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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1118.
Published online 2008 May 21. doi:  10.1107/S1600536808014232
PMCID: PMC2961617

N-[2-(1,3-Benzodioxol-5-yl)eth­yl]-2-chloro­acetamide

Abstract

The title compound, C11H12ClNO3, crystallizes with two independent mol­ecules in the asymmetric unit. Inter­molecular N—H(...)O hydrogen bonds link the mol­ecules related by translation along the b axis into two independent hydrogen-bonded chains. The crystal studied exhibited inversion twinning.

Related literature

For the crystal structures of related compounds, see: Kuehne et al. (1988 [triangle]). For details of the aplication of N-(2-benzo[1,3]dioxol-5-yl-ethyl)-2-chloro-acetamide, see: Bernhard & Snieckus (1971 [triangle]); Ma et al. (2006 [triangle]). For bond-length data, see Allen et al. (1987 [triangle]).

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Object name is e-64-o1118-scheme1.jpg

Experimental

Crystal data

  • C11H12ClNO3
  • M r = 241.67
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1118-efi1.jpg
  • a = 14.429 (3) Å
  • b = 5.1258 (10) Å
  • c = 30.679 (6) Å
  • V = 2269.1 (8) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.33 mm−1
  • T = 293 (2) K
  • 0.20 × 0.12 × 0.09 mm

Data collection

  • Rigaku R-AXIS RAPID IP area-detector diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.937, T max = 0.971
  • 15836 measured reflections
  • 3949 independent reflections
  • 2946 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.110
  • S = 1.13
  • 3949 reflections
  • 290 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.34 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1304 Friedel pairs
  • Flack parameter: 0.47 (8)

Data collection: RAPID-AUTO (Rigaku, 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014232/cv2412sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014232/cv2412Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The title compound (I) is an important intermediate for the synthesis of3, 4-dihydroisoquinoline and some other heterocyclic compounds (Bernhard & Snieckus, 1971; Ma et al., 2006). In this paper, we report its crystal structure.

Compound (I) crystallizes with two independent molecules in the non-centrosymmetric unit cell (Fig. 1). All bond lengths and angles in (I) are normal (Allen et al., 1987) and in a good agreement with those reported previously (Kuehne et al., 1988). The intermolecular N—H···O hydrogen bonds (Table 1) link the molecules related by translation along b axis into two independent hydrogen-bonded chains.

Experimental

2-Benzo[1,3]dioxol-5-yl-ethylamine (20 mmol) was dissolved in CH2Cl2, and K2CO3 (30 mmol) was added, then chloroacetyl chloride (20 mmol) was added during 30 min at 273 K. After 2 h standing at room temperature, the solution was washed with water, the organic layer was separated, dried with Na2SO4 and evaporated to obtain the primary product. The pure product was isolated by recrystallization from ethyl acetate (1.50 g, 68%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethyl acetate at room temperature.

Refinement

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 or 0.97 Å, N—H=0.86Å and with Uiso(H) = 1.2 times Ueq(C, N).

Figures

Fig. 1.
The content of asymmetric unit of (I), with atomic labels and 40% probability displacement ellipsoids for non-H atoms.

Crystal data

C11H12ClNO3F000 = 1008
Mr = 241.67Dx = 1.415 Mg m3
Orthorhombic, Pca21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 2501 reflections
a = 14.429 (3) Åθ = 2.3–25.1º
b = 5.1258 (10) ŵ = 0.33 mm1
c = 30.679 (6) ÅT = 293 (2) K
V = 2269.1 (8) Å3Needle, colourless
Z = 80.20 × 0.12 × 0.09 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer3949 independent reflections
Radiation source: Rotating Anode2946 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
T = 293(2) Kθmax = 25.0º
ω oscillation scansθmin = 3.1º
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)h = −17→17
Tmin = 0.937, Tmax = 0.971k = −5→6
15836 measured reflectionsl = −36→36

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035  w = 1/[σ2(Fo2) + (0.0541P)2 + 0.2974P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.110(Δ/σ)max = 0.001
S = 1.13Δρmax = 0.34 e Å3
3949 reflectionsΔρmin = −0.34 e Å3
290 parametersExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0035 (6)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1304 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.47 (8)

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 (Å2)

xyzUiso*/Ueq
Cl10.80437 (6)0.77974 (17)0.26938 (4)0.0660 (3)
Cl21.04831 (6)0.72284 (17)0.70767 (4)0.0658 (3)
O10.5138 (3)0.4037 (8)0.51198 (14)0.1064 (13)
O20.4074 (2)0.7028 (7)0.53628 (11)0.0873 (10)
O30.86302 (18)0.1950 (5)0.67866 (11)0.0726 (8)
O40.2640 (2)1.1064 (7)0.46419 (14)0.1001 (12)
O50.1615 (2)0.7930 (7)0.43980 (11)0.0826 (9)
O60.61927 (18)1.3095 (5)0.29844 (12)0.0725 (8)
N10.8579 (2)0.6316 (6)0.67326 (12)0.0569 (8)
H1A0.88720.77490.67800.068*
N20.6139 (2)0.8733 (6)0.30282 (13)0.0567 (9)
H2B0.64280.72940.29800.068*
C10.4217 (4)0.4861 (11)0.5078 (3)0.086 (2)
H1B0.37990.34500.51540.103*
H1C0.40930.53710.47790.103*
C20.6047 (3)0.9174 (9)0.60261 (15)0.0694 (11)
H2A0.62261.04280.62280.083*
C30.5145 (3)0.9204 (10)0.58685 (18)0.0766 (12)
H3A0.47201.04420.59640.092*
C40.4904 (3)0.7377 (8)0.55716 (14)0.0607 (10)
C50.5532 (3)0.5584 (11)0.5434 (2)0.0649 (13)
C60.6420 (3)0.5492 (9)0.5578 (2)0.0681 (14)
H6A0.68360.42580.54730.082*
C70.6685 (2)0.7335 (7)0.58913 (13)0.0558 (9)
C80.7652 (2)0.7271 (8)0.60849 (14)0.0671 (11)
H8A0.80340.60820.59170.080*
H8B0.79250.89960.60640.080*
C90.7648 (3)0.6432 (7)0.65481 (14)0.0605 (10)
H9A0.72770.76420.67170.073*
H9B0.73630.47230.65690.073*
C100.8985 (3)0.4085 (7)0.68301 (15)0.0539 (10)
C110.9951 (2)0.4136 (7)0.70259 (15)0.0613 (10)
H11A1.03480.30410.68480.074*
H11B0.99200.33520.73130.074*
C120.1728 (5)1.0074 (11)0.4679 (3)0.088 (2)
H12A0.16110.95390.49770.105*
H12B0.12851.14260.46030.105*
C130.3619 (3)0.5967 (9)0.37410 (14)0.0662 (11)
H13A0.38130.47350.35380.079*
C140.2717 (3)0.5835 (10)0.38929 (18)0.0748 (12)
H14A0.23070.45620.37950.090*
C150.2458 (3)0.7656 (8)0.41918 (13)0.0605 (10)
C160.3067 (3)0.9502 (10)0.43397 (19)0.0592 (12)
C170.3958 (3)0.9658 (9)0.4176 (2)0.0668 (15)
H17A0.43591.09690.42670.080*
C180.4239 (3)0.7821 (7)0.38744 (12)0.0560 (9)
C190.5200 (3)0.7908 (9)0.36873 (14)0.0670 (11)
H19A0.55640.91740.38480.080*
H19B0.54890.62140.37240.080*
C200.5208 (2)0.8615 (7)0.32136 (14)0.0602 (10)
H20A0.48480.73390.30530.072*
H20B0.49121.02990.31770.072*
C210.6554 (2)1.0929 (7)0.29311 (13)0.0506 (9)
C220.7510 (3)1.0888 (7)0.27470 (15)0.0627 (10)
H22A0.79011.19670.29300.075*
H22B0.74911.16960.24610.075*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0492 (5)0.0504 (5)0.0983 (7)0.0069 (4)0.0175 (5)0.0016 (6)
Cl20.0504 (5)0.0516 (5)0.0956 (7)−0.0081 (4)−0.0166 (5)0.0014 (6)
O10.076 (2)0.131 (3)0.112 (3)0.006 (2)−0.031 (2)−0.054 (3)
O20.0487 (16)0.124 (3)0.089 (2)0.0023 (16)−0.0162 (16)0.001 (2)
O30.0640 (17)0.0391 (13)0.115 (2)−0.0078 (11)−0.0205 (16)−0.0023 (16)
O40.075 (2)0.103 (2)0.122 (3)−0.007 (2)0.037 (2)−0.041 (3)
O50.0531 (16)0.107 (2)0.087 (2)−0.0059 (15)0.0207 (16)−0.0081 (19)
O60.0626 (17)0.0394 (13)0.115 (2)0.0078 (11)0.0219 (16)−0.0040 (16)
N10.0437 (16)0.0416 (16)0.085 (2)−0.0045 (13)−0.0175 (16)0.0032 (17)
N20.0424 (16)0.0411 (17)0.087 (3)0.0053 (13)0.0127 (16)−0.0041 (17)
C10.066 (3)0.122 (5)0.069 (5)−0.019 (3)−0.030 (4)0.005 (3)
C20.059 (2)0.075 (3)0.074 (3)0.006 (2)−0.009 (2)−0.012 (3)
C30.059 (3)0.090 (3)0.080 (3)0.026 (2)−0.005 (3)−0.013 (3)
C40.042 (2)0.081 (3)0.058 (2)−0.0002 (19)−0.0040 (17)0.007 (2)
C50.055 (3)0.072 (2)0.067 (3)−0.007 (2)−0.005 (2)−0.010 (3)
C60.053 (3)0.078 (3)0.073 (4)0.009 (2)−0.004 (2)−0.010 (3)
C70.0438 (18)0.068 (2)0.056 (2)−0.0028 (17)−0.0025 (17)0.004 (2)
C80.042 (2)0.093 (3)0.067 (3)−0.0042 (18)−0.0033 (17)−0.001 (2)
C90.040 (2)0.057 (2)0.085 (3)−0.0035 (15)−0.0128 (17)0.007 (2)
C100.052 (2)0.039 (2)0.071 (3)−0.0008 (17)0.001 (2)−0.001 (2)
C110.0459 (19)0.0435 (19)0.094 (3)0.0010 (15)−0.016 (2)0.005 (2)
C120.072 (4)0.103 (5)0.087 (6)0.010 (2)0.007 (4)0.003 (3)
C130.061 (3)0.069 (3)0.068 (3)−0.005 (2)0.013 (2)−0.005 (3)
C140.065 (3)0.086 (3)0.074 (3)−0.025 (2)0.012 (2)−0.008 (3)
C150.046 (2)0.075 (2)0.061 (3)0.0012 (19)0.0091 (17)0.010 (2)
C160.053 (3)0.067 (2)0.058 (3)0.003 (2)0.009 (2)−0.001 (2)
C170.057 (3)0.074 (3)0.070 (4)−0.011 (2)0.012 (3)−0.012 (2)
C180.049 (2)0.066 (2)0.054 (2)0.0020 (17)0.0007 (18)0.0051 (19)
C190.044 (2)0.088 (3)0.068 (3)0.001 (2)0.0021 (17)−0.003 (2)
C200.040 (2)0.060 (2)0.080 (3)0.0049 (16)0.0119 (17)0.006 (2)
C210.0473 (19)0.038 (2)0.067 (2)0.0004 (15)0.0091 (19)−0.002 (2)
C220.054 (2)0.0424 (19)0.092 (3)0.0005 (16)0.015 (2)−0.003 (2)

Geometric parameters (Å, °)

Cl1—C221.769 (4)C7—C81.517 (5)
Cl2—C111.768 (4)C8—C91.485 (6)
O1—C51.372 (7)C8—H8A0.9700
O1—C11.401 (7)C8—H8B0.9700
O2—C41.370 (5)C9—H9A0.9700
O2—C11.428 (7)C9—H9B0.9700
O3—C101.216 (4)C10—C111.518 (5)
O4—C161.371 (6)C11—H11A0.9700
O4—C121.416 (7)C11—H11B0.9700
O5—C151.378 (5)C12—H12A0.9700
O5—C121.405 (7)C12—H12B0.9700
O6—C211.237 (4)C13—C181.367 (6)
N1—C101.319 (5)C13—C141.384 (6)
N1—C91.458 (4)C13—H13A0.9300
N1—H1A0.8600C14—C151.361 (6)
N2—C211.309 (5)C14—H14A0.9300
N2—C201.459 (4)C15—C161.368 (6)
N2—H2B0.8600C16—C171.383 (6)
C1—H1B0.9700C17—C181.381 (6)
C1—H1C0.9700C17—H17A0.9300
C2—C71.381 (6)C18—C191.501 (5)
C2—C31.388 (6)C19—C201.498 (6)
C2—H2A0.9300C19—H19A0.9700
C3—C41.352 (7)C19—H19B0.9700
C3—H3A0.9300C20—H20A0.9700
C4—C51.358 (7)C20—H20B0.9700
C5—C61.355 (6)C21—C221.491 (5)
C6—C71.401 (7)C22—H22A0.9700
C6—H6A0.9300C22—H22B0.9700
C5—O1—C1106.5 (4)C10—C11—H11A108.1
C4—O2—C1105.1 (4)Cl2—C11—H11A108.1
C16—O4—C12105.2 (4)C10—C11—H11B108.1
C15—O5—C12105.0 (4)Cl2—C11—H11B108.1
C10—N1—C9122.2 (3)H11A—C11—H11B107.3
C10—N1—H1A118.9O5—C12—O4109.8 (6)
C9—N1—H1A118.9O5—C12—H12A109.7
C21—N2—C20123.0 (3)O4—C12—H12A109.7
C21—N2—H2B118.5O5—C12—H12B109.7
C20—N2—H2B118.5O4—C12—H12B109.7
O1—C1—O2108.4 (5)H12A—C12—H12B108.2
O1—C1—H1B110.0C18—C13—C14123.2 (4)
O2—C1—H1B110.0C18—C13—H13A118.4
O1—C1—H1C110.0C14—C13—H13A118.4
O2—C1—H1C110.0C15—C14—C13116.8 (4)
H1B—C1—H1C108.4C15—C14—H14A121.6
C7—C2—C3121.8 (4)C13—C14—H14A121.6
C7—C2—H2A119.1C14—C15—C16121.4 (4)
C3—C2—H2A119.1C14—C15—O5128.4 (4)
C4—C3—C2117.9 (4)C16—C15—O5110.1 (4)
C4—C3—H3A121.0C15—C16—O4109.9 (4)
C2—C3—H3A121.0C15—C16—C17121.1 (5)
C3—C4—C5120.4 (4)O4—C16—C17129.0 (5)
C3—C4—O2129.1 (4)C18—C17—C16118.5 (4)
C5—C4—O2110.5 (4)C18—C17—H17A120.8
C6—C5—C4123.6 (5)C16—C17—H17A120.8
C6—C5—O1126.9 (5)C13—C18—C17118.9 (4)
C4—C5—O1109.4 (4)C13—C18—C19120.7 (4)
C5—C6—C7117.2 (5)C17—C18—C19120.4 (4)
C5—C6—H6A121.4C20—C19—C18112.7 (3)
C7—C6—H6A121.4C20—C19—H19A109.0
C2—C7—C6119.0 (4)C18—C19—H19A109.0
C2—C7—C8120.7 (4)C20—C19—H19B109.0
C6—C7—C8120.3 (4)C18—C19—H19B109.0
C9—C8—C7112.2 (3)H19A—C19—H19B107.8
C9—C8—H8A109.2N2—C20—C19113.3 (3)
C7—C8—H8A109.2N2—C20—H20A108.9
C9—C8—H8B109.2C19—C20—H20A108.9
C7—C8—H8B109.2N2—C20—H20B108.9
H8A—C8—H8B107.9C19—C20—H20B108.9
N1—C9—C8112.4 (3)H20A—C20—H20B107.7
N1—C9—H9A109.1O6—C21—N2123.3 (3)
C8—C9—H9A109.1O6—C21—C22116.9 (3)
N1—C9—H9B109.1N2—C21—C22119.8 (3)
C8—C9—H9B109.1C21—C22—Cl1116.8 (3)
H9A—C9—H9B107.9C21—C22—H22A108.1
O3—C10—N1124.7 (4)Cl1—C22—H22A108.1
O3—C10—C11116.4 (3)C21—C22—H22B108.1
N1—C10—C11118.9 (3)Cl1—C22—H22B108.1
C10—C11—Cl2116.7 (3)H22A—C22—H22B107.3
C5—O1—C1—O22.5 (7)C15—O5—C12—O4−0.5 (7)
C4—O2—C1—O1−1.5 (6)C16—O4—C12—O50.0 (7)
C7—C2—C3—C4−0.7 (8)C18—C13—C14—C15−0.5 (7)
C2—C3—C4—C5−0.2 (8)C13—C14—C15—C16−1.0 (7)
C2—C3—C4—O2−178.6 (4)C13—C14—C15—O5−178.8 (4)
C1—O2—C4—C3178.5 (6)C12—O5—C15—C14178.8 (6)
C1—O2—C4—C5−0.1 (5)C12—O5—C15—C160.8 (5)
C3—C4—C5—C6−0.2 (9)C14—C15—C16—O4−179.0 (5)
O2—C4—C5—C6178.5 (5)O5—C15—C16—O4−0.9 (6)
C3—C4—C5—O1−177.1 (5)C14—C15—C16—C172.9 (8)
O2—C4—C5—O11.6 (6)O5—C15—C16—C17−178.9 (5)
C1—O1—C5—C6−179.3 (6)C12—O4—C16—C150.5 (7)
C1—O1—C5—C4−2.5 (7)C12—O4—C16—C17178.4 (6)
C4—C5—C6—C71.3 (9)C15—C16—C17—C18−3.2 (9)
O1—C5—C6—C7177.6 (6)O4—C16—C17—C18179.1 (5)
C3—C2—C7—C61.7 (7)C14—C13—C18—C170.1 (7)
C3—C2—C7—C8−177.1 (5)C14—C13—C18—C19−178.2 (4)
C5—C6—C7—C2−2.0 (8)C16—C17—C18—C131.7 (8)
C5—C6—C7—C8176.9 (5)C16—C17—C18—C19180.0 (5)
C2—C7—C8—C969.1 (5)C13—C18—C19—C2066.7 (5)
C6—C7—C8—C9−109.7 (5)C17—C18—C19—C20−111.5 (5)
C10—N1—C9—C8−109.7 (5)C21—N2—C20—C19−106.4 (5)
C7—C8—C9—N1178.8 (3)C18—C19—C20—N2179.4 (3)
C9—N1—C10—O3−1.6 (6)C20—N2—C21—O6−0.6 (6)
C9—N1—C10—C11−179.3 (4)C20—N2—C21—C22179.3 (4)
O3—C10—C11—Cl2178.4 (3)O6—C21—C22—Cl1177.3 (3)
N1—C10—C11—Cl2−3.7 (6)N2—C21—C22—Cl1−2.6 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.862.182.894 (4)140
N2—H2B···O6ii0.862.182.894 (4)140

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2412).

References

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