Diethyl diprop-2-ynylmalonate

Nan, Y.-F.; Wei, Y.-P.; Li, X.-X.; Hua, C.-H.; Sun, L.-D.

doi:10.1107/S1600536806025505

Diethyl diprop-2-ynylmalonate

Y.-F. Nan, Y.-P. Wei, X.-X. Li, C.-H. Hua and L.-D. Sun

In the title compound, C₁₃H₁₆O₄, the two ester groups adopt syn- and anti-conformations. The two carbonyl O atoms are acceptors of acetylene H atoms in C—H

O interactions which, together with van der Waals contacts, determine the crystal packing.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806025505/kp2029sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536806025505/kp2029Isup2.hkl Contains datablock I

CCDC reference: 618254

checkCIF report

Key indicators

Single-crystal X-ray study
T = 133 K
Mean (C-C) = 0.003 Å
R factor = 0.037
wR factor = 0.094
Data-to-parameter ratio = 10.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C2     -   C3      ..       5.87 su
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          4
            C1  -C2  -C3  -C4   -101.00  5.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          8
            C1  -C5  -C6  -C7      0.00  0.00   1.555   1.555   1.555   1.555

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.46
           From the CIF: _reflns_number_total               1572
           Count of symmetry unique reflns         1589
           Completeness (_total/calc)             98.93%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 1999); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: CrystalStructure.

Diethyl diprop-2-ynylmalonate top

Crystal data top

C₁₃H₁₆O₄	D_x = 1.205 Mg m⁻³
M_r = 236.26	Melting point: 315 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2c -2n	Cell parameters from 817 reflections
a = 17.695 (4) Å	θ = 2.6–27.9°
b = 8.3610 (9) Å	µ = 0.09 mm⁻¹
c = 8.8050 (12) Å	T = 133 K
V = 1302.7 (4) Å³	Block, colourless
Z = 4	0.24 × 0.16 × 0.14 mm
F(000) = 504

Data collection top

Rigaku Saturn diffractometer	1572 independent reflections
Radiation source: fine-focus sealed tube	1448 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
ω scans	h = −13→22
Absorption correction: multi-scan (Jacobson, 1998)	k = −6→10
T_min = 0.979, T_max = 0.988	l = −11→11
5303 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0632P)²] where P = (F_o² + 2F_c²)/3
1572 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.22 e Å⁻³
1 restraint	Δρ_min = −0.20 e Å⁻³

Special details top

Experimental. ¹H NMR (CDCl₃): δ 1.266 (p, 6H), 2.036 (t, 2H), 2.995 (d, 4H), 4.230 (q, 1H).

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.08033 (7)	0.00132 (15)	0.35396 (18)	0.0289 (3)
O2	0.02397 (8)	0.23783 (14)	0.31109 (17)	0.0279 (3)
O3	0.09666 (8)	0.49233 (15)	0.56102 (18)	0.0273 (3)
O4	0.06475 (8)	0.25758 (15)	0.66800 (17)	0.0267 (3)
C1	0.13896 (11)	0.2449 (2)	0.4464 (2)	0.0207 (4)
C2	0.17897 (10)	0.3577 (2)	0.3328 (2)	0.0239 (4)
H2A	0.1406	0.4270	0.2841	0.029*
H2B	0.2143	0.4276	0.3894	0.029*
C3	0.22084 (11)	0.2734 (2)	0.2150 (2)	0.0254 (4)
C4	0.25742 (13)	0.2058 (3)	0.1220 (2)	0.0334 (5)
H4	0.2867	0.1517	0.0475	0.040*
C5	0.19491 (10)	0.1291 (2)	0.5232 (2)	0.0234 (4)
H5A	0.1663	0.0496	0.5834	0.028*
H5B	0.2234	0.0706	0.4440	0.028*
C6	0.24818 (11)	0.2120 (2)	0.6227 (2)	0.0260 (4)
C7	0.29119 (12)	0.2808 (2)	0.7032 (3)	0.0326 (5)
H7	0.3256	0.3358	0.7675	0.039*
C8	0.07870 (9)	0.1446 (2)	0.3650 (2)	0.0210 (4)
C9	−0.04209 (11)	0.1554 (3)	0.2478 (3)	0.0306 (5)
H9A	−0.0254	0.0614	0.1881	0.037*
H9B	−0.0698	0.2284	0.1791	0.037*
C10	−0.09288 (11)	0.1024 (3)	0.3735 (3)	0.0375 (5)
H10A	−0.1370	0.0478	0.3308	0.045*
H10B	−0.1095	0.1958	0.4319	0.045*
H10C	−0.0654	0.0289	0.4404	0.045*
C11	0.09825 (10)	0.3483 (2)	0.5639 (2)	0.0213 (4)
C12	0.02665 (12)	0.3418 (2)	0.7917 (2)	0.0294 (4)
H12A	−0.0118	0.2709	0.8379	0.035*
H12B	0.0006	0.4374	0.7511	0.035*
C13	0.08266 (14)	0.3918 (3)	0.9106 (3)	0.0422 (6)
H13A	0.0563	0.4476	0.9928	0.051*
H13B	0.1202	0.4634	0.8651	0.051*
H13C	0.1081	0.2969	0.9514	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0224 (6)	0.0195 (6)	0.0449 (8)	−0.0003 (5)	−0.0012 (7)	−0.0064 (6)
O2	0.0267 (7)	0.0215 (6)	0.0356 (7)	−0.0007 (5)	−0.0088 (6)	−0.0005 (6)
O3	0.0280 (6)	0.0178 (6)	0.0359 (7)	−0.0004 (5)	0.0046 (6)	−0.0025 (6)
O4	0.0287 (7)	0.0217 (6)	0.0296 (7)	−0.0017 (5)	0.0072 (6)	−0.0016 (6)
C1	0.0194 (8)	0.0168 (7)	0.0260 (9)	−0.0006 (7)	0.0010 (8)	−0.0016 (7)
C2	0.0234 (9)	0.0184 (8)	0.0299 (10)	−0.0011 (7)	0.0032 (8)	−0.0001 (7)
C3	0.0244 (9)	0.0231 (9)	0.0288 (10)	−0.0039 (7)	−0.0010 (8)	0.0034 (8)
C4	0.0356 (11)	0.0284 (10)	0.0361 (11)	−0.0003 (9)	0.0082 (10)	−0.0042 (9)
C5	0.0206 (8)	0.0197 (8)	0.0300 (10)	0.0015 (7)	−0.0007 (7)	−0.0001 (7)
C6	0.0228 (9)	0.0232 (9)	0.0319 (10)	0.0022 (7)	−0.0002 (8)	0.0026 (8)
C7	0.0288 (10)	0.0310 (10)	0.0381 (12)	−0.0015 (8)	−0.0054 (9)	−0.0017 (9)
C8	0.0193 (8)	0.0202 (8)	0.0236 (9)	−0.0007 (7)	0.0022 (7)	−0.0006 (7)
C9	0.0256 (10)	0.0314 (10)	0.0346 (10)	−0.0003 (8)	−0.0114 (8)	−0.0028 (9)
C10	0.0240 (9)	0.0448 (12)	0.0439 (12)	−0.0008 (9)	−0.0010 (9)	−0.0077 (11)
C11	0.0175 (8)	0.0211 (8)	0.0254 (9)	−0.0018 (7)	−0.0024 (7)	−0.0006 (8)
C12	0.0273 (9)	0.0291 (9)	0.0316 (10)	0.0014 (8)	0.0089 (8)	−0.0014 (9)
C13	0.0427 (12)	0.0512 (14)	0.0328 (12)	0.0108 (11)	−0.0003 (10)	−0.0087 (10)

Geometric parameters (Å, º) top

O1—C8	1.202 (2)	C5—H5A	0.9900
O2—C8	1.331 (2)	C5—H5B	0.9900
O2—C9	1.467 (2)	C6—C7	1.188 (3)
O3—C11	1.205 (2)	C7—H7	0.9500
O4—C11	1.329 (2)	C9—C10	1.493 (3)
O4—C12	1.462 (2)	C9—H9A	0.9900
C1—C11	1.529 (3)	C9—H9B	0.9900
C1—C8	1.534 (2)	C10—H10A	0.9800
C1—C5	1.541 (2)	C10—H10B	0.9800
C1—C2	1.546 (2)	C10—H10C	0.9800
C2—C3	1.457 (3)	C12—C13	1.501 (3)
C2—H2A	0.9900	C12—H12A	0.9900
C2—H2B	0.9900	C12—H12B	0.9900
C3—C4	1.187 (3)	C13—H13A	0.9800
C4—H4	0.9500	C13—H13B	0.9800
C5—C6	1.462 (3)	C13—H13C	0.9800

C8—O2—C9	116.11 (14)	O2—C9—C10	109.71 (17)
C11—O4—C12	116.40 (14)	O2—C9—H9A	109.7
C11—C1—C8	107.32 (14)	C10—C9—H9A	109.7
C11—C1—C5	111.14 (15)	O2—C9—H9B	109.7
C8—C1—C5	107.94 (14)	C10—C9—H9B	109.7
C11—C1—C2	107.98 (13)	H9A—C9—H9B	108.2
C8—C1—C2	110.47 (16)	C9—C10—H10A	109.5
C5—C1—C2	111.90 (15)	C9—C10—H10B	109.5
C3—C2—C1	113.47 (14)	H10A—C10—H10B	109.5
C3—C2—H2A	108.9	C9—C10—H10C	109.5
C1—C2—H2A	108.9	H10A—C10—H10C	109.5
C3—C2—H2B	108.9	H10B—C10—H10C	109.5
C1—C2—H2B	108.9	O3—C11—O4	125.10 (17)
H2A—C2—H2B	107.7	O3—C11—C1	124.17 (17)
C4—C3—C2	177.5 (2)	O4—C11—C1	110.73 (14)
C3—C4—H4	180.0	O4—C12—C13	110.44 (16)
C6—C5—C1	112.29 (15)	O4—C12—H12A	109.6
C6—C5—H5A	109.1	C13—C12—H12A	109.6
C1—C5—H5A	109.1	O4—C12—H12B	109.6
C6—C5—H5B	109.1	C13—C12—H12B	109.6
C1—C5—H5B	109.1	H12A—C12—H12B	108.1
H5A—C5—H5B	107.9	C12—C13—H13A	109.5
C7—C6—C5	179.4 (2)	C12—C13—H13B	109.5
C6—C7—H7	180.0	H13A—C13—H13B	109.5
O1—C8—O2	124.90 (16)	C12—C13—H13C	109.5
O1—C8—C1	124.45 (16)	H13A—C13—H13C	109.5
O2—C8—C1	110.63 (14)	H13B—C13—H13C	109.5

C11—C1—C2—C3	179.37 (15)	C11—C1—C8—O2	53.02 (19)
C8—C1—C2—C3	−63.5 (2)	C5—C1—C8—O2	172.89 (15)
C5—C1—C2—C3	56.8 (2)	C2—C1—C8—O2	−64.47 (18)
C1—C2—C3—C4	−101 (5)	C8—O2—C9—C10	79.9 (2)
C11—C1—C5—C6	−54.03 (19)	C12—O4—C11—O3	−3.3 (3)
C8—C1—C5—C6	−171.46 (15)	C12—O4—C11—C1	177.17 (15)
C2—C1—C5—C6	66.8 (2)	C8—C1—C11—O3	−116.5 (2)
C1—C5—C6—C7	−2 (20)	C5—C1—C11—O3	125.65 (19)
C9—O2—C8—O1	6.4 (3)	C2—C1—C11—O3	2.6 (2)
C9—O2—C8—C1	−172.44 (16)	C8—C1—C11—O4	62.99 (18)
C11—C1—C8—O1	−125.85 (19)	C5—C1—C11—O4	−54.83 (19)
C5—C1—C8—O1	−6.0 (3)	C2—C1—C11—O4	−177.91 (14)
C2—C1—C8—O1	116.7 (2)	C11—O4—C12—C13	−81.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3ⁱ	0.95	2.46	3.184 (3)	133
C7—H7···O1ⁱⁱ	0.95	2.29	3.214 (2)	163
C9—H9B···O3ⁱⁱⁱ	0.99	2.60	3.509 (3)	153
C12—H12A···O1^iv	0.99	2.58	3.480 (2)	151

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

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Diethyl diprop-2-ynylmalonate

Supporting information

Key indicators

checkCIF/PLATON results

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