N,N'-(2,2'-Dithiodi-o-phenyl-ene)bis-(furan-2-carboxamide).

The reaction of 2,2'-dithio-bis(benzenamine) with furan-2-carbonyl chloride produced the bis-amide title compound, C(22)H(16)N(2)O(4)S(2), which, in the crystal, formed a helix; the structure consists of two planar furanoylbenzenamines related by an improper rotation of 96.3° about the S-S bond. The N-furanoylbenzenamine units are planar (maximum deviations = 0.316 and 0.132 Å). Each electron-deficient acyl-furan stacks (centroid-centroid separations of the two pairs of π-π stacked aromatic rings are 3.918 and 3.953 Å) with the electron-rich benzenamine of the other N-furan-oyl-benzenamine unit, leading to a spiral structure. The conformation is stabilized by two bifurcated intramolecular N-H⋯(O,S) interactions.

Related literature

For the preparation of multidentate chelating agents using 2,2′-dithio­bis(benzenamine) as starting material, see: Bhowon et al. (2001 ▶, 2005 ▶, 2007 ▶); Nag et al. (2001 ▶); Okachi et al. (1985 ▶); Uma & Palanaindavar (1993 ▶); Jhaumeer & Bhowon (2003 ▶).

Experimental

Crystal data

C22H16N2O4S2

M = 436.49

Triclinic,

a = 9.6173 (11) Å

b = 9.9210 (11) Å

c = 11.9906 (14) Å

α = 109.770 (2)°

β = 103.748 (2)°

γ = 104.643 (2)°

V = 973.84 (19) Å3

Z = 2

Mo Kα radiation

μ = 0.31 mm−1

T = 100 (2) K

0.45 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: none

6177 measured reflections

4327 independent reflections

2911 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.076

S = 0.83

4327 reflections

271 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.30 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; 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: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808038828/ww2132sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038828/ww2132Isup2.hkl

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

C22H16N2O4S2	Z = 2
Mr = 436.49	F(000) = 452
Triclinic, P1	Dx = 1.489 Mg m−3
Hall symbol: -P 1	Melting point: 434 K
a = 9.6173 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9210 (11) Å	Cell parameters from 1625 reflections
c = 11.9906 (14) Å	θ = 2.3–27.2°
α = 109.770 (2)°	µ = 0.31 mm−1
β = 103.748 (2)°	T = 100 K
γ = 104.643 (2)°	Plate, yellow
V = 973.84 (19) Å3	0.45 × 0.30 × 0.20 mm

Bruker SMART APEX diffractometer	2911 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
graphite	θmax = 28.3°, θmin = 1.9°
φ and ω scans	h = −11→12
6177 measured reflections	k = −12→12
4327 independent reflections	l = −12→15

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H-atom parameters constrained
S = 0.83	w = 1/[σ2(Fo2) + (0.0233P)2] where P = (Fo2 + 2Fc2)/3
4327 reflections	(Δ/σ)max < 0.001
271 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.30 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	0.0310 (2)	0.5459 (2)	0.2881 (2)	0.0182 (5)
C2	−0.0923 (2)	0.4603 (2)	0.3075 (2)	0.0222 (5)
H2	−0.1147	0.5039	0.3816	0.027*
C3	−0.1820 (2)	0.3115 (3)	0.2187 (2)	0.0260 (5)
H3	−0.2684	0.2539	0.2301	0.031*
C4	−0.1452 (2)	0.2476 (3)	0.1137 (2)	0.0254 (5)
H4	−0.2047	0.1440	0.0547	0.031*
C5	−0.0240 (2)	0.3304 (2)	0.0922 (2)	0.0210 (5)
H5	−0.0006	0.2842	0.0191	0.025*
C6	0.0639 (2)	0.4823 (2)	0.1783 (2)	0.0175 (5)
C7	0.2528 (2)	0.5374 (2)	0.0722 (2)	0.0191 (5)
C8	0.3733 (2)	0.6694 (2)	0.08069 (19)	0.0177 (5)
C9	0.4744 (2)	0.6804 (2)	0.0208 (2)	0.0208 (5)
H9	0.4866	0.5977	−0.0400	0.025*
C10	0.5592 (2)	0.8391 (2)	0.0659 (2)	0.0269 (5)
H10	0.6394	0.8836	0.0412	0.032*
C11	0.5045 (2)	0.9148 (2)	0.1501 (2)	0.0276 (5)
H11	0.5404	1.0235	0.1946	0.033*
C12	0.4601 (2)	0.7032 (2)	0.45289 (19)	0.0175 (5)
C13	0.4594 (2)	0.5616 (2)	0.37237 (19)	0.0175 (5)
C14	0.5733 (2)	0.5626 (2)	0.3192 (2)	0.0205 (5)
H14	0.5755	0.4683	0.2652	0.025*
C15	0.6830 (2)	0.7001 (2)	0.3446 (2)	0.0247 (5)
H15	0.7581	0.6993	0.3055	0.030*
C16	0.6855 (2)	0.8386 (2)	0.4259 (2)	0.0249 (5)
H16	0.7629	0.9323	0.4441	0.030*
C17	0.5740 (2)	0.8393 (2)	0.4805 (2)	0.0221 (5)
H17	0.5758	0.9341	0.5374	0.027*
C18	0.3246 (2)	0.2766 (2)	0.27812 (19)	0.0193 (5)
C19	0.1878 (2)	0.1613 (2)	0.2705 (2)	0.0193 (5)
C20	0.1276 (2)	0.0073 (2)	0.2061 (2)	0.0259 (5)
H20	0.1682	−0.0548	0.1537	0.031*
C21	−0.0076 (2)	−0.0446 (2)	0.2314 (2)	0.0267 (5)
H21	−0.0758	−0.1480	0.1991	0.032*
C22	−0.0201 (2)	0.0812 (2)	0.3100 (2)	0.0270 (5)
H22	−0.1007	0.0805	0.3429	0.032*
N1	0.18360 (17)	0.57613 (18)	0.15935 (16)	0.0187 (4)
H1	0.2194	0.6744	0.2112	0.022*
N2	0.34384 (17)	0.42539 (18)	0.34788 (15)	0.0180 (4)
H2A	0.2740	0.4374	0.3823	0.022*
O1	0.21966 (16)	0.40672 (16)	−0.00702 (15)	0.0279 (4)
O2	0.39021 (15)	0.81377 (15)	0.16313 (14)	0.0227 (3)
O3	0.41169 (15)	0.23672 (16)	0.22600 (14)	0.0271 (4)
O4	0.09859 (15)	0.21068 (15)	0.33633 (14)	0.0229 (4)
S1	0.14557 (6)	0.73663 (6)	0.40340 (5)	0.02100 (14)
S2	0.31812 (6)	0.70909 (6)	0.52536 (5)	0.02075 (14)

	U11	U22	U33	U12	U13	U23
C1	0.0161 (11)	0.0201 (11)	0.0206 (12)	0.0088 (9)	0.0042 (9)	0.0111 (10)
C2	0.0192 (11)	0.0301 (13)	0.0244 (13)	0.0125 (10)	0.0089 (10)	0.0160 (11)
C3	0.0201 (12)	0.0325 (14)	0.0292 (14)	0.0062 (11)	0.0092 (11)	0.0195 (11)
C4	0.0221 (12)	0.0248 (13)	0.0222 (13)	0.0013 (10)	0.0014 (10)	0.0113 (11)
C5	0.0206 (12)	0.0230 (12)	0.0165 (12)	0.0062 (10)	0.0039 (10)	0.0081 (10)
C6	0.0164 (11)	0.0209 (12)	0.0188 (12)	0.0084 (9)	0.0049 (9)	0.0124 (10)
C7	0.0189 (11)	0.0231 (12)	0.0197 (12)	0.0112 (10)	0.0064 (10)	0.0118 (10)
C8	0.0187 (11)	0.0166 (11)	0.0154 (11)	0.0071 (9)	0.0037 (9)	0.0051 (9)
C9	0.0224 (12)	0.0223 (12)	0.0209 (12)	0.0108 (10)	0.0101 (10)	0.0094 (10)
C10	0.0249 (13)	0.0296 (13)	0.0303 (14)	0.0088 (11)	0.0133 (11)	0.0157 (11)
C11	0.0293 (13)	0.0172 (12)	0.0301 (14)	−0.0004 (10)	0.0119 (11)	0.0084 (11)
C12	0.0188 (11)	0.0220 (12)	0.0135 (11)	0.0092 (9)	0.0049 (9)	0.0087 (9)
C13	0.0189 (11)	0.0192 (11)	0.0135 (11)	0.0076 (9)	0.0025 (9)	0.0078 (9)
C14	0.0213 (12)	0.0230 (12)	0.0188 (12)	0.0106 (10)	0.0072 (10)	0.0089 (10)
C15	0.0213 (12)	0.0297 (13)	0.0280 (14)	0.0111 (10)	0.0108 (11)	0.0150 (11)
C16	0.0218 (12)	0.0206 (12)	0.0317 (14)	0.0051 (10)	0.0068 (11)	0.0140 (11)
C17	0.0242 (12)	0.0183 (12)	0.0226 (13)	0.0100 (10)	0.0047 (10)	0.0080 (10)
C18	0.0217 (11)	0.0205 (12)	0.0132 (11)	0.0091 (10)	0.0025 (10)	0.0058 (9)
C19	0.0199 (11)	0.0214 (12)	0.0168 (12)	0.0104 (10)	0.0070 (10)	0.0059 (10)
C20	0.0274 (13)	0.0214 (12)	0.0229 (13)	0.0079 (10)	0.0087 (11)	0.0033 (10)
C21	0.0269 (13)	0.0189 (12)	0.0267 (14)	0.0034 (10)	0.0066 (11)	0.0065 (11)
C22	0.0232 (12)	0.0266 (13)	0.0326 (14)	0.0061 (10)	0.0116 (11)	0.0149 (11)
N1	0.0201 (9)	0.0137 (9)	0.0188 (10)	0.0031 (8)	0.0067 (8)	0.0052 (8)
N2	0.0183 (9)	0.0185 (10)	0.0170 (10)	0.0077 (8)	0.0077 (8)	0.0057 (8)
O1	0.0297 (9)	0.0186 (8)	0.0307 (10)	0.0066 (7)	0.0153 (8)	0.0035 (7)
O2	0.0251 (8)	0.0186 (8)	0.0218 (9)	0.0048 (7)	0.0122 (7)	0.0051 (7)
O3	0.0283 (9)	0.0227 (8)	0.0306 (10)	0.0107 (7)	0.0162 (8)	0.0068 (7)
O4	0.0237 (8)	0.0202 (8)	0.0244 (9)	0.0080 (7)	0.0113 (7)	0.0073 (7)
S1	0.0238 (3)	0.0201 (3)	0.0221 (3)	0.0114 (2)	0.0109 (3)	0.0080 (2)
S2	0.0248 (3)	0.0218 (3)	0.0155 (3)	0.0092 (2)	0.0085 (2)	0.0063 (2)

C1—C2	1.392 (3)	C12—S2	1.7871 (19)
C1—C6	1.403 (3)	C13—C14	1.392 (3)
C1—S1	1.777 (2)	C13—N2	1.402 (2)
C2—C3	1.383 (3)	C14—C15	1.380 (3)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.378 (3)	C15—C16	1.380 (3)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.380 (3)	C16—C17	1.382 (3)
C4—H4	0.9500	C16—H16	0.9500
C5—C6	1.393 (3)	C17—H17	0.9500
C5—H5	0.9500	C18—O3	1.224 (2)
C6—N1	1.403 (2)	C18—N2	1.366 (2)
C7—O1	1.224 (2)	C18—C19	1.469 (3)
C7—N1	1.368 (2)	C19—C20	1.344 (3)
C7—C8	1.468 (3)	C19—O4	1.369 (2)
C8—C9	1.343 (3)	C20—C21	1.415 (3)
C8—O2	1.380 (2)	C20—H20	0.9500
C9—C10	1.415 (3)	C21—C22	1.340 (3)
C9—H9	0.9500	C21—H21	0.9500
C10—C11	1.341 (3)	C22—O4	1.366 (2)
C10—H10	0.9500	C22—H22	0.9500
C11—O2	1.367 (2)	N1—H1	0.8800
C11—H11	0.9500	N2—H2A	0.8800
C12—C17	1.382 (3)	S1—S2	2.0768 (8)
C12—C13	1.407 (3)
C2—C1—C6	120.24 (19)	N2—C13—C12	119.02 (17)
C2—C1—S1	119.34 (17)	C15—C14—C13	120.27 (19)
C6—C1—S1	120.42 (15)	C15—C14—H14	119.9
C3—C2—C1	119.9 (2)	C13—C14—H14	119.9
C3—C2—H2	120.0	C14—C15—C16	121.12 (19)
C1—C2—H2	120.0	C14—C15—H15	119.4
C4—C3—C2	119.50 (19)	C16—C15—H15	119.4
C4—C3—H3	120.2	C15—C16—C17	119.2 (2)
C2—C3—H3	120.2	C15—C16—H16	120.4
C3—C4—C5	121.6 (2)	C17—C16—H16	120.4
C3—C4—H4	119.2	C12—C17—C16	120.5 (2)
C5—C4—H4	119.2	C12—C17—H17	119.7
C4—C5—C6	119.6 (2)	C16—C17—H17	119.7
C4—C5—H5	120.2	O3—C18—N2	125.09 (19)
C6—C5—H5	120.2	O3—C18—C19	120.47 (18)
C5—C6—N1	122.76 (19)	N2—C18—C19	114.43 (18)
C5—C6—C1	119.09 (18)	C20—C19—O4	110.13 (18)
N1—C6—C1	118.14 (18)	C20—C19—C18	131.36 (19)
O1—C7—N1	124.76 (19)	O4—C19—C18	118.50 (17)
O1—C7—C8	121.70 (19)	C19—C20—C21	106.93 (19)
N1—C7—C8	113.54 (18)	C19—C20—H20	126.5
C9—C8—O2	110.26 (18)	C21—C20—H20	126.5
C9—C8—C7	132.45 (19)	C22—C21—C20	106.23 (19)
O2—C8—C7	117.28 (17)	C22—C21—H21	126.9
C8—C9—C10	106.59 (18)	C20—C21—H21	126.9
C8—C9—H9	126.7	C21—C22—O4	110.92 (18)
C10—C9—H9	126.7	C21—C22—H22	124.5
C11—C10—C9	106.89 (18)	O4—C22—H22	124.5
C11—C10—H10	126.6	C7—N1—C6	129.57 (17)
C9—C10—H10	126.6	C7—N1—H1	115.2
C10—C11—O2	110.59 (18)	C6—N1—H1	115.2
C10—C11—H11	124.7	C18—N2—C13	129.03 (17)
O2—C11—H11	124.7	C18—N2—H2A	115.5
C17—C12—C13	120.33 (18)	C13—N2—H2A	115.5
C17—C12—S2	119.14 (15)	C11—O2—C8	105.66 (16)
C13—C12—S2	120.49 (15)	C22—O4—C19	105.80 (15)
C14—C13—N2	122.53 (18)	C1—S1—S2	103.80 (7)
C14—C13—C12	118.45 (19)	C12—S2—S1	104.78 (7)
C6—C1—C2—C3	0.5 (3)	C15—C16—C17—C12	−0.8 (3)
S1—C1—C2—C3	−179.76 (15)	O3—C18—C19—C20	−5.0 (4)
C1—C2—C3—C4	2.2 (3)	N2—C18—C19—C20	175.9 (2)
C2—C3—C4—C5	−2.5 (3)	O3—C18—C19—O4	176.19 (18)
C3—C4—C5—C6	0.1 (3)	N2—C18—C19—O4	−2.9 (3)
C4—C5—C6—N1	−176.52 (18)	O4—C19—C20—C21	0.4 (3)
C4—C5—C6—C1	2.6 (3)	C18—C19—C20—C21	−178.5 (2)
C2—C1—C6—C5	−2.9 (3)	C19—C20—C21—C22	−0.4 (3)
S1—C1—C6—C5	177.37 (15)	C20—C21—C22—O4	0.2 (3)
C2—C1—C6—N1	176.30 (17)	O1—C7—N1—C6	−0.5 (3)
S1—C1—C6—N1	−3.5 (2)	C8—C7—N1—C6	179.00 (18)
O1—C7—C8—C9	−6.0 (4)	C5—C6—N1—C7	−11.6 (3)
N1—C7—C8—C9	174.5 (2)	C1—C6—N1—C7	169.31 (19)
O1—C7—C8—O2	172.76 (18)	O3—C18—N2—C13	2.0 (3)
N1—C7—C8—O2	−6.8 (3)	C19—C18—N2—C13	−178.95 (18)
O2—C8—C9—C10	−0.6 (2)	C14—C13—N2—C18	3.7 (3)
C7—C8—C9—C10	178.2 (2)	C12—C13—N2—C18	−176.88 (19)
C8—C9—C10—C11	0.0 (2)	C10—C11—O2—C8	−1.0 (2)
C9—C10—C11—O2	0.6 (3)	C9—C8—O2—C11	1.0 (2)
C17—C12—C13—C14	−1.6 (3)	C7—C8—O2—C11	−178.06 (18)
S2—C12—C13—C14	−179.28 (15)	C21—C22—O4—C19	0.0 (2)
C17—C12—C13—N2	178.93 (18)	C20—C19—O4—C22	−0.3 (2)
S2—C12—C13—N2	1.2 (3)	C18—C19—O4—C22	178.75 (18)
N2—C13—C14—C15	178.88 (19)	C2—C1—S1—S2	90.48 (16)
C12—C13—C14—C15	−0.6 (3)	C6—C1—S1—S2	−89.74 (16)
C13—C14—C15—C16	2.1 (3)	C17—C12—S2—S1	88.52 (16)
C14—C15—C16—C17	−1.4 (3)	C13—C12—S2—S1	−93.76 (16)
C13—C12—C17—C16	2.3 (3)	C1—S1—S2—C12	84.72 (10)
S2—C12—C17—C16	−179.97 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S2	0.88	2.52	3.0104 (16)	116
N2—H2A···O4	0.88	2.24	2.688 (2)	111
N1—H1···S1	0.88	2.50	2.9805 (18)	115
N1—H1···O2	0.88	2.19	2.651 (2)	112

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S2	0.88	2.52	3.0104 (16)	116
N2—H2A⋯O4	0.88	2.24	2.688 (2)	111
N1—H1⋯S1	0.88	2.50	2.9805 (18)	115
N1—H1⋯O2	0.88	2.19	2.651 (2)	112