Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807017060/gg3089sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807017060/gg3089Isup2.hkl |
CCDC reference: 647581
Key indicators
- Single-crystal X-ray study
- T = 297 K
- Mean (C-C) = 0.004 Å
- R factor = 0.048
- wR factor = 0.109
- Data-to-parameter ratio = 17.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT480_ALERT_4_C Long H...A H-Bond Reported H7B .. CL1 .. 2.86 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H8B .. CL1 .. 2.87 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 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 0 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 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Bernstein et al. (1995); Bruno et al. (2006); Calas et al. (1997); Cao & Hu (2006); Dega-Szafran, Szafran & Katrusiak (2004); Stone et al. (1958).
To a solution of 4-benzylmorpholine (83 mg, 0.46 mmol) in methanol (10 ml) was added HCl (0.06 ml, 12 M) and the reaction mixture was stirred at room temperature for 1 h. Colourless crystals suitable for X-ray diffraction were grown by slow evaporation of the solution. Yield: 84 mg (90%). M.p.: 244–246°C [243–244 °C (Stone et al., 1958)]. Compound (I) was also obtained during the work up of [2-{O(CH2CH2)2NCH2}C6H4]2SbCl. Spectroscopic analysis: 1H NMR (D2O, 300 MHz): δ 3.16 (m, 2H, CH2), 3.36 (m, 2H, CH2), 3.69 (m, 2H, CH2), 4.01 (m, 2H, CH2), 4.28 (s, 2H, CH2, C6H5CH2), 7.45 (m, 5H, C6H5). 13C NMR (D2O, 75.46 MHz): δ 51.13 (s, N—CH2), 60.72 (s, C6H5CH2), 63.56 (s, O—CH2), 127.77 (s, C6H5, Cp), 129.24 (s, C6H5, Cm), 130.28 (s, C6H5, Co), 131.22 (s, C6H5, Ci).
All C-bound H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and treated using a riding model with Uiso= 1.2Ueq(C) for aryl H atoms. The hydrogen H1 atom bonded to N1 atom was calculated and fixed at a standard N—H distance of 0.88 (2) Å.
Many morpholine derivatives and their salts show bacteriostatic activity and have potential as drugs (Dega-Szafran et al., 2004; Calas et al., 1997). The atomic numbering scheme and the conformation of 4-benzylmorpholin-4-ium chloride (I) are depicted in Fig. 1. The morpholium N—H forms an interaction with the Cl- ion (Table 1) with a H1···Cl1 distance similar to the N—H···Cl interaction in C8H8NO4+.Cl-.H2O (2.3 Å) (Bruno et al., 2006) and C12H15Cl2FNO2 +.Cl- (2.21 Å) (Cao & Hu, 2006). The Cl- ion is also involved in four other intermolecular contacts with three molecules (details in Table 1). These C—H···Cl interactions lead to the formation of a 2-D network which contains units with graph-set motifs R24(10) and R12(6) (Bernstein et al., 1995). There are no hydrogen-bonding interactions between different morpholinium groups.
Bernstein et al. (1995); Bruno et al. (2006); Calas et al. (1997); Cao & Hu (2006); Dega-Szafran, Szafran & Katrusiak (2004); Stone et al. (1958).
Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND 3 (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2007).
C11H16NO+·Cl− | F(000) = 456 |
Mr = 213.70 | Dx = 1.251 Mg m−3 |
Monoclinic, P21/n | Melting point: 518 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0181 (6) Å | Cell parameters from 4130 reflections |
b = 9.3458 (9) Å | θ = 2.4–27.9° |
c = 17.3003 (16) Å | µ = 0.31 mm−1 |
β = 90.958 (2)° | T = 297 K |
V = 1134.56 (18) Å3 | Block, colourless |
Z = 4 | 0.49 × 0.34 × 0.18 mm |
Bruker SMART CCD area-detector diffractometer | 2321 independent reflections |
Radiation source: fine-focus sealed tube | 2180 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
φ and ω scans | θmax = 26.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −8→8 |
Tmin = 0.865, Tmax = 0.947 | k = −11→11 |
11765 measured reflections | l = −21→21 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0345P)2 + 0.5699P] where P = (Fo2 + 2Fc2)/3 |
2321 reflections | (Δ/σ)max = 0.001 |
131 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C11H16NO+·Cl− | V = 1134.56 (18) Å3 |
Mr = 213.70 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.0181 (6) Å | µ = 0.31 mm−1 |
b = 9.3458 (9) Å | T = 297 K |
c = 17.3003 (16) Å | 0.49 × 0.34 × 0.18 mm |
β = 90.958 (2)° |
Bruker SMART CCD area-detector diffractometer | 2321 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2180 reflections with I > 2σ(I) |
Tmin = 0.865, Tmax = 0.947 | Rint = 0.036 |
11765 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | Δρmax = 0.20 e Å−3 |
2321 reflections | Δρmin = −0.21 e Å−3 |
131 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 | ||
C1 | 0.4842 (3) | 0.5884 (2) | 0.61068 (11) | 0.0375 (4) | |
C2 | 0.3416 (4) | 0.6760 (3) | 0.58221 (13) | 0.0550 (6) | |
H2 | 0.2207 | 0.6723 | 0.6033 | 0.066* | |
C3 | 0.3779 (5) | 0.7696 (3) | 0.52235 (15) | 0.0745 (8) | |
H3 | 0.2813 | 0.8286 | 0.5034 | 0.089* | |
C4 | 0.5550 (5) | 0.7758 (3) | 0.49090 (14) | 0.0714 (8) | |
H4 | 0.5789 | 0.8393 | 0.4508 | 0.086* | |
C5 | 0.6962 (4) | 0.6889 (3) | 0.51822 (14) | 0.0624 (7) | |
H5 | 0.8164 | 0.6928 | 0.4965 | 0.075* | |
C6 | 0.6620 (3) | 0.5954 (3) | 0.57785 (12) | 0.0481 (5) | |
H6 | 0.7595 | 0.5364 | 0.5962 | 0.058* | |
C7 | 0.4460 (3) | 0.4873 (2) | 0.67572 (11) | 0.0380 (4) | |
H7A | 0.4997 | 0.3946 | 0.6635 | 0.046* | |
H7B | 0.3094 | 0.4755 | 0.6805 | 0.046* | |
C8 | 0.4605 (3) | 0.68275 (19) | 0.77400 (11) | 0.0344 (4) | |
H8A | 0.3224 | 0.6837 | 0.7756 | 0.041* | |
H8B | 0.5003 | 0.7520 | 0.7358 | 0.041* | |
C9 | 0.5421 (3) | 0.7227 (2) | 0.85218 (11) | 0.0427 (5) | |
H9A | 0.6798 | 0.7282 | 0.8493 | 0.051* | |
H9B | 0.4952 | 0.8164 | 0.8667 | 0.051* | |
C10 | 0.5645 (3) | 0.4847 (2) | 0.89033 (12) | 0.0462 (5) | |
H10A | 0.5334 | 0.4170 | 0.9307 | 0.055* | |
H10B | 0.7022 | 0.4896 | 0.8871 | 0.055* | |
C11 | 0.4822 (3) | 0.4336 (2) | 0.81445 (11) | 0.0404 (5) | |
H11A | 0.5345 | 0.3405 | 0.8021 | 0.049* | |
H11B | 0.3450 | 0.4239 | 0.8183 | 0.049* | |
Cl1 | 0.96354 (7) | 0.55740 (6) | 0.75391 (3) | 0.04869 (18) | |
N1 | 0.5280 (2) | 0.53743 (15) | 0.75195 (8) | 0.0298 (3) | |
O1 | 0.4920 (2) | 0.62161 (16) | 0.90967 (8) | 0.0474 (4) | |
H1 | 0.653 (3) | 0.539 (2) | 0.7483 (11) | 0.035 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0425 (10) | 0.0391 (10) | 0.0307 (9) | −0.0011 (8) | −0.0046 (8) | −0.0078 (8) |
C2 | 0.0561 (14) | 0.0662 (15) | 0.0426 (12) | 0.0132 (12) | −0.0063 (10) | −0.0028 (11) |
C3 | 0.104 (2) | 0.0709 (18) | 0.0483 (14) | 0.0241 (17) | −0.0155 (15) | 0.0058 (13) |
C4 | 0.122 (3) | 0.0585 (16) | 0.0336 (12) | −0.0110 (16) | −0.0023 (14) | 0.0046 (11) |
C5 | 0.0741 (17) | 0.0709 (17) | 0.0426 (12) | −0.0183 (14) | 0.0092 (12) | −0.0018 (12) |
C6 | 0.0469 (12) | 0.0565 (13) | 0.0411 (11) | −0.0007 (10) | 0.0011 (9) | −0.0041 (10) |
C7 | 0.0377 (10) | 0.0376 (10) | 0.0387 (10) | −0.0044 (8) | −0.0013 (8) | −0.0083 (8) |
C8 | 0.0358 (10) | 0.0286 (9) | 0.0388 (10) | −0.0001 (7) | −0.0007 (8) | −0.0012 (7) |
C9 | 0.0502 (12) | 0.0367 (10) | 0.0412 (11) | −0.0036 (9) | −0.0002 (9) | −0.0056 (9) |
C10 | 0.0529 (12) | 0.0467 (12) | 0.0390 (11) | 0.0001 (10) | 0.0021 (9) | 0.0094 (9) |
C11 | 0.0473 (11) | 0.0307 (10) | 0.0434 (11) | −0.0041 (8) | 0.0053 (9) | 0.0050 (8) |
Cl1 | 0.0277 (3) | 0.0459 (3) | 0.0725 (4) | −0.0008 (2) | 0.0016 (2) | 0.0025 (3) |
N1 | 0.0263 (8) | 0.0293 (8) | 0.0339 (8) | −0.0013 (6) | 0.0019 (6) | 0.0002 (6) |
O1 | 0.0565 (9) | 0.0516 (9) | 0.0343 (7) | −0.0019 (7) | 0.0076 (6) | −0.0022 (6) |
C1—C2 | 1.378 (3) | C8—N1 | 1.490 (2) |
C1—C6 | 1.381 (3) | C8—C9 | 1.507 (3) |
C1—C7 | 1.497 (3) | C8—H8A | 0.9700 |
C2—C3 | 1.382 (4) | C8—H8B | 0.9700 |
C2—H2 | 0.9300 | C9—O1 | 1.420 (2) |
C3—C4 | 1.366 (4) | C9—H9A | 0.9700 |
C3—H3 | 0.9300 | C9—H9B | 0.9700 |
C4—C5 | 1.359 (4) | C10—O1 | 1.419 (3) |
C4—H4 | 0.9300 | C10—C11 | 1.504 (3) |
C5—C6 | 1.376 (3) | C10—H10A | 0.9700 |
C5—H5 | 0.9300 | C10—H10B | 0.9700 |
C6—H6 | 0.9300 | C11—N1 | 1.492 (2) |
C7—N1 | 1.505 (2) | C11—H11A | 0.9700 |
C7—H7A | 0.9700 | C11—H11B | 0.9700 |
C7—H7B | 0.9700 | N1—H1 | 0.88 (2) |
C2—C1—C6 | 118.7 (2) | C9—C8—H8B | 109.7 |
C2—C1—C7 | 120.37 (19) | H8A—C8—H8B | 108.2 |
C6—C1—C7 | 120.88 (18) | O1—C9—C8 | 111.65 (16) |
C1—C2—C3 | 120.1 (2) | O1—C9—H9A | 109.3 |
C1—C2—H2 | 119.9 | C8—C9—H9A | 109.3 |
C3—C2—H2 | 119.9 | O1—C9—H9B | 109.3 |
C4—C3—C2 | 120.4 (3) | C8—C9—H9B | 109.3 |
C4—C3—H3 | 119.8 | H9A—C9—H9B | 108.0 |
C2—C3—H3 | 119.8 | O1—C10—C11 | 111.00 (17) |
C5—C4—C3 | 119.9 (2) | O1—C10—H10A | 109.4 |
C5—C4—H4 | 120.0 | C11—C10—H10A | 109.4 |
C3—C4—H4 | 120.0 | O1—C10—H10B | 109.4 |
C4—C5—C6 | 120.3 (3) | C11—C10—H10B | 109.4 |
C4—C5—H5 | 119.8 | H10A—C10—H10B | 108.0 |
C6—C5—H5 | 119.8 | N1—C11—C10 | 109.97 (16) |
C5—C6—C1 | 120.5 (2) | N1—C11—H11A | 109.7 |
C5—C6—H6 | 119.7 | C10—C11—H11A | 109.7 |
C1—C6—H6 | 119.7 | N1—C11—H11B | 109.7 |
C1—C7—N1 | 113.07 (15) | C10—C11—H11B | 109.7 |
C1—C7—H7A | 109.0 | H11A—C11—H11B | 108.2 |
N1—C7—H7A | 109.0 | C8—N1—C11 | 109.52 (14) |
C1—C7—H7B | 109.0 | C8—N1—C7 | 112.93 (14) |
N1—C7—H7B | 109.0 | C11—N1—C7 | 110.42 (14) |
H7A—C7—H7B | 107.8 | C8—N1—H1 | 109.0 (13) |
N1—C8—C9 | 109.75 (15) | C11—N1—H1 | 106.8 (13) |
N1—C8—H8A | 109.7 | C7—N1—H1 | 107.9 (13) |
C9—C8—H8A | 109.7 | C10—O1—C9 | 109.93 (15) |
N1—C8—H8B | 109.7 | ||
C6—C1—C2—C3 | −0.5 (3) | N1—C8—C9—O1 | −57.6 (2) |
C7—C1—C2—C3 | 179.7 (2) | O1—C10—C11—N1 | 58.7 (2) |
C1—C2—C3—C4 | 0.1 (4) | C9—C8—N1—C11 | 54.2 (2) |
C2—C3—C4—C5 | 0.4 (4) | C9—C8—N1—C7 | 177.69 (15) |
C3—C4—C5—C6 | −0.5 (4) | C10—C11—N1—C8 | −55.0 (2) |
C4—C5—C6—C1 | 0.0 (4) | C10—C11—N1—C7 | −179.95 (16) |
C2—C1—C6—C5 | 0.5 (3) | C1—C7—N1—C8 | 56.0 (2) |
C7—C1—C6—C5 | −179.80 (19) | C1—C7—N1—C11 | 179.01 (16) |
C2—C1—C7—N1 | −104.2 (2) | C11—C10—O1—C9 | −61.0 (2) |
C6—C1—C7—N1 | 76.1 (2) | C8—C9—O1—C10 | 60.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.88 (2) | 2.19 (2) | 3.062 (2) | 172 (2) |
C7—H7B···Cl1i | 0.97 | 2.86 | 3.725 (2) | 149 |
C8—H8A···Cl1i | 0.97 | 2.80 | 3.690 (2) | 153 |
C8—H8B···Cl1ii | 0.97 | 2.87 | 3.576 (2) | 130 |
C11—H11A···Cl1iii | 0.97 | 2.82 | 3.731 (2) | 157 |
Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+3/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C11H16NO+·Cl− |
Mr | 213.70 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 297 |
a, b, c (Å) | 7.0181 (6), 9.3458 (9), 17.3003 (16) |
β (°) | 90.958 (2) |
V (Å3) | 1134.56 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.49 × 0.34 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.865, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11765, 2321, 2180 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.109, 1.17 |
No. of reflections | 2321 |
No. of parameters | 131 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.21 |
Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SHELXTL (Bruker, 2001), ORTEP-3 (Farrugia, 1997) and DIAMOND 3 (Brandenburg, 2006), publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.88 (2) | 2.19 (2) | 3.062 (2) | 172 (2) |
C7—H7B···Cl1i | 0.97 | 2.86 | 3.725 (2) | 149 |
C8—H8A···Cl1i | 0.97 | 2.80 | 3.690 (2) | 153 |
C8—H8B···Cl1ii | 0.97 | 2.87 | 3.576 (2) | 130 |
C11—H11A···Cl1iii | 0.97 | 2.82 | 3.731 (2) | 157 |
Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+3/2, y−1/2, −z+3/2. |
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Many morpholine derivatives and their salts show bacteriostatic activity and have potential as drugs (Dega-Szafran et al., 2004; Calas et al., 1997). The atomic numbering scheme and the conformation of 4-benzylmorpholin-4-ium chloride (I) are depicted in Fig. 1. The morpholium N—H forms an interaction with the Cl- ion (Table 1) with a H1···Cl1 distance similar to the N—H···Cl interaction in C8H8NO4+.Cl-.H2O (2.3 Å) (Bruno et al., 2006) and C12H15Cl2FNO2 +.Cl- (2.21 Å) (Cao & Hu, 2006). The Cl- ion is also involved in four other intermolecular contacts with three molecules (details in Table 1). These C—H···Cl interactions lead to the formation of a 2-D network which contains units with graph-set motifs R24(10) and R12(6) (Bernstein et al., 1995). There are no hydrogen-bonding interactions between different morpholinium groups.