Seven supramolecular adducts of 4-dimethylaminopyridine and carboxylic acids constructed by classical H-Bonds and some noncovalent interactions

Journal Pre-proof Seven supramolecular adducts of 4-dimethylaminopyridine and carboxylic acids constructed by classical H-Bonds and some noncovalent interactions Wei Fang, Bangyu Chen, Duoer Chen, Shiqi Wang, Yan Yan, Shouwen Jin, Weiqiang Xu, Daqi Wang PII:

S0022-2860(19)31462-0

DOI:

https://doi.org/10.1016/j.molstruc.2019.127353

Reference:

MOLSTR 127353

To appear in:

Journal of Molecular Structure

Received Date: 5 June 2018 Revised Date:

31 October 2019

Accepted Date: 1 November 2019

Please cite this article as: W. Fang, B. Chen, D. Chen, S. Wang, Y. Yan, S. Jin, W. Xu, D. Wang, Seven supramolecular adducts of 4-dimethylaminopyridine and carboxylic acids constructed by classical H-Bonds and some noncovalent interactions, Journal of Molecular Structure (2019), doi: https:// doi.org/10.1016/j.molstruc.2019.127353. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier B.V.

Graphical abstract Title: Seven

Supramolecular Adducts

of

4-dimethylaminopyridine and

Carboxylic acids Constructed by Classical H-Bonds and Some Noncovalent Interactions

Wei Fanga,b, Bangyu Chena,b, Duoer Chena,b, Shiqi Wanga,b, Yan Yana,b, Shouwen Jina,b*, Weiqiang Xua,b, and Daqi Wangc a

JiYang College ZheJiang A & F University, Zhu'Ji 311800, P. R. China, Tel & fax:

+86-575-8776-0141. *E-mail: [email protected] b

Key Laboratory of Chemical Utilization of Forestry Biomass of Zhejiang Province

Zhejiang A & F University, Lin’an, Zhejiang Province, 311300, China c

Department of Chemistry, Liaocheng University, Liaocheng 252059, P. R. China.

Seven Supramolecular Adducts of 4-dimethylaminopyridine and Carboxylic acids Constructed by Classical H-Bonds and Some Noncovalent Interactions Wei Fanga,b, Bangyu Chena,b, Duoer Chena,b, Shiqi Wanga,b, Yan Yana,b, Shouwen Jina,b*, Weiqiang Xua,b, and Daqi Wangc a

JiYang College ZheJiang A & F University, Zhu'Ji 311800, P. R. China, Tel & fax:

+86-575-8776-0141. *E-mail: [email protected] b

Key Laboratory of Chemical Utilization of Forestry Biomass of Zhejiang Province

Zhejiang A & F University, Lin’an, Zhejiang Province, 311300, China c

Department of Chemistry, Liaocheng University, Liaocheng 252059, P. R. China.

Abstract: Cocrystallization

of

the

commonly

available

pyridine

derivative,

4-dimethylaminopyridine, with a series of carboxylic acids gave a total of seven anhydrous and hydrous multicomponent adducts

(4-dimethylaminopyridine) :

(4-methoxybenzoic acid) [(HDMAP) · (mba) · (Hmba), mba = 4-methoxybenzoate] (1), (4-dimethylaminopyridine) : (4-(aminosulphonyl)benzoic acid) [(HDMAP) · (aspba), aspba

=

4-(aminosulphonyl)benzoate]

(2),

(4-dimethylaminopyridine)

:

(3-methylsalicylic acid)2 [(HDMAP) · (msal) · (Hmsal), msal = 3-methylsalicylate] (3), (4-dimethylaminopyridine) : (3,5,6-trichlorosalicylic acid) [(HDMAP+) · (tcsal-), tcsal- = 3,5,6-trichlorosalicylate] (4), (4-dimethylaminopyridine) : (2-pyrazinecarboxylic acid) : 4H2O [(HDMAP+) ·

(pyza-) ·

4H2O, pyza- = 2-pyrazine carboxylate] (5),

(4-dimethylaminopyridine) : (2,2’-biphenyldicarboxylic acid) [(HDMAP+) · (Hbpda-), Hbpda = hydrogen 2,2’-biphenyldicarboxylate] (6) and (4-dimethylaminopyridine)2 : (dibenzoyltartaric acid) [(HDMAP) · (Hdbta) · CH3OH · H2O, Hdbta = hydrogen dibenzoyltartarate] (7). The seven adducts have been characterised by XRD technique, IR and elemental analysis, and the melting points of all adducts were also reported. Their structural and supramolecular aspects are fully analyzed. The result reveals that all the investigated crystals are organic salts with only the aryl N in DMAP protonated and the crystal packing is interpreted in terms of the strong N-H···O, N-H···N, O-H···N and O-H···O H-bond from DMAP and the acidic groups.

1

Further analysis of the crystal packing of the salts indicated that a different family of additional CH-N, CH-O/CH3-O, CH-π/CH3-π, CH3-CH, CH3-Cl, C-π, O-π, Cl-Cl and π-π associations contribute to the stabilization and expansion of the total high-dimensional (1D-3D) structures. For the delicate balance of the various weak nonbonding interactions these structures adopted homo or hetero supramolecular synthons or both.

Keywords:

Crystal

structure;

Organic

Adducts,

H-bonds;

Carboxylic

acid;

4-dimethylaminopyridine

Introduction Noncovalent interactions of electrostatic forces, H-bond, CH-π, π-stacking, cation-π, anion-π and lone pair-π, as well as other weak forces play significant roles in a wide variety of fields from molecular recognition, host-guest chemistry, crystal engineering, supramolecular chemistry, biochemistry, pharmaceutical chemistry, to materials science [1-4]. In the past few years, great efforts have been made to elucidate these interactions and their relationship to the final supramolecular structures [5]. In the case of pharmaceutical ingredients, solid salts with such biopharmaceutical properties as solubility, stability and hygroscopicity have been studied systematically, and these properties are relevant to the noncovalent interactions [6-7]. The organic acids bear the nice donor-acceptor groups for the supramolecular growth [8] and they aggregate in the crystalline state as dimer, catemer and bridged motifs [9]. It is very significative to study the powerful and directional recognition between the organic acids and the bases of aryl

amine,

aliphatic

amine

and

pyridyl

derivatives

[10].

Among

them,

4-dimethylaminopyridine (DMAP) is an excellent acceptor for H-transfer, although its salts have aroused great interest 20 years ago and the structures of more than 50 salts have been reported previously [11, 12]. Except the ring N, DMAP has the additional N(CH3)2, which can create more complex noncovalent associations when it interacted with the organic acids. In addition to the acidic groups, the CH3, CH, OH, CH3O, C=O, X, SO2NH2 and aryl moieties are all excellent groups in forming the organic crystalline solids via a wide

2

variety of non-covalent interactions [13], thus we select some organic acids possessing the above mentioned groups. Recently, we have converged our continuing efforts on H-bond, π-stacking and halogen bonding concerning N-containing derivatives [14], we will report herein the preparation and structures of seven organic adducts from DMAP and the corresponding carboxylic acids (Scheme 1), respectively. The seven organic adducts

are

[(HDMAP)

·

(4-dimethylaminopyridine) (mba)

·

(Hmba),

mba

:

(4-methoxybenzoic =

acid)

4-methoxybenzoate]

(1),

(4-dimethylaminopyridine) : (4-(aminosulphonyl)benzoic acid) [(HDMAP) · (aspba), aspba

=

4-(aminosulphonyl)benzoate]

(2),

(4-dimethylaminopyridine)

:

(3-methylsalicylic acid)2 [(HDMAP) · (msal) · (Hmsal), msal = 3-methylsalicylate] (3), (4-dimethylaminopyridine) : (3,5,6-trichlorosalicylic acid) [(HDMAP+) · (tcsal-), tcsal- = 3,5,6-trichlorosalicylate] (4), (4-dimethylaminopyridine) : (2-pyrazinecarboxylic acid) : 4H2O [(HDMAP+) ·

(pyza-) ·

4H2O, pyza- = 2-pyrazine carboxylate] (5),

(4-dimethylaminopyridine) : (2,2’-biphenyldicarboxylic acid) [(HDMAP+) · (Hbpda-), Hbpda = hydrogen 2,2’-biphenyldicarboxylate] (6) and (4-dimethylaminopyridine)2 : (dibenzoyltartaric acid) [(HDMAP) · (Hdbta) · CH3OH · H2O, Hdbta = hydrogen dibenzoyltartarate] (7), respectively. The synthons were listed in Scheme 1s.

Experimental Section Materials and Methods The chemicals and solvents in this work were analytical grade commercial products and used without further purification. FT-IR spectra were taken as KBr pellets in 4000-400 cm-1 on a Mattson Alpha-Centauri spectrometer and the IR bands were marked as strong (s), medium (m) and weak (w) at the preparation part. The asymmetrical and symmetrical IR vibration bands of the corresponding groups were shown as νas and νs, respectively. The C/H/N/S data were obtained microanalytically on a Perkin-Elmer elemental analyzer with Model 2400II. The melting points of the adducts were measured by an XT-4 thermal apparatus without correction.

Preparation of the supramolecular compounds

3

a.

(4-dimethylaminopyridine)

:

(4-methoxybenzoic

acid)

[(HDMAP) · (mba) · (Hmba), mba = 4-methoxybenzoate] (1) 4-dimethylaminopyridine (12.2 mg, 0.10 mmol) was dissolved in 3 mL methanol. To this solution was added 4-methoxybenzoic acid (15.2 mg, 0.10 mmol) in 6 mL methanol. Colorless block crystals were afforded after 5 days by slow evaporation of the solvent (yield: 28.0 mg, 65.66%, based on DMAP). mp 150-152°C. Elemental analysis: Calc. for C23H26N2O6 (426.46): C, 64.72; H, 6.10; N, 6.56. Found: C, 64.60; H, 6.02; N, 6.44. Infrared spectrum (KBr disc, cm-1): 3622s(ν(OH)), 3380s(νas(NH)), 3270s(νs(NH)), 3142m, 3087m, 3037m, 2962m, 2865m, 1648s(ν(C=O)), 1606s(νas(CO2-)), 1563m, 1522m, 1478m, 1436m, 1394s(νs(CO2-)), 1350m, 1306m, 1268s(ν(C-O)), 1224m, 1180m, 1136m, 1092m, 1052m, 1008m, 965w, 920m, 876m, 830w, 788w, 744m, 702m, 660w, 625w, 606w. b.

(4-dimethylaminopyridine)

:

(4-(aminosulphonyl)benzoic

acid)

[(HDMAP) · (aspba), aspba = 4-(aminosulphonyl)benzoate] (2) 4-dimethylaminopyridine (12.2 mg, 0.10 mmol) was dissolved in 3 mL methanol. To this solution was added 4-(aminosulphonyl)benzoic acid (20.1 mg, 0.10 mmol) in 8 mL ethanol. Colorless block crystals were obtained after nine days by slow evaporation of the solvent (yield: 24 mg, 74.22%). mp 170-172°C. Elemental analysis: Calc. for C14H17N3O4S (323.37): C, 51.95; H, 5.26; N, 12.99; S, 9.90. Found: C, 51.83; H, 5.12; N, 12.86; S, 9.78. Infrared spectrum (KBr disc, cm-1): 3374s(νas(NH)), 3268s(νs(NH)), 3153m, 3097m, 3058m, 2963m, 2874m, 1599s(νas(CO2-)), 1555m, 1511m, 1468w, 1426m, 1384s(νs(CO2-)), 1340m, 1298m, 1254m, 1212m, 1177m, 1135m, 1093m, 1062m, 1018m, 975m, 933m, 888m, 848m, 810m, 764m, 721m, 677m, 633m, 610m.

c.

(4-dimethylaminopyridine)

:

(3-methylsalicylic

acid)2

[(HDMAP) · (msal) · (Hmsal), msal = 3-methylsalicylate] (3) 4-dimethylaminopyridine (12.2 mg, 0.10 mmol) was dissolved in 3 mL methanol. To this solution was added 3-methylsalicylic acid (15.1 mg, 0.10 mmol) in 8 mL ethanol. Colorless block crystals were obtained after a week by slow evaporation of the solvent (yield: 32 mg, 75.04%, based on DMAP). mp 134-135°C. Elemental analysis: Calc. for

4

C23H26N2O6 (426.46): C, 64.72; H, 6.10; N, 6.56. Found: C, 64.60; H, 6.02; N, 6.46. Infrared spectrum (KBr disc, cm-1): 3548w(ν(HO)), 3358s(νas(NH)), 3246s(νs(NH)), 3145m, 3084m, 2965m, 2874m, 1682s(C=O), 1618s(νas(CO2-)), 1560m, 1517m, 1475m, 1432m, 1394s(νs(CO2-)), 1350m, 1307m, 1265s(ν(C-O)), 1222m, 1180m, 1136m, 1094m, 1054m, 1012m, 870m, 825m, 782m, 742m, 696m, 652m, 610m. d. (4-dimethylaminopyridine) : (3,5,6-trichlorosalicylic acid) [(HDMAP+) · (tcsal-), tcsal- = 3,5,6-trichlorosalicylate] (4) 4-dimethylaminopyridine (12.2 mg, 0.10 mmol) was dissolved in 3 mL methanol. To this solution was added 3,5,6-trichlorosalicylic acid (24.1 mg, 0.10 mmol) in 10 mL ethanol. Colorless block crystals were afforded after ten days by slow evaporation of the solvent (yield: 28 mg, 77.00%). mp 144-145°C. Elemental analysis: Calc. for C14H13Cl3N2O3 (363.61): C, 46.20; H, 3.58; N, 7.70. Found: C, 46.06; H, 3.46; N, 7.58. Infrared spectrum (KBr disc, cm-1): 3685s(br, ν(OH)), 3366s(νas(NH)), 3270s(νs(NH)), 3224m, 3152m, 3110m, 3066m, 2972m, 2874m, 1600s(νas(CO2-)), 1556m, 1514m, 1468m, 1420s(νs(CO2-)), 1377m, 1335m, 1292m, 1250m, 1206m, 1165m, 1123m, 1081m, 1038m, 892m, 850m, 805m, 761m, 717m, 674m, 632m, 604m.

e.

(4-dimethylaminopyridine)

:

(2-pyrazinecarboxylic

acid)

:

4H2O

[(HDMAP+) · (pyza-) · 4H2O, pyza- = 2-pyrazine carboxylate] (5) 4-dimethylaminopyridine (12.2 mg, 0.10 mmol) was dissolved in 3 mL methanol. To this solution was added 2-pyrazine carboxylic acid (12.4 mg, 0.10 mmol) in 9 mL ethanol. Colorless block crystals were obtained after twelve days by slow evaporation of the solvent (yield: 24 mg, 75.39%). mp 160-162°C. Elemental analysis: Calc. for C12H22N4O6 (318.34): C, 45.23; H, 6.91; N, 17.59. Found: C, 45.11; H, 6.82; N, 17.45. Infrared spectrum (KBr disc, cm-1): 3680s(ν(OH)), 3353w(νas(NH)), 3260w(νs(NH)), 3146m, 3094m, 2958m, 2862w, 1622s(νas(CO2-)), 1574m, 1528m, 1484m, 1444m, 1396s(νs(CO2-)), 1350m, 1306m, 1262m, 1218m, 1174m, 1130m, 1085m, 1042m, 998m, 954m, 910m, 866m, 824m, 776m, 738m, 694m, 650m, 608m.

f.

(4-dimethylaminopyridine)

:

(2,2’-biphenyldicarboxylic

5

acid)

[(HDMAP+) · (Hbpda-), Hbpda = hydrogen 2,2’-biphenyldicarboxylate] (6) 4-dimethylaminopyridine (12.2 mg, 0.10 mmol) was dissolved in 3 mL methanol. To this solution was added 2,2’-biphenyldicarboxylic acid (24.2 mg, 0.1 mmol) in ethanol (20 ml). Colorless block crystals were obtained after 20 days by slow evaporation of the solvent (yield: 25 mg, 68.61%). mp 212-213°C. Elemental analysis: Calc. for C21H20N2O4 (364.39): C, 69.16; H, 5.49; N, 7.68. Found: C, 69.04; H, 5.36; N, 7.59. Infrared spectrum (KBr disc, cm-1): 3706s(ν(OH)), 3372s(multiple, νas(NH)), 3256s(νs(NH)), 3128m, 3076m, 2965m, 2874m, 1700s(νas(C=O)), 1614s(νas(CO2-)), 1566m, 1524m, 1480w, 1434m, 1392(νs(CO2-)), 1350m, 1308m, 1270s(ν(C-O)), 1225m, 1171m, 1127m, 1085m, 1042m, 998m, 955m, 914m, 870m, 825m, 780m, 734m, 690m, 655m, 622m. g.

(4-dimethylaminopyridine)2

:

(dibenzoyltartaric

acid)

[(HDMAP) · (Hdbta) · CH3OH · H2O, Hdbta = hydrogen dibenzoyltartarate] (7) 4-dimethylaminopyridine (12.2 mg, 0.10 mmol) was dissolved in 3 mL methanol. To this solution was added dibenzoyltartaric acid (35.8 mg, 0.1 mmol) in 12 mL methanol. Colorless block crystals were afforded after 18 days by slow evaporation of the solvent (yield: 36 mg, 67.86%). mp 142-143°C. Elemental analysis: Calc. for C26H30N2O10 (530.52): C, 58.81; H, 5.65; N, 5.28. Found: C, 58.70; H, 5.55; N, 5.16. Infrared spectrum (KBr disc, cm-1): 3695s(br, ν(OH)), 3360s(multiple, νas(NH)), 3238s(νs(NH)), 1592s(νas(CO2-)),

3174w, 1548m,

3128m, 1505m,

3086m, 1460w,

2974m,

2877m,

1412s(νs(CO2-)),

1712s(νas(C=O)), 1366m,

1324m,

1282s(νs(C-O)), 1236m, 1190m, 1148m, 1106m, 1062m, 1020m, 978m, 933m, 890m, 844m, 798m, 756m, 714m, 670m, 628m, 604m.

X-ray Crystallography SCXRD studies for the seven compounds were carried out via a Bruker SMART 1000 CCD diffractometer operating at 50 kV and 40 mA using Mo Kα radiation (λ = 0.71073 Å, monochromator graphite). Data collection and reduction were completed using the SMART and SAINT softwares [15]. The structures were solved by direct methods and the non-Hs were subjected to anisotropic refinement by full-matrix least

6

squares on F2 using SHELXTL package [16]. All Hs were placed in geometrically calculated positions and included in the refinement in a riding-model approximation. Data collection and structure refinement parameters along with crystallographic data for all compounds are given in Tables 1-2, selected bond lengths, bond angles and H-bond geometries are listed in Tables 3 and 4. Table 1 should be inserted here. Table 2 should be inserted here. HO

N

O

HO

O

S

O

N

O

HO

O

HO

3-methylsalicylic acid

4-(aminosulphonyl)benzoic acid

4-methoxybenzoic acid

4-dimethylaminopyridine

O NH2

OH O HO

Cl

O O

O

OH

OH

O

O O

HO

O

N

HO Cl

Cl

3,5,6-trichlorosalicylic acid

O

N

2-pyrazinecarboxylic acid

O

OH

2,2'-biphenyldicarboxylic acid

dibenzoyltartaric acid

Scheme 1 The building blocks in this paper. Results and Discussion Syntheses and General Characterization 4-dimethylaminopyridine has good solubility in CH3OH, C2H5OH, CH3CN, CH2Cl2 and CHCl3. All adducts were prepared by the same method of mixing the acids with the 4-dimethylaminopyridine at 1:1 in the corresponding solvents and the crystals were obtained at ambient conditions via the common solvent evaporating technique. All compounds crystallized without H2O accompanied except 5 and 7, and the seven crystalline products are not hygroscopic. Fig. 1, Fig. 3, Fig. 5, Fig. 7, Fig. 9, Fig. 11 and Fig. 13 exhibit the molecular structures and their atom labelling schemes for the seven structures, respectively. The O-H/N-H stretching frequencies were at 3706-3238 cm-1 as strong and broad bands in the IR spectra of the seven compounds. The medium intensity bands in 1500-1630 and 600-750 cm-1 are from the aryl ring stretching and bending, respectively.

7

IR spectroscopy is very useful for diagnosing H-transfer compounds [17], for in the H-transfer compounds, the most distinct feature in the IR spectrum are the presence of strong asymmetrical (1592-1622 cm-1) and symmetrical (1384-1420 cm-1) CO2- stretching frequencies [18], respectively. Salts 1, 3 and 6-7 have the bands for CO2H. Table 3 should be inserted here. Table 4 should be inserted here. X-ray

structure

of

(4-dimethylaminopyridine)

:

(4-methoxybenzoic

acid)

[(HDMAP) · (mba) · (Hmba), mba = 4-methoxybenzoate] (1) Figure 1 should be inserted here Figure 2 should be inserted here Compound 1 was prepared by reacting a methanol solution of DMAP and Hmba in 1 : 1, which crystallizes as triclinic colorless block crystals in the space group P-1. The CO2H H atom from one Hmba does not get dissociated and the CO2H H atom from the other Hmba was ionized. The asymmetric unit of 1 consists of one HDMAP, one mba and one Hmba (Fig. 1). This is a salt where one Hmba is ionized by H transfer to the aryl N of the DMAP, which is also verified by the bonds O(1)-C(8) (1.266(3) Å) and O(2)-C(8) (1.248(3) Å) for the CO2- [19]. The C-O bonds at O4-C16-O5 were typical bonds for C=O and C-O, respectively. The mean values of the C-C and N-C bond lengths in the pyridine ring are 1.385(3)/1.339(3) Å, which are between that of a single bond and a double bond. The analysis of the C-N-C angle (120.0(2)°) within the pyridine ring clearly supports the presence

of

the

HDMAP+,

which

fits

well

with

the

C-N-C

angles

in

p-dimethylaminopyridinum picrate (120.2(2) and 119.9(2)°) [20], dichloroacetate (119.1(4)°) [21] and p-nitrophenolate (119.7(2)°) [22]. By contrast, in free DMAP [23], the C-N-C angle is significantly narrower (114.5(2)°). Even when DMAP is involved in strong donor-acceptor associations as in Cp3Al · DMAP [24] and its cocrystals salicylaldehyde-4-(dimethylamino)-pyridine

(1/1)

(114.99(16)°)

[25]

and

3-methyl-4-nitrophenol-4-dimethylaminopyridine (1/1) (115.74(15)°) [26], the C-N-C angle is only marginally larger, which further support the right assignment of 1 as a salt. The rms deviations of the planes N1-C1-C2-C3-C4-C5/C9-C14 were 0.0025/0.0082 Ǻ, both planes canted at 84.1° to each other. The C8-O1-O2 tilted by 3.8° from the

8

C9-C14. The rms deviation of the plane C17-C22 was 0.0015 Ǻ, which canted by 6.1/83.1° from N1-C1-C2-C3-C4-C5/C9-C14. The C16-O4-O5 tilted by 9.2° from the C17-C22. At one O of the CO2- there was adhered a HDMAP by the N-H···O H-bond with N-O separation of 2.694(3) Å, at the other O of the CO2- there was bonded a 4-methoxybenzoic acid by the O-H···O H-bond with O-O separation of 2.521(2) Å, giving a tricomponent aggregate. Two inversionally related tricomponent aggregates were tied into a six-component assembly by the CH-O contact from α-H of the HDMAP and C=O of the Hmba with C-O separation of 3.235 Å. For the classical H-bonds and CH-O contact the six-component assembly exhibited the I R66(22) ring. At the a-axis the six-component assemblies were bundled together by the CH-O associations from the α’-, β’-CH of the HDMAP, the OH of the CO2H, and the O of the CO2- that bears an O-H···O H-bond with C-O separations of 3.418/3.460 Å to show 1D chain (Fig. 2). The two CH-O associations enclosed the II R32(7) synthon.

X-ray structure of (4-dimethylaminopyridine) : (4-(aminosulphonyl)benzoic acid) [(HDMAP) · (aspba), aspba = 4-(aminosulphonyl)benzoate] (2) Figure 3 should be inserted here Figure 4 should be inserted here Compound 2 crystallizes as triclinic colorless crystals in the space group P-1 with Z = 2. The asymmetric unit of 2 contains one HDMAP and one aspba (Fig. 3). Similar with 1, this is also an organic salt with the CO2H of the 4-(aminosulphonyl)benzoic acid deprotonized, which is in line with the bonds of O(3)-C(14) (1.253(3) Å) and O(4)-C(14) (1.242(3) Å). The C(1)-N(1)-C(5) [120.0(2)°] is the same as the corresponding one in 1. Examination of the HDMAP shows that the N1, C1, C2, C3, C4 and C5 of the pyridine ring have a good coplanarity and they define a conjugated plane with mean deviation of 0.0092 Å. The rms deviation of the ring C8-C13 is 0.0077 Å and both planes oriented at 55.8° to each other. The C14-O3-O4 tilted by 21.9° from the C8-C13. The amino-N3 occupies a position almost normal to the aryl ring with the N(2)-S(1)-C(8)-C(9) torsion angle of -99.3(2)° which is similar to the opened file [27]. An aspba associated with a HDMAP by the bifurcated N-H···O H-bonds from NH of

9

the HDMAP and both O of the CO2- with N-O distances of 2.771(3)-3.092(3) Å to make a bicomponent adduct. The bicomponent adducts were glued into 1D chain by the CH3-O association from CH3 of the HDMAP and one O of the SO2 with C-O separation of 3.565 Å. The 1D chains were bridged by the N-H···O H-bond from NH of the SO2NH2 and the CO2- with N-O distance of 2.853(3) Å, CH3-O association from CH3 of the HDMAP and one O of the CO2- with C-O separation of 3.523 Å and CH3-CH contact from CH3 and pyridine 2-CH of the HDMAP with H-H/C-C separations of 2.230/3.579 Å to give 2D sheet (Fig. 4) parallel to the bc plane. Two sheets were held together by the N-H···O H-bonds from the SO2NH2 and the CO2- with N-O distance of 2.874(3) Å, CH3-O association from CH3 of the HDMAP and one O of the SO2 with C-O separation of 3.513 Å and π-π stacking from the aryl kernels of the anions with Cg-Cg separation of 3.384 Å to architecture a doublesheet with the respective units at the two sheets antiparallel to each other. The doublesheets were further packed by the CH-O contacts from the aryl 2-CH of the HDMAP, one O of the SO2 with C-O separation of 3.018 Å and from the aryl 3-CH of the aspba and the same O of the SO2 with C-O separation of 3.385 Å to make 3D net. The net was characterized by III R12(4), IV R22(10), V R22(18), VI R32(14), VII R32(18), VIII R33(10), IX R42(8) and X R42(12) motifs.

X-ray

structure

of

(4-dimethylaminopyridine)

:

(3-methylsalicylic

acid)2

[(HDMAP) · (msal) · (Hmsal), msal = 3-methylsalicylate] (3) Figure 5 should be inserted here Figure 6 should be inserted here The compound 3 of the composition [(HDMAP) · (msal) · (Hmsal)] was successfully solved in the orthorhombic space group Pnma with Z = 4. The aromatic N at the DMAP was protonated by one Hmsal in which only the H at the CO2H was fully transferred to the aryl N of the DMAP giving an organic salt, the phenol H remained intact. Similar to 1, in the asymmetric unit of 3 there occupied one unit of each component of HDMAP, msal and Hmsal (Fig. 5). The total Hmsal was disordered over two sites with equal occupancies; the H at CH3 of the msal was each disordered over two sites with equal occupancies. The C-O bonds are 1.228(4) Ǻ (O(1)-C(5)) and 1.271(4) Ǻ (O(2)-C(5)) with ∆ = 0.043 Ǻ, the relative big ∆ is due to the O2 has more strong H-bonds than O1 (Table

10

4). The O(3)-C(7) (1.339(4) Ǻ) was near the accepted value for the phenol [28]. The C(1)#1-N(1)-C(1) is 119.4(4)° being close to that at 1 and 2. The anticipated intramolecular H-bond is made from the phenol and a carboxyl O (O(3)-H(3)···O(2), 2.554(4) Å, 146.6º; O(6)-H(6)···O(5), 2.574(12) Å, 149.0º), creating the S11(6) circle. Due to the planarity of the H-bonded carboxyl unit (with the torsion angle C7-C6-C5-O1 = 180.0°, O(4)-C(13)-C(14)-C(15) = -179.1(8)°), the O-O separation is toward the upper range of the open data [2.489-2.509 Å] [29]. At the CO2- of the 3-methylsalicylate there was attached a HDMAP by the N-H···O H-bond from the NH and one O of the CO2- with O-N distance of 2.730(4) Å and a Hmsal from the other O of the CO2- with O-O distance of 2.565(6) Å, creating a tricomponent aggregate. There also established the O-π association from the OH in the CO2H of the Hmsal and the pyridine nucleus with O-Cg distance of 3.166 Å at the tricomponent aggregate, the O-Cg distance was shorter than the filed data [30]. Along the b-axis the tricomponent aggregates were mediated into 1D chain by the CH-O associations from 2-CH of the HDMAP and the CO2H with C-O separations of 3.216-3.513 Å, together with CH-π association from the aryl CH of the Hmsal and the aryl core of the msal with C-Cg separation of 3.512 Å. The chains were bundled into 2D sheet (Fig. 6) by the CH3-O associations from CH3 of the Hmsal, the CO2- and CO2H with C-O separations of 3.485-3.636 Å, and CH3-π association from CH3 of the HDMAP and the aryl nucleus of the Hmsal with C-Cg separation of 3.672 Å. In this regard the tricomponent aggregates at the neighboring chains were normal to each other. In the third direction the sheets were further packed by the CH3-O association from CH3 of the Hmsal, the CO2-, and CO2H with C-O separations of 3.485-3.636 Å, and CH3-π association from CH3 of the HDMAP and the aryl nucleus of the Hmsal with C-Cg separation of 3.672 Å to yield 3D net.

X-ray structure of (4-dimethylaminopyridine) : (3,5,6-trichlorosalicylic acid) [(HDMAP+) · (tcsal-), tcsal- = 3,5,6-trichlorosalicylate] (4) Figure 7 should be inserted here Figure 8 should be inserted here The asymmetric unit of 4 bears one HDMAP and one tcsal- (Fig. 7). The C-O bonds

11

at the CO2- ranged from 1.211(8) Å (C(8)-O(1)) to 1.279(8) Å (C(8)-O(2)), the marked large ∆ is resulted from the different H-bonds the O1 and O2 are involved in (Table 4). Structural and conformational characters similar to those already found are appeared at the tcsal- also [31]. The O(3)-C(10) was 1.375(6) Å, the C(5)-N(1)-C(1) was 119.6(8)º. The tcsal- is stabilized by the intramolecular O-H···O H-bond (O(3)-H(3)···O(2), 2.443(6) Å, 148.6º) with the creation of an S(6) ring, thus the CO2- is essentially coplanar with the aryl ring [torsion angle C10-C9-C8-O1 = 170.6(6)°]. This feature is the usual conformation for the salicylic acid [29], the O-O separation is in the lower range of the archived data [2.489-2.509 Ǻ] [29]. The tcsal- also had the intramolecular Cl-O contact from 3-Cl and the CO2- with Cl-O separation of 2.768 Å, which was shorter than the known examples [32]. The r.m.s deviations of the pyridine ring and benzene ring (C(9)-C(14)) from the mean planes of the corresponding rings are 0.0079/0.0097 Å, both rings oriented at 5.8º to each other. The bifurcated N-H···O H-bonds from one H of the NH3+ and both O of the CO2with N-O distances of 2.895(9)-3.024(9) Å, together with the CH-O contact from the 2-CH of the pyridine and the CO2- with C-O separation of 3.079 Å brought one HDMAP and one tcsal- into a heteroadduct with the close joint XI R12(4) and XII R21(5) motifs. In the b-axis the heteroadducts were grown into 1D chain by the CH-O contact from 3-CH of the HDMAP and the phenol with C-O separation of 3.311 Å and Cl-Cl contact from the 6-Cl and 3-Cl of the tcsal- with Cl-Cl separation of 3.486 Å. The Cl-Cl bond was shorter than the opened ones [33]. The chains were bridged together by the CH3-Cl contact from 4-Cl of the tcsal- and CH3 of the HDMAP with C-Cl separation of 3.770 Å into 2D sheet (Fig. 8). Two sheets were held together by the C-π contact from the π-C of the CO2- and the pyridine kernel with C-Cg separation of 3.314 Å to yield a double sheet.

X-ray structure of (4-dimethylaminopyridine) : (2-pyrazinecarboxylic acid) : 4H2O [(HDMAP+) · (pyza-) · 4H2O, pyza- = 2-pyrazine carboxylate] (5) Figure 9 should be inserted here Figure 10 should be inserted here Compound 5 is a tetrahydrate of 1:1 HDMAP+ and pyzca- (Fig. 9), which has the orthorhombic P2(1)2(1)2(1) spacegroup. The C-O bonds in CO2- are 1.254(3) Å for

12

O(1)-C(8) and 1.230(3) Å for O(2)-C(8). The C(5)-N(1)-C(1) was 119.7(2)°. The rms deviations of the aryl rings with N1-C1-C2-C3-C4-C5/N3-N4-C9-C10-C11-C12 were 0.0013/0.0023 Å, both rings are very slightly canted with a dihedral angle of 12.1°. The C8-O1-O2 twisted by 5.9° from the pyrazine ring. One HDMAP+ and one pyzca- created a heteroadduct by the N-H···O H-bond from the NH+ and one O of the CO2- with N-O distance of 2.681(3) Å, N-H···N H-bond from the NH+ and the N neighboring to the CO2- with N-N distance of 3.151(3) Å and CH-N contact between the 2-CH of the pyridine and the N neighboring to the CO2- with C-N distance of 3.285 Å. Four H2O create an almost square planar water tetramer by the O-H···O H-bonds with O-O separations of 2.781(3)-2.854(4) Å. The water tetramer was tied to the heteroadduct by the O-H···N H-bond from the H2O and the 4-N of the pyzcawith O-N distance of 2.953(3) Å to give a sixcomponent aggregate. In the b-axis the sixcomponent aggregates were tied together by the CH-O association from 3-CH of the HDMAP+ and the H2O of the water tetramer with C-O distance of 3.370 Å to yield 1D chain. In the bc plane the 1D chains were knitted together by the CH-O association from 3-CH of the HDMAP+ and the other O of the CO2- with C-O distance of 3.261 Å and CH-O association between 5-CH of the pyzca- and the H2O with C-O distance of 3.479 Å to give 2D sheet (Fig. 10). In the a-axis the sheets were packed by the O-H···O H-bonds with O-O separations of 2.786(3)-2.828(3) Å, CH-O association from 2-CH of the HDMAP+ and the H2O with C-O distance of 3.434 Å, CH-O association from 6-CH of the pyzca- and the H2O with C-O distance of 3.491 Å and π-π stacking from the pyridine and the pyrazine cores with Cg-Cg separation of 3.393 Å to give 3D net. The net was characterized by XIII R12(5), XIV R21(5), XV R44(8), XVI R54(11), XVII R55(15), XVIII R66(20), XIX R76(21) and XX R76(21) rings.

X-ray structure of (4-dimethylaminopyridine) : (2,2’-biphenyldicarboxylic acid) [(HDMAP+) · (Hbpda-), Hbpda = hydrogen 2,2’-biphenyldicarboxylate] (6) Figure 11 should be inserted here Figure 12 should be inserted here The dicarboxylic acid in 6 is partially deprotonated, causing a hydrogen 2,2′-biphenyldicarboxylate salt [(HDMAP+) · (Hbpda-)]. Salt 6 belongs to triclinic space

13

group P-1, having a HDMAP and an Hbpda- in the asymmetric unit (Fig. 11). The C-O bonds at O(1)-C(8)-O(2) were 1.223(2) Å (O(1)-C(8)) and 1.297(2) Å (O(2)-C(8)). The O(3)-C(15) (1.295(2) Å) being pronounced longer than O(4)-C(15) (1.227(2) Å) was due to the more strong H-bonds from O(3) than O(4). The Hbpda- had the intramolecular CO2-··· CO2H H-bond with O-O separation of 2.468(2) Å, creating the S(9) ring. The respective rms deviations of the aryl rings N1-C1-C5/C9-C14 were 0.0092/0.0040 Å, both rings orientated at 66.3° with each other. The rms deviation of the C16-C21 was 0.0086 Å, which subtended at 58.5/90.8° with the above two rings. The C8-O1-O2/C15-O3-O4 twisted by 52.8/52.6° from their attached ring. Both carboxyl intersected at 75.2° with each other. The torsion angle C(9)-C(10)-C(17)-C(16) (-94.1(2)°) was much smaller than the filed value [34]. At the CO2- there was attached a HDMAP by the N-H···O H-bond from the NH+ and one O of the CO2- with N-O distance of 2.928(3) Å and CH-O association from 2-CH of the HDMAP and the other O of the CO2- with C-O distance of 3.335 Å to generate a heteroadduct. Two heteroadducts were joined together by the N-H···O H-bond from the NH+ and the C=O of the CO2H with N-O distance of 2.937(3) Å and CH-O association between 2-CH of the HDMAP and the C=O of the CO2H with C-O distance of 3.126 Å and CH-O association between the CH neighboring to the CO2H of the Hbpda- and the OH of the CO2H with C-O distance of 3.285 Å to form a tetramer with the respective units inversionally related. The tetramers were linked into 1D chain by the CH3-π contact from CH3 of the HDMAP and the aryl core with the CO2- with C-Cg separation of 3.724 Å and CH-π association from the aryl CH of the Hbpda- with the CO2- and the aryl ring with the CO2H with C-Cg separation of 3.627 Å. The 1D chain were united together by the CH-O association from the CH neighboring to the CO2- and the CO2- with C-O distance of 3.348 Å to show 2D sheet (Fig. 12). Three dimensionally the sheets were packed by the CH-O association from the CH meta to the CO2H of the Hbpda- and the OH of the CO2H with C-O distance of 3.187 Å, CH-O association from the 5-CH of the aryl unit with the CO2- and the C=O of the CO2H with C-O distance of 3.536 Å and π-π stacking from the antiparallelly arranged pyridine rings with Cg-Cg separation of 3.390 Å to give 3D net. The sheets were characterized by XXI R21(5), XXII R22(7), XXIII R22(10), XXIV R22(10), XXV R22(16), XXVI R42(10), XXVII R44(12) and XXVIII R44(24)

14

synthons.

X-ray

structure

of

(4-dimethylaminopyridine)2 :

(dibenzoyltartaric

acid)

[(HDMAP) · (Hdbta) · CH3OH · H2O, Hdbta = hydrogen dibenzoyltartarate] (7) Figure 13 should be inserted here Figure 14 should be inserted here Similar to 6 and the published salt from dibenzoyltartaric acid [35], the dicarboxylic acid in 7 is also partially deprotonated, giving a hydrogen dibenzoyltartarate salt [(HDMAP) · (Hdbta) · CH3OH · H2O]. Salt 7 belongs to monoclinic space group P2(1), with a HDMAP, a Hdbta, a CH3OH and a H2O in the asymmetric unit (Fig. 13). The C-O bonds at O(1)-C(8)-O(2) were O(1)-C(8) (1.262(8) Å) and O(2)-C(8) (1.212(9) Å) for the CO2-. In the CO2H, the O(3)-C(11)-O(4) had C-O of 1.263(8)/1.217(9) Å. In the HDMAP, the angle was 121.4(14)° (C(1)-N(1)-C(5)), the widening of the C(1)-N(1)-C(5) is due to the more strong H-bond the N(1) was participated in. The torsion angle C(8)-C(9)-C(10)-C(11) (173.0(6)°) indicated the alkane chain extended fully. The respective rms deviations of the rings N1-C1-C5/C13-C18 were 0.0245/0.0133 Å, both rings orientated at 2.3° with each other. The rms deviation of the ring C20-C25 was 0.0072 Å, which made 79.8° with the N1-C1-C5. The two aryl rings in the same Hdbta subtended at 81.3° with each other, which is marked wider than that in the reported cocrystal of dibenzoyltartaric acid [36], but it was close to that (79.46(6)°) in the filed salt [35]. The C8-O1-O2/C11-O3-O4 canted at 62.6° to each other. At the Hdbta there was bonded a CH3OH by the O-H···O H-bond from one O of the CO2- with O-O separation of 2.807(13) Å, a H2O by the O-H···O H-bond from the C=O of the CO2H with O-O separation of 2.693(13) Å to build a tricomponent adduct. A HDMAP was bonded to the tricomponent adduct by the N-H···O H-bond from the NH of the HDMAP and the H2O with N-O separation of 2.719(16) Å, CH-π association from 3-CH of the HDMAP and the aryl core neighboring to the CO2- with C-Cg separation of 3.712 Å and CH3-π association from one CH3 of the HDMAP and the aryl core as the CH-π association with C-Cg separation of 3.770 Å to yield a tetracomponent assembly. In the a-axis the tetracomponent assemblies were linked by the CO2H···CO2- H-bond with O-O separation of 2.456(7) Å and CH-O association from the aryl 3-CH of the side arm

15

close to the CO2- and the CH3OH with C-O separation of 3.530 Å to give 1D chain. Along the ac plane the 1D chains were connected together by the CH-O association from the aryl 2-CH of the side arm close to the CO2- and the C=O of the benzoyl close to the CO2H with C-O separation of 3.256 Å and CH3-O association from CH3 of the HDMAP, the H2O, and the other O of the CO2- with C-O separations of 3.535 and 3.230 Å to show 2D sheet (Fig. 14). In the b-axis the 2D sheets were further packed by the O-H···O H-bond of 3.14(2) Å from the H2O(donor) and the CH3OH, CH-O association from 2-CH of the HDMAP and the CO2- with C-O separation of 3.435 Å, CH-O association from the aryl 3-CH of the side arm close to the CO2H and the C=O of the CO2H with C-O separation of 3.403 Å and CH3-π associations from CH3 of the HDMAP and the aryl cores of the Hdbta with C-Cg separations of 3.320-3.558 Å to give 3D net. The net presented the XXIX R33(16), XXX R43(9), XXXI R43(12) and XXXII R44(26) rings.

Influence of the carboxylic acids on the architectures of 1-7 In this text, a variety of rigid and flexible acids with additional functional groups, were used to make supramolecular salts, giving seven compounds with 1D chain (for 1) to 3D net (for 2 - 7). Our research indicates that the carboxylic acids have a critical effect on the architectures of 1-7. In 1-7, the carboxylic acids are essential in making the salts. The different acids not only have an effect on protonizing DMAP, but also act a critical role in building the total architectures with different dimensionalities via H-bonds and various non-covalent bonds. All compounds have the non-covalent bonded 1D sub-chain. The major classical H-bonds had akin role in expanding 1-7. The negatively charged O of the anion at all salts participated in the CH-O association except 2 - 3. The CH-O associations from 2-CH of the pyridine were appeared in all salts. For the N atoms reduce the electron density of the neighboring C-H Hs inductively and raise the donor capability of the C-H protons, so the CH-O contacts from the 2-CH of the pyridine were produced in all salts. The aryl nucleus of the anions created the π-interactions in 2, 3 and 5-7 as CH-π/CH3-π, O-π and π-π. In 1 it was the CH-O associations accepted by mba/Hmba which made the 1D chain. For 2 the SO2 of the aspba accepted intrachain CH3-O and inter doublesheet CH-O associations, which was the only force expanding the respective chain and net. For 3 both the chain and sheet

16

substructure together with the total 3D net rely solely on the non-covalent bonds from msal/Hmsal. In 4, the anions exhibited the CH-O, Cl-Cl, CH3-Cl and C-π contacts in building 1D chain - 2D double sheet. For 5 the anions participated in the interchain/intersheet CH-O associations as well as intersheet π-π stacking. In 6, the noncovalent bonds from Hbpda- as CH3-π/CH-π, CH-O and π-π associations governed the chain, sheet and the final 3D net extension. The anion at 7 participated in the 1D chain, 2D sheet and 3D net construction via CH-O, CH3-O and CH3-π contacts, respectively. The results tell that the different species of functional groups, as well as their number and position, have critical effects on both the sub and final structures.

Conclusion In summary, seven 4-dimethylaminopyridinium salts have been structurally characterized and the underlying supramolecular chemistry has been elucidated in this article, which make new knowledge to the study into the search for carboxylic acid-4-dimethylaminopyridine motifs. In all salts the aryl N are protonated and they were anhydrous except 5 and 7. In this report, a complex sets of synthons with small and large rings were created as R12(4), R12(5), R21(5), R22(7), R22(10), R22(16), R22(18), R32(7), R32(14), R32(18), R33(10), R33(16), R42(8), R42(10), R42(12), R43(9), R43(12), R44(8), R44(12), R44(24), R44(26), R54(11), R55(15), R66(20), R66(22) and R76(21). Though prepared via the same common solvent evaporation method, they showed structures as diverse as 1D chain and 3D net. All structures bear the 1D chain substructure, 2-7 had the subsheet, from an inspection of the functions made by each set of interactions; it seems that the intra- and interchain non-covalent bonds had equal importance in structure extension. Despite variations in the carboxylic acids, there all established strong intermolecular N-H···O H-bonds, there are also O-H···O H-bonds in all salts except 2. Besides the robust classical H-bonds, other different series of supramolecular interactions of CH-N, CH-O/CH3-O, CH-π/CH3-π, CH3-CH, CH3-Cl, C-π, O-π, Cl-Cl and π-π are also crucial in structure expansion. The 2-CH of the pyridine participates actively in CH-O association for all salts; the noncovalent bonds from CH3 of the cation were found in 2-4 and 6-7 as CH3-O, CH3-π, CH3-CH and CH3-Cl. The CH-π associations were existed in 3, 6 and 7.

17

The various non-covalent bonds together with distinct geometries and numbers of the acidic units at the carboxylic acids, has resulted in the construction of higher-dimensional assemblies from the discrete blocks. On the basis of molecular salts presented here together with those reports from the literatures, the results clearly tell that dimethylaminopyridine is a good building fragment to be embodied into salts so as to create diversiform and stable H-bonded structures.

Acknowledgement This research was supported by Zhejiang Provincial Natural Science Foundation of China, and the Zhejiang Xinmiao Talents Program.

Supporting Information Available: Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic data center, CCDC Nos. 1547151 for 1, 1538549 for 2, 1539803 for 3, 1538548 for 4, 1542251 for 5, 1539807 for 6 and 1539114 for 7. Copies of this information may be obtained free of charge from the +44(1223)336-033

or

Email:

[email protected]

or

www:

http://www.ccdc.cam.ac.uk.

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Figure captions Fig. 1 Molecular structure of 1 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 2 1D chain structure of 1 running along the a-axis.

Fig. 3 Molecular structure of 2 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 4 2D sheet structure of 2 extending parallel to the bc plane.

Fig. 5 Molecular structure of 3 showing the atomic numbering scheme. For the crowdedness of the structure the atom numbering were not labeled. Displacement ellipsoids are drawn at the 30% probability level. Fig. 6 2D sheet structure of 3.

Fig. 7 Molecular structure of 4 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 8 2D sheet structure of 4.

Fig. 9 Molecular structure of 5 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 10 2D sheet structure of 5 extending along the bc plane.

Fig. 11 Molecular structure of 6 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 2D sheet structure of 6.

Fig. 13 Molecular structure of 7 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 14 2D sheet structure of 7 extending along the ac plane.

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Covering information sheet Journal name: JOURNAL OF MOLECULAR STRUCTURE Title: Seven Supramolecular Adducts of 4-dimethylaminopyridine and Carboxylic acids Constructed by Classical H-Bonds and Some Noncovalent Interactions

Corresponding author: Shouwen Jin Address: aZheJiang A & F University, Lin'An 311300, P. R. China. *E-mail: [email protected]

Numbers of pages: 26pp Figures: 14 Tables: 4

24

Table 1. Summary of X-ray crystallographic data for 1-4. 1

2

3

4

Formula Fw T, K Wavelength, Å Crystal system space group a, Å b, Å c, Å α, °C.

C23H26N2O6 426.46 298(2) 0.71073 Triclinic P-1 9.7359(7) 10.1790(8) 12.3196(9) 73.4550(10)

C14H17N3O4S 323.37 298(2) 0.71073 Triclinic P-1 8.1379(6) 8.3090(7) 11.8981(9) 76.4070(10)

C23H26N2O6 426.46 298(2) 0.71073 Orthorhombic Pnma 13.1229(11) 9.6350(8) 17.8281(15) 90

C14H13Cl3N2O3 363.61 298(2) 0.71073 Monoclinic C2/c 22.4725(17) 9.3205(8) 15.2801(14) 90

β, °C. γ, °C. V, Å3 Z Dcalcd, Mg/m3 Absorption coefficient, mm-1 F(000) Crystal size, mm θ range, deg

85.043(2) 71.2550(10) 1108.25(14) 2 1.278 0.093

75.0200(10) 77.156(2) 744.15(10) 2 1.443 0.240

90 90 2254.2(3) 4 1.257 0.091

99.267(2) 90 3158.7(5) 8 1.529 0.593

452 0.42 x 0.40 x 0.24 2.39 - 25.02 -11 ≤ h ≤ 9 -12 ≤ k ≤ 10 -14 ≤ l ≤ 14 5652 3863 (0.0273)

340 0.47 x 0.40 x 0.24 2.63 - 25.02 -9 ≤ h ≤ 9 -9 ≤ k ≤ 5 -14 ≤ l ≤ 12 3775 2579 (0.0232)

904 0.48 x 0.21 x 0.19 2.28 - 25.02 -14 ≤ h ≤ 15 -11 ≤ k ≤ 11 -18 ≤ l ≤ 21 10625 2121 (0.0842)

1488 0.38 x 0.23 x 0.15 2.37 - 25.02 -21 ≤ h ≤ 26 -10 ≤ k ≤ 11 -18 ≤ l ≤ 18 7547 2768 (0.1233)

0.845 0.0508, 0.1175 0.1105, 0.1388 0.148, -0.171

1.063 0.0497, 0.1373 0.0628, 0.1453 0.220, -0.453

0.840 0.0537, 0.1304 0.1376, 0.1591 0.251, -0.127

0.964 0.0731, 0.1702 0.1866, 0.2153 0.308, -0.275

Limiting indices Reflections collected Reflections independent (Rint) Goodness-of-fit on F2 R indices [I > 2σI] R indices (all data) Largest features in final difference Fourier synthesis peak and hole, e · Å-3

Table 2. Summary of X-ray crystallographic data for 5-7. Formula Fw T, K Wavelength, Å Crystal system space group a, Å b, Å c, Å α, °C. β, °C. γ, °C. V, Å3 Z Dcalcd, Mg/m3 Absorption coefficient, mm-1 F(000) Crystal size, mm θ range, deg Limiting indices Reflections collected Reflections independent (Rint) Goodness-of-fit on F2 R indices [I > 2σI] R indices (all data) Largest features in final difference Fourier synthesis peak and hole, e · Å-3

5

6

7

C12H22N4O6 318.34 298(2) 0.71073 Orthorhombic P2(1)2(1)2(1) 6.9634(6) 13.5123(12) 17.3503(15) 90 90 90 1632.5(2) 4 1.295 0.104

C21H20N2O4 364.39 298(2) 0.71073 Triclinic P-1 7.678(4) 10.848(6) 12.153(7) 71.185(7) 87.738(8) 70.084(7) 898.0(9) 2 1.348 0.094

C26H30N2O10 530.52 298(2) 0.71073 Monoclinic P2(1) 7.4018(7) 17.1846(15) 10.8093(9) 90 96.885(2) 90 1365.0(2) 2 1.291 0.100

680 0.35 x 0.30 x 0.14 2.79 - 25.02 -7 ≤ h ≤ 8 -16 ≤ k ≤ 15 -14 ≤ l ≤ 20 8178 2857 (0.0336)

384 0.43 x 0.34 x 0.27 2.27 - 28.39 -10 ≤ h ≤ 8 -14 ≤ k ≤ 13 -16 ≤ l ≤ 12 5737 4295 (0.0217)

560 0.45 x 0.39 x 0.38 2.77 - 25.02 -8 ≤ h ≤ 8 -14 ≤ k ≤ 20 -12 ≤ l ≤ 12 3500 (0.0402)

1.017

0.867

0.979

0.0412, 0.0915 0.0805, 0.1084 0.146, -0.142

0.0497, 0.1088 0.1035, 0.1289 0.219, -0.235

0.0769, 0.2034

6808

0.1381, 0.2464 0.644, -0.236

Table 3. Selected bond lengths [Å] and angles [°] for 1-7. 1

N(1)-C(1) N(2)-C(3) N(2)-C(7) O(2)-C(8) O(3)-C(15) O(5)-C(16) O(6)-C(23) C(3)-N(2)-C(6) C(6)-N(2)-C(7) O(5)-C(16)-O(4)

2 N(1)-C(1) N(2)-C(3) N(2)-C(6) O(1)-S(1) O(3)-C(14) S(1)-C(8) C(3)-N(2)-C(7) C(7)-N(2)-C(6) O(4)-C(14)-O(3) 3 N(1)-C(1) N(2)-C(4) O(2)-C(5) O(4)-C(13) O(5)-C(13)#1 O(6)-C(18)#1 C(13)-O(4)#1 C(18)-O(6)#1 C(1)-N(1)-C(1)#1 C(4)#1-N(2)-C(4) C(13)#1-O(4)-C(13) O(4)#1-C(13)-O(5) O(5)-C(13)-O(4) O(5)-C(13)-O(5)#1 4 Cl(1)-C(11) Cl(3)-C(14) N(1)-C(1) N(2)-C(6)

O(1)-C(8) O(3)-C(10)

1.338(3) 1.344(3) 1.470(3) 1.248(3) 1.433(3) 1.223(3) 1.400(3) 121.7(2) 117.2(2) 123.8(2)

N(1)-C(5) N(2)-C(6) O(1)-C(8) O(3)-C(12) O(4)-C(16) O(6)-C(20) C(1)-N(1)-C(5) C(3)-N(2)-C(7) O(2)-C(8)-O(1)

1.340(3) 1.456(3) 1.266(3) 1.373(3) 1.315(3) 1.387(3) 120.0(2) 121.1(2) 125.6(2)

1.313(4) 1.339(3) 1.458(3) 1.4200(18) 1.253(3) 1.773(2) 122.4(2) 117.0(2) 124.6(2)

N(1)-C(5) N(2)-C(7) N(3)-S(1) O(2)-S(1) O(4)-C(14) C(1)-N(1)-C(5) C(3)-N(2)-C(6) O(1)-S(1)-O(2)

1.334(4) 1.448(3) 1.593(2) 1.4275(18) 1.242(3) 120.0(2) 120.6(2) 119.24(12)

1.328(3) 1.459(3) 1.271(4) 1.31(2) 1.82(2) 1.189(9) 0.943(11) 1.189(9) 119.4(4) 116.7(4) 24.8(19) 49.8(11) 122.6(14) 150.6(10)

N(2)-C(3) O(1)-C(5) O(3)-C(7) O(5)-C(13) O(6)-C(19)#1 O(6)-C(15) C(13)-O(5)#1 C(19)-O(6)#1 C(3)-N(2)-C(4) C(13)#1-O(4)-O(5)#1 O(1)-C(5)-O(2) O(4)#1-C(13)-O(4) O(4)#1-C(13)-O(5)#1 O(4)-C(13)-O(5)#1

1.345(4) 1.228(4) 1.339(4) 1.23(3) 0.947(12) 1.327(14) 1.82(2) 0.947(12) 121.63(18) 81.0(17) 123.5(4) 73.4(10) 103.4(11) 30.4(5)

1.730(6) 1.694(5) 1.346(9) 1.443(8) 1.211(8) 1.375(6)

Cl(2)-C(13) N(1)-C(5) N(2)-C(3) N(2)-C(7) O(2)-C(8) C(5)-N(1)-C(1)

1.742(6) 1.327(10) 1.331(7) 1.469(8) 1.279(8) 119.6(8)

C(3)-N(2)-C(6) C(6)-N(2)-C(7)

122.2(6) 116.9(6)

C(3)-N(2)-C(7)

O(1)-C(8)-O(2)

120.9(6) 124.5(7)

N(1)-C(5) N(2)-C(3)

1.333(3) 1.343(3)

N(1)-C(1) N(2)-C(6)

1.335(3) 1.459(3)

N(2)-C(7) N(3)-C(9) N(4)-C(10) O(2)-C(8) C(3)-N(2)-C(6) C(6)-N(2)-C(7) C(11)-N(4)-C(10) 6 O(2)-C(8) O(3)-C(15) N(2)-C(3) N(2)-C(7) N(1)-C(1) O(4)-C(15)-O(3) C(3)-N(2)-C(7) C(1)-N(1)-C(5) 7 N(1)-C(1) N(2)-C(3) N(2)-C(6) O(2)-C(8)

1.460(3) 1.339(3) 1.330(4) 1.230(3) 121.2(2) 117.4(2) 115.4(2)

N(3)-C(12) N(4)-C(11) O(1)-C(8) C(5)-N(1)-C(1) C(3)-N(2)-C(7) C(12)-N(3)-C(9) O(2)-C(8)-O(1)

1.331(3) 1.316(4) 1.254(3) 119.7(2) 121.3(2) 116.0(2) 126.0(3)

1.297(2) 1.295(2) 1.332(2) 1.464(3) 1.333(3) 123.64(18) 121.29(18) 120.2(2)

O(1)-C(8)

1.223(2) 1.227(2) 1.464(3) 1.339(3) 121.84(18) 121.70(17) 116.86(18)

5

O(4)-C(11) O(5)-C(9) O(7)-C(19)

O(8)-C(19) C(1)-N(1)-C(5) C(3)-N(2)-C(6) O(2)-C(8)-O(1) O(6)-C(12)-O(5)

1.292(18) 1.367(15) 1.423(18) 1.212(9) 1.217(9) 1.438(8) 1.346(8) 1.206(9) 121.4(14) 123.4(13) 128.0(6) 121.6(6)

O(4)-C(15) N(2)-C(6 C(5)-N(1) O(1)-C(8)-O(2) C(3)-N(2)-C(6)

C(6)-N(2)-C(7)

N(1)-C(5) N(2)-C(7) O(1)-C(8)

O(3)-C(11) O(5)-C(12) O(6)-C(12)

O(7)-C(10) O(9)-C(26) C(3)-N(2)-C(7)

C(7)-N(2)-C(6) O(4)-C(11)-O(3)

O(8)-C(19)-O(7)

1.373(18) 1.397(18) 1.262(8) 1.263(8) 1.349(7) 1.179(8) 1.431(7) 1.394(19) 120.2(12) 116.5(12) 126.4(6) 122.1(6)

Symmetry transformations used to generate equivalent atoms for 3: #1 x, -y+3/2, z.

Table 4. H-bond distances and angles in 1-7. D-H···A

1 O(4)-H(4)···O(1) N(1)-H(1)···O(2) 2 N(3)-H(3B)···O(3)#1 N(3)-H(3A)···O(3)#2 N(1)-H(1)···O(3)#2 N(1)-H(1)···O(4)#2 3 O(6)-H(6)···O(4)#1 O(6)-H(6)···O(5) O(4)-H(4)···O(2)#2 O(3)-H(3)···O(2) N(1)-H(1)···O(1)#2 4 O(3)-H(3)···O(2) N(1)-H(1)···O(1)#1 N(1)-H(1)···O(2)#1 5 O(6)-H(6G)···O(4)#1

O(6)-H(6F)···O(4)#2 O(5)-H(5D)···O(6) O(5)-H(5C)···O(2) O(4)-H(4D)···O(3)#3 O(4)-H(4C)···O(1) O(3)-H(3D)···O(5)#3 O(3)-H(3C)···N(4) N(1)-H(1)···N(3) N(1)-H(1)···O(1) 6 N(1)-H(1)···O(1)#1 N(1)-H(1)···O(3)#2

O(2)-H(2)···O(3) 7 O(10)-H(10D)···O(9)#1 O(10)-H(10C)···O(2) O(9)-H(9)···O(4)#2 O(1)-H(1A)···O(3)#2 N(1)-H(1)···O(10)#3

d(D-H) [Å]

d(H···A) [Å]

d(D···A) [Å]

<(DHA)[°]

0.82 0.86

1.72 1.86

2.521(2) 2.694(3)

164.3 164.5

0.89 0.89 0.86 0.86

2.01 2.00 2.49 1.92

2.853(3) 2.874(3) 3.092(3) 2.771(3)

157.2 168.1 127.2 173.2

0.85 0.85 0.85 0.82 0.86

2.66 1.81 1.72 1.83 1.88

3.340(10) 2.574(12) 2.565(6) 2.554(4) 2.730(4)

138.1 149.0 170.6 146.6 167.5

0.82 0.86 0.86

1.71 2.25 2.19

2.443(6) 2.895(9) 3.024(9)

148.6 131.5 164.5

0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.86 0.86

1.99 2.01 1.99 1.98 2.00 1.94 1.93 2.10 2.52 1.88

2.824(3) 2.854(4) 2.842(3) 2.828(3) 2.843(3) 2.786(3) 2.781(3) 2.953(3) 3.151(3) 2.681(3)

168.8 169.3 178.3 178.2 175.0 175.2 178.3 178.6 131.2 153.9

0.86 0.86 0.82

2.31 2.22 1.67

2.937(3) 2.928(3) 2.468(2)

130.0 138.8 164.6

0.85 0.85 0.82 0.82 0.86

2.30 1.86 2.07 1.64 1.90

3.14(2) 2.693(13) 2.807(13) 2.456(7) 2.719(16)

167.1 166.5 148.9 170.8 158.6

Symmetry transformations used to generate equivalent atoms for 1: #1 x, y-1, z. Symmetry transformations used to generate equivalent atoms for 2: #1 x, y+1, z; #2

-x+1, -y, -z+1. Symmetry transformations used to generate equivalent atoms for 3: #1 x, -y+3/2, z; #2 -x+1, -y+1, -z+1. Symmetry transformations used to generate equivalent atoms for 4: #1 x-1/2, -y+3/2, z-1/2. Symmetry transformations used to generate equivalent atoms for 5: #1 x+1/2, -y+1/2, -z+1; #2 x+1, y, z; #3 x-1/2, -y+3/2, -z+1. Symmetry transformations used to generate equivalent atoms for 6: #1 x, y, z+1; #2 -x+1, -y+1, -z+2. Symmetry transformations used to generate equivalent atoms for 7: #1 -x+1, y-1/2, -z+1; #2 x-1, y, z; #3 -x+1, y+1/2, -z+1.

Highlights

Seven organic adducts have been prepared and structurally characterized. The synthons in the adducts have been ascertained. Classical H-bonds are the driving forces in giving the adducts. Other weak interactions also have important role in structure extension.

Declaration of interest statement Title: Seven

Supramolecular Adducts

of

4-dimethylaminopyridine and

Carboxylic acids Constructed by Classical H-Bonds and Some Noncovalent Interactions

Wei Fanga,b, Bangyu Chena,b, Duoer Chena,b, Shiqi Wanga,b, Yan Yana,b, Shouwen Jina,b*, Weiqiang Xua,b, and Daqi Wangc a

JiYang College ZheJiang A & F University, Zhu'Ji 311800, P. R. China, Tel & fax:

+86-575-8776-0141. *E-mail: [email protected] b

Key Laboratory of Chemical Utilization of Forestry Biomass of Zhejiang Province

Zhejiang A & F University, Lin’an, Zhejiang Province, 311300, China c

Department of Chemistry, Liaocheng University, Liaocheng 252059, P. R. China.

There are no conflicts of interest to declare.