(Z)-2-(Thio­phen-2-ylmethyl­ene)-1-aza­bicyclo­[2.2.2]octan-3-one

Crystals of the title compound, C₁₂H₁₃NOS, were prepared by base-catalyzed reaction of thio­phene-2-carboxaldehyde with 1-aza­bicyclo­[2.2.2]octan-3-one and subsequent crystallization of the product from ethyl acetate. The olefinic bond connecting the 2-thienyl and 1-aza­bicyclo­[2.2.2]octan-3-one moieties has Z geometry. No thienyl ring flip is observed.

Key indicators

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.091
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C12 H13 N O S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 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
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker–Nonius, 2004); cell refinement: SAINT (Bruker–Nonius, 2004); data reduction: SAINT; 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-(Thiophen-2-ylmethylene)-1-azabicyclo[2.2.2]octan-3-one

Crystal data

C12H13NOS	F(000) = 464
Mr = 219.29	Dx = 1.383 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 5645 reflections
a = 11.0171 (2) Å	θ = 2.7–68.0°
b = 5.9253 (1) Å	µ = 2.48 mm^−1
c = 16.1888 (2) Å	T = 90 K
β = 94.640 (1)°	Block, yellow
V = 1053.34 (3) Å^3	0.15 × 0.08 × 0.08 mm
Z = 4

Data collection

Bruker–Nonius X8 Proteum diffractometer	1880 independent reflections
Radiation source: fine-focus rotating anode	1845 reflections with I > 2σ(I)
Graded multilayer optics monochromator	Rint = 0.031
Detector resolution: 18 pixels mm^-1	θmax = 68.0°, θmin = 4.7°
ω scans at fixed χ = 55°	h = −13→13
Absorption correction: multi-scan (SADABS in APEX2; Bruker–Nonius, 2004)	k = −7→7
Tmin = 0.657, Tmax = 0.836	l = −19→18
11773 measured reflections

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) = 0.091	w = 1/[σ^2(Fo^2) + (0.0559P)^2 + 0.4238P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
1880 reflections	Δρmax = 0.29 e Å^−3
137 parameters	Δρmin = −0.36 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0209 (12)

Special details

Experimental. ¹H NMR (CDCl₃): δ 2.02 (m, 4H), 2.63 (p, 1H), 2.93 (p, 2H), 3.18 (p, 2H), 7.04 (t, 1H), 7.31 (d, 1H), 7.35 (1H, d), 7.54 (1H, d). ¹³C NMR (CDCl₃): δ 26.24, 40.57, 47.34, 119.72, 126.49, 133.43, 133.49, 136.85, 141.48, 204.89.

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
S1	−0.00010 (3)	0.00858 (5)	0.24150 (2)	0.01743 (17)
N1	−0.18759 (10)	−0.04388 (19)	0.35875 (7)	0.0162 (3)
O1	−0.14829 (9)	0.29255 (17)	0.54515 (6)	0.0223 (3)
C1	0.03102 (11)	0.2167 (2)	0.31553 (8)	0.0156 (3)
C2	0.10350 (12)	0.1220 (2)	0.17941 (8)	0.0199 (3)
H2	0.1202	0.0605	0.1273	0.024*
C3	0.15901 (12)	0.3098 (2)	0.21300 (8)	0.0200 (3)
H3	0.2186	0.3943	0.1871	0.024*
C4	0.11756 (11)	0.3643 (2)	0.29114 (8)	0.0181 (3)
H4	0.1466	0.4900	0.3234	0.022*
C5	−0.02847 (11)	0.2360 (2)	0.39141 (8)	0.0163 (3)
H5	0.0051	0.3426	0.4307	0.020*
C6	−0.12575 (11)	0.1206 (2)	0.41263 (8)	0.0158 (3)
C7	−0.20399 (13)	−0.2527 (2)	0.40660 (8)	0.0207 (3)
H7A	−0.1233	−0.3100	0.4285	0.025*
H7B	−0.2427	−0.3694	0.3694	0.025*
C8	−0.28423 (13)	−0.2113 (2)	0.47981 (9)	0.0220 (3)
H8A	−0.3624	−0.2933	0.4701	0.026*
H8B	−0.2419	−0.2670	0.5321	0.026*
C9	−0.30797 (12)	0.0440 (2)	0.48599 (8)	0.0184 (3)
H9	−0.3529	0.0802	0.5356	0.022*
C10	−0.18689 (12)	0.1668 (2)	0.48923 (8)	0.0166 (3)
C11	−0.38021 (12)	0.1211 (2)	0.40535 (8)	0.0197 (3)
H11A	−0.3903	0.2871	0.4056	0.024*
H11B	−0.4621	0.0511	0.4010	0.024*
C12	−0.30920 (12)	0.0486 (2)	0.33058 (8)	0.0181 (3)
H12A	−0.3566	−0.0672	0.2978	0.022*
H12B	−0.2991	0.1806	0.2943	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0185 (2)	0.0168 (2)	0.0171 (2)	−0.00049 (11)	0.00228 (15)	−0.00383 (11)
N1	0.0172 (6)	0.0146 (5)	0.0166 (6)	−0.0009 (4)	0.0006 (4)	−0.0021 (4)
O1	0.0259 (5)	0.0232 (5)	0.0181 (5)	−0.0044 (4)	0.0038 (4)	−0.0057 (4)
C1	0.0145 (6)	0.0159 (6)	0.0163 (6)	0.0018 (5)	−0.0002 (5)	−0.0012 (5)
C2	0.0195 (7)	0.0249 (7)	0.0155 (6)	0.0033 (5)	0.0030 (5)	−0.0014 (6)
C3	0.0175 (6)	0.0248 (7)	0.0181 (7)	−0.0004 (5)	0.0035 (5)	0.0019 (5)
C4	0.0169 (6)	0.0189 (7)	0.0185 (6)	0.0000 (5)	0.0009 (5)	−0.0012 (5)
C5	0.0170 (6)	0.0158 (6)	0.0158 (6)	0.0018 (5)	−0.0005 (5)	−0.0014 (5)
C6	0.0174 (6)	0.0146 (6)	0.0151 (6)	0.0008 (5)	0.0003 (5)	−0.0010 (5)
C7	0.0253 (7)	0.0137 (7)	0.0230 (7)	−0.0005 (5)	0.0009 (5)	−0.0002 (5)
C8	0.0267 (7)	0.0186 (7)	0.0206 (7)	−0.0048 (6)	0.0018 (5)	0.0039 (5)
C9	0.0199 (7)	0.0202 (7)	0.0157 (7)	−0.0029 (5)	0.0042 (5)	−0.0002 (5)
C10	0.0192 (6)	0.0144 (6)	0.0164 (6)	0.0010 (5)	0.0022 (5)	0.0017 (5)
C11	0.0170 (6)	0.0216 (7)	0.0206 (7)	−0.0002 (5)	0.0024 (5)	0.0012 (5)
C12	0.0178 (7)	0.0198 (6)	0.0164 (7)	−0.0005 (5)	−0.0001 (5)	0.0006 (5)

Geometric parameters (Å, º)

S1—C2	1.7178 (13)	C6—C10	1.4838 (17)
S1—C1	1.7342 (13)	C7—C8	1.5542 (19)
N1—C6	1.4417 (16)	C7—H7A	0.9900
N1—C7	1.4788 (17)	C7—H7B	0.9900
N1—C12	1.4847 (17)	C8—C9	1.5396 (19)
O1—C10	1.2219 (16)	C8—H8A	0.9900
C1—C4	1.3751 (19)	C8—H8B	0.9900
C1—C5	1.4429 (18)	C9—C10	1.5169 (18)
C2—C3	1.361 (2)	C9—C11	1.5422 (18)
C2—H2	0.9500	C9—H9	1.0000
C3—C4	1.4166 (18)	C11—C12	1.5539 (18)
C3—H3	0.9500	C11—H11A	0.9900
C4—H4	0.9500	C11—H11B	0.9900
C5—C6	1.3394 (19)	C12—H12A	0.9900
C5—H5	0.9500	C12—H12B	0.9900
C2—S1—C1	91.29 (6)	C9—C8—C7	108.35 (11)
C6—N1—C7	108.69 (10)	C9—C8—H8A	110.0
C6—N1—C12	107.86 (10)	C7—C8—H8A	110.0
C7—N1—C12	108.93 (10)	C9—C8—H8B	110.0
C4—C1—C5	124.55 (12)	C7—C8—H8B	110.0
C4—C1—S1	110.90 (10)	H8A—C8—H8B	108.4
C5—C1—S1	124.52 (10)	C10—C9—C8	108.67 (11)
C3—C2—S1	112.60 (10)	C10—C9—C11	106.22 (11)
C3—C2—H2	123.7	C8—C9—C11	108.35 (11)
S1—C2—H2	123.7	C10—C9—H9	111.1
C2—C3—C4	112.09 (12)	C8—C9—H9	111.1
C2—C3—H3	124.0	C11—C9—H9	111.1
C4—C3—H3	124.0	O1—C10—C6	125.27 (12)
C1—C4—C3	113.11 (12)	O1—C10—C9	124.79 (12)
C1—C4—H4	123.4	C6—C10—C9	109.87 (11)
C3—C4—H4	123.4	C9—C11—C12	108.65 (11)
C6—C5—C1	127.29 (12)	C9—C11—H11A	110.0
C6—C5—H5	116.4	C12—C11—H11A	110.0
C1—C5—H5	116.4	C9—C11—H11B	110.0
C5—C6—N1	122.60 (12)	C12—C11—H11B	110.0
C5—C6—C10	123.15 (12)	H11A—C11—H11B	108.3
N1—C6—C10	113.97 (11)	N1—C12—C11	111.19 (11)
N1—C7—C8	111.62 (11)	N1—C12—H12A	109.4
N1—C7—H7A	109.3	C11—C12—H12A	109.4
C8—C7—H7A	109.3	N1—C12—H12B	109.4
N1—C7—H7B	109.3	C11—C12—H12B	109.4
C8—C7—H7B	109.3	H12A—C12—H12B	108.0
H7A—C7—H7B	108.0
C2—S1—C1—C4	0.19 (10)	N1—C7—C8—C9	−7.20 (15)
C2—S1—C1—C5	178.54 (11)	C7—C8—C9—C10	−52.17 (14)
C1—S1—C2—C3	−0.22 (11)	C7—C8—C9—C11	62.83 (14)
S1—C2—C3—C4	0.19 (15)	C5—C6—C10—O1	−9.2 (2)
C5—C1—C4—C3	−178.46 (12)	N1—C6—C10—O1	176.83 (12)
S1—C1—C4—C3	−0.12 (15)	C5—C6—C10—C9	167.94 (12)
C2—C3—C4—C1	−0.05 (17)	N1—C6—C10—C9	−6.06 (15)
C4—C1—C5—C6	168.73 (13)	C8—C9—C10—O1	−122.13 (14)
S1—C1—C5—C6	−9.4 (2)	C11—C9—C10—O1	121.49 (14)
C1—C5—C6—N1	−1.0 (2)	C8—C9—C10—C6	60.74 (13)
C1—C5—C6—C10	−174.52 (12)	C11—C9—C10—C6	−55.63 (13)
C7—N1—C6—C5	130.97 (13)	C10—C9—C11—C12	62.04 (13)
C12—N1—C6—C5	−111.08 (14)	C8—C9—C11—C12	−54.55 (14)
C7—N1—C6—C10	−55.00 (14)	C6—N1—C12—C11	−53.67 (14)
C12—N1—C6—C10	62.96 (13)	C7—N1—C12—C11	64.14 (14)
C6—N1—C7—C8	61.81 (14)	C9—C11—C12—N1	−7.49 (15)
C12—N1—C7—C8	−55.47 (14)