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 title acyclic meta-bromo substituted imide derivatives were synthesized in good yields from condensation reactions of 3-bromo­benzoyl chloride with 2-amino­pyridine or 2-amino­pyrimidine using standard condensation reaction conditions and subsequent column chromatography.

Abstract

The title compounds, C₁₉H₁₂Br₂N₂O₂ and C₁₈H₁₁Br₂N₃O₂, were synthesized in good yields from condensation reactions of 3-bromo­benzoyl chloride with 2-amino­pyridine or 2-amino­pyrimidine using standard condensation reaction conditions and subsequent column chromatography.

Chemical context  

Acyclic imide chemistry, as RCON(R′)COR, (where R,R′ are aryl or alkyl groups) has developed over the past 130 years from condensation reactions of benzoyl chlorides with amino-aromatics such as 2-amino­pyridines or 2-amino­pyrimidines (Marckwald, 1894 ▸; Tschitschibabin & Bylinkin, 1922 ▸; Huntress & Walter, 1948 ▸). From these reactions, a mixture of the benzamide and acyclic imide is usually obtained, with the relative yields of each component dependent on the starting materials and reaction conditions. The imides can also be synthesized directly from a benzamide starting material. The presence of an ortho-N in the benzamide heteroaromatic ring is an important feature needed to obtain the imide derivative in good yields (Mocilac et al., 2010 ▸, 2012 ▸; Khavasi & Tehrani, 2013 ▸).

Several RCON(R′)COR structures have been reported (Groom et al., 2016 ▸) and derive mostly from either R′ = benzene (Baell et al., 2001 ▸) or R′ = 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. LAKXIG adopts an open imide or anti conformation with respect to the benzoyl rings and is notable for having three different ortho-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 ω-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 9-anthryl-N-(naphthyl­carbon­yl)carboxamides having the syn-type structure and has been used in photo­cyclo­addition reactions. Masu et al., (2005 ▸) expanded on this research into di­imides to develop foldamer chemistry with the central moiety in these imide structures usually being an alkyl aromatic group.

In recent research on macrocyclic imides, we and others have noted the role of the imide hinge in the development of macrocyclic imides (Evans & Gale, 2004 ▸; Mocilac & Gallagher, 2013 ▸). Both syn and anti types of acyclic imide conformation have been observed in the macrocycles. It has been noted how this affects the formation of both trezimide and tennimide macrocycles and with the syn conformation essential for trezimide formation (Mocilac & Gallagher, 2013 ▸). Further studies are needed to demonstrate the ease with which the two distinct conformations can inter­convert in acyclic imides.

Structural commentary  

From the condensation reaction of meta-BrC₆H₄COCl with 2-amino­pyridine and 2-amino­pyrimidine, the benzamide and imide products were obtained and separated by standard column chromatography for each reaction. Using 2-amino­pyridine, Brmo and Brmod, (I) were obtained and for 2-amino­pyrimidine, Brmopz and Brmopzd, (II) were isolated. Brmo and Brmopz are the (1:1) benzamide products, whereas Brmod, (I) and Brmopzd, (II) are the (2:1) acyclic imides. Both (I) and (II) (Figs. 1 ▸–2 ▸) adopt similar mol­ecular structures to the majority of published structures (Groom et al., 2016 ▸; Gallagher et al., 2009a ▸,b ▸) but they differ in their supra­molecular features (Figs. 3 ▸–7 ▸ ▸ ▸ ▸). Both mol­ecules lack strong donor groups (no amide group as in the benzamides; Donnelly et al., 2008 ▸) but have strong acceptors such as O=C and N-heteroaromatic rings that are able to participate in many weaker inter­molecular inter­actions in their crystal structures, not to mention potential π-ring aromatic stacking and C—H⋯π inter­actions (Martinez & Iverson, 2012 ▸; Nishio, 2004 ▸).

Figure 1.

An ORTEP view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2.

An ORTEP view of (II) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3.

A schematic diagram of the hydrogen- and halogen-bonding inter­actions in the crystal structure of (I).

Figure 4.

A schematic diagram of the main inter­molecular inter­actions in the crystal structure of (II).

Figure 5.

The inter­molecular inter­actions in (I) (C19 H12 Br2 N2 O2′a) with displacement ellipsoids at the 30% level.

Figure 6.

Inter­molecular inter­actions in (I) with atoms depicted as their van der Waals spheres.

Figure 7.

Inter­molecular inter­actions in (II) (shown with arrows) and with atoms depicted as their van der Waals spheres.

A comparison of acyclic imides and their key torsion angles demonstrates the range of angles observed and the key differences between the syn (carbonyl O⋯O separations of ∼4.5 Å) and anti conformations (O⋯O separations of ∼3.7 Å) in crystal structures (Groom et al., 2016 ▸). In (I) the O1⋯O2 distance is 3.871 (3) Å and the O1=C1⋯C2=O2 torsion angle is −109.3 (5)° compared to an O1⋯O2 = 3.646 (5) Å distance and an O1—C1⋯C2=O2 torsion angle of −96.6 (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 ▸).

Supra­molecular features  

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 (Gallagher et al., 2009a ▸,b ▸) and N-benzene rings in the SEYSUN-type structures (Shukla et al., 2018 ▸).

In (I), the Brmod mol­ecules aggregate as dimers in a cyclical arrangement using the C32—H32⋯Br33ⁱⁱ and C2=O2⋯Br33ⁱⁱ inter­actions with the (6) motif. Two of these combine to form the centrosymmetric (12) motif as formed by the flanking C=O⋯Br—C halogen-bonding inter­actions (Figs. 3 ▸, 5 ▸ and 6 ▸). The hydrogen bonding as H32⋯Br33ⁱⁱ has N _C = 0.986 (Table 1 ▸) where N _C is the ratio of contact distance/sum of contact radii using data from Bondi (Bondi, 1965 ▸; Spek, 2020 ▸). The halogen-bonding geometric details are Br33⋯O2ⁱⁱ = 3.287 Å (symmetry code ii; Table 1 ▸) or N _C = 0.975 with C33—Br33⋯O2ⁱⁱ = 156.85 (9)° and Br33⋯(O2=C2)ⁱⁱ = 134.11 (19)° angles. Centrosymmetric C—H⋯O hydrogen-bonding inter­actions as (10) link dimers into zigzag chains along the b-axis direction, whereas weak C—H⋯N inter­actions link chains into ruffled sheets parallel with the (100) plane (Table 2 ▸).

Table 1. Hydrogen-bond geometry (Å, °) for Brmod .

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O1i	0.93	2.41	3.330 (4)	170
C32—H32⋯Br33ii	0.93	3.01	3.896 (3)	162
C36—H36⋯N22iii	0.93	2.68	3.363 (4)	131

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

Table 2. Hydrogen-bond geometry (Å, °) for Brmopzd .

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C23—H23⋯O1i	0.93	2.65	3.369 (5)	134
C36—H36⋯O2ii	0.93	2.61	3.375 (5)	140
C12—H12⋯C25iii	0.93	2.76	3.677 (5)	168

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

In (II), the Brmopzd mol­ecules aggregate by weak inter­molecular inter­actions, as two C—H⋯O, two C—H⋯π(arene) and a C—Br⋯π(arene) contact per mol­ecule, to generate a 3D structure (Figs. 4 ▸ and 7 ▸). The C36—H36⋯O2ⁱⁱ and C25⋯(H12—C25)ⁱⁱ inter­actions combine together in the aggregation of a pair of tightly bound mol­ecules with graph-set (15), while the remaining C23—H23⋯O1ⁱ hydrogen bond results in the formation of centrosymmetric dimers in tandem with π–π stacking between the pyrimidyl rings, with shortest contact distances for N22⋯C23ⁱ = 3.429 (6) Å and N22⋯C24ⁱ = 3.464 (7) Å. The C13—Br13⋯π(arene)^iv contact [symmetry code: (iv)  + x,  − y, z] has a Br13⋯C15^iv distance of 3.550 (6) Å and C13—Br13⋯C15^iv = 149.44 (16)°, where C15^iv represents the closest Br⋯C contact on the arene ring. The N atoms (two pyrimidyl or tertiary amine N) do not participate in inter­molecular inter­actions and the shortest contact is N26⋯H24^v = 2.76 Å [symmetry code: (v)  − x,  + y, 2 − z) (Spek, 2020 ▸).

Database survey  

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-4-chloro­aniline structures (Usman et al., 2002 ▸) are also similar in structure and conformation.

Shukla and co-workers have detailed six halogenated N-benzoyl-N-phenyl­benzamides (imides) that adopt both syn and anti conformations in the solid state (Shukla et al., 2018 ▸). The reason why they adopt either conformation is not obvious and suggests that a transformation between either conformation as having a low activation energy barrier. Such imide behaviour (in adopting either of the syn or anti structures) has been known for decades although there does not seem to have been much investigation into possible fluxional behaviour and various influences driving towards one particular conformation or other.

Synthesis and crystallization:  

Compound (I) is Brmod and (II) is Brmopzd. (I) and (II) were synthesized as mixtures together with the (1:1) benzamides and separated from the benzamides by standard column chromatography in good yields.

(I): Yield = 30–40% ¹H NMR (CDCl₃) for (I) with J values in Hz: δ 7.10 (1H, dd, ³ J = 7.5, ⁴ J = 5, ⁵ J = 1), 7.29 (1H, t, ³ J = 7.8), 7.33 (1H, t, ³ J = 7.9), 7.65 (2H, dq, ³ J = 8.4, ⁴ J = 1.8, ⁵ J = 1), 7.78 (1H, ddd, ³ J = 8, ⁴ J = 2, ⁵ J = 1), 7.90 (1H, dt, ³ J = 8, ⁴ J = 1), 7.98 (1H, dt, ³ J = 7.8, ⁴ J = 1), 8.17 (1H, dd, ³ J = 1.7), 8.21 (2H, dd, ³ J = 5.2, ⁴ J = 1), 8.40 (1H, d, ³ J = 8.5). IR (ATR): 2921 (m), 1683 (s), 1580 (m). Melting point 418–420 K.

(II): Yield = 45–55%. ¹H NMR (CDCl₃) for (I) with J values in Hz: δ 7.12 (1H, t, ³ J = 4.9), 7.18 (2H, t, ³ J = 12), 7.56 (2H, ddd, ³ J = 8.0, ⁴ J = 2.0, ⁵ J = 1.0), 7.60 (2H, ddd, ³ J = 7.8, ⁴ J = 1.7, ⁵ J = 1.0), 7.88 (2H, t, ⁴ J = 1.6), 8.59 (2H, d, ³ J = 4.8). IR (ATR): 3072 (s), 2963 (s), 1719 (s), 1682 (m). Melting point 406–411 K.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. H atoms attached to C atoms were treated as riding using the SHELXL14/7 (Sheldrick, 2015b ▸) defaults at 294 (1) K with C—H = 0.93 Å (aromatic) and U _iso(H) = 1.2U _eq(C) (aromatic).

Table 3. Experimental details.

	Brmod	Brmopzd
Crystal data
Chemical formula	C19H12Br2N2O2	C18H11Br2N3O2
M r	460.13	461.12
Crystal system, space group	Monoclinic, P21/c	Monoclinic, P21/a
Temperature (K)	294	294
a, b, c (Å)	5.5439 (1), 16.3366 (4), 19.3701 (4)	11.1712 (4), 11.0590 (3), 14.4181 (5)
β (°)	91.459 (2)	102.756 (4)
V (Å3)	1753.75 (6)	1737.28 (10)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	4.64	4.68
Crystal size (mm)	0.43 × 0.35 × 0.18	0.22 × 0.20 × 0.05
Data collection
Diffractometer	Rigaku Xcalibur, Sapphire3, Gemini Ultra	Rigaku Xcalibur, Sapphire3, Gemini Ultra
Absorption correction	Analytical (ABSFAC; Clark & Reid, 1998 ▸)	Analytical (ABSFAC; Clark & Reid, 1998 ▸)
T min, T max	0.228, 0.493	0.425, 0.801
No. of measured, independent and observed [I > 2σ(I)] reflections	16613, 4665, 3025	13616, 3865, 2219
R int	0.037	0.047
(sin θ/λ)max (Å−1)	0.694	0.657
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.042, 0.085, 1.01	0.052, 0.109, 1.02
No. of reflections	4665	3865
No. of parameters	226	226
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.60, −0.42	0.89, −0.67

Computer programs: CrysAlis PRO (Rigaku OD, 2015 ▸), SHELXT14/7 (Sheldrick, 2015a ▸), SHELXL14/7 (Sheldrick, 2015b ▸) and Mercury (Macrae et al., 2020 ▸).

Supplementary Material

CCDC references: 2041345, 2041344

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

3-Bromo-N-(3-bromobenzoyl)-N-(pyridin-2-yl)benzamide (Brmod) . Crystal data

C19H12Br2N2O2	Dx = 1.743 Mg m−3
Mr = 460.13	Melting point: 419 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.5439 (1) Å	Cell parameters from 4432 reflections
b = 16.3366 (4) Å	θ = 2.1–29.5°
c = 19.3701 (4) Å	µ = 4.64 mm−1
β = 91.459 (2)°	T = 294 K
V = 1753.75 (6) Å3	Block, colourless
Z = 4	0.43 × 0.35 × 0.18 mm
F(000) = 904

3-Bromo-N-(3-bromobenzoyl)-N-(pyridin-2-yl)benzamide (Brmod) . Data collection

Rigaku Xcalibur, Sapphire3, Gemini Ultra diffractometer	4665 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3025 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 16.0560 pixels mm-1	θmax = 29.6°, θmin = 2.1°
ω scans	h = −7→7
Absorption correction: analytical (ABSFAC; Clark & Reid, 1998)	k = −22→17
Tmin = 0.228, Tmax = 0.493	l = −26→26
16613 measured reflections

3-Bromo-N-(3-bromobenzoyl)-N-(pyridin-2-yl)benzamide (Brmod) . Refinement

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0295P)2 + 0.9875P] where P = (Fo2 + 2Fc2)/3
4665 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.60 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

3-Bromo-N-(3-bromobenzoyl)-N-(pyridin-2-yl)benzamide (Brmod) . Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

3-Bromo-N-(3-bromobenzoyl)-N-(pyridin-2-yl)benzamide (Brmod) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br13	0.12586 (8)	0.01924 (3)	−0.22896 (2)	0.07723 (16)
Br33	0.25059 (6)	0.58666 (2)	0.07841 (2)	0.04753 (11)
O1	0.2102 (5)	0.05436 (15)	0.05540 (13)	0.0741 (8)
C1	0.2745 (6)	0.11718 (19)	0.02838 (16)	0.0432 (7)
N1	0.2894 (4)	0.19022 (14)	0.06634 (12)	0.0362 (5)
O2	0.1237 (4)	0.27325 (13)	−0.01771 (11)	0.0513 (6)
C2	0.2485 (5)	0.26745 (17)	0.03375 (15)	0.0350 (6)
C11	0.3581 (5)	0.11967 (17)	−0.04341 (15)	0.0393 (7)
C12	0.2308 (6)	0.07512 (18)	−0.09348 (15)	0.0432 (7)
H12	0.0952	0.0451	−0.0820	0.052*
C13	0.3084 (6)	0.0762 (2)	−0.15995 (16)	0.0499 (8)
C14	0.5141 (7)	0.1177 (3)	−0.17788 (19)	0.0648 (10)
H14	0.5647	0.1176	−0.2233	0.078*
C15	0.6432 (7)	0.1592 (3)	−0.1273 (2)	0.0673 (11)
H15	0.7851	0.1859	−0.1384	0.081*
C16	0.5651 (6)	0.1615 (2)	−0.06085 (18)	0.0510 (8)
H16	0.6509	0.1912	−0.0274	0.061*
C21	0.2667 (5)	0.18650 (17)	0.13984 (14)	0.0366 (6)
N22	0.0859 (4)	0.22893 (17)	0.16417 (13)	0.0488 (7)
C23	0.0675 (7)	0.2294 (2)	0.23268 (19)	0.0626 (10)
H23	−0.0594	0.2586	0.2513	0.075*
C24	0.2231 (7)	0.1898 (2)	0.27726 (18)	0.0601 (9)
H24	0.2045	0.1929	0.3248	0.072*
C25	0.4070 (7)	0.1455 (2)	0.24981 (18)	0.0601 (9)
H25	0.5145	0.1170	0.2785	0.072*
C26	0.4310 (6)	0.1437 (2)	0.17975 (16)	0.0494 (8)
H26	0.5550	0.1144	0.1598	0.059*
C31	0.3759 (5)	0.33794 (17)	0.06655 (13)	0.0321 (6)
C32	0.2767 (5)	0.41557 (17)	0.05842 (14)	0.0330 (6)
H32	0.1309	0.4226	0.0344	0.040*
C33	0.3957 (5)	0.48156 (17)	0.08614 (14)	0.0338 (6)
C34	0.6181 (5)	0.47370 (19)	0.11981 (15)	0.0405 (7)
H34	0.6988	0.5193	0.1375	0.049*
C35	0.7172 (5)	0.39622 (19)	0.12645 (15)	0.0399 (7)
H35	0.8668	0.3898	0.1486	0.048*
C36	0.5982 (5)	0.32877 (17)	0.10082 (14)	0.0352 (6)
H36	0.6657	0.2770	0.1063	0.042*

3-Bromo-N-(3-bromobenzoyl)-N-(pyridin-2-yl)benzamide (Brmod) . Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br13	0.0878 (3)	0.0939 (3)	0.0490 (2)	0.0319 (2)	−0.0185 (2)	−0.0193 (2)
Br33	0.0583 (2)	0.03904 (17)	0.04500 (18)	0.00725 (15)	−0.00459 (14)	−0.00051 (14)
O1	0.120 (2)	0.0505 (14)	0.0518 (15)	−0.0332 (15)	0.0154 (15)	0.0002 (12)
C1	0.0492 (19)	0.0393 (17)	0.0412 (17)	−0.0064 (14)	0.0016 (14)	0.0031 (14)
N1	0.0388 (14)	0.0361 (13)	0.0336 (13)	0.0011 (10)	0.0005 (10)	0.0022 (10)
O2	0.0563 (13)	0.0443 (12)	0.0518 (13)	0.0085 (10)	−0.0264 (11)	−0.0012 (10)
C2	0.0307 (15)	0.0375 (16)	0.0365 (16)	0.0056 (12)	−0.0020 (12)	0.0006 (13)
C11	0.0455 (17)	0.0330 (15)	0.0396 (17)	0.0059 (13)	0.0039 (13)	0.0023 (13)
C12	0.0483 (18)	0.0386 (17)	0.0428 (18)	0.0066 (14)	0.0017 (14)	−0.0007 (14)
C13	0.058 (2)	0.053 (2)	0.0384 (17)	0.0204 (16)	−0.0013 (15)	−0.0026 (15)
C14	0.064 (2)	0.087 (3)	0.044 (2)	0.019 (2)	0.0157 (18)	0.005 (2)
C15	0.052 (2)	0.087 (3)	0.063 (3)	0.002 (2)	0.0215 (19)	0.010 (2)
C16	0.0432 (19)	0.053 (2)	0.057 (2)	0.0008 (15)	0.0044 (16)	0.0014 (17)
C21	0.0359 (16)	0.0377 (16)	0.0362 (16)	−0.0010 (12)	−0.0007 (12)	0.0025 (13)
N22	0.0435 (15)	0.0615 (18)	0.0418 (15)	0.0131 (13)	0.0082 (12)	0.0034 (13)
C23	0.064 (2)	0.071 (3)	0.054 (2)	0.0150 (19)	0.0177 (19)	−0.0005 (19)
C24	0.079 (3)	0.066 (2)	0.0359 (18)	−0.006 (2)	0.0035 (18)	0.0029 (17)
C25	0.064 (2)	0.072 (2)	0.0439 (19)	0.0064 (19)	−0.0087 (17)	0.0174 (18)
C26	0.0498 (19)	0.054 (2)	0.0446 (18)	0.0146 (16)	0.0012 (15)	0.0084 (16)
C31	0.0269 (14)	0.0395 (15)	0.0299 (14)	0.0024 (12)	0.0010 (11)	0.0031 (12)
C32	0.0270 (13)	0.0423 (16)	0.0295 (13)	0.0029 (12)	−0.0021 (11)	0.0027 (12)
C33	0.0362 (16)	0.0372 (15)	0.0282 (14)	0.0031 (12)	0.0043 (12)	0.0022 (12)
C34	0.0346 (16)	0.0499 (18)	0.0368 (16)	−0.0065 (14)	−0.0015 (12)	−0.0045 (14)
C35	0.0251 (14)	0.057 (2)	0.0373 (16)	0.0006 (13)	−0.0039 (12)	0.0020 (14)
C36	0.0287 (14)	0.0418 (16)	0.0352 (15)	0.0047 (12)	0.0019 (12)	0.0038 (13)

3-Bromo-N-(3-bromobenzoyl)-N-(pyridin-2-yl)benzamide (Brmod) . Geometric parameters (Å, º)

Br13—C13	1.900 (3)	C21—C26	1.371 (4)
Br33—C33	1.900 (3)	N22—C23	1.334 (4)
O1—C1	1.210 (4)	C23—C24	1.368 (5)
C1—N1	1.403 (4)	C23—H23	0.9300
C1—C11	1.478 (4)	C24—C25	1.368 (5)
N1—C2	1.426 (3)	C24—H24	0.9300
N1—C21	1.434 (3)	C25—C26	1.367 (4)
O2—C2	1.203 (3)	C25—H25	0.9300
C2—C31	1.485 (4)	C26—H26	0.9300
C11—C16	1.385 (4)	C31—C32	1.390 (4)
C11—C12	1.390 (4)	C31—C36	1.393 (4)
C12—C13	1.368 (4)	C32—C33	1.367 (4)
C12—H12	0.9300	C32—H32	0.9300
C13—C14	1.378 (5)	C33—C34	1.386 (4)
C14—C15	1.377 (5)	C34—C35	1.384 (4)
C14—H14	0.9300	C34—H34	0.9300
C15—C16	1.369 (5)	C35—C36	1.371 (4)
C15—H15	0.9300	C35—H35	0.9300
C16—H16	0.9300	C36—H36	0.9300
C21—N22	1.316 (4)
O1—C1—N1	120.6 (3)	N22—C23—C24	124.2 (3)
O1—C1—C11	122.2 (3)	N22—C23—H23	117.9
N1—C1—C11	117.0 (3)	C24—C23—H23	117.9
C1—N1—C2	120.9 (2)	C23—C24—C25	118.0 (3)
C1—N1—C21	118.6 (2)	C23—C24—H24	121.0
C2—N1—C21	117.4 (2)	C25—C24—H24	121.0
O2—C2—N1	121.2 (3)	C26—C25—C24	119.3 (3)
O2—C2—C31	123.4 (3)	C26—C25—H25	120.3
N1—C2—C31	115.3 (2)	C24—C25—H25	120.3
C16—C11—C12	119.8 (3)	C25—C26—C21	117.9 (3)
C16—C11—C1	121.7 (3)	C25—C26—H26	121.0
C12—C11—C1	118.4 (3)	C21—C26—H26	121.0
C13—C12—C11	118.9 (3)	C32—C31—C36	119.7 (3)
C13—C12—H12	120.6	C32—C31—C2	118.5 (2)
C11—C12—H12	120.6	C36—C31—C2	121.7 (2)
C12—C13—C14	121.7 (3)	C33—C32—C31	119.3 (2)
C12—C13—Br13	118.8 (3)	C33—C32—H32	120.3
C14—C13—Br13	119.5 (3)	C31—C32—H32	120.3
C15—C14—C13	118.8 (3)	C32—C33—C34	121.8 (3)
C15—C14—H14	120.6	C32—C33—Br33	118.8 (2)
C13—C14—H14	120.6	C34—C33—Br33	119.4 (2)
C16—C15—C14	120.7 (3)	C35—C34—C33	118.3 (3)
C16—C15—H15	119.6	C35—C34—H34	120.8
C14—C15—H15	119.6	C33—C34—H34	120.8
C15—C16—C11	120.0 (3)	C36—C35—C34	121.0 (3)
C15—C16—H16	120.0	C36—C35—H35	119.5
C11—C16—H16	120.0	C34—C35—H35	119.5
N22—C21—C26	124.6 (3)	C35—C36—C31	119.9 (3)
N22—C21—N1	114.9 (2)	C35—C36—H36	120.1
C26—C21—N1	120.5 (3)	C31—C36—H36	120.1
C21—N22—C23	116.0 (3)
O1—C1—N1—C2	−149.3 (3)	C1—N1—C21—C26	62.3 (4)
C11—C1—N1—C2	35.3 (4)	C2—N1—C21—C26	−137.4 (3)
O1—C1—N1—C21	10.3 (4)	C26—C21—N22—C23	0.4 (5)
C11—C1—N1—C21	−165.1 (2)	N1—C21—N22—C23	−177.1 (3)
C1—N1—C2—O2	26.1 (4)	C21—N22—C23—C24	0.5 (5)
C21—N1—C2—O2	−133.7 (3)	N22—C23—C24—C25	−1.3 (6)
C1—N1—C2—C31	−152.0 (3)	C23—C24—C25—C26	1.2 (6)
C21—N1—C2—C31	48.1 (3)	C24—C25—C26—C21	−0.4 (5)
O1—C1—C11—C16	−133.9 (3)	N22—C21—C26—C25	−0.4 (5)
N1—C1—C11—C16	41.4 (4)	N1—C21—C26—C25	176.9 (3)
O1—C1—C11—C12	42.8 (4)	O2—C2—C31—C32	28.3 (4)
N1—C1—C11—C12	−141.9 (3)	N1—C2—C31—C32	−153.6 (2)
C16—C11—C12—C13	−2.5 (4)	O2—C2—C31—C36	−147.3 (3)
C1—C11—C12—C13	−179.2 (3)	N1—C2—C31—C36	30.8 (4)
C11—C12—C13—C14	2.5 (5)	C36—C31—C32—C33	−2.0 (4)
C11—C12—C13—Br13	−177.3 (2)	C2—C31—C32—C33	−177.7 (2)
C12—C13—C14—C15	−0.3 (5)	C31—C32—C33—C34	2.7 (4)
Br13—C13—C14—C15	179.5 (3)	C31—C32—C33—Br33	−177.05 (19)
C13—C14—C15—C16	−2.1 (6)	C32—C33—C34—C35	−1.5 (4)
C14—C15—C16—C11	2.1 (6)	Br33—C33—C34—C35	178.3 (2)
C12—C11—C16—C15	0.2 (5)	C33—C34—C35—C36	−0.4 (4)
C1—C11—C16—C15	176.9 (3)	C34—C35—C36—C31	1.0 (4)
C1—N1—C21—N22	−120.1 (3)	C32—C31—C36—C35	0.2 (4)
C2—N1—C21—N22	40.3 (3)	C2—C31—C36—C35	175.7 (3)

3-Bromo-N-(3-bromobenzoyl)-N-(pyridin-2-yl)benzamide (Brmod) . Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O1i	0.93	2.41	3.330 (4)	170
C32—H32···Br33ii	0.93	3.01	3.896 (3)	162
C36—H36···N22iii	0.93	2.68	3.363 (4)	131

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

3-Bromo-N-(3-bromobenzoyl)-N-(pyrimidin-2-yl)benzamide (Brmopzd) . Crystal data

C18H11Br2N3O2	Dx = 1.763 Mg m−3
Mr = 461.12	Melting point: 408 K
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
a = 11.1712 (4) Å	Cell parameters from 3165 reflections
b = 11.0590 (3) Å	θ = 3.2–27.8°
c = 14.4181 (5) Å	µ = 4.68 mm−1
β = 102.756 (4)°	T = 294 K
V = 1737.28 (10) Å3	Plate, colourless
Z = 4	0.22 × 0.20 × 0.05 mm
F(000) = 904

3-Bromo-N-(3-bromobenzoyl)-N-(pyrimidin-2-yl)benzamide (Brmopzd) . Data collection

Rigaku Xcalibur, Sapphire3, Gemini Ultra diffractometer	3865 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2219 reflections with I > 2σ(I)
Detector resolution: 16.056 pixels mm-1	Rint = 0.047
ω scans	θmax = 27.9°, θmin = 3.2°
Absorption correction: analytical (ABSFAC; Clark & Reid, 1998)	h = −14→14
Tmin = 0.425, Tmax = 0.801	k = −14→13
13616 measured reflections	l = −18→15

3-Bromo-N-(3-bromobenzoyl)-N-(pyrimidin-2-yl)benzamide (Brmopzd) . Refinement

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0345P)2 + 1.6333P] where P = (Fo2 + 2Fc2)/3
3865 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.89 e Å−3
0 restraints	Δρmin = −0.67 e Å−3

3-Bromo-N-(3-bromobenzoyl)-N-(pyrimidin-2-yl)benzamide (Brmopzd) . Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

3-Bromo-N-(3-bromobenzoyl)-N-(pyrimidin-2-yl)benzamide (Brmopzd) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br13	0.56862 (6)	1.25414 (5)	0.79435 (5)	0.0721 (2)
Br33	0.38119 (6)	0.32158 (5)	0.48956 (4)	0.0757 (2)
O1	0.4800 (3)	0.8188 (3)	0.9503 (2)	0.0537 (9)
C1	0.4245 (4)	0.8174 (4)	0.8691 (3)	0.0381 (10)
N1	0.3759 (3)	0.7061 (3)	0.8250 (2)	0.0371 (9)
O2	0.4771 (3)	0.7308 (3)	0.7062 (2)	0.0625 (10)
C2	0.3990 (4)	0.6770 (4)	0.7352 (3)	0.0408 (11)
C11	0.3956 (4)	0.9282 (4)	0.8105 (3)	0.0355 (10)
C12	0.4786 (4)	1.0231 (4)	0.8278 (3)	0.0392 (11)
H12	0.5518	1.0153	0.8730	0.047*
C13	0.4518 (4)	1.1282 (4)	0.7777 (3)	0.0428 (11)
C14	0.3428 (5)	1.1429 (4)	0.7130 (4)	0.0546 (13)
H14	0.3251	1.2156	0.6804	0.066*
C15	0.2597 (5)	1.0492 (5)	0.6966 (4)	0.0601 (14)
H15	0.1853	1.0587	0.6531	0.072*
C16	0.2864 (4)	0.9413 (4)	0.7445 (3)	0.0449 (12)
H16	0.2309	0.8775	0.7324	0.054*
C21	0.3492 (4)	0.6130 (3)	0.8853 (3)	0.0330 (10)
N22	0.3981 (3)	0.5060 (3)	0.8759 (3)	0.0434 (9)
C23	0.3708 (5)	0.4203 (4)	0.9333 (3)	0.0519 (13)
H23	0.3987	0.3420	0.9278	0.062*
C24	0.3035 (5)	0.4434 (4)	0.9998 (4)	0.0539 (13)
H24	0.2883	0.3837	1.0412	0.065*
C25	0.2596 (4)	0.5580 (4)	1.0027 (3)	0.0507 (12)
H25	0.2134	0.5762	1.0473	0.061*
N26	0.2803 (3)	0.6456 (3)	0.9440 (3)	0.0427 (9)
C31	0.3208 (4)	0.5834 (3)	0.6777 (3)	0.0332 (10)
C32	0.3740 (4)	0.5108 (4)	0.6202 (3)	0.0382 (10)
H32	0.4567	0.5194	0.6199	0.046*
C33	0.3045 (5)	0.4261 (4)	0.5636 (3)	0.0447 (12)
C34	0.1809 (5)	0.4155 (5)	0.5591 (3)	0.0563 (14)
H34	0.1339	0.3595	0.5186	0.068*
C35	0.1276 (5)	0.4898 (5)	0.6159 (4)	0.0546 (13)
H35	0.0439	0.4837	0.6132	0.066*
C36	0.1967 (4)	0.5727 (4)	0.6763 (3)	0.0426 (11)
H36	0.1606	0.6207	0.7156	0.051*

3-Bromo-N-(3-bromobenzoyl)-N-(pyrimidin-2-yl)benzamide (Brmopzd) . Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br13	0.0839 (4)	0.0390 (3)	0.0959 (5)	−0.0179 (3)	0.0255 (4)	0.0052 (3)
Br33	0.1132 (5)	0.0612 (4)	0.0532 (3)	0.0186 (3)	0.0194 (3)	−0.0170 (3)
O1	0.065 (2)	0.0410 (18)	0.049 (2)	−0.0105 (17)	−0.0011 (18)	0.0076 (16)
C1	0.037 (3)	0.034 (2)	0.044 (3)	−0.003 (2)	0.010 (2)	0.001 (2)
N1	0.049 (2)	0.0248 (17)	0.041 (2)	−0.0025 (16)	0.0176 (18)	−0.0013 (16)
O2	0.070 (2)	0.054 (2)	0.078 (3)	−0.0242 (18)	0.048 (2)	−0.0217 (18)
C2	0.043 (3)	0.032 (2)	0.054 (3)	−0.001 (2)	0.025 (2)	−0.002 (2)
C11	0.045 (3)	0.030 (2)	0.035 (2)	0.004 (2)	0.015 (2)	0.0014 (18)
C12	0.042 (3)	0.030 (2)	0.047 (3)	−0.001 (2)	0.011 (2)	−0.004 (2)
C13	0.053 (3)	0.029 (2)	0.051 (3)	0.000 (2)	0.021 (3)	0.004 (2)
C14	0.069 (4)	0.038 (3)	0.058 (3)	0.010 (3)	0.016 (3)	0.014 (2)
C15	0.053 (3)	0.052 (3)	0.068 (4)	0.007 (3)	−0.002 (3)	0.010 (3)
C16	0.049 (3)	0.033 (2)	0.052 (3)	0.000 (2)	0.010 (3)	0.004 (2)
C21	0.037 (3)	0.026 (2)	0.036 (2)	−0.0034 (18)	0.007 (2)	0.0040 (18)
N22	0.055 (3)	0.0293 (19)	0.046 (2)	0.0070 (17)	0.0122 (19)	0.0050 (17)
C23	0.064 (4)	0.030 (2)	0.055 (3)	0.002 (2)	0.000 (3)	0.008 (2)
C24	0.061 (3)	0.050 (3)	0.050 (3)	−0.009 (3)	0.012 (3)	0.015 (2)
C25	0.052 (3)	0.054 (3)	0.049 (3)	−0.005 (2)	0.017 (3)	0.005 (2)
N26	0.047 (2)	0.035 (2)	0.050 (2)	−0.0034 (17)	0.021 (2)	−0.0009 (18)
C31	0.036 (3)	0.031 (2)	0.035 (2)	0.0033 (19)	0.013 (2)	0.0061 (18)
C32	0.042 (3)	0.035 (2)	0.040 (3)	0.003 (2)	0.017 (2)	0.004 (2)
C33	0.063 (3)	0.040 (3)	0.029 (3)	0.006 (2)	0.006 (2)	0.003 (2)
C34	0.068 (4)	0.054 (3)	0.041 (3)	−0.010 (3)	−0.002 (3)	0.002 (2)
C35	0.041 (3)	0.070 (4)	0.049 (3)	−0.007 (3)	0.002 (3)	0.016 (3)
C36	0.046 (3)	0.045 (3)	0.040 (3)	0.005 (2)	0.017 (2)	0.006 (2)

3-Bromo-N-(3-bromobenzoyl)-N-(pyrimidin-2-yl)benzamide (Brmopzd) . Geometric parameters (Å, º)

Br13—C13	1.887 (4)	C21—N26	1.314 (5)
Br33—C33	1.901 (4)	C21—N22	1.323 (5)
O1—C1	1.199 (5)	N22—C23	1.337 (5)
C1—N1	1.435 (5)	C23—C24	1.367 (6)
C1—C11	1.483 (6)	C23—H23	0.9300
N1—C2	1.413 (5)	C24—C25	1.363 (6)
N1—C21	1.421 (5)	C24—H24	0.9300
O2—C2	1.204 (5)	C25—N26	1.340 (5)
C2—C31	1.483 (6)	C25—H25	0.9300
C11—C16	1.379 (6)	C31—C32	1.381 (5)
C11—C12	1.386 (6)	C31—C36	1.388 (6)
C12—C13	1.366 (6)	C32—C33	1.365 (6)
C12—H12	0.9300	C32—H32	0.9300
C13—C14	1.370 (7)	C33—C34	1.373 (7)
C14—C15	1.376 (7)	C34—C35	1.384 (7)
C14—H14	0.9300	C34—H34	0.9300
C15—C16	1.377 (6)	C35—C36	1.378 (6)
C15—H15	0.9300	C35—H35	0.9300
C16—H16	0.9300	C36—H36	0.9300
O1—C1—N1	120.5 (4)	C21—N22—C23	114.5 (4)
O1—C1—C11	123.1 (4)	N22—C23—C24	122.5 (4)
N1—C1—C11	116.3 (4)	N22—C23—H23	118.7
C2—N1—C21	120.1 (3)	C24—C23—H23	118.7
C2—N1—C1	118.2 (3)	C25—C24—C23	116.9 (4)
C21—N1—C1	117.4 (3)	C25—C24—H24	121.5
O2—C2—N1	119.9 (4)	C23—C24—H24	121.5
O2—C2—C31	122.2 (4)	N26—C25—C24	122.7 (5)
N1—C2—C31	117.8 (4)	N26—C25—H25	118.7
C16—C11—C12	119.9 (4)	C24—C25—H25	118.7
C16—C11—C1	121.9 (4)	C21—N26—C25	114.6 (4)
C12—C11—C1	118.1 (4)	C32—C31—C36	120.2 (4)
C13—C12—C11	119.3 (4)	C32—C31—C2	117.6 (4)
C13—C12—H12	120.4	C36—C31—C2	122.1 (4)
C11—C12—H12	120.4	C33—C32—C31	119.7 (4)
C12—C13—C14	121.3 (4)	C33—C32—H32	120.2
C12—C13—Br13	119.7 (4)	C31—C32—H32	120.2
C14—C13—Br13	119.0 (3)	C32—C33—C34	121.3 (4)
C13—C14—C15	119.5 (4)	C32—C33—Br33	119.0 (4)
C13—C14—H14	120.3	C34—C33—Br33	119.6 (4)
C15—C14—H14	120.3	C33—C34—C35	118.7 (5)
C14—C15—C16	120.2 (5)	C33—C34—H34	120.6
C14—C15—H15	119.9	C35—C34—H34	120.6
C16—C15—H15	119.9	C36—C35—C34	121.0 (5)
C15—C16—C11	119.8 (4)	C36—C35—H35	119.5
C15—C16—H16	120.1	C34—C35—H35	119.5
C11—C16—H16	120.1	C35—C36—C31	119.0 (4)
N26—C21—N22	128.7 (4)	C35—C36—H36	120.5
N26—C21—N1	115.3 (4)	C31—C36—H36	120.5
N22—C21—N1	116.0 (4)
O1—C1—N1—C2	−131.1 (4)	C2—N1—C21—N22	28.9 (6)
C11—C1—N1—C2	52.3 (5)	C1—N1—C21—N22	−127.6 (4)
O1—C1—N1—C21	25.8 (6)	N26—C21—N22—C23	1.3 (7)
C11—C1—N1—C21	−150.8 (4)	N1—C21—N22—C23	−179.7 (4)
C21—N1—C2—O2	−141.4 (4)	C21—N22—C23—C24	−3.4 (7)
C1—N1—C2—O2	14.9 (6)	N22—C23—C24—C25	2.9 (7)
C21—N1—C2—C31	41.3 (6)	C23—C24—C25—N26	−0.1 (8)
C1—N1—C2—C31	−162.5 (4)	N22—C21—N26—C25	1.3 (7)
O1—C1—C11—C16	−143.6 (5)	N1—C21—N26—C25	−177.7 (4)
N1—C1—C11—C16	32.9 (6)	C24—C25—N26—C21	−1.9 (7)
O1—C1—C11—C12	32.4 (6)	O2—C2—C31—C32	35.6 (6)
N1—C1—C11—C12	−151.1 (4)	N1—C2—C31—C32	−147.1 (4)
C16—C11—C12—C13	−1.1 (6)	O2—C2—C31—C36	−140.4 (5)
C1—C11—C12—C13	−177.2 (4)	N1—C2—C31—C36	36.9 (6)
C11—C12—C13—C14	2.1 (7)	C36—C31—C32—C33	−1.7 (6)
C11—C12—C13—Br13	−175.8 (3)	C2—C31—C32—C33	−177.8 (4)
C12—C13—C14—C15	−1.4 (7)	C31—C32—C33—C34	3.4 (7)
Br13—C13—C14—C15	176.6 (4)	C31—C32—C33—Br33	−176.9 (3)
C13—C14—C15—C16	−0.4 (8)	C32—C33—C34—C35	−2.3 (7)
C14—C15—C16—C11	1.4 (7)	Br33—C33—C34—C35	177.9 (3)
C12—C11—C16—C15	−0.6 (6)	C33—C34—C35—C36	−0.3 (7)
C1—C11—C16—C15	175.3 (4)	C34—C35—C36—C31	1.8 (7)
C2—N1—C21—N26	−152.0 (4)	C32—C31—C36—C35	−0.8 (6)
C1—N1—C21—N26	51.6 (5)	C2—C31—C36—C35	175.1 (4)

3-Bromo-N-(3-bromobenzoyl)-N-(pyrimidin-2-yl)benzamide (Brmopzd) . Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···O1i	0.93	2.65	3.369 (5)	134
C36—H36···O2ii	0.93	2.61	3.375 (5)	140
C12—H12···C25iii	0.93	2.76	3.677 (5)	168

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1/2, −y+3/2, z; (iii) x+1/2, −y+3/2, z.

Funding Statement

This work was funded by Dublin City University grant . Meath County Council grant . VEC grant .