Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053676/om2177sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053676/om2177Isup2.hkl |
CCDC reference: 672845
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.004 Å
- R factor = 0.054
- wR factor = 0.133
- Data-to-parameter ratio = 19.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 46 Perc. PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C9 PLAT480_ALERT_4_C Long H...A H-Bond Reported H6A .. O2 .. 2.65 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H3B .. O1 .. 2.69 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H7B .. O2 .. 2.69 Ang. PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 Cl
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 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 1 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A mixture of 3-morpholin-4-yl-propionic acid hydrazide (0.01 mol) and 4,4'-methylene-bis(phenylisocyanate) (0.01 mol) was heated at the temperature 383–393 K for 20 h. The product, 4,4'-methylene-bis{[1-(3-morpholin-4-yl-propionic)-4-phenyl]semicarbazide} was washed with diethyl ether to remove the unreacted isocyanate, dried and crystallized from ethanol (yield 83%). The final product, 3-morpholin-4-yl-propionic acid hydrochloride, was prepared by refluxing semicarbazide with 2% NaOH (40 ml) for 15 h. After cooling, the solution was neutralized with dilute hydrochloric acid. The product was filtered and recrystallized from ethanol (m.p. 353–356 K, yield 89%). Anal. Calcd. for C7H14NO3Cl: C, 42.96; H, 7.21; N, 7.15%; found: C, 42.91; H, 7.30; N, 7.18%. 1H NMR (300 MHz, DMSO-d6, p.p.m.): δ 2.87 (2H, t, CH2); 2.98–3.06 (4H, m, 2CH2); 3.27 (2H, t, CH2); 3.77–3.87 (4H, m, 2CH2); 11.98 (1H, s, OH).
H atoms bonded to O1 and N1 atoms were located in the difference Fourier map and refined. Other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H bond distances of 0.97 Å. The displacement parameters of the H atoms were Uiso(H) = 1.2 Ueq(C).
Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and enCIFer (Allen et al., 2004).
C7H14NO3+·Cl− | F(000) = 416 |
Mr = 195.64 | Dx = 1.332 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 62 reflections |
a = 6.024 (2) Å | θ = 5–12° |
b = 11.593 (3) Å | µ = 0.36 mm−1 |
c = 14.095 (6) Å | T = 295 K |
β = 97.72 (3)° | Plate, colourless |
V = 975.4 (6) Å3 | 0.36 × 0.30 × 0.10 mm |
Z = 4 |
Oxford Diffraction Xcalibur diffractometer | Rint = 0.034 |
Radiation source: fine-focus sealed tube | θmax = 27.6°, θmin = 2.3° |
Graphite monochromator | h = −7→7 |
ω/2θ scans | k = 0→15 |
2326 measured reflections | l = −18→0 |
2244 independent reflections | 3 standard reflections every 100 reflections |
1033 reflections with I > 2σ(I) | intensity decay: 0.03% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0671P)2] where P = (Fo2 + 2Fc2)/3 |
2244 reflections | (Δ/σ)max < 0.001 |
115 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C7H14NO3+·Cl− | V = 975.4 (6) Å3 |
Mr = 195.64 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.024 (2) Å | µ = 0.36 mm−1 |
b = 11.593 (3) Å | T = 295 K |
c = 14.095 (6) Å | 0.36 × 0.30 × 0.10 mm |
β = 97.72 (3)° |
Oxford Diffraction Xcalibur diffractometer | Rint = 0.034 |
2326 measured reflections | 3 standard reflections every 100 reflections |
2244 independent reflections | intensity decay: 0.03% |
1033 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.31 e Å−3 |
2244 reflections | Δρmin = −0.26 e Å−3 |
115 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl | −0.11080 (14) | 0.77228 (7) | 0.73370 (6) | 0.0430 (2) | |
O1 | 0.3892 (5) | 0.7281 (2) | 0.44710 (19) | 0.0718 (8) | |
H1O | 0.401 (7) | 0.713 (4) | 0.379 (3) | 0.086* | |
O2 | 0.2681 (4) | 0.5478 (2) | 0.44468 (16) | 0.0580 (7) | |
C9 | 0.3233 (5) | 0.6344 (3) | 0.4881 (2) | 0.0415 (8) | |
C8 | 0.3297 (6) | 0.6491 (3) | 0.5935 (2) | 0.0448 (8) | |
H8A | 0.2363 | 0.7140 | 0.6061 | 0.054* | |
H8B | 0.4819 | 0.6656 | 0.6221 | 0.054* | |
C7 | 0.2479 (6) | 0.5419 (2) | 0.6384 (2) | 0.0406 (7) | |
H7A | 0.1101 | 0.5161 | 0.6008 | 0.049* | |
H7B | 0.3584 | 0.4812 | 0.6374 | 0.049* | |
N1 | 0.2066 (4) | 0.5621 (2) | 0.73937 (16) | 0.0315 (5) | |
H1N | 0.114 (5) | 0.624 (3) | 0.741 (2) | 0.038* | |
C2 | 0.4146 (5) | 0.5824 (3) | 0.8066 (2) | 0.0434 (8) | |
H2A | 0.4905 | 0.6504 | 0.7869 | 0.052* | |
H2B | 0.5145 | 0.5170 | 0.8052 | 0.052* | |
C3 | 0.3592 (6) | 0.5992 (3) | 0.9067 (2) | 0.0511 (8) | |
H3A | 0.4962 | 0.6115 | 0.9501 | 0.061* | |
H3B | 0.2658 | 0.6671 | 0.9086 | 0.061* | |
O4 | 0.2450 (4) | 0.5014 (2) | 0.93676 (16) | 0.0550 (7) | |
C5 | 0.0404 (6) | 0.4839 (3) | 0.8757 (2) | 0.0459 (8) | |
H5A | −0.0541 | 0.5514 | 0.8779 | 0.055* | |
H5B | −0.0376 | 0.4184 | 0.8985 | 0.055* | |
C6 | 0.0796 (5) | 0.4627 (2) | 0.7742 (2) | 0.0397 (7) | |
H6A | −0.0629 | 0.4539 | 0.7338 | 0.048* | |
H6B | 0.1644 | 0.3920 | 0.7708 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0448 (4) | 0.0416 (4) | 0.0444 (4) | −0.0075 (4) | 0.0131 (3) | 0.0005 (4) |
O1 | 0.124 (2) | 0.0516 (13) | 0.0467 (14) | −0.0211 (16) | 0.0360 (16) | −0.0001 (13) |
O2 | 0.0743 (18) | 0.0602 (15) | 0.0420 (13) | −0.0196 (13) | 0.0168 (12) | −0.0035 (11) |
C9 | 0.0377 (17) | 0.0478 (18) | 0.0415 (19) | −0.0011 (15) | 0.0153 (15) | 0.0029 (15) |
C8 | 0.054 (2) | 0.0422 (16) | 0.0411 (19) | −0.0106 (16) | 0.0171 (16) | −0.0017 (15) |
C7 | 0.0509 (19) | 0.0402 (16) | 0.0341 (16) | −0.0062 (15) | 0.0181 (15) | −0.0051 (13) |
N1 | 0.0318 (14) | 0.0330 (12) | 0.0311 (13) | 0.0003 (11) | 0.0090 (11) | 0.0004 (10) |
C2 | 0.0343 (17) | 0.0495 (18) | 0.0464 (19) | −0.0020 (14) | 0.0054 (14) | 0.0033 (15) |
C3 | 0.048 (2) | 0.061 (2) | 0.0410 (19) | −0.0043 (17) | −0.0039 (16) | 0.0017 (17) |
O4 | 0.0500 (14) | 0.0733 (16) | 0.0410 (14) | −0.0037 (13) | 0.0037 (11) | 0.0169 (11) |
C5 | 0.0445 (19) | 0.055 (2) | 0.0409 (18) | −0.0036 (16) | 0.0146 (16) | 0.0072 (15) |
C6 | 0.0399 (19) | 0.0384 (16) | 0.0430 (18) | −0.0038 (13) | 0.0132 (15) | 0.0038 (14) |
O1—C9 | 1.316 (4) | C2—C3 | 1.505 (5) |
O1—H1o | 0.99 (4) | C2—H2A | 0.9700 |
O2—C9 | 1.200 (4) | C2—H2B | 0.9700 |
C9—C8 | 1.492 (4) | C3—O4 | 1.420 (4) |
C8—C7 | 1.506 (4) | C3—H3A | 0.9700 |
C8—H8A | 0.9700 | C3—H3B | 0.9700 |
C8—H8B | 0.9700 | O4—C5 | 1.420 (4) |
C7—N1 | 1.496 (4) | C5—C6 | 1.502 (4) |
C7—H7A | 0.9700 | C5—H5A | 0.9700 |
C7—H7B | 0.9700 | C5—H5B | 0.9700 |
N1—C2 | 1.485 (4) | C6—H6A | 0.9700 |
N1—C6 | 1.502 (3) | C6—H6B | 0.9700 |
N1—H1N | 0.91 (3) | ||
C9—O1—H1o | 111 (2) | C3—C2—H2A | 109.6 |
O2—C9—O1 | 123.1 (3) | N1—C2—H2B | 109.6 |
O2—C9—C8 | 124.9 (3) | C3—C2—H2B | 109.6 |
O1—C9—C8 | 112.0 (3) | H2A—C2—H2B | 108.1 |
C9—C8—C7 | 111.0 (3) | O4—C3—C2 | 110.7 (3) |
C9—C8—H8A | 109.4 | O4—C3—H3A | 109.5 |
C7—C8—H8A | 109.4 | C2—C3—H3A | 109.5 |
C9—C8—H8B | 109.4 | O4—C3—H3B | 109.5 |
C7—C8—H8B | 109.4 | C2—C3—H3B | 109.5 |
H8A—C8—H8B | 108.0 | H3A—C3—H3B | 108.1 |
N1—C7—C8 | 112.1 (2) | C3—O4—C5 | 110.4 (2) |
N1—C7—H7A | 109.2 | O4—C5—C6 | 111.5 (3) |
C8—C7—H7A | 109.2 | O4—C5—H5A | 109.3 |
N1—C7—H7B | 109.2 | C6—C5—H5A | 109.3 |
C8—C7—H7B | 109.2 | O4—C5—H5B | 109.3 |
H7A—C7—H7B | 107.9 | C6—C5—H5B | 109.3 |
C2—N1—C7 | 113.5 (2) | H5A—C5—H5B | 108.0 |
C2—N1—C6 | 109.7 (2) | C5—C6—N1 | 109.7 (2) |
C7—N1—C6 | 110.4 (2) | C5—C6—H6A | 109.7 |
C2—N1—H1N | 109.0 (19) | N1—C6—H6A | 109.7 |
C7—N1—H1N | 108.9 (18) | C5—C6—H6B | 109.7 |
C6—N1—H1N | 105.2 (19) | N1—C6—H6B | 109.7 |
N1—C2—C3 | 110.1 (3) | H6A—C6—H6B | 108.2 |
N1—C2—H2A | 109.6 | ||
O2—C9—C8—C7 | −2.4 (5) | N1—C2—C3—O4 | 58.5 (3) |
O1—C9—C8—C7 | 178.5 (3) | C2—C3—O4—C5 | −60.9 (3) |
C9—C8—C7—N1 | −168.0 (3) | C3—O4—C5—C6 | 60.8 (3) |
C8—C7—N1—C2 | −68.7 (3) | O4—C5—C6—N1 | −57.3 (3) |
C8—C7—N1—C6 | 167.7 (3) | C2—N1—C6—C5 | 54.0 (3) |
C7—N1—C2—C3 | −178.7 (3) | C7—N1—C6—C5 | 179.8 (3) |
C6—N1—C2—C3 | −54.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl | 0.91 (3) | 2.18 (3) | 3.092 (3) | 176 (3) |
O1—H1O···Cli | 0.99 (4) | 2.04 (4) | 3.008 (3) | 164 (4) |
C6—H6A···O2ii | 0.97 | 2.65 | 3.491 (3) | 145 |
C7—H7A···O2ii | 0.97 | 2.40 | 3.337 (3) | 162 |
C3—H3A···O4iii | 0.97 | 2.45 | 3.241 (4) | 138 |
C3—H3B···O1iv | 0.97 | 2.69 | 3.575 (3) | 152 |
C7—H7B···O2v | 0.97 | 2.69 | 3.445 (3) | 136 |
Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+2; (iv) x−1/2, −y+3/2, z+1/2; (v) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C7H14NO3+·Cl− |
Mr | 195.64 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 6.024 (2), 11.593 (3), 14.095 (6) |
β (°) | 97.72 (3) |
V (Å3) | 975.4 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.36 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2326, 2244, 1033 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.133, 0.97 |
No. of reflections | 2244 |
No. of parameters | 115 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.26 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), SHELXS97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997) and enCIFer (Allen et al., 2004).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl | 0.91 (3) | 2.18 (3) | 3.092 (3) | 176 (3) |
O1—H1O···Cli | 0.99 (4) | 2.04 (4) | 3.008 (3) | 164 (4) |
C6—H6A···O2ii | 0.97 | 2.65 | 3.491 (3) | 145 |
C7—H7A···O2ii | 0.97 | 2.40 | 3.337 (3) | 162 |
C3—H3A···O4iii | 0.97 | 2.45 | 3.241 (4) | 138 |
C3—H3B···O1iv | 0.97 | 2.69 | 3.575 (3) | 152 |
C7—H7B···O2v | 0.97 | 2.69 | 3.445 (3) | 136 |
Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+2; (iv) x−1/2, −y+3/2, z+1/2; (v) −x+1, −y+1, −z+1. |
Morpholine derivatives are known to exhibit a wide spectrum of biological activities, including antifungal (Asselin & Humber, 1977), antidepressant (Kelley et al., 1996) or anorectic (Meyer & Weintraub, 1981) properties. Additionally, they are used as an intermediate for the synthesis of the antispasmodic drugs and other biologically active heterocycles (Boronnet et al., 1974). In view of the versatility of these compounds, the title compound was synthesized and we herein report its molecular and crystal structure.
In the crystal structure of the proton is transferred from the hydrochloride molecule to the morpholine N1 atom, as confirmed by location of the H atom in a difference Fourier map, leading to coexistence of the hydrogen-bonded 3-morpholin-4-yl-propionic cation and chloride anion. The morpholine ring adopts the usual chair conformation with the C7 atom at the equatorial and the H1N proton at the axial position. The hydrocarbon (CH2)2COOH chain exists in the extended trans conformation, which is reflected in the values of the N1—C7—C8—C9 and C7—C8—C9—O1 torsion angles of -168.0 (3) and 178.5 (3)°, respectively. The carboxyl group has the typical cis conformation with the O2—C9—O1—H1O torsion angle of 6.0 (4)°. The dihedral angle between the best plane of the hydrocarbon chain and C2/C3/C5/C6 ring atoms is 36.9 (4)°. The bond distances and angles are within the expected ranges observed for related compounds.
The strong N3—H3o···Cl hydrogen bonds (Table 1) are observed between ionic pairs. The Cl- ion forms also H-bond with the carboxylic O1—H1O proton from the adjacent cation. As can be seen in Fig. 2, one-dimensional cationic chains, propagated along the [101] direction, can be distinguished in the structure. Within the chain the cations lacated around the (0, 1/2, 1/2) inversion centre are connected together through chelating C6—H6A···O2ii and C7—H7A···O2ii hydrogen bonds. The C3—H3A···O4iii H-bonds links cations located around the next (1/2, 1, 1) center of symmetry. The cationic layers are associated into three-dimensional structure primarily by interactions involving the chloride anions.