Ethyl N-[2-(2-hydroxy­methyl-1,3-dioxolan-2-yl)phen­yl]carbamate

The title compound, C₁₃H₁₇NO₅, (I), is a precursor of ethyl N-[2-(hydroxy­acet­yl)phen­yl]carbamate, (II), whose structure we reported recently [Garden, Côrrea, Pinto, Wardell, Low & Glidewell (2007). Acta Cryst. C63, o234–o238]. In compound (I), the 1,3-dioxolane ring adopts a twisted conformation and the carbamate ester side chain adopts an almost planar all-trans conformation. Pairs of mol­ecules are linked by O—H...O hydrogen bonds into a cyclic centrosymmetric R₂²(18) dimer to which are fused two S(6) rings generated by an intra­molecular N—H...O hydrogen bond.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.040
• wR factor = 0.108
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: Authors Garden, Corr\^ea & Pinto prepared, purified and characterised the compound; author Wardell prepared the crystals; author Low solved & refined the structure; authors Glidewell & Wardell analysed the structure and wrote the paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

S1. Comment

We report here the structure of the title compound (I) (Fig. 2), which is a precursor (Garden et al., 2003) of ethyl N-[2-(hydroxyacetyl)phenyl]carbamate (II), whose structure we reported recently (Garden et al., 2007).

The 1,3-dioxolane ring in (I) adopts a twisted conformation with ring-puckering parameters (Cremer & Pople, 1975) for the atom sequence (O21, C21, O23, C24, C23) of Q₂ 0.360 (2) Å and φ₂ 347.3 (2)°, with atom displacements from the mean plane indicative of a conformation twisted about the line joining atom O23 to the mid-point of the O21—C23 bond. The carbamate ester side chain adopts an almost planar, all-trans conformation, as indicated by the relevant torsional angles (Table 1). The conformation about the C2—C21 bond is such that atom O21 is close to the plane of the aryl ring: hence it seems unlikely that this conformation is materially influenced by the intramolecular N—H···O hydrogen bond (Table 2).

A single O—H···O hydrogen bond (Table 2) links pairs of molecules into cyclic dimers: the hydroxyl atom O22 at (x, y, z) acts as hydrogen-bond donor to the carbonyl atom O11 in the molecule at (1 - x, 1 - y, 1 - z), so generating by inversion an R²₂(18) ring (Bernstein et al., 1995) centred at (1/2, 1/2, 1/2) to which are fused two S(6) rings generated by the intramolecular N—H···O hydrogen bond (Fig. 3). Two dimers of this type lie in each unit cell, but there are no direction-specific interactions between the dimer units.

Related literature

In the precursor compound (II) (Garden et al., 2007) all of the non-H atoms lie on a mirror plane in space group Pnma and the molecules are linked by a single C—H···O hydrogen bond into a simple C(6) chain.

For related literature, see: Bernstein et al. (1995); Cremer & Pople (1975); Garden et al. (2003).

S2. Experimental

Compound (I) was prepared as previously reported (Garden et al., 2003). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in hexane-dichloromethane (1:1, v/v).

S3. Refinement

All the H atoms were located in difference maps, relocated in idealized positions, and treated as riding atoms with distances C—H 0.95 Å (aromatic), 0.98 Å (CH₃) or 0.99 Å (CH₂), N—H 0.91 Å and O—H 0.84 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.5 fo the hydroxyl and methyl H atoms and 1.2 for all other H atoms.

Computing details

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. Scheme showing (I) and (II).
	Fig. 2. A molecule of compound (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. Part of the crystal structure of compound (I) showing the formation of a hydrogen-bonded dimer centred at (1/2, 1/2, 1/2) and containing one R^22(18) ring and two S(6) rings. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1 - x, 1 - y, 1 - z).

Ethyl N-[2-(2-hydroxymethyl-1,3-dioxolan-2-yl)phenyl]carbamate

Crystal data

C13H17NO5	F(000) = 568
Mr = 267.28	Dx = 1.412 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7223 reflections
a = 7.4469 (2) Å	θ = 2.9–27.5°
b = 20.2814 (6) Å	µ = 0.11 mm^−1
c = 8.3443 (3) Å	T = 120 K
β = 94.1400 (17)°	Plate, colourless
V = 1256.98 (7) Å^3	0.40 × 0.35 × 0.08 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	2859 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2351 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −26→25
Tmin = 0.966, Tmax = 0.991	l = −10→10
15419 measured reflections

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)] = 0.040	Hydrogen site location: difference Fourier map
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0548P)^2 + 0.3663P] where P = (Fo^2 + 2Fc^2)/3
2859 reflections	(Δ/σ)max = 0.001
174 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.80896 (17)	0.55854 (6)	0.58422 (16)	0.0149 (3)
N1	0.78526 (15)	0.52817 (5)	0.43164 (13)	0.0162 (3)
C11	0.70954 (17)	0.46878 (6)	0.39499 (16)	0.0150 (3)
O11	0.65376 (13)	0.42894 (5)	0.48877 (12)	0.0216 (2)
O12	0.70481 (13)	0.45971 (5)	0.23489 (11)	0.0185 (2)
C12	0.63510 (19)	0.39661 (6)	0.17684 (16)	0.0181 (3)
C13	0.6294 (2)	0.39934 (7)	−0.00381 (17)	0.0236 (3)
C2	0.83290 (16)	0.62743 (6)	0.59031 (16)	0.0142 (3)
C21	0.81496 (17)	0.67041 (6)	0.43921 (16)	0.0150 (3)
O21	0.88614 (12)	0.73417 (4)	0.46946 (12)	0.0179 (2)
C23	1.07494 (19)	0.72825 (7)	0.44691 (18)	0.0204 (3)
C24	1.07660 (18)	0.68280 (7)	0.30267 (17)	0.0195 (3)
O23	0.91580 (13)	0.64355 (4)	0.31326 (11)	0.0189 (2)
C22	0.62001 (18)	0.67700 (7)	0.36960 (17)	0.0191 (3)
O22	0.50165 (13)	0.69769 (5)	0.48450 (12)	0.0220 (2)
C3	0.86213 (17)	0.65753 (7)	0.74049 (16)	0.0168 (3)
C4	0.86634 (18)	0.62115 (7)	0.88192 (16)	0.0187 (3)
C5	0.84013 (18)	0.55357 (7)	0.87435 (16)	0.0197 (3)
C6	0.81261 (19)	0.52213 (7)	0.72655 (17)	0.0185 (3)
H1	0.8325	0.5492	0.3486	0.019*
H12A	0.5129	0.3891	0.2128	0.022*
H12B	0.7145	0.3603	0.2181	0.022*
H13A	0.5472	0.4345	−0.0431	0.035*
H13C	0.5869	0.3570	−0.0485	0.035*
H13B	0.7504	0.4084	−0.0374	0.035*
H23A	1.1410	0.7086	0.5425	0.024*
H23B	1.1285	0.7716	0.4242	0.024*
H24A	1.0717	0.7082	0.2012	0.023*
H24B	1.1856	0.6547	0.3092	0.023*
H22A	0.6152	0.7092	0.2802	0.023*
H22B	0.5788	0.6339	0.3250	0.023*
H22	0.4503	0.6647	0.5212	0.033*
H3	0.8795	0.7039	0.7461	0.020*
H4	0.8870	0.6425	0.9829	0.022*
H5	0.8410	0.5286	0.9707	0.024*
H6	0.7962	0.4757	0.7223	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0136 (6)	0.0167 (6)	0.0143 (6)	0.0003 (5)	0.0012 (5)	−0.0023 (5)
N1	0.0210 (6)	0.0147 (5)	0.0132 (5)	−0.0031 (4)	0.0033 (4)	−0.0009 (4)
C11	0.0135 (6)	0.0155 (6)	0.0159 (7)	0.0004 (5)	0.0007 (5)	−0.0013 (5)
O11	0.0279 (5)	0.0186 (5)	0.0185 (5)	−0.0070 (4)	0.0027 (4)	0.0014 (4)
O12	0.0260 (5)	0.0147 (5)	0.0148 (5)	−0.0055 (4)	0.0018 (4)	−0.0027 (4)
C12	0.0215 (7)	0.0138 (6)	0.0188 (7)	−0.0044 (5)	−0.0002 (5)	−0.0023 (5)
C13	0.0338 (8)	0.0185 (7)	0.0181 (7)	−0.0046 (6)	−0.0007 (6)	−0.0020 (5)
C2	0.0100 (6)	0.0164 (6)	0.0164 (7)	0.0004 (5)	0.0023 (5)	−0.0009 (5)
C21	0.0164 (6)	0.0123 (6)	0.0168 (6)	−0.0015 (5)	0.0038 (5)	−0.0023 (5)
O21	0.0173 (5)	0.0125 (5)	0.0246 (5)	−0.0029 (4)	0.0055 (4)	−0.0031 (4)
C23	0.0173 (7)	0.0192 (7)	0.0255 (8)	−0.0047 (5)	0.0072 (6)	−0.0022 (6)
C24	0.0180 (7)	0.0215 (7)	0.0195 (7)	−0.0038 (5)	0.0053 (5)	−0.0009 (5)
O23	0.0229 (5)	0.0168 (5)	0.0178 (5)	−0.0056 (4)	0.0080 (4)	−0.0036 (4)
C22	0.0188 (7)	0.0193 (7)	0.0188 (7)	−0.0017 (5)	−0.0008 (5)	0.0028 (5)
O22	0.0168 (5)	0.0209 (5)	0.0289 (6)	0.0002 (4)	0.0041 (4)	0.0017 (4)
C3	0.0129 (6)	0.0180 (6)	0.0196 (7)	0.0001 (5)	0.0020 (5)	−0.0042 (5)
C4	0.0164 (6)	0.0247 (7)	0.0146 (7)	0.0008 (5)	−0.0019 (5)	−0.0043 (5)
C5	0.0198 (7)	0.0240 (7)	0.0149 (7)	0.0035 (5)	−0.0012 (5)	0.0018 (5)
C6	0.0203 (7)	0.0163 (6)	0.0190 (7)	0.0016 (5)	0.0017 (5)	0.0009 (5)

Geometric parameters (Å, º)

C1—C6	1.3971 (19)	O21—C23	1.4369 (17)
C1—C2	1.4090 (18)	C23—C24	1.5169 (19)
C1—N1	1.4139 (17)	C23—H23A	0.99
N1—C11	1.3555 (17)	C23—H23B	0.99
N1—H1	0.9060	C24—O23	1.4459 (16)
C11—O11	1.2185 (16)	C24—H24A	0.99
C11—O12	1.3464 (16)	C24—H24B	0.99
O12—C12	1.4512 (15)	C22—O22	1.4122 (17)
C12—C13	1.5059 (19)	C22—H22A	0.99
C12—H12A	0.99	C22—H22B	0.99
C12—H12B	0.99	O22—H22	0.84
C13—H13A	0.98	C3—C4	1.390 (2)
C13—H13C	0.98	C3—H3	0.95
C13—H13B	0.98	C4—C5	1.385 (2)
C2—C3	1.3968 (18)	C4—H4	0.95
C2—C21	1.5306 (18)	C5—C6	1.390 (2)
C21—O21	1.4133 (15)	C5—H5	0.95
C21—O23	1.4420 (15)	C6—H6	0.95
C21—C22	1.5300 (19)
C6—C1—C2	119.93 (12)	O21—C23—C24	102.64 (11)
C6—C1—N1	121.91 (12)	O21—C23—H23A	111.2
C2—C1—N1	118.15 (11)	C24—C23—H23A	111.2
C11—N1—C1	127.82 (11)	O21—C23—H23B	111.2
C11—N1—H1	115.1	C24—C23—H23B	111.2
C1—N1—H1	117.0	H23A—C23—H23B	109.2
O11—C11—O12	124.12 (12)	O23—C24—C23	103.41 (10)
O11—C11—N1	126.86 (12)	O23—C24—H24A	111.1
O12—C11—N1	109.02 (11)	C23—C24—H24A	111.1
C11—O12—C12	115.77 (10)	O23—C24—H24B	111.1
O12—C12—C13	106.57 (11)	C23—C24—H24B	111.1
O12—C12—H12A	110.4	H24A—C24—H24B	109.0
C13—C12—H12A	110.4	C21—O23—C24	108.29 (10)
O12—C12—H12B	110.4	O22—C22—C21	112.95 (11)
C13—C12—H12B	110.4	O22—C22—H22A	109.0
H12A—C12—H12B	108.6	C21—C22—H22A	109.0
C12—C13—H13A	109.5	O22—C22—H22B	109.0
C12—C13—H13C	109.5	C21—C22—H22B	109.0
H13A—C13—H13C	109.5	H22A—C22—H22B	107.8
C12—C13—H13B	109.5	C22—O22—H22	109.5
H13A—C13—H13B	109.5	C4—C3—C2	121.47 (13)
H13C—C13—H13B	109.5	C4—C3—H3	119.3
C3—C2—C1	118.48 (12)	C2—C3—H3	119.3
C3—C2—C21	119.26 (12)	C5—C4—C3	119.47 (13)
C1—C2—C21	122.12 (11)	C5—C4—H4	120.3
O21—C21—O23	105.51 (9)	C3—C4—H4	120.3
O21—C21—C22	108.74 (10)	C4—C5—C6	120.37 (13)
O23—C21—C22	106.62 (11)	C4—C5—H5	119.8
O21—C21—C2	111.38 (11)	C6—C5—H5	119.8
O23—C21—C2	111.48 (10)	C5—C6—C1	120.27 (13)
C22—C21—C2	112.74 (10)	C5—C6—H6	119.9
C21—O21—C23	104.96 (9)	C1—C6—H6	119.9
C6—C1—N1—C11	22.4 (2)	C22—C21—O21—C23	−149.12 (11)
C2—C1—N1—C11	−158.84 (13)	C2—C21—O21—C23	86.06 (12)
C1—N1—C11—O11	−3.2 (2)	C21—O21—C23—C24	39.27 (13)
C1—N1—C11—O12	176.87 (12)	O21—C23—C24—O23	−28.36 (13)
O11—C11—O12—C12	−2.81 (18)	O21—C21—O23—C24	16.27 (14)
N1—C11—O12—C12	177.10 (11)	C22—C21—O23—C24	131.78 (11)
C11—O12—C12—C13	175.90 (11)	C2—C21—O23—C24	−104.78 (12)
C6—C1—C2—C3	0.77 (18)	C23—C24—O23—C21	7.74 (14)
N1—C1—C2—C3	−177.99 (11)	O21—C21—C22—O22	−71.69 (13)
C6—C1—C2—C21	−174.92 (11)	O23—C21—C22—O22	174.98 (10)
N1—C1—C2—C21	6.32 (18)	C2—C21—C22—O22	52.33 (15)
C3—C2—C21—O21	18.48 (16)	C1—C2—C3—C4	−0.55 (18)
C1—C2—C21—O21	−165.86 (11)	C21—C2—C3—C4	175.27 (12)
C3—C2—C21—O23	136.05 (12)	C2—C3—C4—C5	−0.33 (19)
C1—C2—C21—O23	−48.29 (16)	C3—C4—C5—C6	1.0 (2)
C3—C2—C21—C22	−104.07 (13)	C4—C5—C6—C1	−0.8 (2)
C1—C2—C21—C22	71.59 (15)	C2—C1—C6—C5	−0.12 (19)
O23—C21—O21—C23	−35.06 (13)	N1—C1—C6—C5	178.59 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O23	0.91	2.04	2.7451 (14)	134
O22—H22···O11^i	0.84	2.05	2.8324 (14)	155

Symmetry code: (i) −x+1, −y+1, −z+1.