Butane-1,2,3,4-tetra-carboxylic acid-4,4'-bipyridine (1/2).

The hydro-thermal reaction of butane-1,2,3,4-tetra-carboxylic acid (H(4)butca), 4,4'-bipyridine (bipy) and Mn(SO(4))(2)·H(2)O afforded a new co-crystal, C(8)H(10)O(8)·2C(10)H(8)N(2) or H(4)butca·2(bipy), in which strong O-H⋯N hydrogen-bonding and weak π-π stacking [centroid-centroid distance = 3.8459 (19) Å] inter-actions assemble the organic mol-ecules into a three-dimensional supra-molecular framework. C-H⋯O inter-actions are also present. The whole mol-ecule has inversion symmetry.

Related literature

For the importance of hydrogen-bonding and π-π stacking inter­actions in supra­molecular chemistry, crystal engineering and biological recognition, see: Wang et al. (2007 ▶). Many organic co-crystals have been assembled from N-heterocycles and polycarboxylic acids, see: Li et al. (2007 ▶). For the 1:1 co-crystal H4butca·bipy, see: Najafpour et al. (2008 ▶).

Experimental

Crystal data

C8H10O8·2C10H8N2

M = 546.53

Triclinic,

a = 7.4435 (11) Å

b = 8.6990 (13) Å

c = 11.438 (2) Å

α = 99.819 (3)°

β = 105.662 (3)°

γ = 111.361 (2)°

V = 633.57 (17) Å3

Z = 1

Mo Kα radiation

μ = 0.11 mm−1

T = 296 K

0.30 × 0.30 × 0.30 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.969, T max = 0.969

3287 measured reflections

2196 independent reflections

1721 reflections with I > 2σ(I)

R int = 0.013

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.176

S = 1.07

2196 reflections

183 parameters

H-atom parameters constrained

Δρmax = 0.78 e Å−3

Δρmin = −0.30 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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 global, I, New_Global_Publ_Block. DOI: 10.1107/S1600536809029237/at2847sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029237/at2847Isup2.hkl

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

C8H10O8·2C10H8N2	Z = 1
Mr = 546.53	F(000) = 286
Triclinic, P1	Dx = 1.432 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4435 (11) Å	Cell parameters from 1387 reflections
b = 8.6990 (13) Å	θ = 2.6–26.6°
c = 11.438 (2) Å	µ = 0.11 mm−1
α = 99.819 (3)°	T = 296 K
β = 105.662 (3)°	Block, colourless
γ = 111.361 (2)°	0.30 × 0.30 × 0.30 mm
V = 633.57 (17) Å3

Bruker SMART APEXII CCD area-detector diffractometer	2196 independent reflections
Radiation source: fine-focus sealed tube	1721 reflections with I > 2σ(I)
graphite	Rint = 0.013
φ and ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.969, Tmax = 0.969	k = −9→10
3287 measured reflections	l = −13→9

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.176	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0797P)2 + 0.4629P] where P = (Fo2 + 2Fc2)/3
2196 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.78 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	−0.1342 (5)	0.6302 (4)	−0.0696 (3)	0.0508 (7)
C2	−0.0232 (5)	0.7892 (4)	0.0456 (3)	0.0597 (9)
H2A	−0.1212	0.7939	0.0858	0.072*
H2B	0.0844	0.7742	0.1058	0.072*
C3	0.0728 (5)	0.9587 (3)	0.0242 (3)	0.0548 (8)
H3	0.1316	0.9400	−0.0410	0.066*
C4	0.2542 (5)	1.0895 (4)	0.1447 (3)	0.0498 (7)
C5	−0.2914 (4)	0.4885 (4)	0.4266 (3)	0.0479 (7)
H5	−0.3917	0.4111	0.4485	0.057*
C6	−0.1373 (4)	0.6347 (4)	0.5207 (3)	0.0449 (7)
H6	−0.1346	0.6548	0.6038	0.054*
C7	0.0146 (4)	0.7522 (3)	0.4900 (2)	0.0368 (6)
C8	−0.0007 (4)	0.7138 (4)	0.3640 (3)	0.0490 (7)
H8	0.0963	0.7888	0.3387	0.059*
C9	−0.1600 (5)	0.5644 (4)	0.2767 (3)	0.0543 (8)
H9	−0.1671	0.5408	0.1928	0.065*
C10	0.1856 (4)	0.9112 (3)	0.5876 (2)	0.0373 (6)
C11	0.2302 (4)	0.9316 (4)	0.7163 (3)	0.0467 (7)
H11	0.1531	0.8442	0.7436	0.056*
C12	0.3888 (4)	1.0814 (4)	0.8037 (3)	0.0515 (7)
H12	0.4160	1.0920	0.8897	0.062*
C13	0.4643 (4)	1.1920 (4)	0.6489 (3)	0.0500 (7)
H13	0.5455	1.2815	0.6249	0.060*
C14	0.3093 (4)	1.0477 (4)	0.5543 (3)	0.0452 (7)
H14	0.2869	1.0409	0.4692	0.054*
N1	−0.3041 (4)	0.4522 (3)	0.3059 (2)	0.0486 (6)
N2	0.5053 (3)	1.2116 (3)	0.7720 (2)	0.0480 (6)
O1	−0.1175 (4)	0.6219 (3)	−0.1724 (2)	0.0646 (6)
O2	−0.2488 (4)	0.5023 (3)	−0.0413 (2)	0.0675 (7)
H2	−0.3115	0.4168	−0.1043	0.101*
O3	0.4001 (3)	1.1949 (3)	0.11635 (17)	0.0535 (6)
H3A	0.4895	1.2695	0.1816	0.080*
O4	0.2601 (3)	1.0897 (3)	0.25184 (19)	0.0617 (6)

	U11	U22	U33	U12	U13	U23
C1	0.0491 (16)	0.0413 (16)	0.0448 (17)	0.0165 (13)	0.0013 (13)	0.0039 (13)
C2	0.0589 (19)	0.0442 (17)	0.0560 (19)	0.0128 (15)	0.0062 (15)	0.0121 (14)
C3	0.0543 (17)	0.0355 (15)	0.0479 (17)	0.0079 (13)	−0.0013 (14)	0.0065 (12)
C4	0.0508 (17)	0.0385 (15)	0.0391 (16)	0.0143 (13)	−0.0039 (13)	0.0051 (12)
C5	0.0422 (15)	0.0415 (15)	0.0449 (16)	0.0070 (13)	0.0106 (12)	0.0105 (12)
C6	0.0477 (15)	0.0451 (15)	0.0353 (14)	0.0143 (13)	0.0142 (12)	0.0103 (12)
C7	0.0358 (13)	0.0365 (13)	0.0354 (13)	0.0156 (11)	0.0095 (11)	0.0098 (11)
C8	0.0465 (16)	0.0501 (16)	0.0375 (15)	0.0092 (13)	0.0148 (12)	0.0096 (12)
C9	0.0551 (17)	0.0537 (17)	0.0353 (15)	0.0106 (14)	0.0126 (13)	0.0038 (13)
C10	0.0348 (13)	0.0363 (13)	0.0370 (14)	0.0146 (11)	0.0102 (11)	0.0079 (11)
C11	0.0471 (15)	0.0432 (15)	0.0377 (14)	0.0086 (13)	0.0138 (12)	0.0100 (12)
C12	0.0498 (16)	0.0526 (17)	0.0360 (15)	0.0120 (14)	0.0100 (13)	0.0068 (13)
C13	0.0447 (16)	0.0410 (15)	0.0536 (17)	0.0087 (13)	0.0148 (13)	0.0159 (13)
C14	0.0453 (15)	0.0460 (15)	0.0395 (15)	0.0142 (13)	0.0145 (12)	0.0150 (12)
N1	0.0450 (13)	0.0419 (13)	0.0417 (14)	0.0105 (11)	0.0060 (10)	0.0056 (10)
N2	0.0398 (12)	0.0424 (13)	0.0469 (14)	0.0088 (10)	0.0098 (10)	0.0079 (10)
O1	0.0678 (15)	0.0481 (13)	0.0711 (16)	0.0150 (11)	0.0286 (12)	0.0185 (11)
O2	0.0788 (16)	0.0500 (13)	0.0436 (12)	0.0084 (12)	0.0114 (11)	0.0034 (10)
O3	0.0456 (11)	0.0456 (12)	0.0373 (11)	0.0028 (9)	−0.0005 (9)	−0.0005 (9)
O4	0.0599 (13)	0.0513 (13)	0.0424 (12)	0.0047 (10)	0.0019 (10)	0.0097 (9)

C1—O1	1.209 (4)	C7—C10	1.484 (4)
C1—O2	1.285 (4)	C8—C9	1.374 (4)
C1—C2	1.513 (4)	C8—H8	0.9300
C2—C3	1.482 (4)	C9—N1	1.325 (4)
C2—H2A	0.9700	C9—H9	0.9300
C2—H2B	0.9700	C10—C11	1.383 (4)
C3—C4	1.536 (4)	C10—C14	1.395 (4)
C3—C3i	1.542 (6)	C11—C12	1.374 (4)
C3—H3	0.9800	C11—H11	0.9300
C4—O4	1.214 (3)	C12—N2	1.327 (4)
C4—O3	1.301 (4)	C12—H12	0.9300
C5—N1	1.332 (4)	C13—N2	1.324 (4)
C5—C6	1.377 (4)	C13—C14	1.373 (4)
C5—H5	0.9300	C13—H13	0.9300
C6—C7	1.393 (4)	C14—H14	0.9300
C6—H6	0.9300	O2—H2	0.8200
C7—C8	1.386 (4)	O3—H3A	0.8200
O1—C1—O2	124.5 (3)	C6—C7—C10	121.7 (2)
O1—C1—C2	126.0 (3)	C9—C8—C7	119.6 (3)
O2—C1—C2	109.5 (3)	C9—C8—H8	120.2
C3—C2—C1	117.3 (3)	C7—C8—H8	120.2
C3—C2—H2A	108.0	N1—C9—C8	123.5 (3)
C1—C2—H2A	108.0	N1—C9—H9	118.3
C3—C2—H2B	108.0	C8—C9—H9	118.3
C1—C2—H2B	108.0	C11—C10—C14	116.6 (2)
H2A—C2—H2B	107.2	C11—C10—C7	121.5 (2)
C2—C3—C4	110.8 (2)	C14—C10—C7	121.8 (2)
C2—C3—C3i	116.5 (3)	C12—C11—C10	119.8 (3)
C4—C3—C3i	108.9 (3)	C12—C11—H11	120.1
C2—C3—H3	106.7	C10—C11—H11	120.1
C4—C3—H3	106.7	N2—C12—C11	123.5 (3)
C3i—C3—H3	106.7	N2—C12—H12	118.2
O4—C4—O3	125.2 (2)	C11—C12—H12	118.2
O4—C4—C3	123.6 (3)	N2—C13—C14	124.0 (3)
O3—C4—C3	111.2 (3)	N2—C13—H13	118.0
N1—C5—C6	123.4 (3)	C14—C13—H13	118.0
N1—C5—H5	118.3	C13—C14—C10	119.2 (3)
C6—C5—H5	118.3	C13—C14—H14	120.4
C5—C6—C7	119.2 (2)	C10—C14—H14	120.4
C5—C6—H6	120.4	C9—N1—C5	117.3 (2)
C7—C6—H6	120.4	C13—N2—C12	116.9 (2)
C8—C7—C6	117.0 (2)	C1—O2—H2	109.5
C8—C7—C10	121.3 (2)	C4—O3—H3A	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O4	0.93	2.56	3.476 (3)	168
C9—H9···O2	0.93	2.51	3.425 (4)	167
O3—H3A···N1ii	0.82	1.78	2.595 (3)	170
O2—H2···N2iii	0.82	1.84	2.642 (3)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O4	0.93	2.56	3.476 (3)	168
C9—H9⋯O2	0.93	2.51	3.425 (4)	167
O3—H3A⋯N1i	0.82	1.78	2.595 (3)	170
O2—H2⋯N2ii	0.82	1.84	2.642 (3)	167

Symmetry codes: (i) ; (ii) .