4-[3-(4-Chloro­benzyl­idene­amino)-2-oxo­oxazolidin-5-yl­methyl]­morpholin-4-ium chloride monohydrate

A series of derivatives of 3-amino-2-oxazolidinone have been prepared. The title derivative, C₁₅H₁₉ClN₃O₃⁺·Cl^-·H₂O, is a potential psychotropic drug. The structure is assembled by strong and weak hydrogen bonds into a three-dimensional infinite framework. In the structure, intramolecular hydrogen bonds link C and O atoms to create a fused three-membered ring system.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.043
• wR factor = 0.120
• Data-to-parameter ratio = 17.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.55
         From the CIF: _reflns_number_total               3858
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         4086
         Completeness (_total/calc)             94.42%
          Alert C: < 95% complete


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

In the Pharmaceutical Research Institute in Warsaw, a series of deriatives of 3-amino-2-oxazolidinone have been prepared (Chilmonczyk et al., 1997). It has recently been found that the oxazolidinone derivative 5-morpholinmethyl-3-(4-chloridebenzylidenamino)-2-oxazolidinone is a potential psychotropic drug (Chilmonczyk, 1995). Preliminary clinical data show that the compound exhibits antidepressive activity in humans (Rybakowski & Araszkiewicz, 1999). It is generally accepted that a specific energetically preferred conformation of a compound (so-called bioactive conformation) decides about the nature of interactions with its molecular target – pharmacological receptor. Therefore, it is of basic importance to get an insight into molecular parameters such as charge distribution, most preferred conformation or distances between specified points within a molecule (Krzywda et al., 2000).

A perspective view of the title structure, (I), together with the atom-numbering scheme are shown in Fig. 1. A l l interatomic distances are normal. The oxazolidinone ring exist in a conformation of an almost ideal half-chair, which can be deduced from the asymmetry parameters (Duax & Norton, 1975). Values and placement of asymmetry parameters are showed in Fig. 2.

The primary place of molecular interaction with an acid residue within a putative receptor site can be detected by hydrogen bonds. The structure of the title compound is assembled by strong and weak hydrogen bonds, to a three-dimensional infinite framework (Fig. 3). The water O4 atom acts as a donor for one strong and three weak intermolecular hydrogen bonds. All these weak hydrogen bonds are created via the same H atom (H41), however, in the difference Fourier map there is no orientational disorder resulting from these. In addition, O4 acts as an acceptor for two intermolecular weak hydrogen bonds with C5 and Cl2. Also noteworthy is the fact that there is a proton transfer from hydrochloric acid to N1 which is stabilized by a weak N1—H1···Cl1 hydrogen bond. In addition, in the structure, intramolecular hydrogen bonds exist linking C1 and O2 which provide additional stabilization of the molecule, creating a fused three-membered ring system.

S2. Experimental

The title compound was prepared according to the method of Chilmonczyk et al. (1997).

Computing details

Data collection: KM-4 Software (Kuma, 1993); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1990) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Values and placement of the asymmetry parameters for the oxazolidinone ring.
	Fig. 3. Part of the molecular packing of title compound showing the intermolecular hydrogen bonds creating a three-dimensional net structure. Hydrogen bonds are indicated by dashed lines.

1-[3-(4-Chlorobenzylideneamino)-2-oxooxazolidin-5-ylmethyl]morpholinium chloride monohydrate

Crystal data

C15H19ClN3O3^+·Cl^−·H2O	Z = 2
Mr = 378.25	F(000) = 396
Triclinic, P1	Dx = 1.420 Mg m^−3
a = 7.122 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.809 (2) Å	Cell parameters from 99 reflections
c = 15.178 (3) Å	θ = 5–60°
α = 95.98 (2)°	µ = 0.39 mm^−1
β = 99.34 (2)°	T = 293 K
γ = 107.43 (2)°	Plate, colourless
V = 884.6 (4) Å^3	0.49 × 0.42 × 0.04 mm

Data collection

Kuma KM-4 diffractometer	3418 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.014
Graphite monochromator	θmax = 27.6°, θmin = 2.5°
ω–2θ scans	h = −1→9
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
Tmin = 0.831, Tmax = 0.985	l = −19→19
4747 measured reflections	3 standard reflections every 100 reflections
3858 independent reflections	intensity decay: 1.1%

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0656P)^2 + 0.312P] where P = (Fo^2 + 2Fc^2)/3
3858 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.38 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
N1	0.1505 (2)	−0.54719 (17)	−0.23337 (10)	0.0340 (3)
C1	0.1150 (3)	−0.4469 (2)	−0.30356 (13)	0.0451 (4)
H1A	−0.0193	−0.4422	−0.3098	0.068*
H1B	0.2078	−0.3392	−0.2862	0.068*
C2	0.1388 (4)	−0.5231 (3)	−0.39256 (14)	0.0559 (5)
H2A	0.1230	−0.4586	−0.4387	0.084*
H2B	0.2725	−0.5296	−0.3848	0.084*
O1	0.0002 (3)	−0.6810 (2)	−0.42041 (11)	0.0657 (5)
C3	0.0337 (4)	−0.7799 (3)	−0.35624 (17)	0.0588 (6)
H3A	−0.0603	−0.8866	−0.3764	0.088*
H3B	0.1665	−0.7873	−0.3526	0.088*
C4	0.0116 (3)	−0.7161 (2)	−0.26318 (15)	0.0486 (5)
H4A	0.0474	−0.7818	−0.2210	0.073*
H4B	−0.1250	−0.7208	−0.2638	0.073*
C5	0.1299 (3)	−0.4825 (2)	−0.14208 (12)	0.0379 (4)
H5A	−0.0050	−0.4802	−0.1458	0.057*
H5B	0.1520	−0.5536	−0.1006	0.057*
C6	0.2702 (3)	−0.3143 (2)	−0.10655 (12)	0.0363 (4)
H6	0.3970	−0.2956	−0.1267	0.044*
O2	0.1872 (2)	−0.19594 (15)	−0.14219 (8)	0.0406 (3)
C7	0.2094 (3)	−0.0743 (2)	−0.07528 (12)	0.0369 (4)
O3	0.1696 (2)	0.04529 (17)	−0.08899 (10)	0.0508 (4)
N2	0.2859 (2)	−0.11091 (17)	0.00459 (10)	0.0370 (3)
C8	0.3015 (3)	−0.2717 (2)	−0.00396 (12)	0.0396 (4)
H8A	0.1984	−0.3454	0.0186	0.059*
H8B	0.4308	−0.2710	0.0267	0.059*
N3	0.3085 (2)	−0.01072 (18)	0.08314 (10)	0.0362 (3)
C9	0.3730 (3)	−0.0571 (2)	0.15540 (12)	0.0375 (4)
H9	0.4039	−0.1575	0.1514	0.056*
C10	0.4031 (3)	0.0378 (2)	0.24492 (12)	0.0358 (4)
C11	0.3085 (3)	0.1509 (2)	0.26179 (14)	0.0462 (4)
H11A	0.2220	0.1740	0.2133	0.055*
C12	0.3394 (3)	0.2327 (3)	0.34890 (14)	0.0499 (5)
H12A	0.2692	0.3074	0.3616	0.060*
Cl1	0.49991 (10)	0.29961 (7)	0.52778 (3)	0.05808 (17)
C13	0.4646 (3)	0.2012 (2)	0.41802 (12)	0.0410 (4)
C14	0.5620 (3)	0.0909 (3)	0.40260 (13)	0.0480 (5)
H14A	0.6514	0.0723	0.4517	0.058*
C15	0.5287 (3)	0.0087 (2)	0.31643 (13)	0.0464 (4)
H15A	0.5925	−0.0713	0.3056	0.056*
Cl2	0.57484 (7)	0.43716 (6)	0.78472 (4)	0.04856 (15)
O4	0.8155 (3)	0.6712 (2)	0.97204 (12)	0.0684 (5)
H41	0.8130	0.7755	0.9863	0.082*
H42	0.7142	0.6181	0.9226	0.082*
H1	0.279 (4)	−0.545 (3)	−0.2297 (15)	0.045 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0278 (7)	0.0367 (7)	0.0391 (7)	0.0137 (6)	0.0066 (6)	0.0045 (6)
C1	0.0471 (11)	0.0479 (10)	0.0433 (10)	0.0218 (9)	0.0042 (8)	0.0096 (8)
C2	0.0632 (14)	0.0600 (13)	0.0395 (10)	0.0186 (11)	0.0017 (9)	0.0041 (9)
O1	0.0585 (10)	0.0719 (11)	0.0519 (9)	0.0141 (8)	−0.0069 (7)	−0.0065 (8)
C3	0.0539 (13)	0.0471 (11)	0.0651 (14)	0.0086 (10)	0.0096 (11)	−0.0099 (10)
C4	0.0410 (10)	0.0392 (10)	0.0600 (12)	0.0057 (8)	0.0128 (9)	0.0008 (8)
C5	0.0356 (9)	0.0389 (9)	0.0411 (9)	0.0124 (7)	0.0126 (7)	0.0061 (7)
C6	0.0316 (8)	0.0385 (9)	0.0411 (9)	0.0143 (7)	0.0085 (7)	0.0063 (7)
O2	0.0453 (7)	0.0401 (7)	0.0383 (6)	0.0189 (6)	0.0044 (5)	0.0062 (5)
C7	0.0328 (8)	0.0367 (9)	0.0411 (9)	0.0109 (7)	0.0076 (7)	0.0063 (7)
O3	0.0648 (9)	0.0439 (7)	0.0496 (8)	0.0282 (7)	0.0061 (7)	0.0104 (6)
N2	0.0379 (8)	0.0338 (7)	0.0396 (7)	0.0136 (6)	0.0054 (6)	0.0046 (6)
C8	0.0428 (10)	0.0370 (9)	0.0407 (9)	0.0176 (7)	0.0050 (7)	0.0054 (7)
N3	0.0334 (7)	0.0336 (7)	0.0397 (7)	0.0091 (6)	0.0069 (6)	0.0036 (6)
C9	0.0380 (9)	0.0326 (8)	0.0419 (9)	0.0111 (7)	0.0091 (7)	0.0055 (7)
C10	0.0379 (9)	0.0312 (8)	0.0385 (9)	0.0099 (7)	0.0100 (7)	0.0077 (7)
C11	0.0514 (11)	0.0473 (10)	0.0460 (10)	0.0259 (9)	0.0058 (8)	0.0105 (8)
C12	0.0600 (13)	0.0481 (11)	0.0527 (11)	0.0333 (10)	0.0128 (9)	0.0069 (9)
Cl1	0.0827 (4)	0.0555 (3)	0.0443 (3)	0.0324 (3)	0.0202 (3)	0.0025 (2)
C13	0.0505 (11)	0.0358 (9)	0.0403 (9)	0.0163 (8)	0.0153 (8)	0.0062 (7)
C14	0.0598 (12)	0.0530 (11)	0.0400 (9)	0.0322 (10)	0.0070 (9)	0.0093 (8)
C15	0.0579 (12)	0.0476 (10)	0.0436 (10)	0.0322 (9)	0.0094 (9)	0.0070 (8)
Cl2	0.0353 (2)	0.0457 (3)	0.0667 (3)	0.02008 (19)	0.0035 (2)	0.0074 (2)
O4	0.0858 (13)	0.0567 (10)	0.0671 (10)	0.0391 (9)	0.0027 (9)	0.0014 (8)

Geometric parameters (Å, º)

N1—C5	1.489 (2)	C7—O3	1.199 (2)
N1—C1	1.490 (2)	C7—N2	1.358 (2)
N1—C4	1.493 (2)	N2—N3	1.364 (2)
N1—H1	0.91 (2)	N2—C8	1.448 (2)
C1—C2	1.502 (3)	C8—H8A	0.9600
C1—H1A	0.9600	C8—H8B	0.9600
C1—H1B	0.9600	N3—C9	1.274 (2)
C2—O1	1.417 (3)	C9—C10	1.467 (2)
C2—H2A	0.9600	C9—H9	0.9721
C2—H2B	0.9600	C10—C11	1.384 (3)
O1—C3	1.411 (3)	C10—C15	1.387 (3)
C3—C4	1.515 (3)	C11—C12	1.389 (3)
C3—H3A	0.9600	C11—H11A	0.9601
C3—H3B	0.9600	C12—C13	1.370 (3)
C4—H4A	0.9600	C12—H12A	0.9600
C4—H4B	0.9600	Cl1—C13	1.7385 (19)
C5—C6	1.502 (2)	C13—C14	1.375 (3)
C5—H5A	0.9600	C14—C15	1.375 (3)
C5—H5B	0.9600	C14—H14A	0.9599
C6—O2	1.453 (2)	C15—H15A	0.9600
C6—C8	1.527 (2)	O4—H41	0.9276
C6—H6	0.9738	O4—H42	0.9227
O2—C7	1.351 (2)
C5—N1—C1	113.56 (14)	O2—C6—H6	104.6
C5—N1—C4	110.35 (14)	C5—C6—H6	111.7
C1—N1—C4	109.60 (15)	C8—C6—H6	112.0
C5—N1—H1	107.9 (14)	C7—O2—C6	110.16 (13)
C1—N1—H1	105.4 (14)	O3—C7—O2	122.80 (17)
C4—N1—H1	109.9 (14)	O3—C7—N2	128.42 (17)
N1—C1—C2	109.08 (16)	O2—C7—N2	108.76 (15)
N1—C1—H1A	109.6	C7—N2—N3	119.48 (14)
C2—C1—H1A	108.8	C7—N2—C8	112.95 (15)
N1—C1—H1B	110.2	N3—N2—C8	126.64 (14)
C2—C1—H1B	110.5	N2—C8—C6	100.83 (14)
H1A—C1—H1B	108.7	N2—C8—H8A	112.1
O1—C2—C1	111.5 (2)	C6—C8—H8A	110.7
O1—C2—H2A	109.7	N2—C8—H8B	111.2
C1—C2—H2A	111.2	C6—C8—H8B	112.5
O1—C2—H2B	108.5	H8A—C8—H8B	109.3
C1—C2—H2B	107.8	C9—N3—N2	115.62 (15)
H2A—C2—H2B	108.1	N3—C9—C10	121.65 (16)
C3—O1—C2	109.93 (17)	N3—C9—H9	119.4
O1—C3—C4	112.23 (19)	C10—C9—H9	118.9
O1—C3—H3A	108.9	C11—C10—C15	118.73 (17)
C4—C3—H3A	109.5	C11—C10—C9	123.38 (17)
O1—C3—H3B	109.3	C15—C10—C9	117.87 (16)
C4—C3—H3B	109.2	C10—C11—C12	120.21 (18)
H3A—C3—H3B	107.6	C10—C11—H11A	120.3
N1—C4—C3	109.69 (17)	C12—C11—H11A	119.5
N1—C4—H4A	108.5	C13—C12—C11	119.58 (17)
C3—C4—H4A	109.0	C13—C12—H12A	119.8
N1—C4—H4B	110.7	C11—C12—H12A	120.6
C3—C4—H4B	110.5	C12—C13—C14	121.18 (17)
H4A—C4—H4B	108.5	C12—C13—Cl1	119.97 (15)
N1—C5—C6	113.23 (14)	C14—C13—Cl1	118.84 (15)
N1—C5—H5A	108.6	C15—C14—C13	118.93 (18)
C6—C5—H5A	107.7	C15—C14—H14A	121.2
N1—C5—H5B	109.2	C13—C14—H14A	119.9
C6—C5—H5B	109.9	C14—C15—C10	121.35 (17)
H5A—C5—H5B	108.0	C14—C15—H15A	119.4
O2—C6—C5	110.87 (14)	C10—C15—H15A	119.3
O2—C6—C8	104.76 (13)	H41—O4—H42	109.0
C5—C6—C8	112.42 (15)
C1—N1—C5—C6	−58.3 (2)	C6—C8—N2—N3	−177.81 (15)
N1—C5—C6—O2	83.06 (17)	C8—N2—N3—C9	8.9 (2)
C5—C6—O2—C7	134.99 (15)	C5—N1—C1—C2	−179.81 (16)
C6—O2—C7—N2	−5.40 (19)	N1—C1—C2—O1	60.0 (2)
O2—C7—N2—N3	−175.44 (14)	C1—C2—O1—C3	−61.2 (2)
C7—N2—N3—C9	177.06 (16)	C2—O1—C3—C4	59.3 (2)
N2—N3—C9—C10	−179.53 (15)	O1—C3—C4—N1	−56.3 (2)
N3—C9—C10—C11	21.5 (3)	C3—C4—N1—C5	179.78 (17)
N3—C9—C10—C15	−160.41 (18)	O2—C7—N2—C8	−5.7 (2)
C4—N1—C5—C6	178.24 (15)	C7—N2—C8—C6	13.38 (19)
N1—C5—C6—C8	−160.06 (14)	N2—C8—C6—O2	−15.35 (17)
C5—C6—C8—N2	−135.83 (15)	C8—C6—O2—C7	13.49 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2^i	0.91 (2)	2.13 (2)	3.0359 (17)	174 (2)
O4—H42···Cl2	0.92	2.36	3.217 (2)	154
O4—H41···O3^ii	0.93	2.06	2.873 (2)	146
O4—H41···N3^ii	0.93	2.72	3.506 (2)	143
O4—H41···O3^iii	0.93	3.36	3.807 (3)	112
C1—H1B···O2	0.96	2.46	2.989 (3)	115
C5—H5B···O4^iv	0.96	2.31	3.245 (3)	163
C9—H9···Cl2^iv	0.97	2.78	3.666 (2)	153

Symmetry codes: (i) x, y−1, z−1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y+1, z+1; (iv) −x+1, −y, −z+1.