Six 1-aroyl-4-(4-meth­oxy­phen­yl)piperazines: similar mol­ecular structures but different patterns of supra­molecular assembly

Kiran Kumar, H.; Yathirajan, H.S.; Sagar, B.K.; Foro, S.; Glidewell, C.

doi:10.1107/S2056989019010491

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 8| August 2019| Pages 1253-1260

https://doi.org/10.1107/S2056989019010491

Open

access

Six 1-aroyl-4-(4-methoxyphenyl)piperazines: similar molecular structures but different patterns of supramolecular assembly

Haruvegowda Kiran Kumar,^a Hemmige S. Yathirajan,^a ^* Belakavadi K. Sagar,^b Sabine Foro ^c and Christopher Glidewell ^d

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore-570 006, India, ^cInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany, and ^dSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: yathirajan@hotmail.com

Edited by M. Zeller, Purdue University, USA (Received 12 July 2019; accepted 23 July 2019; online 26 July 2019)

Six new 1-aroyl-4-(4-methoxyphenyl)piperazines have been prepared, using coupling reactions between benzoic acids and N-(4-methoxyphenyl)piperazine. There are no significant hydrogen bonds in the structure of 1-benzoyl-4-(4-methoxyphenyl)piperazine, C₁₈H₂₀N₂O₂, (I). The molecules of 1-(2-fluorobenzoyl)-4-(4-methoxyphenyl)piperazine, C₁₈H₁₉FN₂O₂, (II), are linked by two C—H⋯O hydrogen bonds to form chains of rings, which are linked into sheets by an aromatic π–π stacking interaction. 1-(2-Chlorobenzoyl)-4-(4-methoxyphenyl)piperazine, C₁₈H₁₉ClN₂O₂, (III), 1-(2-bromobenzoyl)-4-(4-methoxyphenyl)piperazine, C₁₈H₁₉BrN₂O₂, (IV), and 1-(2-iodobenzoyl)-4-(4-methoxyphenyl)piperazine, C₁₈H₁₉IN₂O₂, (V), are isomorphous, but in (III) the aroyl ring is disordered over two sets of atomic sites having occupancies of 0.942 (2) and 0.058 (2). In each of (III)–(V), a combination of two C—H⋯π(arene) hydrogen bonds links the molecules into sheets. A single O—H⋯O hydrogen bond links the molecules of 1-(2-hydroxybenzoyl)-4-(4-methoxyphenyl)piperazine, C₁₈H₂₀N₂O₃, (VI), into simple chains. Comparisons are made with the structures of some related compounds.

Keywords: piperazines; crystal structure; isomorphism; disorder; hydrogen bonding; supramolecular assembly.

CCDC references: 1942579; 1942578; 1942577; 1942576; 1942575; 1942574

1. Chemical context

Piperazines are found in a wide range of compounds which are active across a number of different therapeutic areas such as antibacterial, antidepressant, antifungal, antimalarial, antipsychotic, and antitumour activity (Brockunier et al., 2004 ; Bogatcheva et al., 2006 ), and a number of these areas have recently been reviewed (Elliott, 2011 ; Kharb et al., 2012 ; Asif, 2015 ; Brito et al., 2019 ). 1-(4-Methoxyphenyl)piperazine has been found to inhibit the re-uptake and accelerate the release of monoamine neurotransmitters such as dopamine and serotonin, with a mechanism of action similar to that of recreational drugs such as amphetamines, but with significantly lower abuse potential (Nagai et al., 2007 ). With these considerations in mind, we have now synthesized and characterized a series of closely related 1-aroyl-4-(4-methoxyphenyl)piperazines, using a straightforward coupling reaction between N-(4-methoxyphenyl)piperazine and a benzoic acid, promoted by 1-(3-dimethylaminopropyl)-3-ethylcarbodimide as the dehydrating agent. Here we report the molecular and supramolecular structures of compounds (I)–(VI) (Figs. 1–6 ) which we compare with the structures of some related compounds. As well as these 2-substituted derivatives, we have also synthesized 1-(4-fluorobenzoyl)-4-(4-methoxyphenyl)piperazine (VII), but to date we have been unable to obtain any crystalline material suitable for single crystal X-ray diffraction.

Figure 1
The molecular structure of compound (I)

showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
The molecular structure of compound (II)

showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
The molecular structure of compound (III)

showing the atom-labelling scheme, and the disorder of the 2-chlorobenzoyl unit. The major disorder component is drawn using full lines and the minor disorder component is drawn using broken lines. Displacement ellipsoids are drawn at the 30% probability level.

Figure 4
The molecular structure of compound (IV)

showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 5
The molecular structure of compound (V)

showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 6
The molecular structure of compound (VI)

showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

2. Structural commentary

In the 2-chloro derivative (III), the benzoyl substituent is disordered over two sets of atomic sites having refined occupancies for the crystal selected for data collection of 0.942 (2) and 0.058 (2): in these two disorder forms, the chloro substituents occupy sites on opposite sides of the adjacent aryl ring (Fig. 3). Compounds (III), (IV) and (V) have similar unit-cell dimensions (Table 2) and, discounting the disorder in (III), each can be refined using the atomic coordinates of another as the starting point. However, these three structures exhibit several minor differences: firstly, the benzoyl group is disordered over two sets of atomic sites in (III), but not in (V); in (IV), the disorder was found to be very minor, ca 1.6%, such that attempted refinement of this small fraction was regarded as unrealistic and thus the ordered model was preferable. Secondly, there is a short intermolecular I⋯O contact in (V), which has no Cl⋯O or Br⋯O analogue in (III) and (IV). Hence compounds (III)–(V) can be regarded as isomorphous, but not strictly isostructural (cf. Acosta et al., 2009 ).

Table 2
Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₁₈H₂₀N₂O₂	C₁₈H₁₉FN₂O₂	C₁₈H₁₉ClN₂O₂
M_r	296.36	314.35	330.80
Crystal system, space group	Monoclinic, Cc	Monoclinic, P2₁/c	Orthorhombic, Pbca
Temperature (K)	293	293	293
a, b, c (Å)	29.403 (5), 7.9811 (14), 6.7898 (13)	6.998 (2), 7.938 (2), 28.415 (6)	13.0320 (11), 13.2470 (13), 19.258 (2)
α, β, γ (°)	90, 97.352 (12), 90	90, 92.20 (3), 90	90, 90, 90
V (Å³)	1580.3 (5)	1577.3 (7)	3324.6 (6)
Z	4	4	8
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.08	0.10	0.24
Crystal size (mm)	0.48 × 0.48 × 0.28	0.48 × 0.36 × 0.32	0.50 × 0.40 × 0.38

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	Oxford Diffraction Xcalibur diffractometer with Sapphire CCD
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ )	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ )	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ )
T_min, T_max	0.951, 0.977	0.931, 0.970	0.862, 0.912
No. of measured, independent and observed [I > 2σ(I)] reflections	5476, 2137, 1766	6039, 3315, 1863	13862, 3642, 2407
R_int	0.019	0.049	0.022
(sin θ/λ)_max (Å⁻¹)	0.655	0.651	0.656

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.089, 1.08	0.070, 0.190, 1.08	0.048, 0.127, 1.03
No. of reflections	2137	3315	3642
No. of parameters	201	208	243
No. of restraints	2	0	26
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.13	0.21, −0.27	0.23, −0.45

	(IV)	(V)	(VI)
Crystal data
Chemical formula	C₁₈H₁₉BrN₂O₂	C₁₈H₁₉IN₂O₂	C₁₈H₂₀N₂O₃
M_r	375.26	422.25	312.36
Crystal system, space group	Orthorhombic, Pbca	Orthorhombic, Pbca	Orthorhombic, Pbca
Temperature (K)	293	293	293
a, b, c (Å)	12.9119 (14), 13.3664 (16), 19.5019 (19)	12.7671 (13), 13.5429 (12), 20.2542 (16)	9.7265 (6), 12.9084 (9), 24.861 (1)
α, β, γ (°)	90, 90, 90	90, 90, 90	90, 90, 90
V (Å³)	3365.7 (6)	3502.0 (5)	3121.4 (3)
Z	8	8	8
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	2.45	1.84	0.09
Crystal size (mm)	0.22 × 0.21 × 0.18	0.48 × 0.42 × 0.38	0.50 × 0.40 × 0.16

Data collection
Diffractometer	Bruker D8 Quest	Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	Oxford Diffraction Xcalibur diffractometer with Sapphire CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2015	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ )	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ )
T_min, T_max	0.538, 0.643	0.408, 0.497	0.917, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	47663, 4262, 3135	14215, 3838, 3062	11981, 3474, 2492
R_int	0.039	0.029	0.020
(sin θ/λ)_max (Å⁻¹)	0.672	0.655	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.131, 1.02	0.068, 0.146, 1.18	0.041, 0.100, 1.04
No. of reflections	4262	3838	3474
No. of parameters	209	209	212
No. of restraints	0	0	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.64	1.27, −2.19	0.16, −0.17
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), APEX2 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and PLATON (Spek, 2009).

In each of the compounds reported here, the piperazine ring adopts an almost perfect chair conformation with the 4-methoxyphenyl substituent occupying an equatorial site: the geometry at atom N1 is effectively planar and only in compound (I) is there a very slight pyramidalization at this site. For each compound, the reference molecule was selected as one having a ring-puckering angle θ (Cremer & Pople, 1975 ) for the atom sequence (N1,C2,C3,N4,C5,C6) which was close to zero, as opposed to values close to 180° for the corresponding enantiomers. In all of the compounds, the methoxy carbon atom C441 is very close to being coplanar with the adjacent aryl ring: the maximum displacement of this atom from the ring plane is 0.216 (16) Å in compound (V). Associated with this observation, we note that the two exocyclic O—C—C angles at atom C44 always exhibit differences in the range 8–10°: this behaviour is entirely consistent with the that previously observed in planar or nearly planar alkoxyarenes (Seip & Seip, 1973 ; Ferguson et al., 1996 ). It is interesting to note that the methoxy group is oriented transoid to the carbonyl group in compounds (I) and (VI), but cisoid in compounds (II)–(V), suggesting that the methyl group may simply be acting in a space-filling role.

3. Supramolecular features

The supramolecular assembly in compounds (I)–(V) is dominated by contacts of C—H⋯O and C—H⋯π(arene) types (Table 1) and it is thus appropriate to define explicitly the criteria against which these contacts have been regarded as structurally significant hydrogen bonds. For single-atom acceptors, we adopt the distance criteria recommended in PLATON (Spek, 2009 ), based on the well-established concept of van der Waals radii (Bondi, 1964 ; Nyburg & Faerman, 1985 ; Rowland & Taylor, 1996 ), which provide an upper limit for H⋯O contacts of 2.60 Å, combined with the recommended (Wood et al., 2009 ) lower limit of 140° for the D—H⋯A angle. For the C—H⋯π(arene) contacts in the isomorphous compounds (III)–(V), both the H⋯Cg distances and the C—H⋯Cg angles are entirely typical of C—H⋯π(arene) hydrogen bonds (Braga et al., 1998 ). On this basis the C—H⋯O contacts in (II) can be regarded as significant, while the nearly linear C—H⋯O contacts in (III)–(V), which appear in each case to act cooperatively with a C–H⋯π hydrogen bond should be regarded as of marginal significance in (III) and (V).

Table 1
Hydrogen bonds and short intermolecular contacts (Å, °) in compounds (I)–(VI)

Cg1 and Cg2 are the centroids of the C11–C16 and C41–C46 rings, respectively.

Compound	D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
(I)	C12—H12⋯O17ⁱ	0.93	2.61	3.497 (4)	160
(II)	C2—H2A⋯O17ⁱⁱ	0.97	2.50	3.387 (4)	152
	C16—H16⋯O17ⁱⁱⁱ	0.93	2.43	3.340 (5)	167
(III)	C3—H3A⋯O17^iv	0.97	2.61	3.574 (3)	175
	C2—HA⋯Cg1^iv	0.97	2.84	3.648 (3)	142
	C15—H15⋯Cg2^v	0.93	2.72	3.610 (4)	162
(IV)	C3—H3A⋯O17^iv	0.97	2.56	3.524 (3)	171
	C2—HA⋯Cg1^iv	0.97	2.82	3.630 (3)	142
	C15—H15⋯Cg2^v	0.93	2.68	3.579 (4)	164
(V)	C3—H3A⋯O17^iv	0.97	2.60	3.542 (10)	164
	C2—HA⋯Cg1^iv	0.97	2.87	3.719 (11)	147
	C15—H15⋯Cg2^v	0.93	2.73	3.656 (12)	172
(VI)	O12—H12⋯O17^vi	0.92 (2)	1.81 (2)	3.7327 (15)	175.4 (18)
Symmetry codes: (i) x, 1 − y, − $[{1\over 2}]$ + z; (ii) 1 − x, 1 − y, 1 − z; (iii) 2 − x, 1 − y, 1 − z; (iv) − $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, 1 − z; (v) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, z; (vi) − $[{1\over 2}]$ + x, y, $[{1\over 2}]$ − z.

The sole direction-specific short intermolecular contact in (I) is between molecules related by a glide plane. The molecules of compound (II) are linked by two independent C—H⋯O hydrogen bonds (Table 1) to form a chain of centrosymmetric rings in which R₂²(10) (Etter, 1990 ; Etter et al., 1990 ; Bernstein et al., 1995 ) rings involving atom C2 as the donor and centred at (n + $[1\over2]$ , $[1\over2]$ , $[1\over2]$ ) alternate with R₂²(10) rings involving atom C16 as the donor and centred at (n, $[1\over2]$ , $[1\over2]$ ), where n represents an integer in each case (Fig. 7). Chains of this type are linked into sheets by an aromatic π–π stacking interaction: the fluorinated rings in the molecules at (x, y, z) and (2 − x, 2 − y, 1 − z) are parallel with an interplanar spacing of 3.520 (2) Å; the ring-centroid separation is 3.774 (2) Å and the ring-centroid offset is 1.360 (2) Å. This interaction links the hydrogen-bonded chains into a sheet lying parallel to (001) in the domain $[1\over4]$ < z < $[3\over4]$ : a second such sheet, related to the first by the translational symmetry operation, lies in the domain − $[1\over4]$ < z < $[1\over4]$ , but there are no direction-specific interactions between adjacent sheets.

Figure 7
Part of the crystal structure of compound (II)

showing the formation of a chain of rings running parallel to the [100] direction. Hydrogen bonds are shown as dashed lines and, for the sake of clarity, the H atoms bonded to those C atoms which are not involved in the motif shown have been omitted.

As noted previously (see Section 2), the 2-chlorobenzoyl unit in compound (III) is disordered over two sets of atomic sites: however, the occupancy of the minor disorder component is low, and thus only the major component need be considered here. The supramolecular assembly in each of (III)–(V) is essentially the same. A combination of two C—H⋯π(arene) hydrogen bonds, weakly augmented by a C—H⋯O Interaction, links the molecules into sheets, whose formation is readily analysed in terms of two one-dimensional sub-structures (Ferguson et al., 1998a ,b ; Gregson et al., 2000 ). In the simpler of the two sub-structures, molecules related by the b-glide at x = $[3\over4]$ are linked by a C—H⋯π(arene) hydrogen bond to form a chain running parallel to the [010] direction (Fig. 8). In the second sub-structure, a C—H⋯π(arene) hydrogen bond links molecules which are related by the 2₁ screw axis along (x, $[1\over4]$ , $[1\over2]$ ) to form a chain running parallel to the [100] direction (Fig. 9). These two chain motifs combine to generate a sheet lying parallel to (001) in the domain $[1\over4]$ < z < $[3\over4]$ . A second sheet, related to the first by inversion, lies in the domain $[3\over4]$ < z < $[5\over4]$ , but there are no direction-specific interactions between adjacent sheets. However there is, in (V), a rather short intermolecular I⋯O contact where I12⋯O17ⁱ = 3.362 (7) Å and C12—I12⋯O17ⁱ = 163.5 (2)° [symmetry code: (i) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, z], as compared with the sum of van der Waals radii of 3.56 Å (Rowland & Taylor, 1996). This contact lies within the chain along [010] and so does not affect the overall two-dimensional nature of the supramolecular assembly. However, short contacts of this type are not present in the structures of (III) and (IV), where the corresponding Cl⋯O and Br⋯O distances are 3.707 (4) and 3.708 (3) Å, respectively, as compared with the sums of van der Waals radii of 3.30 Å and 3.41 Å respectively. Simple considerations of electronegativity (Allen, 1989 ) indicate that in carbon–halogen bonds of type (aryl)C—X, the halogen atom carries a residual positive charge when X = I, but a residual negative charge when X = Cl or Br. On this basis (aryl)C—X⋯O=C interactions are expected to be attractive when X = I, but repulsive when X = Cl or Br, so accounting for the much shorter I⋯O distance in (V) as compared with the corresponding distances in (III) and (IV).

Figure 8
Part of the crystal structure of compound (III)

showing the formation of a simple chain running parallel to the [010] direction. Hydrogen bonds are shown as dashed lines and, for the sake of clarity, the minor disorder component and the H atoms bonded to those C atoms which are not involved in the motif shown have been omitted.

Figure 9
Part of the crystal structure of compound (III)

showing the formation of a simple chain running parallel to the [100] direction. Hydrogen bonds are shown as dashed lines and, for the sake of clarity, the minor disorder component and the H atoms bonded to those C atoms which are not involved in the motif shown have been omitted.

The supramolecular assembly in compound (VI) takes the form of simple C(6) chains running parallel to the [100] direction, in which molecules related by the a-glide plane at z = $[1\over4]$ are linked by an O—H⋯O hydrogen bond (Table 1) (Fig. 10). A second chain of this type, related to the first by inversion, and two further chains related to the first pair by the c-glide planes, pass through each unit cell but there are no direction-specific interactions between adjacent chains.

Figure 10
Part of the crystal structure of compound (VI)

showing the formation of a C(6) chain running parallel to the [100] direction. Hydrogen bonds are shown as dashed lines and, for the sake of clarity, the H atoms bonded to C atoms have all been omitted.

Thus in summary, the supramolecular assembly takes the form of a simple chain in compound (VI), a chain of rings in compound (II), and sheets in compounds (III), (IV) and (V).

4. Database survey

It is of interest briefly to compare the structures of compounds (I)–(VI) reported here with those of some closely related analogues. In 4-(4-methoxyphenyl)piperazin-1-ium chloride (Zia-ur-Rehman et al., 2009 ), the ions are linked by two independent N—H⋯Cl hydrogen bonds: although the structure was described in the original report as dimeric, the ions are in fact linked into C₂¹(4) chains. The molecules of 1-acetyl-4-(4-hydroxyphenyl)piperazine (Kavitha et al., 2013 ) are linked by O—H⋯O hydrogen bonds to form simple C(12) chains, while those of 1-(2-iodobenzoyl)-4-(pyrimidin-2-yl)piperazine (Mahesha, Yathirajan et al., 2019 ) are linked by a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds to form a three-dimensional framework structure which is further strengthened by both aromatic π–π stacking interactions and I⋯N halogen bonds. Finally, we note the structures of three closely related 1-(1,3-benzodioxolol-5-yl)methyl-4-(halobenzoyl) piperazines (Mahesha, Sagar et al., 2019 ), where the 3-fluorobenzoyl derivative forms a three-dimensional framework structure built from C—H⋯O and C—H⋯π(arene) hydrogen bonds, whereas the structures of the 2,6-difluorobenzoyl and 2,4-dichlorobenzoyl analogues contain no hydrogen bonds of any sort. Examples of attractive iodo⋯carbonyl interactions, as found here in (V), have also been reported in a number of systems (Glidewell et al., 2005 ; Garden et al., 2006 ; Sirimulla et al., 2013 ).

5. Synthesis and crystallization

For the synthesis of compounds (I)–(VII), 1-(3-dimethylaminopropyl)-3-ethylcarbodimide (134 mg, 0.7 mmol), 1-hydroxybenzotriazole (68 mg, 0.5 mmol) and triethylamine (0.5 ml, 1.5 mmol) were added to a solution of the appropriately substituted benzoic acid [benzoic acid for (I), 2-fluorobenzoic acid for (II), 2-chlorobenzoic acid for (III), 2-bromobenzoic acid for (IV), 2-iodobenzoic acid for (V), salicylic acid for (VI) and 4-fluorobenzoic acid for (VII)] (0.5 mmol) in N,N-dimethylformamide (5 ml) and the resulting mixtures were stirred for 20 min at 273 K. A solution of N-(4-methoxyphenyl)piperazine (100 mg, 0.5 mmol) in N,N-dimethylformamide (5 ml) was then added and stirring was continued overnight at ambient temperature. When the reactions were confirmed to be complete using thin-layer chromatography, each mixture was then quenched with water (10 ml) and extracted with ethyl acetate (20 ml). Each organic fraction was separated and washed successively with an aqueous hydrochloric acid solution (1 mol dm⁻³), a saturated solution of sodium hydrogencarbonate and then with brine. The organic phases were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, of solutions in ethyl acetate.

Compound (I). Yield 81%, m.p. 407–409 K. IR (KBr, cm⁻¹) 1631 (C=O), 1242 (C—N). NMR (CDCl₃) δ(¹H) 3.04 (t, 4H, piperazine), 3.56 (s, 2H, piperazine), 3.75 (s, 3H, O—CH₃), 3.92 (s, 2H, piperazine), 6.83 (d, 2H, methoxyphenyl), 6.89 (d, 2H, methoxyphenyl), 7.42 (m, 5H, phenyl): δ(¹³C) 47.76, 51.22, 55.48 (O—CH₃), 114.46, 118.88, 127.04, 128.46, 129.72, 135.63, 145.19, 154.36, 170.30.

Compound (II). Yield 80%, m.p. 409–411 K. IR (KBr, cm⁻¹) 1626 (C=O), 1242 (C—N). NMR (CDCl₃) δ(¹H) 2.99 (s, 2H, piprazine), 3.13 (t, 2H, piperazine), 3.47 (s, 2H, piperazine) 3.75 (s, 3H, O—CH₃), 3.95 (t, 2H, piperazine), 6.83 (d, 2H, J = 9.2 Hz, methoxyphenyl), 6.89 (d, 2H, J = 9.2 Hz, methoxyphenyl), 7.09 (m, 1H, 2-fluorophenyl), 7.22 (m, 1H, 2-fluorophenyl), 7.40 (m, 2H, 2-fluorophenyl): δ(¹³C) 47.08, 51.29, 55.47 (O—CH₃), 114.47, 118.96, 123.86, 124.60, 129.17, 131.34 145.17, 154.40, 156.82, 159.29, 165.10.

Compound (III). Yield 79%, m.p. 425–427 K. IR (KBr, cm⁻¹) 1632 (C=O), 1240 (C—N). NMR (CDCl₃) δ(¹H) 2.94 (m, 1H, piperazine), 3.07 (m, 3H, piperazine), 3.34 (m, 1H, piperazine), 3.42 (m, 1H, piperazine) 3.75 (s, 3H, O—CH₃), 3.95 (m, 2H, piperazine), 6.83 (d, 2H, J = 9.2Hz, methoxyphenyl), 6.88 (t, 2H, 2-chlorophenyl), 7.33 (m, 4H, methoxyphenyl and 2-chlorophenyl): δ(¹³C) 46.76, 51.22, 55.48 (O—CH₃), 114.47, 118.94, 127.16, 127.73, 129.63 130.19, 130.31, 135.65, 145.10, 154.41, 166.77.

Compound (IV) Yield 80%, m.p. 410–412 K. IR (KBr, cm⁻¹) 1631 (C=O), 1242 (C—N). NMR (CDCl₃) δ(¹H) 2.99 (m, 1H, piperazine), 3.15 (m, 3H, piperazine), 3.38 (q, 1H, piperazine), 3.45 (m, 1H, piperazine), 3.79 (s, 3H, O—CH₃), 3.99 (m, 2H, piperazine), 6.86 (d, 2H, J = 9.2 Hz, methoxyphenyl), 6.92 (d, 2H, J = 9.2 Hz, methoxyphenyl), 7.29 (m, 2H, 2-bromophenyl), 7.39 (t, 1H, 2-bromophenyl), 7.61 (d, 1H, J = 8 Hz, 2-bromophenyl): δ(¹³C) 41.72, 46.86, 50.88, 51.23, 55.54 (O—CH₃), 114.53, 119.00, 119.19, 127.75, 130.32, 132.85, 137.91, 145.20, 154.47.

Compound (V). Yield 79%, m.p. 423–425 K. IR (KBr, cm⁻¹) 1630 (C=O), 1243 (C—N). NMR (CDCl₃) δ(¹H) 2.93 (m, 1H, piperazine), 3.16 (m, 3H, piperazine), 3.32 (m, 1H, piperazine), 3.42 (m, 1H, piperazine), 3.75 (s, 3H, O—CH₃), 3.96 (m, 2H, piperazine), 6.83 (d, 2H, J = 8.8Hz, methoxyphenyl), 6.89 (d, 2H, J = 8.8Hz, methoxyphenyl), 7.08 (m, 1H, 2-iodophenyl), 7.22 (m,1H, 2-iodophenyl), 7.39 (m, 1H, 2-iodophenyl), 7.83 (m, 1H, 2-iodophenyl): δ(¹³C) 46.92, 51.12, 55.49 (O—CH₃), 92.48, 114.46, 118.95, 127.02, 128.37, 130.24, 139.22, 142.03, 145.12, 154.39

Compound (VI). Yield 79%, m.p. 465–467 K. IR (KBr, cm⁻¹) 1631 (C=O), 1228 (C—N). NMR (CDCl₃) δ(¹H) 3.10 (m, 4H, piperazine), 3.76 (s, 3H, O—CH₃), 3.88 (m, 4H, piperazine), 6.85 (m, 5H, methoxyphenyl and 2-hydroxyphenyl), 7.01 (m, 1H, 2-hydroxyphenyl), 7.26 (m,1H, 2-hydroxyphenyl), 7.33 (m,1H, 2-hydroxyphenyl): δ(¹³C) 45.84, 51.16, 55.48 (O—CH₃), 114.51, 116.77, 118.10, 118.53, 118.89, 128.26, 132.69, 145.09, 154.47, 159.09, 170.83.

Compound (VII). Yield 78%, m.p. 401–403 K. IR (KBr, cm⁻¹) 1625 (C=O), 1247 (C—N). NMR (CDCl₃) δ(¹H) 3.05 (s, 4H, piperazine), 3.62 (m, 2H, piperazine), 3.75 (s, 3H, O—CH₃), 3.85 (m, 2H, piperazine), 6.86 (m, 4H, methoxyphenyl), 7.09 (m, 2H, 4-fluorophenyl), 7.44 (m, 2H, 4-fluorophenyl): δ(¹³C) 47.77, 51.15, 55.47 (O—CH₃), 114.47, 115.44, 118.90, 129.43 131.59, 145.11, 154.41, 162.13, 169.39.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Two bad outlier reflections, (080) and (186), were omitted from the final refinements for compound (V). For the minor disorder component of compound (III), the bonded distances and the 1,3 non-bonded distances were restrained to be the same as those in the major disorder component, subject to s.u. values of 0.01 and 0.02 Å, respectively. The anisotropic displacement parameters for pairs of partial-occupancy atoms occupying essentially the same physical space were constrained to be the same: in addition it was found desirable to constrain the minor component of the chloroaryl ring to be planar, and to apply a rigid-bond restraint to the bond C32—Cl32 in the minor disorder component. Subject to these conditions, the occupancies of the two disorder components refined to 0.942 (2) and 0.058 (2), respectively. After refinement of (IV) as a fully ordered structure, the difference map contained indications of some slight disorder similar to that found for (III). However, when this structure was refined using a disorder model analogous to that used for (III), the preliminary values of the occupancies were 0.9837 (7) and 0.0163 (7), so that each C atom in the minor disorder component represented less than 0.1 electron: accordingly, it was regarded as unrealistic to pursue this disorder model and that the fully ordered model was preferable. The principal feature in the difference map for (V) is a minimum, −2.24 e Å⁻³, located 1.80 Å from atom I2 at (x, y, z) and 1.83 Å from atom O17 at ( $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, z), although not co-linear with these two atoms, which subtend an angle of 135° at the minimum. All H atoms apart from those in the minor disorder components of compound (III) were located in difference maps. The H atoms bonded to C atoms were all then treated as riding atoms in geometrically idealized positions with C—H distances of 0.93 Å (aromatic), 0.96 Å (CH₃) or 0.97 Å (CH₂), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms bonded to C atoms. For the H atom bonded to an O atom in compound (VI), the atomic coordinates were refined with U_iso(H) = 1.5U_eq(O), giving an O—H distance of 0.92 (2) Å. In the absence of significant resonant scattering in (I), it was not possible to determine the correct orientation of the structure of (I) relative to the polar axis directions: however, this has no chemical significance.

Supporting information

CCDC references: 1942579; 1942578; 1942577; 1942576; 1942575; 1942574

Crystal structure: contains datablocks global, I, II, III, IV, V, VI. DOI: https://doi.org/10.1107/S2056989019010491/zl2757sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019010491/zl2757Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019010491/zl2757IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989019010491/zl2757IIIsup4.hkl

Structure factors: contains datablock IV. DOI: https://doi.org/10.1107/S2056989019010491/zl2757IVsup5.hkl

Structure factors: contains datablock V. DOI: https://doi.org/10.1107/S2056989019010491/zl2757Vsup6.hkl

Structure factors: contains datablock VI. DOI: https://doi.org/10.1107/S2056989019010491/zl2757VIsup7.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019010491/zl2757Isup8.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019010491/zl2757IIsup9.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019010491/zl2757IIIsup10.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019010491/zl2757Vsup11.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019010491/zl2757VIsup12.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009) for (I), (II), (III), (V), (VI); APEX2 (Bruker, 2015) for (IV). Cell refinement: CrysAlis RED (Oxford Diffraction, 2009) for (I), (II), (III), (V), (VI); SAINT (Bruker, 2015) for (IV). Data reduction: CrysAlis RED (Oxford Diffraction, 2009) for (I), (II), (III), (V), (VI); SAINT (Bruker, 2015) for (IV). For all structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2009).

1-Benzoyl-4-(4-methoxyphenyl)piperazine (I) top

Crystal data top

C₁₈H₂₀N₂O₂	F(000) = 632
M_r = 296.36	D_x = 1.246 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 29.403 (5) Å	Cell parameters from 2137 reflections
b = 7.9811 (14) Å	θ = 2.7–27.7°
c = 6.7898 (13) Å	µ = 0.08 mm⁻¹
β = 97.352 (12)°	T = 293 K
V = 1580.3 (5) Å³	Plate, colourless
Z = 4	0.48 × 0.48 × 0.28 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	2137 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1766 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ω scans	θ_max = 27.7°, θ_min = 2.7°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −37→37
T_min = 0.951, T_max = 0.977	k = −10→10
5476 measured reflections	l = −4→8

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.035	w = 1/[σ²(F_o²) + (0.0414P)² + 0.3311P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.089	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.14 e Å⁻³
2137 reflections	Δρ_min = −0.13 e Å⁻³
201 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0041 (8)
Primary atom site location: difference Fourier map

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.46344 (7)	0.2520 (2)	0.4700 (3)	0.0433 (5)
C2	0.41820 (8)	0.2497 (3)	0.5365 (3)	0.0439 (6)
H2A	0.4189	0.3164	0.6563	0.053*
H2B	0.4105	0.1356	0.5686	0.053*
C3	0.38166 (9)	0.3177 (3)	0.3801 (3)	0.0440 (6)
H3A	0.3518	0.3068	0.4254	0.053*
H3B	0.3872	0.4358	0.3589	0.053*
N4	0.38189 (7)	0.2271 (2)	0.1945 (3)	0.0391 (5)
C5	0.42693 (8)	0.2452 (3)	0.1240 (3)	0.0437 (6)
H5A	0.4329	0.3627	0.1012	0.052*
H5B	0.4268	0.1862	−0.0009	0.052*
C6	0.46440 (9)	0.1755 (3)	0.2747 (4)	0.0453 (6)
H6A	0.4606	0.0552	0.2850	0.054*
H6B	0.4940	0.1963	0.2304	0.054*
C17	0.50023 (9)	0.2585 (3)	0.6128 (4)	0.0458 (6)
O17	0.49611 (7)	0.2708 (3)	0.7894 (3)	0.0697 (6)
C11	0.54739 (9)	0.2548 (3)	0.5486 (4)	0.0479 (6)
C12	0.56066 (10)	0.3679 (4)	0.4144 (5)	0.0638 (8)
H12	0.5399	0.4469	0.3558	0.077*
C13	0.60510 (11)	0.3637 (5)	0.3668 (6)	0.0780 (10)
H13	0.6143	0.4415	0.2778	0.094*
C14	0.63520 (11)	0.2479 (5)	0.4481 (5)	0.0754 (10)
H14	0.6646	0.2443	0.4120	0.091*
C15	0.62257 (11)	0.1350 (5)	0.5841 (5)	0.0776 (10)
H15	0.6435	0.0561	0.6411	0.093*
C16	0.57874 (10)	0.1391 (4)	0.6357 (4)	0.0626 (8)
H16	0.5702	0.0641	0.7292	0.075*
C41	0.34279 (8)	0.2454 (3)	0.0494 (3)	0.0382 (6)
C42	0.30660 (8)	0.3523 (3)	0.0761 (4)	0.0454 (6)
H42	0.3089	0.4215	0.1870	0.055*
C43	0.26735 (9)	0.3569 (3)	−0.0600 (4)	0.0497 (7)
H43	0.2435	0.4282	−0.0379	0.060*
C44	0.26289 (8)	0.2581 (4)	−0.2277 (4)	0.0474 (6)
C45	0.29861 (9)	0.1527 (3)	−0.2590 (4)	0.0464 (6)
H45	0.2963	0.0857	−0.3719	0.056*
C46	0.33796 (9)	0.1470 (3)	−0.1215 (4)	0.0444 (6)
H46	0.3617	0.0754	−0.1443	0.053*
O44	0.22252 (7)	0.2728 (3)	−0.3541 (3)	0.0671 (6)
C441	0.21605 (15)	0.1672 (6)	−0.5223 (6)	0.0907 (12)
H41A	0.1855	0.1811	−0.5889	0.136*
H41B	0.2206	0.0527	−0.4811	0.136*
H41C	0.2377	0.1961	−0.6112	0.136*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0391 (11)	0.0513 (13)	0.0412 (11)	−0.0030 (10)	0.0121 (9)	−0.0049 (9)
C2	0.0445 (14)	0.0484 (14)	0.0410 (14)	−0.0017 (12)	0.0139 (11)	−0.0028 (11)
C3	0.0435 (13)	0.0484 (14)	0.0429 (14)	0.0032 (12)	0.0163 (11)	−0.0018 (11)
N4	0.0364 (11)	0.0447 (11)	0.0384 (11)	0.0040 (10)	0.0136 (9)	−0.0015 (9)
C5	0.0447 (14)	0.0510 (15)	0.0380 (13)	0.0017 (11)	0.0154 (11)	0.0001 (10)
C6	0.0413 (13)	0.0521 (14)	0.0442 (13)	0.0038 (12)	0.0124 (11)	−0.0035 (11)
C17	0.0454 (15)	0.0482 (15)	0.0448 (15)	−0.0057 (13)	0.0093 (12)	−0.0004 (11)
O17	0.0558 (11)	0.1098 (18)	0.0448 (11)	−0.0141 (12)	0.0117 (9)	−0.0072 (11)
C11	0.0444 (14)	0.0553 (16)	0.0440 (14)	−0.0069 (13)	0.0055 (11)	−0.0037 (12)
C12	0.0483 (16)	0.074 (2)	0.0703 (19)	−0.0011 (15)	0.0131 (14)	0.0196 (15)
C13	0.056 (2)	0.103 (3)	0.078 (2)	−0.0136 (18)	0.0197 (17)	0.020 (2)
C14	0.0406 (17)	0.110 (3)	0.078 (2)	−0.0040 (18)	0.0141 (16)	−0.005 (2)
C15	0.0518 (19)	0.093 (3)	0.085 (2)	0.0120 (18)	−0.0028 (16)	0.0019 (19)
C16	0.0510 (17)	0.074 (2)	0.0608 (18)	−0.0008 (15)	0.0009 (14)	0.0100 (15)
C41	0.0386 (13)	0.0376 (13)	0.0407 (13)	−0.0028 (11)	0.0144 (11)	0.0050 (10)
C42	0.0402 (14)	0.0471 (16)	0.0511 (15)	0.0014 (11)	0.0143 (11)	−0.0046 (11)
C43	0.0396 (14)	0.0489 (16)	0.0633 (17)	0.0069 (13)	0.0165 (13)	0.0004 (13)
C44	0.0371 (14)	0.0555 (16)	0.0504 (15)	−0.0032 (13)	0.0093 (11)	0.0081 (13)
C45	0.0504 (15)	0.0488 (16)	0.0413 (14)	−0.0014 (13)	0.0117 (11)	−0.0033 (11)
C46	0.0468 (14)	0.0449 (15)	0.0439 (14)	0.0085 (12)	0.0155 (11)	0.0000 (11)
O44	0.0461 (11)	0.0883 (16)	0.0651 (13)	0.0030 (11)	0.0007 (9)	−0.0011 (12)
C441	0.076 (2)	0.110 (3)	0.078 (3)	0.001 (2)	−0.0201 (18)	−0.015 (2)

Geometric parameters (Å, º) top

N1—C17	1.358 (3)	C13—C14	1.348 (5)
N1—C2	1.458 (3)	C13—H13	0.9300
N1—C6	1.463 (3)	C14—C15	1.375 (5)
C2—C3	1.511 (4)	C14—H14	0.9300
C2—H2A	0.9700	C15—C16	1.378 (4)
C2—H2B	0.9700	C15—H15	0.9300
C3—N4	1.454 (3)	C16—H16	0.9300
C3—H3A	0.9700	C41—C46	1.393 (4)
C3—H3B	0.9700	C41—C42	1.394 (3)
N4—C41	1.422 (3)	C42—C43	1.384 (4)
N4—C5	1.472 (3)	C42—H42	0.9300
C5—C6	1.511 (4)	C43—C44	1.378 (4)
C5—H5A	0.9700	C43—H43	0.9300
C5—H5B	0.9700	C44—O44	1.378 (3)
C6—H6A	0.9700	C44—C45	1.383 (4)
C6—H6B	0.9700	C45—C46	1.391 (4)
C17—O17	1.225 (3)	C45—H45	0.9300
C17—C11	1.506 (3)	C46—H46	0.9300
C11—C12	1.374 (4)	O44—C441	1.412 (4)
C11—C16	1.383 (4)	C441—H41A	0.9600
C12—C13	1.386 (4)	C441—H41B	0.9600
C12—H12	0.9300	C441—H41C	0.9600

C17—N1—C2	117.04 (19)	C13—C12—H12	120.2
C17—N1—C6	123.82 (19)	C14—C13—C12	120.7 (3)
C2—N1—C6	113.5 (2)	C14—C13—H13	119.7
N1—C2—C3	111.88 (19)	C12—C13—H13	119.7
N1—C2—H2A	109.2	C13—C14—C15	120.3 (3)
C3—C2—H2A	109.2	C13—C14—H14	119.8
N1—C2—H2B	109.2	C15—C14—H14	119.8
C3—C2—H2B	109.2	C14—C15—C16	119.8 (3)
H2A—C2—H2B	107.9	C14—C15—H15	120.1
N4—C3—C2	110.4 (2)	C16—C15—H15	120.1
N4—C3—H3A	109.6	C15—C16—C11	120.1 (3)
C2—C3—H3A	109.6	C15—C16—H16	120.0
N4—C3—H3B	109.6	C11—C16—H16	120.0
C2—C3—H3B	109.6	C46—C41—C42	117.1 (2)
H3A—C3—H3B	108.1	C46—C41—N4	120.4 (2)
C41—N4—C3	117.17 (18)	C42—C41—N4	122.4 (2)
C41—N4—C5	116.48 (17)	C43—C42—C41	121.0 (2)
C3—N4—C5	109.71 (19)	C43—C42—H42	119.5
N4—C5—C6	110.63 (18)	C41—C42—H42	119.5
N4—C5—H5A	109.5	C44—C43—C42	121.3 (2)
C6—C5—H5A	109.5	C44—C43—H43	119.3
N4—C5—H5B	109.5	C42—C43—H43	119.3
C6—C5—H5B	109.5	C43—C44—O44	116.7 (2)
H5A—C5—H5B	108.1	C43—C44—C45	118.8 (2)
N1—C6—C5	111.3 (2)	O44—C44—C45	124.5 (3)
N1—C6—H6A	109.4	C44—C45—C46	120.0 (2)
C5—C6—H6A	109.4	C44—C45—H45	120.0
N1—C6—H6B	109.4	C46—C45—H45	120.0
C5—C6—H6B	109.4	C45—C46—C41	121.9 (2)
H6A—C6—H6B	108.0	C45—C46—H46	119.1
O17—C17—N1	122.2 (2)	C41—C46—H46	119.1
O17—C17—C11	119.7 (2)	C44—O44—C441	118.0 (3)
N1—C17—C11	118.1 (2)	O44—C441—H41A	109.5
C12—C11—C16	119.5 (3)	O44—C441—H41B	109.5
C12—C11—C17	122.0 (3)	H41A—C441—H41B	109.5
C16—C11—C17	118.5 (2)	O44—C441—H41C	109.5
C11—C12—C13	119.6 (3)	H41A—C441—H41C	109.5
C11—C12—H12	120.2	H41B—C441—H41C	109.5

C17—N1—C2—C3	154.8 (2)	C12—C13—C14—C15	−1.9 (6)
C6—N1—C2—C3	−50.5 (3)	C13—C14—C15—C16	0.8 (6)
N1—C2—C3—N4	55.1 (3)	C14—C15—C16—C11	1.0 (5)
C2—C3—N4—C41	164.3 (2)	C12—C11—C16—C15	−1.6 (4)
C2—C3—N4—C5	−59.9 (3)	C17—C11—C16—C15	−178.4 (3)
C41—N4—C5—C6	−163.8 (2)	C3—N4—C41—C46	−172.1 (2)
C3—N4—C5—C6	60.1 (3)	C5—N4—C41—C46	55.1 (3)
C17—N1—C6—C5	−157.0 (2)	C3—N4—C41—C42	3.6 (3)
C2—N1—C6—C5	50.3 (3)	C5—N4—C41—C42	−129.2 (2)
N4—C5—C6—N1	−54.7 (3)	C46—C41—C42—C43	1.3 (4)
C2—N1—C17—O17	−3.7 (4)	N4—C41—C42—C43	−174.5 (2)
C6—N1—C17—O17	−155.6 (3)	C41—C42—C43—C44	−0.9 (4)
C2—N1—C17—C11	177.9 (2)	C42—C43—C44—O44	−179.7 (2)
C6—N1—C17—C11	26.1 (3)	C42—C43—C44—C45	0.0 (4)
O17—C17—C11—C12	−123.5 (3)	C43—C44—C45—C46	0.5 (4)
N1—C17—C11—C12	54.9 (4)	O44—C44—C45—C46	−179.8 (2)
O17—C17—C11—C16	53.2 (4)	C44—C45—C46—C41	−0.1 (4)
N1—C17—C11—C16	−128.4 (3)	C42—C41—C46—C45	−0.8 (4)
C16—C11—C12—C13	0.6 (5)	N4—C41—C46—C45	175.1 (2)
C17—C11—C12—C13	177.2 (3)	C43—C44—O44—C441	−177.0 (3)
C11—C12—C13—C14	1.2 (6)	C45—C44—O44—C441	3.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O17ⁱ	0.93	2.61	3.497 (4)	160

Symmetry code: (i) x, −y+1, z−1/2.

1-(2-Fluorobenzoyl)-4-(4-methoxyphenyl)piperazine (II) top

Crystal data top

C₁₈H₁₉FN₂O₂	F(000) = 664
M_r = 314.35	D_x = 1.324 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.998 (2) Å	Cell parameters from 3334 reflections
b = 7.938 (2) Å	θ = 2.7–28.4°
c = 28.415 (6) Å	µ = 0.10 mm⁻¹
β = 92.20 (3)°	T = 293 K
V = 1577.3 (7) Å³	Block, colourless
Z = 4	0.48 × 0.36 × 0.32 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	3315 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1863 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ω scans	θ_max = 27.6°, θ_min = 2.7°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −8→5
T_min = 0.931, T_max = 0.970	k = −10→5
6039 measured reflections	l = −36→28

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.070	H-atom parameters constrained
wR(F²) = 0.190	w = 1/[σ²(F_o²) + (0.0566P)² + 1.2906P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3315 reflections	Δρ_max = 0.21 e Å⁻³
208 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.7575 (4)	0.5325 (4)	0.41972 (9)	0.0547 (8)
C2	0.5981 (5)	0.4154 (5)	0.42224 (11)	0.0560 (9)
H2A	0.5401	0.4256	0.4526	0.067*
H2B	0.6439	0.3008	0.4191	0.067*
C3	0.4517 (5)	0.4532 (5)	0.38354 (11)	0.0541 (9)
H3A	0.3490	0.3714	0.3845	0.065*
H3B	0.3976	0.5639	0.3887	0.065*
N4	0.5348 (3)	0.4485 (3)	0.33706 (9)	0.0475 (7)
C5	0.6957 (5)	0.5657 (5)	0.33544 (11)	0.0567 (9)
H5A	0.6492	0.6801	0.3386	0.068*
H5B	0.7543	0.5563	0.3052	0.068*
C6	0.8428 (5)	0.5301 (5)	0.37396 (11)	0.0623 (10)
H6A	0.8999	0.4207	0.3688	0.075*
H6B	0.9433	0.6142	0.3733	0.075*
C17	0.7990 (4)	0.6422 (4)	0.45441 (11)	0.0464 (8)
O17	0.7152 (3)	0.6409 (3)	0.49118 (8)	0.0632 (7)
C11	0.9578 (4)	0.7658 (4)	0.44823 (10)	0.0436 (8)
C12	0.9203 (4)	0.9299 (5)	0.43559 (11)	0.0516 (8)
F12	0.7371 (3)	0.9715 (3)	0.42311 (8)	0.0805 (7)
C13	1.0575 (5)	1.0534 (5)	0.43537 (12)	0.0628 (10)
H13	1.0261	1.1635	0.4270	0.075*
C14	1.2416 (5)	1.0101 (5)	0.44775 (12)	0.0630 (10)
H14	1.3371	1.0916	0.4479	0.076*
C15	1.2868 (5)	0.8473 (6)	0.45996 (12)	0.0623 (10)
H15	1.4129	0.8190	0.4678	0.075*
C16	1.1467 (5)	0.7253 (5)	0.46063 (11)	0.0542 (9)
H16	1.1785	0.6156	0.4694	0.065*
C41	0.4022 (4)	0.4532 (4)	0.29834 (11)	0.0466 (8)
C42	0.2375 (5)	0.3540 (4)	0.29751 (11)	0.0516 (8)
H42	0.2144	0.2861	0.3234	0.062*
C43	0.1076 (5)	0.3529 (5)	0.25972 (11)	0.0545 (9)
H43	−0.0010	0.2857	0.2606	0.065*
C44	0.1383 (5)	0.4511 (5)	0.22074 (11)	0.0529 (9)
C45	0.3014 (5)	0.5483 (5)	0.22029 (12)	0.0567 (9)
H45	0.3256	0.6126	0.1938	0.068*
C46	0.4291 (5)	0.5518 (4)	0.25840 (11)	0.0538 (9)
H46	0.5358	0.6214	0.2575	0.065*
O44	0.0183 (4)	0.4587 (4)	0.18145 (8)	0.0718 (8)
C441	−0.1580 (5)	0.3703 (6)	0.18248 (13)	0.0756 (12)
H41A	−0.2281	0.3857	0.1531	0.113*
H41B	−0.1334	0.2525	0.1874	0.113*
H41C	−0.2317	0.4128	0.2077	0.113*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0531 (16)	0.062 (2)	0.0495 (15)	−0.0161 (15)	0.0145 (12)	−0.0028 (14)
C2	0.059 (2)	0.054 (2)	0.0556 (19)	−0.0119 (18)	0.0113 (16)	0.0044 (17)
C3	0.0531 (19)	0.058 (2)	0.0528 (19)	−0.0110 (18)	0.0184 (15)	0.0043 (16)
N4	0.0481 (14)	0.0478 (18)	0.0474 (14)	−0.0074 (13)	0.0150 (12)	−0.0020 (13)
C5	0.0568 (19)	0.065 (2)	0.0496 (18)	−0.0130 (19)	0.0224 (16)	−0.0017 (17)
C6	0.0518 (19)	0.081 (3)	0.056 (2)	−0.013 (2)	0.0173 (16)	−0.0064 (19)
C17	0.0458 (17)	0.046 (2)	0.0478 (18)	0.0034 (16)	0.0095 (14)	0.0067 (16)
O17	0.0736 (16)	0.0618 (17)	0.0561 (13)	−0.0101 (13)	0.0245 (12)	−0.0006 (12)
C11	0.0442 (17)	0.048 (2)	0.0396 (15)	0.0010 (15)	0.0066 (12)	0.0047 (14)
C12	0.0423 (17)	0.055 (2)	0.058 (2)	0.0062 (17)	0.0018 (14)	0.0089 (17)
F12	0.0519 (12)	0.0683 (16)	0.1207 (19)	0.0103 (11)	−0.0041 (11)	0.0252 (13)
C13	0.065 (2)	0.049 (2)	0.074 (2)	−0.003 (2)	0.0074 (18)	0.0086 (19)
C14	0.060 (2)	0.069 (3)	0.061 (2)	−0.017 (2)	0.0079 (17)	−0.009 (2)
C15	0.0420 (18)	0.089 (3)	0.056 (2)	−0.001 (2)	0.0027 (15)	−0.001 (2)
C16	0.0522 (19)	0.058 (2)	0.0523 (19)	0.0106 (18)	0.0058 (15)	0.0086 (17)
C41	0.0496 (18)	0.0407 (19)	0.0511 (18)	−0.0006 (16)	0.0218 (14)	−0.0056 (15)
C42	0.061 (2)	0.047 (2)	0.0485 (18)	−0.0089 (18)	0.0179 (15)	−0.0018 (16)
C43	0.0552 (19)	0.051 (2)	0.058 (2)	−0.0096 (18)	0.0163 (16)	−0.0074 (18)
C44	0.0569 (19)	0.055 (2)	0.0479 (18)	0.0019 (18)	0.0114 (16)	−0.0065 (17)
C45	0.064 (2)	0.053 (2)	0.054 (2)	−0.0051 (19)	0.0201 (17)	0.0065 (17)
C46	0.0523 (18)	0.053 (2)	0.057 (2)	−0.0109 (18)	0.0163 (16)	0.0021 (17)
O44	0.0685 (16)	0.087 (2)	0.0598 (15)	−0.0122 (15)	0.0054 (12)	0.0035 (14)
C441	0.063 (2)	0.097 (3)	0.067 (2)	−0.014 (2)	0.0057 (18)	−0.009 (2)

Geometric parameters (Å, º) top

N1—C17	1.338 (4)	C13—C14	1.367 (5)
N1—C6	1.452 (4)	C13—H13	0.9300
N1—C2	1.456 (4)	C14—C15	1.371 (5)
C2—C3	1.504 (4)	C14—H14	0.9300
C2—H2A	0.9700	C15—C16	1.379 (5)
C2—H2B	0.9700	C15—H15	0.9300
C3—N4	1.464 (4)	C16—H16	0.9300
C3—H3A	0.9700	C41—C42	1.396 (4)
C3—H3B	0.9700	C41—C46	1.397 (4)
N4—C41	1.412 (4)	C42—C43	1.380 (4)
N4—C5	1.462 (4)	C42—H42	0.9300
C5—C6	1.500 (5)	C43—C44	1.378 (4)
C5—H5A	0.9700	C43—H43	0.9300
C5—H5B	0.9700	C44—O44	1.373 (4)
C6—H6A	0.9700	C44—C45	1.378 (5)
C6—H6B	0.9700	C45—C46	1.378 (5)
C17—O17	1.218 (3)	C45—H45	0.9300
C17—C11	1.498 (4)	C46—H46	0.9300
C11—C12	1.374 (5)	O44—C441	1.421 (4)
C11—C16	1.393 (4)	C441—H41A	0.9600
C12—F12	1.358 (4)	C441—H41B	0.9600
C12—C13	1.372 (5)	C441—H41C	0.9600

C17—N1—C6	125.6 (3)	C13—C12—C11	123.5 (3)
C17—N1—C2	121.6 (3)	C14—C13—C12	118.2 (4)
C6—N1—C2	112.2 (3)	C14—C13—H13	120.9
N1—C2—C3	109.8 (3)	C12—C13—H13	120.9
N1—C2—H2A	109.7	C13—C14—C15	120.5 (4)
C3—C2—H2A	109.7	C13—C14—H14	119.7
N1—C2—H2B	109.7	C15—C14—H14	119.7
C3—C2—H2B	109.7	C14—C15—C16	120.6 (3)
H2A—C2—H2B	108.2	C14—C15—H15	119.7
N4—C3—C2	111.8 (3)	C16—C15—H15	119.7
N4—C3—H3A	109.2	C15—C16—C11	120.2 (3)
C2—C3—H3A	109.2	C15—C16—H16	119.9
N4—C3—H3B	109.2	C11—C16—H16	119.9
C2—C3—H3B	109.2	C42—C41—C46	116.1 (3)
H3A—C3—H3B	107.9	C42—C41—N4	121.0 (3)
C41—N4—C5	116.3 (2)	C46—C41—N4	122.8 (3)
C41—N4—C3	115.5 (2)	C43—C42—C41	122.4 (3)
C5—N4—C3	110.2 (2)	C43—C42—H42	118.8
N4—C5—C6	111.4 (3)	C41—C42—H42	118.8
N4—C5—H5A	109.3	C44—C43—C42	120.3 (3)
C6—C5—H5A	109.3	C44—C43—H43	119.9
N4—C5—H5B	109.3	C42—C43—H43	119.9
C6—C5—H5B	109.3	O44—C44—C45	116.7 (3)
H5A—C5—H5B	108.0	O44—C44—C43	124.7 (3)
N1—C6—C5	110.9 (3)	C45—C44—C43	118.6 (3)
N1—C6—H6A	109.5	C46—C45—C44	121.1 (3)
C5—C6—H6A	109.5	C46—C45—H45	119.5
N1—C6—H6B	109.5	C44—C45—H45	119.5
C5—C6—H6B	109.5	C45—C46—C41	121.6 (3)
H6A—C6—H6B	108.0	C45—C46—H46	119.2
O17—C17—N1	121.9 (3)	C41—C46—H46	119.2
O17—C17—C11	119.3 (3)	C44—O44—C441	117.8 (3)
N1—C17—C11	118.7 (2)	O44—C441—H41A	109.5
C12—C11—C16	117.0 (3)	O44—C441—H41B	109.5
C12—C11—C17	121.1 (3)	H41A—C441—H41B	109.5
C16—C11—C17	121.4 (3)	O44—C441—H41C	109.5
F12—C12—C13	118.6 (3)	H41A—C441—H41C	109.5
F12—C12—C11	117.9 (3)	H41B—C441—H41C	109.5

C17—N1—C2—C3	116.2 (3)	C11—C12—C13—C14	1.0 (5)
C6—N1—C2—C3	−55.9 (4)	C12—C13—C14—C15	0.1 (5)
N1—C2—C3—N4	56.2 (4)	C13—C14—C15—C16	−1.0 (5)
C2—C3—N4—C41	169.4 (3)	C14—C15—C16—C11	0.9 (5)
C2—C3—N4—C5	−56.4 (4)	C12—C11—C16—C15	0.1 (4)
C41—N4—C5—C6	−170.6 (3)	C17—C11—C16—C15	−172.2 (3)
C3—N4—C5—C6	55.5 (4)	C5—N4—C41—C42	−176.2 (3)
C17—N1—C6—C5	−115.8 (4)	C3—N4—C41—C42	−44.8 (4)
C2—N1—C6—C5	55.9 (4)	C5—N4—C41—C46	5.7 (4)
N4—C5—C6—N1	−55.4 (4)	C3—N4—C41—C46	137.2 (3)
C6—N1—C17—O17	176.7 (3)	C46—C41—C42—C43	−0.3 (5)
C2—N1—C17—O17	5.7 (5)	N4—C41—C42—C43	−178.4 (3)
C6—N1—C17—C11	−5.5 (5)	C41—C42—C43—C44	0.5 (5)
C2—N1—C17—C11	−176.4 (3)	C42—C43—C44—O44	179.9 (3)
O17—C17—C11—C12	−81.2 (4)	C42—C43—C44—C45	0.6 (5)
N1—C17—C11—C12	100.9 (4)	O44—C44—C45—C46	178.8 (3)
O17—C17—C11—C16	90.8 (4)	C43—C44—C45—C46	−1.8 (5)
N1—C17—C11—C16	−87.2 (4)	C44—C45—C46—C41	2.1 (5)
C16—C11—C12—F12	179.6 (3)	C42—C41—C46—C45	−1.0 (5)
C17—C11—C12—F12	−8.1 (4)	N4—C41—C46—C45	177.1 (3)
C16—C11—C12—C13	−1.0 (5)	C45—C44—O44—C441	−175.1 (3)
C17—C11—C12—C13	171.2 (3)	C43—C44—O44—C441	5.5 (5)
F12—C12—C13—C14	−179.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O17ⁱ	0.97	2.50	3.387 (4)	152
C16—H16···O17ⁱⁱ	0.93	2.43	3.340 (5)	167

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

1-(2-Chlorobenzoyl)-4-(4-methoxyphenyl)piperazine (III) top

Crystal data top

C₁₈H₁₉ClN₂O₂	D_x = 1.322 Mg m⁻³
M_r = 330.80	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3642 reflections
a = 13.0320 (11) Å	θ = 2.6–27.8°
b = 13.2470 (13) Å	µ = 0.24 mm⁻¹
c = 19.258 (2) Å	T = 293 K
V = 3324.6 (6) Å³	Block, yellow
Z = 8	0.50 × 0.40 × 0.38 mm
F(000) = 1392

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	3642 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2407 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.8°, θ_min = 2.6°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −16→17
T_min = 0.862, T_max = 0.912	k = −16→17
13862 measured reflections	l = −12→25

Refinement top

Refinement on F²	26 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0484P)² + 1.4776P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3642 reflections	Δρ_max = 0.23 e Å⁻³
243 parameters	Δρ_min = −0.45 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.68382 (12)	0.28146 (13)	0.41176 (9)	0.0526 (4)
C2	0.58246 (16)	0.25886 (18)	0.43972 (13)	0.0642 (6)
H2A	0.5883	0.2424	0.4886	0.077*
H2B	0.5542	0.2006	0.4160	0.077*
C3	0.51117 (15)	0.34757 (17)	0.43087 (11)	0.0560 (6)
H3A	0.4428	0.3292	0.4463	0.067*
H3B	0.5349	0.4035	0.4592	0.067*
N4	0.50753 (11)	0.37844 (12)	0.35839 (8)	0.0447 (4)
C5	0.60999 (14)	0.40544 (16)	0.33358 (10)	0.0488 (5)
H5A	0.6361	0.4619	0.3604	0.059*
H5B	0.6061	0.4261	0.2853	0.059*
C6	0.68172 (15)	0.31756 (17)	0.34028 (11)	0.0539 (5)
H6A	0.6595	0.2635	0.3098	0.065*
H6B	0.7502	0.3378	0.3263	0.065*
C17	0.76756 (19)	0.26749 (18)	0.45027 (14)	0.0534 (6)	0.942 (2)
O17	0.76535 (19)	0.2354 (2)	0.50989 (12)	0.0936 (9)	0.942 (2)
C11	0.86962 (18)	0.29271 (17)	0.41824 (14)	0.0470 (5)	0.942 (2)
C12	0.9128 (2)	0.38720 (18)	0.42449 (16)	0.0535 (6)	0.942 (2)
Cl12	0.84046 (7)	0.48603 (5)	0.46012 (3)	0.0799 (3)	0.942 (2)
C13	1.0112 (3)	0.4066 (3)	0.4020 (2)	0.0726 (8)	0.942 (2)
H13	1.0393	0.4707	0.4073	0.087*	0.942 (2)
C14	1.0670 (3)	0.3318 (4)	0.3718 (3)	0.0882 (11)	0.942 (2)
H14	1.1339	0.3446	0.3573	0.106*	0.942 (2)
C15	1.0253 (3)	0.2376 (3)	0.36267 (19)	0.0843 (11)	0.942 (2)
H15	1.0628	0.1871	0.3407	0.101*	0.942 (2)
C16	0.9270 (2)	0.2185 (2)	0.38639 (15)	0.0670 (7)	0.942 (2)
H16	0.8991	0.1544	0.3808	0.080*	0.942 (2)
C37	0.773 (2)	0.2975 (19)	0.454 (2)	0.0534 (6)	0.058 (2)
O37	0.777 (3)	0.285 (4)	0.517 (2)	0.0936 (9)	0.058 (2)
C31	0.871 (3)	0.3261 (14)	0.418 (2)	0.0470 (5)	0.058 (2)
C32	0.935 (2)	0.2481 (15)	0.3977 (18)	0.0670 (7)	0.058 (2)
Cl32	0.8826 (19)	0.1267 (11)	0.4022 (13)	0.162 (10)	0.058 (2)
C33	1.035 (3)	0.264 (3)	0.379 (3)	0.0843 (11)	0.058 (2)
H33	1.0769	0.2102	0.3661	0.101*	0.058 (2)
C34	1.073 (3)	0.360 (3)	0.381 (5)	0.0882 (11)	0.058 (2)
H34	1.1407	0.3717	0.3675	0.106*	0.058 (2)
C35	1.013 (4)	0.439 (3)	0.403 (4)	0.0726 (8)	0.058 (2)
H35	1.0396	0.5039	0.4036	0.087*	0.058 (2)
C36	0.913 (3)	0.4206 (16)	0.424 (3)	0.0535 (6)	0.058 (2)
H36	0.8746	0.4729	0.4429	0.064*	0.058 (2)
C41	0.42740 (14)	0.44424 (14)	0.33779 (10)	0.0415 (4)
C42	0.35531 (15)	0.48382 (16)	0.38335 (11)	0.0523 (5)
H42	0.3599	0.4687	0.4304	0.063*
C43	0.27626 (15)	0.54574 (17)	0.35992 (11)	0.0547 (5)
H43	0.2290	0.5716	0.3914	0.066*
C44	0.26749 (14)	0.56901 (15)	0.29086 (10)	0.0469 (5)
C45	0.33768 (16)	0.52910 (16)	0.24458 (11)	0.0527 (5)
H45	0.3323	0.5440	0.1975	0.063*
C46	0.41523 (16)	0.46762 (16)	0.26773 (10)	0.0519 (5)
H46	0.4611	0.4407	0.2357	0.062*
O44	0.19396 (11)	0.62997 (12)	0.26191 (8)	0.0676 (5)
C441	0.1267 (2)	0.6808 (2)	0.30737 (15)	0.0838 (8)
H41A	0.0850	0.7271	0.2814	0.126*
H41B	0.1658	0.7173	0.3413	0.126*
H41C	0.0834	0.6325	0.3303	0.126*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0402 (9)	0.0602 (11)	0.0574 (10)	0.0018 (8)	−0.0043 (8)	0.0178 (9)
C2	0.0463 (12)	0.0702 (15)	0.0760 (15)	−0.0061 (11)	−0.0039 (11)	0.0334 (12)
C3	0.0438 (11)	0.0697 (14)	0.0546 (12)	−0.0020 (10)	0.0042 (9)	0.0198 (11)
N4	0.0396 (8)	0.0489 (9)	0.0455 (9)	0.0011 (7)	0.0009 (7)	0.0096 (7)
C5	0.0410 (10)	0.0582 (12)	0.0472 (11)	0.0023 (10)	0.0022 (8)	0.0129 (9)
C6	0.0442 (11)	0.0664 (14)	0.0510 (12)	0.0062 (10)	−0.0026 (9)	0.0051 (10)
C17	0.0481 (12)	0.0511 (14)	0.0610 (14)	0.0011 (12)	−0.0065 (10)	0.0135 (12)
O17	0.0598 (12)	0.147 (2)	0.0735 (12)	−0.0024 (16)	−0.0080 (9)	0.0564 (16)
C11	0.0435 (11)	0.0495 (13)	0.0482 (11)	0.0035 (12)	−0.0107 (9)	0.0073 (12)
C12	0.0615 (13)	0.0566 (15)	0.0424 (11)	−0.0085 (15)	−0.0129 (10)	0.0079 (13)
Cl12	0.1176 (7)	0.0594 (4)	0.0626 (4)	−0.0059 (4)	−0.0025 (4)	−0.0119 (3)
C13	0.0680 (16)	0.092 (2)	0.0575 (14)	−0.0303 (18)	−0.0207 (12)	0.024 (2)
C14	0.0466 (14)	0.143 (3)	0.075 (3)	0.000 (2)	−0.0060 (14)	0.041 (2)
C15	0.0634 (17)	0.113 (3)	0.076 (3)	0.0371 (19)	0.0043 (16)	0.0098 (19)
C16	0.0605 (15)	0.0611 (17)	0.0794 (18)	0.0121 (14)	−0.0092 (13)	−0.0010 (14)
C37	0.0481 (12)	0.0511 (14)	0.0610 (14)	0.0011 (12)	−0.0065 (10)	0.0135 (12)
O37	0.0598 (12)	0.147 (2)	0.0735 (12)	−0.0024 (16)	−0.0080 (9)	0.0564 (16)
C31	0.0435 (11)	0.0495 (13)	0.0482 (11)	0.0035 (12)	−0.0107 (9)	0.0073 (12)
C32	0.0605 (15)	0.0611 (17)	0.0794 (18)	0.0121 (14)	−0.0092 (13)	−0.0010 (14)
Cl32	0.22 (2)	0.072 (9)	0.19 (2)	0.000 (11)	−0.011 (17)	−0.030 (11)
C33	0.0634 (17)	0.113 (3)	0.076 (3)	0.0371 (19)	0.0043 (16)	0.0098 (19)
C34	0.0466 (14)	0.143 (3)	0.075 (3)	0.000 (2)	−0.0060 (14)	0.041 (2)
C35	0.0680 (16)	0.092 (2)	0.0575 (14)	−0.0303 (18)	−0.0207 (12)	0.024 (2)
C36	0.0615 (13)	0.0566 (15)	0.0424 (11)	−0.0085 (15)	−0.0129 (10)	0.0079 (13)
C41	0.0383 (9)	0.0408 (10)	0.0454 (10)	−0.0011 (8)	0.0000 (8)	0.0008 (8)
C42	0.0483 (11)	0.0649 (13)	0.0436 (11)	0.0045 (10)	0.0057 (9)	0.0076 (10)
C43	0.0422 (11)	0.0633 (14)	0.0586 (13)	0.0070 (10)	0.0122 (9)	0.0011 (10)
C44	0.0411 (10)	0.0433 (11)	0.0563 (12)	0.0035 (9)	−0.0017 (9)	−0.0012 (9)
C45	0.0588 (12)	0.0577 (12)	0.0417 (10)	0.0126 (11)	−0.0039 (9)	−0.0020 (9)
C46	0.0523 (12)	0.0603 (13)	0.0431 (11)	0.0163 (10)	0.0025 (9)	−0.0064 (9)
O44	0.0592 (9)	0.0722 (10)	0.0715 (10)	0.0277 (8)	−0.0029 (8)	0.0013 (8)
C441	0.0720 (16)	0.0823 (18)	0.097 (2)	0.0365 (15)	0.0069 (15)	0.0016 (16)

Geometric parameters (Å, º) top

N1—C17	1.332 (3)	C16—H16	0.9300
N1—C37	1.43 (4)	C37—O37	1.222 (10)
N1—C2	1.458 (3)	C37—C31	1.508 (9)
N1—C6	1.458 (3)	C31—C36	1.372 (10)
C2—C3	1.508 (3)	C31—C32	1.381 (9)
C2—H2A	0.9700	C32—C33	1.371 (10)
C2—H2B	0.9700	C32—Cl32	1.749 (10)
C3—N4	1.455 (2)	C33—C34	1.362 (10)
C3—H3A	0.9700	C33—H33	0.9300
C3—H3B	0.9700	C34—C35	1.372 (11)
N4—C41	1.417 (2)	C34—H34	0.9300
N4—C5	1.463 (2)	C35—C36	1.385 (10)
C5—C6	1.499 (3)	C35—H35	0.9300
C5—H5A	0.9700	C36—H36	0.9300
C5—H5B	0.9700	C41—C42	1.388 (3)
C6—H6A	0.9700	C41—C46	1.393 (3)
C6—H6B	0.9700	C42—C43	1.392 (3)
C17—O17	1.225 (3)	C42—H42	0.9300
C17—C11	1.504 (3)	C43—C44	1.370 (3)
C11—C12	1.378 (3)	C43—H43	0.9300
C11—C16	1.379 (3)	C44—O44	1.372 (2)
C12—C13	1.378 (4)	C44—C45	1.382 (3)
C12—Cl12	1.753 (3)	C45—C46	1.372 (3)
C13—C14	1.359 (4)	C45—H45	0.9300
C13—H13	0.9300	C46—H46	0.9300
C14—C15	1.373 (5)	O44—C441	1.410 (3)
C14—H14	0.9300	C441—H41A	0.9600
C15—C16	1.384 (4)	C441—H41B	0.9600
C15—H15	0.9300	C441—H41C	0.9600

C17—N1—C2	120.55 (18)	C11—C16—C15	121.2 (3)
C37—N1—C2	123.8 (13)	C11—C16—H16	119.4
C17—N1—C6	125.92 (18)	C15—C16—H16	119.4
C37—N1—C6	120.1 (13)	O37—C37—N1	125 (3)
C2—N1—C6	113.53 (16)	O37—C37—C31	116.5 (17)
N1—C2—C3	110.89 (17)	N1—C37—C31	118 (3)
N1—C2—H2A	109.5	C36—C31—C32	117.9 (11)
C3—C2—H2A	109.5	C36—C31—C37	122.0 (14)
N1—C2—H2B	109.5	C32—C31—C37	116.9 (12)
C3—C2—H2B	109.5	C33—C32—C31	122.1 (11)
H2A—C2—H2B	108.0	C33—C32—Cl32	121.7 (12)
N4—C3—C2	110.33 (18)	C31—C32—Cl32	116.1 (11)
N4—C3—H3A	109.6	C34—C33—C32	118.9 (13)
C2—C3—H3A	109.6	C34—C33—H33	120.6
N4—C3—H3B	109.6	C32—C33—H33	120.6
C2—C3—H3B	109.6	C33—C34—C35	120.7 (13)
H3A—C3—H3B	108.1	C33—C34—H34	119.7
C41—N4—C3	117.74 (15)	C35—C34—H34	119.7
C41—N4—C5	115.52 (14)	C34—C35—C36	119.6 (13)
C3—N4—C5	110.63 (15)	C34—C35—H35	120.2
N4—C5—C6	110.57 (17)	C36—C35—H35	120.2
N4—C5—H5A	109.5	C31—C36—C35	120.5 (13)
C6—C5—H5A	109.5	C31—C36—H36	119.8
N4—C5—H5B	109.5	C35—C36—H36	119.8
C6—C5—H5B	109.5	C42—C41—C46	116.81 (17)
H5A—C5—H5B	108.1	C42—C41—N4	123.64 (17)
N1—C6—C5	110.36 (17)	C46—C41—N4	119.46 (16)
N1—C6—H6A	109.6	C41—C42—C43	121.23 (19)
C5—C6—H6A	109.6	C41—C42—H42	119.4
N1—C6—H6B	109.6	C43—C42—H42	119.4
C5—C6—H6B	109.6	C44—C43—C42	120.60 (18)
H6A—C6—H6B	108.1	C44—C43—H43	119.7
O17—C17—N1	123.4 (2)	C42—C43—H43	119.7
O17—C17—C11	118.9 (2)	C43—C44—O44	125.84 (18)
N1—C17—C11	117.7 (2)	C43—C44—C45	118.99 (18)
C12—C11—C16	117.7 (2)	O44—C44—C45	115.18 (18)
C12—C11—C17	121.8 (2)	C46—C45—C44	120.32 (19)
C16—C11—C17	120.2 (2)	C46—C45—H45	119.8
C13—C12—C11	121.5 (3)	C44—C45—H45	119.8
C13—C12—Cl12	119.0 (2)	C45—C46—C41	122.02 (18)
C11—C12—Cl12	119.53 (19)	C45—C46—H46	119.0
C14—C13—C12	119.8 (3)	C41—C46—H46	119.0
C14—C13—H13	120.1	C44—O44—C441	117.58 (18)
C12—C13—H13	120.1	O44—C441—H41A	109.5
C13—C14—C15	120.4 (3)	O44—C441—H41B	109.5
C13—C14—H14	119.8	H41A—C441—H41B	109.5
C15—C14—H14	119.8	O44—C441—H41C	109.5
C14—C15—C16	119.4 (3)	H41A—C441—H41C	109.5
C14—C15—H15	120.3	H41B—C441—H41C	109.5
C16—C15—H15	120.3

C17—N1—C2—C3	127.9 (2)	C6—N1—C37—O37	168 (2)
C37—N1—C2—C3	108.7 (12)	C17—N1—C37—C31	99 (5)
C6—N1—C2—C3	−52.9 (3)	C2—N1—C37—C31	−176.6 (10)
N1—C2—C3—N4	54.7 (3)	C6—N1—C37—C31	−16 (2)
C2—C3—N4—C41	165.51 (16)	O37—C37—C31—C36	−73 (4)
C2—C3—N4—C5	−58.6 (2)	N1—C37—C31—C36	110 (3)
C41—N4—C5—C6	−163.56 (16)	O37—C37—C31—C32	86 (3)
C3—N4—C5—C6	59.5 (2)	N1—C37—C31—C32	−90 (3)
C17—N1—C6—C5	−127.5 (2)	C36—C31—C32—C33	−5 (2)
C37—N1—C6—C5	−109.0 (12)	C37—C31—C32—C33	−165 (3)
C2—N1—C6—C5	53.4 (2)	C36—C31—C32—Cl32	171 (3)
N4—C5—C6—N1	−55.8 (2)	C37—C31—C32—Cl32	11 (4)
C37—N1—C17—O17	107 (5)	C31—C32—C33—C34	0 (3)
C2—N1—C17—O17	0.2 (4)	Cl32—C32—C33—C34	−176 (4)
C6—N1—C17—O17	−178.8 (2)	C32—C33—C34—C35	2 (6)
C37—N1—C17—C11	−73 (5)	C33—C34—C35—C36	1 (8)
C2—N1—C17—C11	−179.8 (2)	C32—C31—C36—C35	8 (5)
C6—N1—C17—C11	1.2 (3)	C37—C31—C36—C35	167 (5)
O17—C17—C11—C12	−89.1 (3)	C34—C35—C36—C31	−6 (8)
N1—C17—C11—C12	90.9 (3)	C3—N4—C41—C42	2.8 (3)
O17—C17—C11—C16	85.4 (3)	C5—N4—C41—C42	−131.0 (2)
N1—C17—C11—C16	−94.6 (3)	C3—N4—C41—C46	−173.72 (19)
C16—C11—C12—C13	−2.1 (4)	C5—N4—C41—C46	52.5 (2)
C17—C11—C12—C13	172.5 (3)	C46—C41—C42—C43	−1.4 (3)
C16—C11—C12—Cl12	176.4 (2)	N4—C41—C42—C43	−178.03 (18)
C17—C11—C12—Cl12	−8.9 (3)	C41—C42—C43—C44	0.2 (3)
C11—C12—C13—C14	1.0 (5)	C42—C43—C44—O44	−179.13 (19)
Cl12—C12—C13—C14	−177.5 (3)	C42—C43—C44—C45	0.7 (3)
C12—C13—C14—C15	1.1 (5)	C43—C44—C45—C46	−0.4 (3)
C13—C14—C15—C16	−2.1 (5)	O44—C44—C45—C46	179.50 (19)
C12—C11—C16—C15	1.2 (4)	C44—C45—C46—C41	−0.9 (3)
C17—C11—C16—C15	−173.6 (3)	C42—C41—C46—C45	1.8 (3)
C14—C15—C16—C11	0.9 (4)	N4—C41—C46—C45	178.55 (19)
C17—N1—C37—O37	−76 (5)	C43—C44—O44—C441	6.1 (3)
C2—N1—C37—O37	7 (3)	C45—C44—O44—C441	−173.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O17ⁱ	0.97	2.61	3.574 (3)	175
C2—H2A···Cg1ⁱ	0.97	2.84	3.648 (3)	142
C15—H15···Cg2ⁱⁱ	0.93	2.72	3.610 (4)	161

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

1-(2-Bromoobenzoyl)-4-(4-methoxyphenyl)piperazine (IV) top

Crystal data top

C₁₈H₁₉BrN₂O₂	D_x = 1.481 Mg m⁻³
M_r = 375.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 10112 reflections
a = 12.9119 (14) Å	θ = 2.2–30.6°
b = 13.3664 (16) Å	µ = 2.45 mm⁻¹
c = 19.5019 (19) Å	T = 293 K
V = 3365.7 (6) Å³	Block, colourless
Z = 8	0.22 × 0.21 × 0.18 mm
F(000) = 1536

Data collection top

Bruker D8 Quest diffractometer	4262 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3135 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
φ and ω scans	θ_max = 28.6°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2015	h = −17→17
T_min = 0.538, T_max = 0.643	k = −17→17
47663 measured reflections	l = −25→26

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.131	w = 1/[σ²(F_o²) + (0.0626P)² + 2.0275P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
4262 reflections	Δρ_max = 0.54 e Å⁻³
209 parameters	Δρ_min = −0.64 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.68078 (15)	0.28092 (16)	0.41388 (11)	0.0487 (5)
C2	0.57868 (19)	0.2622 (2)	0.44328 (15)	0.0590 (7)
H2A	0.5856	0.2493	0.4920	0.071*
H2B	0.5487	0.2032	0.4221	0.071*
C3	0.50766 (18)	0.3504 (2)	0.43240 (12)	0.0519 (6)
H3A	0.4388	0.3340	0.4487	0.062*
H3B	0.5328	0.4072	0.4584	0.062*
N4	0.50316 (13)	0.37615 (15)	0.35983 (9)	0.0419 (4)
C5	0.60654 (17)	0.4002 (2)	0.33390 (12)	0.0473 (5)
H5A	0.6341	0.4572	0.3587	0.057*
H5B	0.6021	0.4180	0.2858	0.057*
C6	0.67798 (19)	0.3122 (2)	0.34234 (12)	0.0521 (6)
H6A	0.6541	0.2572	0.3140	0.062*
H6B	0.7471	0.3304	0.3274	0.062*
C17	0.76628 (19)	0.2666 (2)	0.45102 (13)	0.0512 (6)
O17	0.76512 (15)	0.2365 (2)	0.50994 (12)	0.0946 (9)
C11	0.86917 (17)	0.28780 (19)	0.41712 (12)	0.0454 (5)
C12	0.91561 (19)	0.3799 (2)	0.42084 (11)	0.0497 (6)
Br12	0.84357 (3)	0.49042 (2)	0.45966 (2)	0.07101 (15)
C13	1.0151 (2)	0.3952 (3)	0.39598 (13)	0.0650 (8)
H13	1.0461	0.4579	0.3993	0.078*
C14	1.0668 (2)	0.3174 (4)	0.36663 (16)	0.0789 (11)
H14	1.1339	0.3267	0.3504	0.095*
C15	1.0212 (3)	0.2262 (3)	0.36096 (17)	0.0798 (10)
H15	1.0563	0.1741	0.3396	0.096*
C16	0.9229 (2)	0.2107 (2)	0.38671 (15)	0.0650 (7)
H16	0.8928	0.1477	0.3835	0.078*
C41	0.42268 (16)	0.44128 (16)	0.33883 (11)	0.0390 (5)
C42	0.35098 (18)	0.4829 (2)	0.38304 (13)	0.0491 (6)
H42	0.3559	0.4695	0.4297	0.059*
C43	0.27162 (18)	0.5446 (2)	0.35948 (13)	0.0527 (6)
H43	0.2243	0.5715	0.3903	0.063*
C44	0.26318 (17)	0.56563 (19)	0.29071 (11)	0.0450 (5)
C45	0.3328 (2)	0.5236 (2)	0.24572 (13)	0.0527 (6)
H45	0.3271	0.5368	0.1990	0.063*
C46	0.41060 (19)	0.4627 (2)	0.26907 (12)	0.0498 (6)
H46	0.4565	0.4348	0.2377	0.060*
O44	0.18982 (15)	0.62631 (15)	0.26166 (10)	0.0658 (5)
C441	0.1221 (3)	0.6779 (3)	0.30621 (19)	0.0798 (10)
H41A	0.0799	0.7232	0.2801	0.120*
H41B	0.1618	0.7148	0.3392	0.120*
H41C	0.0785	0.6307	0.3295	0.120*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0384 (10)	0.0551 (12)	0.0527 (11)	0.0020 (9)	−0.0042 (8)	0.0126 (9)
C2	0.0415 (13)	0.0652 (17)	0.0704 (16)	−0.0037 (12)	−0.0026 (12)	0.0291 (14)
C3	0.0411 (12)	0.0667 (16)	0.0478 (12)	0.0014 (12)	0.0032 (10)	0.0187 (12)
N4	0.0346 (9)	0.0492 (11)	0.0420 (9)	0.0031 (8)	−0.0005 (7)	0.0078 (8)
C5	0.0384 (11)	0.0606 (15)	0.0429 (11)	0.0028 (11)	0.0015 (9)	0.0121 (11)
C6	0.0410 (12)	0.0690 (17)	0.0462 (12)	0.0091 (12)	−0.0034 (10)	0.0019 (12)
C17	0.0444 (13)	0.0526 (14)	0.0566 (14)	0.0029 (11)	−0.0065 (10)	0.0121 (11)
O17	0.0535 (11)	0.158 (3)	0.0728 (14)	0.0043 (14)	−0.0081 (10)	0.0598 (15)
C11	0.0395 (11)	0.0524 (14)	0.0442 (12)	0.0042 (10)	−0.0099 (9)	0.0036 (10)
C12	0.0519 (13)	0.0615 (15)	0.0357 (11)	−0.0014 (12)	−0.0091 (9)	0.0028 (10)
Br12	0.1004 (3)	0.0570 (2)	0.0557 (2)	−0.00293 (15)	−0.00205 (15)	−0.01036 (12)
C13	0.0542 (15)	0.091 (2)	0.0494 (14)	−0.0214 (16)	−0.0125 (12)	0.0166 (14)
C14	0.0434 (15)	0.134 (3)	0.0594 (17)	0.0089 (19)	−0.0024 (13)	0.025 (2)
C15	0.0631 (19)	0.107 (3)	0.070 (2)	0.034 (2)	−0.0001 (15)	0.0001 (19)
C16	0.0592 (16)	0.0640 (17)	0.0720 (18)	0.0157 (14)	−0.0086 (13)	−0.0041 (14)
C41	0.0361 (10)	0.0400 (11)	0.0409 (11)	−0.0010 (9)	−0.0020 (8)	0.0017 (9)
C42	0.0418 (12)	0.0658 (16)	0.0398 (12)	0.0062 (11)	0.0061 (9)	0.0092 (11)
C43	0.0413 (13)	0.0646 (16)	0.0520 (13)	0.0094 (12)	0.0085 (10)	0.0035 (12)
C44	0.0380 (11)	0.0454 (13)	0.0514 (12)	0.0051 (10)	−0.0051 (9)	−0.0012 (10)
C45	0.0575 (15)	0.0621 (15)	0.0386 (11)	0.0137 (12)	−0.0058 (10)	−0.0035 (11)
C46	0.0512 (13)	0.0608 (15)	0.0373 (11)	0.0171 (12)	−0.0018 (10)	−0.0071 (10)
O44	0.0611 (11)	0.0735 (13)	0.0629 (11)	0.0303 (10)	−0.0045 (9)	0.0034 (10)
C441	0.0693 (19)	0.081 (2)	0.089 (2)	0.0359 (18)	0.0017 (17)	−0.0007 (18)

Geometric parameters (Å, º) top

N1—C17	1.334 (3)	C13—C14	1.363 (5)
N1—C6	1.457 (3)	C13—H13	0.9300
N1—C2	1.459 (3)	C14—C15	1.358 (5)
C2—C3	1.508 (4)	C14—H14	0.9300
C2—H2A	0.9700	C15—C16	1.381 (5)
C2—H2B	0.9700	C15—H15	0.9300
C3—N4	1.458 (3)	C16—H16	0.9300
C3—H3A	0.9700	C41—C42	1.382 (3)
C3—H3B	0.9700	C41—C46	1.399 (3)
N4—C41	1.416 (3)	C42—C43	1.393 (3)
N4—C5	1.463 (3)	C42—H42	0.9300
C5—C6	1.504 (3)	C43—C44	1.375 (3)
C5—H5A	0.9700	C43—H43	0.9300
C5—H5B	0.9700	C44—O44	1.370 (3)
C6—H6A	0.9700	C44—C45	1.376 (3)
C6—H6B	0.9700	C45—C46	1.371 (4)
C17—O17	1.218 (3)	C45—H45	0.9300
C17—C11	1.511 (3)	C46—H46	0.9300
C11—C12	1.371 (4)	O44—C441	1.413 (4)
C11—C16	1.377 (4)	C441—H41A	0.9600
C12—C13	1.389 (4)	C441—H41B	0.9600
C12—Br12	1.903 (3)	C441—H41C	0.9600

C17—N1—C6	125.6 (2)	C13—C12—Br12	118.4 (2)
C17—N1—C2	120.6 (2)	C14—C13—C12	119.2 (3)
C6—N1—C2	113.77 (19)	C14—C13—H13	120.4
N1—C2—C3	111.1 (2)	C12—C13—H13	120.4
N1—C2—H2A	109.4	C15—C14—C13	120.4 (3)
C3—C2—H2A	109.4	C15—C14—H14	119.8
N1—C2—H2B	109.4	C13—C14—H14	119.8
C3—C2—H2B	109.4	C14—C15—C16	120.3 (3)
H2A—C2—H2B	108.0	C14—C15—H15	119.9
N4—C3—C2	110.2 (2)	C16—C15—H15	119.9
N4—C3—H3A	109.6	C11—C16—C15	120.5 (3)
C2—C3—H3A	109.6	C11—C16—H16	119.8
N4—C3—H3B	109.6	C15—C16—H16	119.8
C2—C3—H3B	109.6	C42—C41—C46	116.7 (2)
H3A—C3—H3B	108.1	C42—C41—N4	124.0 (2)
C41—N4—C3	117.09 (18)	C46—C41—N4	119.25 (19)
C41—N4—C5	115.76 (18)	C41—C42—C43	121.7 (2)
C3—N4—C5	110.56 (17)	C41—C42—H42	119.2
N4—C5—C6	110.5 (2)	C43—C42—H42	119.2
N4—C5—H5A	109.6	C44—C43—C42	120.1 (2)
C6—C5—H5A	109.6	C44—C43—H43	120.0
N4—C5—H5B	109.6	C42—C43—H43	120.0
C6—C5—H5B	109.6	O44—C44—C43	125.4 (2)
H5A—C5—H5B	108.1	O44—C44—C45	115.4 (2)
N1—C6—C5	110.1 (2)	C43—C44—C45	119.1 (2)
N1—C6—H6A	109.6	C46—C45—C44	120.6 (2)
C5—C6—H6A	109.6	C46—C45—H45	119.7
N1—C6—H6B	109.6	C44—C45—H45	119.7
C5—C6—H6B	109.6	C45—C46—C41	121.7 (2)
H6A—C6—H6B	108.1	C45—C46—H46	119.1
O17—C17—N1	123.3 (2)	C41—C46—H46	119.1
O17—C17—C11	119.1 (2)	C44—O44—C441	117.6 (2)
N1—C17—C11	117.6 (2)	O44—C441—H41A	109.5
C12—C11—C16	118.3 (2)	O44—C441—H41B	109.5
C12—C11—C17	122.0 (2)	H41A—C441—H41B	109.5
C16—C11—C17	119.4 (2)	O44—C441—H41C	109.5
C11—C12—C13	121.3 (3)	H41A—C441—H41C	109.5
C11—C12—Br12	120.29 (19)	H41B—C441—H41C	109.5

C17—N1—C2—C3	129.3 (3)	Br12—C12—C13—C14	−178.5 (2)
C6—N1—C2—C3	−52.6 (3)	C12—C13—C14—C15	0.8 (4)
N1—C2—C3—N4	54.3 (3)	C13—C14—C15—C16	−1.9 (5)
C2—C3—N4—C41	165.8 (2)	C12—C11—C16—C15	0.2 (4)
C2—C3—N4—C5	−58.7 (3)	C17—C11—C16—C15	−174.1 (3)
C41—N4—C5—C6	−163.87 (19)	C14—C15—C16—C11	1.4 (5)
C3—N4—C5—C6	60.0 (3)	C3—N4—C41—C42	1.7 (3)
C17—N1—C6—C5	−128.8 (3)	C5—N4—C41—C42	−131.6 (2)
C2—N1—C6—C5	53.1 (3)	C3—N4—C41—C46	−175.5 (2)
N4—C5—C6—N1	−56.0 (3)	C5—N4—C41—C46	51.3 (3)
C6—N1—C17—O17	−176.9 (3)	C46—C41—C42—C43	−1.1 (4)
C2—N1—C17—O17	1.1 (4)	N4—C41—C42—C43	−178.3 (2)
C6—N1—C17—C11	2.2 (4)	C41—C42—C43—C44	−0.2 (4)
C2—N1—C17—C11	−179.9 (2)	C42—C43—C44—O44	−178.8 (2)
O17—C17—C11—C12	−89.6 (3)	C42—C43—C44—C45	1.2 (4)
N1—C17—C11—C12	91.3 (3)	O44—C44—C45—C46	179.1 (3)
O17—C17—C11—C16	84.4 (4)	C43—C44—C45—C46	−0.9 (4)
N1—C17—C11—C16	−94.7 (3)	C44—C45—C46—C41	−0.4 (4)
C16—C11—C12—C13	−1.3 (4)	C42—C41—C46—C45	1.4 (4)
C17—C11—C12—C13	172.8 (2)	N4—C41—C46—C45	178.7 (2)
C16—C11—C12—Br12	178.01 (19)	C43—C44—O44—C441	5.3 (4)
C17—C11—C12—Br12	−7.9 (3)	C45—C44—O44—C441	−174.7 (3)
C11—C12—C13—C14	0.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O17ⁱ	0.97	2.56	3.524 (3)	171
C2—H2A···Cg1ⁱ	0.97	2.82	3.630 (3)	142
C15—H15···Cg2ⁱⁱ	0.93	2.68	3.579 (4)	164

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

1-(2-Iodobenzoyl)-4-(4-methoxyphenyl)piperazine (V) top

Crystal data top

C₁₈H₁₉IN₂O₂	D_x = 1.602 Mg m⁻³
M_r = 422.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3838 reflections
a = 12.7671 (13) Å	θ = 2.6–27.7°
b = 13.5429 (12) Å	µ = 1.84 mm⁻¹
c = 20.2542 (16) Å	T = 293 K
V = 3502.0 (5) Å³	Block, orange
Z = 8	0.48 × 0.42 × 0.38 mm
F(000) = 1680

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	3838 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3062 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.7°, θ_min = 2.6°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −16→9
T_min = 0.408, T_max = 0.497	k = −17→12
14215 measured reflections	l = −25→26

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.068	H-atom parameters constrained
wR(F²) = 0.146	w = 1/[σ²(F_o²) + 37.1584P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max < 0.001
3838 reflections	Δρ_max = 1.27 e Å⁻³
209 parameters	Δρ_min = −2.19 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.6767 (5)	0.2532 (5)	0.4083 (3)	0.0444 (15)
C2	0.5718 (6)	0.2371 (7)	0.4337 (5)	0.061 (3)
H2A	0.5755	0.2250	0.4808	0.073*
H2B	0.5421	0.1789	0.4130	0.073*
C3	0.5017 (6)	0.3231 (7)	0.4213 (4)	0.052 (2)
H3A	0.4312	0.3075	0.4358	0.062*
H3B	0.5261	0.3796	0.4465	0.062*
N4	0.5006 (4)	0.3478 (4)	0.3506 (3)	0.0390 (14)
C5	0.6074 (5)	0.3718 (6)	0.3295 (4)	0.0445 (18)
H5A	0.6329	0.4278	0.3545	0.053*
H5B	0.6070	0.3899	0.2831	0.053*
C6	0.6796 (6)	0.2846 (6)	0.3397 (4)	0.0453 (18)
H6A	0.6582	0.2305	0.3114	0.054*
H6B	0.7506	0.3030	0.3279	0.054*
C17	0.7611 (6)	0.2329 (6)	0.4454 (4)	0.0467 (18)
O17	0.7546 (5)	0.1949 (5)	0.5001 (3)	0.0697 (19)
C11	0.8673 (5)	0.2557 (6)	0.4170 (4)	0.0386 (15)
C12	0.9137 (6)	0.3478 (5)	0.4227 (3)	0.0397 (16)
I12	0.83463 (5)	0.46721 (5)	0.46533 (3)	0.0580 (2)
C13	1.0151 (6)	0.3627 (6)	0.4001 (4)	0.0489 (19)
H13	1.0461	0.4246	0.4041	0.059*
C14	1.0693 (7)	0.2870 (8)	0.3723 (5)	0.064 (3)
H14	1.1371	0.2976	0.3571	0.077*
C15	1.0243 (8)	0.1942 (9)	0.3665 (5)	0.075 (3)
H15	1.0614	0.1423	0.3476	0.090*
C16	0.9247 (7)	0.1806 (7)	0.3889 (5)	0.063 (2)
H16	0.8945	0.1184	0.3851	0.076*
C41	0.4211 (5)	0.4122 (5)	0.3293 (3)	0.0362 (15)
C42	0.3441 (6)	0.4490 (6)	0.3699 (4)	0.0471 (19)
H42	0.3446	0.4326	0.4145	0.057*
C43	0.2655 (6)	0.5101 (6)	0.3459 (4)	0.0446 (18)
H43	0.2138	0.5329	0.3744	0.053*
C44	0.2632 (6)	0.5375 (6)	0.2800 (4)	0.0427 (16)
C45	0.3388 (6)	0.5001 (6)	0.2392 (3)	0.0473 (19)
H45	0.3379	0.5169	0.1947	0.057*
C46	0.4155 (6)	0.4388 (6)	0.2622 (4)	0.0471 (19)
H46	0.4651	0.4141	0.2329	0.056*
O44	0.1910 (5)	0.5988 (5)	0.2516 (3)	0.0615 (16)
C441	0.1209 (8)	0.6484 (8)	0.2934 (5)	0.078 (3)
H41A	0.0746	0.6886	0.2674	0.117*
H41B	0.1595	0.6896	0.3234	0.117*
H41C	0.0807	0.6011	0.3179	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.036 (3)	0.044 (3)	0.053 (4)	0.000 (3)	−0.004 (3)	0.022 (3)
C2	0.037 (4)	0.076 (6)	0.070 (6)	−0.001 (4)	−0.004 (4)	0.037 (5)
C3	0.037 (4)	0.071 (6)	0.048 (4)	−0.001 (4)	0.006 (3)	0.029 (4)
N4	0.030 (3)	0.045 (3)	0.042 (3)	0.000 (3)	0.000 (2)	0.013 (3)
C5	0.034 (4)	0.060 (5)	0.040 (4)	0.002 (3)	0.000 (3)	0.017 (4)
C6	0.037 (4)	0.055 (5)	0.044 (4)	0.005 (3)	−0.001 (3)	0.010 (4)
C17	0.037 (4)	0.046 (4)	0.057 (5)	−0.006 (3)	−0.009 (4)	0.012 (4)
O17	0.048 (3)	0.094 (5)	0.067 (4)	−0.001 (3)	−0.008 (3)	0.039 (4)
C11	0.034 (3)	0.041 (4)	0.041 (4)	0.000 (3)	−0.008 (3)	0.003 (3)
C12	0.041 (4)	0.042 (4)	0.036 (4)	0.003 (3)	−0.009 (3)	−0.001 (3)
I12	0.0702 (4)	0.0501 (3)	0.0538 (3)	0.0045 (3)	−0.0031 (3)	−0.0162 (3)
C13	0.047 (4)	0.056 (5)	0.044 (4)	−0.012 (4)	−0.007 (4)	−0.001 (4)
C14	0.036 (4)	0.098 (8)	0.059 (5)	0.005 (5)	0.003 (4)	0.001 (5)
C15	0.056 (6)	0.088 (8)	0.081 (7)	0.036 (6)	−0.007 (5)	−0.017 (6)
C16	0.055 (5)	0.057 (6)	0.077 (6)	0.004 (4)	−0.012 (5)	−0.008 (5)
C41	0.031 (3)	0.038 (4)	0.040 (4)	−0.002 (3)	−0.002 (3)	0.000 (3)
C42	0.041 (4)	0.061 (5)	0.039 (4)	0.003 (4)	0.008 (3)	0.015 (4)
C43	0.036 (4)	0.044 (4)	0.053 (4)	0.003 (3)	0.010 (3)	0.006 (3)
C44	0.036 (4)	0.043 (4)	0.049 (4)	0.003 (3)	−0.005 (3)	0.002 (3)
C45	0.059 (5)	0.054 (5)	0.030 (3)	0.012 (4)	−0.006 (3)	0.002 (3)
C46	0.048 (4)	0.055 (5)	0.038 (4)	0.017 (4)	0.002 (3)	−0.003 (3)
O44	0.057 (4)	0.066 (4)	0.062 (4)	0.026 (3)	−0.004 (3)	0.008 (3)
C441	0.062 (6)	0.084 (7)	0.089 (7)	0.032 (6)	−0.001 (6)	−0.001 (6)

Geometric parameters (Å, º) top

N1—C17	1.342 (9)	C13—C14	1.358 (12)
N1—C2	1.452 (9)	C13—H13	0.9300
N1—C6	1.453 (9)	C14—C15	1.387 (14)
C2—C3	1.490 (11)	C14—H14	0.9300
C2—H2A	0.9700	C15—C16	1.362 (13)
C2—H2B	0.9700	C15—H15	0.9300
C3—N4	1.471 (9)	C16—H16	0.9300
C3—H3A	0.9700	C41—C42	1.375 (10)
C3—H3B	0.9700	C41—C46	1.407 (10)
N4—C41	1.406 (9)	C42—C43	1.388 (10)
N4—C5	1.464 (8)	C42—H42	0.9300
C5—C6	1.512 (10)	C43—C44	1.386 (10)
C5—H5A	0.9700	C43—H43	0.9300
C5—H5B	0.9700	C44—O44	1.368 (9)
C6—H6A	0.9700	C44—C45	1.368 (10)
C6—H6B	0.9700	C45—C46	1.365 (10)
C17—O17	1.224 (9)	C45—H45	0.9300
C17—C11	1.505 (10)	C46—H46	0.9300
C11—C16	1.377 (11)	O44—C441	1.403 (10)
C11—C12	1.385 (10)	C441—H41A	0.9600
C12—C13	1.389 (10)	C441—H41B	0.9600
C12—I12	2.093 (7)	C441—H41C	0.9600

C17—N1—C2	120.8 (6)	C13—C12—I12	118.2 (6)
C17—N1—C6	125.0 (6)	C14—C13—C12	120.1 (8)
C2—N1—C6	114.0 (6)	C14—C13—H13	119.9
N1—C2—C3	112.1 (7)	C12—C13—H13	119.9
N1—C2—H2A	109.2	C13—C14—C15	120.5 (8)
C3—C2—H2A	109.2	C13—C14—H14	119.7
N1—C2—H2B	109.2	C15—C14—H14	119.7
C3—C2—H2B	109.2	C16—C15—C14	118.7 (9)
H2A—C2—H2B	107.9	C16—C15—H15	120.6
N4—C3—C2	110.3 (7)	C14—C15—H15	120.6
N4—C3—H3A	109.6	C15—C16—C11	122.3 (9)
C2—C3—H3A	109.6	C15—C16—H16	118.8
N4—C3—H3B	109.6	C11—C16—H16	118.8
C2—C3—H3B	109.6	C42—C41—N4	123.9 (6)
H3A—C3—H3B	108.1	C42—C41—C46	116.6 (7)
C41—N4—C5	116.5 (6)	N4—C41—C46	119.4 (6)
C41—N4—C3	116.5 (6)	C41—C42—C43	121.6 (7)
C5—N4—C3	109.0 (6)	C41—C42—H42	119.2
N4—C5—C6	110.8 (6)	C43—C42—H42	119.2
N4—C5—H5A	109.5	C44—C43—C42	120.8 (7)
C6—C5—H5A	109.5	C44—C43—H43	119.6
N4—C5—H5B	109.5	C42—C43—H43	119.6
C6—C5—H5B	109.5	O44—C44—C45	116.5 (7)
H5A—C5—H5B	108.1	O44—C44—C43	125.6 (7)
N1—C6—C5	110.1 (6)	C45—C44—C43	117.9 (7)
N1—C6—H6A	109.6	C46—C45—C44	121.7 (7)
C5—C6—H6A	109.6	C46—C45—H45	119.2
N1—C6—H6B	109.6	C44—C45—H45	119.2
C5—C6—H6B	109.6	C45—C46—C41	121.4 (7)
H6A—C6—H6B	108.2	C45—C46—H46	119.3
O17—C17—N1	122.6 (7)	C41—C46—H46	119.3
O17—C17—C11	119.6 (7)	C44—O44—C441	117.8 (7)
N1—C17—C11	117.8 (6)	O44—C441—H41A	109.5
C16—C11—C12	118.2 (7)	O44—C441—H41B	109.5
C16—C11—C17	119.1 (7)	H41A—C441—H41B	109.5
C12—C11—C17	122.6 (7)	O44—C441—H41C	109.5
C11—C12—C13	120.1 (7)	H41A—C441—H41C	109.5
C11—C12—I12	121.6 (5)	H41B—C441—H41C	109.5

C17—N1—C2—C3	133.1 (8)	I12—C12—C13—C14	179.8 (6)
C6—N1—C2—C3	−51.4 (11)	C12—C13—C14—C15	−0.3 (13)
N1—C2—C3—N4	54.7 (10)	C13—C14—C15—C16	0.3 (15)
C2—C3—N4—C41	166.2 (6)	C14—C15—C16—C11	0.1 (15)
C2—C3—N4—C5	−59.6 (9)	C12—C11—C16—C15	−0.4 (13)
C41—N4—C5—C6	−165.0 (6)	C17—C11—C16—C15	−175.2 (8)
C3—N4—C5—C6	60.7 (8)	C5—N4—C41—C42	−133.4 (8)
C17—N1—C6—C5	−133.5 (8)	C3—N4—C41—C42	−2.6 (10)
C2—N1—C6—C5	51.2 (9)	C5—N4—C41—C46	49.2 (10)
N4—C5—C6—N1	−56.1 (8)	C3—N4—C41—C46	−180.0 (7)
C2—N1—C17—O17	4.4 (13)	N4—C41—C42—C43	−178.1 (7)
C6—N1—C17—O17	−170.6 (8)	C46—C41—C42—C43	−0.6 (12)
C2—N1—C17—C11	−177.2 (8)	C41—C42—C43—C44	−1.1 (12)
C6—N1—C17—C11	7.8 (12)	C42—C43—C44—O44	−178.5 (7)
O17—C17—C11—C16	79.4 (11)	C42—C43—C44—C45	1.9 (12)
N1—C17—C11—C16	−99.0 (9)	O44—C44—C45—C46	179.5 (7)
O17—C17—C11—C12	−95.1 (10)	C43—C44—C45—C46	−0.9 (12)
N1—C17—C11—C12	86.5 (9)	C44—C45—C46—C41	−0.8 (13)
C16—C11—C12—C13	0.4 (11)	C42—C41—C46—C45	1.6 (12)
C17—C11—C12—C13	174.9 (7)	N4—C41—C46—C45	179.2 (7)
C16—C11—C12—I12	−179.4 (6)	C45—C44—O44—C441	−171.8 (8)
C17—C11—C12—I12	−4.9 (9)	C43—C44—O44—C441	8.6 (13)
C11—C12—C13—C14	0.0 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O17ⁱ	0.97	2.60	3.542 (10)	164
C2—H2A···Cg1ⁱ	0.97	2.87	3.719 (11)	147
C15—H15···Cg2ⁱⁱ	0.93	2.73	3.656 (12)	172

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

1-(2-Hydroxybenzoyl)-4-(4-methoxyphenyl)piperazine (VI) top

Crystal data top

C₁₈H₂₀N₂O₃	D_x = 1.329 Mg m⁻³
M_r = 312.36	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3474 reflections
a = 9.7265 (6) Å	θ = 2.7–27.9°
b = 12.9084 (9) Å	µ = 0.09 mm⁻¹
c = 24.861 (1) Å	T = 293 K
V = 3121.4 (3) Å³	Plate, yellow
Z = 8	0.50 × 0.40 × 0.16 mm
F(000) = 1328

Data collection top

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD	3474 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2492 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω scans	θ_max = 27.9°, θ_min = 2.7°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −12→5
T_min = 0.917, T_max = 0.986	k = −13→16
11981 measured reflections	l = −31→31

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.038P)² + 0.9467P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3474 reflections	Δρ_max = 0.16 e Å⁻³
212 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.65619 (12)	0.42451 (10)	0.35751 (5)	0.0368 (3)
C2	0.64088 (15)	0.36047 (14)	0.40542 (6)	0.0448 (4)
H2A	0.5498	0.3298	0.4057	0.054*
H2B	0.6498	0.4035	0.4372	0.054*
C3	0.74781 (15)	0.27547 (13)	0.40711 (6)	0.0432 (4)
H3A	0.7390	0.2367	0.4404	0.052*
H3B	0.7334	0.2281	0.3774	0.052*
N4	0.88519 (12)	0.32027 (10)	0.40359 (5)	0.0384 (3)
C5	0.89929 (15)	0.38044 (13)	0.35376 (6)	0.0429 (4)
H5A	0.8865	0.3351	0.3230	0.051*
H5B	0.9912	0.4094	0.3517	0.051*
C6	0.79474 (14)	0.46694 (12)	0.35178 (6)	0.0401 (4)
H6A	0.8126	0.5159	0.3806	0.048*
H6B	0.8023	0.5035	0.3178	0.048*
C17	0.54733 (14)	0.44756 (11)	0.32643 (5)	0.0324 (3)
O17	0.43132 (10)	0.41265 (8)	0.33693 (4)	0.0404 (3)
C11	0.56584 (14)	0.52022 (11)	0.28009 (6)	0.0329 (3)
C12	0.64738 (14)	0.49883 (11)	0.23528 (6)	0.0349 (3)
O12	0.71754 (12)	0.40749 (9)	0.23434 (4)	0.0461 (3)
H12	0.789 (2)	0.4130 (15)	0.2100 (8)	0.069*
C13	0.65334 (16)	0.56961 (12)	0.19321 (6)	0.0412 (4)
H13	0.7060	0.5548	0.1629	0.049*
C14	0.58174 (17)	0.66145 (13)	0.19606 (6)	0.0471 (4)
H14	0.5888	0.7092	0.1682	0.057*
C15	0.49942 (17)	0.68344 (13)	0.23996 (7)	0.0483 (4)
H15	0.4501	0.7451	0.2415	0.058*
C16	0.49147 (15)	0.61263 (12)	0.28139 (6)	0.0408 (4)
H16	0.4354	0.6268	0.3108	0.049*
C41	0.99766 (14)	0.25442 (12)	0.41654 (6)	0.0355 (3)
C42	0.98274 (16)	0.15034 (13)	0.42966 (6)	0.0419 (4)
H42	0.8956	0.1207	0.4291	0.050*
C43	1.09521 (16)	0.08983 (13)	0.44351 (6)	0.0450 (4)
H43	1.0825	0.0204	0.4523	0.054*
C44	1.22554 (15)	0.13157 (13)	0.44442 (6)	0.0407 (4)
C45	1.24231 (15)	0.23528 (13)	0.43236 (7)	0.0451 (4)
H45	1.3295	0.2648	0.4335	0.054*
C46	1.13003 (15)	0.29544 (13)	0.41862 (7)	0.0446 (4)
H46	1.1432	0.3651	0.4106	0.054*
O44	1.33074 (12)	0.06448 (10)	0.45724 (5)	0.0569 (3)
C441	1.46702 (17)	0.10399 (16)	0.45482 (7)	0.0576 (5)
H41A	1.5311	0.0492	0.4622	0.086*
H41B	1.4778	0.1579	0.4811	0.086*
H41C	1.4842	0.1315	0.4196	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0309 (6)	0.0442 (7)	0.0354 (6)	−0.0022 (5)	−0.0010 (5)	0.0077 (6)
C2	0.0336 (8)	0.0634 (11)	0.0374 (8)	0.0013 (7)	0.0034 (6)	0.0138 (8)
C3	0.0354 (8)	0.0504 (10)	0.0437 (8)	−0.0035 (7)	0.0016 (7)	0.0152 (7)
N4	0.0308 (6)	0.0418 (7)	0.0425 (7)	−0.0002 (5)	0.0028 (5)	0.0091 (6)
C5	0.0340 (7)	0.0480 (10)	0.0466 (9)	−0.0019 (7)	0.0044 (6)	0.0096 (7)
C6	0.0340 (8)	0.0407 (9)	0.0454 (8)	−0.0053 (6)	−0.0044 (6)	0.0076 (7)
C17	0.0336 (7)	0.0309 (8)	0.0327 (7)	0.0007 (6)	0.0008 (6)	−0.0043 (6)
O17	0.0318 (5)	0.0467 (6)	0.0428 (6)	−0.0038 (4)	−0.0005 (4)	0.0058 (5)
C11	0.0317 (7)	0.0342 (8)	0.0328 (7)	−0.0023 (6)	−0.0033 (6)	0.0008 (6)
C12	0.0340 (7)	0.0356 (8)	0.0352 (8)	−0.0029 (6)	−0.0019 (6)	−0.0021 (6)
O12	0.0488 (7)	0.0439 (7)	0.0456 (6)	0.0073 (5)	0.0128 (5)	0.0021 (5)
C13	0.0437 (9)	0.0464 (9)	0.0334 (8)	−0.0071 (7)	0.0001 (6)	0.0016 (7)
C14	0.0597 (10)	0.0429 (9)	0.0388 (8)	−0.0052 (8)	−0.0061 (7)	0.0100 (7)
C15	0.0574 (10)	0.0369 (9)	0.0507 (10)	0.0068 (7)	−0.0067 (8)	0.0035 (7)
C16	0.0414 (8)	0.0408 (9)	0.0402 (8)	0.0029 (7)	0.0008 (7)	−0.0020 (7)
C41	0.0339 (7)	0.0398 (8)	0.0328 (7)	0.0008 (6)	0.0017 (6)	−0.0008 (6)
C42	0.0386 (8)	0.0441 (9)	0.0430 (8)	−0.0059 (7)	−0.0040 (7)	0.0038 (7)
C43	0.0512 (9)	0.0375 (9)	0.0464 (9)	−0.0011 (7)	−0.0037 (7)	0.0073 (7)
C44	0.0407 (8)	0.0472 (10)	0.0343 (7)	0.0075 (7)	0.0020 (6)	0.0006 (7)
C45	0.0316 (7)	0.0491 (10)	0.0545 (10)	−0.0004 (7)	0.0036 (7)	0.0016 (8)
C46	0.0390 (8)	0.0359 (8)	0.0589 (10)	−0.0003 (7)	0.0040 (7)	0.0032 (8)
O44	0.0447 (7)	0.0560 (8)	0.0700 (8)	0.0120 (6)	−0.0018 (6)	0.0148 (6)
C441	0.0427 (10)	0.0790 (14)	0.0509 (10)	0.0160 (9)	0.0008 (7)	0.0129 (9)

Geometric parameters (Å, º) top

N1—C17	1.3440 (18)	C13—C14	1.377 (2)
N1—C2	1.4575 (18)	C13—H13	0.9300
N1—C6	1.4616 (18)	C14—C15	1.383 (2)
C2—C3	1.512 (2)	C14—H14	0.9300
C2—H2A	0.9700	C15—C16	1.379 (2)
C2—H2B	0.9700	C15—H15	0.9300
C3—N4	1.4587 (18)	C16—H16	0.9300
C3—H3A	0.9700	C41—C42	1.390 (2)
C3—H3B	0.9700	C41—C46	1.393 (2)
N4—C41	1.4222 (18)	C42—C43	1.388 (2)
N4—C5	1.4686 (19)	C42—H42	0.9300
C5—C6	1.511 (2)	C43—C44	1.378 (2)
C5—H5A	0.9700	C43—H43	0.9300
C5—H5B	0.9700	C44—O44	1.3779 (18)
C6—H6A	0.9700	C44—C45	1.382 (2)
C6—H6B	0.9700	C45—C46	1.383 (2)
C17—O17	1.2428 (16)	C45—H45	0.9300
C17—C11	1.496 (2)	C46—H46	0.9300
C11—C12	1.395 (2)	O44—C441	1.422 (2)
C11—C16	1.395 (2)	C441—H41A	0.9600
C12—O12	1.3625 (18)	C441—H41B	0.9600
C12—C13	1.390 (2)	C441—H41C	0.9600
O12—H12	0.92 (2)

C17—N1—C2	120.99 (12)	C12—O12—H12	108.7 (12)
C17—N1—C6	125.97 (12)	C14—C13—C12	120.40 (14)
C2—N1—C6	112.73 (11)	C14—C13—H13	119.8
N1—C2—C3	111.34 (12)	C12—C13—H13	119.8
N1—C2—H2A	109.4	C13—C14—C15	120.69 (15)
C3—C2—H2A	109.4	C13—C14—H14	119.7
N1—C2—H2B	109.4	C15—C14—H14	119.7
C3—C2—H2B	109.4	C16—C15—C14	119.06 (15)
H2A—C2—H2B	108.0	C16—C15—H15	120.5
N4—C3—C2	109.92 (13)	C14—C15—H15	120.5
N4—C3—H3A	109.7	C15—C16—C11	121.35 (14)
C2—C3—H3A	109.7	C15—C16—H16	119.3
N4—C3—H3B	109.7	C11—C16—H16	119.3
C2—C3—H3B	109.7	C42—C41—C46	117.07 (14)
H3A—C3—H3B	108.2	C42—C41—N4	123.40 (13)
C41—N4—C3	117.01 (12)	C46—C41—N4	119.48 (14)
C41—N4—C5	115.80 (11)	C43—C42—C41	121.33 (14)
C3—N4—C5	110.23 (11)	C43—C42—H42	119.3
N4—C5—C6	110.83 (12)	C41—C42—H42	119.3
N4—C5—H5A	109.5	C44—C43—C42	120.62 (15)
C6—C5—H5A	109.5	C44—C43—H43	119.7
N4—C5—H5B	109.5	C42—C43—H43	119.7
C6—C5—H5B	109.5	C43—C44—O44	116.19 (15)
H5A—C5—H5B	108.1	C43—C44—C45	118.95 (14)
N1—C6—C5	109.90 (13)	O44—C44—C45	124.86 (14)
N1—C6—H6A	109.7	C44—C45—C46	120.29 (15)
C5—C6—H6A	109.7	C44—C45—H45	119.9
N1—C6—H6B	109.7	C46—C45—H45	119.9
C5—C6—H6B	109.7	C45—C46—C41	121.71 (15)
H6A—C6—H6B	108.2	C45—C46—H46	119.1
O17—C17—N1	120.95 (13)	C41—C46—H46	119.1
O17—C17—C11	119.87 (12)	C44—O44—C441	117.20 (14)
N1—C17—C11	119.11 (12)	O44—C441—H41A	109.5
C12—C11—C16	118.83 (13)	O44—C441—H41B	109.5
C12—C11—C17	123.99 (13)	H41A—C441—H41B	109.5
C16—C11—C17	117.11 (12)	O44—C441—H41C	109.5
O12—C12—C13	122.33 (13)	H41A—C441—H41C	109.5
O12—C12—C11	118.02 (13)	H41B—C441—H41C	109.5
C13—C12—C11	119.64 (14)

C17—N1—C2—C3	131.68 (15)	C11—C12—C13—C14	1.4 (2)
C6—N1—C2—C3	−54.39 (18)	C12—C13—C14—C15	−2.0 (2)
N1—C2—C3—N4	55.85 (17)	C13—C14—C15—C16	0.9 (2)
C2—C3—N4—C41	166.38 (12)	C14—C15—C16—C11	0.7 (2)
C2—C3—N4—C5	−58.51 (16)	C12—C11—C16—C15	−1.3 (2)
C41—N4—C5—C6	−164.75 (13)	C17—C11—C16—C15	−178.57 (14)
C3—N4—C5—C6	59.54 (17)	C3—N4—C41—C42	3.0 (2)
C17—N1—C6—C5	−132.34 (15)	C5—N4—C41—C42	−129.62 (15)
C2—N1—C6—C5	54.10 (17)	C3—N4—C41—C46	−174.21 (14)
N4—C5—C6—N1	−56.31 (17)	C5—N4—C41—C46	53.14 (19)
C2—N1—C17—O17	−1.9 (2)	C46—C41—C42—C43	−0.8 (2)
C6—N1—C17—O17	−174.98 (14)	N4—C41—C42—C43	−178.14 (14)
C2—N1—C17—C11	175.29 (13)	C41—C42—C43—C44	−0.2 (2)
C6—N1—C17—C11	2.2 (2)	C42—C43—C44—O44	−178.28 (14)
O17—C17—C11—C12	−117.64 (16)	C42—C43—C44—C45	1.3 (2)
N1—C17—C11—C12	65.13 (19)	C43—C44—C45—C46	−1.2 (2)
O17—C17—C11—C16	59.44 (18)	O44—C44—C45—C46	178.31 (15)
N1—C17—C11—C16	−117.79 (15)	C44—C45—C46—C41	0.1 (2)
C16—C11—C12—O12	−178.98 (13)	C42—C41—C46—C45	0.9 (2)
C17—C11—C12—O12	−1.9 (2)	N4—C41—C46—C45	178.32 (14)
C16—C11—C12—C13	0.2 (2)	C43—C44—O44—C441	175.77 (14)
C17—C11—C12—C13	177.27 (13)	C45—C44—O44—C441	−3.8 (2)
O12—C12—C13—C14	−179.40 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O17ⁱ	0.92 (2)	1.81 (2)	2.7327 (15)	175.4 (18)

Symmetry code: (i) x+1/2, y, −z+1/2.

Hydrogen bonds and short intermolecular contacts (Å, °) in compounds (I)–(VI) top

Cg1 and Cg2 are the centroids of the C11–C16 and C41–C46 rings, respectively.

Compound	D—H···A	D—H	H···A	D···A	D—H···A
(I)	C12—H12···O17ⁱ	0.93	2.61	3.497 (4)	160
(II)	C2—H2A···O17ⁱⁱ	0.97	2.50	3.387 (4)	152
	C16—H16···O17ⁱⁱⁱ	0.93	2.43	3.340 (5)	167
(III)	C3—H3A···O17^iv	0.97	2.61	3.574 (3)	175
	C2—HA···Cg1^iv	0.97	2.84	3.648 (3)	142
	C15—H15···Cg2^v	0.93	2.72	3.610 (4)	162
(IV)	C3—H3A···O17^iv	0.97	2.56	3.524 (3)	171
	C2—HA···Cg1^iv	0.97	2.82	3.630 (3)	142
	C15—H15···Cg2^v	0.93	2.68	3.579 (4)	164
(V)	C3—H3A···O17^iv	0.97	2.60	3.542 (10)	164
	C2—HA···Cg1^iv	0.97	2.87	3.719 (11)	147
	C15—H15···Cg2^v	0.93	2.73	3.656 (12)	172
(VI)	O12—H12···O17^vi	0.92 (2)	1.81 (2)	3.7327 (15)	175.4 (18)

Symmetry codes: (i) x, 1 - y, -1/2 + z; (ii) 1 - x, 1 - y, 1 - z; (iii) 2 - x, 1 - y, 1 - z; (iv) -1/2 + x, 1/2 - y, 1 - z; (v) 3/2 - x, -1/2 + y, z; (vi) -1/2 + x, y, 1/2 - z.

Acknowledgements

HKK thanks the University of Mysore for research facilities, and the UGC–BSR for a stipend. HSY thanks Professor S. Kabilan and Dr Elancheran of Annamalai University for the data collection for compound (IV).

Funding information

HSY thanks the University Grants Commission, New Delhi, for the award of a BSR Faculty Fellowship for three years.

References

Acosta, L. M., Bahsas, A., Palma, A., Cobo, J., Hursthouse, M. B. & Glidewell, C. (2009). Acta Cryst. C65, o92–o96. Web of Science CSD CrossRef IUCr Journals Google Scholar
Allen, L. C. (1989). J. Am. Chem. Soc. 111, 9003–9014. CrossRef CAS Web of Science Google Scholar
Asif, M. (2015). Int. J. Adv. Sci. Res. 1, 05–11. CrossRef Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bogatcheva, E., Hanrahan, C., Nikonenko, B., Samala, R., Chen, P., Gearhart, J., Barbosa, F., Einck, L., Nacy, C. A. & Protopopova, M. (2006). J. Med. Chem. 49, 3045–3048. Web of Science CrossRef PubMed CAS Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Braga, D., Grepioni, F. & Tedesco, E. (1998). Organometallics, 17, 2669–2672. Web of Science CrossRef CAS Google Scholar
Brito, A., Moreira, L. K. S., Menegatti, R. & Costa, E. A. (2019). Fundam. Clin. Pharmacol. 33, 13–24. CrossRef CAS PubMed Google Scholar
Brockunier, L. L., He, J., Colwell, L. F. Jr, Habulihaz, B., He, H., Leiting, B., Lyons, K. A., Marsilio, F., Patel, R. A., Teffera, Y., Wu, J. K., Thornberry, N. A., Weber, A. E. & Parmee, E. R. (2004). Bioorg. Med. Chem. Lett. 14, 4763–4766. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2015). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Elliott, S. (2011). Drug Test. Anal. 3, 430–438. Web of Science CrossRef CAS PubMed Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Ferguson, G., Glidewell, C., Gregson, R. M. & Meehan, P. R. (1998a). Acta Cryst. B54, 129–138. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ferguson, G., Glidewell, C., Gregson, R. M. & Meehan, P. R. (1998b). Acta Cryst. B54, 139–150. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ferguson, G., Glidewell, C. & Patterson, I. L. J. (1996). Acta Cryst. C52, 420–423. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Garden, S. J., Pinto, A. C., Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o321–o323. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Glidewell, C., Low, J. N., Skakle, J. M. S., Wardell, S. M. S. V. & Wardell, J. L. (2005). Acta Cryst. B61, 227–237. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Gregson, R. M., Glidewell, C., Ferguson, G. & Lough, A. J. (2000). Acta Cryst. B56, 39–57. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Kavitha, C. N., Jasinski, J. P., Anderson, B. J., Yathirajan, H. S. & Kaur, M. (2013). Acta Cryst. E69, o1671. CSD CrossRef IUCr Journals Google Scholar
Kharb, R., Bansal, K. & Sharma, A. K. (2012). Pharma Chemica, 4, 2470–2488. CAS Google Scholar
Mahesha, N., Sagar, B. K., Yathirajan, H. S., Furuya, T., Haraguchi, T., Akitsu, T. & Glidewell, C. (2019). Acta Cryst. E75, 202–207. CSD CrossRef IUCr Journals Google Scholar
Mahesha, N., Yathirajan, H. S., Furuya, T., Akitsu, T. & Glidewell, C. (2019). Acta Cryst. E75, 129–133. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nagai, F., Nonaka, R. & Satoh Hisashi Kamimura, K. (2007). Eur. J. Pharm. 559, 132–137. CrossRef CAS Google Scholar
Nyburg, S. C. & Faerman, C. H. (1985). Acta Cryst. B41, 274–279. CrossRef CAS Web of Science IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Rowland, R. S. & Taylor, R. (1996). J. Phys. Chem. 100, 7384–7391. CrossRef CAS Web of Science Google Scholar
Seip, H. M. & Seip, R. (1973). Acta Chem. Scand. 27, 4024–4027. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sirimulla, S., Bailey, J. B., Vegesna, R. & Narayan, M. (2013). J. Chem. Inf. Model. 53, 2781–2791. Web of Science CrossRef CAS PubMed Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wood, P. A., Allen, F. H. & Pidcock, E. (2009). CrystEngComm, 11, 1563–1571. Web of Science CrossRef CAS Google Scholar
Zia-ur-Rehman, Tahir, M. N., Danish, M., Muhammad, N. & Ali, S. (2009). Acta Cryst. E65, o503. CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 8| August 2019| Pages 1253-1260

https://doi.org/10.1107/S2056989019010491

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Six 1-aroyl-4-(4-meth­­oxy­phen­yl)piperazines: similar mol­ecular structures but different patterns of supra­molecular assembly

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Six 1-aroyl-4-(4-methoxyphenyl)piperazines: similar molecular structures but different patterns of supramolecular assembly

3. Supramolecular features