rel-(1R,4R,9R)-1-Acetyl-9-(1-pyrrolidin­yl)-1,4-dihydro-1,4-ethanona­phthalene-9-carbonitrile: the major [4+2]-photocyclo­adduct of 1-acetonaphthone with 2-(1-pyrrolidin­yl)propenenitrile

The mol­ecular structure of the title compound, C₁₉H₂₀N₂O, shows elongated C—C single bonds due to their thermal lability. The methyl group forms an inter­molecular C—H...N hydrogen bond.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.095
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C2     -   C19     ..       8.27 su

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

Alert level G
RADNT01_ALERT_1_G  Extra text has been found in the _diffrn_radiation_type field.
            Radiation given as MoK\a, rotating anode
            Radiation identified as Mo K\a

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

rel-(1R,4R,9R)-1-Acetyl-9-(1-pyrrolidinyl)-1,4-dihydro-1,4-ethanonaphthalene- 9-carbonitrile

Crystal data

C19H20N2O	F(000) = 624
Mr = 292.37	Dx = 1.278 Mg m^−3
Monoclinic, P21/c	Mo Kα, rotating anode radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 9.910 (2) Å	θ = 10–20°
b = 19.443 (3) Å	µ = 0.08 mm^−1
c = 8.557 (2) Å	T = 150 K
β = 112.80 (1)°	Prism, colourless
V = 1519.9 (5) Å^3	0.50 × 0.25 × 0.22 mm
Z = 4

Data collection

Siemens P4 diffractometer	2964 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 27.0°, θmin = 2.1°
ω scans	h = −12→7
Absorption correction: ψ scan (North et al., 1968)	k = −24→0
Tmin = 0.961, Tmax = 0.981	l = −10→10
5650 measured reflections	3 standard reflections every 100 reflections
3319 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0398P)^2 + 0.57P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
3319 reflections	Δρmax = 0.34 e Å^−3
202 parameters	Δρmin = −0.18 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: 0.0073 (14)

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
C1	0.37848 (11)	0.87523 (6)	0.08623 (14)	0.0183 (2)
H1A	0.3763	0.8243	0.0869	0.022*
H1B	0.4048	0.8902	−0.0089	0.022*
C2	0.22443 (11)	0.90404 (5)	0.06129 (13)	0.0172 (2)
C3	0.24236 (12)	0.95262 (6)	0.21613 (14)	0.0193 (2)
H3A	0.1475	0.9742	0.2053	0.023*
C4	0.35627 (13)	1.00587 (6)	0.22251 (14)	0.0221 (2)
H4A	0.3358	1.0538	0.2104	0.027*
C5	0.48672 (12)	0.98018 (6)	0.24638 (14)	0.0208 (2)
H5A	0.5683	1.0082	0.2564	0.025*
C6	0.49469 (11)	0.90182 (5)	0.25645 (13)	0.0173 (2)
C7	0.44129 (11)	0.87914 (6)	0.39386 (13)	0.0176 (2)
C8	0.30529 (12)	0.90757 (6)	0.37153 (14)	0.0186 (2)
C9	0.23973 (12)	0.89271 (6)	0.48415 (14)	0.0231 (2)
H9A	0.1475	0.9121	0.4689	0.028*
C10	0.31086 (14)	0.84895 (7)	0.61997 (15)	0.0262 (3)
H10A	0.2679	0.8394	0.6994	0.031*
C11	0.44409 (14)	0.81914 (6)	0.64051 (15)	0.0254 (3)
H11A	0.4911	0.7890	0.7330	0.031*
C12	0.50907 (12)	0.83341 (6)	0.52567 (14)	0.0215 (2)
H12A	0.5987	0.8120	0.5376	0.026*
C13	0.64719 (12)	0.87440 (6)	0.28841 (15)	0.0215 (2)
C14	0.77286 (12)	0.90462 (7)	0.43597 (16)	0.0270 (3)
H14A	0.8396	0.8678	0.4979	0.040*
H14B	0.7351	0.9281	0.5119	0.040*
H14C	0.8256	0.9376	0.3940	0.040*
C15	−0.02374 (12)	0.86979 (6)	0.03972 (15)	0.0233 (3)
H15A	−0.0542	0.9134	−0.0240	0.028*
H15B	−0.0229	0.8763	0.1549	0.028*
C16	−0.12746 (13)	0.81083 (7)	−0.05296 (16)	0.0287 (3)
H16A	−0.1761	0.7913	0.0187	0.034*
H16B	−0.2034	0.8273	−0.1606	0.034*
C17	−0.02942 (13)	0.75724 (7)	−0.08678 (16)	0.0274 (3)
H17A	0.0064	0.7231	0.0061	0.033*
H17B	−0.0817	0.7330	−0.1953	0.033*
C18	0.09520 (12)	0.80055 (6)	−0.09435 (14)	0.0211 (2)
H18A	0.1824	0.7721	−0.0782	0.025*
H18B	0.0657	0.8256	−0.2033	0.025*
C19	0.16519 (12)	0.94733 (6)	−0.09624 (15)	0.0218 (4)
N1	0.12268 (10)	0.84811 (5)	0.04858 (11)	0.0175 (2)
N2	0.10925 (12)	0.97718 (6)	−0.22025 (14)	0.0303 (4)
O1	0.66525 (10)	0.83048 (5)	0.19816 (12)	0.0358 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0145 (5)	0.0205 (5)	0.0193 (5)	0.0012 (4)	0.0060 (4)	−0.0024 (4)
C2	0.0147 (5)	0.0177 (5)	0.0181 (5)	0.0009 (4)	0.0051 (4)	−0.0002 (4)
C3	0.0159 (5)	0.0196 (5)	0.0218 (5)	0.0023 (4)	0.0066 (4)	−0.0032 (4)
C4	0.0238 (6)	0.0165 (5)	0.0236 (5)	−0.0001 (4)	0.0066 (4)	−0.0022 (4)
C5	0.0210 (5)	0.0184 (5)	0.0219 (5)	−0.0040 (4)	0.0072 (4)	−0.0015 (4)
C6	0.0140 (5)	0.0180 (5)	0.0189 (5)	−0.0010 (4)	0.0054 (4)	−0.0011 (4)
C7	0.0154 (5)	0.0182 (5)	0.0184 (5)	−0.0035 (4)	0.0058 (4)	−0.0038 (4)
C8	0.0166 (5)	0.0191 (5)	0.0190 (5)	−0.0021 (4)	0.0057 (4)	−0.0053 (4)
C9	0.0186 (5)	0.0285 (6)	0.0234 (6)	−0.0059 (4)	0.0095 (4)	−0.0094 (5)
C10	0.0275 (6)	0.0317 (6)	0.0221 (6)	−0.0120 (5)	0.0126 (5)	−0.0060 (5)
C11	0.0277 (6)	0.0250 (6)	0.0199 (5)	−0.0071 (5)	0.0052 (5)	0.0006 (4)
C12	0.0187 (5)	0.0206 (5)	0.0225 (5)	−0.0019 (4)	0.0050 (4)	−0.0011 (4)
C13	0.0157 (5)	0.0250 (6)	0.0241 (6)	0.0005 (4)	0.0081 (4)	0.0016 (4)
C14	0.0144 (5)	0.0328 (6)	0.0311 (6)	−0.0015 (5)	0.0057 (5)	−0.0012 (5)
C15	0.0151 (5)	0.0283 (6)	0.0266 (6)	0.0007 (4)	0.0081 (4)	−0.0010 (5)
C16	0.0171 (6)	0.0404 (7)	0.0276 (6)	−0.0059 (5)	0.0077 (5)	−0.0063 (5)
C17	0.0228 (6)	0.0283 (6)	0.0286 (6)	−0.0073 (5)	0.0072 (5)	−0.0041 (5)
C18	0.0185 (5)	0.0227 (5)	0.0212 (5)	−0.0020 (4)	0.0066 (4)	−0.0040 (4)
C19	0.0193 (6)	0.0215 (6)	0.0252 (7)	0.0008 (4)	0.0092 (5)	−0.0007 (4)
N1	0.0136 (4)	0.0195 (4)	0.0190 (4)	−0.0004 (3)	0.0059 (3)	−0.0019 (3)
N2	0.0324 (7)	0.0306 (6)	0.0274 (6)	0.0057 (5)	0.0109 (5)	0.0073 (5)
O1	0.0211 (4)	0.0446 (6)	0.0394 (5)	0.0069 (4)	0.0093 (4)	−0.0133 (4)

Geometric parameters (Å, º)

C1—C6	1.5541 (15)	C11—C12	1.3956 (17)
C1—C2	1.5612 (14)	C11—H11A	0.9500
C1—H1A	0.9900	C12—H12A	0.9500
C1—H1B	0.9900	C13—O1	1.2102 (15)
C2—N1	1.4582 (14)	C13—C14	1.5072 (16)
C2—C19	1.5023 (15)	C14—H14A	0.9800
C2—C3	1.5801 (15)	C14—H14B	0.9800
C3—C8	1.5105 (16)	C14—H14C	0.9800
C3—C4	1.5171 (16)	C15—N1	1.4844 (14)
C3—H3A	1.0000	C15—C16	1.5388 (17)
C4—C5	1.3258 (17)	C15—H15A	0.9900
C4—H4A	0.9500	C15—H15B	0.9900
C5—C6	1.5263 (15)	C16—C17	1.5268 (18)
C5—H5A	0.9500	C16—H16A	0.9900
C6—C13	1.5240 (15)	C16—H16B	0.9900
C6—C7	1.5294 (15)	C17—C18	1.5167 (16)
C7—C12	1.3881 (16)	C17—H17A	0.9900
C7—C8	1.3997 (15)	C17—H17B	0.9900
C8—C9	1.3854 (16)	C18—N1	1.4721 (14)
C9—C10	1.3917 (18)	C18—H18A	0.9900
C9—H9A	0.9500	C18—H18B	0.9900
C10—C11	1.3894 (18)	C19—N2	1.1464 (16)
C10—H10A	0.9500
C6—C1—C2	109.81 (8)	C10—C11—H11A	119.9
C6—C1—H1A	109.7	C12—C11—H11A	119.9
C2—C1—H1A	109.7	C7—C12—C11	119.31 (11)
C6—C1—H1B	109.7	C7—C12—H12A	120.3
C2—C1—H1B	109.7	C11—C12—H12A	120.3
H1A—C1—H1B	108.2	O1—C13—C14	122.08 (11)
N1—C2—C19	109.42 (9)	O1—C13—C6	120.92 (10)
N1—C2—C1	110.73 (9)	C14—C13—C6	117.00 (10)
C19—C2—C1	110.19 (9)	C13—C14—H14A	109.5
N1—C2—C3	110.98 (8)	C13—C14—H14B	109.5
C19—C2—C3	107.18 (9)	H14A—C14—H14B	109.5
C1—C2—C3	108.28 (8)	C13—C14—H14C	109.5
C8—C3—C4	108.45 (9)	H14A—C14—H14C	109.5
C8—C3—C2	105.40 (9)	H14B—C14—H14C	109.5
C4—C3—C2	106.17 (9)	N1—C15—C16	105.03 (9)
C8—C3—H3A	112.1	N1—C15—H15A	110.7
C4—C3—H3A	112.1	C16—C15—H15A	110.7
C2—C3—H3A	112.1	N1—C15—H15B	110.7
C5—C4—C3	114.58 (10)	C16—C15—H15B	110.7
C5—C4—H4A	122.7	H15A—C15—H15B	108.8
C3—C4—H4A	122.7	C17—C16—C15	105.01 (9)
C4—C5—C6	114.26 (10)	C17—C16—H16A	110.7
C4—C5—H5A	122.9	C15—C16—H16A	110.7
C6—C5—H5A	122.9	C17—C16—H16B	110.7
C13—C6—C5	112.66 (9)	C15—C16—H16B	110.7
C13—C6—C7	112.07 (9)	H16A—C16—H16B	108.8
C5—C6—C7	107.78 (9)	C18—C17—C16	102.57 (10)
C13—C6—C1	112.02 (9)	C18—C17—H17A	111.3
C5—C6—C1	106.01 (9)	C16—C17—H17A	111.3
C7—C6—C1	105.85 (8)	C18—C17—H17B	111.3
C12—C7—C8	120.07 (10)	C16—C17—H17B	111.3
C12—C7—C6	127.35 (10)	H17A—C17—H17B	109.2
C8—C7—C6	112.52 (9)	N1—C18—C17	101.82 (9)
C9—C8—C7	120.60 (11)	N1—C18—H18A	111.4
C9—C8—C3	126.04 (10)	C17—C18—H18A	111.4
C7—C8—C3	113.35 (9)	N1—C18—H18B	111.4
C8—C9—C10	119.09 (11)	C17—C18—H18B	111.4
C8—C9—H9A	120.5	H18A—C18—H18B	109.3
C10—C9—H9A	120.5	N2—C19—C2	174.18 (12)
C11—C10—C9	120.64 (11)	C2—N1—C18	115.49 (8)
C11—C10—H10A	119.7	C2—N1—C15	115.22 (9)
C9—C10—H10A	119.7	C18—N1—C15	105.87 (8)
C10—C11—C12	120.21 (11)
C6—C1—C2—N1	−119.85 (9)	C2—C3—C8—C9	−118.48 (11)
C6—C1—C2—C19	118.96 (10)	C4—C3—C8—C7	−52.96 (12)
C6—C1—C2—C3	2.04 (11)	C2—C3—C8—C7	60.39 (11)
N1—C2—C3—C8	61.88 (11)	C7—C8—C9—C10	−0.11 (16)
C19—C2—C3—C8	−178.70 (8)	C3—C8—C9—C10	178.68 (10)
C1—C2—C3—C8	−59.84 (10)	C8—C9—C10—C11	−1.55 (17)
N1—C2—C3—C4	176.82 (9)	C9—C10—C11—C12	0.69 (18)
C19—C2—C3—C4	−63.76 (11)	C8—C7—C12—C11	−3.48 (16)
C1—C2—C3—C4	55.10 (11)	C6—C7—C12—C11	179.59 (10)
C8—C3—C4—C5	52.01 (13)	C10—C11—C12—C7	1.84 (17)
C2—C3—C4—C5	−60.83 (12)	C5—C6—C13—O1	−128.01 (12)
C3—C4—C5—C6	2.05 (14)	C7—C6—C13—O1	110.23 (12)
C4—C5—C6—C13	−178.54 (10)	C1—C6—C13—O1	−8.58 (15)
C4—C5—C6—C7	−54.38 (12)	C5—C6—C13—C14	51.77 (13)
C4—C5—C6—C1	58.60 (12)	C7—C6—C13—C14	−69.99 (12)
C2—C1—C6—C13	179.24 (9)	C1—C6—C13—C14	171.20 (10)
C2—C1—C6—C5	−57.50 (11)	N1—C15—C16—C17	1.66 (12)
C2—C1—C6—C7	56.82 (11)	C15—C16—C17—C18	−26.95 (12)
C13—C6—C7—C12	−6.64 (15)	C16—C17—C18—N1	42.50 (11)
C5—C6—C7—C12	−131.16 (11)	C19—C2—N1—C18	60.54 (12)
C1—C6—C7—C12	115.75 (12)	C1—C2—N1—C18	−61.11 (11)
C13—C6—C7—C8	176.24 (9)	C3—C2—N1—C18	178.61 (9)
C5—C6—C7—C8	51.72 (12)	C19—C2—N1—C15	−63.48 (11)
C1—C6—C7—C8	−61.37 (11)	C1—C2—N1—C15	174.87 (9)
C12—C7—C8—C9	2.64 (16)	C3—C2—N1—C15	54.59 (11)
C6—C7—C8—C9	180.00 (10)	C17—C18—N1—C2	−171.46 (9)
C12—C7—C8—C3	−176.29 (10)	C17—C18—N1—C15	−42.68 (11)
C6—C7—C8—C3	1.07 (13)	C16—C15—N1—C2	154.41 (9)
C4—C3—C8—C9	128.17 (11)	C16—C15—N1—C18	25.47 (12)