Di­methyl 1,3-di­chloro-8-phenyl-5-phenyl­sulfanyl­iso­quinoline-6,7-di­carboxyl­ate

In the title mol­ecule, C₂₅H₁₇Cl₂NO₄S, one of the phenyl rings is nearly perpendicular to the iso­quinoline moiety. The angle subtended at the S atom joining another phenyl ring to the iso­quinoline is 102.2 (1)°. The extended structure is built from infinite molecular chains parallel to the b axis which are stabilized by C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 183 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.052
• wR factor = 0.138
• Data-to-parameter ratio = 18.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Lignans, which are characterized by the presence of two phenylpropane moieties bonded through C8—C8', as in (I) in the Scheme below, have generated much interest in view of their widespread occurance in the nature and their biological activities (Ward, 1993). In recent years, a class of compounds having the lignan skeleton with one or two heteroatoms in the phenylpropane units has been developed in various research laboratories (Ramos et al., 1999). This class of compounds, i.e. heterolignans, are of wide structural diversity and possess not only biological activities comparable to lignans but also display either enhanced biological activities or variety of other properties. In view of the importance of these heterolignans, we have conducted a synthesis program in order to investigate the structure–activity relationship of lignans (II) and (III). During the course of this work, we have synthesized the substituted isoquinoline (IV) which is related to the heterolignans (II) and (III). An X-ray structure determination of (IV) was undertaken in order to elucidate the molecular conformation.

In the structure of (IV) (Fig. 1), the bond lengths and angles are normal (Allen et al., 1987). Atoms Cl1 and Cl2 lie on the isoquinoline (C1–C9/N1) plane, with displacements of 0.031 (1) and 0.050 (1) Å, respectively. Both of the attached methyl carboxylates (O1/O2/C24/C25 and O3/O4/C22/C25) form planes, and the two planes are twisted out of the isoquinoline by 64.8 (1) and 63.0 (1)°, respectively.

The C10–C15 phenyl ring attached to atom C9 is nearly perpendicular to the isoquinoline plane, with a twisted angle of 82.7 (1)°, The C6—S1—C16 angle joining the C16–C21 phenyl ring to the isoquinoline system is 102.2 (1)°, while the dihedral angle between this phenyl ring and the isoquinoline is 76.6 (1)°.

In the crystal packing structure of (IV), the molecules are linked by C23—H23B···O1ⁱ hydrogen bonds (Table 1) to form an infinite chain along the b direction (Fig. 2). The molecular chains form sheets perpendicular to the a direction. An intermolecular C—H···π interaction is observed involving the centroid of the phenyl C16–C21 ring. In Table 1, the center of gravity of the phenyl ring is denoted Cg(A).

S2. Experimental

To a stirred solution of bridged diester (75 g, 0.14 mol), prepared from the Pummerer reaction of a keto-sulfoxide (Sarkar et al., 2002) in dry toluene (12 ml), was added 1,8-iazabicyclo[5,4.0]undec-7-ene (0.21 ml, 1.45 mol). The mixture was refluxed for 1.5 h. After cooling to room temperature, water was added to the mixture. The aqueous layer was separated and extracted with ether, dried with Na₂SO₄, and concentrated in vacuo. The residue was purified by column chromatography on silica gel, and finally recrystallized from an ethyl acetate-petroleum ether solution to give yellow single crystals.

S3. Refinement

After checking their presence in a difference map, all the H atoms were placed at geometrically calculated positions and were refined as riding-model atoms.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

	Fig. 1. The structure of (IV) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The packing structure of (IV) viewed down the a axis showing the molecular chains along the b direction.

Dimethyl 1,3-Dichloro-8-phenyl-5-phenylsulfanyl-isoquinoline-6,7-dicarboxylate

Crystal data

C25H17Cl2NO4S	Dx = 1.472 Mg m^−3
Mr = 498.36	Melting point: 451-452 K K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 10.8487 (1) Å	Cell parameters from 6457 reflections
b = 12.6944 (1) Å	θ = 2.6–28.3°
c = 32.6567 (3) Å	µ = 0.42 mm^−1
V = 4497.4 (1) Å^3	T = 183 K
Z = 8	Slab, yellow
F(000) = 2048	0.40 × 0.32 × 0.12 mm

Data collection

Siemens SMART CCD area-detector diffractometer	5513 independent reflections
Radiation source: fine-focus sealed tube	3836 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 2.6°
ω scans	h = −14→13
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −16→10
Tmin = 0.851, Tmax = 0.952	l = −39→43
25577 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)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.0709P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
5513 reflections	Δρmax = 0.46 e Å^−3
301 parameters	Δρmin = −0.41 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: 0.0052 (6)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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	0.25989 (5)	0.66546 (5)	0.105916 (18)	0.02257 (16)
Cl1	−0.07308 (8)	0.23165 (6)	0.04895 (2)	0.0452 (2)
Cl2	0.20583 (6)	0.45899 (6)	−0.039946 (18)	0.03696 (19)
O1	0.07394 (15)	0.64709 (14)	0.20668 (5)	0.0324 (4)
O2	0.26755 (15)	0.58816 (14)	0.19865 (5)	0.0269 (4)
O3	−0.12207 (15)	0.43194 (15)	0.20996 (5)	0.0313 (4)
O4	0.07793 (15)	0.40436 (13)	0.22478 (5)	0.0260 (4)
N1	0.07058 (19)	0.35817 (17)	0.01297 (6)	0.0258 (5)
C1	0.04441 (19)	0.40293 (17)	0.08513 (7)	0.0173 (5)
C2	0.0226 (2)	0.34076 (18)	0.04884 (7)	0.0230 (5)
C3	0.1462 (2)	0.4410 (2)	0.00896 (7)	0.0246 (5)
C4	0.1771 (2)	0.50744 (19)	0.03971 (7)	0.0228 (5)
H4	0.2303	0.5636	0.0351	0.027*
C5	0.12649 (19)	0.48959 (17)	0.07909 (7)	0.0172 (5)
C6	0.15881 (19)	0.55593 (17)	0.11310 (7)	0.0169 (4)
C7	0.11659 (19)	0.53105 (17)	0.15154 (6)	0.0163 (4)
C8	0.03230 (19)	0.44653 (17)	0.15714 (6)	0.0164 (4)
C9	−0.00699 (19)	0.38438 (17)	0.12492 (6)	0.0162 (4)
C10	−0.10114 (19)	0.30140 (17)	0.13418 (6)	0.0170 (4)
C11	−0.2251 (2)	0.3207 (2)	0.12660 (8)	0.0305 (6)
H11	−0.2493	0.3844	0.1151	0.037*
C12	−0.3123 (2)	0.2457 (2)	0.13612 (9)	0.0353 (7)
H12	−0.3952	0.2595	0.1314	0.042*
C13	−0.2775 (2)	0.1510 (2)	0.15255 (8)	0.0316 (6)
H13	−0.3363	0.0994	0.1578	0.038*
C14	−0.1560 (2)	0.1323 (2)	0.16122 (8)	0.0310 (6)
H14	−0.1328	0.0689	0.1732	0.037*
C15	−0.0677 (2)	0.20730 (18)	0.15218 (7)	0.0224 (5)
H15	0.0147	0.1943	0.1583	0.027*
C16	0.1544 (2)	0.77203 (17)	0.09981 (7)	0.0193 (5)
C17	0.0859 (2)	0.7843 (2)	0.06419 (8)	0.0302 (6)
H17	0.0888	0.7333	0.0438	0.036*
C18	0.0131 (3)	0.8735 (2)	0.05930 (8)	0.0372 (7)
H18	−0.0326	0.8823	0.0354	0.045*
C19	0.0081 (2)	0.9494 (2)	0.08964 (9)	0.0339 (6)
H19	−0.0402	1.0092	0.0861	0.041*
C20	0.0742 (2)	0.9362 (2)	0.12486 (8)	0.0282 (6)
H20	0.0701	0.9872	0.1453	0.034*
C21	0.1473 (2)	0.84774 (19)	0.13057 (7)	0.0241 (5)
H21	0.1912	0.8391	0.1548	0.029*
C22	−0.0166 (2)	0.42686 (17)	0.19974 (7)	0.0208 (5)
C23	0.0460 (3)	0.3898 (2)	0.26773 (7)	0.0391 (7)
H23A	0.1200	0.3827	0.2836	0.059*
H23B	−0.0032	0.3274	0.2707	0.059*
H23C	0.0002	0.4497	0.2772	0.059*
C24	0.1489 (2)	0.59632 (17)	0.18847 (7)	0.0204 (5)
C25	0.3041 (3)	0.6502 (2)	0.23393 (8)	0.0388 (7)
H25A	0.3909	0.6417	0.2386	0.058*
H25B	0.2594	0.6268	0.2576	0.058*
H25C	0.2862	0.7231	0.2289	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0181 (3)	0.0151 (3)	0.0346 (3)	−0.0031 (2)	−0.0003 (2)	0.0037 (3)
Cl1	0.0735 (5)	0.0363 (4)	0.0260 (3)	−0.0305 (4)	0.0003 (3)	−0.0059 (3)
Cl2	0.0466 (4)	0.0403 (4)	0.0240 (3)	0.0075 (3)	0.0116 (3)	0.0048 (3)
O1	0.0322 (10)	0.0284 (10)	0.0367 (10)	0.0036 (8)	0.0032 (8)	−0.0138 (9)
O2	0.0240 (9)	0.0295 (10)	0.0273 (9)	−0.0012 (7)	−0.0055 (7)	−0.0060 (8)
O3	0.0265 (9)	0.0354 (11)	0.0320 (9)	−0.0034 (8)	0.0108 (7)	−0.0060 (8)
O4	0.0336 (9)	0.0245 (9)	0.0199 (8)	0.0008 (7)	−0.0016 (7)	0.0043 (7)
N1	0.0324 (11)	0.0252 (11)	0.0197 (10)	0.0020 (9)	−0.0034 (8)	−0.0009 (9)
C1	0.0185 (10)	0.0134 (11)	0.0201 (11)	0.0010 (9)	−0.0020 (8)	0.0032 (9)
C2	0.0265 (12)	0.0154 (11)	0.0272 (12)	−0.0033 (10)	−0.0052 (9)	0.0022 (10)
C3	0.0290 (13)	0.0249 (13)	0.0199 (11)	0.0069 (10)	0.0037 (9)	0.0050 (10)
C4	0.0217 (11)	0.0203 (12)	0.0264 (12)	0.0026 (9)	0.0050 (9)	0.0051 (10)
C5	0.0163 (10)	0.0125 (10)	0.0230 (11)	0.0019 (8)	−0.0009 (8)	0.0019 (9)
C6	0.0138 (10)	0.0113 (10)	0.0256 (11)	0.0009 (8)	−0.0008 (8)	0.0010 (9)
C7	0.0151 (10)	0.0118 (10)	0.0219 (11)	0.0020 (8)	−0.0007 (8)	−0.0007 (9)
C8	0.0161 (10)	0.0131 (11)	0.0201 (10)	0.0007 (8)	0.0001 (8)	0.0017 (9)
C9	0.0151 (10)	0.0117 (10)	0.0217 (11)	0.0004 (8)	−0.0014 (8)	0.0025 (9)
C10	0.0189 (10)	0.0137 (11)	0.0184 (10)	−0.0026 (9)	0.0010 (8)	−0.0002 (9)
C11	0.0237 (12)	0.0213 (13)	0.0465 (16)	−0.0020 (10)	−0.0057 (11)	0.0074 (12)
C12	0.0202 (12)	0.0351 (16)	0.0506 (17)	−0.0057 (11)	−0.0045 (11)	0.0075 (14)
C13	0.0297 (13)	0.0275 (14)	0.0375 (15)	−0.0159 (11)	0.0049 (11)	0.0043 (12)
C14	0.0373 (14)	0.0176 (12)	0.0381 (14)	0.0005 (11)	0.0069 (11)	0.0111 (11)
C15	0.0186 (11)	0.0191 (12)	0.0293 (12)	0.0022 (9)	0.0019 (9)	0.0049 (10)
C16	0.0207 (11)	0.0114 (11)	0.0258 (12)	−0.0044 (9)	0.0004 (9)	0.0023 (9)
C17	0.0429 (15)	0.0227 (13)	0.0250 (12)	0.0069 (11)	−0.0050 (11)	−0.0032 (11)
C18	0.0448 (16)	0.0362 (16)	0.0306 (14)	0.0121 (13)	−0.0101 (12)	0.0031 (13)
C19	0.0307 (14)	0.0185 (13)	0.0524 (17)	0.0056 (11)	0.0007 (12)	0.0062 (13)
C20	0.0312 (13)	0.0160 (12)	0.0373 (14)	−0.0038 (10)	0.0051 (11)	−0.0067 (11)
C21	0.0256 (12)	0.0200 (12)	0.0266 (12)	−0.0051 (10)	−0.0014 (9)	−0.0011 (10)
C22	0.0269 (12)	0.0103 (11)	0.0253 (12)	−0.0021 (9)	0.0016 (9)	−0.0025 (9)
C23	0.065 (2)	0.0324 (16)	0.0203 (13)	−0.0022 (14)	0.0025 (12)	0.0061 (12)
C24	0.0256 (12)	0.0126 (11)	0.0231 (11)	−0.0024 (9)	0.0005 (9)	0.0013 (9)
C25	0.0462 (16)	0.0390 (17)	0.0312 (14)	−0.0123 (14)	−0.0136 (12)	−0.0059 (13)

Geometric parameters (Å, º)

S1—C16	1.783 (2)	C11—C12	1.377 (3)
S1—C6	1.786 (2)	C11—H11	0.9300
Cl1—C2	1.731 (2)	C12—C13	1.370 (4)
Cl2—C3	1.738 (2)	C12—H12	0.9300
O1—C24	1.196 (3)	C13—C14	1.368 (4)
O2—C24	1.334 (3)	C13—H13	0.9300
O2—C25	1.451 (3)	C14—C15	1.383 (3)
O3—C22	1.194 (3)	C14—H14	0.9300
O4—C22	1.342 (3)	C15—H15	0.9300
O4—C23	1.456 (3)	C16—C17	1.389 (3)
N1—C2	1.301 (3)	C16—C21	1.392 (3)
N1—C3	1.340 (3)	C17—C18	1.390 (4)
C1—C5	1.429 (3)	C17—H17	0.9300
C1—C9	1.433 (3)	C18—C19	1.383 (4)
C1—C2	1.443 (3)	C18—H18	0.9300
C3—C4	1.353 (3)	C19—C20	1.365 (4)
C4—C5	1.416 (3)	C19—H19	0.9300
C4—H4	0.9300	C20—C21	1.387 (3)
C5—C6	1.437 (3)	C20—H20	0.9300
C6—C7	1.373 (3)	C21—H21	0.9300
C7—C8	1.422 (3)	C23—H23A	0.9600
C7—C24	1.505 (3)	C23—H23B	0.9600
C8—C9	1.383 (3)	C23—H23C	0.9600
C8—C22	1.510 (3)	C25—H25A	0.9600
C9—C10	1.498 (3)	C25—H25B	0.9600
C10—C15	1.380 (3)	C25—H25C	0.9600
C10—C11	1.389 (3)
C16—S1—C6	102.19 (10)	C13—C14—C15	120.3 (2)
C24—O2—C25	114.82 (19)	C13—C14—H14	119.9
C22—O4—C23	115.6 (2)	C15—C14—H14	119.9
C2—N1—C3	117.8 (2)	C10—C15—C14	120.3 (2)
C5—C1—C9	119.6 (2)	C10—C15—H15	119.9
C5—C1—C2	114.20 (19)	C14—C15—H15	119.9
C9—C1—C2	126.2 (2)	C17—C16—C21	119.8 (2)
N1—C2—C1	125.5 (2)	C17—C16—S1	121.47 (18)
N1—C2—Cl1	112.20 (18)	C21—C16—S1	118.59 (17)
C1—C2—Cl1	122.31 (17)	C16—C17—C18	119.4 (2)
N1—C3—C4	124.6 (2)	C16—C17—H17	120.3
N1—C3—Cl2	114.88 (18)	C18—C17—H17	120.3
C4—C3—Cl2	120.52 (19)	C19—C18—C17	120.5 (2)
C3—C4—C5	118.6 (2)	C19—C18—H18	119.8
C3—C4—H4	120.7	C17—C18—H18	119.8
C5—C4—H4	120.7	C20—C19—C18	119.9 (2)
C4—C5—C1	119.3 (2)	C20—C19—H19	120.1
C4—C5—C6	120.9 (2)	C18—C19—H19	120.1
C1—C5—C6	119.76 (19)	C19—C20—C21	120.8 (2)
C7—C6—C5	119.36 (19)	C19—C20—H20	119.6
C7—C6—S1	120.26 (17)	C21—C20—H20	119.6
C5—C6—S1	120.29 (16)	C20—C21—C16	119.6 (2)
C6—C7—C8	120.39 (19)	C20—C21—H21	120.2
C6—C7—C24	121.90 (19)	C16—C21—H21	120.2
C8—C7—C24	117.53 (18)	O3—C22—O4	125.0 (2)
C9—C8—C7	122.08 (19)	O3—C22—C8	125.8 (2)
C9—C8—C22	119.91 (19)	O4—C22—C8	109.17 (18)
C7—C8—C22	118.00 (19)	O4—C23—H23A	109.5
C8—C9—C1	118.43 (19)	O4—C23—H23B	109.5
C8—C9—C10	117.25 (19)	H23A—C23—H23B	109.5
C1—C9—C10	124.32 (19)	O4—C23—H23C	109.5
C15—C10—C11	118.9 (2)	H23A—C23—H23C	109.5
C15—C10—C9	121.01 (19)	H23B—C23—H23C	109.5
C11—C10—C9	120.0 (2)	O1—C24—O2	125.0 (2)
C12—C11—C10	120.2 (2)	O1—C24—C7	122.5 (2)
C12—C11—H11	119.9	O2—C24—C7	112.46 (18)
C10—C11—H11	119.9	O2—C25—H25A	109.5
C13—C12—C11	120.4 (2)	O2—C25—H25B	109.5
C13—C12—H12	119.8	H25A—C25—H25B	109.5
C11—C12—H12	119.8	O2—C25—H25C	109.5
C14—C13—C12	119.9 (2)	H25A—C25—H25C	109.5
C14—C13—H13	120.1	H25B—C25—H25C	109.5
C12—C13—H13	120.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23B···O1^i	0.96	2.52	3.447 (3)	161
C12—H12···Cg(A)^ii	0.93	2.67	3.524 (3)	153

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