PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o2038.
Published online 2008 September 27. doi:  10.1107/S1600536808030742
PMCID: PMC2959283

(2SR,3RS)-Benz­yl[4-chloro-1-(4-chloro­phen­yl)-1-methoxy­carbon­yl-2-but­yl]­ammonium chloride

Abstract

In the racemic hydro­chloride salt of the title ester, C19H22Cl2NO2 +·Cl, the penta­noic acid chain shows a mixture of trans and gauche orientations to give an overall helical conformation. The dihedral angle between the two aromatic rings is 26.11 (10)°. The charged secondary amine function participates in two N—H(...)Cl hydrogen bonds.

Related literature

For a related structure, see: Froimowitz et al. (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2038-scheme1.jpg

Experimental

Crystal data

  • C19H22Cl2NO2 +·Cl
  • M r = 402.73
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2038-efi1.jpg
  • a = 9.263 (2) Å
  • b = 10.432 (3) Å
  • c = 11.490 (3) Å
  • α = 115.954 (3)°
  • β = 93.925 (3)°
  • γ = 103.015 (3)°
  • V = 954.8 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.49 mm−1
  • T = 296 (2) K
  • 0.60 × 0.38 × 0.18 mm

Data collection

  • Bruker APEX II CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.782, T max = 0.915
  • 8767 measured reflections
  • 4422 independent reflections
  • 3320 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.159
  • S = 1.03
  • 4422 reflections
  • 227 parameters
  • H-atom parameters constrained
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT-Plus (Bruker, 2007 [triangle]); data reduction: SAINT-Plus; 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/S1600536808030742/hb2801sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030742/hb2801Isup2.hkl

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

supplementary crystallographic information

Comment

The title molecule, (I), is a β-amino acid ester resulting from a rhodium-catalyzed C—H insertion reaction between methyl-(4-chlorophenyl)diazo acetate and Boc-protected N-benzyl-3-chloropropanamine. Full details will be published elsewhere.

Experimental

Colourless blocks of (I) were grown by diffusion of diethylether into 100 µl of a solution containing about 5 mg of the title compound in methanol.

Refinement

The H atoms were positioned with idealized geometry (N–H = 0.90 Å, C–H = 0.93-0.98 Å) and refined as riding with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(methyl C).

Figures

Fig. 1.
: The molecular structure of (I). Displacement ellipsoids are shown at the 50% probability level and H-atoms are shown as spheres of arbitrary size.
Fig. 2.
: Molecular packing and unit cell of (I) viewed along the a axis. Hydrogen bonding is indicated by dashed lines, H-atoms bonded to C have been omitted for clarity.

Crystal data

C19H22Cl2NO2+·ClZ = 2
Mr = 402.73F(000) = 420
Triclinic, P1Dx = 1.401 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.263 (2) ÅCell parameters from 3509 reflections
b = 10.432 (3) Åθ = 2.0–28.7°
c = 11.490 (3) ŵ = 0.49 mm1
α = 115.954 (3)°T = 296 K
β = 93.925 (3)°Block, colourless
γ = 103.015 (3)°0.60 × 0.38 × 0.18 mm
V = 954.8 (4) Å3

Data collection

Bruker APEXII CCD diffractometer4422 independent reflections
Radiation source: fine-focus sealed tube3320 reflections with I > 2σ(I)
graphiteRint = 0.024
Detector resolution: 8.3 pixels mm-1θmax = 28.7°, θmin = 2.0°
sets of exposures each taken over 0.5° ω rotation scansh = −12→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)k = −13→12
Tmin = 0.782, Tmax = 0.915l = −15→15
8767 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.097P)2 + 0.1562P] where P = (Fo2 + 2Fc2)/3
4422 reflections(Δ/σ)max = 0.002
227 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = −0.36 e Å3

Special details

Experimental. Crystal grew over 48 h.
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. Data were collected by measuring three sets of exposures with the detector set at 2θ = 29°, crystal-to-detector distance 6.00 cm. Refinement of F2 against ALL reflections.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.64470 (8)0.98821 (8)0.38456 (7)0.0691 (2)
Cl20.26825 (11)−0.01534 (7)−0.06864 (6)0.0787 (3)
Cl30.17315 (6)0.47020 (7)−0.12520 (5)0.05352 (19)
O10.11480 (18)0.6582 (2)0.40412 (15)0.0512 (4)
O20.28993 (18)0.62358 (19)0.52192 (14)0.0473 (4)
N10.18786 (18)0.67376 (17)0.17013 (15)0.0330 (3)
H10.11420.65050.21070.040*
H20.18380.59030.09660.040*
C10.2347 (2)0.6371 (2)0.41927 (17)0.0346 (4)
C20.3435 (2)0.6218 (2)0.32432 (17)0.0321 (4)
H210.44520.65830.37730.039*
C30.3372 (2)0.7230 (2)0.25943 (17)0.0314 (4)
H310.34970.82370.32990.038*
C40.4634 (2)0.7305 (2)0.18192 (19)0.0377 (4)
H410.45710.63020.11660.045*
H420.44640.78520.13490.045*
C50.6210 (2)0.8022 (3)0.2633 (2)0.0457 (5)
H510.69300.80140.20580.055*
H520.64180.74460.30640.055*
C60.3211 (2)0.4594 (2)0.22692 (18)0.0338 (4)
C70.4464 (2)0.4091 (3)0.1945 (2)0.0431 (5)
H710.54250.47440.23440.052*
C80.4308 (3)0.2642 (3)0.1046 (2)0.0507 (6)
H810.51540.23150.08330.061*
C90.2888 (3)0.1685 (2)0.0466 (2)0.0495 (6)
C100.1623 (3)0.2137 (3)0.0776 (2)0.0494 (5)
H1010.06680.14690.03800.059*
C110.1778 (2)0.3591 (2)0.1681 (2)0.0423 (5)
H1110.09250.39030.18990.051*
C120.1968 (3)0.6398 (3)0.6215 (2)0.0590 (7)
H1210.25420.64800.69840.088*
H1220.11000.55450.58720.088*
H1230.16460.72780.64450.088*
C130.1553 (3)0.7857 (2)0.1302 (2)0.0416 (5)
H1310.22400.79830.07350.050*
H1320.05350.74610.07900.050*
C140.1697 (2)0.9353 (2)0.2434 (2)0.0387 (4)
C150.0533 (3)0.9580 (3)0.3120 (3)0.0589 (6)
H151−0.03190.87910.29070.071*
C160.0627 (4)1.0968 (3)0.4118 (3)0.0726 (8)
H161−0.01561.11040.45830.087*
C170.1861 (4)1.2151 (3)0.4434 (3)0.0646 (7)
H1710.19061.30890.50970.077*
C180.3036 (3)1.1941 (3)0.3761 (2)0.0562 (6)
H1810.38831.27360.39740.067*
C190.2947 (3)1.0547 (3)0.2771 (2)0.0456 (5)
H1910.37421.04080.23220.055*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0507 (4)0.0516 (4)0.0684 (4)−0.0046 (3)0.0023 (3)0.0063 (3)
Cl20.1402 (8)0.0425 (4)0.0514 (4)0.0395 (4)0.0239 (4)0.0128 (3)
Cl30.0418 (3)0.0546 (4)0.0430 (3)0.0064 (2)0.0086 (2)0.0077 (2)
O10.0410 (9)0.0740 (12)0.0479 (8)0.0263 (8)0.0165 (7)0.0306 (8)
O20.0516 (9)0.0586 (10)0.0389 (7)0.0191 (8)0.0122 (6)0.0269 (7)
N10.0316 (8)0.0309 (8)0.0339 (7)0.0081 (6)0.0027 (6)0.0138 (6)
C10.0379 (10)0.0281 (9)0.0313 (9)0.0053 (8)0.0045 (7)0.0103 (7)
C20.0278 (9)0.0334 (10)0.0332 (8)0.0074 (7)0.0039 (7)0.0149 (7)
C30.0289 (9)0.0284 (9)0.0306 (8)0.0048 (7)0.0015 (7)0.0106 (7)
C40.0349 (10)0.0377 (11)0.0375 (9)0.0058 (8)0.0077 (8)0.0170 (8)
C50.0351 (11)0.0457 (12)0.0527 (12)0.0067 (9)0.0097 (9)0.0220 (10)
C60.0390 (10)0.0330 (10)0.0340 (9)0.0136 (8)0.0097 (7)0.0176 (8)
C70.0411 (11)0.0451 (12)0.0520 (11)0.0188 (9)0.0169 (9)0.0261 (10)
C80.0627 (15)0.0514 (14)0.0564 (13)0.0329 (12)0.0298 (11)0.0307 (11)
C90.0855 (18)0.0354 (11)0.0353 (10)0.0277 (12)0.0167 (11)0.0175 (9)
C100.0565 (14)0.0359 (11)0.0491 (12)0.0099 (10)−0.0034 (10)0.0175 (10)
C110.0390 (11)0.0360 (11)0.0491 (11)0.0110 (9)0.0030 (9)0.0180 (9)
C120.0731 (17)0.0678 (17)0.0396 (11)0.0207 (14)0.0212 (11)0.0263 (12)
C130.0464 (12)0.0381 (11)0.0405 (10)0.0126 (9)−0.0013 (8)0.0194 (9)
C140.0373 (11)0.0360 (11)0.0447 (10)0.0133 (8)0.0010 (8)0.0201 (9)
C150.0377 (12)0.0492 (14)0.0818 (17)0.0139 (10)0.0119 (11)0.0227 (13)
C160.0671 (19)0.0614 (18)0.087 (2)0.0355 (15)0.0280 (16)0.0221 (15)
C170.083 (2)0.0421 (14)0.0609 (15)0.0286 (14)0.0017 (14)0.0136 (12)
C180.0662 (16)0.0382 (12)0.0588 (14)0.0058 (11)−0.0061 (12)0.0246 (11)
C190.0476 (12)0.0427 (12)0.0502 (11)0.0100 (9)0.0065 (9)0.0267 (10)

Geometric parameters (Å, °)

Cl1—C51.776 (2)C8—C91.370 (4)
Cl2—C91.745 (2)C8—H810.9300
O1—C11.196 (3)C9—C101.372 (3)
O2—C11.330 (2)C10—C111.379 (3)
O2—C121.454 (3)C10—H1010.9300
N1—C31.502 (2)C11—H1110.9300
N1—C131.508 (3)C12—H1210.9600
N1—H10.9000C12—H1220.9600
N1—H20.9000C12—H1230.9600
C1—C21.517 (3)C13—C141.501 (3)
C2—C61.522 (3)C13—H1310.9700
C2—C31.544 (3)C13—H1320.9700
C2—H210.9800C14—C151.381 (3)
C3—C41.526 (3)C14—C191.381 (3)
C3—H310.9800C15—C161.376 (4)
C4—C51.508 (3)C15—H1510.9300
C4—H410.9700C16—C171.370 (4)
C4—H420.9700C16—H1610.9300
C5—H510.9700C17—C181.380 (4)
C5—H520.9700C17—H1710.9300
C6—C71.387 (3)C18—C191.379 (3)
C6—C111.395 (3)C18—H1810.9300
C7—C81.374 (3)C19—H1910.9300
C7—H710.9300
C1—O2—C12116.08 (18)C9—C8—H81120.4
C3—N1—C13115.50 (15)C7—C8—H81120.4
C3—N1—H1108.4C8—C9—C10121.5 (2)
C13—N1—H1108.4C8—C9—Cl2119.32 (19)
C3—N1—H2108.4C10—C9—Cl2119.2 (2)
C13—N1—H2108.4C9—C10—C11119.5 (2)
H1—N1—H2107.5C9—C10—H101120.3
O1—C1—O2124.21 (18)C11—C10—H101120.3
O1—C1—C2124.68 (17)C10—C11—C6120.2 (2)
O2—C1—C2111.11 (17)C10—C11—H111119.9
C1—C2—C6111.18 (15)C6—C11—H111119.9
C1—C2—C3111.11 (15)O2—C12—H121109.5
C6—C2—C3114.25 (14)O2—C12—H122109.5
C1—C2—H21106.6H121—C12—H122109.5
C6—C2—H21106.6O2—C12—H123109.5
C3—C2—H21106.6H121—C12—H123109.5
N1—C3—C4109.14 (15)H122—C12—H123109.5
N1—C3—C2111.71 (14)C14—C13—N1114.43 (16)
C4—C3—C2112.34 (16)C14—C13—H131108.7
N1—C3—H31107.8N1—C13—H131108.7
C4—C3—H31107.8C14—C13—H132108.7
C2—C3—H31107.8N1—C13—H132108.7
C5—C4—C3115.28 (16)H131—C13—H132107.6
C5—C4—H41108.5C15—C14—C19118.5 (2)
C3—C4—H41108.5C15—C14—C13120.1 (2)
C5—C4—H42108.5C19—C14—C13121.3 (2)
C3—C4—H42108.5C16—C15—C14120.4 (2)
H41—C4—H42107.5C16—C15—H151119.8
C4—C5—Cl1111.82 (16)C14—C15—H151119.8
C4—C5—H51109.3C17—C16—C15120.8 (3)
Cl1—C5—H51109.3C17—C16—H161119.6
C4—C5—H52109.3C15—C16—H161119.6
Cl1—C5—H52109.3C16—C17—C18119.6 (2)
H51—C5—H52107.9C16—C17—H171120.2
C7—C6—C11118.70 (19)C18—C17—H171120.2
C7—C6—C2119.31 (18)C19—C18—C17119.6 (2)
C11—C6—C2121.99 (17)C19—C18—H181120.2
C8—C7—C6121.0 (2)C17—C18—H181120.2
C8—C7—H71119.5C18—C19—C14121.2 (2)
C6—C7—H71119.5C18—C19—H191119.4
C9—C8—C7119.1 (2)C14—C19—H191119.4
C1—C2—C3—C4170.19 (15)C3—C2—C6—C11−84.9 (2)
C2—C3—C4—C5−65.1 (2)C11—C6—C7—C81.2 (3)
C3—C4—C5—Cl1−59.2 (2)C2—C6—C7—C8−178.37 (18)
C3—C2—C1—O2−145.64 (16)C6—C7—C8—C9−0.2 (3)
C2—C1—O2—C12178.60 (18)C7—C8—C9—C10−0.8 (3)
C1—C2—C6—C7−138.62 (18)C7—C8—C9—Cl2179.55 (17)
C2—C3—N1—C13164.81 (16)C8—C9—C10—C110.7 (3)
C3—N1—C13—C14−53.8 (2)Cl2—C9—C10—C11−179.63 (16)
N1—C13—C14—C15−80.7 (3)C9—C10—C11—C60.3 (3)
C12—O2—C1—O1−1.5 (3)C7—C6—C11—C10−1.3 (3)
O1—C1—C2—C6−93.9 (2)C2—C6—C11—C10178.28 (18)
O2—C1—C2—C685.91 (19)N1—C13—C14—C19102.7 (2)
O1—C1—C2—C334.5 (3)C19—C14—C15—C16−0.1 (4)
C13—N1—C3—C4−70.3 (2)C13—C14—C15—C16−176.8 (2)
C1—C2—C3—N1−66.78 (18)C14—C15—C16—C171.1 (5)
C6—C2—C3—N160.0 (2)C15—C16—C17—C18−1.4 (5)
C6—C2—C3—C4−63.0 (2)C16—C17—C18—C190.7 (4)
N1—C3—C4—C5170.40 (17)C17—C18—C19—C140.3 (3)
C3—C2—C6—C794.6 (2)C15—C14—C19—C18−0.6 (3)
C1—C2—C6—C1141.8 (2)C13—C14—C19—C18176.10 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H2···Cl30.902.283.0890 (18)150
N1—H1···Cl3i0.902.593.2447 (18)131

Symmetry codes: (i) −x, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2801).

References

  • Bruker (2007). APEX2 and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Froimowitz, M., Wu, K.-M., George, C., VanDerveer, D., Shi, Q. & Deutsch, H. M. (1998). Struct. Chem.9, 295–303.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography