18-Iso­propyl-15-(4-nitro­phenyl)-5,8,11-trioxa-2,14-di­thia­bi­cyclo­[14.4.1]­henicosa-1(20),16,18-trien-21-one

In the title 7-17 fused ring compound, C₂₅H₃₁NO₆S₂, the tropone ring is deformed to be a flattened boat conformation, with dihedral angles of 7.7 (3) and 16.9 (5)°. The best plane of the tropone ring intersects the crown S₂O₃ plane at an angle of 58.5 (1)°.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.055
• wR factor = 0.167
• Data-to-parameter ratio = 16.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

---

S1. Comment

Mercurophilic dithiocrown derivatives having a troponoid pendant (Mori et al., 1996, 1997; Kubo et al., 1998) were recently prepared since these molecules are excellent carriers of the mercury(II) ion. Particularly noteworthy is, based on their reversible complexation behaviors with mercury(II) salts, the exclusive and selective transport of the mercury(II) ion among various metal ions through a liquid membrane.

As a matter of efficiency in the transport of the mercury(II) ion, the dithiocrown derivatives condensed with a tropone system showed a dependence on the cavity size of the crown ethers (Mori et al., 1996). This was confirmed by the X-ray analyses (Kubo et al., 1995, 1996, 2000a,b; Kato et al., 1995; Mori et al., 1998). In order to reveal the detailed structure of troponoid dithiocrown ether derivatives, the title compound, (I), has been investigated by X-ray analysis.

In (I), the tropone ring (O1 and C1—C7) makes angles of 58.5 (1), 59.6 (1) and 60.0 (2)° with the crown ether ring (defined by S1—S2 and O2—O4), the benzene ring (C20—C25), and the isopropyl group (C8—C10), respectively. The conformation of the ethereal moiety is: C11(g)S1(g)C12(g)C13(t)O2(g)C14(g)C15(t)O3(t)C16(g)C17(t)O4(t)C18(g)C19(t)S2, where t and g denote trans and gauche forms, respectively.

The tropone ring adopts an flattened boat conformation. The angle between the least-squares plane defined by C2/C3/C6/C7 and the plane defined by C3/C4/C5/C6 is 7.7 (3)°. The flattened boat form of the tropone ring was also observed in related compounds. In (I), the angle between the C1/C2/C7 and C2/C3/C6/C7 planes is 16.9 (5)°, which is smaller than that [20.8 (4)°] of 5,8,11-trioxa-2,14-dithiabicyclo[13.4.1]icosa-1(19),15,17-trien-20-one (Kubo et al., 2000a) and that [33.8 (6)°] of 5-oxa-2,8-dithiabicyclo[7.4.1]tetradeca-9,11,13-trien-14-one (Mori et al., 1998). This result suggests that the smaller size of the crown ethers let the deformation of the tropone ring increased.

S2. Experimental

The title compound, (I), was obtained by condensation from NaH-mediated 3,6,9-trioxa-1,11-undecanedithiol and 4-isopropyl-2-(α-tosyloxy-4-nitrobenzyl)tropone (Mori et al., 1992). Single crystals of (I) were obtained by recrystallization from CHCl₃.

S3. Refinement

All H atoms were located at ideal positions and restrained with U_iso held fixed to 1.2 times or 1.5 times (H₂O) U_eq of the parent atoms.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal_GX (Hall & du Boulay, 1995); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids.

(1)

Crystal data

C25H31NO6S2	F(000) = 1072
Mr = 505.63	Dx = 1.348 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.663 (1) Å	Cell parameters from 20 reflections
b = 18.862 (2) Å	θ = 10.1–18.0°
c = 11.363 (1) Å	µ = 0.26 mm^−1
β = 94.882 (6)°	T = 296 K
V = 2490.6 (3) Å^3	Prism, yellow
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection

Enraf-Nonius FR590 diffractometer	2259 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 26.3°, θmin = 2.6°
ω–2θ scans	h = −14→14
Absorption correction: ψ scan (North et al., 1968)	k = 0→23
Tmin = 0.982, Tmax = 1.000	l = 0→14
5321 measured reflections	3 standard reflections every 120 min
5059 independent reflections	intensity decay: 0.6%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.167	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0606P)^2 + 0.8224P] where P = (Fo^2 + 2Fc^2)/3
5059 reflections	(Δ/σ)max < 0.001
307 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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
S1	0.81595 (9)	−0.01427 (6)	0.56115 (10)	0.0506 (3)
S2	0.46212 (9)	0.22020 (6)	0.32535 (11)	0.0579 (3)
O1	0.6073 (2)	0.17902 (16)	0.5094 (3)	0.0653 (9)
O2	0.6767 (3)	−0.08465 (17)	0.3318 (3)	0.0685 (9)
O3	0.4360 (4)	−0.0311 (2)	0.2020 (3)	0.1099 (14)
O4	0.3702 (3)	0.11006 (19)	0.1300 (3)	0.0876 (11)
O5	1.0530 (3)	0.2891 (2)	0.9126 (4)	0.1081 (14)
O6	1.1901 (3)	0.2278 (2)	0.8541 (3)	0.1036 (14)
N1	1.0883 (4)	0.2428 (2)	0.8531 (3)	0.0656 (11)
C1	0.6497 (3)	0.1583 (2)	0.4195 (4)	0.0456 (10)
C2	0.7467 (3)	0.10843 (19)	0.4312 (3)	0.0408 (9)
C3	0.8217 (3)	0.0921 (2)	0.3509 (4)	0.0486 (10)
H3	0.8797	0.0613	0.3797	0.058*
C4	0.8300 (3)	0.1124 (2)	0.2318 (4)	0.0482 (10)
C5	0.7444 (4)	0.1476 (2)	0.1657 (4)	0.0561 (12)
H5	0.7591	0.1557	0.0877	0.067*
C6	0.6376 (4)	0.1735 (2)	0.1966 (4)	0.0562 (12)
H6	0.5888	0.1894	0.1331	0.067*
C7	0.5938 (3)	0.1792 (2)	0.3032 (4)	0.0452 (10)
C8	0.9397 (4)	0.0905 (2)	0.1787 (4)	0.0593 (12)
H8	1.0019	0.0978	0.2412	0.071*
C9	0.9719 (4)	0.1331 (3)	0.0762 (4)	0.0781 (16)
H9A	1.0433	0.1158	0.0510	0.117*
H9B	0.9805	0.1819	0.0989	0.117*
H9C	0.9128	0.1289	0.0124	0.117*
C10	0.9374 (4)	0.0110 (2)	0.1542 (4)	0.0735 (14)
H10A	0.9181	−0.0139	0.2234	0.110*
H10B	1.0118	−0.0041	0.1337	0.110*
H10C	0.8809	0.0010	0.0899	0.110*
C11	0.7674 (3)	0.07791 (19)	0.5566 (3)	0.0418 (9)
H11	0.6939	0.0796	0.5924	0.050*
C12	0.6801 (4)	−0.0610 (2)	0.5373 (4)	0.0629 (13)
H12A	0.6947	−0.1111	0.5499	0.076*
H12B	0.6309	−0.0455	0.5970	0.076*
C13	0.6148 (4)	−0.0520 (2)	0.4183 (4)	0.0626 (13)
H13A	0.5393	−0.0735	0.4186	0.075*
H13B	0.6048	−0.0020	0.4005	0.075*
C14	0.6350 (5)	−0.0687 (3)	0.2141 (4)	0.0869 (17)
H14A	0.6825	−0.0934	0.1613	0.104*
H14B	0.6448	−0.0183	0.2014	0.104*
C15	0.5119 (5)	−0.0872 (3)	0.1798 (5)	0.0970 (19)
H15A	0.5029	−0.0989	0.0964	0.116*
H15B	0.4914	−0.1288	0.2237	0.116*
C16	0.3625 (5)	−0.0142 (3)	0.1077 (5)	0.0846 (16)
H16A	0.3088	−0.0530	0.0920	0.101*
H16B	0.4057	−0.0086	0.0391	0.101*
C17	0.2976 (4)	0.0509 (3)	0.1246 (5)	0.0799 (15)
H17A	0.2386	0.0566	0.0597	0.096*
H17B	0.2598	0.0475	0.1972	0.096*
C18	0.3107 (4)	0.1729 (3)	0.1419 (5)	0.0912 (18)
H18A	0.2554	0.1667	0.2001	0.109*
H18B	0.2685	0.1846	0.0671	0.109*
C19	0.3905 (4)	0.2333 (2)	0.1792 (4)	0.0663 (13)
H19A	0.3468	0.2771	0.1782	0.080*
H19B	0.4480	0.2380	0.1228	0.080*
C20	0.8527 (3)	0.1218 (2)	0.6332 (3)	0.0425 (10)
C21	0.9691 (3)	0.1202 (2)	0.6194 (4)	0.0502 (11)
H21	0.9961	0.0922	0.5603	0.060*
C22	1.0461 (4)	0.1593 (2)	0.6917 (4)	0.0549 (11)
H22	1.1245	0.1569	0.6826	0.066*
C23	1.0067 (4)	0.2015 (2)	0.7762 (4)	0.0484 (10)
C24	0.8917 (4)	0.2062 (2)	0.7908 (4)	0.0550 (11)
H24	0.8656	0.2362	0.8478	0.066*
C25	0.8148 (4)	0.1660 (2)	0.7196 (4)	0.0528 (11)
H25	0.7366	0.1685	0.7297	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0535 (6)	0.0444 (6)	0.0535 (7)	0.0040 (5)	0.0024 (5)	0.0071 (6)
S2	0.0490 (7)	0.0513 (7)	0.0724 (8)	0.0109 (5)	−0.0010 (6)	0.0080 (6)
O1	0.068 (2)	0.077 (2)	0.052 (2)	0.0287 (17)	0.0085 (16)	−0.0043 (17)
O2	0.067 (2)	0.078 (2)	0.059 (2)	0.0078 (17)	−0.0008 (17)	−0.0060 (18)
O3	0.143 (3)	0.095 (3)	0.080 (3)	0.056 (3)	−0.055 (2)	−0.032 (2)
O4	0.070 (2)	0.065 (2)	0.126 (3)	0.010 (2)	−0.003 (2)	−0.012 (2)
O5	0.112 (3)	0.103 (3)	0.105 (3)	0.000 (3)	−0.012 (2)	−0.057 (3)
O6	0.065 (2)	0.142 (4)	0.102 (3)	−0.021 (2)	−0.006 (2)	−0.033 (3)
N1	0.078 (3)	0.065 (3)	0.051 (2)	−0.015 (2)	−0.009 (2)	−0.010 (2)
C1	0.043 (2)	0.041 (2)	0.052 (3)	−0.0034 (19)	−0.001 (2)	−0.007 (2)
C2	0.039 (2)	0.036 (2)	0.047 (2)	0.0004 (18)	−0.0003 (19)	0.0020 (19)
C3	0.048 (2)	0.047 (3)	0.051 (3)	0.003 (2)	0.009 (2)	0.003 (2)
C4	0.055 (3)	0.047 (3)	0.044 (3)	0.004 (2)	0.008 (2)	0.005 (2)
C5	0.063 (3)	0.067 (3)	0.039 (2)	−0.002 (2)	0.011 (2)	0.003 (2)
C6	0.056 (3)	0.060 (3)	0.051 (3)	0.002 (2)	−0.003 (2)	0.016 (2)
C7	0.037 (2)	0.040 (2)	0.057 (3)	0.0014 (18)	−0.005 (2)	0.008 (2)
C8	0.064 (3)	0.066 (3)	0.049 (3)	0.012 (2)	0.011 (2)	0.005 (2)
C9	0.081 (4)	0.072 (4)	0.085 (4)	0.000 (3)	0.031 (3)	0.008 (3)
C10	0.086 (4)	0.062 (3)	0.075 (3)	0.016 (3)	0.020 (3)	−0.003 (3)
C11	0.045 (2)	0.037 (2)	0.044 (2)	0.0070 (18)	0.0069 (18)	0.0063 (19)
C12	0.068 (3)	0.055 (3)	0.067 (3)	−0.011 (2)	0.015 (3)	0.006 (2)
C13	0.057 (3)	0.061 (3)	0.071 (3)	−0.005 (2)	0.008 (3)	−0.005 (3)
C14	0.103 (4)	0.092 (4)	0.064 (4)	−0.009 (3)	−0.005 (3)	0.000 (3)
C15	0.104 (5)	0.079 (4)	0.100 (5)	0.019 (4)	−0.037 (4)	−0.031 (3)
C16	0.097 (4)	0.075 (4)	0.077 (4)	0.002 (3)	−0.021 (3)	−0.003 (3)
C17	0.079 (4)	0.081 (4)	0.076 (4)	0.003 (3)	−0.016 (3)	0.004 (3)
C18	0.074 (4)	0.085 (4)	0.109 (5)	0.012 (3)	−0.024 (3)	−0.007 (4)
C19	0.057 (3)	0.059 (3)	0.080 (3)	0.015 (2)	−0.013 (2)	0.017 (3)
C20	0.051 (2)	0.040 (2)	0.037 (2)	0.0063 (19)	0.0042 (19)	0.005 (2)
C21	0.050 (3)	0.051 (3)	0.050 (3)	0.004 (2)	0.010 (2)	0.001 (2)
C22	0.043 (2)	0.066 (3)	0.055 (3)	−0.005 (2)	0.003 (2)	0.002 (2)
C23	0.059 (3)	0.043 (2)	0.042 (3)	0.001 (2)	0.001 (2)	0.003 (2)
C24	0.063 (3)	0.059 (3)	0.043 (3)	0.009 (2)	0.003 (2)	−0.008 (2)
C25	0.046 (2)	0.060 (3)	0.052 (3)	0.007 (2)	0.003 (2)	0.002 (2)

Geometric parameters (Å, º)

S1—C12	1.813 (4)	C3—C4	1.417 (5)
S1—C11	1.828 (4)	C4—C5	1.369 (6)
S2—C7	1.756 (4)	C4—C8	1.517 (5)
S2—C19	1.811 (4)	C5—C6	1.410 (6)
O1—C1	1.236 (4)	C6—C7	1.359 (6)
O2—C13	1.409 (5)	C8—C9	1.489 (6)
O2—C14	1.417 (5)	C8—C10	1.525 (6)
O3—C16	1.352 (5)	C11—C20	1.512 (5)
O3—C15	1.416 (6)	C12—C13	1.504 (6)
O4—C18	1.386 (6)	C14—C15	1.497 (7)
O4—C17	1.399 (6)	C16—C17	1.464 (7)
O5—N1	1.198 (5)	C18—C19	1.509 (7)
O6—N1	1.219 (5)	C20—C21	1.379 (5)
N1—C23	1.462 (5)	C20—C25	1.389 (5)
C1—C2	1.469 (5)	C21—C22	1.379 (6)
C1—C7	1.476 (5)	C22—C23	1.356 (6)
C2—C3	1.352 (5)	C23—C24	1.368 (6)
C2—C11	1.537 (5)	C24—C25	1.383 (6)
C12—S1—C11	101.1 (2)	C9—C8—C10	112.8 (4)
C7—S2—C19	105.6 (2)	C4—C8—C10	109.7 (4)
C13—O2—C14	114.2 (4)	C20—C11—C2	111.8 (3)
C16—O3—C15	113.5 (4)	C20—C11—S1	108.5 (3)
C18—O4—C17	112.3 (4)	C2—C11—S1	114.0 (3)
O5—N1—O6	123.0 (4)	C13—C12—S1	116.7 (3)
O5—N1—C23	119.3 (4)	O2—C13—C12	109.1 (4)
O6—N1—C23	117.7 (4)	O2—C14—C15	116.1 (5)
O1—C1—C2	119.1 (4)	O3—C15—C14	112.3 (5)
O1—C1—C7	118.6 (4)	O3—C16—C17	113.2 (4)
C2—C1—C7	122.0 (4)	O4—C17—C16	110.9 (5)
C3—C2—C1	128.5 (4)	O4—C18—C19	111.8 (4)
C3—C2—C11	118.8 (3)	C18—C19—S2	112.3 (3)
C1—C2—C11	112.5 (3)	C21—C20—C25	118.0 (4)
C2—C3—C4	133.1 (4)	C21—C20—C11	121.9 (4)
C5—C4—C3	123.3 (4)	C25—C20—C11	120.1 (4)
C5—C4—C8	120.9 (4)	C22—C21—C20	121.2 (4)
C3—C4—C8	115.8 (4)	C23—C22—C21	119.5 (4)
C4—C5—C6	130.6 (4)	C22—C23—C24	121.3 (4)
C7—C6—C5	131.0 (4)	C22—C23—N1	119.5 (4)
C6—C7—C1	127.3 (4)	C24—C23—N1	119.2 (4)
C6—C7—S2	124.2 (3)	C23—C24—C25	119.1 (4)
C1—C7—S2	108.3 (3)	C24—C25—C20	120.9 (4)
C9—C8—C4	116.3 (4)
O1—C1—C2—C3	−163.2 (4)	C14—O2—C13—C12	−169.0 (4)
C7—C1—C2—C3	23.0 (6)	S1—C12—C13—O2	67.5 (4)
O1—C1—C2—C11	10.8 (5)	C13—O2—C14—C15	−57.9 (6)
C7—C1—C2—C11	−163.0 (3)	C16—O3—C15—C14	128.6 (5)
C1—C2—C3—C4	−4.1 (7)	O2—C14—C15—O3	89.5 (6)
C11—C2—C3—C4	−177.8 (4)	C15—O3—C16—C17	−170.5 (5)
C2—C3—C4—C5	−11.2 (7)	C18—O4—C17—C16	177.9 (5)
C2—C3—C4—C8	170.7 (4)	O3—C16—C17—O4	67.5 (6)
C3—C4—C5—C6	3.1 (8)	C17—O4—C18—C19	165.1 (4)
C8—C4—C5—C6	−179.0 (4)	O4—C18—C19—S2	−64.9 (6)
C4—C5—C6—C7	9.2 (8)	C7—S2—C19—C18	93.3 (4)
C5—C6—C7—C1	−0.3 (8)	C2—C11—C20—C21	−74.2 (5)
C5—C6—C7—S2	174.4 (4)	S1—C11—C20—C21	52.4 (4)
O1—C1—C7—C6	166.7 (4)	C2—C11—C20—C25	105.2 (4)
C2—C1—C7—C6	−19.4 (6)	S1—C11—C20—C25	−128.3 (3)
O1—C1—C7—S2	−8.6 (5)	C25—C20—C21—C22	2.1 (6)
C2—C1—C7—S2	165.3 (3)	C11—C20—C21—C22	−178.5 (4)
C19—S2—C7—C6	11.9 (4)	C20—C21—C22—C23	−1.5 (6)
C19—S2—C7—C1	−172.5 (3)	C21—C22—C23—C24	−0.3 (6)
C5—C4—C8—C9	25.1 (6)	C21—C22—C23—N1	179.8 (4)
C3—C4—C8—C9	−156.8 (4)	O5—N1—C23—C22	166.6 (4)
C5—C4—C8—C10	−104.5 (5)	O6—N1—C23—C22	−13.9 (6)
C3—C4—C8—C10	73.6 (5)	O5—N1—C23—C24	−13.2 (6)
C3—C2—C11—C20	83.1 (4)	O6—N1—C23—C24	166.3 (4)
C1—C2—C11—C20	−91.5 (4)	C22—C23—C24—C25	1.5 (6)
C3—C2—C11—S1	−40.4 (4)	N1—C23—C24—C25	−178.7 (4)
C1—C2—C11—S1	144.9 (3)	C23—C24—C25—C20	−0.8 (6)
C12—S1—C11—C20	151.2 (3)	C21—C20—C25—C24	−0.9 (6)
C12—S1—C11—C2	−83.5 (3)	C11—C20—C25—C24	179.7 (4)
C11—S1—C12—C13	66.4 (4)