Methyl 7-oxo-12-propyl-amino-13-nitro-deisopropyl-dehydro-abietate.

In the title compound, C(21)H(28)N(2)O(5) (systematic name: methyl 1,4a-dimethyl-7-nitro-9-oxo-6-propyl-amino-1,2,3,4,4a,9,10,10a-octa-hydro-phenanthrene-1-carboxyl-ate) the cyclo-hexane ring (A) and the central cyclo-hexene ring (B) exist at a trans ring junction, with the two methyl groups in the axial positions of the six-membered rings. Ring A has a chair conformation and ring B a half-chair conformation. An intra-molecular N-H⋯O hydrogen bond occurs. The crystal structure is stabilized by inter-molecular C-H⋯O and N-H⋯O inter-actions.

Related literature

For inhibition of viruses by resin acid derivatives, see: Fonseca et al. (2004 ▶); Gigante et al. (2003 ▶). For related structures, see: Hamodrakas et al. (1978 ▶); Silvestre et al. (1998 ▶).

Experimental

Crystal data

C21H28N2O5

M = 388.45

Orthorhombic,

a = 8.2915 (15) Å

b = 11.344 (2) Å

c = 20.288 (4) Å

V = 1908.3 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 223 K

0.40 × 0.18 × 0.14 mm

Data collection

Rigaku Saturn diffractometer

Absorption correction: multi-scan (Jacobson, 1998 ▶) T min = 0.956, T max = 0.987

9263 measured reflections

2492 independent reflections

2249 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.122

S = 1.19

2492 reflections

262 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.16 e Å−3

Δρmin = −0.20 e Å−3

Data collection: CrystalClear (Rigaku, 1999 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2000 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810032824/ng5010sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032824/ng5010Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H28N2O5	F(000) = 832
Mr = 388.45	Dx = 1.352 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6184 reflections
a = 8.2915 (15) Å	θ = 3.0–27.5°
b = 11.344 (2) Å	µ = 0.10 mm−1
c = 20.288 (4) Å	T = 223 K
V = 1908.3 (6) Å3	Block, yellow
Z = 4	0.40 × 0.18 × 0.14 mm

Rigaku Saturn diffractometer	2492 independent reflections
Radiation source: fine-focus sealed tube	2249 reflections with I > 2σ(I)
graphite	Rint = 0.047
Detector resolution: 14.63 pixels mm-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (Jacobson, 1998)	k = −13→14
Tmin = 0.956, Tmax = 0.987	l = −26→18
9263 measured reflections

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	w = 1/[σ2(Fo2) + (0.040P)2 + 0.3656P] where P = (Fo2 + 2Fc2)/3
2492 reflections	(Δ/σ)max < 0.001
262 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	−0.0800 (3)	0.5805 (2)	0.50671 (13)	0.0413 (7)
O2	0.1082 (3)	0.8201 (2)	0.32927 (14)	0.0428 (7)
O3	0.3574 (3)	0.8723 (2)	0.31899 (13)	0.0374 (6)
O4	0.1294 (4)	0.3814 (3)	0.75394 (15)	0.0594 (9)
O5	0.2387 (3)	0.5514 (2)	0.72342 (13)	0.0393 (6)
N1	0.5809 (3)	0.7320 (3)	0.37018 (15)	0.0301 (7)
H1A	0.552 (4)	0.784 (3)	0.3368 (19)	0.034 (10)*
N2	0.2510 (3)	0.8110 (3)	0.34543 (14)	0.0296 (6)
C1	0.4799 (4)	0.5968 (3)	0.45202 (16)	0.0273 (7)
H1B	0.5847	0.5672	0.4583	0.033*
C2	0.4562 (4)	0.6880 (3)	0.40463 (16)	0.0261 (7)
C3	0.2948 (4)	0.7264 (3)	0.39580 (16)	0.0264 (7)
C4	0.1710 (4)	0.6826 (3)	0.43411 (16)	0.0272 (7)
H4	0.0662	0.7126	0.4284	0.033*
C5	0.1976 (4)	0.5958 (3)	0.48066 (16)	0.0259 (7)
C6	0.3556 (4)	0.5500 (3)	0.48907 (15)	0.0249 (7)
C7	0.0594 (4)	0.5512 (3)	0.51883 (17)	0.0306 (8)
C8	0.0933 (4)	0.4657 (3)	0.57383 (17)	0.0291 (7)
H8A	0.0626	0.3863	0.5595	0.035*
H8B	0.0262	0.4863	0.6119	0.035*
C9	0.2698 (4)	0.4647 (3)	0.59499 (15)	0.0255 (7)
H9	0.2930	0.5455	0.6106	0.031*
C10	0.2965 (4)	0.3826 (3)	0.65599 (17)	0.0285 (7)
C11	0.4779 (4)	0.3807 (3)	0.67347 (18)	0.0336 (8)
H11A	0.5099	0.4585	0.6899	0.040*
H11B	0.4962	0.3233	0.7088	0.040*
C12	0.5822 (5)	0.3488 (4)	0.61471 (19)	0.0382 (9)
H12A	0.5536	0.2697	0.5992	0.046*
H12B	0.6958	0.3477	0.6281	0.046*
C13	0.5592 (4)	0.4378 (3)	0.55853 (18)	0.0339 (8)
H13A	0.6285	0.4154	0.5214	0.041*
H13B	0.5933	0.5160	0.5737	0.041*
C14	0.3833 (4)	0.4444 (3)	0.53470 (16)	0.0264 (7)
C15	0.7445 (4)	0.6817 (3)	0.36949 (17)	0.0294 (7)
H15A	0.7771	0.6639	0.4148	0.035*
H15B	0.8197	0.7406	0.3520	0.035*
C16	0.7571 (4)	0.5698 (3)	0.32818 (18)	0.0346 (8)
H16A	0.7319	0.5881	0.2821	0.042*
H16B	0.6781	0.5120	0.3439	0.042*
C17	0.9260 (4)	0.5170 (3)	0.33244 (19)	0.0364 (9)
H17A	1.0049	0.5762	0.3202	0.055*
H17B	0.9340	0.4504	0.3026	0.055*
H17C	0.9465	0.4909	0.3772	0.055*
C18	0.2105 (4)	0.4364 (3)	0.71584 (18)	0.0326 (8)
C19	0.1741 (5)	0.6042 (4)	0.7827 (2)	0.0500 (11)
H19A	0.0574	0.5989	0.7821	0.075*
H19B	0.2061	0.6864	0.7848	0.075*
H19C	0.2156	0.5627	0.8210	0.075*
C20	0.2305 (5)	0.2577 (3)	0.6477 (2)	0.0412 (9)
H20A	0.2449	0.2143	0.6885	0.062*
H20B	0.2882	0.2182	0.6125	0.062*
H20C	0.1167	0.2613	0.6369	0.062*
C21	0.3452 (5)	0.3342 (3)	0.49327 (18)	0.0376 (9)
H21A	0.4110	0.3344	0.4538	0.056*
H21B	0.2321	0.3347	0.4811	0.056*
H21C	0.3684	0.2640	0.5189	0.056*

	U11	U22	U33	U12	U13	U23
O1	0.0236 (12)	0.0637 (19)	0.0365 (15)	0.0019 (13)	0.0007 (11)	0.0130 (14)
O2	0.0259 (13)	0.0531 (16)	0.0492 (17)	0.0044 (13)	−0.0076 (13)	0.0179 (14)
O3	0.0346 (13)	0.0395 (14)	0.0382 (15)	−0.0046 (12)	0.0018 (12)	0.0126 (12)
O4	0.077 (2)	0.0477 (17)	0.053 (2)	0.0017 (17)	0.0362 (18)	0.0111 (15)
O5	0.0461 (15)	0.0413 (14)	0.0305 (14)	0.0002 (13)	0.0097 (12)	−0.0060 (12)
N1	0.0234 (14)	0.0372 (17)	0.0299 (16)	−0.0009 (13)	0.0009 (12)	0.0100 (13)
N2	0.0298 (15)	0.0315 (15)	0.0275 (14)	0.0017 (14)	−0.0013 (13)	0.0004 (13)
C1	0.0216 (14)	0.0353 (19)	0.0248 (17)	0.0028 (14)	0.0011 (13)	0.0005 (15)
C2	0.0239 (16)	0.0304 (18)	0.0239 (17)	−0.0055 (15)	0.0017 (13)	−0.0018 (15)
C3	0.0275 (16)	0.0288 (17)	0.0228 (16)	0.0026 (15)	−0.0052 (13)	0.0015 (14)
C4	0.0210 (15)	0.0338 (18)	0.0268 (17)	−0.0007 (15)	0.0008 (13)	−0.0020 (14)
C5	0.0214 (14)	0.0314 (17)	0.0250 (17)	0.0004 (14)	0.0019 (12)	−0.0001 (14)
C6	0.0251 (15)	0.0306 (17)	0.0191 (15)	−0.0040 (14)	−0.0012 (13)	−0.0021 (13)
C7	0.0255 (16)	0.039 (2)	0.0271 (18)	−0.0021 (16)	0.0007 (14)	−0.0005 (16)
C8	0.0255 (16)	0.0344 (19)	0.0274 (18)	−0.0031 (15)	0.0029 (13)	0.0044 (15)
C9	0.0261 (17)	0.0260 (17)	0.0245 (16)	0.0017 (15)	0.0013 (13)	−0.0003 (13)
C10	0.0323 (17)	0.0271 (17)	0.0261 (17)	0.0002 (15)	0.0035 (14)	0.0041 (14)
C11	0.0343 (18)	0.039 (2)	0.0271 (18)	0.0047 (16)	0.0000 (15)	0.0068 (16)
C12	0.0332 (19)	0.046 (2)	0.036 (2)	0.0116 (18)	0.0032 (17)	0.0074 (17)
C13	0.0305 (17)	0.042 (2)	0.0290 (19)	0.0076 (17)	0.0032 (14)	0.0060 (16)
C14	0.0274 (16)	0.0258 (17)	0.0259 (17)	0.0019 (15)	0.0030 (13)	−0.0010 (14)
C15	0.0202 (15)	0.0356 (19)	0.0326 (18)	0.0007 (16)	−0.0007 (14)	0.0027 (15)
C16	0.0302 (17)	0.040 (2)	0.0332 (19)	−0.0007 (17)	0.0017 (15)	−0.0035 (16)
C17	0.0303 (17)	0.041 (2)	0.038 (2)	0.0018 (17)	0.0047 (16)	−0.0022 (17)
C18	0.0332 (18)	0.0372 (19)	0.0272 (18)	0.0019 (16)	0.0003 (14)	0.0058 (16)
C19	0.061 (3)	0.059 (3)	0.030 (2)	0.010 (2)	0.007 (2)	−0.013 (2)
C20	0.051 (2)	0.0318 (19)	0.041 (2)	0.0020 (19)	0.0046 (19)	0.0052 (17)
C21	0.051 (2)	0.035 (2)	0.0275 (19)	−0.0011 (18)	0.0040 (17)	−0.0043 (16)

O1—C7	1.227 (4)	C10—C11	1.545 (5)
O2—N2	1.233 (3)	C11—C12	1.517 (5)
O3—N2	1.245 (3)	C11—H11A	0.9800
O4—C18	1.200 (4)	C11—H11B	0.9800
O5—C18	1.334 (4)	C12—C13	1.535 (5)
O5—C19	1.447 (4)	C12—H12A	0.9800
N1—C2	1.344 (4)	C12—H12B	0.9800
N1—C15	1.472 (4)	C13—C14	1.539 (5)
N1—H1A	0.93 (4)	C13—H13A	0.9800
N2—C3	1.448 (4)	C13—H13B	0.9800
C1—C6	1.382 (4)	C14—C21	1.540 (5)
C1—C2	1.426 (5)	C15—C16	1.525 (5)
C1—H1B	0.9400	C15—H15A	0.9800
C2—C3	1.418 (4)	C15—H15B	0.9800
C3—C4	1.380 (5)	C16—C17	1.525 (5)
C4—C5	1.383 (5)	C16—H16A	0.9800
C4—H4	0.9400	C16—H16B	0.9800
C5—C6	1.419 (4)	C17—H17A	0.9700
C5—C7	1.472 (4)	C17—H17B	0.9700
C6—C14	1.531 (5)	C17—H17C	0.9700
C7—C8	1.505 (5)	C19—H19A	0.9700
C8—C9	1.525 (4)	C19—H19B	0.9700
C8—H8A	0.9800	C19—H19C	0.9700
C8—H8B	0.9800	C20—H20A	0.9700
C9—C14	1.560 (4)	C20—H20B	0.9700
C9—C10	1.564 (5)	C20—H20C	0.9700
C9—H9	0.9900	C21—H21A	0.9700
C10—C20	1.529 (5)	C21—H21B	0.9700
C10—C18	1.535 (5)	C21—H21C	0.9700
C18—O5—C19	115.8 (3)	C11—C12—H12B	109.5
C2—N1—C15	124.8 (3)	C13—C12—H12B	109.5
C2—N1—H1A	115 (2)	H12A—C12—H12B	108.1
C15—N1—H1A	118 (2)	C12—C13—C14	112.5 (3)
O2—N2—O3	121.3 (3)	C12—C13—H13A	109.1
O2—N2—C3	119.0 (3)	C14—C13—H13A	109.1
O3—N2—C3	119.7 (3)	C12—C13—H13B	109.1
C6—C1—C2	122.8 (3)	C14—C13—H13B	109.1
C6—C1—H1B	118.6	H13A—C13—H13B	107.8
C2—C1—H1B	118.6	C6—C14—C13	111.8 (3)
N1—C2—C3	123.1 (3)	C6—C14—C21	105.9 (3)
N1—C2—C1	120.9 (3)	C13—C14—C21	109.0 (3)
C3—C2—C1	116.0 (3)	C6—C14—C9	105.6 (3)
C4—C3—C2	121.4 (3)	C13—C14—C9	109.4 (3)
C4—C3—N2	116.7 (3)	C21—C14—C9	115.1 (3)
C2—C3—N2	122.0 (3)	N1—C15—C16	113.0 (3)
C3—C4—C5	121.5 (3)	N1—C15—H15A	109.0
C3—C4—H4	119.3	C16—C15—H15A	109.0
C5—C4—H4	119.3	N1—C15—H15B	109.0
C4—C5—C6	119.3 (3)	C16—C15—H15B	109.0
C4—C5—C7	118.7 (3)	H15A—C15—H15B	107.8
C6—C5—C7	122.0 (3)	C15—C16—C17	111.0 (3)
C1—C6—C5	118.9 (3)	C15—C16—H16A	109.4
C1—C6—C14	121.1 (3)	C17—C16—H16A	109.4
C5—C6—C14	119.8 (3)	C15—C16—H16B	109.4
O1—C7—C5	122.3 (3)	C17—C16—H16B	109.4
O1—C7—C8	119.9 (3)	H16A—C16—H16B	108.0
C5—C7—C8	117.8 (3)	C16—C17—H17A	109.5
C7—C8—C9	113.1 (3)	C16—C17—H17B	109.5
C7—C8—H8A	109.0	H17A—C17—H17B	109.5
C9—C8—H8A	109.0	C16—C17—H17C	109.5
C7—C8—H8B	109.0	H17A—C17—H17C	109.5
C9—C8—H8B	109.0	H17B—C17—H17C	109.5
H8A—C8—H8B	107.8	O4—C18—O5	122.2 (4)
C8—C9—C14	111.1 (3)	O4—C18—C10	124.3 (3)
C8—C9—C10	111.3 (3)	O5—C18—C10	113.5 (3)
C14—C9—C10	116.6 (3)	O5—C19—H19A	109.5
C8—C9—H9	105.7	O5—C19—H19B	109.5
C14—C9—H9	105.7	H19A—C19—H19B	109.5
C10—C9—H9	105.7	O5—C19—H19C	109.5
C20—C10—C18	106.8 (3)	H19A—C19—H19C	109.5
C20—C10—C11	111.1 (3)	H19B—C19—H19C	109.5
C18—C10—C11	106.1 (3)	C10—C20—H20A	109.5
C20—C10—C9	114.5 (3)	C10—C20—H20B	109.5
C18—C10—C9	108.9 (3)	H20A—C20—H20B	109.5
C11—C10—C9	109.2 (3)	C10—C20—H20C	109.5
C12—C11—C10	112.2 (3)	H20A—C20—H20C	109.5
C12—C11—H11A	109.2	H20B—C20—H20C	109.5
C10—C11—H11A	109.2	C14—C21—H21A	109.5
C12—C11—H11B	109.2	C14—C21—H21B	109.5
C10—C11—H11B	109.2	H21A—C21—H21B	109.5
H11A—C11—H11B	107.9	C14—C21—H21C	109.5
C11—C12—C13	110.8 (3)	H21A—C21—H21C	109.5
C11—C12—H12A	109.5	H21B—C21—H21C	109.5
C13—C12—H12A	109.5
C15—N1—C2—C3	−169.2 (3)	C14—C9—C10—C18	164.2 (3)
C15—N1—C2—C1	9.6 (5)	C8—C9—C10—C11	177.6 (3)
C6—C1—C2—N1	179.2 (3)	C14—C9—C10—C11	48.8 (4)
C6—C1—C2—C3	−2.0 (5)	C20—C10—C11—C12	73.9 (4)
N1—C2—C3—C4	−177.2 (3)	C18—C10—C11—C12	−170.4 (3)
C1—C2—C3—C4	4.0 (5)	C9—C10—C11—C12	−53.2 (4)
N1—C2—C3—N2	4.2 (5)	C10—C11—C12—C13	59.8 (4)
C1—C2—C3—N2	−174.6 (3)	C11—C12—C13—C14	−59.2 (4)
O2—N2—C3—C4	−15.9 (5)	C1—C6—C14—C13	26.8 (4)
O3—N2—C3—C4	164.6 (3)	C5—C6—C14—C13	−157.9 (3)
O2—N2—C3—C2	162.7 (3)	C1—C6—C14—C21	−91.8 (4)
O3—N2—C3—C2	−16.7 (5)	C5—C6—C14—C21	83.5 (4)
C2—C3—C4—C5	−3.0 (5)	C1—C6—C14—C9	145.7 (3)
N2—C3—C4—C5	175.7 (3)	C5—C6—C14—C9	−39.0 (4)
C3—C4—C5—C6	−0.3 (5)	C12—C13—C14—C6	168.4 (3)
C3—C4—C5—C7	−178.7 (3)	C12—C13—C14—C21	−74.8 (4)
C2—C1—C6—C5	−1.1 (5)	C12—C13—C14—C9	51.8 (4)
C2—C1—C6—C14	174.2 (3)	C8—C9—C14—C6	62.4 (3)
C4—C5—C6—C1	2.3 (5)	C10—C9—C14—C6	−168.7 (3)
C7—C5—C6—C1	−179.4 (3)	C8—C9—C14—C13	−177.2 (3)
C4—C5—C6—C14	−173.1 (3)	C10—C9—C14—C13	−48.3 (4)
C7—C5—C6—C14	5.2 (5)	C8—C9—C14—C21	−54.0 (4)
C4—C5—C7—O1	6.8 (5)	C10—C9—C14—C21	74.9 (4)
C6—C5—C7—O1	−171.5 (3)	C2—N1—C15—C16	75.2 (4)
C4—C5—C7—C8	−174.0 (3)	N1—C15—C16—C17	−176.5 (3)
C6—C5—C7—C8	7.7 (5)	C19—O5—C18—O4	3.8 (5)
O1—C7—C8—C9	−164.0 (3)	C19—O5—C18—C10	−173.9 (3)
C5—C7—C8—C9	16.8 (4)	C20—C10—C18—O4	11.4 (5)
C7—C8—C9—C14	−53.1 (4)	C11—C10—C18—O4	−107.1 (4)
C7—C8—C9—C10	175.2 (3)	C9—C10—C18—O4	135.5 (4)
C8—C9—C10—C20	52.4 (4)	C20—C10—C18—O5	−170.8 (3)
C14—C9—C10—C20	−76.4 (4)	C11—C10—C18—O5	70.6 (4)
C8—C9—C10—C18	−67.0 (3)	C9—C10—C18—O5	−46.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.93 (4)	1.94 (4)	2.654 (4)	133 (3)
C8—H8B···O3i	0.98	2.55	3.454 (4)	154
C15—H15A···O1ii	0.98	2.40	3.344 (4)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3	0.93 (4)	1.94 (4)	2.654 (4)	133 (3)
C8—H8B⋯O3i	0.98	2.55	3.454 (4)	154
C15—H15A⋯O1ii	0.98	2.40	3.344 (4)	161

Symmetry codes: (i) ; (ii) .