3-Benzoyl-1-[(4-methyl­phen­yl)sulfon­yl]-1a,2,3,7b-tetra­hydro-1H-azireno[2,3-c]quinoline-2-carbonitrile

The title compound, C₂₄H₁₉N₃O₃S, is the result of a diastereoselective aziridination reaction performed on the corresponding Reissert adduct (1-benzoyl-1,2-dihydro­quinoline-2-carbonitrile). The aziridine ring is trans disposed to the nitrile group.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.066
• wR factor = 0.157
• Data-to-parameter ratio = 22.3

checkCIF/PLATON results

No syntax errors found



Alert level C
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      2.060
PLAT087_ALERT_2_C Unsatisfactory S value (Too High) ..............       2.06
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.53 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C21
PLAT320_ALERT_2_C Check Hybridisation of  C3     in Main Residue .          ?

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT793_ALERT_1_G Check the Absolute Configuration of C2     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C3     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C4     = ...          R
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         76

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Stereoselective additions to the double bond of 1-benzoyl-1,2-dihydroquinoline-2-carbonitrile (Reissert, 1905) have not been extensively studied in the past decades. Recently, an epoxidation reaction has been performed on an optically active Reissert-type compound (Takamura et al., 2001) resulting in the formation of an epoxide ring trans disposed to the nitrile group.

In the course of an ongoing project directed towards the synthesis of sumanirole, a non-natural compound exhibiting anti-parkinsonian activities (Moon et al., 1993), we were interested in introducing an aziridine ring at the C3—C4 positions of the racemic 1-benzoyl-1,2-dihydroquinoline-2-carbonitrile. Subsequent regioselective opening of this strained ring at its benzylic position would allow installation of the amine functionality found in sumanirole at carbon C3.

The aziridination reaction was performed using PhI=NTs (N-(p-tolylsulfonyl)imino)phenyliodinane (Gillespie, 2001) as a nitrene precursor and Cu(acac)₂ as a catalyst (Evans et al., 1991, 1994). The reaction led to the formation of a single diastereoisomer in 70% isolated yield. To ascertain the stereochemical relationships between the two newly created stereogenic carbons (C3 and C4) and the carbon bearing the nitrile group (C2), compound (I) was subjected to X-ray crystal structure analysis.

The molecular structure of (I) reveals the trans relative stereochemistry between the aziridine ring and the nitrile group (Fig. 1).

Related literature

For related literature, see: Evans et al. (1991, 1994); Gillespie (2001); Moon et al. (1993); Reissert (1905); Takamura et al. (2001).

S2. Experimental

To a solution of 1-benzoyl-1,2-dihydroquinoline-2-carbonitrile (855 mg, 4.0 mmol) in dry CH₃CN (14 ml), Cu(acac)₂ (524 mg, 2.0 mmol) and PhI=NTs (10.4 g, 27.9 mmol) were added at room temperature. After 2 minutes of vigorous stirring, the temperature of the reaction mixture increased significantly and the initial blue suspension turned brown. The mixture was then allowed to cool to room temperature, filtered through a pad of silica and the filter cake was rinsed thoroughly with CH₂Cl₂. The filtrate was then concentrated in vacuo and the resulting solid was recrystallized in methylene chloride. The obtained crystals were filtered off. After being kept for 1 h at RT, the organic layer was filtered again. The resulting filtrate was concentrated in vacuo and the crude product was purified by silica gel chromatography (eluting with CH₂Cl₂) to afford (I) as a white solid in a 70% yield (1.2 g, 2.8 mmol). Single crystals of (I) suitable for X-ray analysis were obtained by slow crystallization from CH₂Cl₂/petroleum ether, at room temperature and without evaporation (m.p. 459 K).

S3. Refinement

C—H H atoms were positioned with idealized geometry and were refined isotropic (U_iso(H) = 1.2× U_eq(C)) using a riding model. The O—H H atoms were located in difference map syntheses and were refined isotropic (U_iso(H) = 1.2× U_eq(O)) with varying coordinates.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: COLLECT (Nonius, 1998); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petricek et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petricek et al., 2006).

Figures

Fig. 1. Molecular structure showing 30% probability displacement ellipsoids. H atoms are omitted for clarity.

3-Benzoyl-1-[(4-methylphenyl)sulfonyl]-1a,2,3,7 b-tetrahydro-1H-azireno [2,3-c]quinoline-2-carbonitrile

Crystal data

C24H19N3O3S	V = 1102.36 (11) Å^3
Mr = 429.5	Z = 2
Triclinic, P1	F(000) = 448
Hall symbol: -P 1	Dx = 1.294 Mg m^−3
a = 8.7215 (5) Å	Mo Kα radiation, λ = 0.71069 Å
b = 12.1042 (4) Å	µ = 0.18 mm^−1
c = 12.4678 (7) Å	T = 293 K
α = 64.267 (3)°	Thick plate, colourless
β = 69.759 (5)°	0.6 × 0.3 × 0.09 mm
γ = 87.895 (3)°

Data collection

Nonius KappaCCD diffractometer	6242 independent reflections
Radiation source: X-ray tube	4445 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	Rint = 0.055
Detector resolution: 9 pixels mm^-1	θmax = 30.0°, θmin = 6.5°
CCD, φ and ω frames scans	h = −12→11
Absorption correction: gaussian (JANA2006; Petricek et al., 2006)	k = −17→16
Tmin = 0.922, Tmax = 0.977	l = −17→17
34014 measured reflections

Refinement

Refinement on F^2	76 restraints
R[F > 3σ(F)] = 0.066	H-atom parameters constrained
wR(F) = 0.157	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.001936I^2)
S = 2.06	(Δ/σ)max = 0.001
6242 reflections	Δρmax = 0.36 e Å^−3
280 parameters	Δρmin = −0.36 e Å^−3

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

	x	y	z	Uiso*/Ueq
S	0.03291 (6)	0.08922 (4)	0.64456 (4)	0.0454 (2)
N1	0.38331 (17)	0.30804 (12)	0.24992 (13)	0.0384 (6)
N2	0.4895 (3)	0.0724 (2)	0.1684 (2)	0.0835 (12)
N3	0.18953 (17)	0.17068 (13)	0.50524 (13)	0.0390 (6)
O1	0.2135 (2)	0.41987 (14)	0.15447 (16)	0.0669 (9)
O2	−0.11266 (16)	0.12656 (15)	0.61889 (14)	0.0612 (8)
O3	0.04832 (19)	−0.04033 (13)	0.69441 (14)	0.0638 (7)
C1	0.4044 (3)	0.12536 (18)	0.21482 (18)	0.0519 (9)
C2	0.2965 (2)	0.18988 (15)	0.28240 (16)	0.0402 (7)
C3	0.2444 (2)	0.10530 (15)	0.42537 (16)	0.0403 (7)
C4	0.3496 (2)	0.11772 (15)	0.49134 (16)	0.0399 (7)
C5	0.5036 (2)	0.20893 (15)	0.41258 (16)	0.0383 (7)
C6	0.6338 (2)	0.20193 (17)	0.45378 (19)	0.0472 (9)
C7	0.7791 (2)	0.28230 (19)	0.3736 (2)	0.0548 (10)
C8	0.7955 (2)	0.36839 (19)	0.2523 (2)	0.0545 (10)
C9	0.6662 (2)	0.37820 (17)	0.20927 (18)	0.0456 (8)
C10	0.5196 (2)	0.29989 (15)	0.29066 (16)	0.0371 (7)
C11	0.3119 (2)	0.41407 (16)	0.20566 (17)	0.0426 (8)
C12	0.3561 (2)	0.51944 (17)	0.22680 (18)	0.0434 (8)
C13	0.3917 (2)	0.63836 (18)	0.1289 (2)	0.0573 (10)
C14	0.4231 (3)	0.7372 (2)	0.1500 (3)	0.0724 (12)
C15	0.4171 (3)	0.7182 (2)	0.2673 (3)	0.0734 (14)
C16	0.3781 (3)	0.6006 (2)	0.3665 (3)	0.0701 (14)
C17	0.3481 (3)	0.5005 (2)	0.3467 (2)	0.0570 (10)
C18	0.0664 (2)	0.14759 (17)	0.74182 (17)	0.0442 (8)
C19	0.1465 (3)	0.0827 (2)	0.82352 (19)	0.0556 (10)
C20	0.1657 (3)	0.1281 (2)	0.9038 (2)	0.0664 (11)
C21	0.1063 (3)	0.2348 (2)	0.90398 (19)	0.0602 (10)
C22	0.0286 (3)	0.2989 (2)	0.8193 (2)	0.0716 (14)
C23	0.0073 (3)	0.2564 (2)	0.7379 (2)	0.0623 (12)
C24	0.1240 (4)	0.2816 (3)	0.9939 (3)	0.0935 (16)
H1	0.203733	0.20999	0.254501	0.0483*
H2	0.199338	0.03397	0.424107	0.0484*
H3	0.398591	0.05981	0.548829	0.0479*
H4	0.623121	0.140591	0.539025	0.0567*
H5	0.869957	0.27826	0.402578	0.0657*
H6	0.899022	0.422553	0.196621	0.0654*
H7	0.678118	0.438968	0.123512	0.0548*
H8	0.394574	0.652419	0.045403	0.0688*
H9	0.449713	0.821142	0.081592	0.0869*
H10	0.44065	0.788185	0.280272	0.088*
H11	0.371761	0.588293	0.450215	0.0841*
H12	0.321681	0.417394	0.416576	0.0684*
H13	0.188175	0.006955	0.824521	0.0667*
H14	0.222353	0.083944	0.961486	0.0797*
H15	−0.011942	0.375303	0.816864	0.0859*
H16	−0.047788	0.301988	0.679431	0.0748*
H17	0.030292	0.328238	1.014529	0.1122*
H18	0.122915	0.209872	1.074466	0.1122*
H19	0.230573	0.337637	0.952164	0.1122*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0484 (3)	0.0468 (3)	0.0412 (2)	−0.00713 (18)	−0.01196 (18)	−0.0223 (2)
N1	0.0433 (7)	0.0354 (7)	0.0410 (7)	0.0015 (6)	−0.0209 (6)	−0.0167 (6)
N2	0.1091 (17)	0.0649 (13)	0.0662 (13)	0.0108 (12)	−0.0106 (12)	−0.0371 (11)
N3	0.0449 (8)	0.0370 (7)	0.0382 (7)	0.0010 (6)	−0.0151 (6)	−0.0194 (6)
O1	0.0785 (10)	0.0601 (9)	0.0908 (11)	0.0173 (7)	−0.0626 (9)	−0.0350 (9)
O2	0.0460 (7)	0.0875 (11)	0.0615 (9)	−0.0034 (7)	−0.0203 (6)	−0.0419 (8)
O3	0.0841 (10)	0.0413 (8)	0.0518 (8)	−0.0131 (6)	−0.0115 (7)	−0.0173 (6)
C1	0.0706 (13)	0.0428 (10)	0.0406 (10)	−0.0025 (9)	−0.0155 (9)	−0.0203 (8)
C2	0.0473 (9)	0.0389 (9)	0.0403 (9)	0.0002 (7)	−0.0194 (7)	−0.0198 (7)
C3	0.0511 (9)	0.0347 (8)	0.0404 (9)	−0.0012 (7)	−0.0163 (7)	−0.0213 (7)
C4	0.0498 (9)	0.0358 (8)	0.0397 (9)	0.0079 (7)	−0.0204 (7)	−0.0189 (7)
C5	0.0441 (9)	0.0365 (8)	0.0435 (9)	0.0081 (6)	−0.0200 (7)	−0.0231 (7)
C6	0.0565 (11)	0.0452 (10)	0.0551 (11)	0.0146 (8)	−0.0324 (9)	−0.0269 (9)
C7	0.0468 (10)	0.0600 (12)	0.0752 (14)	0.0122 (9)	−0.0351 (10)	−0.0362 (11)
C8	0.0417 (10)	0.0539 (12)	0.0700 (13)	0.0019 (8)	−0.0213 (9)	−0.0288 (11)
C9	0.0432 (9)	0.0424 (10)	0.0503 (10)	0.0009 (7)	−0.0171 (8)	−0.0197 (9)
C10	0.0388 (8)	0.0365 (8)	0.0438 (9)	0.0066 (6)	−0.0201 (7)	−0.0211 (7)
C11	0.0441 (9)	0.0425 (9)	0.0460 (9)	0.0047 (7)	−0.0220 (7)	−0.0198 (8)
C12	0.0411 (9)	0.0441 (10)	0.0513 (10)	0.0091 (7)	−0.0191 (7)	−0.0255 (8)
C13	0.0661 (13)	0.0449 (11)	0.0544 (12)	0.0037 (9)	−0.0157 (9)	−0.0213 (9)
C14	0.0865 (17)	0.0441 (12)	0.0748 (16)	−0.0027 (11)	−0.0144 (13)	−0.0272 (12)
C15	0.0778 (15)	0.0608 (15)	0.0934 (18)	0.0045 (11)	−0.0202 (13)	−0.0532 (14)
C16	0.0884 (16)	0.0706 (15)	0.0749 (16)	0.0185 (12)	−0.0350 (13)	−0.0498 (14)
C17	0.0729 (13)	0.0514 (12)	0.0575 (12)	0.0137 (10)	−0.0291 (10)	−0.0303 (10)
C18	0.0431 (9)	0.0515 (10)	0.0384 (9)	−0.0032 (7)	−0.0123 (7)	−0.0220 (8)
C19	0.0618 (12)	0.0534 (12)	0.0525 (11)	0.0030 (9)	−0.0254 (9)	−0.0208 (10)
C20	0.0790 (15)	0.0690 (15)	0.0489 (12)	−0.0123 (11)	−0.0330 (11)	−0.0155 (11)
C21	0.0654 (13)	0.0712 (14)	0.0427 (10)	−0.0187 (10)	−0.0136 (9)	−0.0273 (10)
C22	0.0804 (16)	0.0755 (16)	0.0899 (17)	0.0158 (12)	−0.0390 (14)	−0.0583 (14)
C23	0.0741 (14)	0.0674 (14)	0.0749 (15)	0.0198 (11)	−0.0444 (12)	−0.0452 (12)
C24	0.131 (2)	0.096 (2)	0.0582 (15)	−0.0318 (17)	−0.0286 (16)	−0.0393 (15)

Geometric parameters (Å, º)

S—N3	1.6809 (12)	C16—C17	1.387 (4)
S—O2	1.4255 (16)	C18—C19	1.378 (3)
S—O3	1.4350 (15)	C18—C23	1.384 (3)
S—C18	1.749 (3)	C19—C20	1.390 (4)
N1—C2	1.465 (3)	C20—C21	1.375 (4)
N1—C10	1.431 (3)	C21—C22	1.386 (4)
N1—C11	1.380 (2)	C21—C24	1.509 (5)
N2—C1	1.134 (4)	C22—C23	1.384 (5)
N3—C3	1.474 (3)	C2—H1	0.970
N3—C4	1.501 (2)	C3—H2	0.970
O1—C11	1.218 (3)	C4—H3	0.970
C1—C2	1.474 (3)	C6—H4	0.970
C2—C3	1.523 (2)	C7—H5	0.970
C3—C4	1.477 (3)	C8—H6	0.970
C4—C5	1.497 (2)	C9—H7	0.970
C5—C6	1.385 (3)	C13—H8	0.970
C5—C10	1.398 (2)	C14—H9	0.970
C6—C7	1.386 (2)	C15—H10	0.970
C7—C8	1.374 (3)	C16—H11	0.970
C8—C9	1.388 (3)	C17—H12	0.970
C9—C10	1.385 (2)	C19—H13	0.970
C11—C12	1.498 (3)	C20—H14	0.970
C12—C13	1.380 (2)	C22—H15	0.970
C12—C17	1.387 (4)	C23—H16	0.970
C13—C14	1.388 (4)	C24—H17	1.000
C14—C15	1.360 (5)	C24—H18	1.000
C15—C16	1.373 (3)	C24—H19	1.000
N3—S—O2	105.04 (8)	C8—C9—C10	119.04 (17)
N3—S—O3	110.74 (8)	N1—C10—C5	118.70 (13)
N3—S—C18	101.40 (9)	N1—C10—C9	120.56 (15)
O2—S—O3	117.70 (11)	C5—C10—C9	120.71 (19)
O2—S—C18	110.99 (11)	N1—C11—O1	120.9 (2)
O3—S—C18	109.65 (10)	N1—C11—C12	117.40 (19)
C2—N1—C10	115.81 (14)	O1—C11—C12	121.66 (18)
C2—N1—C11	118.48 (16)	C11—C12—C13	119.7 (2)
C10—N1—C11	124.53 (17)	C11—C12—C17	120.77 (16)
S—N3—C3	113.62 (11)	C13—C12—C17	119.3 (2)
S—N3—C4	115.41 (9)	C12—C13—C14	120.0 (2)
C3—N3—C4	59.51 (13)	C13—C14—C15	120.5 (2)
N2—C1—C2	176.4 (3)	C14—C15—C16	120.1 (3)
N1—C2—C1	110.98 (14)	C15—C16—C17	120.1 (3)
N1—C2—C3	110.03 (18)	C12—C17—C16	119.87 (19)
C1—C2—C3	107.33 (14)	S—C18—C19	119.53 (18)
N3—C3—C2	113.77 (14)	S—C18—C23	119.17 (19)
N3—C3—C4	61.15 (13)	C19—C18—C23	121.3 (3)
C2—C3—C4	117.69 (14)	C18—C19—C20	118.5 (2)
N3—C4—C3	59.33 (13)	C19—C20—C21	121.8 (2)
N3—C4—C5	116.36 (13)	C20—C21—C22	118.2 (3)
C3—C4—C5	117.95 (15)	C20—C21—C24	121.3 (2)
C4—C5—C6	122.16 (15)	C22—C21—C24	120.5 (3)
C4—C5—C10	118.65 (18)	C21—C22—C23	121.6 (3)
C6—C5—C10	119.09 (14)	C18—C23—C22	118.6 (2)
C5—C6—C7	120.20 (18)	H17—C24—H18	109.5
C6—C7—C8	120.2 (2)	H17—C24—H19	109.5
C7—C8—C9	120.70 (17)	H18—C24—H19	109.5