organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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N,N-Di­methyl-3-oxo-3-(thio­phen-2-yl)propanaminium chloride

aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and cDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, 574 199, India
*Correspondence e-mail: jjasinski@keene.edu

(Received 1 August 2011; accepted 2 August 2011; online 6 August 2011)

In the title mol­ecular salt, C9H14NOS+·Cl, the crystal packing is stabilized by weak inter­molecular N—H⋯Cl, C—H⋯Cl and C—H⋯π inter­actions, which lead to the formation of a two-dimensional supra­molecular layer which stacks along the b axis.

Related literature

For the management of major depressive disorders, see: Gupta et al. (2007[Gupta, S., Nihalani, N. & Masand, P. (2007). Ann. Clin. Psychiatry, 19, 125-132.]). For the dual re-uptake inhibitor drug, duloxetine [systematic name (+)-(S)-N-methyl-3-(naphthalen-1-yl­oxy)-3-(thio­phen-2-yl)propan-1-amine], see: Waitekus & Kirkpatrick, (2004[Waitekus, A. B. & Kirkpatrick, P. (2004). Nat. Rev. Drug Discov. 3, 907-908.]). For related structures, see: Bhadbhade et al. (2009[Bhadbhade, M., Hook, J., Marjo, C., Rich, A. & Lin, Q. (2009). Acta Cryst. E65, o2294.]); Tao et al. (2006[Tao, X., Bin, X., Zhu, H.-J., Yuan, L. & Wang, J.-T. (2006). Acta Cryst. E62, o5202-o5203.], 2008[Tao, X., Zhang, X.-Q., Yuan, L. & Wang, J.-T. (2008). Acta Cryst. E64, o553.]).

[Scheme 1]

Experimental

Crystal data
  • C9H14NOS+·Cl

  • Mr = 219.72

  • Monoclinic, P 21 /n

  • a = 5.8663 (3) Å

  • b = 27.0109 (9) Å

  • c = 7.1385 (4) Å

  • β = 110.767 (6)°

  • V = 1057.63 (9) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.52 mm−1

  • T = 173 K

  • 0.24 × 0.21 × 0.11 mm

Data collection
  • Oxford Diffraction Xcalibur Eos Gemini diffractometer

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.885, Tmax = 0.945

  • 14443 measured reflections

  • 3538 independent reflections

  • 3290 reflections with I > 2σ(I)

  • Rint = 0.033

Refinement
  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.097

  • S = 1.13

  • 3538 reflections

  • 124 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.37 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the S1/C1–C4 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1N⋯Cl1 0.87 (1) 2.17 (1) 3.0317 (11) 171 (2)
C1—H1A⋯Cl1i 0.95 2.82 3.5641 (13) 136
C6—H6ACg1ii 0.99 2.97 3.8183 (13) 144
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) [x-{\script{3\over 2}}, -y-{\script{1\over 2}}, z-{\script{3\over 2}}].

Data collection: CrysAlis PRO (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The title salt, (I), C9H14NOS+, Cl-, is an intermediate in the synthesis of duloxetine, which is a new generation drug indicated for the management of major depressive disorders as well as for neuropathic pain (Waitekus & Kirkpatrick, 2004). Duloxetine is a dual re-uptake inhibitor with actions on serotonin as well as norepinephrine (Gupta et al., 2007). The crystal structures of related structures, (R)-3-hydroxy-N,N-dimethyl-3-(2-thienyl)-propanamine (Tao et al., 2006), N,N-dimethyl-3-(1-naphthyloxy)-3-(2-thienyl)propan-1-amine (Tao et al., 2008) and duloxetine hydrochloride (Bhadbhade et al., 2009) have been reported. In view of the importance of duloxetine, the crystal structure of the title compound, (I), is reported.

In the molecular salt, C9H14NOS+, Cl-, one cation-anion pair makes up the asymmetric unit (Fig. 1). The crystal packing is stabilized by weak N—H···Cl, C—H···Cl and C—H..Cg π-ring intermolecular interactions (Table 1) forming a 2-D supramolecular layer which stacks along the b axis (Fig. 2).

Related literature top

For the management of major depressive disorders, see: Gupta et al. (2007). For the dual re-uptake inhibitor drug, duloxetine [systematic name (+)-(S)-N-methyl-3-(naphthalen-1-yloxy)-3-(thiophen-2-yl)propan-1-amine], see: Waitekus & Kirkpatrick, (2004). For related structures, see: Bhadbhade et al. (2009); Tao et al. (2006, 2008).

Experimental top

The title compound was obtained as a gift sample from R. L. Fine chem., Bangalore. X-ray quality crystals were obtained from slow evaporation of methanol solution (M.pt.: 451–454 K).

Refinement top

The N—H atom was located from a difference Fourier map and refined with N—H = 0.87±0.02 Å, and with Uiso(H) = 1.19Ueq(N). All of the remaining H atoms were placed in their calculated positions and then refined using the riding model with C—H lengths of 0.95 Å (CH), 0.99 Å (CH2) or 0.98 Å (CH3). The isotropic displacement parameters for these atoms were set to 1.20 (CH), 1.19 (CH2) or 1.49–1.51 (CH3) times Ueq of the parent atom.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the ion pair in the title compound showing the atom labeling scheme and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed down the a axis. Dashed lines indicate weak N—H···Cl and C—H···Cl intermolecular interactions forming a 2-D supramolecular layer which stacks along the b axis.
N,N-Dimethyl-3-oxo-3-(thiophen-2-yl)propanaminium chloride top
Crystal data top
C9H14NOS+·ClF(000) = 464
Mr = 219.72Dx = 1.380 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6745 reflections
a = 5.8663 (3) Åθ = 3.1–32.2°
b = 27.0109 (9) ŵ = 0.52 mm1
c = 7.1385 (4) ÅT = 173 K
β = 110.767 (6)°Block, colorless
V = 1057.63 (9) Å30.24 × 0.21 × 0.11 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur Eos Gemini
diffractometer
3538 independent reflections
Radiation source: Enhance (Mo) X-ray Source3290 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 16.1500 pixels mm-1θmax = 32.3°, θmin = 3.1°
ω scansh = 88
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2010)
k = 3940
Tmin = 0.885, Tmax = 0.945l = 1010
14443 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097 w = 1/[σ2(Fo2) + (0.0412P)2 + 0.4408P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max = 0.003
3538 reflectionsΔρmax = 0.37 e Å3
124 parametersΔρmin = 0.28 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0190 (18)
Crystal data top
C9H14NOS+·ClV = 1057.63 (9) Å3
Mr = 219.72Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.8663 (3) ŵ = 0.52 mm1
b = 27.0109 (9) ÅT = 173 K
c = 7.1385 (4) Å0.24 × 0.21 × 0.11 mm
β = 110.767 (6)°
Data collection top
Oxford Diffraction Xcalibur Eos Gemini
diffractometer
3538 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2010)
3290 reflections with I > 2σ(I)
Tmin = 0.885, Tmax = 0.945Rint = 0.033
14443 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0381 restraint
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.13Δρmax = 0.37 e Å3
3538 reflectionsΔρmin = 0.28 e Å3
124 parameters
Special details top

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) top
xyzUiso*/Ueq
S10.52202 (6)0.201976 (12)0.22248 (5)0.02281 (9)
Cl10.25260 (7)0.437297 (12)0.73047 (5)0.02698 (10)
O10.59639 (18)0.31119 (4)0.23658 (16)0.0269 (2)
N10.1628 (2)0.42989 (4)0.28618 (16)0.0202 (2)
H1N0.185 (3)0.4283 (6)0.413 (2)0.024*
C10.3315 (2)0.15653 (5)0.24400 (19)0.0232 (2)
H1A0.35840.12220.23070.028*
C20.1360 (2)0.17494 (5)0.2825 (2)0.0232 (2)
H2A0.01250.15490.30080.028*
C30.1380 (2)0.22742 (4)0.29226 (19)0.0200 (2)
H3A0.01570.24650.31720.024*
C40.3377 (2)0.24739 (4)0.26137 (17)0.0176 (2)
C50.4056 (2)0.29935 (4)0.25738 (17)0.0183 (2)
C60.2273 (2)0.33779 (4)0.27755 (18)0.0193 (2)
H6A0.06310.33120.17800.023*
H6B0.21740.33580.41290.023*
C70.3098 (2)0.38907 (4)0.24408 (19)0.0209 (2)
H7A0.48260.39340.33110.025*
H7B0.30060.39180.10330.025*
C80.1028 (3)0.42606 (5)0.1722 (2)0.0301 (3)
H8A0.18590.45500.20090.045*
H8B0.16650.39590.21180.045*
H8C0.13130.42480.02840.045*
C90.2585 (3)0.47836 (5)0.2479 (2)0.0278 (3)
H9A0.16680.50520.28060.042*
H9B0.24050.48060.10630.042*
H9C0.43130.48120.33150.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.01902 (15)0.02573 (16)0.02610 (16)0.00399 (11)0.01097 (12)0.00015 (11)
Cl10.03912 (19)0.02268 (15)0.02328 (15)0.00231 (12)0.01617 (13)0.00105 (11)
O10.0213 (4)0.0274 (5)0.0360 (5)0.0029 (4)0.0150 (4)0.0012 (4)
N10.0250 (5)0.0182 (4)0.0199 (5)0.0021 (4)0.0109 (4)0.0013 (4)
C10.0259 (6)0.0205 (5)0.0226 (6)0.0040 (4)0.0078 (5)0.0007 (4)
C20.0221 (6)0.0213 (5)0.0265 (6)0.0012 (4)0.0090 (5)0.0012 (5)
C30.0169 (5)0.0199 (5)0.0243 (5)0.0010 (4)0.0086 (4)0.0001 (4)
C40.0149 (5)0.0197 (5)0.0174 (5)0.0016 (4)0.0050 (4)0.0003 (4)
C50.0173 (5)0.0221 (5)0.0156 (5)0.0002 (4)0.0060 (4)0.0002 (4)
C60.0187 (5)0.0196 (5)0.0209 (5)0.0008 (4)0.0086 (4)0.0006 (4)
C70.0228 (5)0.0200 (5)0.0234 (5)0.0008 (4)0.0126 (5)0.0007 (4)
C80.0240 (6)0.0232 (6)0.0421 (8)0.0012 (5)0.0106 (6)0.0032 (5)
C90.0377 (7)0.0177 (5)0.0315 (7)0.0056 (5)0.0167 (6)0.0020 (5)
Geometric parameters (Å, º) top
S1—C11.7032 (14)C4—C51.4620 (16)
S1—C41.7216 (12)C5—C61.5165 (16)
O1—C51.2224 (15)C6—C71.5139 (16)
N1—C81.4834 (18)C6—H6A0.9900
N1—C91.4876 (16)C6—H6B0.9900
N1—C71.4947 (16)C7—H7A0.9900
N1—H1N0.870 (13)C7—H7B0.9900
C1—C21.3647 (18)C8—H8A0.9800
C1—H1A0.9500C8—H8B0.9800
C2—C31.4191 (17)C8—H8C0.9800
C2—H2A0.9500C9—H9A0.9800
C3—C41.3769 (16)C9—H9B0.9800
C3—H3A0.9500C9—H9C0.9800
C1—S1—C491.69 (6)C7—C6—H6A109.7
C8—N1—C9110.60 (11)C5—C6—H6A109.7
C8—N1—C7114.01 (10)C7—C6—H6B109.7
C9—N1—C7109.27 (10)C5—C6—H6B109.7
C8—N1—H1N108.0 (12)H6A—C6—H6B108.2
C9—N1—H1N107.8 (11)N1—C7—C6113.80 (9)
C7—N1—H1N106.8 (11)N1—C7—H7A108.8
C2—C1—S1112.38 (10)C6—C7—H7A108.8
C2—C1—H1A123.8N1—C7—H7B108.8
S1—C1—H1A123.8C6—C7—H7B108.8
C1—C2—C3112.40 (11)H7A—C7—H7B107.7
C1—C2—H2A123.8N1—C8—H8A109.5
C3—C2—H2A123.8N1—C8—H8B109.5
C4—C3—C2112.10 (11)H8A—C8—H8B109.5
C4—C3—H3A124.0N1—C8—H8C109.5
C2—C3—H3A124.0H8A—C8—H8C109.5
C3—C4—C5129.24 (11)H8B—C8—H8C109.5
C3—C4—S1111.43 (9)N1—C9—H9A109.5
C5—C4—S1119.33 (9)N1—C9—H9B109.5
O1—C5—C4121.40 (11)H9A—C9—H9B109.5
O1—C5—C6121.64 (11)N1—C9—H9C109.5
C4—C5—C6116.96 (10)H9A—C9—H9C109.5
C7—C6—C5109.97 (9)H9B—C9—H9C109.5
C4—S1—C1—C20.93 (11)S1—C4—C5—O13.55 (17)
S1—C1—C2—C30.86 (15)C3—C4—C5—C64.03 (19)
C1—C2—C3—C40.29 (16)S1—C4—C5—C6175.70 (8)
C2—C3—C4—C5179.34 (12)O1—C5—C6—C76.42 (16)
C2—C3—C4—S10.40 (14)C4—C5—C6—C7172.82 (10)
C1—S1—C4—C30.75 (10)C8—N1—C7—C655.48 (14)
C1—S1—C4—C5179.02 (10)C9—N1—C7—C6179.79 (11)
C3—C4—C5—O1176.73 (13)C5—C6—C7—N1172.73 (10)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the S1/C1–C4 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl10.87 (1)2.17 (1)3.0317 (11)171 (2)
C1—H1A···Cl1i0.952.823.5641 (13)136
C6—H6A···Cg1ii0.992.973.8183 (13)144
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x3/2, y1/2, z3/2.

Experimental details

Crystal data
Chemical formulaC9H14NOS+·Cl
Mr219.72
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)5.8663 (3), 27.0109 (9), 7.1385 (4)
β (°) 110.767 (6)
V3)1057.63 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.52
Crystal size (mm)0.24 × 0.21 × 0.11
Data collection
DiffractometerOxford Diffraction Xcalibur Eos Gemini
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2010)
Tmin, Tmax0.885, 0.945
No. of measured, independent and
observed [I > 2σ(I)] reflections
14443, 3538, 3290
Rint0.033
(sin θ/λ)max1)0.751
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.097, 1.13
No. of reflections3538
No. of parameters124
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.37, 0.28

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the S1/C1–C4 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl10.870 (13)2.170 (14)3.0317 (11)170.7 (15)
C1—H1A···Cl1i0.952.823.5641 (13)136.2
C6—H6A···Cg1ii0.992.973.8183 (13)144
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x3/2, y1/2, z3/2.
 

Acknowledgements

ASD thanks the University of Mysore for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

References

First citationBhadbhade, M., Hook, J., Marjo, C., Rich, A. & Lin, Q. (2009). Acta Cryst. E65, o2294.  CSD CrossRef IUCr Journals Google Scholar
First citationGupta, S., Nihalani, N. & Masand, P. (2007). Ann. Clin. Psychiatry, 19, 125–132.  CrossRef Google Scholar
First citationOxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTao, X., Bin, X., Zhu, H.-J., Yuan, L. & Wang, J.-T. (2006). Acta Cryst. E62, o5202–o5203.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationTao, X., Zhang, X.-Q., Yuan, L. & Wang, J.-T. (2008). Acta Cryst. E64, o553.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationWaitekus, A. B. & Kirkpatrick, P. (2004). Nat. Rev. Drug Discov. 3, 907–908.  Web of Science CrossRef PubMed CAS Google Scholar

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