Ethyl 4-(3-hydroxy-6-methyl-4-oxo-4H-pyran-2-yl­methyl)­piperazine-1-carboxyl­ate

The title compound, C₁₄H₂₀N₂O₅, was synthesized as a Mannich base and characterized by IR, ¹H NMR, GC mass spectra and elemental analysis. The piperazine ring displays a chair conformation, and the crystal structure is stabilized by O—H...O and C—H...O intra- and intermolecular hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.049
• wR factor = 0.162
• Data-to-parameter ratio = 15.1

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1997) and PARST (Nardelli, 1995).

Ethyl 4-(3-hydroxy-6-methyl-4-oxo-4H-pyran-2-ylmethyl)piperazine-1-carboxylate

Crystal data

C14H20N2O5	F(000) = 1264
Mr = 296.32	Dx = 1.344 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 15639 reflections
a = 24.069 (3) Å	θ = 1.7–29.6°
b = 6.1796 (4) Å	µ = 0.10 mm^−1
c = 19.788 (2) Å	T = 293 K
β = 95.513 (8)°	Prism., colourless
V = 2929.7 (5) Å^3	0.60 × 0.55 × 0.32 mm
Z = 8

Data collection

STOE IPDS-II diffractometer	2888 independent reflections
Radiation source: fine-focus sealed tube	2388 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 1.7°
w scans	h = −29→29
Absorption correction: integration X-RED32 (Stoe & Cie, 2002)	k = −7→7
Tmin = 0.937, Tmax = 0.970	l = −24→24
16025 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.162	w = 1/[σ^2(Fo^2) + (0.0946P)^2 + 0.909P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
2888 reflections	Δρmax = 0.37 e Å^−3
191 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0072 (13)

Special details

Experimental. Melting points were determined with a Thomas Hoover capillary melting point apparatus (Philadelphia, PA, USA) and were uncorrected. IR spectra were recorded on Perkin Elmer FT—IR Spectrometer 1720 X (Beaconsfield, UK) as KBr disc (γ, cm-1). ¹H-NMR spectra were obtained on Bruker AC 80 MHz s pectrophotometer using TMS as an internal standard (chemical shift in δ, p.p.m.). GC(MS) were recorded on Agilent 6890 N Gas chromatography, Agilent 5973 Mass selective dedector and Agilent G 1030 AX computer. The elemental analyses were performed at Leco CHNS-932 Elemental Analyzer (Philadelphia, USA) by The Scientific and Technical Research Council of Turkey Instrumental Analysis Laboratories (Ankara, Turkey).

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
C14	0.54328 (11)	0.5698 (6)	0.34589 (18)	0.1022 (10)
H14A	0.5787	0.6109	0.3688	0.153*
H14B	0.5281	0.6888	0.3190	0.153*
H14C	0.5483	0.4479	0.3170	0.153*
O1	0.34507 (5)	0.0754 (2)	0.06885 (6)	0.0515 (3)
C4	0.31840 (7)	0.4685 (3)	0.00371 (8)	0.0481 (4)
C5	0.29002 (7)	0.3915 (3)	0.06089 (8)	0.0465 (4)
O2	0.24879 (6)	0.5142 (2)	0.08327 (7)	0.0599 (4)
H2	0.2450	0.6250	0.0605	0.090*
C1	0.30327 (6)	0.2017 (3)	0.09075 (8)	0.0464 (4)
O3	0.30488 (6)	0.6408 (2)	−0.02497 (6)	0.0606 (4)
C9	0.32208 (7)	0.3268 (3)	0.23710 (8)	0.0470 (4)
H9A	0.2885	0.4147	0.2339	0.056*
H9B	0.3477	0.3892	0.2076	0.056*
O5	0.45124 (6)	0.4410 (2)	0.36469 (8)	0.0696 (4)
N2	0.39646 (6)	0.1812 (3)	0.31632 (8)	0.0553 (4)
C3	0.36185 (7)	0.3299 (3)	−0.01489 (8)	0.0518 (4)
H3	0.3825	0.3711	−0.0501	0.062*
C2	0.37371 (7)	0.1418 (3)	0.01714 (8)	0.0507 (4)
O4	0.48543 (6)	0.1026 (3)	0.35555 (9)	0.0790 (5)
C10	0.34862 (8)	0.3273 (3)	0.30947 (9)	0.0541 (4)
H10A	0.3607	0.4727	0.3222	0.065*
H10B	0.3214	0.2817	0.3397	0.065*
C8	0.38287 (9)	−0.0368 (3)	0.29380 (10)	0.0623 (5)
H8A	0.3567	−0.1006	0.3224	0.075*
H8B	0.4164	−0.1249	0.2972	0.075*
C11	0.44741 (8)	0.2310 (3)	0.34554 (9)	0.0572 (5)
C7	0.35729 (8)	−0.0307 (3)	0.22060 (9)	0.0550 (5)
H7A	0.3843	0.0248	0.1917	0.066*
H7B	0.3470	−0.1759	0.2056	0.066*
C13	0.41739 (9)	−0.0160 (4)	0.00268 (12)	0.0668 (5)
H13A	0.4175	−0.1342	0.0342	0.100*
H13B	0.4532	0.0538	0.0072	0.100*
H13C	0.4097	−0.0699	−0.0428	0.100*
C12	0.50464 (10)	0.5110 (5)	0.39646 (13)	0.0818 (7)
H12A	0.5210	0.3958	0.4251	0.098*
H12B	0.4993	0.6351	0.4251	0.098*
N1	0.30806 (6)	0.1076 (2)	0.21530 (7)	0.0461 (4)
C6	0.27632 (7)	0.1009 (3)	0.14844 (8)	0.0500 (4)
H6A	0.2408	0.1725	0.1518	0.060*
H6B	0.2684	−0.0494	0.1371	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C14	0.0656 (15)	0.117 (2)	0.127 (2)	−0.0139 (14)	0.0241 (16)	−0.0152 (18)
O1	0.0493 (7)	0.0594 (7)	0.0467 (6)	0.0004 (5)	0.0093 (5)	0.0022 (5)
C4	0.0433 (8)	0.0600 (10)	0.0405 (8)	−0.0056 (7)	0.0012 (6)	0.0005 (7)
C5	0.0422 (8)	0.0590 (9)	0.0385 (7)	−0.0029 (7)	0.0045 (6)	−0.0023 (7)
O2	0.0604 (8)	0.0675 (8)	0.0543 (7)	0.0104 (6)	0.0181 (6)	0.0072 (6)
C1	0.0412 (8)	0.0571 (10)	0.0409 (8)	−0.0040 (7)	0.0031 (6)	−0.0036 (7)
O3	0.0600 (8)	0.0671 (8)	0.0554 (7)	0.0051 (6)	0.0098 (6)	0.0134 (6)
C9	0.0454 (8)	0.0471 (9)	0.0489 (9)	0.0038 (7)	0.0064 (7)	−0.0011 (7)
O5	0.0525 (8)	0.0746 (10)	0.0805 (10)	−0.0054 (6)	0.0005 (7)	−0.0118 (7)
N2	0.0539 (8)	0.0568 (9)	0.0534 (8)	0.0071 (7)	−0.0042 (6)	−0.0039 (7)
C3	0.0454 (9)	0.0694 (11)	0.0415 (8)	−0.0035 (8)	0.0087 (6)	0.0018 (8)
C2	0.0434 (8)	0.0655 (11)	0.0437 (8)	−0.0045 (7)	0.0067 (7)	−0.0036 (7)
O4	0.0602 (9)	0.0878 (11)	0.0865 (11)	0.0165 (8)	−0.0065 (7)	0.0060 (8)
C10	0.0513 (9)	0.0599 (10)	0.0509 (9)	0.0077 (8)	0.0044 (7)	−0.0077 (8)
C8	0.0726 (12)	0.0505 (10)	0.0611 (11)	0.0064 (9)	−0.0071 (9)	0.0059 (8)
C11	0.0522 (10)	0.0686 (12)	0.0507 (9)	0.0053 (9)	0.0035 (7)	0.0058 (8)
C7	0.0651 (11)	0.0433 (9)	0.0553 (10)	0.0047 (8)	−0.0004 (8)	−0.0024 (7)
C13	0.0599 (11)	0.0723 (13)	0.0705 (12)	0.0066 (9)	0.0184 (9)	−0.0017 (10)
C12	0.0598 (12)	0.0990 (18)	0.0848 (16)	−0.0106 (12)	−0.0019 (11)	−0.0170 (13)
N1	0.0466 (7)	0.0495 (7)	0.0425 (7)	−0.0034 (6)	0.0059 (5)	0.0020 (6)
C6	0.0444 (8)	0.0608 (10)	0.0450 (8)	−0.0098 (7)	0.0058 (7)	0.0020 (7)

Geometric parameters (Å, º)

C14—C12	1.476 (4)	N2—C10	1.459 (2)
C14—H14A	0.9600	C3—C2	1.342 (3)
C14—H14B	0.9600	C3—H3	0.9300
C14—H14C	0.9600	C2—C13	1.482 (3)
O1—C2	1.351 (2)	O4—C11	1.213 (2)
O1—C1	1.376 (2)	C10—H10A	0.9700
C4—O3	1.235 (2)	C10—H10B	0.9700
C4—C3	1.427 (3)	C8—C7	1.519 (3)
C4—C5	1.457 (2)	C8—H8A	0.9700
C5—C1	1.338 (2)	C8—H8B	0.9700
C5—O2	1.357 (2)	C7—N1	1.457 (2)
O2—H2	0.8200	C7—H7A	0.9700
C1—C6	1.501 (2)	C7—H7B	0.9700
C9—N1	1.452 (2)	C13—H13A	0.9600
C9—C10	1.511 (2)	C13—H13B	0.9600
C9—H9A	0.9700	C13—H13C	0.9600
C9—H9B	0.9700	C12—H12A	0.9700
O5—C11	1.353 (3)	C12—H12B	0.9700
O5—C12	1.442 (3)	N1—C6	1.463 (2)
N2—C11	1.340 (2)	C6—H6A	0.9700
N2—C8	1.446 (2)	C6—H6B	0.9700
C12—C14—H14A	109.5	H10A—C10—H10B	108.1
C12—C14—H14B	109.5	N2—C8—C7	109.25 (14)
H14A—C14—H14B	109.5	N2—C8—H8A	109.8
C12—C14—H14C	109.5	C7—C8—H8A	109.8
H14A—C14—H14C	109.5	N2—C8—H8B	109.8
H14B—C14—H14C	109.5	C7—C8—H8B	109.8
C2—O1—C1	120.55 (14)	H8A—C8—H8B	108.3
O3—C4—C3	124.47 (16)	O4—C11—N2	124.4 (2)
O3—C4—C5	121.06 (16)	O4—C11—O5	123.48 (18)
C3—C4—C5	114.47 (15)	N2—C11—O5	112.09 (16)
C1—C5—O2	119.77 (15)	N1—C7—C8	109.62 (15)
C1—C5—C4	121.32 (16)	N1—C7—H7A	109.7
O2—C5—C4	118.90 (15)	C8—C7—H7A	109.7
C5—O2—H2	109.5	N1—C7—H7B	109.7
C5—C1—O1	120.56 (14)	C8—C7—H7B	109.7
C5—C1—C6	126.70 (16)	H7A—C7—H7B	108.2
O1—C1—C6	112.74 (15)	C2—C13—H13A	109.5
N1—C9—C10	110.40 (14)	C2—C13—H13B	109.5
N1—C9—H9A	109.6	H13A—C13—H13B	109.5
C10—C9—H9A	109.6	C2—C13—H13C	109.5
N1—C9—H9B	109.6	H13A—C13—H13C	109.5
C10—C9—H9B	109.6	H13B—C13—H13C	109.5
H9A—C9—H9B	108.1	O5—C12—C14	111.8 (2)
C11—O5—C12	116.35 (18)	O5—C12—H12A	109.3
C11—N2—C8	121.14 (16)	C14—C12—H12A	109.3
C11—N2—C10	125.39 (17)	O5—C12—H12B	109.3
C8—N2—C10	113.23 (15)	C14—C12—H12B	109.3
C2—C3—C4	121.75 (15)	H12A—C12—H12B	107.9
C2—C3—H3	119.1	C9—N1—C7	111.21 (13)
C4—C3—H3	119.1	C9—N1—C6	112.41 (13)
C3—C2—O1	121.31 (16)	C7—N1—C6	113.51 (14)
C3—C2—C13	127.00 (16)	N1—C6—C1	116.72 (13)
O1—C2—C13	111.70 (16)	N1—C6—H6A	108.1
N2—C10—C9	110.17 (14)	C1—C6—H6A	108.1
N2—C10—H10A	109.6	N1—C6—H6B	108.1
C9—C10—H10A	109.6	C1—C6—H6B	108.1
N2—C10—H10B	109.6	H6A—C6—H6B	107.3
C9—C10—H10B	109.6
O3—C4—C5—C1	177.84 (16)	C11—N2—C8—C7	−128.72 (19)
C3—C4—C5—C1	−2.3 (2)	C10—N2—C8—C7	56.6 (2)
O3—C4—C5—O2	−1.1 (2)	C8—N2—C11—O4	−0.1 (3)
C3—C4—C5—O2	178.70 (15)	C10—N2—C11—O4	173.93 (19)
O2—C5—C1—O1	−179.80 (14)	C8—N2—C11—O5	−178.23 (17)
C4—C5—C1—O1	1.2 (2)	C10—N2—C11—O5	−4.2 (3)
O2—C5—C1—C6	0.9 (3)	C12—O5—C11—O4	2.1 (3)
C4—C5—C1—C6	−178.09 (15)	C12—O5—C11—N2	−179.74 (18)
C2—O1—C1—C5	0.5 (2)	N2—C8—C7—N1	−57.6 (2)
C2—O1—C1—C6	179.90 (13)	C11—O5—C12—C14	83.9 (3)
O3—C4—C3—C2	−178.30 (17)	C10—C9—N1—C7	−58.22 (18)
C5—C4—C3—C2	1.9 (2)	C10—C9—N1—C6	173.25 (13)
C4—C3—C2—O1	−0.3 (3)	C8—C7—N1—C9	59.70 (19)
C4—C3—C2—C13	179.81 (17)	C8—C7—N1—C6	−172.36 (15)
C1—O1—C2—C3	−1.0 (2)	C9—N1—C6—C1	58.0 (2)
C1—O1—C2—C13	178.92 (15)	C7—N1—C6—C1	−69.3 (2)
C11—N2—C10—C9	130.36 (18)	C5—C1—C6—N1	−105.18 (19)
C8—N2—C10—C9	−55.2 (2)	O1—C1—C6—N1	75.45 (19)
N1—C9—C10—N2	54.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3^i	0.82	1.97	2.6941 (18)	147
O2—H2···O3	0.82	2.33	2.7527 (18)	113
C6—H6A···O2	0.97	2.53	2.909 (2)	103
C7—H7A···O1	0.97	2.54	3.060 (2)	114
C8—H8B···O4	0.97	2.39	2.784 (3)	104
C10—H10A···O5	0.97	2.27	2.696 (2)	106

Symmetry code: (i) −x+1/2, −y+3/2, −z.