Aggregation in isomeric imides: analysis of the weak interactions in six N-(benzoyl)-N-(2-pyridyl)benzamides

Abstract

ĞƉĂƌƚŵĞŶƚ ŽĨ ŚĞŵŝƐƚƌLJ͕ ϴϬ ^ƚ͘ 'ĞŽƌŐĞ ^ƚƌĞĞƚ͕ hŶŝ|ĞƌƐŝƚLJ ŽĨ dŽƌŽŶƚŽ͕ dŽƌŽŶƚŽ͕ Dϱ^ ϯ,ϲ͕ KE͕ ĂŶĂĚĂ Đ ZDϮ͕ EZ^͕ &ĂĐƵůƚĠ ĚĞƐ ^ĐŝĞŶĐĞƐ Ğƚ dĞĐŚŶŽůŽŐŝĞƐ͕ hŶŝ|ĞƌƐŝƚĠ ĚĞ >ŽƌƌĂŝŶĞ͕ W͕ ϳϬϮϯϵ͕ ŽƵůĞ|ĂƌĚ ĚĞƐ ŝŐƵĞůůĞƚƚĞƐ͕ ϱϰϱϬϲ sĂŶĚŽĞƵ|ƌĞͲĚğƐͲEĂŶĐLJ͕ &ƌĂŶĐĞ Ύ ŽƌƌĞƐƉŽŶĚŝŶŐ ĂƵƚŚŽƌ͗ ƌ͘ :ŽŚŶ &͘ 'ĂůůĂŐŚĞƌ ͲŵĂŝů͗ ũŽŚŶ͘ŐĂůůĂŐŚĞƌΛĚĐƵ͘ŝĞ dĞůĞƉŚŽŶĞ͗ нϯϱϯͲϭͲϳϬϬϱϭϭϰ &Ădž͗ нϯϱϯͲϭͲϳϬϬϱϱϬϯ ďƐƚƌĂĐƚ ƌLJƐƚĂů ƐƚƌƵĐƚƵƌĞƐ ŽĨ ϰͲŚůŽƌŽͲEͲ;ϰͲĐŚůŽƌŽďĞŶnjŽLJůͿͲEͲ;ϮͲƉLJƌŝĚLJůͿďĞŶnjĂŵŝĚĞ ;/Ϳ ůƉŽĚ͕ ϯͲ ŚůŽƌŽͲEͲ;ϯͲĐŚůŽƌŽďĞŶnjŽLJůͿͲEͲ;ϮͲƉLJƌŝĚLJůͿďĞŶnjĂŵŝĚĞ ;//Ϳ ůŵŽĚ ĂŶĚ ϮͲŚůŽƌŽͲEͲ;ϮͲ ĐŚůŽƌŽďĞŶnjŽLJůͿͲEͲ;ϮͲƉLJƌŝĚLJůͿďĞŶnjĂŵŝĚĞ ;///Ϳ ůŽŽĚ ƚŽŐĞƚŚĞƌ ǁŝƚŚ ƚŚƌĞĞ ŵĞƚŚLJůĂƚĞĚ ĂŶĂůŽŐƵĞƐ DƉŽĚ͕ DŵŽĚ͕ DŽŽĚ ĂƌĞ ƉƌĞƐĞŶƚĞĚ ŚĞƌĞŝŶ͘ dŚĞ ůdžŽĚ ĂĐLJĐůŝĐ ŝŵŝĚĞƐ ĂƌĞ ƉƌŽĚƵĐĞĚ ĨƌŽŵ ƌĞĂĐƚŝŶŐ ƚŚĞ ϰͲͬϯͲͬϮͲĐŚůŽƌŽďĞŶnjŽLJů ĐŚůŽƌŝĚĞƐ ;ůdžͿ ǁŝƚŚ ϮͲĂŵŝŶŽƉLJƌŝĚŝŶĞ ;ŽͿ͕ ƌĞƐƉĞĐƚŝ|ĞůLJ͕ ƚŽŐĞƚŚĞƌ ǁŝƚŚ ƚŚĞŝƌ ďĞŶnjĂŵŝĚĞ ĂŶĂůŽŐƵĞƐ ůdžŽ͖ ƚŚĞ DdžŽĚͬDdžŽ ƚƌŝĂĚ ĂƌĞ ƉƌŽĚƵĐĞĚ ƐŝŵŝůĂƌůLJ ĂŶĚ ŝŶ ŐŽŽĚ LJŝĞůĚ͘ dŚĞ Ĩŝ|Ğ ůdžŽĚ͕ DƉŽĚ ĂŶĚ DŵŽĚ ƐƚƌƵĐƚƵƌĞƐ ĂĚŽƉƚ ƚŚĞ ŽƉĞŶ ƚƌĂŶƐŽŝĚ ĐŽŶĨŽƌŵĂƚŝŽŶƐ ĂƐ ĞdžƉĞĐƚĞĚ͕ ďƵƚ DŽŽĚ ĐƌLJƐƚĂůůŝƐĞƐ ǁŝƚŚ ĐŝƐŽŝĚ ŽƌŝĞŶƚĞĚ ďĞŶnjŽLJů ŐƌŽƵƉƐ͕ ĂŶĚ ƚŚŝƐ ĐŽŶĨŽƌŵĂƚŝŽŶ ǁĂƐ ƵŶĞdžƉĞĐƚĞĚ͕ ƚŚŽƵŐŚ ŶŽƚ ƵŶŬŶŽǁŶ͘ ,ĂůŽŐĞŶ ďŽŶĚŝŶŐ ĐŽŶƚĂĐƚƐ ĂŶĚ ǁĞĂŬ ŚLJĚƌŽŐĞŶ ďŽŶĚŝŶŐ Ͳ,ͼͼͼEͬKͬS ĐŽŶƚĂĐƚƐ ĂƌĞ ŶŽƚĞĚ ŝŶ ƚŚĞ ƐƚƌƵĐƚƵƌĞƐ ůĂĐŬŝŶŐ ƐƚƌŽŶŐ ŚLJĚƌŽŐĞŶ ďŽŶĚŝŶŐ ĚŽŶŽƌ ĂƚŽŵƐͬŐƌŽƵƉƐ ďƵƚ ƉŽƐƐĞƐƐŝŶŐ Ă |ĂƌŝĞƚLJ ŽĨ ƐƚƌŽŶŐ ĂŶĚ ǁĞĂŬĞƌ ĂĐĐĞƉƚŽƌ ĂƚŽŵƐͬŐƌŽƵƉƐ͘ &Žƌ ůdžŽĚ͕ ĐŽŶƚĂĐƚ ƐƚƵĚŝĞƐ ƐŚŽǁ ƚŚĂƚ ďŽƚŚ ŚLJĚƌŽŐĞŶ ĂŶĚ ĐĂƌďŽŶ ĂĐĐŽƵŶƚ ĨŽƌ Ă ŚŝŐŚ ƉĞƌĐĞŶƚĂŐĞ ŽĨ ĞůĞŵĞŶƚƐ ;ϳϬͲϳϱйͿ ŽŶ ƚŚĞ ŵŽůĞĐƵůĂƌ ƐƵƌĨĂĐĞ ĂŶĚ ďĞŝŶŐ ƚŚĞ ŵŽƐƚ ĂďƵŶĚĂŶƚ ŚĂ|Ğ ͼͼͼ, ĨŽƌŵŝŶŐ ϮϲͲϯϬй ŽĨ ƚŚĞ ĐŽŶƚĂĐƚƐ͘ ŽŶƚĂĐƚ ĞŶƌŝĐŚŵĞŶƚ ƌĂƚŝŽƐ ĂƌĞ ĂŶ ŝŶĚŝĐĂƚŽƌ ŽĨ ƚŚĞ ůŝŬĞůŝŚŽŽĚ ŽĨ ĐŚĞŵŝĐĂů ƐƉĞĐŝĞƐ ƚŽ ĨŽƌŵ ŝŶƚĞƌŵŽůĞĐƵůĂƌ ŝŶƚĞƌĂĐƚŝŽŶƐ ǁŝƚŚ ƚŚĞŵƐĞů|ĞƐ ĂŶĚ ŽƚŚĞƌ ƐƉĞĐŝĞƐ͘ dŚĞ Ͳ,ͼͼͼE ĂŶĚ Ͳ,ͼͼͼK ĂƌĞ ƚŚĞ ŵŽƐƚ ĞŶƌŝĐŚĞĚ ;ǁŝƚŚ ,E х Ϯ͘ϭϱͿ͕ ŝŶĚŝĐĂƚŝŶŐ ƚŚĂƚ ƚŚĞƐĞ ǁĞĂŬ ŚLJĚƌŽŐĞŶ ďŽŶĚƐ ĂƌĞ ƚŚĞ Ěƌŝ|ŝŶŐ ĨŽƌĐĞ ŝŶ ƚŚĞ ůdžŽĚ ĐƌLJƐƚĂů ƉĂĐŬŝŶŐ ĨŽƌŵĂƚŝŽŶ͘ &Žƌ DdžŽĚ͕ ƚŚĞ ͼͼͼ, ĐŽŶƚĂĐƚ ƚLJƉĞ Ăƚ ϰϬͲ ϱϮй ŝƐ ƚŚĞ ŵŽƐƚ ĂďƵŶĚĂŶƚ ĐŽŶƚĂĐƚ ƚLJƉĞ ĂŶĚ Ͳ,ͼͼͼK ĂŶĚ Ͳ,ͼͼͼE ǁĞĂŬ ŚLJĚƌŽŐĞŶ ďŽŶĚƐ ĚŽŵŝŶĂƚĞ ǁŝƚŚ ĞŶƌŝĐŚŵĞŶƚ |ĂůƵĞƐ ŝŶ ƚŚĞ ϭ͘ϰϴͲϭ͘ϳϴ ƌĂŶŐĞ͘ /Ŷ DdžŽĚ EͬKͼͼͼEͬK ĐŽŶƚĂĐƚƐ ĂƌĞ ĞĨĨĞĐƚŝ|ĞůLJ ĂďƐĞŶƚ͕ ĞdžĐĞƉƚ ĨŽƌ DƉŽĚ ;Ϭ͘Ϯй͕ EͼͼͼE ĐŽŶƚĂĐƚƐͿ ĂŶĚ ďŽƚŚ ,ͼͼͼ, ĂŶĚ ͼͼͼ ŶŽŶͲ ƉŽůĂƌ ĐŽŶƚĂĐƚƐ ĂƌĞ ŵŽĚĞƌĂƚĞůLJ ŝŵƉŽ|ĞƌŝƐŚĞĚ ǁŚŝůĞ ƚŚĞ ͼͼͼ, ŝŶƚĞƌĂĐƚŝŽŶƐ ĂƌĞ ƐůŝŐŚƚůLJ ĞŶƌŝĐŚĞĚ ;сϭ͘ϭͲϭ͘ϮϭͿ͘ <ĞLJǁŽƌĚƐ͗ ŚůŽƌŝŶĞ͖ ŽŶƚĂĐƚ ŶƌŝĐŚŵĞŶƚ ƌĂƚŝŽ͖ ƌLJƐƚĂů ƐƚƌƵĐƚƵƌĞ͖ /ŵŝĚĞ͖ DĞƚŚLJů͖ tĞĂŬ ŝŶƚĞƌĂĐƚŝŽŶƐ͘

Two acyclic imides: 3-bromo-N-(3-bromobenzoyl)-N-(pyridin-2-yl)benzamide and 3-bromo-N-(3-bromobenzoyl)-N-(pyrimidin-2-yl)benzamide

“…The prevalent anti-conformation imide structural type is demonstrated in the structures of both (I) and (II) and is similar to the molecular structures of the ortho-F (SOLSUI) and meta-F (DOKXOR) imide structures (Gallagher et al, 2009a,b), the chloro-and methyl-imides (Mocilac et al, 2018) and two benzene relatives (Shukla et al, 2018). This contrasts with the syn type as observed in the crystal structure of Mood, a 2-methylbenzoyl imide (Mocilac et al, 2018) and the four recently described SEYSUN/SEYTIC/SEYTOI/SEYTUO structures (Shukla et al, 2018). A key difference between these structures is the central N-pyridine ring in Mood An ORTEP view of (II) with the atomic numbering scheme.…”

“…Several RCON(R 0 )COR structures have been reported (Groom et al, 2016) and derive mostly from either R 0 = benzene (Baell et al, 2001) or R 0 = pyridine or pyrimidine groups (Gallagher et al, 2009a,b;Mocilac et al, 2018). Related imide structures include the haloimide N-(2,4-dichlorophenyl)-2-methyl-N-(2-nitrobenzoyl)benzamide (Saeed et al, 2010) or CSD (Groom et al, 2016) refcode LAKXIG.…”

“…In (I) the O1Á Á ÁO2 distance is 3.871 (3) Å and the O1 C1Á Á ÁC2 O2 torsion angle is À109.3 (5) compared to an O1Á Á ÁO2 = 3.646 (5) Å distance and an O1-C1Á Á ÁC2 O2 torsion angle of À96.6 (5) in (II). We have also previously used the cisoid and transoid terminology for the disposition of the two C O groups; this is used to describe the orientation and direction of the C O groups/aromatic rings with respect to one another (Mocilac et al, 2018).…”

“…A literature search for acyclic imides provides several 2-aminopyridine structures of which DOKXOR a meta-F benzene derivative (Gallagher et al, 2009a) and CIJPET a meta-Cl derivative (Mocilac et al, 2018), are similar to (I) and (II). MEYYUK, an N-anthracene-9-carboxamide derivative (Kohmoto et al, 2001) and MOCTUT or N,N-dibenzoyl-4chloroaniline structures (Usman et al, 2002) are also similar in structure and conformation.…”

“…LAKXIG adopts an open imide or anti conformation with respect to the benzoyl rings and is notable for having three different ortho- ISSN 2056-9890 benzene substituents. QADPER or N-(3-methoxyphenyl)-N-(3-methoxybenzoyl)benzamide, a methoxyimide derivative has been studied in the design and synthesis of type-III mimetics of the !-conotoxin GVIA polypeptide (Baell et al, 2001) and is similar in structure to several haloaromatic imides (Gallagher et al, 2009a,b;Mocilac et al, 2018;Shukla et al, 2018). Kohmoto et al, (2001) have described a series of 9anthryl-N-(naphthylcarbonyl)carboxamides having the syntype structure and has been used in photocycloaddition reactions.…”