N,N′-Bis­[2-(methyl­sulfanyl)­phenyl]­pyridine-2,6-dicarbox­amide

In the title compound, C₂₁H₁₉N₃O₂S₂, there are intramolecular hydrogen bonds and steric strain. Hydro­gen bonds involving the amide groups and the pyridine N atoms force the two carbox­amide groups and the central pyridine ring into the same plane (r.m.s. deviation = 0.054 Å). Steric strain between the two methyl­sulfanyl substituents results in the benzene rings of the two arms of the ligand being inclined to one another by 45.23 (9)°. In the crystal structure, intermolecular C—H...O interactions are present and lead to the formation of a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.103
• Data-to-parameter ratio = 13.7

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Computing details

Data collection: XSCANS (Bruker, 2000); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

N,N'-Bis[2-(methylsulfanyl)phenyl]pyridine-2,6-dicarboxamide

Crystal data

C21H19N3O2S2	F(000) = 856
Mr = 409.51	Dx = 1.363 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3904 reflections
a = 8.8370 (18) Å	θ = 1.3–2.6°
b = 15.488 (3) Å	µ = 0.29 mm^−1
c = 15.155 (3) Å	T = 293 K
β = 105.87 (3)°	Prism, white
V = 1995.2 (7) Å^3	0.35 × 0.22 × 0.21 mm
Z = 4

Data collection

Siemens P4 diffractometer	2135 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.062
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
2θ/ω scans	h = 0→10
Absorption correction: ψ scan (XPREP; Bruker, 2000)	k = 0→18
Tmin = 0.93, Tmax = 0.94	l = −17→17
3742 measured reflections	3 standard reflections every 97 reflections
3499 independent reflections	intensity decay: 0.01%

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.04P)^2] where P = (Fo^2 + 2Fc^2)/3
3499 reflections	(Δ/σ)max = 0.003
255 parameters	Δρmax = 0.65 e Å^−3
0 restraints	Δρmin = −0.37 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

7.5099 (0.0068) x + 4.9540 (0.0174) y - 9.6285 (0.0146) z = 3.0202 (0.0168)

* 0.0100 (0.0020) C1 * -0.0085 (0.0021) C2 * 0.0017 (0.0022) C3 * 0.0037 (0.0022) C4 * -0.0023 (0.0021) C5 * -0.0047 (0.0020) C6

Rms deviation of fitted atoms = 0.0060

- 7.3012 (0.0074) x + 6.8969 (0.0175) y + 8.4544 (0.0161) z = 2.0150 (0.0079)

Angle to previous plane (with approximate e.s.d.) = 45.23 (0.09)

* 0.0074 (0.0021) C14 * -0.0026 (0.0022) C15 * -0.0029 (0.0023) C16 * 0.0036 (0.0024) C17 * 0.0012 (0.0023) C18 * -0.0067 (0.0022) C19

Rms deviation of fitted atoms = 0.0046

- 6.7640 (0.0044) x + 3.5357 (0.0088) y + 11.9430 (0.0079) z = 2.6564 (0.0054)

Angle to previous plane (with approximate e.s.d.) = 19.66 (0.11)

* -0.0806 (0.0018) N1 * 0.0022 (0.0020) N2 * 0.0983 (0.0017) N3 * 0.0257 (0.0022) C7 * 0.0462 (0.0025) C8 * 0.0543 (0.0023) C9 * 0.0001 (0.0022) C10 * -0.0425 (0.0024) C11 * -0.0501 (0.0026) C12 * -0.0536 (0.0021) C13

Rms deviation of fitted atoms = 0.0539

7.5099 (0.0068) x + 4.9540 (0.0174) y - 9.6285 (0.0146) z = 3.0202 (0.0168)

Angle to previous plane (with approximate e.s.d.) = 33.95 (0.08)

* 0.0100 (0.0020) C1 * -0.0085 (0.0021) C2 * 0.0017 (0.0022) C3 * 0.0037 (0.0022) C4 * -0.0023 (0.0021) C5 * -0.0047 (0.0020) C6

Rms deviation of fitted atoms = 0.0060

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	1.05337 (9)	0.21342 (4)	0.61157 (5)	0.0641 (3)
S2	0.59847 (10)	0.18067 (5)	0.57724 (5)	0.0718 (3)
C19	0.4391 (3)	0.17435 (17)	0.47455 (19)	0.0583 (8)
N1	0.9838 (3)	0.38965 (13)	0.65753 (14)	0.0538 (6)
H1	0.9106	0.3565	0.6262	0.065*
N2	0.7382 (3)	0.43443 (13)	0.51209 (15)	0.0495 (6)
N3	0.5225 (3)	0.31273 (14)	0.43400 (15)	0.0565 (6)
H3	0.6012	0.3080	0.4819	0.068*
O1	1.0619 (2)	0.52912 (11)	0.67501 (12)	0.0578 (5)
O2	0.4087 (2)	0.40713 (12)	0.32000 (13)	0.0618 (5)
C1	1.1470 (3)	0.26533 (17)	0.71643 (18)	0.0538 (7)
C2	1.2614 (3)	0.22392 (18)	0.78626 (19)	0.0620 (8)
H2	1.2886	0.1667	0.7800	0.074*
C3	1.3326 (4)	0.27010 (19)	0.8645 (2)	0.0664 (9)
H3A	1.4101	0.2439	0.9109	0.080*
C4	1.2907 (4)	0.35470 (18)	0.8752 (2)	0.0675 (9)
H4	1.3400	0.3847	0.9285	0.081*
C5	1.1776 (3)	0.39443 (18)	0.80796 (19)	0.0604 (8)
H5	1.1498	0.4513	0.8158	0.073*
C6	1.1024 (3)	0.34983 (17)	0.72664 (18)	0.0527 (7)
C7	0.9721 (3)	0.47365 (17)	0.63493 (19)	0.0539 (7)
C8	0.8374 (3)	0.49672 (17)	0.55350 (19)	0.0530 (7)
C9	0.8258 (3)	0.58194 (18)	0.52240 (19)	0.0584 (8)
H9	0.8960	0.6239	0.5532	0.070*
C10	0.7096 (3)	0.60193 (18)	0.4461 (2)	0.0606 (8)
H10	0.7001	0.6580	0.4234	0.073*
C11	0.6054 (3)	0.53906 (17)	0.4022 (2)	0.0585 (8)
H11	0.5242	0.5522	0.3504	0.070*
C12	0.6248 (3)	0.45622 (17)	0.4370 (2)	0.0549 (7)
C13	0.5079 (3)	0.38950 (18)	0.39029 (19)	0.0546 (7)
C14	0.4253 (3)	0.23941 (18)	0.41121 (19)	0.0569 (8)
C15	0.3206 (3)	0.23240 (18)	0.3253 (2)	0.0660 (9)
H15	0.3133	0.2763	0.2824	0.079*
C16	0.2254 (4)	0.15906 (18)	0.3029 (2)	0.0722 (9)
H16	0.1540	0.1533	0.2454	0.087*
C17	0.2404 (4)	0.09599 (19)	0.3681 (2)	0.0715 (9)
H17	0.1771	0.0472	0.3540	0.086*
C18	0.3454 (3)	0.10195 (18)	0.4536 (2)	0.0652 (8)
H18	0.3530	0.0580	0.4965	0.078*
C20	1.0713 (3)	0.10119 (17)	0.6377 (2)	0.0727 (9)
H20A	1.1774	0.0829	0.6437	0.109*
H20B	1.0008	0.0692	0.5893	0.109*
H20C	1.0453	0.0909	0.6943	0.109*
C21	0.5491 (4)	0.11973 (18)	0.65366 (19)	0.0720 (9)
H21A	0.4469	0.1364	0.6583	0.108*
H21B	0.6247	0.1268	0.7122	0.108*
H21C	0.5467	0.0604	0.6352	0.108*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0804 (6)	0.0409 (4)	0.0586 (5)	0.0009 (4)	−0.0020 (4)	−0.0002 (3)
S2	0.0798 (6)	0.0634 (5)	0.0629 (5)	−0.0259 (4)	0.0040 (4)	0.0070 (4)
C19	0.0638 (19)	0.0502 (16)	0.0563 (17)	−0.0141 (15)	0.0085 (15)	−0.0018 (15)
N1	0.0586 (15)	0.0453 (13)	0.0531 (14)	−0.0031 (11)	0.0079 (12)	−0.0016 (11)
N2	0.0524 (14)	0.0477 (13)	0.0489 (13)	0.0018 (11)	0.0146 (12)	0.0043 (11)
N3	0.0618 (15)	0.0536 (14)	0.0485 (13)	−0.0020 (12)	0.0059 (12)	−0.0014 (12)
O1	0.0665 (13)	0.0432 (10)	0.0566 (12)	−0.0068 (10)	0.0049 (10)	−0.0055 (9)
O2	0.0635 (13)	0.0609 (12)	0.0563 (12)	0.0040 (10)	0.0081 (11)	0.0082 (10)
C1	0.0575 (18)	0.0505 (17)	0.0476 (17)	−0.0034 (14)	0.0045 (14)	0.0012 (13)
C2	0.065 (2)	0.0556 (17)	0.0572 (19)	0.0054 (15)	0.0038 (16)	0.0025 (15)
C3	0.070 (2)	0.065 (2)	0.0531 (19)	0.0045 (16)	−0.0007 (16)	0.0027 (16)
C4	0.072 (2)	0.063 (2)	0.0572 (19)	−0.0038 (17)	−0.0007 (17)	−0.0043 (16)
C5	0.0625 (19)	0.0534 (17)	0.0577 (18)	0.0006 (15)	0.0034 (16)	−0.0059 (15)
C6	0.0560 (18)	0.0505 (16)	0.0467 (16)	−0.0039 (14)	0.0059 (14)	−0.0016 (13)
C7	0.0579 (18)	0.0462 (16)	0.0567 (18)	−0.0013 (15)	0.0143 (15)	−0.0034 (15)
C8	0.0570 (18)	0.0492 (16)	0.0535 (18)	0.0041 (14)	0.0161 (15)	0.0026 (14)
C9	0.063 (2)	0.0503 (17)	0.0629 (19)	0.0048 (15)	0.0188 (17)	0.0007 (14)
C10	0.067 (2)	0.0516 (17)	0.065 (2)	0.0117 (16)	0.0209 (17)	0.0125 (16)
C11	0.0603 (19)	0.0550 (18)	0.0615 (19)	0.0116 (16)	0.0187 (16)	0.0133 (15)
C12	0.0611 (19)	0.0504 (17)	0.0557 (18)	0.0032 (15)	0.0203 (16)	0.0059 (14)
C13	0.0569 (19)	0.0539 (17)	0.0529 (18)	0.0050 (15)	0.0149 (16)	0.0063 (15)
C14	0.0608 (19)	0.0528 (18)	0.0542 (18)	−0.0105 (15)	0.0111 (15)	−0.0039 (14)
C15	0.074 (2)	0.0557 (18)	0.0579 (19)	−0.0148 (16)	0.0005 (17)	−0.0057 (15)
C16	0.076 (2)	0.063 (2)	0.066 (2)	−0.0233 (17)	−0.0010 (17)	−0.0054 (17)
C17	0.074 (2)	0.0576 (19)	0.071 (2)	−0.0291 (17)	0.0001 (18)	−0.0043 (17)
C18	0.075 (2)	0.0550 (18)	0.0610 (19)	−0.0213 (16)	0.0105 (17)	−0.0014 (15)
C20	0.074 (2)	0.0537 (18)	0.080 (2)	−0.0178 (16)	0.0039 (18)	0.0134 (16)
C21	0.080 (2)	0.066 (2)	0.065 (2)	−0.0231 (17)	0.0108 (17)	−0.0001 (16)

Geometric parameters (Å, º)

S1—C1	1.771 (3)	C5—H5	0.9300
S1—C20	1.780 (3)	C7—C8	1.505 (4)
S2—C21	1.643 (3)	C8—C9	1.396 (4)
S2—C19	1.793 (3)	C9—C10	1.356 (4)
C19—C14	1.374 (4)	C9—H9	0.9300
C19—C18	1.378 (3)	C10—C11	1.380 (4)
N1—C7	1.342 (3)	C10—H10	0.9300
N1—C6	1.405 (3)	C11—C12	1.380 (3)
N1—H1	0.8600	C11—H11	0.9300
N2—C12	1.338 (3)	C12—C13	1.495 (4)
N2—C8	1.339 (3)	C14—C15	1.380 (3)
N3—C13	1.350 (3)	C15—C16	1.399 (3)
N3—C14	1.409 (3)	C15—H15	0.9300
N3—H3	0.8600	C16—C17	1.370 (4)
O1—C7	1.213 (3)	C16—H16	0.9300
O2—C13	1.211 (3)	C17—C18	1.375 (4)
C1—C6	1.388 (3)	C17—H17	0.9300
C1—C2	1.403 (4)	C18—H18	0.9300
C2—C3	1.380 (4)	C20—H20A	0.9600
C2—H2	0.9300	C20—H20B	0.9600
C3—C4	1.383 (4)	C20—H20C	0.9600
C3—H3A	0.9300	C21—H21A	0.9600
C4—C5	1.363 (4)	C21—H21B	0.9600
C4—H4	0.9300	C21—H21C	0.9600
C5—C6	1.411 (3)
C1—S1—C20	104.59 (13)	C9—C10—C11	120.0 (3)
C21—S2—C19	106.47 (14)	C9—C10—H10	120.0
C14—C19—C18	120.2 (3)	C11—C10—H10	120.0
C14—C19—S2	117.7 (2)	C10—C11—C12	118.4 (3)
C18—C19—S2	121.6 (2)	C10—C11—H11	120.8
C7—N1—C6	127.2 (2)	C12—C11—H11	120.8
C7—N1—H1	116.4	N2—C12—C11	123.0 (3)
C6—N1—H1	116.4	N2—C12—C13	119.2 (2)
C12—N2—C8	117.3 (2)	C11—C12—C13	117.7 (3)
C13—N3—C14	128.3 (2)	O2—C13—N3	125.4 (3)
C13—N3—H3	115.9	O2—C13—C12	120.0 (3)
C14—N3—H3	115.9	N3—C13—C12	114.6 (2)
C6—C1—C2	121.0 (2)	C19—C14—C15	120.7 (3)
C6—C1—S1	116.8 (2)	C19—C14—N3	119.2 (2)
C2—C1—S1	122.2 (2)	C15—C14—N3	120.1 (3)
C3—C2—C1	118.4 (3)	C14—C15—C16	119.8 (3)
C3—C2—H2	120.8	C14—C15—H15	120.1
C1—C2—H2	120.8	C16—C15—H15	120.1
C2—C3—C4	121.2 (3)	C17—C16—C15	118.1 (3)
C2—C3—H3A	119.4	C17—C16—H16	121.0
C4—C3—H3A	119.4	C15—C16—H16	121.0
C5—C4—C3	120.4 (3)	C16—C17—C18	122.6 (3)
C5—C4—H4	119.8	C16—C17—H17	118.7
C3—C4—H4	119.8	C18—C17—H17	118.7
C4—C5—C6	120.4 (3)	C17—C18—C19	118.7 (3)
C4—C5—H5	119.8	C17—C18—H18	120.7
C6—C5—H5	119.8	C19—C18—H18	120.7
C1—C6—N1	120.5 (2)	S1—C20—H20A	109.5
C1—C6—C5	118.6 (2)	S1—C20—H20B	109.5
N1—C6—C5	120.9 (2)	H20A—C20—H20B	109.5
O1—C7—N1	124.4 (3)	S1—C20—H20C	109.5
O1—C7—C8	120.3 (2)	H20A—C20—H20C	109.5
N1—C7—C8	115.3 (2)	H20B—C20—H20C	109.5
N2—C8—C9	123.0 (3)	S2—C21—H21A	109.5
N2—C8—C7	118.9 (2)	S2—C21—H21B	109.5
C9—C8—C7	118.0 (3)	H21A—C21—H21B	109.5
C10—C9—C8	118.2 (3)	S2—C21—H21C	109.5
C10—C9—H9	120.9	H21A—C21—H21C	109.5
C8—C9—H9	120.9	H21B—C21—H21C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1	0.86	2.59	2.924 (2)	104
N1—H1···N2	0.86	2.31	2.726 (3)	110
N3—H3···S2	0.86	2.45	2.924 (2)	115
N3—H3···N2	0.86	2.28	2.712 (3)	111
C2—H2···O1^i	0.93	2.50	3.374 (3)	156
C5—H5···O1	0.93	2.39	2.886 (3)	113
C15—H15···O2	0.93	2.21	2.823 (3)	123
C20—H20C···O2^ii	0.96	2.52	3.448 (3)	163

Symmetry codes: (i) −x+5/2, y−1/2, −z+3/2; (ii) x+1/2, −y+1/2, z+1/2.