(Z)-2-(Benzo­[b]­thio­phen-3-yl­methyl­ene)-1-aza­bi­cyclo­[2.2.2]­octan-3-one

Crystals of the title compound, C₁₆H₁₅NOS, were obtained from a condensation reaction of benzo­[b]­thio­phene-3-carbox­aldehyde with 1-aza­bi­cyclo­[2.2.2]­octan-3-one and subsequent crystallization of the product from methanol. The title compound, containing a double bond that connects an aza­bicyclic ring system to a benzo­[b]­thio­phen-3-yl­methyl­ene group, was obtained as the Z geometric isomer, crystallizing in the triclinic space group P1.

Key indicators

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.026
• wR factor = 0.070
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

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           27.46
           From the CIF: _reflns_number_total               2858
           Count of symmetry unique reflns         1469
           Completeness (_total/calc)            194.55%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1389
           Fraction of Friedel pairs measured     0.946
           Are heavy atom types Z>Si present          yes

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

   1 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; 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: SHELX97-2 (Sheldrick, 1997) and local procedures.

(Z)-(2-Benzo[b]thiophen-3-ylmethylene)-1-azabicyclo[2.2.2]octan-3-one

Crystal data

C16H15NOS	Z = 1
Mr = 269.35	F(000) = 142
Triclinic, P1	Dx = 1.390 Mg m^−3
a = 6.2144 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.8078 (1) Å	Cell parameters from 1439 reflections
c = 8.4492 (2) Å	θ = 1.0–27.5°
α = 102.8959 (9)°	µ = 0.24 mm^−1
β = 94.7214 (9)°	T = 90 K
γ = 110.2617 (10)°	Irregular block, yellow
V = 321.86 (1) Å^3	0.30 × 0.30 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer	2858 independent reflections
Radiation source: fine-focus sealed tube	2811 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 18 pixels mm^-1	θmax = 27.5°, θmin = 2.5°
ω scans at fixed χ = 55°	h = −8→8
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor)	k = −8→8
Tmin = 0.931, Tmax = 0.965	l = −10→10
7534 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)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.070	w = 1/[σ^2(Fo^2) + (0.0582P)^2 + 0.0899P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max = 0.002
2858 reflections	Δρmax = 0.23 e Å^−3
172 parameters	Δρmin = −0.18 e Å^−3
3 restraints	Absolute structure: Flack (1983), 1389 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (4)

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.

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	−0.45339 (5)	−0.05949 (4)	0.92604 (4)	0.01895 (9)
O1	0.30246 (18)	−0.22984 (16)	0.40849 (13)	0.0201 (2)
C2	−0.2831 (2)	−0.0260 (2)	0.77530 (18)	0.0175 (3)
H2	−0.2842	0.0675	0.7072	0.021*
C3	−0.1468 (2)	−0.1465 (2)	0.76330 (17)	0.0140 (3)
C4	−0.1761 (2)	−0.2711 (2)	0.88341 (16)	0.0136 (2)
C5	−0.0619 (2)	−0.4074 (2)	0.91554 (17)	0.0165 (3)
H5	0.0470	−0.4338	0.8496	0.020*
C6	−0.1090 (3)	−0.5027 (2)	1.04343 (18)	0.0205 (3)
H6	−0.0297	−0.5928	1.0662	0.025*
C7	−0.2724 (3)	−0.4681 (2)	1.14027 (19)	0.0217 (3)
H7	−0.3022	−0.5351	1.2277	0.026*
C8	−0.3907 (2)	−0.3375 (2)	1.11008 (18)	0.0190 (3)
H8	−0.5032	−0.3157	1.1743	0.023*
C9	−0.3396 (2)	−0.2391 (2)	0.98267 (17)	0.0151 (3)
C10	0.0068 (2)	−0.1606 (2)	0.64313 (16)	0.0141 (2)
H10	0.0462	−0.2858	0.6253	0.017*
C11	0.1001 (2)	−0.0225 (2)	0.55452 (16)	0.0138 (3)
N12	0.0745 (2)	0.18312 (18)	0.56664 (15)	0.0146 (2)
C13	−0.0075 (2)	0.1911 (2)	0.39986 (18)	0.0175 (3)
H13A	−0.0234	0.3325	0.4073	0.021*
H13B	−0.1634	0.0749	0.3561	0.021*
C14	0.1610 (2)	0.1619 (2)	0.27835 (16)	0.0167 (3)
H14A	0.0774	0.0346	0.1828	0.020*
H14B	0.2214	0.2925	0.2372	0.020*
C15	0.3634 (2)	0.1282 (2)	0.37065 (15)	0.0133 (2)
H15	0.4737	0.1038	0.2959	0.016*
C16	0.2599 (2)	−0.0651 (2)	0.44003 (16)	0.0140 (3)
C17	0.4883 (2)	0.3298 (2)	0.51823 (16)	0.0151 (3)
H17A	0.5534	0.4609	0.4784	0.018*
H17B	0.6181	0.3112	0.5812	0.018*
C18	0.3092 (2)	0.3571 (2)	0.63084 (18)	0.0175 (3)
H18A	0.3649	0.3537	0.7430	0.021*
H18B	0.2979	0.5004	0.6390	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01812 (16)	0.01885 (15)	0.02312 (17)	0.00879 (12)	0.01053 (12)	0.00645 (12)
O1	0.0246 (5)	0.0186 (5)	0.0218 (5)	0.0117 (4)	0.0109 (4)	0.0062 (4)
C2	0.0172 (7)	0.0176 (7)	0.0196 (7)	0.0068 (6)	0.0077 (5)	0.0065 (5)
C3	0.0133 (6)	0.0132 (6)	0.0138 (6)	0.0031 (5)	0.0039 (5)	0.0029 (4)
C4	0.0130 (6)	0.0123 (5)	0.0111 (5)	0.0008 (4)	0.0016 (5)	0.0010 (4)
C5	0.0134 (6)	0.0163 (6)	0.0188 (6)	0.0043 (5)	0.0041 (5)	0.0040 (5)
C6	0.0220 (7)	0.0202 (7)	0.0195 (7)	0.0067 (6)	0.0031 (6)	0.0084 (5)
C7	0.0258 (8)	0.0207 (7)	0.0167 (7)	0.0038 (6)	0.0071 (6)	0.0079 (5)
C8	0.0190 (7)	0.0164 (6)	0.0165 (6)	0.0012 (5)	0.0076 (5)	0.0016 (5)
C9	0.0126 (6)	0.0131 (6)	0.0157 (6)	0.0022 (5)	0.0024 (5)	0.0005 (5)
C10	0.0144 (6)	0.0134 (6)	0.0137 (6)	0.0049 (5)	0.0025 (5)	0.0025 (5)
C11	0.0151 (6)	0.0138 (6)	0.0126 (6)	0.0058 (5)	0.0040 (5)	0.0025 (5)
N12	0.0151 (5)	0.0128 (5)	0.0172 (5)	0.0057 (4)	0.0058 (4)	0.0045 (4)
C13	0.0146 (6)	0.0211 (6)	0.0196 (7)	0.0089 (5)	0.0038 (5)	0.0068 (5)
C14	0.0150 (6)	0.0217 (7)	0.0140 (6)	0.0069 (5)	0.0033 (5)	0.0057 (5)
C15	0.0128 (6)	0.0149 (6)	0.0123 (6)	0.0050 (5)	0.0043 (5)	0.0033 (4)
C16	0.0125 (6)	0.0149 (6)	0.0134 (6)	0.0042 (5)	0.0020 (5)	0.0030 (5)
C17	0.0125 (6)	0.0166 (6)	0.0158 (6)	0.0043 (5)	0.0028 (5)	0.0051 (5)
C18	0.0175 (7)	0.0152 (6)	0.0170 (6)	0.0038 (5)	0.0067 (5)	0.0014 (5)

Geometric parameters (Å, º)

S1—C2	1.7259 (14)	C11—N12	1.4447 (17)
S1—C9	1.7404 (15)	C11—C16	1.4966 (17)
O1—C16	1.2174 (16)	N12—C13	1.4777 (19)
C2—C3	1.3631 (19)	N12—C18	1.4867 (18)
C2—H2	0.9500	C13—C14	1.5556 (18)
C3—C4	1.4460 (19)	C13—H13A	0.9900
C3—C10	1.4598 (18)	C13—H13B	0.9900
C4—C5	1.405 (2)	C14—C15	1.5369 (18)
C4—C9	1.4125 (17)	C14—H14A	0.9900
C5—C6	1.381 (2)	C14—H14B	0.9900
C5—H5	0.9500	C15—C16	1.5196 (17)
C6—C7	1.404 (2)	C15—C17	1.5426 (17)
C6—H6	0.9500	C15—H15	1.0000
C7—C8	1.386 (2)	C17—C18	1.5545 (18)
C7—H7	0.9500	C17—H17A	0.9900
C8—C9	1.392 (2)	C17—H17B	0.9900
C8—H8	0.9500	C18—H18A	0.9900
C10—C11	1.3374 (18)	C18—H18B	0.9900
C10—H10	0.9500
C2—S1—C9	91.66 (7)	N12—C13—C14	112.39 (11)
C3—C2—S1	113.61 (11)	N12—C13—H13A	109.1
C3—C2—H2	123.2	C14—C13—H13A	109.1
S1—C2—H2	123.2	N12—C13—H13B	109.1
C2—C3—C4	111.74 (12)	C14—C13—H13B	109.1
C2—C3—C10	126.39 (13)	H13A—C13—H13B	107.9
C4—C3—C10	121.83 (12)	C15—C14—C13	108.35 (11)
C5—C4—C9	118.30 (12)	C15—C14—H14A	110.0
C5—C4—C3	129.41 (12)	C13—C14—H14A	110.0
C9—C4—C3	112.25 (12)	C15—C14—H14B	110.0
C6—C5—C4	119.65 (13)	C13—C14—H14B	110.0
C6—C5—H5	120.2	H14A—C14—H14B	108.4
C4—C5—H5	120.2	C16—C15—C14	107.76 (10)
C5—C6—C7	120.88 (14)	C16—C15—C17	107.37 (11)
C5—C6—H6	119.6	C14—C15—C17	108.28 (11)
C7—C6—H6	119.6	C16—C15—H15	111.1
C8—C7—C6	120.90 (14)	C14—C15—H15	111.1
C8—C7—H7	119.6	C17—C15—H15	111.1
C6—C7—H7	119.6	O1—C16—C11	124.87 (12)
C7—C8—C9	117.88 (13)	O1—C16—C15	125.04 (12)
C7—C8—H8	121.1	C11—C16—C15	110.09 (10)
C9—C8—H8	121.1	C15—C17—C18	108.65 (11)
C8—C9—C4	122.38 (13)	C15—C17—H17A	110.0
C8—C9—S1	126.86 (11)	C18—C17—H17A	110.0
C4—C9—S1	110.73 (10)	C15—C17—H17B	110.0
C11—C10—C3	129.26 (12)	C18—C17—H17B	110.0
C11—C10—H10	115.4	H17A—C17—H17B	108.3
C3—C10—H10	115.4	N12—C18—C17	111.92 (11)
C10—C11—N12	125.28 (12)	N12—C18—H18A	109.2
C10—C11—C16	120.76 (12)	C17—C18—H18A	109.2
N12—C11—C16	113.80 (11)	N12—C18—H18B	109.2
C11—N12—C13	108.78 (11)	C17—C18—H18B	109.2
C11—N12—C18	107.29 (11)	H18A—C18—H18B	107.9
C13—N12—C18	108.71 (11)
C9—S1—C2—C3	1.03 (11)	C3—C10—C11—C16	178.37 (12)
S1—C2—C3—C4	−1.04 (15)	C10—C11—N12—C13	−127.91 (14)
S1—C2—C3—C10	176.91 (11)	C16—C11—N12—C13	56.65 (14)
C2—C3—C4—C5	−177.23 (13)	C10—C11—N12—C18	114.66 (15)
C10—C3—C4—C5	4.7 (2)	C16—C11—N12—C18	−60.78 (14)
C2—C3—C4—C9	0.48 (16)	C11—N12—C13—C14	−58.09 (14)
C10—C3—C4—C9	−177.58 (11)	C18—N12—C13—C14	58.43 (14)
C9—C4—C5—C6	−1.04 (19)	N12—C13—C14—C15	1.21 (15)
C3—C4—C5—C6	176.54 (13)	C13—C14—C15—C16	56.20 (14)
C4—C5—C6—C7	1.1 (2)	C13—C14—C15—C17	−59.63 (14)
C5—C6—C7—C8	0.0 (2)	C10—C11—C16—O1	6.1 (2)
C6—C7—C8—C9	−1.0 (2)	N12—C11—C16—O1	−178.27 (13)
C7—C8—C9—C4	1.0 (2)	C10—C11—C16—C15	−173.27 (12)
C7—C8—C9—S1	−176.94 (10)	N12—C11—C16—C15	2.40 (15)
C5—C4—C9—C8	0.00 (18)	C14—C15—C16—O1	121.22 (14)
C3—C4—C9—C8	−177.99 (12)	C17—C15—C16—O1	−122.34 (14)
C5—C4—C9—S1	178.26 (10)	C14—C15—C16—C11	−59.45 (13)
C3—C4—C9—S1	0.28 (13)	C17—C15—C16—C11	56.99 (13)
C2—S1—C9—C8	177.45 (12)	C16—C15—C17—C18	−57.50 (13)
C2—S1—C9—C4	−0.72 (10)	C14—C15—C17—C18	58.60 (14)
C2—C3—C10—C11	21.3 (2)	C11—N12—C18—C17	58.05 (15)
C4—C3—C10—C11	−160.94 (14)	C13—N12—C18—C17	−59.42 (14)
C3—C10—C11—N12	3.2 (2)	C15—C17—C18—N12	0.72 (16)