(Z)-2-(4-Methyl­benzyl­idene)-1-aza­bicyclo­[2.2.2]octan-3-one

The title compound, C₁₅H₁₇NO, was synthesized by base-catalyzed condensation of 4-methyl­benzaldehyde with 1-aza­bicyclo­[2.2.2]octan-3-one and crystallization of the product from ethyl acetate. The geometry of the C=C bond is Z.

Key indicators

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.128
• Data-to-parameter ratio = 10.3

checkCIF/PLATON results

No syntax errors found



Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.48
           From the CIF: _reflns_number_total               1602
           Count of symmetry unique reflns         1601
           Completeness (_total/calc)            100.06%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         1
           Fraction of Friedel pairs measured     0.001
           Are heavy atom types Z>Si present         no

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

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

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Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 and local procedures.

(Z)-2-(4-Methylbenzylidene)-1-azabicyclo[2.2.2]octan-3-one

Crystal data

C15H17NO	F(000) = 488
Mr = 227.30	Dx = 1.271 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1619 reflections
a = 5.8527 (2) Å	θ = 1.0–27.5°
b = 9.9840 (3) Å	µ = 0.08 mm^−1
c = 20.3309 (6) Å	T = 90 K
V = 1188.00 (6) Å^3	Block, yellow
Z = 4	0.25 × 0.20 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer	1602 independent reflections
Radiation source: fine-focus sealed tube	1262 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 18 pixels mm^-1	θmax = 27.5°, θmin = 2.0°
ω scans at fixed χ = 55°	h = −7→7
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −12→12
Tmin = 0.980, Tmax = 0.982	l = −26→26
2724 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0819P)^2] where P = (Fo^2 + 2Fc^2)/3
1602 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. ¹H NMR (CDCl₃, δ, p.p.m.): 2.03 (m, 4H), 2.37 (s, 3H), 2.62 (p, 1H), 2.98 (p, 2H), 3.13 (p, 2H), 7.00 (s, 1H), 7.18 (d, 2H), 7.94 (d, 2H); ¹³C NMR (CDCl₃, δ, p.p.m.): 21.6, 26.0, 40.3, 47.5, 125.1, 129.1, 131.1, 132.0, 139.8, 143.9, 206.2.

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.

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

	x	y	z	Uiso*/Ueq
C1	0.5858 (4)	0.5276 (2)	0.38226 (11)	0.0167 (5)
C2	0.4250 (4)	0.6220 (2)	0.36096 (11)	0.0191 (5)
H2	0.2886	0.6353	0.3854	0.023*
C3	0.4638 (5)	0.6959 (2)	0.30453 (12)	0.0220 (6)
H3	0.3518	0.7585	0.2905	0.026*
C4	0.6636 (4)	0.6809 (2)	0.26760 (11)	0.0202 (6)
C5	0.8206 (5)	0.5861 (2)	0.28855 (11)	0.0214 (6)
H5	0.9571	0.5735	0.2640	0.026*
C6	0.7839 (5)	0.5088 (2)	0.34456 (11)	0.0190 (6)
H6	0.8931	0.4434	0.3573	0.023*
C7	0.5558 (5)	0.4446 (2)	0.44123 (11)	0.0172 (5)
H7	0.6321	0.3607	0.4405	0.021*
C8	0.4368 (4)	0.4703 (2)	0.49567 (11)	0.0156 (5)
N9	0.3166 (4)	0.5927 (2)	0.50949 (9)	0.0178 (5)
C10	0.0731 (4)	0.5604 (3)	0.52208 (12)	0.0206 (6)
H10A	0.0050	0.5212	0.4819	0.025*
H10B	−0.0108	0.6439	0.5324	0.025*
C11	0.0451 (5)	0.4603 (2)	0.57997 (12)	0.0202 (6)
H11A	−0.0476	0.5014	0.6153	0.024*
H11B	−0.0342	0.3785	0.5646	0.024*
C12	0.2845 (5)	0.4238 (2)	0.60652 (12)	0.0205 (6)
H12	0.2740	0.3573	0.6432	0.025*
O13	0.5189 (3)	0.26066 (16)	0.55027 (8)	0.0217 (4)
C13	0.4252 (4)	0.3700 (2)	0.55038 (11)	0.0165 (5)
C14	0.4016 (5)	0.5535 (2)	0.62937 (12)	0.0226 (6)
H14A	0.5576	0.5336	0.6454	0.027*
H14B	0.3138	0.5942	0.6659	0.027*
C15	0.4133 (5)	0.6524 (2)	0.57049 (11)	0.0211 (6)
H15A	0.3275	0.7348	0.5816	0.025*
H15B	0.5745	0.6777	0.5626	0.025*
C16	0.7073 (5)	0.7674 (3)	0.20801 (12)	0.0259 (6)
H16A	0.7866	0.8494	0.2215	0.039*
H16B	0.5614	0.7909	0.1873	0.039*
H16C	0.8022	0.7182	0.1765	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0204 (12)	0.0151 (11)	0.0148 (11)	0.0009 (11)	−0.0002 (10)	−0.0057 (10)
C2	0.0189 (12)	0.0203 (12)	0.0181 (12)	−0.0008 (12)	0.0014 (11)	−0.0020 (10)
C3	0.0271 (14)	0.0188 (12)	0.0202 (12)	0.0036 (12)	−0.0034 (12)	−0.0012 (11)
C4	0.0257 (14)	0.0180 (12)	0.0168 (11)	−0.0042 (12)	−0.0018 (12)	−0.0020 (11)
C5	0.0205 (12)	0.0256 (14)	0.0181 (12)	−0.0011 (12)	0.0020 (12)	−0.0025 (11)
C6	0.0207 (13)	0.0173 (12)	0.0189 (12)	0.0006 (11)	0.0001 (11)	−0.0022 (11)
C7	0.0177 (12)	0.0132 (11)	0.0206 (12)	0.0013 (11)	−0.0002 (11)	−0.0017 (10)
C8	0.0140 (11)	0.0132 (11)	0.0195 (12)	0.0000 (11)	−0.0016 (10)	−0.0003 (10)
N9	0.0198 (10)	0.0165 (11)	0.0173 (10)	0.0046 (10)	0.0011 (10)	0.0007 (9)
C10	0.0153 (12)	0.0245 (14)	0.0220 (13)	0.0026 (12)	0.0004 (11)	0.0007 (11)
C11	0.0179 (13)	0.0184 (12)	0.0244 (13)	0.0003 (11)	0.0040 (11)	0.0022 (11)
C12	0.0234 (14)	0.0208 (13)	0.0173 (12)	−0.0013 (12)	0.0021 (12)	0.0040 (11)
O13	0.0245 (10)	0.0155 (8)	0.0250 (9)	0.0018 (8)	−0.0003 (9)	0.0010 (8)
C13	0.0146 (11)	0.0168 (12)	0.0181 (12)	−0.0044 (11)	−0.0008 (11)	−0.0025 (11)
C14	0.0257 (14)	0.0224 (13)	0.0196 (13)	0.0026 (13)	0.0000 (12)	−0.0049 (10)
C15	0.0235 (14)	0.0176 (13)	0.0222 (13)	0.0004 (12)	0.0006 (12)	−0.0042 (11)
C16	0.0326 (15)	0.0250 (14)	0.0200 (12)	−0.0017 (14)	−0.0011 (13)	0.0008 (11)

Geometric parameters (Å, º)

C1—C2	1.400 (3)	C10—C11	1.553 (3)
C1—C6	1.402 (3)	C10—H10A	0.9900
C1—C7	1.468 (3)	C10—H10B	0.9900
C2—C3	1.383 (3)	C11—C12	1.545 (4)
C2—H2	0.9500	C11—H11A	0.9900
C3—C4	1.397 (4)	C11—H11B	0.9900
C3—H3	0.9500	C12—C13	1.507 (3)
C4—C5	1.386 (3)	C12—C14	1.537 (3)
C4—C16	1.510 (3)	C12—H12	1.0000
C5—C6	1.392 (3)	O13—C13	1.221 (3)
C5—H5	0.9500	C14—C15	1.553 (3)
C6—H6	0.9500	C14—H14A	0.9900
C7—C8	1.332 (3)	C14—H14B	0.9900
C7—H7	0.9500	C15—H15A	0.9900
C8—N9	1.438 (3)	C15—H15B	0.9900
C8—C13	1.498 (3)	C16—H16A	0.9800
N9—C10	1.484 (3)	C16—H16B	0.9800
N9—C15	1.488 (3)	C16—H16C	0.9800
C2—C1—C6	118.4 (2)	C12—C11—C10	108.71 (19)
C2—C1—C7	123.5 (2)	C12—C11—H11A	109.9
C6—C1—C7	118.0 (2)	C10—C11—H11A	109.9
C3—C2—C1	120.3 (2)	C12—C11—H11B	109.9
C3—C2—H2	119.8	C10—C11—H11B	109.9
C1—C2—H2	119.8	H11A—C11—H11B	108.3
C2—C3—C4	121.7 (2)	C13—C12—C14	106.6 (2)
C2—C3—H3	119.1	C13—C12—C11	108.4 (2)
C4—C3—H3	119.1	C14—C12—C11	108.1 (2)
C5—C4—C3	117.6 (2)	C13—C12—H12	111.2
C5—C4—C16	121.7 (2)	C14—C12—H12	111.2
C3—C4—C16	120.8 (2)	C11—C12—H12	111.2
C4—C5—C6	121.8 (2)	O13—C13—C8	125.1 (2)
C4—C5—H5	119.1	O13—C13—C12	124.5 (2)
C6—C5—H5	119.1	C8—C13—C12	110.4 (2)
C5—C6—C1	120.1 (2)	C12—C14—C15	108.80 (19)
C5—C6—H6	120.0	C12—C14—H14A	109.9
C1—C6—H6	120.0	C15—C14—H14A	109.9
C8—C7—C1	129.2 (2)	C12—C14—H14B	109.9
C8—C7—H7	115.4	C15—C14—H14B	109.9
C1—C7—H7	115.4	H14A—C14—H14B	108.3
C7—C8—N9	125.5 (2)	N9—C15—C14	111.78 (19)
C7—C8—C13	120.8 (2)	N9—C15—H15A	109.3
N9—C8—C13	113.62 (19)	C14—C15—H15A	109.3
C8—N9—C10	108.6 (2)	N9—C15—H15B	109.3
C8—N9—C15	108.50 (19)	C14—C15—H15B	109.3
C10—N9—C15	108.0 (2)	H15A—C15—H15B	107.9
N9—C10—C11	111.8 (2)	C4—C16—H16A	109.5
N9—C10—H10A	109.2	C4—C16—H16B	109.5
C11—C10—H10A	109.2	H16A—C16—H16B	109.5
N9—C10—H10B	109.2	C4—C16—H16C	109.5
C11—C10—H10B	109.2	H16A—C16—H16C	109.5
H10A—C10—H10B	107.9	H16B—C16—H16C	109.5
C6—C1—C2—C3	−0.9 (3)	C8—N9—C10—C11	58.0 (3)
C7—C1—C2—C3	−179.4 (2)	C15—N9—C10—C11	−59.5 (3)
C1—C2—C3—C4	−0.9 (4)	N9—C10—C11—C12	−0.5 (3)
C2—C3—C4—C5	1.7 (4)	C10—C11—C12—C13	−56.0 (2)
C2—C3—C4—C16	−177.0 (2)	C10—C11—C12—C14	59.2 (3)
C3—C4—C5—C6	−0.6 (4)	C7—C8—C13—O13	0.0 (4)
C16—C4—C5—C6	178.1 (2)	N9—C8—C13—O13	−178.1 (2)
C4—C5—C6—C1	−1.2 (4)	C7—C8—C13—C12	178.9 (2)
C2—C1—C6—C5	2.0 (3)	N9—C8—C13—C12	0.8 (3)
C7—C1—C6—C5	−179.4 (2)	C14—C12—C13—O13	119.7 (2)
C2—C1—C7—C8	−27.5 (4)	C11—C12—C13—O13	−124.1 (2)
C6—C1—C7—C8	154.0 (3)	C14—C12—C13—C8	−59.3 (3)
C1—C7—C8—N9	−3.1 (4)	C11—C12—C13—C8	56.9 (3)
C1—C7—C8—C13	179.0 (2)	C13—C12—C14—C15	58.5 (3)
C7—C8—N9—C10	122.8 (3)	C11—C12—C14—C15	−57.8 (3)
C13—C8—N9—C10	−59.2 (3)	C8—N9—C15—C14	−56.5 (3)
C7—C8—N9—C15	−120.0 (3)	C10—N9—C15—C14	61.0 (3)
C13—C8—N9—C15	58.0 (2)	C12—C14—C15—N9	−1.8 (3)