Diethyl 2-[(1-methyl-1H-pyrrol-2-yl)methyl­ene­amino]-5-(2-thienylmethyl­ene­amino)thio­phene-3,4-dicarboxyl­ate

Dufresne, S.; Skene, W.G.

doi:10.1107/S160053680800799X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o782

doi:10.1107/S160053680800799X

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Diethyl 2-[(1-methyl-1H-pyrrol-2-yl)methyleneamino]-5-(2-thienylmethyleneamino)thiophene-3,4-dicarboxylate

Stéphane Dufresne ^a and W. G. Skene ^a ^*

^aDepartment of Chemistry, University of Montreal, CP 6128, succ. Centre-ville, Montréal, Québec, Canada H3C 3J7
^*Correspondence e-mail: w.skene@umontreal.ca

(Received 5 March 2008; accepted 25 March 2008; online 2 April 2008)

Both imine bonds of the title compound, C₂₁H₂₁N₃O₄S₂, were found to be in the E configuration. The terminal pyrrole and thiophene rings are twisted by 2.5 (3) and 2.3 (2)°, respectively, from the mean plane of the central thiophene to which they are attached. The structure is disordered by exchange of the terminal heterocyclic rings; the site occupancy factors are ca 0.8 and 0.2. The crystal packing involves some π–π stacking [3.449 (4) Å between pyrrole and terminal thiophene rings].

Related literature

For general background, see: Dufresne et al. (2007 ). For a similar compound, see: Dufresne et al. (2006 ).

Experimental

Crystal data

C₂₁H₂₁N₃O₄S₂
M_r = 443.53
Monoclinic, C 2/c
a = 30.7355 (14) Å
b = 6.9617 (4) Å
c = 19.5163 (9) Å
β = 92.732 (2)°
V = 4171.2 (4) Å³
Z = 8
Cu Kα radiation
μ = 2.60 mm⁻¹
T = 150 (2) K
0.14 × 0.09 × 0.05 mm

Data collection

Bruker SMART 6K diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.712, T_max = 0.881
24275 measured reflections
4076 independent reflections
3330 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.115
S = 1.03
4076 reflections
394 parameters
544 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: SMART (Bruker, 2003 ); cell refinement: SMART; data reduction: SAINT (Bruker, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: UdMX (Marris, 2004 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S160053680800799X/fl2192sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800799X/fl2192Isup2.hkl

checkCIF report

Comment top

The title comound (I), seen in Fig. 1, was synthesized during the course of our ongoing research relating to conjugated imines (Dufresne et al., 2007). Despite the terminal heterounits of (I) being disordered by 18%, both imines were found to adopt the E isomer. Neither solvent nor counter-ions were found in the closed-packed stacking (Fig. 2).

A major point of interest is the imine bonds, 1.446 (9), 1.278 (2) and 1.377 (2)Å for C4—C5, N1—C5 and N1—C6, respectively. Similarly, the bond lengths for C10—C11, N2—C10 and N2—C9 are 1.423 (9), 1.299 (17) and 1.373 (2) Å. These distances are comparable to those fournd for an analogous all-thiophene compound, 1.441 (4), 1.272 (3) and 1.388 (3)Å (Dufresne et al., 2006).

The terminal heteroaryl groups are slightly twisted from the mean plane of the central thiophene to which they are connected with a dihedral angle of 2.3 (2)° for the terminal thiophene and 2.5 (3)° for the N-methylpyrrole. The small dihedral angles show that the aryl groups of compound (I) are nearly coplanar. This is in contrast to its all-thiophene analogue whose comparable mean plane angles are 9.04 (4)° and 25.07 (6)°.

The crystal packing of (I) is also different from that found for the all-thiophene analogue. The molecules in the all-thiophene network are linearly aligned in one direction. In contrast, the molecules of (I) are misaligned by up to 16.84 (4)°. No traditional H-bonding was found, but π-π-stacking does occur as shown in Figure 2. π-π-stacking interactions occur between the pyrrole and the terminal thiophene of two different molecules, which are separated by 3.449 (4) Å.

Related literature top

For general background, see: Dufresne et al. (2007). For a similar comound, see: Dufresne et al. (2006)

Experimental top

In a 50 ml round bottom flask was added 1-methyl-2-pyrrole-carboxaldehyde (40 mg, 0.37 mmol) dissolved in 25 ml of anhydrous toluene to which was subsequently added 1,4-diazabicyclo[2.2.2]octane (159 mg, 1.42 mmol) and TiCl₄ (0.28 ml, 0.28 mmol) as a 1.0 M solution in toluene at 0 °C followed by diethyl 2-((thiophen-2-yl)methyleneamino)-5-aminothiophene-3,4-dicarboxylate (100 mg, 0.28 mmol). The mixture was then refluxed for four hours followed by solvent removal. Purification by flash chromatography yielded the title product as a red solid (63 mg). The selected crystal was obtained by slow evaporation of a concentrated solution in acetone.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: UdMX (Marris, 2004).

Figures top

	Fig. 1. ORTEP representation of (I) showing the disorder present in the terminal rings with the numbering scheme adopted (Farrugia, 1997). Ellipsoids drawn at 30% probability level.
	Fig. 2. Supramolecular structure showing the intermolecular π-stacking giving the structural arrangement. Dashed lines indicate the π-stacking. The H atoms and disorder was omitted for clarity. [Symmetry codes: (none) x, 1 - y, -1/2 + z; (i) 1/2 - x, -1/2 + y, 1.5 - z.]

Diethyl 2-[(1-methyl-1H-pyrrol-2-yl)methyleneamino]-5- (2-thienylmethyleneamino)thiophene-3,4-dicarboxylate top

Crystal data top

C₂₁H₂₁N₃O₄S₂	F(000) = 1856
M_r = 443.53	D_x = 1.413 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 30.7355 (14) Å	θ = 15.0–30.0°
b = 6.9617 (4) Å	µ = 2.60 mm⁻¹
c = 19.5163 (9) Å	T = 150 K
β = 92.732 (2)°	Block, red
V = 4171.2 (4) Å³	0.14 × 0.09 × 0.05 mm
Z = 8

Data collection top

Bruker SMART 6K diffractometer	4076 independent reflections
Radiation source: Rotating Anode	3330 reflections with I > 2σ(I)
Montel 200 optics monochromator	R_int = 0.041
Detector resolution: 5.5 pixels mm^-1	θ_max = 71.9°, θ_min = 2.9°
ω scans	h = −37→36
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −7→8
T_min = 0.712, T_max = 0.881	l = −23→24
24275 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0781P)²] where P = (F_o² + 2F_c²)/3
4076 reflections	(Δ/σ)_max = 0.001
394 parameters	Δρ_max = 0.28 e Å⁻³
544 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₂₁H₂₁N₃O₄S₂	V = 4171.2 (4) Å³
M_r = 443.53	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 30.7355 (14) Å	µ = 2.60 mm⁻¹
b = 6.9617 (4) Å	T = 150 K
c = 19.5163 (9) Å	0.14 × 0.09 × 0.05 mm
β = 92.732 (2)°

Data collection top

Bruker SMART 6K diffractometer	4076 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3330 reflections with I > 2σ(I)
T_min = 0.712, T_max = 0.881	R_int = 0.041
24275 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	544 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.03	Δρ_max = 0.28 e Å⁻³
4076 reflections	Δρ_min = −0.38 e Å⁻³
394 parameters

Special details top

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	Occ. (<1)
O1	0.10022 (4)	1.12212 (19)	0.84005 (7)	0.0407 (3)
O2	0.10797 (4)	0.80068 (19)	0.84277 (7)	0.0389 (3)
O3	0.17783 (4)	1.0055 (2)	0.75085 (6)	0.0409 (3)
O4	0.25038 (4)	1.00854 (18)	0.76690 (6)	0.0336 (3)
N1	0.12908 (5)	0.9423 (2)	0.99876 (7)	0.0313 (3)
N2	0.28368 (5)	1.0327 (2)	0.90462 (7)	0.0300 (3)
S2	0.219461 (14)	0.98751 (6)	0.99760 (2)	0.03223 (14)
C6	0.16602 (6)	0.9698 (2)	0.96274 (9)	0.0306 (4)
C7	0.16479 (6)	0.9824 (2)	0.89280 (9)	0.0298 (4)
C8	0.20672 (6)	1.0028 (2)	0.86477 (9)	0.0288 (4)
C9	0.24011 (6)	1.0096 (2)	0.91492 (8)	0.0290 (4)
C16	0.12129 (6)	0.9810 (3)	0.85451 (9)	0.0321 (4)
C17	0.06400 (6)	0.7790 (3)	0.81304 (11)	0.0482 (5)
H17A	0.0637	0.7996	0.7628	0.058*
H17B	0.0444	0.8747	0.8330	0.058*
C18	0.04913 (8)	0.5837 (4)	0.82806 (14)	0.0711 (8)
H18A	0.0697	0.4902	0.8105	0.107*
H18B	0.0202	0.5629	0.8060	0.107*
H18C	0.0476	0.5677	0.8778	0.107*
C19	0.20984 (6)	1.0069 (2)	0.78909 (9)	0.0302 (4)
C20	0.25276 (6)	1.0069 (3)	0.69247 (8)	0.0351 (4)
H20A	0.2385	1.1227	0.6724	0.042*
H20B	0.2379	0.8918	0.6729	0.042*
C21	0.30039 (6)	1.0039 (3)	0.67686 (10)	0.0399 (4)
H21A	0.3148	1.1182	0.6965	0.060*
H21B	0.3032	1.0032	0.6271	0.060*
H21C	0.3141	0.8884	0.6968	0.060*
S1	0.04126 (2)	0.87795 (11)	1.05416 (4)	0.0370 (3)	0.824 (3)
C1	0.01520 (10)	0.8382 (8)	1.1284 (2)	0.0404 (7)	0.824 (3)
H1	−0.0153	0.8193	1.1302	0.049*	0.824 (3)
C2	0.04307 (17)	0.8370 (10)	1.1840 (3)	0.0417 (10)	0.824 (3)
H2	0.0342	0.8170	1.2294	0.050*	0.824 (3)
C3	0.08692 (15)	0.8685 (7)	1.1675 (2)	0.0352 (8)	0.824 (3)
H3	0.1106	0.8741	1.2005	0.042*	0.824 (3)
C4	0.09117 (17)	0.8899 (18)	1.0984 (3)	0.0307 (6)	0.824 (3)
C5	0.1310 (4)	0.925 (5)	1.0640 (5)	0.0317 (7)	0.824 (3)
H5	0.1581	0.9349	1.0894	0.038*	0.824 (3)
C10	0.3117 (3)	1.0332 (16)	0.9566 (10)	0.0321 (10)	0.824 (3)
H10	0.3007	1.0101	1.0005	0.038*	0.824 (3)
C11	0.3573 (2)	1.065 (3)	0.9540 (3)	0.0333 (6)	0.824 (3)
C12	0.38669 (14)	1.0773 (7)	1.01056 (16)	0.0390 (7)	0.824 (3)
H12	0.3798	1.0662	1.0573	0.047*	0.824 (3)
C13	0.42795 (12)	1.1086 (7)	0.98639 (14)	0.0409 (7)	0.824 (3)
H13	0.4545	1.1207	1.0130	0.049*	0.824 (3)
C14	0.42238 (10)	1.1186 (6)	0.91597 (15)	0.0400 (7)	0.824 (3)
H14	0.4451	1.1407	0.8855	0.048*	0.824 (3)
N3	0.38014 (10)	1.0927 (4)	0.89645 (15)	0.0357 (6)	0.824 (3)
C15	0.36240 (9)	1.0926 (4)	0.82465 (15)	0.0449 (6)	0.824 (3)
H15A	0.3479	1.2155	0.8146	0.067*	0.824 (3)
H15B	0.3414	0.9877	0.8182	0.067*	0.824 (3)
H15C	0.3862	1.0747	0.7936	0.067*	0.824 (3)
S1'	0.37454 (15)	1.1247 (7)	0.8684 (3)	0.0464 (14)	0.176 (3)
C1'	0.4267 (4)	1.143 (3)	0.8980 (8)	0.0400 (9)	0.176 (3)
H1'	0.4507	1.1708	0.8707	0.048*	0.176 (3)
C2'	0.4294 (6)	1.113 (4)	0.9662 (8)	0.0407 (9)	0.176 (3)
H2'	0.4559	1.1263	0.9927	0.049*	0.176 (3)
C3'	0.3897 (7)	1.060 (4)	0.9958 (8)	0.0390 (9)	0.176 (3)
H3'	0.3874	1.0219	1.0421	0.047*	0.176 (3)
C4'	0.3551 (9)	1.072 (16)	0.9488 (14)	0.0333 (8)	0.176 (3)
C5'	0.128 (2)	0.92 (2)	1.064 (2)	0.0318 (9)	0.176 (3)
H5'	0.1560	0.9212	1.0873	0.038*	0.176 (3)
C10'	0.3104 (14)	1.053 (8)	0.957 (5)	0.0321 (11)	0.176 (3)
H10'	0.2995	1.0542	1.0014	0.039*	0.176 (3)
C11'	0.0926 (8)	0.881 (9)	1.1072 (13)	0.0307 (8)	0.176 (3)
C12'	0.0912 (8)	0.835 (4)	1.1755 (12)	0.0351 (9)	0.176 (3)
H12'	0.1155	0.8234	1.2073	0.042*	0.176 (3)
C13'	0.0477 (9)	0.809 (5)	1.1897 (12)	0.0416 (11)	0.176 (3)
H13'	0.0362	0.7884	1.2334	0.050*	0.176 (3)
C14'	0.0245 (6)	0.819 (4)	1.1278 (10)	0.0406 (9)	0.176 (3)
H14'	−0.0061	0.8035	1.1212	0.049*	0.176 (3)
N3'	0.0527 (4)	0.8565 (19)	1.0768 (6)	0.041 (3)	0.176 (3)
C15'	0.0380 (4)	0.8571 (17)	1.0042 (6)	0.040 (3)	0.176 (3)
H15D	0.0084	0.8052	0.9994	0.059*	0.176 (3)
H15E	0.0576	0.7776	0.9780	0.059*	0.176 (3)
H15F	0.0382	0.9890	0.9867	0.059*	0.176 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0392 (7)	0.0416 (8)	0.0411 (7)	0.0086 (6)	0.0006 (6)	0.0000 (6)
O2	0.0287 (7)	0.0390 (7)	0.0488 (8)	−0.0035 (5)	−0.0020 (6)	−0.0017 (6)
O3	0.0338 (7)	0.0578 (9)	0.0313 (7)	−0.0018 (6)	0.0021 (6)	−0.0045 (6)
O4	0.0316 (7)	0.0439 (7)	0.0256 (6)	−0.0015 (5)	0.0058 (5)	−0.0011 (5)
N1	0.0290 (8)	0.0329 (8)	0.0327 (8)	−0.0002 (6)	0.0090 (6)	−0.0012 (6)
N2	0.0288 (8)	0.0312 (8)	0.0302 (7)	−0.0012 (6)	0.0042 (6)	−0.0008 (6)
S2	0.0290 (2)	0.0407 (3)	0.0274 (2)	0.00037 (17)	0.00565 (17)	−0.00015 (17)
C6	0.0293 (9)	0.0304 (9)	0.0325 (9)	−0.0006 (7)	0.0052 (7)	−0.0023 (7)
C7	0.0303 (9)	0.0280 (9)	0.0316 (9)	0.0006 (7)	0.0049 (7)	−0.0006 (7)
C8	0.0294 (9)	0.0282 (9)	0.0292 (8)	0.0003 (6)	0.0057 (7)	−0.0026 (7)
C9	0.0301 (9)	0.0293 (9)	0.0280 (8)	0.0010 (6)	0.0061 (7)	−0.0011 (7)
C16	0.0298 (9)	0.0381 (10)	0.0289 (8)	−0.0020 (7)	0.0080 (7)	−0.0026 (7)
C17	0.0331 (10)	0.0482 (12)	0.0622 (13)	−0.0047 (9)	−0.0093 (9)	0.0014 (10)
C18	0.0580 (16)	0.0732 (18)	0.0798 (18)	−0.0287 (13)	−0.0214 (14)	0.0224 (14)
C19	0.0299 (9)	0.0297 (9)	0.0315 (9)	−0.0018 (7)	0.0046 (7)	−0.0013 (7)
C20	0.0407 (11)	0.0407 (10)	0.0243 (9)	−0.0030 (8)	0.0068 (7)	−0.0017 (7)
C21	0.0411 (11)	0.0450 (11)	0.0346 (10)	−0.0044 (8)	0.0112 (8)	−0.0025 (8)
S1	0.0284 (4)	0.0440 (4)	0.0388 (6)	−0.0025 (3)	0.0032 (3)	−0.0030 (3)
C1	0.0288 (16)	0.0424 (16)	0.0513 (11)	−0.0017 (15)	0.0147 (12)	−0.0097 (10)
C2	0.0397 (15)	0.046 (2)	0.0412 (13)	−0.0025 (14)	0.0167 (11)	−0.0029 (12)
C3	0.0323 (14)	0.039 (2)	0.0350 (15)	0.0005 (12)	0.0062 (10)	0.0008 (12)
C4	0.0291 (10)	0.0334 (15)	0.0299 (16)	−0.0004 (9)	0.0041 (10)	−0.0020 (18)
C5	0.027 (2)	0.0327 (10)	0.0354 (9)	0.000 (2)	0.0052 (10)	−0.0023 (7)
C10	0.0342 (11)	0.031 (3)	0.0311 (9)	0.0010 (13)	0.0056 (9)	0.001 (2)
C11	0.0328 (11)	0.0312 (11)	0.0360 (14)	0.0008 (12)	0.0025 (9)	0.000 (2)
C12	0.0371 (12)	0.0433 (15)	0.0364 (16)	0.0017 (10)	0.0007 (12)	−0.0064 (14)
C13	0.0331 (11)	0.0445 (12)	0.0444 (17)	−0.0007 (9)	−0.0045 (14)	−0.0032 (17)
C14	0.0296 (11)	0.0443 (15)	0.0469 (19)	−0.0015 (9)	0.0115 (11)	0.0047 (13)
N3	0.0340 (12)	0.0396 (14)	0.0336 (14)	0.0007 (9)	0.0031 (12)	0.0051 (11)
C15	0.0393 (14)	0.0672 (18)	0.0285 (14)	0.0014 (12)	0.0060 (11)	0.0073 (12)
S1'	0.036 (2)	0.054 (2)	0.051 (3)	−0.0032 (14)	0.011 (2)	0.002 (2)
C1'	0.0299 (14)	0.0443 (17)	0.047 (2)	−0.0016 (13)	0.0112 (14)	0.0045 (16)
C2'	0.0328 (13)	0.0445 (14)	0.044 (2)	−0.0007 (12)	−0.0038 (17)	−0.003 (2)
C3'	0.0372 (15)	0.0431 (17)	0.0367 (18)	0.0018 (13)	0.0010 (15)	−0.0061 (17)
C4'	0.0328 (13)	0.0312 (13)	0.0358 (16)	0.0009 (15)	0.0020 (12)	−0.001 (2)
C5'	0.028 (2)	0.0327 (13)	0.0353 (12)	0.000 (2)	0.0048 (13)	−0.0023 (11)
C10'	0.0341 (13)	0.031 (3)	0.0312 (12)	0.0011 (15)	0.0055 (12)	0.000 (2)
C11'	0.0288 (12)	0.0333 (17)	0.0303 (18)	−0.0003 (12)	0.0040 (13)	−0.002 (2)
C12'	0.0324 (16)	0.039 (2)	0.0349 (17)	0.0005 (15)	0.0064 (13)	0.0009 (15)
C13'	0.0397 (17)	0.045 (3)	0.0411 (15)	−0.0021 (16)	0.0160 (14)	−0.0028 (14)
C14'	0.0293 (19)	0.0423 (18)	0.0512 (14)	−0.0018 (17)	0.0142 (15)	−0.0094 (13)
N3'	0.041 (4)	0.041 (4)	0.040 (4)	0.001 (3)	−0.003 (3)	0.007 (3)
C15'	0.040 (5)	0.047 (6)	0.032 (6)	−0.005 (4)	−0.006 (4)	0.001 (4)

Geometric parameters (Å, º) top

O1—C16	1.203 (2)	C5—H5	0.9500
O2—C16	1.337 (2)	C10—C11	1.423 (9)
O2—C17	1.453 (2)	C10—H10	0.9500
O3—C19	1.206 (2)	C11—N3	1.366 (5)
O4—C19	1.339 (2)	C11—C12	1.395 (5)
O4—C20	1.4578 (19)	C12—C13	1.391 (4)
N1—C5	1.278 (9)	C12—H12	0.9500
N1—C5'	1.28 (4)	C13—C14	1.379 (4)
N1—C6	1.377 (2)	C13—H13	0.9500
N2—C10'	1.28 (8)	C14—N3	1.347 (4)
N2—C10	1.299 (17)	C14—H14	0.9500
N2—C9	1.373 (2)	N3—C15	1.479 (3)
S2—C6	1.7519 (18)	C15—H15A	0.9800
S2—C9	1.7685 (16)	C15—H15B	0.9800
C6—C7	1.367 (2)	C15—H15C	0.9800
C7—C8	1.431 (2)	S1'—C1'	1.683 (14)
C7—C16	1.500 (2)	S1'—C4'	1.744 (16)
C8—C9	1.385 (2)	C1'—C2'	1.345 (14)
C8—C19	1.485 (2)	C1'—H1'	0.9500
C17—C18	1.468 (3)	C2'—C3'	1.422 (15)
C17—H17A	0.9900	C2'—H2'	0.9500
C17—H17B	0.9900	C3'—C4'	1.374 (17)
C18—H18A	0.9800	C3'—H3'	0.9500
C18—H18B	0.9800	C4'—C10'	1.40 (4)
C18—H18C	0.9800	C5'—C11'	1.44 (4)
C20—C21	1.509 (3)	C5'—H5'	0.9500
C20—H20A	0.9900	C10'—H10'	0.9500
C20—H20B	0.9900	C11'—N3'	1.348 (17)
C21—H21A	0.9800	C11'—C12'	1.374 (18)
C21—H21B	0.9800	C12'—C13'	1.391 (18)
C21—H21C	0.9800	C12'—H12'	0.9500
S1—C1	1.711 (4)	C13'—C14'	1.375 (18)
S1—C4	1.726 (4)	C13'—H13'	0.9500
C1—C2	1.350 (5)	C14'—N3'	1.375 (16)
C1—H1	0.9500	C14'—H14'	0.9500
C2—C3	1.418 (4)	N3'—C15'	1.467 (12)
C2—H2	0.9500	C15'—H15D	0.9800
C3—C4	1.368 (5)	C15'—H15E	0.9800
C3—H3	0.9500	C15'—H15F	0.9800
C4—C5	1.446 (9)

C16—O2—C17	115.94 (15)	N1—C5—C4	118.5 (10)
C19—O4—C20	114.46 (14)	N1—C5—H5	120.7
C5—N1—C6	121.4 (5)	C4—C5—H5	120.7
C5'—N1—C6	126 (3)	N2—C10—C11	126.2 (13)
C10'—N2—C9	119 (3)	N2—C10—H10	116.9
C10—N2—C9	120.1 (6)	C11—C10—H10	116.9
C6—S2—C9	91.28 (8)	N3—C11—C12	107.7 (4)
C7—C6—N1	122.32 (17)	N3—C11—C10	126.6 (9)
C7—C6—S2	111.36 (13)	C12—C11—C10	125.7 (9)
N1—C6—S2	126.31 (13)	C13—C12—C11	107.9 (3)
C6—C7—C8	113.93 (16)	C13—C12—H12	126.0
C6—C7—C16	118.61 (16)	C11—C12—H12	126.1
C8—C7—C16	127.42 (15)	C14—C13—C12	105.9 (3)
C9—C8—C7	112.57 (15)	C14—C13—H13	127.0
C9—C8—C19	128.43 (16)	C12—C13—H13	127.1
C7—C8—C19	118.96 (16)	N3—C14—C13	110.3 (3)
N2—C9—C8	126.55 (15)	N3—C14—H14	124.8
N2—C9—S2	122.60 (13)	C13—C14—H14	124.8
C8—C9—S2	110.85 (13)	C14—N3—C11	108.2 (3)
O1—C16—O2	124.72 (17)	C14—N3—C15	125.1 (3)
O1—C16—C7	124.68 (17)	C11—N3—C15	126.8 (3)
O2—C16—C7	110.46 (15)	C1'—S1'—C4'	94.0 (9)
O2—C17—C18	108.00 (17)	C2'—C1'—S1'	109.9 (11)
O2—C17—H17A	110.1	C2'—C1'—H1'	125.0
C18—C17—H17A	110.1	S1'—C1'—H1'	125.1
O2—C17—H17B	110.1	C1'—C2'—C3'	115.3 (14)
C18—C17—H17B	110.1	C1'—C2'—H2'	122.3
H17A—C17—H17B	108.4	C3'—C2'—H2'	122.3
C17—C18—H18A	109.5	C4'—C3'—C2'	111.5 (15)
C17—C18—H18B	109.5	C4'—C3'—H3'	124.3
H18A—C18—H18B	109.5	C2'—C3'—H3'	124.2
C17—C18—H18C	109.5	C3'—C4'—C10'	131 (4)
H18A—C18—H18C	109.5	C3'—C4'—S1'	108.9 (14)
H18B—C18—H18C	109.5	C10'—C4'—S1'	120 (4)
O3—C19—O4	122.97 (16)	N1—C5'—C11'	131 (5)
O3—C19—C8	121.73 (16)	N1—C5'—H5'	114.2
O4—C19—C8	115.29 (15)	C11'—C5'—H5'	114.3
O4—C20—C21	107.25 (15)	N2—C10'—C4'	121 (7)
O4—C20—H20A	110.3	N2—C10'—H10'	119.7
C21—C20—H20A	110.3	C4'—C10'—H10'	119.9
O4—C20—H20B	110.3	N3'—C11'—C12'	109.1 (17)
C21—C20—H20B	110.3	N3'—C11'—C5'	118 (3)
H20A—C20—H20B	108.5	C12'—C11'—C5'	132 (3)
C20—C21—H21A	109.5	C11'—C12'—C13'	107.3 (16)
C20—C21—H21B	109.5	C11'—C12'—H12'	126.4
H21A—C21—H21B	109.5	C13'—C12'—H12'	126.3
C20—C21—H21C	109.5	C14'—C13'—C12'	106.5 (16)
H21A—C21—H21C	109.5	C14'—C13'—H13'	126.8
H21B—C21—H21C	109.5	C12'—C13'—H13'	126.8
C1—S1—C4	91.4 (2)	N3'—C14'—C13'	109.0 (15)
C2—C1—S1	112.1 (3)	N3'—C14'—H14'	125.5
C2—C1—H1	123.9	C13'—C14'—H14'	125.5
S1—C1—H1	123.9	C11'—N3'—C14'	107.4 (14)
C1—C2—C3	113.0 (4)	C11'—N3'—C15'	131.1 (14)
C1—C2—H2	123.5	C14'—N3'—C15'	121.5 (13)
C3—C2—H2	123.5	N3'—C15'—H15D	109.5
C4—C3—C2	112.2 (4)	N3'—C15'—H15E	109.5
C4—C3—H3	123.9	H15D—C15'—H15E	109.5
C2—C3—H3	123.9	N3'—C15'—H15F	109.5
C3—C4—C5	126.8 (6)	H15D—C15'—H15F	109.5
C3—C4—S1	111.3 (3)	H15E—C15'—H15F	109.5
C5—C4—S1	121.9 (6)

C5—N1—C6—C7	177.8 (17)	C1—S1—C4—C3	−1.4 (8)
C5'—N1—C6—C7	175 (9)	C1—S1—C4—C5	−179.5 (18)
C5—N1—C6—S2	−0.6 (17)	C5'—N1—C5—C4	−27 (91)
C5'—N1—C6—S2	−3 (9)	C6—N1—C5—C4	−177.9 (15)
C9—S2—C6—C7	−0.63 (13)	C3—C4—C5—N1	−179.7 (16)
C9—S2—C6—N1	177.95 (16)	S1—C4—C5—N1	−2 (3)
N1—C6—C7—C8	−177.47 (15)	C9—N2—C10—C11	−176.7 (13)
S2—C6—C7—C8	1.18 (19)	N2—C10—C11—N3	−3 (3)
N1—C6—C7—C16	4.7 (2)	N2—C10—C11—C12	175.7 (13)
S2—C6—C7—C16	−176.64 (12)	N3—C11—C12—C13	−1.3 (17)
C6—C7—C8—C9	−1.3 (2)	C10—C11—C12—C13	179.8 (16)
C16—C7—C8—C9	176.33 (16)	C11—C12—C13—C14	1.2 (11)
C6—C7—C8—C19	176.62 (15)	C12—C13—C14—N3	−0.7 (5)
C16—C7—C8—C19	−5.8 (3)	C13—C14—N3—C11	−0.1 (11)
C10'—N2—C9—C8	174 (3)	C13—C14—N3—C15	−179.4 (3)
C10—N2—C9—C8	−178.8 (6)	C12—C11—N3—C14	0.8 (16)
C10'—N2—C9—S2	−5 (3)	C10—C11—N3—C14	179.7 (17)
C10—N2—C9—S2	2.1 (6)	C12—C11—N3—C15	−179.8 (7)
C7—C8—C9—N2	−178.42 (16)	C10—C11—N3—C15	−1 (3)
C19—C8—C9—N2	4.0 (3)	C4'—S1'—C1'—C2'	−1 (4)
C7—C8—C9—S2	0.73 (19)	S1'—C1'—C2'—C3'	4 (3)
C19—C8—C9—S2	−176.89 (14)	C1'—C2'—C3'—C4'	−7 (6)
C6—S2—C9—N2	179.12 (15)	C2'—C3'—C4'—C10'	−173 (9)
C6—S2—C9—C8	−0.07 (13)	C2'—C3'—C4'—S1'	6 (8)
C17—O2—C16—O1	−2.7 (3)	C1'—S1'—C4'—C3'	−3 (7)
C17—O2—C16—C7	173.15 (15)	C1'—S1'—C4'—C10'	176 (8)
C6—C7—C16—O1	90.3 (2)	C5—N1—C5'—C11'	151 (100)
C8—C7—C16—O1	−87.2 (2)	C6—N1—C5'—C11'	−178 (10)
C6—C7—C16—O2	−85.62 (19)	C9—N2—C10'—C4'	178 (6)
C8—C7—C16—O2	96.9 (2)	C3'—C4'—C10'—N2	−167 (8)
C16—O2—C17—C18	−158.52 (19)	S1'—C4'—C10'—N2	15 (11)
C20—O4—C19—O3	−0.5 (2)	N1—C5'—C11'—N3'	5 (19)
C20—O4—C19—C8	178.27 (14)	N1—C5'—C11'—C12'	173 (10)
C9—C8—C19—O3	−177.86 (18)	N3'—C11'—C12'—C13'	−9 (5)
C7—C8—C19—O3	4.7 (2)	C5'—C11'—C12'—C13'	−177 (10)
C9—C8—C19—O4	3.4 (2)	C11'—C12'—C13'—C14'	6 (4)
C7—C8—C19—O4	−174.11 (15)	C12'—C13'—C14'—N3'	−2 (4)
C19—O4—C20—C21	−178.59 (14)	C12'—C11'—N3'—C14'	8 (5)
C4—S1—C1—C2	0.8 (6)	C5'—C11'—N3'—C14'	178 (8)
S1—C1—C2—C3	0.0 (7)	C12'—C11'—N3'—C15'	−170 (2)
C1—C2—C3—C4	−1.0 (9)	C5'—C11'—N3'—C15'	1 (10)
C2—C3—C4—C5	179.6 (19)	C13'—C14'—N3'—C11'	−4 (4)
C2—C3—C4—S1	1.6 (10)	C13'—C14'—N3'—C15'	174 (2)

Experimental details

Crystal data
Chemical formula	C₂₁H₂₁N₃O₄S₂
M_r	443.53
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	30.7355 (14), 6.9617 (4), 19.5163 (9)
β (°)	92.732 (2)
V (Å³)	4171.2 (4)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	2.60
Crystal size (mm)	0.14 × 0.09 × 0.05

Data collection
Diffractometer	Bruker SMART 6K diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.712, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	24275, 4076, 3330
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.115, 1.03
No. of reflections	4076
No. of parameters	394
No. of restraints	544
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.38

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), UdMX (Marris, 2004).

Acknowledgements

The authors acknowledge financial support from the Natural Sciences and Engineering Research Council Canada, the Centre for Self-Assembled Chemical Structures, and Canada Foundation for Innovation. SD thanks the Université de Montréal for a graduate scholarship.

References

Bruker (2003). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dufresne, S., Bourgeaux, M. & Skene, W. G. (2006). Acta Cryst. E62, o5602–o5604. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dufresne, S., Bourgeaux, M. & Skene, W. G. (2007). J. Mater. Chem. 17, 1166–1177. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Marris, T. (2004). UdMX. Université de Montréal, Montréal, Québec, Canada. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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