1-Substituted derivatives of 2-phenylpyrrolidine-2-carboxamide

The structures of two potential anti-human immunodeficiency virus type 1 (HIV-1) non-nucleoside reverse transcriptase inhibitors (NNRTI), namely 1-(2-chloro­benzoyl)-2-phenyl­pyrrol­idine-2-carbox­amide, C₁₈H₁₇ClN₂O₂, and 1-(2-furoyl)-2-phenyl­pyrrolidine-2-carbox­amide, C₁₆H₁₆N₂O₃, have been investigated by X-ray diffraction and the butterfly-like conformation established in each case. The pyrrolidine ring has the same half-chair conformation in both structures.

S1. Comment

The compounds under current investigation belong to the family of non-nucleoside reverse transcriptase inhibitors (NNRTIs). Formally, the structures of such compounds may be considered as derivatives from Loviride (Pauvels et al., 1993), with a common structural feature being the butterfly-like conformation (De Clercq, 1996). A new method for the synthesis of 1,2-substituted derivatives of 1-(alkyl/arylcarbonyl)-2-phenylpyrrolidine-2-carboxamide, (I), has been developed by Martirosyan et al. (2000), and thus 1-(2-chlorobenzoyl)-2-phenylpyrrolidine-2-carboxamide, (II), and 1-(2-furoyl)-2-phenylpyrrolidine-2-carboxamide, (III), have been synthesized as racemic mixtures. The crystal structures of these two compounds are presented here. \sch

Views of molecules (II) and (III) with the atomic numbering schemes are shown in Figs. 1 and 2, respectively. In the crystal structures of both molecules, two neighbouring asymmetric molecules, related by inversion centres, are connected into a dimeric unit with double hydrogen bonding through the amide groups (Figs. 3 and 4). However, only one of the amide H atoms of each molecule [H15A in (II) and H14A in (III)] takes part in the dimer formed through intermolecular interactions. The other H atoms (H15B and H14B, respectively) of the amide form intramolecular hydrogen bonds with the carbonyl O atoms at O7.

The interatomic distances and angles for the hydrogen bonds in (II) and (III) are listed in Tables 1 and 2, respectively. The formation of intramolecular hydrogen bonds in (II) and (III) could bring additional rigidity to the molecular conformation relative to 1-benzyl-2-phenyl-5-oxopyrrolidine-2-carboxamide (Karapetyan et al., 2002), in which the corresponding H atoms take part in intermolecular bonding.

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), describing the orientation relations between the `wings' and `bodies' of these butterfly-like structures, for planes W1/W2, B/W1 and B/W2, are 40.05 (12), 72.02 (10) and 86.69 (10)°, respectively, for (II), and 89.99 (7), 76.69 (6) and 29.04 (10)°, respectively, for (III). The differences in these dihedral angles are caused by the reorientation of plane W2. Probably, in this reorientation, the essential role played by the Cl atom in the o-position of phenyl ring is prominent. In both structures, the pyrrolidine ring has the same half-chair conformation.

Table 1. Short N—H···O contacts (Å, °) for compound (II)

Table 2. Short N—H···O contacts (Å, °) for compound (III)

S2. Experimental

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

S3. Refinement

Both molecules (II) and (III) crystallized in the monoclinic system, space group P2₁/c as determined from the systematic absences. H atoms were constrained, with C—H = 0.93–9.97 Å and N—H = 0.86 Å. Are these the correct constraints?

Computing details

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

	Fig. 1. A view of (II) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 2. 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.
	Fig. 3. The connection of molecules of (II) into dimers [symmetry code: (i) 2 - x, 1 - y, 2 - z].
	Fig. 4. The connection of molecules of (III) into dimers [symmetry code: (i) 1 - x, 2 - y, 2 - z].

(II) 1-(2-chlorobenzoyl)-2-phenylpyrrolidine-2-carboxamide

Crystal data

C18H17ClN2O2	F(000) = 688
Mr = 328.79	Dx = 1.280 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 22 reflections
a = 10.661 (2) Å	θ = 13.9–20.0°
b = 11.690 (2) Å	µ = 0.23 mm^−1
c = 20.698 (4) Å	T = 293 K
β = 138.60 (3)°	Prism, colourless
V = 1706.1 (11) Å^3	0.20 × 0.13 × 0.10 mm
Z = 4

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.022
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.1°
Graphite monochromator	h = −12→11
ω/2θ scans	k = 0→13
3296 measured reflections	l = −11→24
2948 independent reflections	3 standard reflections every 60 min
1928 reflections with I > 2σ(I)	intensity decay: variation +−1.0%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0453P)^2 + 0.4186P] where P = (Fo^2 + 2Fc^2)/3
2948 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3
0 constraints

Special details

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

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)

- 7.3815(0.0092)x + 8.0424(0.0105)y + 7.7720(0.0222)z = 3.5064(0.0121)

* -0.0006 (0.0017) C17 * 0.0042 (0.0017) C18 * -0.0037 (0.0020) C19 * -0.0004 (0.0022) C20 * 0.0040 (0.0024) C21 * -0.0035 (0.0022) C22

Rms deviation of fitted atoms = 0.0032

1.6738 (0.0116)x - 8.7969(0.0087)y + 6.3182(0.0225)z = 2.8236(0.0163)

Angle to previous plane (with approximate e.s.d.) = 40.05 (0.12)

* 0.0050 (0.0016) C8 * -0.0069 (0.0018) C9 * 0.0029 (0.0020) C10 * 0.0029 (0.0021) C11 * -0.0046 (0.0020) C12 * 0.0007 (0.0017) C13

Rms deviation of fitted atoms = 0.0043

- 1.2833(0.0131)x + 6.8014(0.0113)y + 12.8802(0.0202)z = 11.4644(0.0085)

Angle to previous plane (with approximate e.s.d.) = 86.69 (0.10)

* 0.1488 (0.0013) C1 * -0.0121 (0.0014) N2 * -0.1301 (0.0015) C3 * 0.2353 (0.0016) C4 * -0.2418 (0.0014) C5

Rms deviation of fitted atoms = 0.1749

- 7.3815(0.0092)x + 8.0424(0.0105)y + 7.7720(0.0222)z = 3.5064(0.0121)

Angle to previous plane (with approximate e.s.d.) = 72.02 (0.10)

* -0.0006 (0.0017) C17 * 0.0042 (0.0017) C18 * -0.0037 (0.0020) C19 * -0.0004 (0.0022) C20 * 0.0040 (0.0024) C21 * -0.0035 (0.0022) C22

Rms deviation of fitted atoms = 0.0032

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl	0.38166 (9)	0.39708 (8)	0.89412 (5)	0.1006 (3)
C1	0.7034 (2)	0.27365 (16)	0.82721 (13)	0.0492 (5)
N2	0.54952 (18)	0.24601 (13)	0.81398 (10)	0.0468 (4)
C3	0.5887 (3)	0.13935 (18)	0.86505 (15)	0.0598 (6)
H3A	0.5056	0.0781	0.8189	0.072*
H3B	0.5728	0.1506	0.9050	0.072*
C4	0.7932 (3)	0.11314 (19)	0.92763 (15)	0.0657 (6)
H4A	0.8793	0.1512	0.9905	0.079*
H4B	0.8173	0.0315	0.9380	0.079*
C5	0.8132 (3)	0.15965 (18)	0.86803 (15)	0.0617 (6)
H5A	0.7585	0.1076	0.8155	0.074*
H5B	0.9455	0.1722	0.9084	0.074*
C6	0.3931 (2)	0.30874 (17)	0.76166 (12)	0.0481 (5)
O7	0.36799 (17)	0.40254 (13)	0.72605 (10)	0.0643 (4)
C8	0.2414 (2)	0.26030 (17)	0.74616 (13)	0.0504 (5)
C9	0.2215 (3)	0.2977 (2)	0.80155 (15)	0.0643 (6)
C10	0.0791 (3)	0.2580 (3)	0.78564 (17)	0.0836 (8)
H10A	0.0692	0.2832	0.8243	0.100*
C11	−0.0484 (3)	0.1809 (3)	0.71209 (19)	0.0868 (8)
H11A	−0.1456	0.1537	0.7007	0.104*
C12	−0.0343 (3)	0.1436 (3)	0.65522 (19)	0.0818 (8)
H12A	−0.1222	0.0918	0.6050	0.098*
C13	0.1115 (3)	0.1833 (2)	0.67266 (15)	0.0653 (6)
H13A	0.1215	0.1574	0.6341	0.078*
C14	0.8327 (3)	0.36954 (18)	0.90327 (14)	0.0554 (5)
N15	0.7537 (2)	0.45281 (16)	0.90496 (13)	0.0702 (5)
H15A	0.8222	0.5078	0.9462	0.084*
H15B	0.6332	0.4527	0.8649	0.084*
O16	1.00387 (19)	0.36549 (15)	0.95883 (12)	0.0816 (6)
C17	0.6261 (2)	0.30452 (18)	0.73065 (13)	0.0536 (5)
C18	0.7097 (3)	0.38739 (19)	0.72489 (15)	0.0626 (5)
H18A	0.8121	0.4288	0.7804	0.075*
C19	0.6427 (3)	0.4094 (2)	0.63752 (18)	0.0822 (7)
H19A	0.7012	0.4648	0.6347	0.099*
C20	0.4912 (3)	0.3501 (3)	0.55536 (18)	0.0923 (9)
H20B	0.4459	0.3653	0.4966	0.111*
C21	0.4058 (4)	0.2681 (3)	0.55967 (18)	0.1004 (10)
H21A	0.3020	0.2279	0.5037	0.120*
C22	0.4731 (3)	0.2453 (3)	0.64620 (16)	0.0805 (7)
H22A	0.4150	0.1889	0.6485	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.0938 (3)	0.1270 (6)	0.0864 (3)	−0.0225 (4)	0.0692 (2)	−0.0389 (4)
C1	0.0447 (6)	0.0371 (10)	0.0613 (8)	−0.0065 (7)	0.0385 (6)	−0.0074 (7)
N2	0.0467 (5)	0.0363 (8)	0.0534 (6)	0.0006 (6)	0.0364 (5)	0.0016 (6)
C3	0.0611 (8)	0.0419 (11)	0.0704 (10)	0.0077 (9)	0.0476 (7)	0.0142 (9)
C4	0.0575 (9)	0.0440 (12)	0.0708 (11)	0.0074 (9)	0.0409 (8)	0.0088 (9)
C5	0.0513 (7)	0.0428 (11)	0.0805 (11)	−0.0018 (8)	0.0463 (7)	−0.0077 (9)
C6	0.0503 (7)	0.0414 (11)	0.0473 (8)	0.0045 (8)	0.0350 (6)	0.0032 (7)
O7	0.0657 (6)	0.0481 (8)	0.0733 (7)	0.0113 (6)	0.0505 (5)	0.0162 (6)
C8	0.0445 (7)	0.0473 (11)	0.0539 (8)	0.0083 (8)	0.0353 (6)	0.0084 (8)
C9	0.0520 (8)	0.0764 (16)	0.0595 (9)	0.0073 (10)	0.0404 (7)	0.0054 (10)
C10	0.0649 (9)	0.115 (2)	0.0802 (11)	0.0079 (13)	0.0572 (8)	0.0028 (13)
C11	0.0585 (8)	0.107 (2)	0.1024 (13)	0.0039 (13)	0.0624 (9)	0.0099 (14)
C12	0.0514 (9)	0.0802 (18)	0.0886 (14)	−0.0082 (12)	0.0451 (10)	−0.0091 (13)
C13	0.0580 (8)	0.0607 (14)	0.0741 (10)	−0.0004 (10)	0.0487 (8)	−0.0033 (10)
C14	0.0566 (8)	0.0419 (11)	0.0625 (9)	−0.0050 (9)	0.0431 (7)	−0.0032 (8)
N15	0.0596 (7)	0.0466 (10)	0.0862 (10)	−0.0114 (8)	0.0494 (7)	−0.0224 (8)
O16	0.0517 (6)	0.0610 (10)	0.0937 (9)	−0.0136 (7)	0.0433 (6)	−0.0282 (8)
C17	0.0543 (7)	0.0482 (12)	0.0642 (9)	−0.0052 (8)	0.0462 (6)	−0.0075 (8)
C18	0.0722 (8)	0.0471 (12)	0.0844 (10)	−0.0006 (9)	0.0633 (7)	−0.0007 (9)
C19	0.1090 (10)	0.0654 (16)	0.1142 (13)	0.0068 (12)	0.0959 (9)	0.0124 (11)
C20	0.1021 (11)	0.113 (2)	0.0818 (11)	0.0165 (16)	0.0748 (9)	0.0153 (13)
C21	0.0927 (12)	0.141 (3)	0.0726 (12)	−0.0289 (17)	0.0635 (10)	−0.0227 (15)
C22	0.0844 (9)	0.0936 (19)	0.0757 (11)	−0.0385 (12)	0.0636 (8)	−0.0278 (11)

Geometric parameters (Å, º)

Cl—C9	1.741 (2)	C10—H10A	0.9300
C1—N2	1.482 (3)	C11—C12	1.366 (4)
C1—C17	1.528 (3)	C11—H11A	0.9300
C1—C14	1.543 (3)	C12—C13	1.385 (3)
C1—C5	1.542 (3)	C12—H12A	0.9300
N2—C6	1.335 (2)	C13—H13A	0.9300
N2—C3	1.478 (3)	C14—O16	1.227 (2)
C3—C4	1.513 (3)	C14—N15	1.305 (3)
C3—H3A	0.9700	N15—H15A	0.8600
C3—H3B	0.9700	N15—H15B	0.8600
C4—C5	1.502 (4)	C17—C18	1.381 (3)
C4—H4A	0.9700	C17—C22	1.385 (3)
C4—H4B	0.9700	C18—C19	1.382 (3)
C5—H5A	0.9700	C18—H18A	0.9300
C5—H5B	0.9700	C19—C20	1.364 (4)
C6—O7	1.234 (2)	C19—H19A	0.9300
C6—C8	1.504 (3)	C20—C21	1.370 (4)
C8—C13	1.372 (3)	C20—H20B	0.9300
C8—C9	1.384 (3)	C21—C22	1.366 (4)
C9—C10	1.371 (3)	C21—H21A	0.9300
C10—C11	1.369 (4)	C22—H22A	0.9300
N2—C1—C17	111.95 (13)	C11—C10—C9	119.1 (3)
N2—C1—C14	111.40 (17)	C11—C10—H10A	120.4
C17—C1—C14	110.84 (17)	C9—C10—H10A	120.4
N2—C1—C5	101.13 (16)	C10—C11—C12	120.6 (2)
C17—C1—C5	111.34 (18)	C10—C11—H11A	119.7
C14—C1—C5	109.81 (14)	C12—C11—H11A	119.7
C6—N2—C3	123.68 (17)	C11—C12—C13	119.8 (2)
C6—N2—C1	124.50 (16)	C11—C12—H12A	120.1
C3—N2—C1	111.82 (14)	C13—C12—H12A	120.1
N2—C3—C4	103.66 (17)	C8—C13—C12	120.7 (2)
N2—C3—H3A	111.0	C8—C13—H13A	119.7
C4—C3—H3A	111.0	C12—C13—H13A	119.7
N2—C3—H3B	111.0	O16—C14—N15	122.65 (19)
C4—C3—H3B	111.0	O16—C14—C1	119.38 (19)
H3A—C3—H3B	109.0	N15—C14—C1	117.96 (16)
C5—C4—C3	102.97 (17)	C14—N15—H15A	120.0
C5—C4—H4A	111.2	C14—N15—H15B	120.0
C3—C4—H4A	111.2	H15A—N15—H15B	120.0
C5—C4—H4B	111.2	C18—C17—C22	117.8 (2)
C3—C4—H4B	111.2	C18—C17—C1	121.94 (17)
H4A—C4—H4B	109.1	C22—C17—C1	120.1 (2)
C4—C5—C1	104.23 (18)	C17—C18—C19	120.7 (2)
C4—C5—H5A	110.9	C17—C18—H18A	119.7
C1—C5—H5A	110.9	C19—C18—H18A	119.7
C4—C5—H5B	110.9	C20—C19—C18	120.2 (3)
C1—C5—H5B	110.9	C20—C19—H19A	119.9
H5A—C5—H5B	108.9	C18—C19—H19A	119.9
O7—C6—N2	123.49 (19)	C19—C20—C21	119.8 (3)
O7—C6—C8	119.40 (16)	C19—C20—H20B	120.1
N2—C6—C8	117.11 (17)	C21—C20—H20B	120.1
C13—C8—C9	118.2 (2)	C20—C21—C22	120.0 (3)
C13—C8—C6	120.9 (2)	C20—C21—H21A	120.0
C9—C8—C6	120.86 (18)	C22—C21—H21A	120.0
C10—C9—C8	121.6 (2)	C21—C22—C17	121.4 (3)
C10—C9—Cl	119.1 (2)	C21—C22—H22A	119.3
C8—C9—Cl	119.30 (17)	C17—C22—H22A	119.3
C17—C1—N2—C6	−46.9 (2)	Cl—C9—C10—C11	179.2 (2)
C14—C1—N2—C6	77.8 (2)	C9—C10—C11—C12	0.1 (4)
C5—C1—N2—C6	−165.53 (17)	C10—C11—C12—C13	0.6 (4)
C17—C1—N2—C3	132.51 (17)	C9—C8—C13—C12	−0.5 (3)
C14—C1—N2—C3	−102.75 (18)	C6—C8—C13—C12	−176.4 (2)
C5—C1—N2—C3	13.9 (2)	C11—C12—C13—C8	−0.4 (4)
C6—N2—C3—C4	−169.88 (18)	N2—C1—C14—O16	142.9 (2)
C1—N2—C3—C4	10.7 (2)	C17—C1—C14—O16	−91.7 (2)
N2—C3—C4—C5	−31.5 (2)	C5—C1—C14—O16	31.7 (3)
C3—C4—C5—C1	40.9 (2)	N2—C1—C14—N15	−37.7 (3)
N2—C1—C5—C4	−33.44 (18)	C17—C1—C14—N15	87.7 (2)
C17—C1—C5—C4	−152.51 (16)	C5—C1—C14—N15	−148.9 (2)
C14—C1—C5—C4	84.3 (2)	N2—C1—C17—C18	143.89 (19)
C3—N2—C6—O7	173.63 (19)	C14—C1—C17—C18	18.8 (3)
C1—N2—C6—O7	−7.0 (3)	C5—C1—C17—C18	−103.7 (2)
C3—N2—C6—C8	−6.6 (3)	N2—C1—C17—C22	−39.1 (3)
C1—N2—C6—C8	172.76 (16)	C14—C1—C17—C22	−164.2 (2)
O7—C6—C8—C13	96.3 (2)	C5—C1—C17—C22	73.3 (2)
N2—C6—C8—C13	−83.5 (2)	C22—C17—C18—C19	−0.5 (3)
O7—C6—C8—C9	−79.5 (2)	C1—C17—C18—C19	176.6 (2)
N2—C6—C8—C9	100.7 (2)	C17—C18—C19—C20	0.8 (4)
C13—C8—C9—C10	1.2 (3)	C18—C19—C20—C21	−0.3 (4)
C6—C8—C9—C10	177.2 (2)	C19—C20—C21—C22	−0.4 (5)
C13—C8—C9—Cl	−178.99 (17)	C20—C21—C22—C17	0.7 (5)
C6—C8—C9—Cl	−3.0 (3)	C18—C17—C22—C21	−0.3 (4)
C8—C9—C10—C11	−1.1 (4)	C1—C17—C22—C21	−177.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15B···O7	0.86	2.10	2.851 (2)	146
N15—H15A···O16^i	0.86	2.01	2.865 (2)	175

Symmetry code: (i) −x+2, −y+1, −z+2.

(III) 1-(2-furoyl)-2-phenylpyrrolidine-2-carboxamide

Crystal data

C16H16N2O3	F(000) = 600
Mr = 284.31	Dx = 1.307 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 22 reflections
a = 12.665 (3) Å	θ = 17.7–23.2°
b = 12.214 (2) Å	µ = 0.09 mm^−1
c = 9.3453 (19) Å	T = 293 K
β = 91.98 (3)°	Prism, colourless
V = 1444.8 (5) Å^3	0.26 × 0.16 × 0.14 mm
Z = 4

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.012
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.6°
Graphite monochromator	h = 0→15
ω/2θ scans	k = −14→0
2652 measured reflections	l = −11→11
2533 independent reflections	3 standard reflections every 60 min
2185 reflections with I > 2σ(I)	intensity decay: variation +−1.0%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.125	w = 1/[σ^2(Fo^2) + (0.0453P)^2 + 0.4186P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2533 reflections	Δρmax = 0.20 e Å^−3
191 parameters	Δρmin = −0.19 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.081 (6)
Primary atom site location: structure-invariant direct methods

Special details

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)

- 9.9829(0.0081)x + 0.3869(0.0091)y + 5.9938(0.0065)z = 0.9670(0.0115)

* -0.0044 (0.0011) C16 * 0.0002 (0.0014) C17 * 0.0022 (0.0016) C18 * -0.0004 (0.0015) C19 * -0.0038 (0.0013) C20 * 0.0062 (0.0011) C21

Rms deviation of fitted atoms = 0.0036

6.6224(0.0112)x - 6.0077(0.0115)y + 6.3336(0.0080)z = 0.9889(0.0116)

Angle to previous plane (with approximate e.s.d.) = 89.99 (0.07)

* -0.0018 (0.0011) C8 * 0.0012 (0.0011) O9 * -0.0003 (0.0013) C10 * -0.0007 (0.0013) C11 * 0.0015 (0.0012) C12

Rms deviation of fitted atoms = 0.0012

5.2477(0.0099)x - 0.6201(0.0102)y + 8.3535(0.0056)z = 6.7555(0.0097)

Angle to previous plane (with approximate e.s.d.) = 29.04 (0.10)

* 0.1418 (0.0009) C1 * 0.0032 (0.0009) N2 * -0.1499 (0.0011) C3 * 0.2513 (0.0012) C4 * -0.2463 (0.0011) C5

Rms deviation of fitted atoms = 0.1824

- 9.9829(0.0081)x + 0.3869(0.0091)y + 5.9938(0.0065)z = 0.9670(0.0115)

Angle to previous plane (with approximate e.s.d.) = 76.69 (0.06)

* -0.0044 (0.0011) C16 * 0.0002 (0.0014) C17 * 0.0022 (0.0016) C18 * -0.0004 (0.0015) C19 * -0.0038 (0.0013) C20 * 0.0062 (0.0011) C21

Rms deviation of fitted atoms = 0.0036

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.35795 (10)	0.92974 (11)	0.66983 (14)	0.0370 (3)
N2	0.28449 (9)	0.83592 (9)	0.69242 (12)	0.0393 (3)
C3	0.32912 (13)	0.73216 (12)	0.63835 (19)	0.0528 (4)
H3A	0.2941	0.7103	0.5489	0.063*
H3B	0.3227	0.6737	0.7077	0.063*
C4	0.44323 (13)	0.76008 (13)	0.6168 (2)	0.0579 (5)
H4A	0.4730	0.7142	0.5437	0.070*
H4B	0.4850	0.7522	0.7051	0.070*
C5	0.43776 (12)	0.87852 (13)	0.56942 (16)	0.0469 (4)
H5A	0.4133	0.8843	0.4702	0.056*
H5B	0.5063	0.9136	0.5806	0.056*
C6	0.18955 (11)	0.84671 (11)	0.75226 (15)	0.0407 (3)
O7	0.16134 (8)	0.93179 (8)	0.81089 (11)	0.0483 (3)
C8	0.11512 (12)	0.75375 (12)	0.75045 (16)	0.0467 (4)
O9	0.12379 (11)	0.66701 (11)	0.65957 (15)	0.0722 (4)
C10	0.03949 (17)	0.60068 (17)	0.6846 (3)	0.0778 (6)
H10A	0.0256	0.5351	0.6369	0.093*
C11	−0.01849 (16)	0.64090 (19)	0.7833 (3)	0.0774 (6)
H11A	−0.0798	0.6103	0.8181	0.093*
C12	0.02967 (14)	0.74068 (17)	0.8279 (2)	0.0677 (5)
H12A	0.0061	0.7880	0.8979	0.081*
C13	0.41766 (11)	0.96223 (11)	0.81232 (14)	0.0400 (3)
N14	0.35976 (10)	0.98565 (11)	0.92272 (12)	0.0461 (3)
H14A	0.3897	1.0049	1.0028	0.055*
H14B	0.2920	0.9817	0.9147	0.055*
O15	0.51443 (8)	0.96638 (12)	0.81726 (12)	0.0629 (4)
C16	0.30340 (11)	1.02866 (11)	0.59953 (14)	0.0392 (3)
C17	0.23334 (15)	1.01476 (15)	0.48449 (17)	0.0613 (5)
H17A	0.2134	0.9445	0.4561	0.074*
C18	0.19252 (18)	1.10448 (19)	0.4111 (2)	0.0811 (6)
H18A	0.1454	1.0940	0.3338	0.097*
C19	0.22095 (17)	1.20915 (17)	0.4512 (2)	0.0752 (6)
H19A	0.1934	1.2693	0.4016	0.090*
C20	0.28994 (15)	1.22343 (14)	0.5646 (2)	0.0632 (5)
H20A	0.3101	1.2938	0.5921	0.076*
C21	0.33032 (12)	1.13408 (12)	0.63933 (17)	0.0484 (4)
H21A	0.3764	1.1453	0.7176	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0385 (7)	0.0333 (7)	0.0393 (7)	−0.0012 (5)	0.0003 (5)	−0.0004 (5)
N2	0.0412 (6)	0.0305 (6)	0.0461 (6)	−0.0016 (5)	−0.0001 (5)	−0.0024 (5)
C3	0.0564 (9)	0.0337 (8)	0.0683 (10)	0.0034 (7)	0.0030 (8)	−0.0083 (7)
C4	0.0532 (9)	0.0448 (9)	0.0761 (11)	0.0104 (7)	0.0060 (8)	−0.0100 (8)
C5	0.0463 (8)	0.0472 (9)	0.0476 (8)	0.0014 (7)	0.0049 (6)	−0.0055 (6)
C6	0.0409 (7)	0.0382 (7)	0.0425 (7)	−0.0006 (6)	−0.0049 (6)	0.0031 (6)
O7	0.0438 (6)	0.0414 (6)	0.0598 (6)	0.0023 (4)	0.0042 (5)	−0.0046 (5)
C8	0.0457 (8)	0.0428 (8)	0.0510 (8)	−0.0058 (6)	−0.0079 (7)	0.0024 (6)
O9	0.0738 (8)	0.0615 (8)	0.0810 (9)	−0.0211 (7)	−0.0014 (7)	−0.0176 (7)
C10	0.0730 (13)	0.0552 (11)	0.1033 (16)	−0.0256 (10)	−0.0251 (12)	−0.0007 (11)
C11	0.0582 (11)	0.0750 (14)	0.0984 (16)	−0.0272 (10)	−0.0058 (11)	0.0167 (12)
C12	0.0527 (10)	0.0725 (12)	0.0783 (12)	−0.0119 (9)	0.0088 (9)	−0.0042 (10)
C13	0.0426 (8)	0.0343 (7)	0.0428 (7)	−0.0010 (6)	−0.0041 (6)	0.0010 (6)
N14	0.0463 (7)	0.0509 (8)	0.0407 (6)	−0.0036 (6)	−0.0043 (5)	−0.0051 (5)
O15	0.0413 (6)	0.0906 (9)	0.0564 (7)	−0.0028 (6)	−0.0056 (5)	−0.0134 (6)
C16	0.0411 (7)	0.0372 (8)	0.0395 (7)	0.0007 (6)	0.0028 (6)	0.0029 (6)
C17	0.0772 (12)	0.0539 (10)	0.0514 (9)	0.0010 (8)	−0.0178 (8)	0.0005 (7)
C18	0.0972 (16)	0.0805 (15)	0.0634 (11)	0.0144 (12)	−0.0279 (11)	0.0126 (10)
C19	0.0894 (14)	0.0636 (13)	0.0724 (12)	0.0182 (11)	0.0002 (11)	0.0282 (10)
C20	0.0715 (11)	0.0400 (9)	0.0785 (12)	0.0008 (8)	0.0086 (9)	0.0151 (8)
C21	0.0513 (8)	0.0378 (8)	0.0561 (9)	−0.0030 (6)	−0.0004 (7)	0.0043 (6)

Geometric parameters (Å, º)

C1—N2	1.4956 (18)	C10—H10A	0.9300
C1—C16	1.5288 (19)	C11—C12	1.419 (3)
C1—C5	1.5359 (19)	C11—H11A	0.9300
C1—C13	1.5599 (19)	C12—H12A	0.9300
N2—C6	1.3498 (19)	C13—O15	1.2260 (18)
N2—C3	1.4834 (18)	C13—N14	1.3175 (19)
C3—C4	1.505 (2)	N14—H14A	0.8600
C3—H3A	0.9700	N14—H14B	0.8600
C3—H3B	0.9700	C16—C21	1.380 (2)
C4—C5	1.514 (2)	C16—C17	1.381 (2)
C4—H4A	0.9700	C17—C18	1.384 (3)
C4—H4B	0.9700	C17—H17A	0.9300
C5—H5A	0.9700	C18—C19	1.377 (3)
C5—H5B	0.9700	C18—H18A	0.9300
C6—O7	1.2335 (18)	C19—C20	1.361 (3)
C6—C8	1.475 (2)	C19—H19A	0.9300
C8—C12	1.332 (2)	C20—C21	1.384 (2)
C8—O9	1.365 (2)	C20—H20A	0.9300
O9—C10	1.367 (2)	C21—H21A	0.9300
C10—C11	1.296 (3)
N2—C1—C16	113.09 (11)	C11—C10—O9	111.23 (18)
N2—C1—C5	101.53 (11)	C11—C10—H10A	124.4
C16—C1—C5	110.89 (11)	O9—C10—H10A	124.4
N2—C1—C13	111.10 (10)	C10—C11—C12	106.65 (18)
C16—C1—C13	111.36 (11)	C10—C11—H11A	126.7
C5—C1—C13	108.38 (11)	C12—C11—H11A	126.7
C6—N2—C3	125.44 (12)	C8—C12—C11	106.99 (18)
C6—N2—C1	123.44 (11)	C8—C12—H12A	126.5
C3—N2—C1	111.12 (11)	C11—C12—H12A	126.5
N2—C3—C4	103.35 (12)	O15—C13—N14	122.97 (13)
N2—C3—H3A	111.1	O15—C13—C1	119.82 (13)
C4—C3—H3A	111.1	N14—C13—C1	117.21 (12)
N2—C3—H3B	111.1	C13—N14—H14A	120.0
C4—C3—H3B	111.1	C13—N14—H14B	120.0
H3A—C3—H3B	109.1	H14A—N14—H14B	120.0
C3—C4—C5	102.78 (13)	C21—C16—C17	118.09 (14)
C3—C4—H4A	111.2	C21—C16—C1	121.19 (13)
C5—C4—H4A	111.2	C17—C16—C1	120.41 (13)
C3—C4—H4B	111.2	C16—C17—C18	120.52 (17)
C5—C4—H4B	111.2	C16—C17—H17A	119.7
H4A—C4—H4B	109.1	C18—C17—H17A	119.7
C4—C5—C1	103.60 (12)	C19—C18—C17	120.70 (18)
C4—C5—H5A	111.0	C19—C18—H18A	119.7
C1—C5—H5A	111.0	C17—C18—H18A	119.7
C4—C5—H5B	111.0	C20—C19—C18	119.07 (17)
C1—C5—H5B	111.0	C20—C19—H19A	120.5
H5A—C5—H5B	109.0	C18—C19—H19A	120.5
O7—C6—N2	122.82 (13)	C19—C20—C21	120.52 (17)
O7—C6—C8	117.30 (13)	C19—C20—H20A	119.7
N2—C6—C8	119.87 (13)	C21—C20—H20A	119.7
C12—C8—O9	109.24 (15)	C16—C21—C20	121.08 (16)
C12—C8—C6	128.08 (15)	C16—C21—H21A	119.5
O9—C8—C6	122.64 (14)	C20—C21—H21A	119.5
C8—O9—C10	105.89 (16)
C16—C1—N2—C6	−48.28 (16)	O9—C10—C11—C12	0.0 (3)
C5—C1—N2—C6	−167.13 (12)	O9—C8—C12—C11	−0.3 (2)
C13—C1—N2—C6	77.81 (15)	C6—C8—C12—C11	177.31 (16)
C16—C1—N2—C3	130.68 (13)	C10—C11—C12—C8	0.2 (2)
C5—C1—N2—C3	11.83 (14)	N2—C1—C13—O15	125.78 (14)
C13—C1—N2—C3	−103.23 (13)	C16—C1—C13—O15	−107.19 (15)
C6—N2—C3—C4	−167.03 (14)	C5—C1—C13—O15	15.05 (18)
C1—N2—C3—C4	14.03 (17)	N2—C1—C13—N14	−55.12 (16)
N2—C3—C4—C5	−34.48 (17)	C16—C1—C13—N14	71.92 (16)
C3—C4—C5—C1	42.69 (16)	C5—C1—C13—N14	−165.85 (12)
N2—C1—C5—C4	−33.07 (14)	N2—C1—C16—C21	142.35 (13)
C16—C1—C5—C4	−153.48 (12)	C5—C1—C16—C21	−104.37 (15)
C13—C1—C5—C4	84.00 (14)	C13—C1—C16—C21	16.40 (18)
C3—N2—C6—O7	171.10 (14)	N2—C1—C16—C17	−44.18 (18)
C1—N2—C6—O7	−10.1 (2)	C5—C1—C16—C17	69.10 (18)
C3—N2—C6—C8	−8.2 (2)	C13—C1—C16—C17	−170.12 (13)
C1—N2—C6—C8	170.57 (12)	C21—C16—C17—C18	0.6 (3)
O7—C6—C8—C12	−14.8 (2)	C1—C16—C17—C18	−173.06 (17)
N2—C6—C8—C12	164.61 (16)	C16—C17—C18—C19	0.0 (3)
O7—C6—C8—O9	162.59 (14)	C17—C18—C19—C20	−0.1 (3)
N2—C6—C8—O9	−18.0 (2)	C18—C19—C20—C21	−0.5 (3)
C12—C8—O9—C10	0.30 (19)	C17—C16—C21—C20	−1.2 (2)
C6—C8—O9—C10	−177.49 (15)	C1—C16—C21—C20	172.43 (14)
C8—O9—C10—C11	−0.2 (2)	C19—C20—C21—C16	1.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N14—H14A···O15^i	0.86	2.07	2.919 (2)	169
N14—H14B···O7	0.86	1.99	2.768 (2)	151

Symmetry code: (i) −x+1, −y+2, −z+2.