A diastereoisomer of pyrano­[3,2-c]­quinoline

The title compound, 5-(4-nitro­phenyl)-3,4,4a,5,6,10b-hexa­hydro-2H-pyrano­[3,2-c]­quinoline, C₁₈H₁₈N₂O₃, was obtained from the Diels–Alder reaction of N-benyl­idene­aniline and di­hydro­pyran, catalyzed by zirconium tetrachloride. This mol­ecule is an exo-cyclo­adduct isomer. The pyran ring adopts a chair conformation, while the N-heterocyclic ring prefers a half-chair conformation. Molecules are associated into centrosymmetric dimers by N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.061
• wR factor = 0.139
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

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Computing details

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: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

5-(4-nitrophenyl)-3,4,4a,5,6,10b-hexahydro-2H-pyrano[3,2-c]quinoline

Crystal data

C18H18N2O3	Z = 2
Mr = 310.34	F(000) = 328
Triclinic, P1	Dx = 1.309 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5001 (10) Å	Cell parameters from 2569 reflections
b = 9.8823 (10) Å	θ = 2.2–26.7°
c = 9.9403 (10) Å	µ = 0.09 mm^−1
α = 98.039 (2)°	T = 273 K
β = 115.157 (2)°	Block, colorless
γ = 104.092 (2)°	0.20 × 0.15 × 0.10 mm
V = 787.18 (14) Å^3

Data collection

CCD Area Detector diffractometer	2344 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω scans	h = −11→11
7650 measured reflections	k = −11→11
2770 independent reflections	l = −11→11

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0514P)^2 + 0.2373P] where P = (Fo^2 + 2Fc^2)/3
2770 reflections	(Δ/σ)max < 0.001
212 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.5979 (3)	0.8189 (2)	1.1103 (2)	0.0633 (6)
H1N	0.700 (3)	0.845 (3)	1.171 (3)	0.068 (8)*
N2	0.9753 (2)	0.9282 (2)	0.7131 (2)	0.0614 (5)
O1	0.2223 (2)	0.49447 (16)	0.88797 (18)	0.0605 (4)
O2	1.0328 (3)	0.8449 (2)	0.6707 (3)	0.0950 (7)
O3	1.0069 (2)	1.0536 (2)	0.7075 (2)	0.0857 (6)
C1	0.1396 (4)	0.4255 (3)	0.7255 (3)	0.0763 (8)
H1A	0.0376	0.4462	0.6764	0.092*
H1B	0.1117	0.3212	0.7080	0.092*
C2	0.2467 (4)	0.4781 (3)	0.6543 (3)	0.0767 (8)
H2A	0.1876	0.4319	0.5438	0.092*
H2B	0.3460	0.4525	0.6988	0.092*
C3	0.2927 (3)	0.6409 (3)	0.6840 (3)	0.0616 (6)
H3A	0.1952	0.6643	0.6241	0.074*
H3B	0.3727	0.6757	0.6495	0.074*
C4	0.3654 (3)	0.7188 (2)	0.8548 (2)	0.0474 (5)
H4	0.3664	0.8190	0.8623	0.057*
C5	0.5427 (3)	0.7245 (2)	0.9584 (2)	0.0498 (5)
H5	0.5411	0.6267	0.9675	0.060*
C6	0.4998 (3)	0.7882 (3)	1.1804 (3)	0.0539 (6)
C7	0.5660 (3)	0.8426 (3)	1.3395 (3)	0.0720 (7)
H7	0.6772	0.8989	1.3992	0.086*
C8	0.4692 (4)	0.8142 (3)	1.4090 (3)	0.0752 (8)
H8	0.5155	0.8502	1.5156	0.090*
C9	0.3040 (3)	0.7331 (3)	1.3229 (3)	0.0682 (7)
H9	0.2387	0.7136	1.3706	0.082*
C10	0.2373 (3)	0.6814 (2)	1.1663 (3)	0.0563 (6)
H10	0.1252	0.6279	1.1079	0.068*
C11	0.3321 (3)	0.7064 (2)	1.0918 (2)	0.0478 (5)
C12	0.2562 (3)	0.6479 (2)	0.9197 (2)	0.0486 (5)
H12	0.1511	0.6656	0.8710	0.058*
C13	0.6592 (3)	0.7803 (2)	0.8970 (2)	0.0478 (5)
C14	0.7181 (3)	0.6864 (2)	0.8361 (3)	0.0577 (6)
H14	0.6877	0.5897	0.8367	0.069*
C15	0.8203 (3)	0.7333 (2)	0.7749 (3)	0.0580 (6)
H15	0.8588	0.6695	0.7340	0.070*
C16	0.8640 (2)	0.8762 (2)	0.7756 (2)	0.0488 (5)
C17	0.8087 (3)	0.9725 (2)	0.8354 (3)	0.0570 (6)
H17	0.8401	1.0693	0.8352	0.068*
C18	0.7064 (3)	0.9235 (2)	0.8953 (3)	0.0564 (6)
H18	0.6680	0.9880	0.9355	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0414 (12)	0.0900 (16)	0.0446 (12)	0.0119 (11)	0.0155 (10)	0.0133 (10)
N2	0.0474 (11)	0.0708 (14)	0.0615 (13)	0.0120 (10)	0.0253 (10)	0.0218 (11)
O1	0.0653 (10)	0.0502 (9)	0.0578 (10)	0.0125 (8)	0.0257 (8)	0.0152 (7)
O2	0.0970 (15)	0.1009 (15)	0.1311 (19)	0.0418 (13)	0.0857 (15)	0.0414 (13)
O3	0.0796 (13)	0.0763 (13)	0.1152 (17)	0.0176 (10)	0.0578 (12)	0.0449 (12)
C1	0.0798 (19)	0.0594 (15)	0.0636 (17)	0.0066 (13)	0.0255 (15)	0.0008 (13)
C2	0.0825 (19)	0.0743 (18)	0.0563 (16)	0.0183 (15)	0.0287 (15)	−0.0015 (13)
C3	0.0588 (14)	0.0763 (17)	0.0473 (13)	0.0219 (12)	0.0230 (11)	0.0191 (12)
C4	0.0510 (12)	0.0491 (12)	0.0439 (12)	0.0222 (10)	0.0204 (10)	0.0168 (9)
C5	0.0483 (12)	0.0556 (13)	0.0485 (13)	0.0197 (10)	0.0229 (10)	0.0203 (10)
C6	0.0500 (13)	0.0654 (14)	0.0485 (13)	0.0214 (11)	0.0233 (11)	0.0195 (11)
C7	0.0587 (15)	0.095 (2)	0.0451 (14)	0.0167 (14)	0.0170 (12)	0.0126 (13)
C8	0.0797 (19)	0.098 (2)	0.0451 (14)	0.0286 (16)	0.0299 (14)	0.0154 (14)
C9	0.0753 (18)	0.0886 (19)	0.0592 (16)	0.0344 (15)	0.0421 (14)	0.0296 (14)
C10	0.0542 (13)	0.0601 (14)	0.0599 (15)	0.0222 (11)	0.0288 (12)	0.0218 (11)
C11	0.0484 (12)	0.0512 (12)	0.0497 (13)	0.0228 (10)	0.0234 (10)	0.0207 (10)
C12	0.0433 (12)	0.0545 (13)	0.0483 (13)	0.0205 (10)	0.0187 (10)	0.0186 (10)
C13	0.0447 (12)	0.0521 (12)	0.0469 (12)	0.0196 (10)	0.0191 (10)	0.0182 (10)
C14	0.0600 (14)	0.0486 (13)	0.0776 (16)	0.0238 (11)	0.0388 (13)	0.0261 (12)
C15	0.0574 (14)	0.0570 (14)	0.0724 (16)	0.0263 (11)	0.0378 (13)	0.0206 (12)
C16	0.0399 (11)	0.0542 (13)	0.0454 (12)	0.0115 (10)	0.0164 (10)	0.0146 (10)
C17	0.0620 (14)	0.0438 (12)	0.0604 (14)	0.0136 (11)	0.0273 (12)	0.0151 (11)
C18	0.0616 (14)	0.0516 (13)	0.0605 (14)	0.0215 (11)	0.0325 (12)	0.0135 (11)

Geometric parameters (Å, º)

N1—C6	1.385 (3)	C6—C7	1.393 (3)
N1—C5	1.457 (3)	C6—C11	1.396 (3)
N1—H1N	0.84 (3)	C7—C8	1.368 (4)
N2—O2	1.214 (3)	C7—H7	0.9300
N2—O3	1.217 (3)	C8—C9	1.375 (4)
N2—C16	1.466 (3)	C8—H8	0.9300
O1—C1	1.429 (3)	C9—C10	1.367 (3)
O1—C12	1.429 (2)	C9—H9	0.9300
C1—C2	1.505 (4)	C10—C11	1.389 (3)
C1—H1A	0.9700	C10—H10	0.9300
C1—H1B	0.9700	C11—C12	1.501 (3)
C2—C3	1.511 (4)	C12—H12	0.9800
C2—H2A	0.9700	C13—C18	1.382 (3)
C2—H2B	0.9700	C13—C14	1.387 (3)
C3—C4	1.526 (3)	C14—C15	1.375 (3)
C3—H3A	0.9700	C14—H14	0.9300
C3—H3B	0.9700	C15—C16	1.370 (3)
C4—C12	1.525 (3)	C15—H15	0.9300
C4—C5	1.538 (3)	C16—C17	1.374 (3)
C4—H4	0.9800	C17—C18	1.369 (3)
C5—C13	1.506 (3)	C17—H17	0.9300
C5—H5	0.9800	C18—H18	0.9300
C6—N1—C5	118.0 (2)	C8—C7—C6	120.6 (2)
C6—N1—H1N	114.3 (17)	C8—C7—H7	119.7
C5—N1—H1N	114.8 (17)	C6—C7—H7	119.7
O2—N2—O3	122.9 (2)	C7—C8—C9	120.7 (2)
O2—N2—C16	118.6 (2)	C7—C8—H8	119.6
O3—N2—C16	118.5 (2)	C9—C8—H8	119.6
C1—O1—C12	111.62 (17)	C10—C9—C8	119.1 (2)
O1—C1—C2	111.0 (2)	C10—C9—H9	120.5
O1—C1—H1A	109.4	C8—C9—H9	120.5
C2—C1—H1A	109.4	C9—C10—C11	121.9 (2)
O1—C1—H1B	109.4	C9—C10—H10	119.0
C2—C1—H1B	109.4	C11—C10—H10	119.0
H1A—C1—H1B	108.0	C10—C11—C6	118.6 (2)
C1—C2—C3	109.5 (2)	C10—C11—C12	120.9 (2)
C1—C2—H2A	109.8	C6—C11—C12	120.50 (19)
C3—C2—H2A	109.8	O1—C12—C11	106.74 (16)
C1—C2—H2B	109.8	O1—C12—C4	111.84 (17)
C3—C2—H2B	109.8	C11—C12—C4	112.93 (17)
H2A—C2—H2B	108.2	O1—C12—H12	108.4
C2—C3—C4	112.26 (19)	C11—C12—H12	108.4
C2—C3—H3A	109.2	C4—C12—H12	108.4
C4—C3—H3A	109.2	C18—C13—C14	118.2 (2)
C2—C3—H3B	109.2	C18—C13—C5	121.70 (19)
C4—C3—H3B	109.2	C14—C13—C5	120.08 (19)
H3A—C3—H3B	107.9	C15—C14—C13	121.4 (2)
C12—C4—C3	110.30 (18)	C15—C14—H14	119.3
C12—C4—C5	108.21 (16)	C13—C14—H14	119.3
C3—C4—C5	114.84 (18)	C16—C15—C14	118.5 (2)
C12—C4—H4	107.7	C16—C15—H15	120.8
C3—C4—H4	107.7	C14—C15—H15	120.8
C5—C4—H4	107.7	C15—C16—C17	121.8 (2)
N1—C5—C13	110.25 (18)	C15—C16—N2	119.1 (2)
N1—C5—C4	106.65 (17)	C17—C16—N2	119.1 (2)
C13—C5—C4	112.94 (17)	C18—C17—C16	118.8 (2)
N1—C5—H5	109.0	C18—C17—H17	120.6
C13—C5—H5	109.0	C16—C17—H17	120.6
C4—C5—H5	109.0	C17—C18—C13	121.3 (2)
N1—C6—C7	120.4 (2)	C17—C18—H18	119.3
N1—C6—C11	120.5 (2)	C13—C18—H18	119.3
C7—C6—C11	119.1 (2)
C12—O1—C1—C2	63.0 (3)	C10—C11—C12—O1	−72.1 (2)
O1—C1—C2—C3	−58.1 (3)	C6—C11—C12—O1	108.3 (2)
C1—C2—C3—C4	51.7 (3)	C10—C11—C12—C4	164.56 (19)
C2—C3—C4—C12	−48.7 (3)	C6—C11—C12—C4	−15.0 (3)
C2—C3—C4—C5	73.9 (3)	C3—C4—C12—O1	51.9 (2)
C6—N1—C5—C13	176.45 (19)	C5—C4—C12—O1	−74.5 (2)
C6—N1—C5—C4	53.5 (3)	C3—C4—C12—C11	172.32 (17)
C12—C4—C5—N1	−64.0 (2)	C5—C4—C12—C11	45.9 (2)
C3—C4—C5—N1	172.33 (18)	N1—C5—C13—C18	−50.0 (3)
C12—C4—C5—C13	174.78 (17)	C4—C5—C13—C18	69.1 (3)
C3—C4—C5—C13	51.1 (3)	N1—C5—C13—C14	131.9 (2)
C5—N1—C6—C7	160.0 (2)	C4—C5—C13—C14	−108.9 (2)
C5—N1—C6—C11	−22.2 (3)	C18—C13—C14—C15	−0.2 (3)
N1—C6—C7—C8	179.1 (2)	C5—C13—C14—C15	177.9 (2)
C11—C6—C7—C8	1.3 (4)	C13—C14—C15—C16	0.2 (4)
C6—C7—C8—C9	−0.9 (4)	C14—C15—C16—C17	0.0 (4)
C7—C8—C9—C10	−0.3 (4)	C14—C15—C16—N2	179.0 (2)
C8—C9—C10—C11	1.1 (4)	O2—N2—C16—C15	−4.2 (3)
C9—C10—C11—C6	−0.7 (3)	O3—N2—C16—C15	176.5 (2)
C9—C10—C11—C12	179.7 (2)	O2—N2—C16—C17	174.8 (2)
N1—C6—C11—C10	−178.3 (2)	O3—N2—C16—C17	−4.5 (3)
C7—C6—C11—C10	−0.5 (3)	C15—C16—C17—C18	−0.2 (3)
N1—C6—C11—C12	1.3 (3)	N2—C16—C17—C18	−179.2 (2)
C7—C6—C11—C12	179.1 (2)	C16—C17—C18—C13	0.3 (3)
C1—O1—C12—C11	176.27 (19)	C14—C13—C18—C17	−0.1 (3)
C1—O1—C12—C4	−59.8 (2)	C5—C13—C18—C17	−178.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3^i	0.84 (3)	2.38 (3)	3.200 (3)	165 (2)
C1—H1B···O3^ii	0.97	2.59	3.535 (3)	166

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) x−1, y−1, z.