4,4'-Bipyridine-2-(carb-oxy-methyl-sulfan-yl)pyridine-3-carb-oxy-lic acid (1/1).

In the title co-crystal, C(10)H(8)N(2)·C(8)H(7)NO(4)S, the formate group is coplanar with the pyridyl ring of the acid [dihedral angle = 6.2 (7)°], while the carb-oxy-methyl-sulfanyl group makes a C-S-C-C torsion angle of 70.2 (1)° with the pyridine ring. The dihedral angle between the pyridyl rings of the 4,4'-bipyridine mol-ecule is 27.4 (1)°. The acid and the 4,4'-bipyridine mol-ecules are involved in hydrogen bonding via carb-oxy-lic O and pyridyl N atoms. The structure is further consolidated by inter-molecular C-H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

For related structures, see: Wang & Feng (2010 ▶); Zhu et al. (2002 ▶); Smith & Sagatys (2003 ▶).

Experimental

Crystal data

C10H8N2·C8H7NO4S

M = 369.40

Monoclinic,

a = 9.3684 (3) Å

b = 10.3044 (3) Å

c = 18.2264 (5) Å

β = 106.494 (2)°

V = 1687.09 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 296 K

0.41 × 0.25 × 0.10 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.935, T max = 0.978

24834 measured reflections

3927 independent reflections

3106 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.144

S = 1.08

3927 reflections

241 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); 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/S1600536810048385/pv2357sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048385/pv2357Isup2.hkl

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

C10H8N2·C8H7NO4S	F(000) = 768
Mr = 369.40	Dx = 1.454 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7490 reflections
a = 9.3684 (3) Å	θ = 2.3–27.7°
b = 10.3044 (3) Å	µ = 0.22 mm−1
c = 18.2264 (5) Å	T = 296 K
β = 106.494 (2)°	Block, colourless
V = 1687.09 (9) Å3	0.41 × 0.25 × 0.10 mm
Z = 4

Bruker APEXII area-detector diffractometer	3927 independent reflections
Radiation source: fine-focus sealed tube	3106 reflections with I > 2σ(I)
graphite	Rint = 0.028
ω scans	θmax = 27.7°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.935, Tmax = 0.978	k = −13→13
24834 measured reflections	l = −23→23

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
3927 reflections	(Δ/σ)max < 0.001
241 parameters	Δρmax = 0.27 e Å−3
2 restraints	Δρmin = −0.25 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
S1	0.58161 (5)	0.38154 (4)	0.14705 (2)	0.04516 (16)
O1	0.80222 (16)	0.58013 (13)	−0.00541 (8)	0.0686 (4)
H1B	0.837 (2)	0.6539 (17)	0.0143 (12)	0.082*
O2	0.72352 (16)	0.57771 (12)	0.09792 (7)	0.0640 (4)
O3	0.70285 (16)	0.13228 (12)	0.22294 (9)	0.0705 (4)
H3B	0.740 (2)	0.0553 (17)	0.2308 (13)	0.085*
O4	0.49171 (15)	0.02161 (13)	0.18621 (8)	0.0722 (4)
N1	0.52552 (13)	0.21214 (12)	0.03258 (7)	0.0418 (3)
C1	0.58945 (15)	0.32661 (14)	0.05633 (7)	0.0368 (3)
C2	0.65886 (15)	0.40173 (13)	0.01174 (8)	0.0382 (3)
C3	0.65803 (17)	0.35450 (15)	−0.05940 (9)	0.0439 (4)
H3A	0.7020	0.4022	−0.0905	0.053*
C4	0.59198 (17)	0.23668 (16)	−0.08426 (8)	0.0472 (4)
H4A	0.5906	0.2035	−0.1319	0.057*
C5	0.52829 (17)	0.17006 (15)	−0.03640 (9)	0.0453 (4)
H5A	0.4842	0.0904	−0.0530	0.054*
C6	0.73076 (16)	0.52758 (14)	0.03952 (8)	0.0424 (3)
C7	0.48104 (17)	0.25100 (16)	0.17466 (8)	0.0467 (4)
H7A	0.4508	0.2794	0.2187	0.056*
H7B	0.3909	0.2367	0.1333	0.056*
C8	0.5588 (2)	0.12241 (15)	0.19413 (9)	0.0475 (4)
N2	−0.08632 (19)	−0.19297 (15)	0.05293 (10)	0.0635 (4)
N3	0.16287 (17)	0.40694 (14)	0.23065 (9)	0.0560 (4)
C9	0.0353 (2)	−0.18397 (18)	0.11218 (13)	0.0652 (5)
H9A	0.0884	−0.2595	0.1296	0.078*
C10	−0.1626 (2)	−0.0845 (2)	0.03031 (12)	0.0622 (5)
H10A	−0.2482	−0.0888	−0.0108	0.075*
C11	0.08680 (19)	−0.07012 (17)	0.14907 (10)	0.0551 (4)
H11A	0.1739	−0.0690	0.1893	0.066*
C12	−0.12119 (17)	0.03452 (18)	0.06467 (9)	0.0529 (4)
H12A	−0.1787	0.1079	0.0472	0.064*
C13	0.00740 (16)	0.04348 (15)	0.12563 (9)	0.0415 (3)
C14	0.05830 (16)	0.16981 (15)	0.16269 (8)	0.0401 (3)
C15	0.14430 (19)	0.17679 (16)	0.23814 (9)	0.0500 (4)
H15A	0.1683	0.1018	0.2675	0.060*
C16	0.02397 (18)	0.28557 (16)	0.12271 (10)	0.0513 (4)
H16A	−0.0352	0.2859	0.0722	0.062*
C17	0.0788 (2)	0.39998 (17)	0.15887 (11)	0.0584 (5)
H17A	0.0554	0.4768	0.1313	0.070*
C18	0.19387 (19)	0.29589 (19)	0.26931 (9)	0.0558 (4)
H18A	0.2520	0.2990	0.3200	0.067*

	U11	U22	U33	U12	U13	U23
S1	0.0619 (3)	0.0338 (2)	0.0371 (2)	0.00022 (15)	0.00974 (18)	−0.00146 (13)
O1	0.0904 (9)	0.0499 (7)	0.0768 (9)	−0.0340 (7)	0.0421 (7)	−0.0215 (7)
O2	0.0957 (9)	0.0453 (7)	0.0505 (7)	−0.0223 (6)	0.0201 (6)	−0.0118 (5)
O3	0.0620 (8)	0.0418 (7)	0.0978 (11)	0.0049 (5)	0.0069 (7)	0.0182 (7)
O4	0.0866 (9)	0.0450 (7)	0.0837 (9)	−0.0169 (6)	0.0219 (7)	−0.0054 (6)
N1	0.0473 (7)	0.0326 (6)	0.0419 (6)	−0.0030 (5)	0.0066 (5)	−0.0008 (5)
C1	0.0382 (7)	0.0311 (7)	0.0360 (7)	0.0029 (5)	0.0021 (5)	0.0002 (5)
C2	0.0377 (7)	0.0323 (7)	0.0402 (7)	0.0007 (5)	0.0038 (6)	−0.0013 (6)
C3	0.0503 (8)	0.0385 (8)	0.0432 (8)	−0.0029 (6)	0.0136 (7)	−0.0021 (6)
C4	0.0578 (9)	0.0420 (9)	0.0402 (7)	−0.0048 (7)	0.0113 (6)	−0.0091 (6)
C5	0.0513 (8)	0.0337 (8)	0.0446 (8)	−0.0048 (6)	0.0035 (6)	−0.0057 (6)
C6	0.0441 (7)	0.0346 (7)	0.0441 (8)	−0.0022 (6)	0.0053 (6)	−0.0012 (6)
C7	0.0519 (8)	0.0475 (9)	0.0423 (7)	0.0013 (7)	0.0159 (6)	0.0000 (7)
C8	0.0648 (10)	0.0396 (9)	0.0400 (8)	−0.0031 (7)	0.0180 (7)	0.0010 (6)
N2	0.0739 (10)	0.0459 (9)	0.0798 (11)	−0.0249 (7)	0.0365 (8)	−0.0189 (8)
N3	0.0591 (8)	0.0457 (8)	0.0636 (9)	−0.0107 (6)	0.0180 (7)	−0.0158 (7)
C9	0.0743 (12)	0.0388 (9)	0.0883 (14)	−0.0044 (8)	0.0326 (11)	−0.0061 (9)
C10	0.0542 (10)	0.0619 (12)	0.0694 (12)	−0.0208 (8)	0.0157 (9)	−0.0180 (10)
C11	0.0557 (10)	0.0412 (9)	0.0656 (11)	−0.0013 (7)	0.0129 (8)	−0.0010 (7)
C12	0.0454 (8)	0.0477 (9)	0.0611 (10)	−0.0055 (7)	0.0077 (7)	−0.0079 (8)
C13	0.0412 (7)	0.0378 (8)	0.0466 (7)	−0.0066 (6)	0.0141 (6)	−0.0018 (6)
C14	0.0396 (7)	0.0361 (8)	0.0445 (7)	−0.0038 (6)	0.0114 (6)	−0.0025 (6)
C15	0.0582 (9)	0.0453 (9)	0.0437 (8)	−0.0038 (7)	0.0097 (7)	0.0010 (7)
C16	0.0546 (9)	0.0411 (9)	0.0513 (8)	−0.0014 (7)	0.0035 (7)	0.0008 (7)
C17	0.0675 (11)	0.0355 (9)	0.0692 (11)	−0.0010 (7)	0.0143 (9)	0.0013 (8)
C18	0.0603 (10)	0.0592 (11)	0.0447 (8)	−0.0069 (8)	0.0098 (7)	−0.0095 (8)

S1—C1	1.7688 (14)	N2—C10	1.328 (3)
S1—C7	1.7943 (17)	N2—C9	1.332 (3)
O1—C6	1.3127 (19)	N3—C17	1.324 (2)
O1—H1B	0.864 (16)	N3—C18	1.332 (2)
O2—C6	1.2023 (19)	C9—C11	1.370 (2)
O3—C8	1.305 (2)	C9—H9A	0.9300
O3—H3B	0.861 (16)	C10—C12	1.382 (2)
O4—C8	1.2015 (19)	C10—H10A	0.9300
N1—C5	1.3373 (19)	C11—C13	1.388 (2)
N1—C1	1.3379 (18)	C11—H11A	0.9300
C1—C2	1.408 (2)	C12—C13	1.391 (2)
C2—C3	1.383 (2)	C12—H12A	0.9300
C2—C6	1.4827 (19)	C13—C14	1.482 (2)
C3—C4	1.379 (2)	C14—C15	1.384 (2)
C3—H3A	0.9300	C14—C16	1.387 (2)
C4—C5	1.372 (2)	C15—C18	1.377 (2)
C4—H4A	0.9300	C15—H15A	0.9300
C5—H5A	0.9300	C16—C17	1.377 (2)
C7—C8	1.505 (2)	C16—H16A	0.9300
C7—H7A	0.9700	C17—H17A	0.9300
C7—H7B	0.9700	C18—H18A	0.9300
C1—S1—C7	100.76 (7)	C17—N3—C18	117.10 (15)
C6—O1—H1B	107.7 (15)	N2—C9—C11	123.95 (18)
C8—O3—H3B	108.5 (15)	N2—C9—H9A	118.0
C5—N1—C1	117.62 (13)	C11—C9—H9A	118.0
N1—C1—C2	122.38 (13)	N2—C10—C12	123.33 (17)
N1—C1—S1	116.80 (11)	N2—C10—H10A	118.3
C2—C1—S1	120.81 (11)	C12—C10—H10A	118.3
C3—C2—C1	117.85 (13)	C9—C11—C13	119.21 (16)
C3—C2—C6	120.60 (14)	C9—C11—H11A	120.4
C1—C2—C6	121.55 (13)	C13—C11—H11A	120.4
C4—C3—C2	120.01 (14)	C10—C12—C13	119.28 (16)
C4—C3—H3A	120.0	C10—C12—H12A	120.4
C2—C3—H3A	120.0	C13—C12—H12A	120.4
C5—C4—C3	117.84 (14)	C11—C13—C12	117.19 (14)
C5—C4—H4A	121.1	C11—C13—C14	121.72 (13)
C3—C4—H4A	121.1	C12—C13—C14	121.08 (14)
N1—C5—C4	124.29 (14)	C15—C14—C16	117.39 (14)
N1—C5—H5A	117.9	C15—C14—C13	121.31 (14)
C4—C5—H5A	117.9	C16—C14—C13	121.29 (13)
O2—C6—O1	122.82 (14)	C18—C15—C14	119.29 (15)
O2—C6—C2	122.94 (14)	C18—C15—H15A	120.4
O1—C6—C2	114.24 (13)	C14—C15—H15A	120.4
C8—C7—S1	117.93 (12)	C17—C16—C14	119.04 (15)
C8—C7—H7A	107.8	C17—C16—H16A	120.5
S1—C7—H7A	107.8	C14—C16—H16A	120.5
C8—C7—H7B	107.8	N3—C17—C16	123.77 (17)
S1—C7—H7B	107.8	N3—C17—H17A	118.1
H7A—C7—H7B	107.2	C16—C17—H17A	118.1
O4—C8—O3	124.16 (16)	N3—C18—C15	123.39 (15)
O4—C8—C7	122.06 (17)	N3—C18—H18A	118.3
O3—C8—C7	113.72 (14)	C15—C18—H18A	118.3
C10—N2—C9	117.01 (15)
C5—N1—C1—C2	−0.4 (2)	C10—N2—C9—C11	−1.7 (3)
C5—N1—C1—S1	178.95 (11)	C9—N2—C10—C12	0.4 (3)
C7—S1—C1—N1	−0.26 (12)	N2—C9—C11—C13	1.7 (3)
C7—S1—C1—C2	179.13 (11)	N2—C10—C12—C13	0.7 (3)
N1—C1—C2—C3	0.8 (2)	C9—C11—C13—C12	−0.5 (2)
S1—C1—C2—C3	−178.52 (11)	C9—C11—C13—C14	−179.32 (15)
N1—C1—C2—C6	−179.22 (12)	C10—C12—C13—C11	−0.6 (2)
S1—C1—C2—C6	1.43 (18)	C10—C12—C13—C14	178.20 (15)
C1—C2—C3—C4	−0.7 (2)	C11—C13—C14—C15	−27.4 (2)
C6—C2—C3—C4	179.39 (14)	C12—C13—C14—C15	153.82 (17)
C2—C3—C4—C5	0.1 (2)	C11—C13—C14—C16	151.38 (17)
C1—N1—C5—C4	−0.2 (2)	C12—C13—C14—C16	−27.4 (2)
C3—C4—C5—N1	0.3 (2)	C16—C14—C15—C18	−1.3 (2)
C3—C2—C6—O2	173.56 (15)	C13—C14—C15—C18	177.51 (15)
C1—C2—C6—O2	−6.4 (2)	C15—C14—C16—C17	1.3 (2)
C3—C2—C6—O1	−6.0 (2)	C13—C14—C16—C17	−177.48 (15)
C1—C2—C6—O1	174.06 (14)	C18—N3—C17—C16	−0.6 (3)
C1—S1—C7—C8	70.16 (12)	C14—C16—C17—N3	−0.4 (3)
S1—C7—C8—O4	−152.53 (14)	C17—N3—C18—C15	0.6 (3)
S1—C7—C8—O3	30.22 (19)	C14—C15—C18—N3	0.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···N2i	0.86 (2)	1.79 (2)	2.6564 (18)	178 (2)
O3—H3B···N3ii	0.86 (2)	1.82 (2)	2.6618 (18)	167 (2)
C4—H4A···O4iii	0.93	2.55	3.213 (2)	128
C15—H15A···O2ii	0.93	2.39	3.0664 (19)	130
C18—H18A···o2ii	0.93	2.70	3.232 (2)	117

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯N2i	0.86 (2)	1.79 (2)	2.6564 (18)	178 (2)
O3—H3B⋯N3ii	0.86 (2)	1.82 (2)	2.6618 (18)	167 (2)
C4—H4A⋯O4iii	0.93	2.55	3.213 (2)	128
C15—H15A⋯O2ii	0.93	2.39	3.0664 (19)	130
C18—H18A⋯o2ii	0.93	2.70	3.232 (2)	117

Symmetry codes: (i) ; (ii) ; (iii) .