4-Benzyl­morpholin-4-ium chloride

Ions of the title compound, C₁₁H₁₆NO⁺·Cl⁻, are linked by an N—H...Cl⁻ and four C—H...Cl⁻ inter­actions, generating a two-dimensional layer with no inter­actions between different morpholinium groups; the morpholinium group adopts an approximately ideal chair conformation.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](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

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S1. Comment

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.

Related literature

Bernstein et al. (1995); Bruno et al. (2006); Calas et al. (1997); Cao & Hu (2006); Dega-Szafran, Szafran & Katrusiak (2004); Stone et al. (1958).

S2. Experimental

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, C_p), 129.24 (s, C₆H₅, C_m), 130.28 (s, C₆H₅, C_o), 131.22 (s, C₆H₅, C_i).

S3. Refinement

All C-bound H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and treated using a riding model with U_iso= 1.2U_eq(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.

Computing details

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).

Figures

	Fig. 1. : A view of compound (I) showing the atom-numbering scheme at 30% probability displacement ellipsoids.
	Fig. 2. : A view of the two-dimensional supramolecular motif showing the hydrogen bonds (indicated as dotted lines).

4-Benzylmorpholin-4-ium chloride

Crystal data

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) Å^3	Block, colourless
Z = 4	0.49 × 0.34 × 0.18 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0345P)^2 + 0.5699P] where P = (Fo^2 + 2Fc^2)/3
2321 reflections	(Δ/σ)max = 0.001
131 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

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 (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···Cl1^i	0.97	2.86	3.725 (2)	149
C8—H8A···Cl1^i	0.97	2.80	3.690 (2)	153
C8—H8B···Cl1^ii	0.97	2.87	3.576 (2)	130
C11—H11A···Cl1^iii	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.