The ethyl tetra­ester of ranelic acid

Wei, H.-T.; Ji, M.

doi:10.1107/S1600536807006654

The ethyl tetraester of ranelic acid

The title compound, 5-[bis(ethoxycarbonylmethyl)amino]-4-cyano-2-ethoxycarbonyl-3-thiophenepropionate, C₂₀H₂₆N₂O₈S, is a highly substituted thiophene ring with a crystal structure stabilized by intermolecular C—H

O hydrogen bonds, which are, however, weak in strength.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807006654/bh2078sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807006654/bh2078Isup2.hkl Contains datablock I

CCDC reference: 641503

checkCIF report

Key indicators

Single-crystal X-ray study
T = 193 K
Mean (C-C) = 0.002 Å
R factor = 0.037
wR factor = 0.088
Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.744     0.927
            Tmin(prime) and Tmax expected:      0.889     0.927
            RR(prime) =      0.836
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.83
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C2     -   C13     ..       5.08 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C2     -   C13    ...       1.43 Ang.

   0 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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Computing details top

Data collection: CrystalClear (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-Plus (Sheldrick, 1998); software used to prepare material for publication: PLATON (Spek, 2003).

5-[bis(ethoxycarbonylmethyl)amino]-4-cyano-2-ethoxycarbonyl- 3-thiophenepropionate top

Crystal data top

C₂₀H₂₆N₂O₈S	Z = 2
M_r = 454.49	F(000) = 480
Triclinic, P1	D_x = 1.367 Mg m⁻³
Hall symbol: -P 1	Melting point = 376–379 K
a = 8.725 (3) Å	Mo Kα radiation, λ = 0.71070 Å
b = 11.422 (4) Å	Cell parameters from 4485 reflections
c = 11.475 (4) Å	θ = 3.2–25.3°
α = 99.428 (6)°	µ = 0.20 mm⁻¹
β = 99.354 (8)°	T = 193 K
γ = 95.424 (6)°	Block, colourless
V = 1104.5 (6) Å³	0.59 × 0.40 × 0.39 mm

Data collection top

Rigaku Mercury diffractometer	3997 independent reflections
Radiation source: fine-focus sealed tube	3635 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.3°, θ_min = 3.2°
ω scans	h = −10→10
Absorption correction: multi-scan (Jacobson, 1998)	k = −13→13
T_min = 0.744, T_max = 0.927	l = −13→13
10705 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) = 0.088	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0372P)² + 0.4372P] where P = (F_o² + 2F_c²)/3
3997 reflections	(Δ/σ)_max < 0.001
285 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Special details top

Experimental. Spectroscopic analysis: IR (KBr, ν cm^-1): 2982, 2216, 1739, 1691, 1563, 1517, 1415, 1367, 1275, 1208, 1185, 1113, 1016, 670; ¹H-NMR (500 MHz, CDCl₃, δ, p.p.m.): 1.27 (t, 3H, CH₃, J=7.00 Hz), 1.30–1.33 (m, 9H, 3× CH₃), 4.03 (s, 2H, CH₂), 4.18 (q, 2H, OCH₂, J=7.00 Hz), 4.24–4.29 (m, 6H, 3× OCH₂), 4.27 (s, 4H, 2× NCH₂); MS: m/z 453.1 (M-1)⁺, 455.1 (M+1)⁺, 477.1 (M+Na)⁺.

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

	x	y	z	U_iso*/U_eq
S1	0.31619 (4)	0.40259 (3)	0.06546 (3)	0.02487 (12)
O1	0.36781 (14)	0.65452 (12)	0.46745 (11)	0.0417 (3)
O2	0.13639 (13)	0.65286 (11)	0.52965 (10)	0.0337 (3)
O3	0.12086 (14)	0.21980 (11)	0.25811 (13)	0.0441 (3)
O4	0.35615 (13)	0.15829 (10)	0.30183 (11)	0.0352 (3)
O5	0.38480 (16)	0.79345 (13)	0.00479 (19)	0.0735 (6)
O6	0.18175 (14)	0.88407 (10)	−0.05890 (12)	0.0362 (3)
O7	0.25572 (16)	0.52605 (11)	−0.23561 (11)	0.0406 (3)
O8	0.35722 (13)	0.36751 (10)	−0.17344 (10)	0.0304 (3)
N1	0.25403 (16)	0.45602 (12)	0.28822 (12)	0.0269 (3)
N2	0.06248 (19)	0.75284 (14)	0.25821 (14)	0.0406 (4)
C1	0.24198 (17)	0.48707 (13)	0.17794 (14)	0.0231 (3)
C2	0.17533 (17)	0.58234 (13)	0.13685 (14)	0.0229 (3)
C3	0.18501 (17)	0.58582 (13)	0.01414 (14)	0.0228 (3)
C4	0.25683 (17)	0.49443 (13)	−0.03602 (14)	0.0235 (3)
C5	0.15677 (19)	0.50003 (14)	0.37310 (15)	0.0286 (4)
H5A	0.1309	0.4366	0.4186	0.034*
H5B	0.0574	0.5178	0.3282	0.034*
C6	0.23520 (19)	0.61161 (15)	0.46084 (14)	0.0280 (4)
C7	0.1949 (2)	0.76039 (17)	0.62015 (16)	0.0393 (4)
H7A	0.3093	0.7632	0.6462	0.047*
H7B	0.1446	0.7576	0.6912	0.047*
C8	0.1611 (3)	0.86992 (19)	0.5706 (2)	0.0565 (6)
H8A	0.2169	0.8755	0.5038	0.085*
H8B	0.1958	0.9407	0.6337	0.085*
H8C	0.0482	0.8655	0.5418	0.085*
C9	0.35074 (19)	0.36463 (14)	0.31718 (15)	0.0288 (4)
H9A	0.3962	0.3830	0.4039	0.035*
H9B	0.4382	0.3660	0.2720	0.035*
C10	0.25992 (19)	0.24043 (15)	0.28739 (14)	0.0283 (4)
C11	0.2816 (2)	0.03549 (15)	0.28948 (19)	0.0412 (5)
H11A	0.2195	0.0077	0.2077	0.049*
H11B	0.2110	0.0310	0.3484	0.049*
C12	0.4098 (3)	−0.04000 (18)	0.3121 (2)	0.0542 (6)
H12A	0.4711	−0.0426	0.2476	0.081*
H12B	0.3646	−0.1213	0.3145	0.081*
H12C	0.4780	−0.0058	0.3892	0.081*
C13	0.11216 (18)	0.67470 (14)	0.20676 (14)	0.0267 (4)
C14	0.12630 (18)	0.68401 (14)	−0.04588 (15)	0.0259 (3)
H14A	0.0342	0.7095	−0.0130	0.031*
H14B	0.0917	0.6528	−0.1329	0.031*
C15	0.24808 (19)	0.79105 (14)	−0.02904 (15)	0.0296 (4)
C16	0.2838 (2)	0.99203 (15)	−0.05880 (18)	0.0405 (4)
H16A	0.3552	0.9758	−0.1167	0.049*
H16B	0.3476	1.0217	0.0221	0.049*
C17	0.1814 (3)	1.08232 (16)	−0.0940 (2)	0.0521 (5)
H17A	0.1150	1.0502	−0.1723	0.078*
H17B	0.2465	1.1554	−0.0991	0.078*
H17C	0.1153	1.1007	−0.0337	0.078*
C18	0.28794 (18)	0.46745 (14)	−0.15840 (14)	0.0266 (3)
C19	0.4050 (2)	0.33184 (17)	−0.28850 (16)	0.0366 (4)
H19A	0.4991	0.2900	−0.2763	0.044*
H19B	0.4333	0.4041	−0.3215	0.044*
C20	0.2789 (2)	0.25192 (19)	−0.37622 (17)	0.0476 (5)
H20A	0.2444	0.1836	−0.3411	0.071*
H20B	0.3188	0.2232	−0.4494	0.071*
H20C	0.1903	0.2963	−0.3960	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0266 (2)	0.0213 (2)	0.0279 (2)	0.00595 (16)	0.00553 (16)	0.00561 (16)
O1	0.0266 (7)	0.0562 (8)	0.0372 (7)	−0.0029 (6)	0.0085 (5)	−0.0044 (6)
O2	0.0307 (6)	0.0388 (7)	0.0320 (6)	0.0030 (5)	0.0120 (5)	0.0021 (5)
O3	0.0293 (7)	0.0361 (7)	0.0643 (9)	0.0020 (5)	0.0002 (6)	0.0109 (6)
O4	0.0317 (6)	0.0244 (6)	0.0502 (8)	0.0045 (5)	0.0049 (5)	0.0103 (5)
O5	0.0276 (8)	0.0481 (9)	0.1448 (17)	−0.0027 (6)	−0.0116 (9)	0.0490 (10)
O6	0.0312 (6)	0.0232 (6)	0.0541 (8)	0.0018 (5)	0.0003 (6)	0.0147 (6)
O7	0.0558 (8)	0.0403 (7)	0.0320 (7)	0.0150 (6)	0.0124 (6)	0.0146 (6)
O8	0.0345 (6)	0.0293 (6)	0.0288 (6)	0.0084 (5)	0.0102 (5)	0.0025 (5)
N1	0.0307 (7)	0.0260 (7)	0.0265 (7)	0.0073 (6)	0.0064 (6)	0.0083 (6)
N2	0.0509 (10)	0.0373 (9)	0.0375 (9)	0.0184 (8)	0.0120 (7)	0.0065 (7)
C1	0.0198 (7)	0.0220 (8)	0.0263 (8)	−0.0002 (6)	0.0031 (6)	0.0040 (6)
C2	0.0193 (7)	0.0206 (7)	0.0281 (8)	0.0021 (6)	0.0029 (6)	0.0041 (6)
C3	0.0183 (7)	0.0213 (8)	0.0276 (8)	0.0004 (6)	0.0010 (6)	0.0049 (6)
C4	0.0224 (8)	0.0217 (8)	0.0268 (8)	0.0018 (6)	0.0036 (6)	0.0068 (6)
C5	0.0287 (8)	0.0304 (9)	0.0293 (9)	0.0033 (7)	0.0090 (7)	0.0099 (7)
C6	0.0276 (9)	0.0350 (9)	0.0232 (8)	0.0052 (7)	0.0056 (7)	0.0086 (7)
C7	0.0392 (10)	0.0463 (11)	0.0288 (9)	0.0034 (9)	0.0085 (8)	−0.0052 (8)
C8	0.0747 (16)	0.0419 (12)	0.0488 (12)	−0.0013 (11)	0.0126 (11)	−0.0005 (10)
C9	0.0299 (9)	0.0282 (8)	0.0291 (8)	0.0053 (7)	0.0019 (7)	0.0100 (7)
C10	0.0315 (9)	0.0283 (8)	0.0262 (8)	0.0054 (7)	0.0042 (7)	0.0077 (7)
C11	0.0420 (11)	0.0231 (9)	0.0588 (12)	0.0010 (8)	0.0111 (9)	0.0082 (8)
C12	0.0517 (13)	0.0325 (10)	0.0855 (17)	0.0107 (9)	0.0222 (12)	0.0184 (11)
C13	0.0258 (8)	0.0273 (8)	0.0280 (8)	0.0045 (7)	0.0040 (7)	0.0080 (7)
C14	0.0234 (8)	0.0239 (8)	0.0301 (8)	0.0036 (6)	0.0018 (6)	0.0065 (7)
C15	0.0278 (9)	0.0263 (8)	0.0355 (9)	0.0040 (7)	0.0027 (7)	0.0107 (7)
C16	0.0424 (11)	0.0268 (9)	0.0509 (11)	−0.0050 (8)	0.0037 (9)	0.0138 (8)
C17	0.0664 (14)	0.0259 (10)	0.0666 (14)	0.0080 (9)	0.0100 (11)	0.0165 (10)
C18	0.0230 (8)	0.0266 (8)	0.0294 (9)	0.0006 (7)	0.0044 (6)	0.0042 (7)
C19	0.0370 (10)	0.0385 (10)	0.0352 (10)	0.0058 (8)	0.0166 (8)	−0.0009 (8)
C20	0.0513 (12)	0.0504 (12)	0.0365 (11)	−0.0060 (10)	0.0126 (9)	−0.0026 (9)

Geometric parameters (Å, º) top

S1—C1	1.7315 (16)	C7—H7B	0.9900
S1—C4	1.7411 (16)	C8—H8A	0.9800
O1—C6	1.199 (2)	C8—H8B	0.9800
O2—C6	1.328 (2)	C8—H8C	0.9800
O2—C7	1.463 (2)	C9—C10	1.516 (2)
O3—C10	1.195 (2)	C9—H9A	0.9900
O4—C10	1.329 (2)	C9—H9B	0.9900
O4—C11	1.464 (2)	C11—C12	1.491 (3)
O5—C15	1.189 (2)	C11—H11A	0.9900
O6—C15	1.324 (2)	C11—H11B	0.9900
O6—C16	1.451 (2)	C12—H12A	0.9800
O7—C18	1.209 (2)	C12—H12B	0.9800
O8—C18	1.341 (2)	C12—H12C	0.9800
O8—C19	1.455 (2)	C14—C15	1.507 (2)
N1—C1	1.360 (2)	C14—H14A	0.9900
N1—C9	1.450 (2)	C14—H14B	0.9900
N1—C5	1.453 (2)	C16—C17	1.490 (3)
N2—C13	1.148 (2)	C16—H16A	0.9900
C1—C2	1.394 (2)	C16—H16B	0.9900
C2—C13	1.427 (2)	C17—H17A	0.9800
C2—C3	1.431 (2)	C17—H17B	0.9800
C3—C4	1.363 (2)	C17—H17C	0.9800
C3—C14	1.497 (2)	C19—C20	1.485 (3)
C4—C18	1.462 (2)	C19—H19A	0.9900
C5—C6	1.516 (2)	C19—H19B	0.9900
C5—H5A	0.9900	C20—H20A	0.9800
C5—H5B	0.9900	C20—H20B	0.9800
C7—C8	1.491 (3)	C20—H20C	0.9800
C7—H7A	0.9900

C1—S1—C4	91.82 (8)	O4—C11—C12	106.88 (15)
C6—O2—C7	116.82 (13)	O4—C11—H11A	110.3
C10—O4—C11	116.01 (13)	C12—C11—H11A	110.3
C15—O6—C16	117.65 (13)	O4—C11—H11B	110.3
C18—O8—C19	117.34 (13)	C12—C11—H11B	110.3
C1—N1—C9	119.63 (13)	H11A—C11—H11B	108.6
C1—N1—C5	121.84 (13)	C11—C12—H12A	109.5
C9—N1—C5	118.02 (13)	C11—C12—H12B	109.5
N1—C1—C2	129.25 (14)	H12A—C12—H12B	109.5
N1—C1—S1	120.02 (12)	C11—C12—H12C	109.5
C2—C1—S1	110.73 (11)	H12A—C12—H12C	109.5
C1—C2—C13	126.27 (14)	H12B—C12—H12C	109.5
C1—C2—C3	112.98 (13)	N2—C13—C2	176.16 (17)
C13—C2—C3	120.61 (14)	C3—C14—C15	112.90 (13)
C4—C3—C2	112.37 (14)	C3—C14—H14A	109.0
C4—C3—C14	126.08 (15)	C15—C14—H14A	109.0
C2—C3—C14	121.50 (14)	C3—C14—H14B	109.0
C3—C4—C18	128.63 (14)	C15—C14—H14B	109.0
C3—C4—S1	112.09 (12)	H14A—C14—H14B	107.8
C18—C4—S1	119.28 (12)	O5—C15—O6	123.80 (16)
N1—C5—C6	112.84 (13)	O5—C15—C14	125.95 (15)
N1—C5—H5A	109.0	O6—C15—C14	110.25 (13)
C6—C5—H5A	109.0	O6—C16—C17	107.02 (15)
N1—C5—H5B	109.0	O6—C16—H16A	110.3
C6—C5—H5B	109.0	C17—C16—H16A	110.3
H5A—C5—H5B	107.8	O6—C16—H16B	110.3
O1—C6—O2	125.52 (16)	C17—C16—H16B	110.3
O1—C6—C5	124.44 (15)	H16A—C16—H16B	108.6
O2—C6—C5	110.03 (13)	C16—C17—H17A	109.5
O2—C7—C8	110.60 (15)	C16—C17—H17B	109.5
O2—C7—H7A	109.5	H17A—C17—H17B	109.5
C8—C7—H7A	109.5	C16—C17—H17C	109.5
O2—C7—H7B	109.5	H17A—C17—H17C	109.5
C8—C7—H7B	109.5	H17B—C17—H17C	109.5
H7A—C7—H7B	108.1	O7—C18—O8	124.47 (15)
C7—C8—H8A	109.5	O7—C18—C4	125.27 (15)
C7—C8—H8B	109.5	O8—C18—C4	110.27 (13)
H8A—C8—H8B	109.5	O8—C19—C20	111.83 (14)
C7—C8—H8C	109.5	O8—C19—H19A	109.3
H8A—C8—H8C	109.5	C20—C19—H19A	109.3
H8B—C8—H8C	109.5	O8—C19—H19B	109.3
N1—C9—C10	112.53 (13)	C20—C19—H19B	109.3
N1—C9—H9A	109.1	H19A—C19—H19B	107.9
C10—C9—H9A	109.1	C19—C20—H20A	109.5
N1—C9—H9B	109.1	C19—C20—H20B	109.5
C10—C9—H9B	109.1	H20A—C20—H20B	109.5
H9A—C9—H9B	107.8	C19—C20—H20C	109.5
O3—C10—O4	124.90 (15)	H20A—C20—H20C	109.5
O3—C10—C9	124.59 (15)	H20B—C20—H20C	109.5
O4—C10—C9	110.48 (14)

C9—N1—C1—C2	−169.92 (15)	N1—C5—C6—O1	−5.9 (2)
C5—N1—C1—C2	18.4 (2)	N1—C5—C6—O2	175.08 (13)
C9—N1—C1—S1	10.01 (19)	C6—O2—C7—C8	91.25 (19)
C5—N1—C1—S1	−161.66 (11)	C1—N1—C9—C10	−90.94 (17)
C4—S1—C1—N1	179.74 (13)	C5—N1—C9—C10	81.04 (17)
C4—S1—C1—C2	−0.32 (12)	C11—O4—C10—O3	−5.0 (2)
N1—C1—C2—C13	4.3 (3)	C11—O4—C10—C9	173.18 (14)
S1—C1—C2—C13	−175.65 (13)	N1—C9—C10—O3	−9.2 (2)
N1—C1—C2—C3	180.00 (15)	N1—C9—C10—O4	172.61 (13)
S1—C1—C2—C3	0.06 (16)	C10—O4—C11—C12	−178.55 (16)
C1—C2—C3—C4	0.33 (19)	C4—C3—C14—C15	−89.64 (19)
C13—C2—C3—C4	176.31 (14)	C2—C3—C14—C15	87.81 (18)
C1—C2—C3—C14	−177.44 (13)	C16—O6—C15—O5	4.9 (3)
C13—C2—C3—C14	−1.5 (2)	C16—O6—C15—C14	−174.41 (15)
C2—C3—C4—C18	179.72 (15)	C3—C14—C15—O5	15.1 (3)
C14—C3—C4—C18	−2.6 (3)	C3—C14—C15—O6	−165.65 (14)
C2—C3—C4—S1	−0.57 (17)	C15—O6—C16—C17	−179.49 (16)
C14—C3—C4—S1	177.08 (12)	C19—O8—C18—O7	3.9 (2)
C1—S1—C4—C3	0.52 (12)	C19—O8—C18—C4	−176.36 (13)
C1—S1—C4—C18	−179.74 (13)	C3—C4—C18—O7	1.5 (3)
C1—N1—C5—C6	−94.22 (17)	S1—C4—C18—O7	−178.17 (13)
C9—N1—C5—C6	93.98 (16)	C3—C4—C18—O8	−178.22 (15)
C7—O2—C6—O1	0.6 (2)	S1—C4—C18—O8	2.09 (18)
C7—O2—C6—C5	179.60 (13)	C18—O8—C19—C20	−89.94 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O3ⁱ	0.99	2.50	3.295 (2)	137

Symmetry code: (i) −x, −y+1, −z+1.

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The ethyl tetra­ester of ranelic acid

Supporting information

Key indicators

checkCIF/PLATON results

The ethyl tetraester of ranelic acid