(2-Chloro­thia­zol-5-yl)methyl 4-nitro­phenyl carbonate

In the mol­ecule of the title compound, C₁₁H₇ClN₂O₅S, the benzene and thia­zole rings are oriented at a dihedral angle of 56.52 (3)°. In the crystal structure, inter­molecular C—H...O and C—H...N hydrogen bonds link the mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.052
• wR factor = 0.159
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT707_ALERT_1_A D...A   Calc   14.974(6), Rep    3.325(5), Dev..    1941.50 Sigma
              C8   -N2      1.555   4.565
PLAT726_ALERT_1_A H...A   Calc    15.61000, Rep     2.54000 Dev...      13.07 Ang.
              H8B  -N2      1.555   4.565
PLAT728_ALERT_1_A D-H..A  Calc       48.00, Rep      138.00 Dev...      90.00 Deg.
              C8   -H8B  -N2      1.555   1.555   4.565

Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT322_ALERT_2_C Check Hybridisation of  S      in Main Residue .          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl     ..  O1      ..       3.13 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C11 H7 Cl N2 O5 S

   3 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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound, (I), is one of the aromatic carbonates, which are an important class of esters compounds and have widespread applications from pharmaceuticals (Kempf et al., 1998) to agronomy (Sicker, 1989). As part of our studies in this area, we report herein the synthesis and crystal structure of (I).

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). Rings A (C1—C6) and B (C9/C10/N2/C11/S) are, of course, planar and they are oriented at a dihedral angle of 56.52 (3)°.

In the crystal structure, intermolecular C—H···O and C—H···N hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they seem to be effective in the stabilization of the structure.

Related literature

For related literature, see: Kempf et al. (1998); Sicker (1989). For bond-length data, see: Allen et al. (1987).

S2. Experimental

For the preparation of the title compound, (I), a solution of 2-chloro-5 -(hydroxymethyl)thiazole (1.5 g, 10 mmol) and excess N-methyl morpholine in methylene chloride (50 ml) was cooled to 273 K, and treated with 4-nitophenyl chloroformate (3.0 g, 15 mmol). After being stirred for 6 h, the reaction mixture was diluted with CHCl₃, washed successively with 1 N HCl, saturated aqueous NaHCO₃, and saturated bine, dried over NaSO₄, and concentrated in vacuo. The residue was recrystallized by methylene chloride to give the title compound, (I) (yield; 2.6 g, 82%). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

S3. Refinement

H atoms were positioned geometrically, with C—H = 0.93 and 0.97 Å for aromatic and methyl H, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

(2-Chlorothiazol-5-yl)methyl 4-nitrophenyl carbonate

Crystal data

C11H7ClN2O5S	F(000) = 640
Mr = 314.70	Dx = 1.607 Mg m^−3
Monoclinic, P21/c	Melting point: 375(2) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.7380 (19) Å	Cell parameters from 25 reflections
b = 10.717 (2) Å	θ = 9–14°
c = 13.197 (3) Å	µ = 0.47 mm^−1
β = 109.17 (3)°	T = 294 K
V = 1300.9 (5) Å^3	Block, colorless
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection

Nonius CAD-4 diffractometer	1581 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Graphite monochromator	θmax = 26.0°, θmin = 2.2°
ω/2θ scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→13
Tmin = 0.871, Tmax = 0.954	l = 0→16
2692 measured reflections	3 standard reflections every 120 min
2539 independent reflections	intensity decay: none

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.080P)^2 + 0.3P] where P = (Fo^2 + 2Fc^2)/3
2539 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.26 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
Cl	0.24960 (15)	1.05190 (11)	0.01610 (10)	0.0831 (4)
S	0.15104 (13)	0.93594 (9)	0.18446 (8)	0.0600 (3)
O1	−0.5209 (5)	1.3043 (4)	0.4410 (3)	0.1144 (14)
O2	−0.4109 (4)	1.2199 (3)	0.5931 (3)	0.0860 (10)
O3	−0.2637 (3)	0.8347 (2)	0.2886 (2)	0.0632 (7)
O4	−0.0348 (3)	0.9101 (2)	0.33757 (19)	0.0497 (6)
O5	−0.1038 (3)	0.7334 (2)	0.2417 (2)	0.0549 (7)
N1	−0.4482 (4)	1.2216 (4)	0.4954 (3)	0.0667 (10)
N2	0.1425 (4)	0.8250 (3)	0.0107 (2)	0.0581 (8)
C1	−0.4004 (4)	1.1203 (4)	0.4410 (3)	0.0529 (9)
C2	−0.3176 (4)	1.0258 (4)	0.5019 (3)	0.0548 (9)
H2B	−0.2938	1.0261	0.5761	0.066*
C3	−0.2704 (4)	0.9307 (4)	0.4510 (3)	0.0552 (9)
H3A	−0.2147	0.8656	0.4904	0.066*
C4	−0.3069 (4)	0.9335 (3)	0.3415 (3)	0.0514 (9)
C5	−0.3905 (4)	1.0269 (4)	0.2806 (3)	0.0626 (11)
H5A	−0.4142	1.0262	0.2063	0.075*
C6	−0.4390 (4)	1.1221 (4)	0.3310 (3)	0.0622 (11)
H6A	−0.4967	1.1860	0.2914	0.075*
C7	−0.1240 (4)	0.8346 (3)	0.2937 (3)	0.0470 (8)
C8	0.0458 (4)	0.7103 (3)	0.2462 (3)	0.0544 (10)
H8A	0.0572	0.6223	0.2337	0.065*
H8B	0.1109	0.7304	0.3175	0.065*
C9	0.0881 (4)	0.7848 (3)	0.1659 (3)	0.0439 (8)
C10	0.0921 (4)	0.7439 (3)	0.0710 (3)	0.0505 (9)
H10A	0.0619	0.6637	0.0468	0.061*
C11	0.1761 (4)	0.9284 (3)	0.0624 (3)	0.0510 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.0979 (9)	0.0693 (7)	0.0924 (9)	−0.0089 (6)	0.0452 (7)	0.0247 (6)
S	0.0931 (8)	0.0394 (5)	0.0513 (6)	−0.0082 (5)	0.0287 (5)	−0.0050 (4)
O1	0.130 (3)	0.100 (3)	0.105 (3)	0.063 (3)	0.027 (2)	−0.015 (2)
O2	0.097 (2)	0.099 (3)	0.073 (2)	0.0029 (19)	0.0421 (19)	−0.0249 (19)
O3	0.0549 (16)	0.0571 (17)	0.0818 (19)	−0.0087 (13)	0.0281 (14)	−0.0242 (14)
O4	0.0570 (15)	0.0408 (13)	0.0552 (15)	−0.0032 (12)	0.0236 (12)	−0.0034 (11)
O5	0.0724 (18)	0.0385 (14)	0.0627 (16)	−0.0042 (12)	0.0341 (14)	−0.0075 (11)
N1	0.057 (2)	0.071 (2)	0.078 (3)	0.0045 (18)	0.0303 (19)	−0.016 (2)
N2	0.072 (2)	0.062 (2)	0.0472 (18)	−0.0016 (18)	0.0303 (16)	−0.0028 (16)
C1	0.046 (2)	0.055 (2)	0.059 (2)	0.0014 (18)	0.0188 (18)	−0.0096 (18)
C2	0.052 (2)	0.065 (2)	0.051 (2)	−0.0027 (19)	0.0220 (18)	−0.0049 (19)
C3	0.048 (2)	0.051 (2)	0.062 (2)	0.0034 (18)	0.0134 (18)	0.0034 (19)
C4	0.044 (2)	0.046 (2)	0.066 (2)	−0.0047 (17)	0.0189 (18)	−0.0144 (18)
C5	0.063 (3)	0.069 (3)	0.052 (2)	0.004 (2)	0.0142 (19)	−0.001 (2)
C6	0.059 (2)	0.062 (3)	0.062 (3)	0.016 (2)	0.014 (2)	0.001 (2)
C7	0.064 (2)	0.0289 (18)	0.050 (2)	−0.0006 (17)	0.0199 (17)	−0.0022 (15)
C8	0.075 (3)	0.0382 (19)	0.059 (2)	0.0129 (18)	0.035 (2)	0.0015 (17)
C9	0.061 (2)	0.0342 (18)	0.0402 (18)	0.0061 (15)	0.0211 (16)	0.0001 (14)
C10	0.059 (2)	0.044 (2)	0.048 (2)	−0.0019 (17)	0.0174 (18)	−0.0057 (16)
C11	0.054 (2)	0.052 (2)	0.052 (2)	0.0010 (18)	0.0242 (17)	0.0101 (18)

Geometric parameters (Å, º)

Cl—C11	1.710 (4)	C1—C6	1.375 (5)
S—C9	1.721 (3)	C2—C3	1.380 (6)
S—C11	1.709 (4)	C3—C4	1.370 (5)
O1—N1	1.212 (6)	C4—C5	1.371 (5)
O2—N1	1.219 (5)	C5—C6	1.383 (6)
O3—C4	1.407 (4)	C8—C9	1.489 (5)
O3—C7	1.340 (5)	C9—C10	1.339 (5)
O4—C7	1.189 (4)	C2—H2B	0.9293
O5—C7	1.332 (4)	C3—H3A	0.9306
O5—C8	1.460 (5)	C5—H5A	0.9307
N1—C1	1.459 (6)	C6—H6A	0.9300
N2—C10	1.373 (5)	C8—H8A	0.9700
N2—C11	1.286 (5)	C8—H8B	0.9705
C1—C2	1.377 (6)	C10—H10A	0.9303
C9—S—C11	88.61 (18)	S—C9—C10	108.8 (3)
C4—O3—C7	116.1 (3)	C8—C9—C10	126.1 (3)
C7—O5—C8	115.6 (3)	N2—C10—C9	117.4 (3)
O1—N1—O2	123.4 (4)	Cl—C11—S	120.4 (2)
O1—N1—C1	118.1 (4)	Cl—C11—N2	122.7 (3)
O2—N1—C1	118.5 (4)	S—C11—N2	116.8 (3)
C10—N2—C11	108.4 (3)	C1—C2—H2B	120.54
N1—C1—C2	118.7 (3)	C3—C2—H2B	120.52
N1—C1—C6	119.2 (4)	C2—C3—H3A	120.53
C2—C1—C6	122.1 (4)	C4—C3—H3A	120.49
C1—C2—C3	118.9 (4)	C4—C5—H5A	120.37
C2—C3—C4	119.0 (4)	C6—C5—H5A	120.46
O3—C4—C3	119.4 (3)	C1—C6—H6A	120.59
O3—C4—C5	118.4 (3)	C5—C6—H6A	120.78
C3—C4—C5	122.2 (4)	O5—C8—H8A	109.05
C4—C5—C6	119.2 (3)	O5—C8—H8B	109.10
C1—C6—C5	118.6 (4)	C9—C8—H8A	109.05
O3—C7—O4	126.2 (3)	C9—C8—H8B	109.01
O3—C7—O5	107.1 (3)	H8A—C8—H8B	107.81
O4—C7—O5	126.7 (4)	N2—C10—H10A	121.24
O5—C8—C9	112.7 (3)	C9—C10—H10A	121.35
S—C9—C8	124.9 (3)
C6—C1—N1—O1	−0.1 (6)	C8—O5—C7—O4	4.4 (5)
C2—C1—N1—O1	179.9 (4)	C8—O5—C7—O3	−174.8 (3)
C6—C1—N1—O2	−178.7 (4)	C4—O3—C7—O4	−0.7 (5)
C2—C1—N1—O2	1.3 (5)	C4—O3—C7—O5	178.6 (3)
C6—C1—C2—C3	0.8 (6)	C7—O5—C8—C9	−82.1 (4)
N1—C1—C2—C3	−179.2 (3)	O5—C8—C9—C10	−99.7 (4)
C1—C2—C3—C4	0.3 (6)	O5—C8—C9—S	84.7 (4)
C2—C3—C4—C5	−0.9 (6)	C11—S—C9—C10	0.0 (3)
C2—C3—C4—O3	−177.8 (3)	C11—S—C9—C8	176.3 (3)
C7—O3—C4—C3	−77.0 (4)	C8—C9—C10—N2	−176.2 (3)
C7—O3—C4—C5	106.1 (4)	S—C9—C10—N2	0.1 (4)
C3—C4—C5—C6	0.5 (6)	C11—N2—C10—C9	−0.2 (5)
O3—C4—C5—C6	177.3 (3)	C10—N2—C11—S	0.2 (4)
C2—C1—C6—C5	−1.3 (6)	C10—N2—C11—Cl	177.6 (3)
N1—C1—C6—C5	178.7 (4)	C9—S—C11—N2	−0.2 (3)
C4—C5—C6—C1	0.6 (6)	C9—S—C11—Cl	−177.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O4^i	0.97	2.44	3.392 (4)	166
C8—H8B···N2^ii	0.97	2.54	3.325 (5)	138

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2.