)x + 3.8377(0.0075)y + 14.1729 (0.0134)z = 10.7279(0.0073)

Angle to previous plane (with approximate e.s.d.) = 62.62 (0.07)

* 0.0023 (0.0011) C10 * -0.0002 (0.0012) C11 * -0.0025 (0.0013) C12 * 0.0031 (0.0013) C13 * -0.0010 (0.0013) C14 * -0.0017 (0.0012) C15

Rms deviation of fitted atoms = 0.0021

- 8.5711(0.0090)x - 6.6200(0.0078)y + 9.2876(0.0194)z = 2.1794(0.0156)

Angle to previous plane (with approximate e.s.d.) = 68.45 (0.10)

* 0.1188 (0.0010) C1 * -0.1036 (0.0010) N2 * 0.0371 (0.0011) C3 * 0.0442 (0.0012) C4 * -0.0965 (0.0013) C5

Rms deviation of fitted atoms = 0.0866

- 9.7401(0.0072)x + 5.8400(0.0067)y + 15.8704(0.0131)z = 15.0765(0.0089)

Angle to previous plane (with approximate e.s.d.) = 79.28 (0.06)

* 0.0016 (0.0011) C16 * -0.0023 (0.0012) C17 * 0.0022 (0.0013) C18 * -0.0013 (0.0014) C19 * 0.0007 (0.0013) C20 * -0.0008 (0.0012) C21

Rms deviation of fitted atoms = 0.0016

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.0371 (2)0.65500 (14)0.68005 (11)0.0357 (3)
N20.08982 (17)0.56065 (12)0.70601 (10)0.0386 (3)
C30.2231 (2)0.50549 (16)0.80483 (12)0.0408 (4)
C40.2324 (3)0.5814 (2)0.86831 (15)0.0549 (5)
H4B0.357 (4)0.612 (2)0.935 (2)0.102 (8)*
H4A0.197 (4)0.523 (2)0.887 (2)0.097 (8)*
C50.0860 (3)0.68926 (18)0.79491 (14)0.0515 (4)
H5B0.006 (3)0.7011 (19)0.7938 (16)0.070 (6)*
H5A0.155 (3)0.769 (2)0.8207 (18)0.082 (7)*
C60.2286 (2)0.58553 (15)0.61218 (13)0.0396 (3)
O70.26259 (17)0.47483 (10)0.57911 (10)0.0528 (3)
N80.3505 (2)0.65171 (15)0.59320 (14)0.0508 (4)
H8B0.326 (3)0.730 (2)0.6158 (15)0.054 (5)*
H8A0.467 (3)0.6151 (18)0.5468 (15)0.056 (5)*
C90.0408 (2)0.50055 (17)0.62371 (13)0.0434 (4)
H9B0.083 (3)0.5341 (16)0.5548 (14)0.045 (4)*
H9A0.028 (2)0.4055 (17)0.6265 (13)0.046 (5)*
C100.1896 (2)0.52620 (15)0.64126 (11)0.0412 (4)
C110.1923 (3)0.64239 (18)0.61001 (14)0.0509 (4)
H110.101 (3)0.7103 (18)0.5776 (14)0.053 (5)*
C120.3257 (3)0.6624 (2)0.62318 (16)0.0597 (5)
H120.324 (3)0.741 (2)0.5997 (16)0.070 (6)*
C130.4573 (3)0.5671 (2)0.66788 (15)0.0602 (5)
H130.547 (3)0.580 (2)0.6749 (18)0.079 (7)*
C140.4558 (3)0.4515 (2)0.69869 (15)0.0569 (5)
H140.544 (3)0.3792 (19)0.7272 (15)0.062 (5)*
C150.3229 (2)0.43054 (18)0.68562 (14)0.0487 (4)
H150.316 (2)0.3487 (18)0.7048 (14)0.050 (5)*
C160.0823 (2)0.76929 (14)0.61646 (12)0.0355 (3)
C170.2595 (2)0.77757 (17)0.50444 (13)0.0447 (4)
H170.363 (3)0.7138 (18)0.4652 (15)0.057 (5)*
C180.2962 (3)0.87665 (19)0.44572 (17)0.0581 (5)
H180.418 (3)0.880 (2)0.3696 (19)0.079 (7)*
C190.1562 (3)0.96808 (19)0.49780 (18)0.0604 (5)
H190.186 (3)1.038 (2)0.4551 (17)0.077 (6)*
C200.0197 (3)0.96190 (18)0.60813 (19)0.0591 (5)
H200.122 (3)1.026 (2)0.6472 (17)0.078 (6)*
C210.0576 (3)0.86323 (16)0.66764 (15)0.0486 (4)
H210.182 (2)0.8586 (16)0.7458 (14)0.046 (5)*
O220.31807 (18)0.40861 (12)0.83481 (10)0.0567 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0360 (7)0.0325 (7)0.0326 (7)0.0002 (6)0.0269 (7)0.0005 (6)
N20.0336 (6)0.0361 (7)0.0307 (6)0.0033 (5)0.0234 (6)0.0010 (5)
C30.0307 (7)0.0425 (8)0.0366 (7)0.0023 (7)0.0250 (7)0.0067 (7)
C40.0472 (10)0.0718 (12)0.0384 (9)0.0024 (9)0.0336 (9)0.0072 (9)
C50.0593 (11)0.0464 (10)0.0391 (9)0.0028 (9)0.0384 (9)0.0039 (8)
C60.0453 (8)0.0337 (7)0.0437 (8)0.0009 (7)0.0372 (8)0.0018 (6)
O70.0538 (7)0.0341 (6)0.0694 (8)0.0068 (5)0.0503 (7)0.0080 (5)
N80.0534 (9)0.0416 (8)0.0700 (10)0.0106 (7)0.0531 (9)0.0126 (7)
C90.0352 (8)0.0416 (9)0.0347 (8)0.0015 (7)0.0249 (7)0.0050 (7)
C100.0336 (7)0.0440 (9)0.0302 (7)0.0010 (6)0.0230 (7)0.0075 (6)
C110.0529 (10)0.0452 (9)0.0475 (10)0.0034 (8)0.0397 (9)0.0021 (8)
C120.0644 (12)0.0597 (12)0.0523 (11)0.0098 (10)0.0473 (11)0.0075 (10)
C130.0470 (10)0.0851 (15)0.0454 (10)0.0071 (10)0.0373 (9)0.0098 (10)
C140.0433 (9)0.0738 (13)0.0462 (10)0.0095 (9)0.0352 (9)0.0002 (9)
C150.0425 (9)0.0499 (10)0.0419 (9)0.0060 (8)0.0323 (8)0.0011 (8)
C160.0356 (7)0.0326 (7)0.0386 (8)0.0013 (6)0.0305 (7)0.0004 (6)
C170.0415 (9)0.0466 (9)0.0382 (8)0.0015 (7)0.0311 (8)0.0014 (7)
C180.0585 (11)0.0633 (12)0.0482 (10)0.0120 (10)0.0428 (10)0.0167 (9)
C190.0763 (14)0.0512 (11)0.0800 (14)0.0156 (10)0.0694 (13)0.0216 (10)
C200.0634 (12)0.0448 (10)0.0855 (14)0.0044 (9)0.0643 (13)0.0029 (10)
C210.0376 (9)0.0440 (9)0.0514 (10)0.0019 (7)0.0339 (9)0.0002 (8)
O220.0497 (7)0.0534 (7)0.0586 (7)0.0163 (6)0.0427 (7)0.0226 (6)
Geometric parameters (Å, º) top
C1—N21.4740 (19)C10—C151.389 (2)
C1—C161.528 (2)C11—C121.388 (3)
C1—C61.552 (2)C11—H110.957 (18)
C1—C51.558 (2)C12—C131.373 (3)
N2—C31.351 (2)C12—H120.94 (2)
N2—C91.468 (2)C13—C141.370 (3)
C3—O221.2255 (19)C13—H130.97 (2)
C3—C41.495 (3)C14—C151.386 (3)
C4—C51.504 (3)C14—H140.989 (19)
C4—H4B0.94 (3)C15—H150.972 (18)
C4—H4A0.99 (3)C16—C171.389 (2)
C5—H5B0.94 (2)C16—C211.389 (2)
C5—H5A0.96 (2)C17—C181.385 (2)
C6—O71.2237 (18)C17—H170.979 (19)
C6—N81.335 (2)C18—C191.368 (3)
N8—H8B0.86 (2)C18—H180.94 (2)
N8—H8A0.89 (2)C19—C201.369 (3)
C9—C101.509 (2)C19—H190.98 (2)
C9—H9B0.953 (17)C20—C211.387 (3)
C9—H9A1.002 (17)C20—H200.98 (2)
C10—C111.386 (2)C21—H210.969 (17)
N2—C1—C16110.27 (12)C11—C10—C15118.40 (16)
N2—C1—C6108.67 (12)C11—C10—C9121.41 (15)
C16—C1—C6110.31 (12)C15—C10—C9120.13 (16)
N2—C1—C5101.95 (13)C10—C11—C12120.58 (18)
C16—C1—C5115.11 (13)C10—C11—H11121.3 (11)
C6—C1—C5110.11 (14)C12—C11—H11118.1 (11)
C3—N2—C9120.52 (13)C13—C12—C11120.2 (2)
C3—N2—C1113.24 (13)C13—C12—H12119.7 (13)
C9—N2—C1123.50 (12)C11—C12—H12120.0 (13)
O22—C3—N2124.06 (16)C14—C13—C12119.89 (19)
O22—C3—C4127.05 (15)C14—C13—H13120.0 (13)
N2—C3—C4108.89 (14)C12—C13—H13120.1 (14)
C3—C4—C5106.12 (14)C13—C14—C15120.29 (18)
C3—C4—H4B114.4 (16)C13—C14—H14121.8 (11)
C5—C4—H4B112.4 (17)C15—C14—H14117.9 (11)
C3—C4—H4A108.1 (14)C14—C15—C10120.61 (19)
C5—C4—H4A111.1 (15)C14—C15—H15122.1 (10)
H4B—C4—H4A105 (2)C10—C15—H15117.2 (10)
C4—C5—C1105.68 (15)C17—C16—C21117.75 (15)
C4—C5—H5B114.0 (12)C17—C16—C1121.07 (14)
C1—C5—H5B111.5 (13)C21—C16—C1121.02 (15)
C4—C5—H5A108.6 (14)C18—C17—C16121.21 (17)
C1—C5—H5A111.0 (13)C18—C17—H17118.4 (11)
H5B—C5—H5A106.1 (18)C16—C17—H17120.4 (11)
O7—C6—N8122.60 (15)C19—C18—C17120.05 (19)
O7—C6—C1120.51 (14)C19—C18—H18120.6 (14)
N8—C6—C1116.89 (14)C17—C18—H18119.4 (14)
C6—N8—H8B121.7 (12)C18—C19—C20119.83 (18)
C6—N8—H8A115.8 (12)C18—C19—H19118.8 (13)
H8B—N8—H8A121.7 (17)C20—C19—H19121.4 (13)
N2—C9—C10113.60 (13)C19—C20—C21120.54 (18)
N2—C9—H9B107.3 (10)C19—C20—H20121.4 (12)
C10—C9—H9B109.6 (10)C21—C20—H20118.1 (13)
N2—C9—H9A105.5 (10)C20—C21—C16120.62 (18)
C10—C9—H9A111.3 (9)C20—C21—H21120.7 (10)
H9B—C9—H9A109.1 (14)C16—C21—H21118.7 (10)
C16—C1—N2—C3143.19 (13)N2—C9—C10—C1180.13 (19)
C6—C1—N2—C395.79 (15)N2—C9—C10—C15102.47 (17)
C5—C1—N2—C320.47 (17)C15—C10—C11—C120.2 (2)
C16—C1—N2—C955.53 (18)C9—C10—C11—C12177.63 (15)
C6—C1—N2—C965.48 (18)C10—C11—C12—C130.3 (3)
C5—C1—N2—C9178.25 (15)C11—C12—C13—C140.6 (3)
C9—N2—C3—O224.0 (2)C12—C13—C14—C150.4 (3)
C1—N2—C3—O22165.94 (14)C13—C14—C15—C100.0 (3)
C9—N2—C3—C4175.78 (15)C11—C10—C15—C140.3 (2)
C1—N2—C3—C413.89 (18)C9—C10—C15—C14177.81 (15)
O22—C3—C4—C5179.26 (17)N2—C1—C16—C17100.93 (16)
N2—C3—C4—C50.6 (2)C6—C1—C16—C1719.10 (19)
C3—C4—C5—C111.7 (2)C5—C1—C16—C17144.44 (16)
N2—C1—C5—C418.57 (19)N2—C1—C16—C2174.30 (18)
C16—C1—C5—C4137.92 (16)C6—C1—C16—C21165.66 (14)
C6—C1—C5—C496.64 (18)C5—C1—C16—C2140.3 (2)
N2—C1—C6—O77.89 (19)C21—C16—C17—C180.5 (2)
C16—C1—C6—O7113.10 (16)C1—C16—C17—C18175.90 (15)
C5—C1—C6—O7118.77 (16)C16—C17—C18—C190.6 (3)
N2—C1—C6—N8171.58 (13)C17—C18—C19—C200.5 (3)
C16—C1—C6—N867.43 (17)C18—C19—C20—C210.3 (3)
C5—C1—C6—N860.70 (18)C19—C20—C21—C160.3 (3)
C3—N2—C9—C1078.84 (19)C17—C16—C21—C200.4 (2)
C1—N2—C9—C10121.18 (16)C1—C16—C21—C20175.76 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N8—H8A···O7i0.89 (2)2.07 (2)2.955 (2)169 (2)
N8—H8B···O22ii0.86 (2)2.08 (2)2.927 (2)165 (2)
C5—H5A···O7ii0.96 (3)2.50 (2)3.329 (2)145 (4)
Symmetry codes: (i) x1, y+1, z+1; (ii) x, y+1/2, z+3/2.
(IV) 2-(4-isopropoxyphenyl)-5-oxo-1-(4-tolyl)pyrrolidine-2-carbonitrile top
Crystal data top
C21H22N2O2F(000) = 712
Mr = 334.41Dx = 1.153 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 7.5182 (15) Åθ = 14.4–18.5°
b = 25.125 (5) ŵ = 0.08 mm1
c = 10.612 (2) ÅT = 293 K
β = 106.07 (3)°Sphere, colourless
V = 1926.3 (7) Å30.17 mm (radius)
Z = 4
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.027
Radiation source: fine-focus sealed tubeθmax = 28.0°, θmin = 1.6°
Graphite monochromatorh = 90
ω/2θ scansk = 033
5212 measured reflectionsl = 013
4621 independent reflections3 standard reflections every 60 min
3067 reflections with I > 2σ(I) intensity decay: variation +1.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.142 w = 1/[σ2(Fo2) + (0.0453P)2 + 0.4186P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
4621 reflectionsΔρmax = 0.18 e Å3
282 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraintsExtinction coefficient: 0.0064 (12)
Primary atom site location: structure-invariant direct methods
Crystal data top
C21H22N2O2V = 1926.3 (7) Å3
Mr = 334.41Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.5182 (15) ŵ = 0.08 mm1
b = 25.125 (5) ÅT = 293 K
c = 10.612 (2) Å0.17 mm (radius)
β = 106.07 (3)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.027
5212 measured reflections3 standard reflections every 60 min
4621 independent reflections intensity decay: variation +1.0%
3067 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.142H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.18 e Å3
4621 reflectionsΔρmin = 0.20 e Å3
282 parameters
Special details top

Geometry. Mean-plane data from final SHELXL refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 4.1633 (0.0048) x + 3.4424 (0.0196) y + 10.0021 (0.0058) z = 8.8817 (0.0100)

* 0.0066 (0.0012) C16 * -0.0032 (0.0014) C17 * -0.0028 (0.0014) C18 * 0.0052 (0.0013) C19 * -0.0016 (0.0012) C20 * -0.0043 (0.0012) C21

Rms deviation of fitted atoms = 0.0043

1.6974 (0.0071) x + 22.9531 (0.0159) y + 2.7868 (0.0092) z = 10.3939 (0.0065)

Angle to previous plane (with approximate e.s.d.) = 73.86 (0.08)

* 0.0054 (0.0014) C9 * -0.0002 (0.0016) C10 * -0.0048 (0.0017) C11 * 0.0045 (0.0017) C12 * 0.0007 (0.0017) C13 * -0.0057 (0.0015) C14

Rms deviation of fitted atoms = 0.0042

- 4.5455 (0.0067) x + 16.1467 (0.0213) y - 3.0230 (0.0107) z = 0.4438 (0.0126)

Angle to previous plane (with approximate e.s.d.) = 73.06 (0.07)

* 0.1851 (0.0011) C1 * -0.1067 (0.0011) N2 * -0.0193 (0.0012) C3 * 0.1372 (0.0014) C4 * -0.1963 (0.0014) C5

Rms deviation of fitted atoms = 0.1438

- 4.1633 (0.0048) x + 3.4424 (0.0196) y + 10.0021 (0.0058) z = 8.8817 (0.0100)

Angle to previous plane (with approximate e.s.d.) = 87.92 (0.07)

* 0.0066 (0.0012) C16 * -0.0032 (0.0014) C17 * -0.0028 (0.0014) C18 * 0.0052 (0.0013) C19 * -0.0016 (0.0012) C20 * -0.0043 (0.0012) C21

Rms deviation of fitted atoms = 0.0043

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.4694 (2)0.35322 (7)0.97282 (16)0.0421 (4)
N20.45809 (18)0.31272 (5)0.87004 (13)0.0422 (3)
C30.3170 (2)0.27728 (7)0.86394 (18)0.0499 (4)
C40.2408 (3)0.28702 (10)0.9788 (2)0.0565 (5)
H4B0.119 (3)0.3068 (9)0.945 (2)0.070 (6)*
H4A0.218 (3)0.2543 (10)1.021 (2)0.081 (7)*
C50.3826 (3)0.32297 (9)1.06784 (19)0.0527 (5)
H5B0.334 (3)0.3477 (8)1.1171 (19)0.059 (6)*
H5A0.483 (3)0.3011 (9)1.128 (2)0.069 (6)*
C60.3435 (3)0.39776 (8)0.9125 (2)0.0614 (5)
N70.2384 (3)0.42897 (9)0.8638 (3)0.1005 (8)
O80.2639 (2)0.24484 (6)0.77767 (14)0.0749 (5)
C90.5338 (2)0.32114 (7)0.76151 (16)0.0450 (4)
C100.4264 (3)0.34283 (9)0.64623 (19)0.0613 (5)
H100.296 (3)0.3521 (9)0.641 (2)0.072 (6)*
C110.5008 (4)0.34988 (10)0.5412 (2)0.0746 (7)
H110.422 (3)0.3650 (10)0.460 (2)0.091 (8)*
C120.6809 (4)0.33590 (9)0.5500 (2)0.0706 (6)
C130.7859 (3)0.31389 (11)0.6659 (2)0.0725 (6)
H130.917 (3)0.3057 (10)0.676 (2)0.084 (7)*
C140.7128 (3)0.30627 (9)0.7710 (2)0.0595 (5)
H140.786 (3)0.2902 (9)0.852 (2)0.068 (6)*
C150.7614 (5)0.34374 (14)0.4349 (3)0.1120 (11)
H15A0.87390.32360.44930.168*
H15B0.78720.38080.42680.168*
H15C0.67400.33170.35580.168*
C160.6632 (2)0.37380 (6)1.03602 (15)0.0404 (4)
C170.7079 (3)0.42681 (7)1.03542 (18)0.0515 (4)
H170.618 (3)0.4528 (9)0.989 (2)0.071 (6)*
C180.8823 (3)0.44570 (8)1.1015 (2)0.0569 (5)
H180.908 (3)0.4828 (10)1.104 (2)0.075 (7)*
C191.0153 (2)0.41069 (7)1.16977 (16)0.0466 (4)
C200.9732 (2)0.35670 (7)1.17012 (16)0.0445 (4)
H201.067 (3)0.3345 (8)1.2167 (18)0.050 (5)*
C210.8000 (2)0.33879 (7)1.10394 (17)0.0437 (4)
H210.766 (3)0.3020 (8)1.1070 (18)0.056 (5)*
O221.19148 (18)0.42441 (6)1.23838 (13)0.0614 (4)
C231.2387 (3)0.47973 (9)1.2584 (3)0.0751 (7)
H231.191 (3)0.4974 (10)1.171 (2)0.087 (7)*
C241.4478 (4)0.48140 (13)1.2958 (3)0.1030 (10)
H24A1.49090.46521.22780.155*
H24D1.49660.46241.37640.155*
H24B1.48870.51771.30700.155*
C251.1600 (5)0.50233 (15)1.3620 (3)0.1234 (13)
H25D1.02750.49961.33400.185*
H25A1.19500.53911.37620.185*
H25B1.20700.48281.44210.185*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0415 (8)0.0404 (9)0.0447 (9)0.0011 (7)0.0123 (7)0.0037 (7)
N20.0453 (7)0.0430 (8)0.0396 (7)0.0053 (6)0.0141 (6)0.0036 (6)
C30.0496 (10)0.0493 (10)0.0503 (10)0.0098 (8)0.0129 (8)0.0033 (8)
C40.0489 (11)0.0686 (13)0.0554 (11)0.0128 (10)0.0200 (9)0.0035 (10)
C50.0495 (10)0.0627 (12)0.0512 (11)0.0066 (9)0.0226 (9)0.0086 (9)
C60.0478 (10)0.0528 (11)0.0770 (14)0.0049 (9)0.0061 (9)0.0093 (10)
N70.0759 (13)0.0633 (13)0.141 (2)0.0239 (11)0.0049 (13)0.0004 (13)
O80.0893 (11)0.0740 (10)0.0658 (9)0.0381 (8)0.0291 (8)0.0253 (8)
C90.0516 (10)0.0461 (9)0.0384 (8)0.0096 (8)0.0142 (7)0.0038 (7)
C100.0605 (12)0.0708 (14)0.0506 (11)0.0045 (10)0.0119 (9)0.0082 (9)
C110.0947 (18)0.0827 (16)0.0453 (11)0.0084 (14)0.0174 (11)0.0105 (11)
C120.0939 (17)0.0759 (15)0.0508 (12)0.0210 (13)0.0348 (11)0.0095 (10)
C130.0672 (14)0.0962 (18)0.0634 (14)0.0081 (13)0.0334 (11)0.0140 (12)
C140.0564 (12)0.0774 (14)0.0472 (10)0.0018 (10)0.0186 (9)0.0023 (10)
C150.154 (3)0.129 (3)0.0764 (17)0.020 (2)0.0715 (19)0.0030 (17)
C160.0432 (8)0.0411 (9)0.0381 (8)0.0009 (7)0.0131 (7)0.0032 (7)
C170.0537 (10)0.0396 (9)0.0549 (10)0.0033 (8)0.0043 (8)0.0033 (8)
C180.0598 (11)0.0380 (10)0.0649 (12)0.0069 (8)0.0040 (9)0.0016 (8)
C190.0448 (9)0.0510 (10)0.0430 (9)0.0027 (8)0.0105 (7)0.0054 (7)
C200.0436 (9)0.0456 (10)0.0452 (9)0.0054 (8)0.0137 (7)0.0028 (7)
C210.0473 (9)0.0395 (9)0.0477 (9)0.0020 (7)0.0190 (7)0.0003 (7)
O220.0495 (7)0.0592 (8)0.0674 (9)0.0066 (6)0.0026 (6)0.0073 (6)
C230.0766 (15)0.0621 (14)0.0686 (14)0.0235 (11)0.0099 (12)0.0015 (11)
C240.0766 (17)0.115 (2)0.101 (2)0.0424 (16)0.0033 (14)0.0027 (17)
C250.109 (2)0.112 (2)0.123 (3)0.0133 (19)0.0106 (19)0.062 (2)
Geometric parameters (Å, º) top
C1—N21.477 (2)C15—H15A0.9600
C1—C61.491 (3)C15—H15B0.9600
C1—C161.516 (2)C15—H15C0.9600
C1—C51.544 (2)C16—C171.374 (2)
N2—C31.373 (2)C16—C211.393 (2)
N2—C91.434 (2)C17—C181.388 (3)
C3—O81.208 (2)C17—H170.97 (2)
C3—C41.503 (3)C18—C191.377 (3)
C4—C51.513 (3)C18—H180.95 (2)
C4—H4B1.02 (2)C19—O221.367 (2)
C4—H4A0.97 (2)C19—C201.393 (3)
C5—H5B0.95 (2)C20—C211.373 (2)
C5—H5A1.01 (2)C20—H200.927 (19)
C6—N71.132 (3)C21—H210.96 (2)
C9—C141.374 (3)O22—C231.436 (3)
C9—C101.378 (3)C23—C251.497 (4)
C10—C111.390 (3)C23—C241.512 (3)
C10—H101.00 (2)C23—H231.00 (3)
C11—C121.376 (4)C24—H24A0.9600
C11—H110.98 (2)C24—H24D0.9600
C12—C131.380 (3)C24—H24B0.9600
C12—C151.519 (3)C25—H25D0.9600
C13—C141.386 (3)C25—H25A0.9600
C13—H130.99 (2)C25—H25B0.9600
C14—H140.97 (2)
N2—C1—C6107.47 (14)C12—C15—H15A109.5
N2—C1—C16114.43 (13)C12—C15—H15B109.5
C6—C1—C16110.60 (15)H15A—C15—H15B109.5
N2—C1—C5101.23 (14)C12—C15—H15C109.5
C6—C1—C5108.51 (16)H15A—C15—H15C109.5
C16—C1—C5114.01 (14)H15B—C15—H15C109.5
C3—N2—C9122.07 (14)C17—C16—C21117.88 (16)
C3—N2—C1111.56 (13)C17—C16—C1122.35 (15)
C9—N2—C1122.47 (13)C21—C16—C1119.67 (15)
O8—C3—N2124.20 (17)C16—C17—C18121.81 (17)
O8—C3—C4127.19 (17)C16—C17—H17121.1 (13)
N2—C3—C4108.60 (15)C18—C17—H17117.1 (13)
C3—C4—C5104.08 (15)C19—C18—C17119.61 (18)
C3—C4—H4B107.4 (12)C19—C18—H18119.9 (14)
C5—C4—H4B109.9 (12)C17—C18—H18120.4 (14)
C3—C4—H4A112.9 (14)O22—C19—C18125.05 (17)
C5—C4—H4A113.6 (14)O22—C19—C20115.57 (16)
H4B—C4—H4A108.8 (19)C18—C19—C20119.37 (16)
C4—C5—C1103.75 (15)C21—C20—C19120.14 (16)
C4—C5—H5B115.1 (12)C21—C20—H20123.3 (12)
C1—C5—H5B109.5 (12)C19—C20—H20116.5 (12)
C4—C5—H5A110.3 (13)C20—C21—C16121.17 (17)
C1—C5—H5A107.5 (12)C20—C21—H21121.3 (11)
H5B—C5—H5A110.3 (17)C16—C21—H21117.5 (11)
N7—C6—C1175.1 (2)C19—O22—C23119.09 (16)
C14—C9—C10119.60 (18)O22—C23—C25110.1 (2)
C14—C9—N2119.96 (16)O22—C23—C24105.2 (2)
C10—C9—N2120.41 (17)C25—C23—C24113.0 (2)
C9—C10—C11119.7 (2)O22—C23—H23106.5 (15)
C9—C10—H10117.8 (12)C25—C23—H23113.3 (15)
C11—C10—H10122.4 (12)C24—C23—H23108.2 (14)
C12—C11—C10121.3 (2)C23—C24—H24A109.5
C12—C11—H11120.2 (15)C23—C24—H24D109.5
C10—C11—H11118.5 (15)H24A—C24—H24D109.5
C11—C12—C13118.2 (2)C23—C24—H24B109.5
C11—C12—C15121.0 (2)H24A—C24—H24B109.5
C13—C12—C15120.8 (2)H24D—C24—H24B109.5
C12—C13—C14121.1 (2)C23—C25—H25D109.5
C12—C13—H13119.1 (14)C23—C25—H25A109.5
C14—C13—H13119.7 (14)H25D—C25—H25A109.5
C9—C14—C13120.1 (2)C23—C25—H25B109.5
C9—C14—H14118.9 (13)H25D—C25—H25B109.5
C13—C14—H14120.9 (13)H25A—C25—H25B109.5
C6—C1—N2—C387.82 (18)C11—C12—C13—C140.3 (4)
C16—C1—N2—C3148.95 (15)C15—C12—C13—C14179.5 (2)
C5—C1—N2—C325.88 (18)C10—C9—C14—C131.1 (3)
C6—C1—N2—C970.32 (19)N2—C9—C14—C13179.42 (18)
C16—C1—N2—C952.9 (2)C12—C13—C14—C90.7 (4)
C5—C1—N2—C9175.99 (15)N2—C1—C16—C17121.97 (18)
C9—N2—C3—O811.7 (3)C6—C1—C16—C170.4 (2)
C1—N2—C3—O8169.96 (18)C5—C1—C16—C17122.15 (19)
C9—N2—C3—C4166.93 (16)N2—C1—C16—C2161.8 (2)
C1—N2—C3—C48.7 (2)C6—C1—C16—C21176.72 (15)
O8—C3—C4—C5168.5 (2)C5—C1—C16—C2154.1 (2)
N2—C3—C4—C512.9 (2)C21—C16—C17—C181.0 (3)
C3—C4—C5—C128.0 (2)C1—C16—C17—C18175.34 (17)
N2—C1—C5—C432.24 (19)C16—C17—C18—C190.1 (3)
C6—C1—C5—C480.66 (19)C17—C18—C19—O22179.94 (18)
C16—C1—C5—C4155.61 (16)C17—C18—C19—C200.7 (3)
C3—N2—C9—C14113.3 (2)O22—C19—C20—C21179.90 (15)
C1—N2—C9—C1490.8 (2)C18—C19—C20—C210.6 (3)
C3—N2—C9—C1065.0 (2)C19—C20—C21—C160.3 (3)
C1—N2—C9—C1090.9 (2)C17—C16—C21—C201.1 (2)
C14—C9—C10—C110.6 (3)C1—C16—C21—C20175.34 (15)
N2—C9—C10—C11178.88 (19)C18—C19—O22—C239.3 (3)
C9—C10—C11—C120.4 (4)C20—C19—O22—C23171.41 (18)
C10—C11—C12—C130.8 (4)C19—O22—C23—C2575.7 (2)
C10—C11—C12—C15180.0 (2)C19—O22—C23—C24162.24 (18)

Experimental details

(III)(IV)
Crystal data
Chemical formulaC18H18N2O2C21H22N2O2
Mr294.34334.41
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)293293
a, b, c (Å)11.959 (2), 10.303 (2), 21.489 (4)7.5182 (15), 25.125 (5), 10.612 (2)
β (°) 145.05 (3) 106.07 (3)
V3)1516.7 (12)1926.3 (7)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.090.08
Crystal size (mm)0.25 × 0.15 × 0.100.17 (radius)
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Enraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4601, 4411, 2559 5212, 4621, 3067
Rint0.0250.027
(sin θ/λ)max1)0.7030.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.121, 1.01 0.049, 0.142, 1.05
No. of reflections44114621
No. of parameters272282
H-atom treatmentAll H-atom parameters refinedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.20, 0.160.18, 0.20

Computer programs: CAD-4 Software (Enraf-Nonius, 1988), SETANG in CAD-4 Software, local program, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N8—H8A···O7i0.89 (2)2.07 (2)2.955 (2)169 (2)
N8—H8B···O22ii0.86 (2)2.08 (2)2.927 (2)165 (2)
C5—H5A···O7ii0.96 (3)2.50 (2)3.329 (2)145 (4)
Symmetry codes: (i) x1, y+1, z+1; (ii) x, y+1/2, z+3/2.
 

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