Diethyl (4-tert-butyl-1,3-thia­zol-2-yl­amino­methyl­ene)­malonate

Lynch, D.E.; McClenaghan, I.

doi:10.1107/S1600536803001302

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Diethyl (4-tert-butyl-1,3-thiazol-2-ylaminomethylene)malonate

D. E. Lynch and I. McClenaghan

The molecule of the title compound, C₁₅H₂₃N₂O₄S, is essentially planar, except for the tert-butyl group, with disorder of the aminomethylene atoms. These are equally disordered over two sites each, giving two alternative intramolecular hydrogen bonds from the partial amine H atoms to the adjacent carbonyl O atoms. An additional, intermolecular, C—H

O close contact is observed from the only thiazole ring H atom to one of the carbonyl O atoms.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803001302/cf6233sup1.cif Contains datablocks I, default
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803001302/cf6233Isup2.hkl Contains datablock I

CCDC reference: 204719

checkCIF report

Key indicators

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.007 Å
H-atom completeness 96%
R factor = 0.096
wR factor = 0.299
Data-to-parameter ratio = 17.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



RFACR_01  Alert C The value of the weighted R factor is > 0.25
          Weighted R factor given   0.299

RINTA_01  Alert C The value of Rint is greater than 0.10
          Rint given   0.113

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and the formula from the _atom_site* data.
          Atom count from _chemical_formula_sum:C15 H23 N2 O4 S1
          Atom count from the _atom_site data:  C15 H22 N2 O4 S1

CELLZ_01
         From the CIF: _cell_formula_units_Z    8
         From the CIF: _chemical_formula_sum  C15 H23 N2 O4 S
         TEST: Compare cell contents of formula and atom_site data

         atom    Z*formula  cif sites diff
         C        120.00    120.00    0.00
         H        184.00    176.00    8.00
         N         16.00     16.00    0.00
         O         32.00     32.00    0.00
         S          8.00      8.00    0.00
          Difference between formula and atom_site contents detected.
          WARNING: H atoms missing from atom site list. Is this intentional?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

Comment top

2-Aminothiazole derivatives have a variety of pharmaceutical properties and recent experience has shown us that they are generally easy compounds to crystallize, or cocrystallize. There are currently 157 crystal structures (Cambridge Structural Database, September 2002 release; Allen, 2002) containing a 2-aminothiazole moiety. Only two of these structures have a 4-tert-butyl group, namely 4-tert-butyl-2-(N-methyl-N-phenylamino)thiazole-5-carbaldehyde (Gillon et al., 1983) and anti-5-acetyl-2-dimethylamino-4-tert-butylthiazole (Caldwell et al., 1987). The crystallographic quality of these two structures is very good, considering the potential for disorder in tert-butyl groups. Ironically, in the title compound, (I), the groups where disorder might be more likely, such as the tert-butyl and/or the ethyl esters, are relatively rigid, compared to the rest of the molecule. Large and very anisotropic displacement ellipsoids for three of the thiazole ring atoms (S1, C2 and N3) and the malonate atoms means that several atoms could be split into two positions each, but attempts to do so resulted in totally unrealistic bond distances and angles. The crystallographic results for (I) are of low precision, and a poor data set was the direct result of poor crystal quality. However, the resolvable disorder in this molecule and the probable unresolved disorder in the atoms with high displacement parameters is worth reporting. The structure of (I) comprises an essentially planar molecule, except for the tert-butyl group, with resolved disorder of the aminomethylene atoms (Fig. 1). All the molecules in the unit cell lie essentially parallel to the ab plane. The aminomethylene atoms (N21 and C22) are both equally disordered over two sites; thus, two alternative intramolecular hydrogen bonds exists from the partial amine H atoms to the adjacent carbonyl O atoms (Table 1). An additional C—H···O close contact is observed from the only thiazole ring H atom to one of the carbonyl O atoms in an adjacent molecule.

Experimental top

The title compound was obtained from Key Organics Ltd and crystals were grown from iso-octane.

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. The molecular structure and atom-numbering scheme for the title compound, showing 50% probability ellipsoids and the resolved twofold disorder.

Diethyl (4-tert-butyl-1,3-thiazol-2-ylaminomethylene)malonate top

Crystal data top

C₁₅H₂₃N₂O₄S	D_x = 1.257 Mg m⁻³
M_r = 327.41	Melting point: 335-336 K K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.663 (4) Å	Cell parameters from 7703 reflections
b = 13.177 (3) Å	θ = 2.9–27.5°
c = 13.708 (3) Å	µ = 0.21 mm⁻¹
β = 103.69 (3)°	T = 150 K
V = 3450.8 (13) Å³	Needle, colourless
Z = 8	0.34 × 0.10 × 0.08 mm
F(000) = 1392

Data collection top

Bruker–Nonius KappaCCD area-detector diffractometer	3916 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	1830 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.113
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ϕ and ω scans	h = −25→25
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −17→17
T_min = 0.933, T_max = 0.984	l = −16→17
12347 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.096	H-atom parameters constrained
wR(F²) = 0.300	w = 1/[σ²(F_o²) + (0.1206P)² + 1.7968P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max < 0.001
3916 reflections	Δρ_max = 0.44 e Å⁻³
226 parameters	Δρ_min = −0.94 e Å⁻³
32 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0067 (16)

Crystal data top

C₁₅H₂₃N₂O₄S	V = 3450.8 (13) Å³
M_r = 327.41	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 19.663 (4) Å	µ = 0.21 mm⁻¹
b = 13.177 (3) Å	T = 150 K
c = 13.708 (3) Å	0.34 × 0.10 × 0.08 mm
β = 103.69 (3)°

Data collection top

Bruker–Nonius KappaCCD area-detector diffractometer	3916 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	1830 reflections with I > 2σ(I)
T_min = 0.933, T_max = 0.984	R_int = 0.113
12347 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.096	32 restraints
wR(F²) = 0.300	H-atom parameters constrained
S = 1.16	Δρ_max = 0.44 e Å⁻³
3916 reflections	Δρ_min = −0.94 e Å⁻³
226 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.24097 (9)	0.28058 (17)	0.25123 (11)	0.1142 (8)
C2	0.2113 (3)	0.4050 (6)	0.2379 (3)	0.106 (2)
N3	0.2571 (2)	0.4739 (4)	0.2616 (3)	0.0794 (13)
C4	0.3231 (2)	0.4311 (3)	0.2963 (3)	0.0542 (10)
C41	0.3839 (2)	0.5007 (3)	0.3288 (3)	0.0613 (11)
C42	0.3709 (3)	0.5699 (4)	0.4120 (4)	0.0876 (15)
H41	0.3279	0.6088	0.3869	0.109*
H42	0.4105	0.6166	0.4329	0.109*
H43	0.3662	0.5286	0.4695	0.109*
C43	0.3915 (3)	0.5650 (4)	0.2384 (4)	0.0886 (16)
H44	0.4036	0.5209	0.1875	0.111*
H45	0.4285	0.6155	0.2604	0.111*
H46	0.3471	0.5996	0.2097	0.111*
C44	0.4510 (2)	0.4391 (4)	0.3677 (4)	0.0772 (14)
H47	0.4464	0.3986	0.4258	0.097*
H48	0.4909	0.4854	0.3876	0.097*
H49	0.4586	0.3938	0.3145	0.097*
C5	0.3236 (2)	0.3286 (4)	0.2952 (3)	0.0656 (12)
H5	0.3645	0.2882	0.3162	0.082*
N21A	0.1424 (4)	0.4661 (8)	0.2026 (6)	0.055 (2)	0.50
H21A	0.1411	0.5328	0.2054	0.069*	0.50
N21B	0.1382 (3)	0.3847 (5)	0.1981 (4)	0.0399 (14)	0.50
H21B	0.1190	0.3243	0.1859	0.050*	0.50
C22A	0.0865 (4)	0.4115 (9)	0.1684 (6)	0.053 (2)	0.50
H22A	0.0855	0.3396	0.1637	0.067*	0.50
C22B	0.1035 (5)	0.4758 (7)	0.1825 (6)	0.038 (2)	0.50
H22B	0.1279	0.5380	0.1991	0.047*	0.50
C23	0.0287 (3)	0.4745 (5)	0.1399 (3)	0.0792 (16)
C24	−0.0184 (4)	0.3869 (5)	0.1094 (4)	0.094 (2)
O24	0.0001 (3)	0.2990 (3)	0.1145 (3)	0.136 (2)
O25	−0.08609 (18)	0.4120 (2)	0.0742 (2)	0.0738 (10)
C26	−0.1363 (4)	0.3312 (4)	0.0391 (4)	0.0941 (19)
H261	−0.1395	0.2856	0.0951	0.118*
H262	−0.1222	0.2908	−0.0138	0.118*
C27	−0.2053 (4)	0.3834 (4)	−0.0023 (4)	0.0972 (19)
H271	−0.2180	0.4237	0.0508	0.121*
H272	−0.2415	0.3324	−0.0270	0.121*
H273	−0.2011	0.4282	−0.0577	0.111 (18)*
C28	0.0096 (2)	0.5791 (4)	0.1345 (3)	0.0664 (13)
O28	0.05313 (16)	0.6464 (3)	0.1580 (2)	0.0939 (13)
O29	−0.05840 (13)	0.5982 (2)	0.1018 (2)	0.0588 (8)
C30	−0.0786 (2)	0.7033 (3)	0.0974 (3)	0.0608 (11)
H301	−0.0563	0.7410	0.0508	0.076*
H302	−0.0643	0.7348	0.1647	0.076*
C31	−0.1565 (2)	0.7051 (4)	0.0607 (3)	0.0674 (13)
H311	−0.1697	0.6762	−0.0070	0.084*
H312	−0.1732	0.7753	0.0592	0.084*
H313	−0.1776	0.6649	0.1060	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0885 (12)	0.1802 (18)	0.0810 (10)	−0.0665 (11)	0.0342 (8)	−0.0454 (10)
N3	0.046 (2)	0.138 (4)	0.056 (2)	0.032 (2)	0.0141 (18)	0.027 (2)
C4	0.043 (2)	0.072 (3)	0.047 (2)	0.015 (2)	0.0091 (17)	0.0065 (19)
C41	0.051 (2)	0.062 (3)	0.069 (3)	0.010 (2)	0.011 (2)	−0.003 (2)
C42	0.089 (4)	0.081 (3)	0.091 (3)	0.006 (3)	0.018 (3)	−0.014 (3)
C43	0.085 (4)	0.082 (4)	0.105 (4)	0.005 (3)	0.036 (3)	0.014 (3)
C44	0.039 (2)	0.099 (4)	0.088 (3)	−0.003 (2)	0.003 (2)	−0.007 (3)
C5	0.057 (3)	0.085 (4)	0.055 (2)	−0.005 (2)	0.013 (2)	−0.007 (2)
C24	0.126 (5)	0.112 (5)	0.061 (3)	0.078 (4)	0.055 (3)	0.045 (3)
O24	0.198 (5)	0.111 (3)	0.121 (3)	0.090 (4)	0.084 (3)	0.048 (3)
O25	0.091 (3)	0.065 (2)	0.0689 (19)	0.0110 (19)	0.0272 (18)	0.0047 (15)
C26	0.151 (6)	0.063 (3)	0.082 (3)	−0.015 (4)	0.055 (4)	0.001 (3)
C27	0.130 (5)	0.091 (4)	0.069 (3)	−0.053 (4)	0.022 (3)	0.002 (3)
C28	0.042 (3)	0.116 (4)	0.041 (2)	0.019 (3)	0.0111 (18)	0.015 (2)
O28	0.0385 (17)	0.169 (4)	0.070 (2)	−0.023 (2)	0.0053 (15)	−0.004 (2)
O29	0.0391 (15)	0.073 (2)	0.0623 (16)	0.0056 (14)	0.0083 (12)	0.0036 (14)
C30	0.047 (2)	0.071 (3)	0.062 (2)	−0.006 (2)	0.0081 (19)	0.001 (2)
C31	0.053 (3)	0.081 (3)	0.068 (3)	0.009 (2)	0.013 (2)	0.001 (2)
C2	0.047 (3)	0.228 (6)	0.044 (2)	0.000 (4)	0.014 (2)	−0.003 (4)
N21A	0.043 (5)	0.072 (7)	0.048 (4)	0.007 (5)	0.004 (4)	0.001 (4)
N21B	0.038 (4)	0.029 (4)	0.050 (3)	−0.003 (3)	0.006 (3)	−0.002 (3)
C22A	0.053 (6)	0.057 (6)	0.050 (5)	0.013 (6)	0.012 (4)	0.005 (5)
C22B	0.044 (6)	0.032 (5)	0.038 (4)	0.001 (5)	0.012 (5)	0.004 (4)
C23	0.060 (3)	0.132 (5)	0.051 (2)	0.033 (3)	0.023 (2)	0.024 (3)

Geometric parameters (Å, º) top

S1—C5	1.715 (5)	N21B—C22B	1.371 (9)
S1—C2	1.736 (8)	N21B—H21B	0.88
C2—N21A	1.552 (9)	C22B—H22B	0.95
N3—C2	1.266 (7)	C24—O24	1.212 (6)
N3—C4	1.392 (5)	C24—O25	1.345 (6)
C4—C5	1.352 (6)	C24—C23	1.478 (8)
C4—C41	1.487 (6)	O25—C26	1.453 (6)
C41—C42	1.528 (6)	C26—C27	1.507 (8)
C41—C44	1.534 (6)	C26—H261	0.99
C41—C43	1.537 (6)	C26—H262	0.99
C42—H41	0.98	C27—H271	0.98
C42—H42	0.98	C27—H272	0.98
C42—H43	0.98	C27—H273	0.98
C43—H44	0.98	C28—O28	1.222 (6)
C43—H45	0.98	C28—O29	1.329 (5)
C43—H46	0.98	C28—C23	1.426 (7)
C44—H47	0.98	O29—C30	1.439 (5)
C44—H48	0.98	C30—C31	1.494 (5)
C44—H49	0.98	C30—H301	0.99
C5—H5	0.95	C30—H302	0.99
N21A—C22A	1.305 (11)	C31—H311	0.98
N21A—H21A	0.88	C31—H312	0.98
C22A—C23	1.386 (10)	C31—H313	0.98
C22A—H22A	0.95

C5—S1—C2	87.4 (3)	O25—C26—H262	110.6
C2—N3—C4	110.3 (5)	C27—C26—H262	110.6
C5—C4—N3	114.2 (4)	H261—C26—H262	108.7
C5—C4—C41	127.7 (4)	C26—C27—H271	109.5
N3—C4—C41	118.1 (4)	C26—C27—H272	109.5
C4—C41—C42	109.1 (4)	H271—C27—H272	109.5
C4—C41—C44	110.0 (4)	C26—C27—H273	109.5
C42—C41—C44	109.7 (4)	H271—C27—H273	109.5
C4—C41—C43	108.8 (4)	H272—C27—H273	109.5
C42—C41—C43	109.7 (4)	O28—C28—O29	122.5 (5)
C44—C41—C43	109.4 (4)	O28—C28—C23	121.9 (4)
C41—C42—H41	109.5	O29—C28—C23	115.6 (5)
C41—C42—H42	109.5	C28—O29—C30	116.2 (4)
H41—C42—H42	109.5	O29—C30—C31	106.3 (3)
C41—C42—H43	109.5	O29—C30—H301	110.5
H41—C42—H43	109.5	C31—C30—H301	110.5
H42—C42—H43	109.5	O29—C30—H302	110.5
C41—C43—H44	109.5	C31—C30—H302	110.5
C41—C43—H45	109.5	H301—C30—H302	108.7
H44—C43—H45	109.5	C30—C31—H311	109.5
C41—C43—H46	109.5	C30—C31—H312	109.5
H44—C43—H46	109.5	H311—C31—H312	109.5
H45—C43—H46	109.5	C30—C31—H313	109.5
C41—C44—H47	109.5	H311—C31—H313	109.5
C41—C44—H48	109.5	H312—C31—H313	109.5
H47—C44—H48	109.5	N3—C2—N21A	102.9 (7)
C41—C44—H49	109.5	N3—C2—S1	116.8 (4)
H47—C44—H49	109.5	N21A—C2—S1	140.3 (6)
H48—C44—H49	109.5	C22A—N21A—C2	115.2 (9)
C4—C5—S1	111.3 (4)	C22A—N21A—H21A	122.4
C4—C5—H5	124.3	C2—N21A—H21A	122.4
S1—C5—H5	124.3	N21A—C22A—C23	109.6 (10)
O24—C24—O25	121.0 (8)	N21A—C22A—H22A	125.2
O24—C24—C23	124.8 (6)	C23—C22A—H22A	125.2
O25—C24—C23	114.3 (4)	C22A—C23—C28	141.5 (7)
C24—O25—C26	118.4 (5)	C22A—C23—C24	91.7 (6)
O25—C26—C27	105.7 (4)	C28—C23—C24	126.9 (4)
O25—C26—H261	110.6	C22B—N21B—H21B	125.9
C27—C26—H261	110.6	N21B—C22B—H22B	120.9

C2—N3—C4—C5	1.2 (5)	C4—N3—C2—N21A	179.5 (4)
C2—N3—C4—C41	−179.4 (4)	C4—N3—C2—S1	−1.4 (5)
C5—C4—C41—C42	−123.1 (4)	C5—S1—C2—N3	1.0 (4)
N3—C4—C41—C42	57.6 (5)	C5—S1—C2—N21A	179.7 (6)
C5—C4—C41—C44	−2.7 (5)	N3—C2—N21A—C22A	176.4 (6)
N3—C4—C41—C44	178.0 (3)	S1—C2—N21A—C22A	−2.4 (10)
C5—C4—C41—C43	117.2 (4)	C2—N21A—C22A—C23	179.7 (5)
N3—C4—C41—C43	−62.1 (4)	N21A—C22A—C23—C28	0.6 (11)
N3—C4—C5—S1	−0.4 (4)	N21A—C22A—C23—C24	−179.6 (6)
C41—C4—C5—S1	−179.8 (3)	O28—C28—C23—C22A	2.8 (9)
C2—S1—C5—C4	−0.3 (3)	O29—C28—C23—C22A	−177.7 (6)
O24—C24—O25—C26	−2.1 (6)	O28—C28—C23—C24	−177.0 (4)
C23—C24—O25—C26	177.9 (4)	O29—C28—C23—C24	2.5 (6)
C24—O25—C26—C27	−175.8 (3)	O24—C24—C23—C22A	−0.4 (6)
O28—C28—O29—C30	−1.3 (5)	O25—C24—C23—C22A	179.6 (4)
C23—C28—O29—C30	179.1 (3)	O24—C24—C23—C28	179.4 (4)
C28—O29—C30—C31	−179.0 (3)	O25—C24—C23—C28	−0.6 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21A—H21A···O28	0.88	2.26	2.931 (10)	133
N21B—H21B···O24	0.88	2.33	2.913 (9)	123
C5—H5···O28ⁱ	0.95	2.44	3.363 (7)	163

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₂₃N₂O₄S
M_r	327.41
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	19.663 (4), 13.177 (3), 13.708 (3)
β (°)	103.69 (3)
V (Å³)	3450.8 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.34 × 0.10 × 0.08

Data collection
Diffractometer	Bruker–Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.933, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	12347, 3916, 1830
R_int	0.113
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.096, 0.300, 1.16
No. of reflections	3916
No. of parameters	226
No. of restraints	32
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.94

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON97 (Spek, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21A—H21A···O28	0.88	2.26	2.931 (10)	132.5
N21B—H21B···O24	0.88	2.33	2.913 (9)	123.4
C5—H5···O28ⁱ	0.95	2.44	3.363 (7)	163.0

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

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