Two-dimensional hydrogen-bonded supramolecular networks in the compounds of benzene-1,2,4,5-tetracarboxylic acid (pyromellitic acid) with 2,2′-biimidazole and 4,4′-dimethyl-2,2′-bipyridine

DOI: 10.1107/S0108270113030801

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Acta Crystallographica, Section C: Crystal Structure Communications p. 1537 - 1540 (2013)

Update date:2022-07-30

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Zhong, Kai-Long

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Article abstract of DOI:10.1107/S0108270113030801

Two products from the proton-transfer reactions of benzene-1,2,4,5- tetracarboxylic acid (pyromellitic acid, PMA) with 2,2′-biimidazole and 4,4′-dimethyl-2,2′-bipyridine, namely 2,2′-biimidazole-3, 3′-diium 2,5-dicarboxybenzene-1,4-dicarboxylate, C₆H ₈N₄ ²⁺,C₁₀H₄O₈ ^2-, (I), and 4-methyl-2-(4-methylpyridin-2-yl)pyridinium 2,4,5-tricarboxybenzoate monohydrate, C₁₂H₁₃N₂ ⁺·C₁₀H₅O₈ ^-·H₂O, (II), have been prepared and their structures determined. Both compounds crystallize in the space group P . The asymmetric unit of (I) is composed of two independent ion pairs. Both the 2,2′-biimidazole-3,3′-diium dication and the PMA^2- anion are located on special positions (inversion centres). The protonated 2,2′-biimidazole-3,3′-diium ring H atoms are involved in hydrogen bonding with carboxylate O atoms to form one-dimensional hydrogen-bonded chain structures. Adjacent chains are further linked via carboxyl-carboxyl O - H...O hydrogen bonding, resulting in a two-dimensional supramolecular sheet with the R 6 ⁵(34) motif extending in the (1 1) plane. In (II), classical O - H...O hydrogen-bond-linked anion-anion units are extended into a one-dimensional chain running parallel to the [100] direction, giving an R 2 ²(8)R 4 ⁴(30) motif. The chains are connected by water-carboxyl O - H...O hydrogen bonds to form a two-dimensional network parallel to the (01) plane. The 4-methyl-2-(4-methylpyridin-2-yl)pyridinium cations lie between the two-dimensional supramolecular layers linked via N - H...O hydrogen-bonding interactions.

Full text of DOI:10.1107/S0108270113030801

organic compounds

Acta Crystallographica Section C

Crystal Structure

Communications

& Robson, 1998; Juan et al., 2002; Qiu et al., 2008), owing to

the fact that moderately directional intermolecular interaction

can effectively control short-range packing. Polycarboxylic

acids, such as benzene-1,2,4,5-tetracarboxylic acid (pyromel-

litic acid, PMA; Li et al., 2003; Oscar et al., 2008), benzene-

1,3,5-tricarboxylic acid (Pasdar et al., 2011) and benzene-

1,2,3,4-tetracarboxylic acid (Zhang et al., 2010), have been

applied widely in constructing interesting supramolecular

networks because they act not only as hydrogen-bond accep-

ters but also as hydrogen-bond donors, depending upon the

number of deprotonated carboxylic acid groups. Many tran-

sition-metal complexes with benzene-1,2,4,5-tetracarboxylate

have previously been synthesized and reported, such as the

zinc (Rochon & Massarweh, 2000), nickel (Poleti et al., 1988;

Murugavel et al., 2002), manganese (Hu et al., 2001), cobalt

ISSN 0108-2701

Two-dimensional hydrogen-bonded

supramolecular networks in the

compounds of benzene-1,2,4,5-tetra-

carboxylic acid (pyromellitic acid)

with 2,2⁰-biimidazole and 4,4⁰-di-

methyl-2,2⁰-bipyridine

Kai-Long Zhong

Department of Applied Chemistry, Nanjing College of Chemical Technology,

Nanjing 210048, People’s Republic of China

Correspondence e-mail: zklong76@163.com

Received 24 September 2013

Accepted 9 November 2013

Two products from the proton-transfer reactions of benzene-

1,2,4,5-tetracarboxylic acid (pyromellitic acid, PMA) with 2,2⁰-

biimidazole and 4,4⁰-dimethyl-2,2⁰-bipyridine, namely 2,2⁰-

biimidazole-3,3⁰-diium 2,5-dicarboxybenzene-1,4-dicarboxylate,

C₆H₈N₄²⁺,C₁₀H₄O₈^2ꢀ, (I), and 4-methyl-2-(4-methylpyridin-2-

yl)pyridinium 2,4,5-tricarboxybenzoate monohydrate, C₁₂H₁₃-

N₂ꢁC₁₀H₅O₈^ꢀꢁH₂O, (II), have been prepared and their

structures determined. Both compounds crystallize in the space

group P1. The asymmetric unit of (I) is composed of two

independent ion pairs. Both the 2,2⁰-biimidazole-3,3⁰-diium

dication and the PMA^2ꢀanion are located on special positions

(inversion centres). The protonated 2,2⁰-biimidazole-3,3⁰-diium

ring H atoms are involved in hydrogen bonding with carboxyl-

ate O atoms to form one-dimensional hydrogen-bonded chain

structures. Adjacent chains are further linked via carboxyl–

carboxyl O—Hꢁ ꢁ ꢁO hydrogen bonding, resulting in a two-

dimensional supramolecular sheet with the R⁵₆(34) motif

extending in the (121) plane. In (II), classical O—Hꢁ ꢁ ꢁO

hydrogen-bond-linked anion–anion units are extended into a

one-dimensional chain running parallel to the [100] direction,

giving an R²₂(8)R⁴₄(30) motif. The chains are connected by

water–carboxyl O—Hꢁ ꢁ ꢁO hydrogen bonds to form a two-

dimensional network parallel to the (011) plane. The 4-methyl-

2-(4-methylpyridin-2-yl)pyridinium cations lie between the

two-dimensional supramolecular layers linked via N—Hꢁ ꢁ ꢁO

hydrogen-bonding interactions.

(Cheng et al., 2002), copper (Cao et al., 2002), silver (Jaber et

al., 1997) and iron complexes (Chu et al., 2001). As far as we

know, reports on benzene-1,2,4,5-tetracarboxylate salts with

organic Lewis bases are few, e.g. guanidinium pyromellitate

trihydrate monoperhydrate (Adams & Ramdas, 1978), 2,2⁰-

bipyridinium hemi[benzene-1,2,4,5-tetracarboxylate(2ꢀ)] hemi-

(benzene-1,2,4,5-tetracarboxylic acid) (Mrvos-Sermek et al.,

1996), guanidinuium pyromellite (Sun et al., 2002a), imidazo-

lium trihydrogen benzene-1,2,4,5-tetracarboxylate (Sun et al.,

2002b), 6,21-diaza-3,9,18,24-tetraazoniatricyclo[22.2.2.2^11,14]-

triaconta-11,13,24,26(1),27,29-hexaene benzene-1,2,4,5-tetra-

carboxylate(4ꢀ) hexahydrate (Zhu et al., 2002), ethylene-

diammonium bis(trihydrogen benzene-1,2,4,5-tetracarboxyl-

ate) dehydrate (Li et al., 2006). Recently, we attempted to

utilize polycarboxylate acids and N-containing bidentate

ligands as mixed ligands for the design of coordination

networks. The title PMA salts of 2,2⁰-biimidazole and 4,4⁰-

dimethyl-2,2⁰-bipyridine, namely 2,2⁰-biimidazole-3,3⁰-diium

2,5-dicarboxybenzene-1,4-dicarboxylate, (I), and 4-methyl-2-

Keywords: crystal structure; hydrogen bonding; pyromellitic

acid; 2,2⁰-biimidazole; 4,4⁰-dimethyl-2,2⁰-bipyridine.

(4-methylpyridin-2-yl)pyridinium

2,4,5-tricarboxybenzoate

monohydrate, (II), were obtained unintentionally during an

attempt to synthesize mixed-ligand transition-metal com-

plexes with PMA and N-containing ligands via a solvothermal

reaction. Their crystal structures have not been reported

previously.

1. Introduction

It is well established that hydrogen bonds play vital roles in

molecular recognition and supramolecular chemistry (Batten

Acta Cryst. (2013). C69, 1537–1540

doi:10.1107/S0108270113030801

# 2013 International Union of Crystallography 1537

organic compounds

Table 1

Experimental details.

(I)

(II)

Crystal data

Chemical formula

M_r

C₆H₈N₄ꢁC₁₀H₄O₈

2ꢀ

C₁₂H₁₃N₂ꢁC₁₀H₅O₈^ꢀꢁH₂O

388.30

456.40

Triclinic, P1

223

9.5166 (7), 9.9970 (8), 12.4106 (8)

77.979 (6), 73.421 (6), 62.655 (8)

1001.03 (13)

Crystal system, space group

Temperature (K)

Triclinic, P1

223

8.2246 (16), 8.7495 (17), 11.454 (2)

100.67 (3), 97.26 (3), 94.68 (3)

798.8 (3)

a, b, c (A)

ꢀ, ꢁ, ꢂ (^ꢂ)

V (A )

Radiation type

Mo Kꢀ

0.13

0.40 ꢄ 0.27 ꢄ 0.20

Mo Kꢀ

0.12

0.30 ꢄ 0.22 ꢄ 0.10

ꢃ (mm^ꢀ1

Crystal size (mm)

)

Data collection

Diffractometer

Absorption correction

T_min, T_max

Rigaku Mercury CCD diffractometer

Multi-scan (REQAB; Jacobson, 1998)

0.720, 1.000

Rigaku Mercury CCD diffractometer

Multi-scan (REQAB; Jacobson, 1998)

0.997, 1.000

No. of measured, independent and

observed reﬂections

R_int

7722, 3595, 2808 [I > ꢄ(I)]

9371, 3516, 2681 [I > 2ꢄ(I)]

0.032

0.649

0.041

0.595

ꢀ1

(sin ꢅ/ꢆ)_max(A

)

Reﬁnement

R[F²> 2ꢄ(F²)], wR(F²), S

No. of reﬂections

No. of parameters

No. of restraints

H-atom treatment

0.046, 0.122, 1.02

3595

254

H-atom parameters constrained

0.051, 0.126, 1.01

3516

304

H atoms treated by a mixture of

independent and constrained

reﬁnement

0.39, ꢀ0.40

ꢀ3

Áꢇ_max, Áꢇ_min(e A

)

0.35, ꢀ0.57

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and SHELXTL.

signiﬁcant so the discussion considers each structure indivi-

dually. Compound (I) crystallizes in the space group P1. Its

asymmetric unit consists of two halves of the 2,2⁰-biimidazole-

3,3⁰-diium dication, each protonated at two imidazole ring N

atoms and two halves of the 2,5-dicarboxybenzene-1,4-di-

carboxylate dianion (PMA^2ꢀ), each with two of the carboxylic

acid groups deprotonated (Fig. 1). In (I), the two PMA^2ꢀ

2. Experimental

2.1. Synthesis and crystallization

2,2⁰-Biimidazole (0.1 mmol, 0.0134 g), benzene-1,2,4,5-tetra-

carboxylic acid (0.1 mmol, 0.0254 g), ZnSO₄ꢁ7H₂O (0.1 mmol,

0.0287 g) and water (2.0 ml) were mixed and placed in a thick

Pyrex tube, which was sealed and heated to 383 K for 72 h,

whereupon colourless block-shaped crystals of (I) were

obtained. Colourless block-shaped crystals of (II) were

obtained by a procedure similar to that described for (I), using

4,4⁰-dimethyl-2,2⁰-bipyridine instead of 2,2⁰-biimidazole.

anions lie on crystallographic centres of symmetry at (0, , )

and (¹₂, , 0), respectively. They are connected by an O1—

H1ꢁ ꢁ ꢁO7 hydrogen bond (Table 2). The two 2,2⁰-biimidazole-

3,3⁰-diium dications lie on crystallographic centres of

symmetry at (¹₂, 0, 0) and (0, ¹₂, 0), respectively, and are linked

by N3—H3Aꢁ ꢁ ꢁO3, N4—H4Bꢁ ꢁ ꢁO4ⁱⁱ, N1—H1Bꢁ ꢁ ꢁO7^ivand

N2—H2Bꢁ ꢁ ꢁO8ⁱⁱⁱhydrogen bonds with adjacent PMA^2ꢀ

dianions (Fig. 1; see Table 2 for symmetry codes and geometric

details). The environments of the two independent 2,2⁰-bi-

imidazole-3,3⁰-diium cations is similar. In contrast, both

independent PMA^2ꢀanions are different in that only one

anion has an intramolecular O—Hꢁ ꢁ ꢁO hydrogen bond (O6—

H6ꢁ ꢁ ꢁO8ⁱ; Table 2). The bond lengths and angles of the

PMA^2ꢀdianion are comparable with values reported

previously in guanidinuium pyromellite (Sun et al., 2002a).

The benzene rings of the two PMA^2ꢀdianions are planar

except for the carboxyl groups. The planes deﬁned by the

COO^ꢀgroups (C17/O7/O8 and C11/O3/O4) and the least-

squares plane of the benzene ring subtend dihedral angles of

32.2 (1) and 60.6 (1)^ꢂ, respectively, while the planes deﬁned by

the COOH groups (C13/O5/O6 and C7/O1/O2) are oriented at

15.2 (1) and 25.4 (1)^ꢂ, respectively, to that of the benzene ring.

2.2. Refinement

Crystal data, data collection and structure reﬁnement details

are summarized in Table 1. H atoms bound to C, N and O atoms

were positioned geometrically and allowed to ride on their

parent atoms, with C—H = 0.93 A and U_iso(H) = 1.2U_eq(C),

N—H = 0.96 A and U_iso(H) = 1.2U_eq(N), and O—H = 0.82 A

and U_iso(H) = 1.5U_eq(O). The H atoms of water molecules were

located in difference Fourier maps and placed in calculated

positions so as to form a reasonable hydrogen-bond network, as

far as possible. Their positions were reﬁned with tight restraints

on the O—H and Hꢁ ꢁ ꢁH distances [0.820 (1) and 1.35 (1) A,

respectively], and with U_iso(H) = 1.5U_eq(O).

3. Results and discussion

In both title compounds, (I) and (II), proton transfer has

occurred. However, the differences between the structures are

2ꢀ

1538 Kai-Long Zhong C₆H₈N₄ꢁC₁₀H₄O₈and C₁₂H₁₃N₂ꢁC₁₀H₅O₈^ꢀꢁH₂O

Acta Cryst. (2013). C69, 1537–1540

ꢃ

organic compounds

Table 2

Hydrogen-bond geometry (A, ) for (I).

ꢂ

D—Hꢁ ꢁ ꢁA

D—H

Hꢁ ꢁ ꢁA

Dꢁ ꢁ ꢁA

D—Hꢁ ꢁ ꢁA

O6—H6ꢁ ꢁ ꢁO8ⁱ

0.82

0.86

1.67

1.91

1.75

1.89

1.83

1.90

2.4939 (18)

2.7228 (18)

2.553 (2)

2.738 (2)

2.676 (2)

2.733 (2)

177

173

154

170

168

162

O1—H1ꢁ ꢁ ꢁO7

N3—H3Aꢁ ꢁ ꢁO3

N4—H4Bꢁ ꢁ ꢁO4ⁱⁱ

N2—H2Bꢁ ꢁ ꢁO8ⁱⁱⁱ

N1—H1Bꢁ ꢁ ꢁO7^iv

Symmetry codes: (i) ꢀx þ 1; ꢀy þ 1; ꢀz þ 2; (ii) ꢀx þ 1; ꢀy; ꢀz; (iii) ꢀx; ꢀy þ 1,

ꢀz þ 1; (iv) x; y þ 1; z.

asymmetric intermolecular N—Hꢁ ꢁ ꢁO hydrogen bonds that

form a primary cyclic R²₂(9) association (Bernstein et al., 1995)

(Fig. 2). These aggregate units generate a one-dimensional

supramolecular chain. Adjacent chains are further linked via

carboxyl–carboxyl O—Hꢁ ꢁ ꢁO hydrogen bonds, resulting in a

two-dimensional supramolecular sheet extending parallel to

the (121) plane. Within the sheet, the R⁵₆(34) motif can be

discerned (Fig. 2).

Hydrated salt (II) crystallizes in the space group P1. The

asymmetric unit is comprised of a 4-methyl-2-(4-methylpyri-

din-2-yl)pyridinium cation, a 2,4,5-tricarboxybenzoate anion

and a water molecule (Fig. 3). Only one carboxyl group of the

benzene-1,2,3,4-tetracarboxylic acid molecule is deproton-

ated, which is different from what was observed in the

nonsubstituted 2,2⁰-bipyridine analogue (Mrvos-Sermek et al.,

1996). Proton transfer from a carboxylic acid group of PMA to

a ring N atom (N2) of 4,4⁰-dimethyl-2,2⁰-bipyridine is mani-

fested in an increased internal angle [C10—N2—C6 =

123.4 (2)^ꢂ] of the pyridine ring, compared with that at the

Figure 1

The unique species in the structure of (I), showing the atom-numbering

scheme and with displacement ellipsoids drawn at the 35% probability

level. The dashed lines represent O—Hꢁ ꢁ ꢁO and N—Hꢁ ꢁ ꢁO intra- and

intermolecular interactions. H atoms are shown as small spheres of

arbitrary radii. [Symmetry codes: (i) ꢀx + 1, ꢀy + 1, ꢀz + 2; (ii) ꢀx + 1,

ꢀy, ꢀz; (v) ꢀx + 2, ꢀy + 1, ꢀz + 1; (vi) ꢀx, ꢀy + 2, ꢀz + 1.]

The two imidazole rings of the two cations are almost

coplanar, the mean deviations from the least-squares planes

being 0.0126 (5) and 0.0055 (4) A, respectively. The dihedral

angle between the mean planes of the two cations is 51.7 (1)^ꢂ.

The C—N and C—C bond lengths in the cations are consistent

with those usually found (Liu & Zhu, 2010). The dication

interacts with two neighbouring PMA^2ꢀanions via pairs of

Figure 2

Aview of the two-dimensional hydrogen-bonded network of (I) along the

b axis, showing the formation of R²₂(9) and R⁵₆(34) motifs. The dashed

lines represent O—Hꢁ ꢁ ꢁO interactions. [Symmetry codes: (i) ꢀx + 1,

ꢀy + 1, ꢀz + 2; (ii) ꢀx + 1, ꢀy, ꢀz; (iii) ꢀx, ꢀy + 1, ꢀz + 1; (v) ꢀx + 2,

ꢀy + 1, ꢀz + 1; (vii) x, y ꢀ 1, z.]

Figure 3

The asymmetric unit of (II), showing the atom-numbering scheme and

with displacement ellipsoids drawn at the 30% probability level. The

dashed line represents an intramolecular O—Hꢁ ꢁ ꢁO interaction.

2ꢀ

C₆H₈N₄ꢁC₁₀H₄O₈and C₁₂H₁₃N₂ꢁC₁₀H₅O₈^ꢀꢁH₂O 1539

ꢃ

Kai-Long Zhong

Acta Cryst. (2013). C69, 1537–1540

organic compounds

Table 3

Hydrogen-bond geometry (A, ) for (II).

ꢂ

D—Hꢁ ꢁ ꢁA

D—H

Hꢁ ꢁ ꢁA

Dꢁ ꢁ ꢁA

D—Hꢁ ꢁ ꢁA

O1W—H1WAꢁ ꢁ ꢁO5ⁱ

O1W—H1WBꢁ ꢁ ꢁO4ⁱⁱ

N2—H2Bꢁ ꢁ ꢁO3ⁱⁱ

O6—H6ꢁ ꢁ ꢁO1ⁱⁱⁱ

0.82 (1)

0.86

0.82

2.12 (1)

2.06 (1)

1.99

1.79

1.84

2.916 (3)

2.880 (3)

2.792 (3)

2.609 (2)

2.644 (2)

163 (3)

175 (3)

154

174

166

O8—H8ꢁ ꢁ ꢁO7^iv

Symmetry codes: (i) ꢀx; ꢀy þ 1; ꢀz þ 1; (ii) x; y ꢀ 1; z; (iii) x ꢀ 1; y; z; (iv)

ꢀx þ 1; ꢀy þ 1; ꢀz.

unprotonated N1 atom of the pyridine ring [C1—N1—C5 =

116.7 (2)^ꢂ]. Protonated atom N2 diminishes the steric effect of

the lone pair of electrons and is responsible for the slightly

increased C10—N2—C6 angle (Fig. 3). The two rings of the

cation are twisted slightly away from each other, forming a

dihedral angle of 7.03 (8)^ꢂ. The planes of the benzene ring of

the PMA^ꢀanion and the two pyridine rings (C1–C5/N1 and

C6–C10/N2) of the cation are oriented at 6.22 (8) and

10.99 (9)^ꢂ, respectively. The dihedral angles between the least-

squares plane of the benzene ring of PMA^ꢀand those of the

the carboxylic acid groups (COOH) are 13.35 (7) (O1/C21/

O2), 31.20 (2) (O7/C20/O8) and 53.0_ꢀ4 (9)^ꢂ(O5/C19/O6). The

O3/C22/O4 carboxylate group (COO ) is twisted by 16.22 (1)^ꢂ

with respect to the plane of the benzene ring, which is similar

to the value found in a previously reported PMA^ꢀcompound

(Sun et al., 2002b). The PMA^ꢀanions form a one-dimensional

chain along the [100] direction via O6^vi—H6^viꢁ ꢁ ꢁO1, O8—

H8ꢁ ꢁ ꢁO7^ivand O8^iv—H8^ivꢁ ꢁ ꢁO7 hydrogen bonds, enclosing

R²₂(8)R⁴₄(30) rings (Fig. 4; see Table 3 for symmetry codes).

Such chains are further joined together through water–

carboxylate O—Hꢁ ꢁ ꢁO hydrogen bonds, viz O1W—

H1WAꢁ ꢁ ꢁO5ⁱand O1W—H1WBꢁ ꢁ ꢁO4ⁱⁱ, to yield a two-

dimensional supramolecular layer extending in the (011)

plane, involving R⁴₄(20) and R⁶₆(26) motifs (Fig. 4 and Table 3).

The 4-methyl-2-(4-methylpyridin-2-yl)pyridinium cations are

linked to the PMA^ꢀanions through N2—H2ꢁ ꢁ ꢁO3ⁱⁱhydrogen

bonds and lie between the above-mentioned two-dimensional

supramolecular layers (Table 3).

Figure 4

The two-dimensional hydrogen-bonded anionic layer in (II), extending

parallel to the (102) crystallographic plane, showing the formation of

R²₂(8), R⁴₄(30), R₄⁴(20) and R⁶₆(26) motifs. Hydrogen bonds are represented

by dashed lines. [Symmetry codes: (i) ꢀx, ꢀy + 1, ꢀz + 1; (iv) ꢀx + 1,

ꢀy + 1, ꢀz; (v) ꢀx + 2, ꢀy + 1, ꢀz; (vi) x + 1, y, z; (vii) ꢀx, ꢀy + 2, ꢀz + 1;

(viii) x, y + 1, z; (ix) ꢀx + 1, ꢀy + 2, ꢀz + 1; (x) ꢀx + 1, ꢀy + 1, ꢀz + 1.]

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Rochon, F . D. & Massarweh, G. (2000). Inorg. Chim. Acta , 304 , 190–198.

Sheldrick, G. M. (2008). Acta Cryst. A 64 , 112–122.

Sun, Y .-Q., Zhang, J. & Yang, G.-Y. (2002 a ). Acta Cryst. E 58 , o904–o906.

Sun, Y .-Q., Zhang, J. & Yang, G.-Y. (2002 b ). Acta Cryst. E 58 , o1100–o1102.

Zhang, L.-P ., Ma, J.-F ., Yang, J., Pang, Y.-Y. & Ma, J.-C. (2010). Inorg. Chem.

49 , 1535–1550.

References

Adams, J. M. & Ramdas, V . (1978). Acta Cryst. B 34 , 2781–2785.

Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37 , 1460–1494.

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.

Int. Ed. Engl. 34 , 1555–1573.

Cao, R., Shi, Q., Sun, D., Hong, M., Bi, W . & Z hao, Y . (2002). Inorg. Chem. 41 ,

6161–6168.

Zhu, L.-G., Ellern, A. M. & Kostic, N. M. (2002). Acta Cryst. C 58 , o129–o130.

2ꢀ

1540 Kai-Long Zhong C₆H₈N₄ꢁC₁₀H₄O₈and C₁₂H₁₃N₂ꢁC₁₀H₅O₈^ꢀꢁH₂O

Acta Cryst. (2013). C69, 1537–1540

ꢃ

supplementary materials

Acta Cryst. (2013). C69, 1537-1540 [doi:10.1107/S0108270113030801]

Two-dimensional hydrogen-bonded supramolecular networks in the compounds

of benzene-1,2,4,5-tetracarboxylic acid (pyromellitic acid) with 2,2′-bi-

imidazole and 4,4′-dimethyl-2,2′-bipyridine

Kai-Long Zhong

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data

reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s)

used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software

used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(I) 2-(Imidazol-1-ium-2-yl)imidazol-1-ium 2,5-dicarboxybenzene-1,4-dicarboxylate

Crystal data

C₆H₈N₄²⁺·C₁₀H₄O₈²⁻

M_r= 388.30

Triclinic, P1

Hall symbol: -p 1

a = 8.2246 (16) Å

b = 8.7495 (17) Å

c = 11.454 (2) Å

α = 100.67 (3)°

β = 97.26 (3)°

Z = 2

F(000) = 400

D_x= 1.614 Mg m⁻³

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 3731 reflections

θ = 3.3–27.5°

µ = 0.13 mm⁻¹

T = 223 K

Block, colourless

0.40 × 0.27 × 0.20 mm

γ = 94.68 (3)°

V = 798.8 (3) Å³

Data collection

Rigaku Mercury CCD

diffractometer

7722 measured reflections

3595 independent reflections

2808 reflections with I > σ(I)

R_int= 0.032

Radiation source: fine-focus sealed tube

Graphite Monochromator monochromator

Detector resolution: 28.5714 pixels mm^-1

ω scans

Absorption correction: multi-scan

(REQAB: Jacobson, 1998)

_max= 27.5°, θ_min= 3.3°

h = −10→10

k = −11→9

l = −13→14

_min= 0.720, T_max= 1.000

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.046

wR(F²) = 0.122

3595 reflections

254 parameters

0 restraints

Primary atom site location: structure-invariant

direct methods

S = 1.02

Acta Cryst. (2013). C69, 1537-1540

sup-1

supplementary materials

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

H-atom parameters constrained

w = 1/[σ²(F_o²) + (0.072P)²]

where P = (F_o²+ 2F_c²)/3

(Δ/σ)_max< 0.001

Δρ_max= 0.35 e Å⁻³

Δρ_min= −0.57 e Å⁻³

Extinction correction: SHELXL97 (Sheldrick,

2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4

Extinction coefficient: 0.074 (7)

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.

Refinement. Refinement of F²against 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)

U_iso*/U_eq

0.62669 (16)

0.5411

0.47277 (17)

0.4294

0.63757 (13)

0.6516

0.0491 (4)

0.074*

0.62998 (16)

0.65637 (14)

0.83769 (16)

0.82217 (15)

0.94434 (13)

0.9227

0.24608 (15)

0.31690 (14)

0.14191 (15)

0.24782 (15)

0.42861 (15)

0.5087

0.51284 (12)

0.27534 (11)

0.27634 (12)

0.95079 (12)

1.10085 (10)

1.1430

0.0423 (4)

0.0352 (3)

0.0417 (3)

0.0384 (3)

0.0320 (3)

0.048*

0.35869 (14)

0.13262 (13)

0.20074 (17)

0.2289

0.30795 (14)

0.33080 (14)

1.10573 (16)

1.1748

0.68918 (10)

0.77385 (10)

0.48835 (13)

0.5533

0.0321 (3)

0.0312 (3)

0.0305 (3)

0.037*

H1B

0.06550 (17)

−0.0088

0.91666 (16)

0.8421

0.35546 (12)

0.3198

0.0285 (3)

0.034*

H2B

0.43654 (16)

0.5170

0.15350 (16)

0.1808

0.11289 (12)

0.1708

0.0272 (3)

0.033*

H3A

0.28846 (16)

0.2594

0.03652 (16)

−0.0243

−0.05601 (12)

−0.1250

0.0268 (3)

0.032*

H4B

0.2026 (2)

0.2319

0.9631 (2)

0.9213

0.31045 (16)

0.2363

0.0350 (4)

0.042*

H1A

0.2880 (2)

0.3876

1.0814 (2)

1.1361

0.39394 (16)

0.3882

0.0373 (4)

0.045*

H2A

0.0645 (2)

0.2873 (2)

0.2552

1.00457 (18)

0.2127 (2)

0.2900

0.46313 (14)

0.10564 (16)

0.1629

0.0255 (4)

0.0308 (4)

0.037*

H4A

0.1944 (2)

0.0874

0.1398 (2)

0.1567

0.00105 (16)

−0.0266

0.0307 (4)

0.037*

H5A

0.43411 (18)

0.68894 (19)

0.84615 (18)

0.04627 (18)

0.3774 (2)

0.44614 (18)

0.01405 (13)

0.55609 (14)

0.52423 (13)

0.0232 (3)

0.0274 (4)

0.0229 (3)

Acta Cryst. (2013). C69, 1537-1540

sup-2

supplementary materials

0.89777 (18)

0.78931 (19)

1.05207 (18)

1.0881

0.38360 (18)

0.26791 (19)

0.43707 (18)

0.3944

0.41569 (13)

0.31646 (13)

0.39288 (14)

0.3213

0.0226 (3)

0.0247 (4)

0.0242 (3)

0.029*

C11

C12

H12A

C13

C14

C15

H15A

C16

C17

0.81518 (19)

0.65816 (18)

0.54537 (18)

0.5764

0.36793 (19)

0.44640 (18)

0.38997 (18)

0.3147

1.02148 (14)

1.01819 (13)

0.91379 (13)

0.8546

0.0250 (4)

0.0208 (3)

0.0216 (3)

0.026*

0.39022 (18)

0.28687 (18)

0.43945 (17)

0.35632 (18)

0.89325 (13)

0.77638 (13)

0.0202 (3)

0.0225 (3)

Atomic displacement parameters (Å²)

U¹¹

U²²

U³³

U¹²

U¹³

U²³

0.0338 (7)

0.0370 (7)

0.0285 (6)

0.0375 (7)

0.0313 (7)

0.0236 (6)

0.0273 (6)

0.0209 (6)

0.0320 (8)

0.0273 (7)

0.0251 (7)

0.0218 (7)

0.0330 (9)

0.0349 (10)

0.0275 (8)

0.0287 (9)

0.0230 (8)

0.0220 (8)

0.0222 (8)

0.0197 (7)

0.0210 (8)

0.0233 (8)

0.0232 (8)

0.0241 (8)

0.0199 (7)

0.0223 (8)

0.0213 (7)

0.0220 (8)

0.0558 (9)

0.0389 (8)

0.0337 (7)

0.0345 (7)

0.0376 (7)

0.0388 (7)

0.0420 (7)

0.0371 (7)

0.0297 (8)

0.0273 (7)

0.0318 (7)

0.0282 (7)

0.0418 (10)

0.0407 (10)

0.0230 (8)

0.0331 (9)

0.0332 (9)

0.0227 (8)

0.0361 (9)

0.0270 (8)

0.0237 (8)

0.0268 (9)

0.0282 (8)

0.0289 (9)

0.0225 (7)

0.0225 (8)

0.0203 (7)

0.0241 (8)

0.0483 (8)

−0.0146 (6)

−0.0106 (6)

0.0065 (5)

0.0114 (6)

0.0124 (6)

0.0067 (5)

−0.0038 (5)

−0.0036 (5)

−0.0047 (6)

−0.0008 (6)

−0.0005 (6)

0.0013 (6)

0.0001 (8)

−0.0055 (8)

0.0004 (6)

0.0051 (7)

0.0052 (7)

−0.0015 (6)

−0.0015 (7)

0.0025 (6)

0.0014 (6)

−0.0007 (7)

0.0022 (7)

0.0031 (7)

−0.0002 (6)

0.0005 (6)

−0.0022 (6)

−0.0002 (6)

0.0210 (6)

0.0112 (6)

−0.0115 (5)

−0.0127 (6)

−0.0024 (5)

0.0038 (5)

0.0007 (5)

−0.0012 (6)

−0.0036 (6)

0.0003 (5)

−0.0037 (5)

0.0026 (7)

0.0042 (8)

−0.0034 (6)

0.0079 (7)

0.0024 (7)

0.0003 (6)

0.0000 (6)

0.0006 (6)

−0.0012 (6)

0.0009 (6)

0.0023 (6)

0.0030 (6)

0.0035 (6)

0.0041 (6)

0.0028 (6)

0.0014 (6)

−0.0158 (7)

−0.0017 (6)

−0.0039 (5)

−0.0119 (6)

−0.0098 (6)

−0.0047 (5)

−0.0078 (5)

−0.0063 (5)

−0.0032 (6)

−0.0045 (6)

−0.0005 (6)

0.0005 (6)

−0.0019 (8)

−0.0013 (8)

0.0015 (6)

0.0019 (7)

0.0074 (7)

0.0025 (6)

0.0029 (7)

0.0029 (6)

0.0024 (6)

0.0007 (6)

0.0002 (6)

0.0035 (7)

0.0034 (6)

−0.0002 (6)

0.0012 (6)

0.0011 (6)

0.0459 (8)

0.0356 (7)

0.0419 (7)

0.0391 (7)

0.0281 (6)

0.0203 (6)

0.0287 (6)

0.0237 (7)

0.0247 (7)

0.0210 (6)

0.0264 (7)

0.0257 (8)

0.0313 (9)

0.0227 (7)

0.0303 (9)

0.0361 (9)

0.0227 (7)

0.0211 (7)

0.0208 (7)

0.0209 (7)

0.0211 (7)

0.0192 (7)

0.0216 (7)

0.0194 (7)

0.0182 (7)

0.0174 (7)

0.0194 (7)

C11

C12

C13

C14

C15

C16

C17

Geometric parameters (Å, º)

O1—C7

O1—H1

O2—C7

O3—C11

O4—C11

1.316 (2)

C1—C2

1.351 (2)

0.8200

C1—H1A

C2—H2A

C3—C3ⁱ

C4—C5

0.9300

1.199 (2)

1.274 (2)

1.231 (2)

0.9300

1.443 (3)

1.354 (2)

Acta Cryst. (2013). C69, 1537-1540

sup-3

supplementary materials

O5—C13

O6—C13

O6—H6

O7—C17

O8—C17

N1—C3

N1—C2

N1—H1B

N2—C3

N2—C1

N2—H2B

N3—C6

N3—C4

N3—H3A

N4—C6

N4—C5

N4—H4B

1.212 (2)

1.312 (2)

0.8200

C4—H4A

C5—H5A

C6—C6ⁱⁱ

0.9300

1.438 (3)

1.497 (2)

1.394 (2)

1.395 (2)

1.389 (2)

1.511 (2)

1.395 (2)

0.9300

1.2485 (18)

1.2658 (18)

1.336 (2)

1.366 (2)

0.8600

C7—C8

C8—C9

C8—C12ⁱⁱⁱ

C9—C12

C9—C11

1.329 (2)

1.361 (2)

0.8600

C12—C8ⁱⁱⁱ

C12—H12A

C13—C14

C14—C15

C14—C16^iv

C15—C16

C15—H15A

C16—C14^iv

C16—C17

1.511 (2)

1.400 (2)

1.406 (2)

1.387 (2)

0.9300

1.327 (2)

1.370 (2)

0.8600

1.342 (2)

1.366 (2)

0.8600

1.406 (2)

1.515 (2)

C7—O1—H1

C13—O6—H6

C3—N1—C2

C3—N1—H1B

C2—N1—H1B

C3—N2—C1

C3—N2—H2B

C1—N2—H2B

C6—N3—C4

C6—N3—H3A

C4—N3—H3A

C6—N4—C5

C6—N4—H4B

C5—N4—H4B

C2—C1—N2

C2—C1—H1A

N2—C1—H1A

C1—C2—N1

C1—C2—H2A

N1—C2—H2A

N2—C3—N1

N2—C3—C3ⁱ

N1—C3—C3ⁱ

C5—C4—N3

C5—C4—H4A

N3—C4—H4A

C4—C5—N4

C4—C5—H5A

N4—C5—H5A

N3—C6—N4

N3—C6—C6ⁱⁱ

109.5

N4—C6—C6ⁱⁱ

124.99 (17)

124.22 (15)

122.18 (16)

113.57 (14)

119.91 (13)

119.72 (14)

120.13 (14)

119.12 (14)

117.45 (13)

123.28 (13)

125.17 (15)

119.76 (14)

114.88 (14)

120.96 (14)

119.5

109.5

O2—C7—O1

108.77 (14)

125.6

O2—C7—C8

O1—C7—C8

C9—C8—C12ⁱⁱⁱ

125.6

109.35 (14)

125.3

C9—C8—C7

C12ⁱⁱⁱ—C8—C7

C12—C9—C8

C12—C9—C11

C8—C9—C11

125.3

107.37 (14)

126.3

O4—C11—O3

O4—C11—C9

O3—C11—C9

C9—C12—C8ⁱⁱⁱ

C9—C12—H12A

C8ⁱⁱⁱ—C12—H12A

O5—C13—O6

O5—C13—C14

O6—C13—C14

C15—C14—C16^iv

C15—C14—C13

C16^iv—C14—C13

C16—C15—C14

C16—C15—H15A

C14—C15—H15A

C15—C16—C14^iv

C15—C16—C17

C14^iv—C16—C17

O7—C17—O8

O7—C17—C16

O8—C17—C16

108.23 (14)

125.9

107.01 (16)

126.5

119.5

126.5

119.60 (15)

119.99 (14)

120.41 (14)

117.36 (14)

113.78 (13)

128.79 (14)

124.03 (14)

118.0

107.15 (15)

126.4

107.72 (14)

125.75 (18)

126.50 (18)

108.43 (15)

125.8

118.0

125.8

118.61 (14)

114.57 (13)

126.77 (14)

122.99 (14)

118.47 (13)

118.39 (13)

106.62 (15)

126.7

109.35 (14)

125.66 (18)

Acta Cryst. (2013). C69, 1537-1540

sup-4

supplementary materials

C3—N2—C1—C2

N2—C1—C2—N1

C3—N1—C2—C1

C1—N2—C3—N1

C1—N2—C3—C3ⁱ

C2—N1—C3—N2

C2—N1—C3—C3ⁱ

C6—N3—C4—C5

N3—C4—C5—N4

C6—N4—C5—C4

C4—N3—C6—N4

C4—N3—C6—C6ⁱⁱ

C5—N4—C6—N3

C5—N4—C6—C6ⁱⁱ

O2—C7—C8—C9

O1—C7—C8—C9

O2—C7—C8—C12ⁱⁱⁱ

O1—C7—C8—C12ⁱⁱⁱ

C12ⁱⁱⁱ—C8—C9—C12

C7—C8—C9—C12

0.7 (2)

C12ⁱⁱⁱ—C8—C9—C11

−174.20 (15)

11.4 (2)

−0.4 (2)

C7—C8—C9—C11

−0.1 (2)

C12—C9—C11—O4

C8—C9—C11—O4

59.3 (2)

−0.79 (19)

177.1 (2)

0.6 (2)

−125.24 (18)

−115.92 (17)

59.6 (2)

C12—C9—C11—O3

C8—C9—C11—O3

−177.3 (2)

0.05 (18)

−0.51 (18)

0.79 (18)

0.45 (17)

−179.20 (19)

−0.78 (17)

178.87 (19)

22.7 (3)

C8—C9—C12—C8ⁱⁱⁱ

C11—C9—C12—C8ⁱⁱⁱ

O5—C13—C14—C15

O6—C13—C14—C15

O5—C13—C14—C16^iv

O6—C13—C14—C16^iv

C16^iv—C14—C15—C16

C13—C14—C15—C16

C14—C15—C16—C14^iv

C14—C15—C16—C17

C15—C16—C17—O7

C14^iv—C16—C17—O7

C15—C16—C17—O8

C14^iv—C16—C17—O8

−1.2 (3)

174.46 (15)

−14.0 (2)

166.32 (13)

162.91 (15)

−16.8 (2)

−0.2 (2)

177.05 (14)

0.2 (2)

−159.27 (16)

−151.64 (17)

26.4 (2)

−177.27 (13)

−30.5 (2)

152.22 (15)

145.24 (15)

−32.0 (2)

1.2 (3)

−173.14 (15)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y, −z; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A

D—H

H···A

D···A

D—H···A

O6—H6···O8^iv

O1—H1···O7

0.82

0.86

1.67

1.91

1.75

1.89

1.83

1.90

2.4939 (18)

2.7228 (18)

2.553 (2)

2.738 (2)

2.676 (2)

2.733 (2)

177

173

154

170

168

162

N3—H3A···O3

N4—H4B···O4ⁱⁱ

N2—H2B···O8^v

N1—H1B···O7^vi

Symmetry codes: (ii) −x+1, −y, −z; (iv) −x+1, −y+1, −z+2; (v) −x, −y+1, −z+1; (vi) x, y+1, z.

(II) 4-Methyl-2-(4-methylpyridin-2-yl)pyridinium 2,4,5-tricarboxybenzoate monohydrate

Crystal data

C₁₂H₁₃N₂⁺·C₁₀H₅O₈⁻·H₂O

M_r= 456.40

Triclinic, P1

Z = 2

F(000) = 476

D_x= 1.514 Mg m⁻³

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 2637 reflections

θ = 3.5–29.2°

µ = 0.12 mm⁻¹

T = 223 K

Block, colourless

0.30 × 0.22 × 0.10 mm

Hall symbol: -P 1

a = 9.5166 (7) Å

b = 9.9970 (8) Å

c = 12.4106 (8) Å

α = 77.979 (6)°

β = 73.421 (6)°

γ = 62.655 (8)°

V = 1001.03 (13) Å³

Acta Cryst. (2013). C69, 1537-1540

sup-5

supplementary materials

Data collection

Rigaku Mercury CCD

9371 measured reflections

diffractometer

3516 independent reflections

2681 reflections with I > 2σ(I)

R_int= 0.041

Radiation source: fine-focus sealed tube

Graphite Monochromator monochromator

Detector resolution: 28.5714 pixels mm^-1

ω scans

Absorption correction: multi-scan

(REQAB: Jacobson, 1998)

_max= 25.0°, θ_min= 3.0°

h = −11→11

k = −11→11

l = −14→14

_min= 0.997, T_max= 1.000

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.051

wR(F²) = 0.126

Secondary atom site location: difference Fourier

map

Hydrogen site location: inferred from

neighbouring sites

S = 1.01

3516 reflections

304 parameters

3 restraints

H atoms treated by a mixture of independent

and constrained refinement

w = 1/[σ²(F_o²) + (0.0474P)²+ 0.9963P]

where P = (F_o²+ 2F_c²)/3

Primary atom site location: structure-invariant

direct methods

(Δ/σ)_max< 0.001

Δρ_max= 0.39 e Å⁻³

Δρ_min= −0.39 e Å⁻³