Methyl 5-[N,N-bis-(methoxy-carbonyl-meth-yl)amino]-4-cyano-2-methoxy-carbonyl-3-thio-phene-ethan-o-ate.

In the title compound, C(16)H(18)N(2)O(8)S, derived from ranelic acid, there is a highly substituted thio-phene ring. The crystal structure involves inter-molecular C-H⋯O and C-H⋯S hydrogen bonds.

Related literature

For related literature, see: Bonnelye et al. (2008 ▶); Fonseca (2008 ▶).

Experimental

Crystal data

C16H18N2O8S

M = 398.38

Triclinic,

a = 9.7164 (19) Å

b = 9.790 (2) Å

c = 10.170 (2) Å

α = 98.05 (3)°

β = 96.71 (3)°

γ = 95.81 (3)°

V = 944.5 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.22 mm−1

T = 293 (2) K

0.25 × 0.20 × 0.18 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.942, T max = 0.988

9976 measured reflections

4313 independent reflections

3561 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.130

S = 1.03

4313 reflections

246 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.38 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick,2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808028699/sg2258sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028699/sg2258Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H18N2O8S	Z = 2
Mr = 398.38	F(000) = 416
Triclinic, P1	Dx = 1.401 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7164 (19) Å	Cell parameters from 6733 reflections
b = 9.790 (2) Å	θ = 3.3–27.3°
c = 10.170 (2) Å	µ = 0.22 mm−1
α = 98.05 (3)°	T = 293 K
β = 96.71 (3)°	Prism, colorless
γ = 95.81 (3)°	0.25 × 0.20 × 0.18 mm
V = 944.5 (3) Å3

Rigaku SCXmini diffractometer	4313 independent reflections
Radiation source: fine-focus sealed tube	3561 reflections with I > 2σ(I)
graphite	Rint = 0.027
Detector resolution: 8.192 pixels mm-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
Tmin = 0.942, Tmax = 0.988	l = −13→13
9976 measured reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.062P)2 + 0.411P] where P = (Fo2 + 2Fc2)/3
4313 reflections	(Δ/σ)max < 0.001
246 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.0925 (5)	0.8277 (4)	0.4871 (3)	0.0967 (13)
H1A	0.165 (3)	0.894 (3)	0.4933 (6)	0.145*
H1B	0.116 (3)	0.7635 (17)	0.5387 (14)	0.145*
H1C	0.018 (2)	0.866 (3)	0.5154 (12)	0.145*
C2	0.0887 (2)	0.8372 (2)	0.2560 (2)	0.0414 (5)
C3	0.03705 (19)	0.7542 (2)	0.11943 (19)	0.0374 (4)
H3A	0.0661	0.6620	0.1164	0.045*
H3B	−0.0642	0.7441	0.1059	0.045*
C4	−0.01502 (19)	0.8243 (2)	−0.1025 (2)	0.0366 (4)
H4A	0.0231	0.8874	−0.1582	0.044*
H4B	−0.0962	0.8606	−0.0702	0.044*
C5	−0.0589 (2)	0.6829 (2)	−0.1857 (2)	0.0427 (5)
C6	−0.2176 (5)	0.5578 (4)	−0.3673 (4)	0.1086 (14)
H6A	−0.2891	0.5740	−0.4348	0.163*
H6B	−0.2567	0.4957	−0.3126	0.163*
H6C	−0.1448	0.5171	−0.4094	0.163*
C7	0.22416 (18)	0.80692 (18)	−0.00849 (18)	0.0312 (4)
C8	0.30195 (18)	0.86329 (19)	−0.09923 (18)	0.0321 (4)
C9	0.2567 (2)	0.9617 (2)	−0.18082 (19)	0.0369 (4)
C10	0.43987 (18)	0.82416 (19)	−0.09451 (18)	0.0335 (4)
C11	0.5374 (2)	0.8694 (2)	−0.18941 (19)	0.0404 (4)
H11A	0.5404	0.9690	−0.1876	0.048*
H11B	0.6307	0.8498	−0.1592	0.048*
C12	0.4935 (2)	0.7974 (2)	−0.3310 (2)	0.0446 (5)
C13	0.5241 (4)	0.8027 (4)	−0.5571 (3)	0.0940 (11)
H13A	0.5736	0.8606	−0.6092	0.141*
H13B	0.4257	0.7956	−0.5864	0.141*
H13C	0.5541	0.7119	−0.5686	0.141*
C14	0.46807 (18)	0.7442 (2)	0.00257 (18)	0.0335 (4)
C15	0.59750 (19)	0.6869 (2)	0.04245 (19)	0.0360 (4)
C16	0.7100 (2)	0.5700 (2)	0.2060 (2)	0.0501 (5)
H16A	0.6891	0.5245	0.2802	0.075*
H16B	0.7815	0.6466	0.2366	0.075*
H16C	0.7418	0.5053	0.1396	0.075*
O1	0.0564 (2)	0.76176 (18)	0.34904 (16)	0.0637 (5)
O2	0.1471 (2)	0.95261 (18)	0.27677 (18)	0.0673 (5)
O3	−0.0096 (2)	0.57999 (18)	−0.1647 (2)	0.0719 (6)
O4	−0.15997 (19)	0.68911 (18)	−0.28405 (17)	0.0626 (5)
O5	0.4141 (3)	0.6943 (2)	−0.3638 (2)	0.1020 (9)
O6	0.5525 (2)	0.8633 (2)	−0.41698 (17)	0.0695 (5)
O7	0.70142 (14)	0.69773 (18)	−0.01103 (16)	0.0520 (4)
O8	0.58547 (14)	0.62078 (16)	0.14789 (15)	0.0438 (3)
N1	0.08891 (15)	0.81812 (17)	0.01103 (16)	0.0346 (3)
N2	0.2253 (2)	1.0438 (2)	−0.2444 (2)	0.0535 (5)
S	0.32536 (5)	0.71175 (5)	0.08736 (5)	0.03457 (14)

	U11	U22	U33	U12	U13	U23
C1	0.151 (4)	0.103 (3)	0.0364 (14)	0.029 (2)	0.0078 (17)	0.0058 (15)
C2	0.0371 (10)	0.0491 (12)	0.0399 (11)	0.0130 (9)	0.0055 (8)	0.0071 (9)
C3	0.0266 (9)	0.0471 (11)	0.0394 (10)	0.0020 (7)	0.0078 (7)	0.0087 (8)
C4	0.0280 (9)	0.0392 (10)	0.0447 (11)	0.0078 (7)	0.0016 (8)	0.0136 (8)
C5	0.0412 (11)	0.0444 (11)	0.0418 (11)	0.0083 (9)	−0.0004 (8)	0.0071 (9)
C6	0.132 (3)	0.080 (2)	0.088 (2)	0.010 (2)	−0.054 (2)	−0.0192 (19)
C7	0.0275 (8)	0.0346 (9)	0.0308 (9)	0.0026 (7)	0.0019 (7)	0.0052 (7)
C8	0.0301 (9)	0.0364 (9)	0.0297 (9)	0.0015 (7)	0.0031 (7)	0.0069 (7)
C9	0.0335 (9)	0.0429 (10)	0.0348 (10)	0.0016 (8)	0.0064 (7)	0.0084 (8)
C10	0.0292 (9)	0.0388 (10)	0.0312 (9)	−0.0010 (7)	0.0047 (7)	0.0039 (8)
C11	0.0329 (10)	0.0530 (12)	0.0366 (10)	−0.0014 (8)	0.0081 (8)	0.0128 (9)
C12	0.0494 (12)	0.0491 (12)	0.0391 (11)	0.0046 (10)	0.0171 (9)	0.0112 (9)
C13	0.137 (3)	0.106 (3)	0.0417 (15)	−0.002 (2)	0.0369 (17)	0.0125 (16)
C14	0.0259 (8)	0.0432 (10)	0.0318 (9)	0.0027 (7)	0.0055 (7)	0.0068 (8)
C15	0.0280 (9)	0.0429 (10)	0.0358 (10)	0.0015 (7)	0.0030 (7)	0.0045 (8)
C16	0.0396 (11)	0.0547 (13)	0.0573 (13)	0.0102 (9)	−0.0046 (10)	0.0188 (11)
O1	0.0920 (13)	0.0632 (11)	0.0376 (8)	0.0077 (9)	0.0124 (8)	0.0119 (8)
O2	0.0858 (13)	0.0538 (10)	0.0547 (10)	−0.0060 (9)	−0.0015 (9)	0.0011 (8)
O3	0.0808 (13)	0.0454 (9)	0.0806 (13)	0.0218 (9)	−0.0235 (10)	−0.0024 (9)
O4	0.0680 (11)	0.0608 (10)	0.0513 (10)	0.0112 (8)	−0.0206 (8)	0.0029 (8)
O5	0.161 (2)	0.0805 (14)	0.0505 (11)	−0.0555 (15)	0.0369 (13)	−0.0065 (10)
O6	0.0858 (13)	0.0810 (12)	0.0413 (9)	−0.0148 (10)	0.0204 (9)	0.0163 (9)
O7	0.0305 (7)	0.0792 (11)	0.0519 (9)	0.0127 (7)	0.0118 (6)	0.0202 (8)
O8	0.0322 (7)	0.0563 (9)	0.0478 (8)	0.0104 (6)	0.0060 (6)	0.0207 (7)
N1	0.0255 (7)	0.0430 (9)	0.0366 (8)	0.0047 (6)	0.0049 (6)	0.0094 (7)
N2	0.0579 (12)	0.0532 (11)	0.0536 (11)	0.0069 (9)	0.0061 (9)	0.0237 (9)
S	0.0279 (2)	0.0437 (3)	0.0358 (3)	0.00654 (18)	0.00741 (17)	0.0147 (2)

C1—O1	1.448 (3)	C8—C9	1.427 (3)
C1—H1A	0.9033	C8—C10	1.428 (3)
C1—H1B	0.9033	C9—N2	1.143 (3)
C1—H1C	0.9033	C10—C14	1.363 (3)
C2—O2	1.191 (3)	C10—C11	1.508 (3)
C2—O1	1.325 (3)	C11—C12	1.504 (3)
C2—C3	1.510 (3)	C11—H11A	0.9700
C3—N1	1.456 (2)	C11—H11B	0.9700
C3—H3A	0.9700	C12—O5	1.189 (3)
C3—H3B	0.9700	C12—O6	1.308 (3)
C4—N1	1.455 (2)	C13—O6	1.448 (3)
C4—C5	1.511 (3)	C13—H13A	0.9600
C4—H4A	0.9700	C13—H13B	0.9600
C4—H4B	0.9700	C13—H13C	0.9600
C5—O3	1.193 (3)	C14—C15	1.466 (3)
C5—O4	1.330 (2)	C14—S	1.7420 (18)
C6—O4	1.457 (3)	C15—O7	1.204 (2)
C6—H6A	0.9600	C15—O8	1.338 (2)
C6—H6B	0.9600	C16—O8	1.448 (2)
C6—H6C	0.9600	C16—H16A	0.9600
C7—N1	1.365 (2)	C16—H16B	0.9600
C7—C8	1.396 (2)	C16—H16C	0.9600
C7—S	1.7323 (19)
O1—C1—H1A	109.5	C14—C10—C11	126.48 (17)
O1—C1—H1B	109.5	C8—C10—C11	121.39 (17)
H1A—C1—H1B	109.5	C12—C11—C10	112.45 (16)
O1—C1—H1C	109.5	C12—C11—H11A	109.1
H1A—C1—H1C	109.5	C10—C11—H11A	109.1
H1B—C1—H1C	109.5	C12—C11—H11B	109.1
O2—C2—O1	125.5 (2)	C10—C11—H11B	109.1
O2—C2—C3	125.5 (2)	H11A—C11—H11B	107.8
O1—C2—C3	108.99 (18)	O5—C12—O6	122.9 (2)
N1—C3—C2	112.93 (16)	O5—C12—C11	125.5 (2)
N1—C3—H3A	109.0	O6—C12—C11	111.64 (19)
C2—C3—H3A	109.0	O6—C13—H13A	109.5
N1—C3—H3B	109.0	O6—C13—H13B	109.5
C2—C3—H3B	109.0	H13A—C13—H13B	109.5
H3A—C3—H3B	107.8	O6—C13—H13C	109.5
N1—C4—C5	111.64 (16)	H13A—C13—H13C	109.5
N1—C4—H4A	109.3	H13B—C13—H13C	109.5
C5—C4—H4A	109.3	C10—C14—C15	129.21 (17)
N1—C4—H4B	109.3	C10—C14—S	112.01 (14)
C5—C4—H4B	109.3	C15—C14—S	118.78 (14)
H4A—C4—H4B	108.0	O7—C15—O8	124.03 (18)
O3—C5—O4	125.0 (2)	O7—C15—C14	125.19 (18)
O3—C5—C4	124.21 (19)	O8—C15—C14	110.78 (16)
O4—C5—C4	110.76 (17)	O8—C16—H16A	109.5
O4—C6—H6A	109.5	O8—C16—H16B	109.5
O4—C6—H6B	109.5	H16A—C16—H16B	109.5
H6A—C6—H6B	109.5	O8—C16—H16C	109.5
O4—C6—H6C	109.5	H16A—C16—H16C	109.5
H6A—C6—H6C	109.5	H16B—C16—H16C	109.5
H6B—C6—H6C	109.5	C2—O1—C1	116.7 (2)
N1—C7—C8	129.48 (17)	C5—O4—C6	116.3 (2)
N1—C7—S	120.44 (14)	C12—O6—C13	117.7 (2)
C8—C7—S	110.07 (13)	C15—O8—C16	116.74 (16)
C7—C8—C9	124.59 (17)	C7—N1—C4	119.77 (16)
C7—C8—C10	113.62 (16)	C7—N1—C3	117.45 (15)
C9—C8—C10	121.51 (16)	C4—N1—C3	115.49 (15)
N2—C9—C8	177.3 (2)	C7—S—C14	92.11 (9)
C14—C10—C8	112.12 (16)
O2—C2—C3—N1	11.3 (3)	S—C14—C15—O7	177.27 (17)
O1—C2—C3—N1	−169.76 (17)	C10—C14—C15—O8	176.21 (19)
N1—C4—C5—O3	−3.4 (3)	S—C14—C15—O8	−3.1 (2)
N1—C4—C5—O4	176.17 (17)	O2—C2—O1—C1	1.7 (4)
N1—C7—C8—C9	8.5 (3)	C3—C2—O1—C1	−177.2 (2)
S—C7—C8—C9	−171.41 (15)	O3—C5—O4—C6	3.0 (4)
N1—C7—C8—C10	−177.50 (17)	C4—C5—O4—C6	−176.6 (3)
S—C7—C8—C10	2.6 (2)	O5—C12—O6—C13	−3.2 (4)
C7—C8—C9—N2	129 (5)	C11—C12—O6—C13	177.7 (2)
C10—C8—C9—N2	−45 (5)	O7—C15—O8—C16	5.2 (3)
C7—C8—C10—C14	−2.7 (2)	C14—C15—O8—C16	−174.41 (17)
C9—C8—C10—C14	171.57 (17)	C8—C7—N1—C4	34.7 (3)
C7—C8—C10—C11	177.14 (16)	S—C7—N1—C4	−145.47 (15)
C9—C8—C10—C11	−8.6 (3)	C8—C7—N1—C3	−176.48 (18)
C14—C10—C11—C12	109.2 (2)	S—C7—N1—C3	3.4 (2)
C8—C10—C11—C12	−70.6 (2)	C5—C4—N1—C7	76.6 (2)
C10—C11—C12—O5	−17.2 (4)	C5—C4—N1—C3	−72.8 (2)
C10—C11—C12—O6	161.94 (19)	C2—C3—N1—C7	76.1 (2)
C8—C10—C14—C15	−177.92 (18)	C2—C3—N1—C4	−133.71 (17)
C11—C10—C14—C15	2.3 (3)	N1—C7—S—C14	178.60 (15)
C8—C10—C14—S	1.4 (2)	C8—C7—S—C14	−1.50 (14)
C11—C10—C14—S	−178.35 (15)	C10—C14—S—C7	0.03 (15)
C10—C14—C15—O7	−3.4 (3)	C15—C14—S—C7	179.46 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O3i	0.97	2.51	3.355 (3)	146.
C16—H16A···O5ii	0.96	2.57	3.421 (3)	148.
C16—H16C···Sii	0.96	2.87	3.727 (3)	149.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O3i	0.97	2.51	3.355 (3)	146
C16—H16A⋯O5ii	0.96	2.57	3.421 (3)	148
C16—H16C⋯Sii	0.96	2.87	3.727 (3)	149

Symmetry codes: (i) ; (ii) .