Structures and energetic properties of 4-halo­benzamides

Piontek, A.; Bisz, E.; Dziuk, B.; Szostak, R.; Szostak, M.

doi:10.1107/S2053229618013463

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Structures and energetic properties of 4-halobenzamides

A. Piontek, E. Bisz, B. Dziuk, R. Szostak and M. Szostak

The amide bond represents one of the most fundamental functional groups in chemistry. The properties of amides are defined by amidic resonance (n_N→π*_C=O conjugation), which enforces planarity of the six atoms comprising the amide bond. Despite the importance of 4-halo-substituted benzamides in organic synthesis, molecular interactions and medicinal chemistry, the effect of 4-halo-substitution on the properties of the amide bond in N,N-disubstituted benzamides has not been studied. Herein, we report the crystal structures and energetic properties of a full series of 4-halobenzamides. The structures of four 4-halobenzamides (halo = iodo, bromo, chloro and fluoro) in the N-morpholinyl series have been determined, namely 4-[(4-halophenyl)carbonyl]morpholine, C₁₁H₁₂XNO₂, for halo = iodo (X = I), bromo (X = Br), chloro (X = Cl) and fluoro (X = F). Computations have been used to determine the effect of halogen substitution on the structures and resonance energies. 4-Iodo-N-morpholinylbenzamide crystallized with a significant distortion of the amide bond (τ + χ_N = 33°). The present study supports the correlation between the Ar—C(O) axis twist angle and the twist angle of the amide N—C(O) bond. Comparison of resonance energies in synthetically valuable N-morpholinyl and N-piperidinyl amides demonstrates that the O atom of the morpholinyl ring has a negligible effect on amidic resonance in the series.

Keywords: amide bonds; morpholinyl amides; resonance energies; crystal structure; twisted amides.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618013463/fn3272sup1.cif Contains datablocks BD268_a, BD144_a, BD138_1_a, BD264_a, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618013463/fn3272BD268_asup2.hkl Contains datablock BD268_a
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618013463/fn3272BD144_asup3.hkl Contains datablock BD144_a
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618013463/fn3272BD138_1_asup4.hkl Contains datablock BD138_1_a
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618013463/fn3272BD264_asup5.hkl Contains datablock BD264_a
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229618013463/fn3272sup6.pdf Computational details

CCDC references: 1850333; 1538098; 1850324; 1850335

Computing details top

For all structures, data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis CCD (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

4-[(4-Iodophenyl)carbonyl]morpholine (BD268_a) top

Crystal data top

C₁₁H₁₂INO₂	F(000) = 616
M_r = 317.12	D_x = 1.854 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.5193 (3) Å	Cell parameters from 7452 reflections
b = 12.2078 (4) Å	θ = 3.3–26.0°
c = 8.8674 (3) Å	µ = 2.80 mm⁻¹
β = 93.763 (3)°	T = 100 K
V = 1136.27 (6) Å³	Plate, colourless
Z = 4	0.5 × 0.4 × 0.3 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	2207 independent reflections
Radiation source: fine-focus sealed tube	2019 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω–scan	h = −12→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −15→10
T_min = 0.518, T_max = 1.000	l = −10→10
7452 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.017	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.044	w = 1/[σ²(F_o²) + (0.0253P)² + 0.2684P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
2207 reflections	Δρ_max = 0.42 e Å⁻³
144 parameters	Δρ_min = −0.52 e Å⁻³

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
C1	0.25090 (19)	0.49287 (16)	0.2721 (2)	0.0151 (4)
H1	0.2332	0.5498	0.2043	0.018*
C2	0.3772 (2)	0.46360 (16)	0.3106 (2)	0.0132 (4)
C3	0.4023 (2)	0.38039 (16)	0.4160 (2)	0.0141 (4)
H3	0.4862	0.3612	0.4436	0.017*
C4	0.3037 (2)	0.32591 (16)	0.4801 (2)	0.0148 (4)
H4	0.3212	0.2714	0.5517	0.018*
C5	0.1784 (2)	0.35334 (16)	0.4365 (2)	0.0150 (4)
C6	0.1518 (2)	0.43780 (17)	0.3340 (2)	0.0164 (4)
H6	0.0678	0.4572	0.3071	0.020*
N9	0.58356 (16)	0.47781 (13)	0.19736 (19)	0.0133 (4)
O8	0.46903 (13)	0.63067 (11)	0.24035 (16)	0.0163 (3)
C7	0.47978 (18)	0.53010 (16)	0.2454 (2)	0.0124 (4)
C10	0.6874 (2)	0.54433 (17)	0.1424 (2)	0.0149 (4)
H10A	0.6855	0.6172	0.1859	0.018*
H10B	0.6769	0.5511	0.0333	0.018*
C11	0.8136 (2)	0.48979 (16)	0.1873 (3)	0.0191 (5)
H11A	0.8820	0.5313	0.1462	0.023*
H11B	0.8273	0.4902	0.2965	0.023*
O12	0.81748 (14)	0.37967 (12)	0.13401 (19)	0.0229 (4)
C13	0.7192 (2)	0.31622 (17)	0.1958 (3)	0.0191 (5)
H13A	0.7318	0.3155	0.3051	0.023*
H13B	0.7239	0.2413	0.1602	0.023*
C14	0.5893 (2)	0.36269 (16)	0.1504 (2)	0.0144 (4)
H14A	0.576 (2)	0.3567 (17)	0.042 (2)	0.011 (5)*
H14B	0.522 (2)	0.322 (2)	0.192 (3)	0.020 (6)*
I15	0.02903 (2)	0.26585 (2)	0.52607 (2)	0.01825 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0153 (11)	0.0142 (10)	0.0158 (10)	0.0032 (8)	−0.0003 (8)	−0.0004 (8)
C2	0.0145 (11)	0.0119 (9)	0.0134 (10)	0.0017 (8)	0.0026 (8)	−0.0035 (8)
C3	0.0118 (10)	0.0151 (10)	0.0154 (10)	0.0040 (8)	0.0009 (8)	−0.0024 (8)
C4	0.0181 (11)	0.0134 (10)	0.0131 (10)	0.0024 (8)	0.0015 (8)	−0.0006 (8)
C5	0.0153 (11)	0.0136 (10)	0.0167 (10)	−0.0014 (8)	0.0065 (8)	−0.0033 (8)
C6	0.0111 (11)	0.0183 (10)	0.0198 (11)	0.0034 (8)	0.0003 (8)	−0.0004 (8)
N9	0.0113 (9)	0.0088 (8)	0.0200 (9)	−0.0012 (7)	0.0036 (7)	0.0002 (7)
O8	0.0161 (8)	0.0112 (7)	0.0218 (8)	0.0019 (6)	0.0019 (6)	−0.0007 (6)
C7	0.0122 (11)	0.0137 (9)	0.0111 (9)	0.0009 (8)	−0.0013 (8)	0.0001 (8)
C10	0.0152 (11)	0.0128 (10)	0.0172 (10)	−0.0020 (8)	0.0052 (8)	0.0011 (8)
C11	0.0140 (11)	0.0167 (11)	0.0272 (12)	−0.0017 (9)	0.0062 (9)	0.0014 (9)
O12	0.0145 (8)	0.0155 (7)	0.0403 (10)	0.0022 (6)	0.0129 (7)	0.0027 (7)
C13	0.0154 (11)	0.0126 (10)	0.0302 (12)	0.0009 (9)	0.0082 (9)	0.0043 (9)
C14	0.0152 (11)	0.0104 (10)	0.0183 (11)	−0.0012 (8)	0.0060 (8)	0.0001 (8)
I15	0.01462 (9)	0.01995 (9)	0.02094 (9)	−0.00115 (5)	0.00690 (6)	0.00172 (5)

Geometric parameters (Å, º) top

C1—C6	1.384 (3)	N9—C10	1.470 (3)
C1—C2	1.397 (3)	O8—C7	1.233 (2)
C1—H1	0.9300	C10—C11	1.515 (3)
C2—C3	1.394 (3)	C10—H10A	0.9700
C2—C7	1.496 (3)	C10—H10B	0.9700
C3—C4	1.385 (3)	C11—O12	1.426 (2)
C3—H3	0.9300	C11—H11A	0.9700
C4—C5	1.390 (3)	C11—H11B	0.9700
C4—H4	0.9300	O12—C13	1.430 (2)
C5—C6	1.391 (3)	C13—C14	1.509 (3)
C5—I15	2.098 (2)	C13—H13A	0.9700
C6—H6	0.9300	C13—H13B	0.9700
N9—C7	1.357 (2)	C14—H14A	0.97 (2)
N9—C14	1.468 (3)	C14—H14B	0.96 (2)

C6—C1—C2	120.56 (19)	N9—C10—H10A	109.9
C6—C1—H1	119.7	C11—C10—H10A	109.9
C2—C1—H1	119.7	N9—C10—H10B	109.9
C3—C2—C1	119.1 (2)	C11—C10—H10B	109.9
C3—C2—C7	123.02 (18)	H10A—C10—H10B	108.3
C1—C2—C7	117.73 (18)	O12—C11—C10	111.76 (17)
C4—C3—C2	120.74 (19)	O12—C11—H11A	109.3
C4—C3—H3	119.6	C10—C11—H11A	109.3
C2—C3—H3	119.6	O12—C11—H11B	109.3
C3—C4—C5	119.50 (19)	C10—C11—H11B	109.3
C3—C4—H4	120.2	H11A—C11—H11B	107.9
C5—C4—H4	120.2	C11—O12—C13	110.29 (16)
C4—C5—C6	120.44 (19)	O12—C13—C14	111.03 (17)
C4—C5—I15	119.48 (15)	O12—C13—H13A	109.4
C6—C5—I15	120.07 (16)	C14—C13—H13A	109.4
C1—C6—C5	119.64 (19)	O12—C13—H13B	109.4
C1—C6—H6	120.2	C14—C13—H13B	109.4
C5—C6—H6	120.2	H13A—C13—H13B	108.0
C7—N9—C14	126.05 (17)	N9—C14—C13	109.75 (17)
C7—N9—C10	118.35 (17)	N9—C14—H14A	110.4 (13)
C14—N9—C10	112.92 (16)	C13—C14—H14A	107.7 (13)
O8—C7—N9	122.04 (18)	N9—C14—H14B	110.2 (14)
O8—C7—C2	119.17 (18)	C13—C14—H14B	112.4 (14)
N9—C7—C2	118.77 (17)	H14A—C14—H14B	106.3 (19)
N9—C10—C11	109.13 (16)

C6—C1—C2—C3	−2.0 (3)	C10—N9—C7—C2	−176.20 (17)
C6—C1—C2—C7	−177.07 (18)	C3—C2—C7—O8	−132.8 (2)
C1—C2—C3—C4	1.1 (3)	C1—C2—C7—O8	42.1 (3)
C7—C2—C3—C4	175.86 (18)	C3—C2—C7—N9	45.5 (3)
C2—C3—C4—C5	1.2 (3)	C1—C2—C7—N9	−139.70 (19)
C3—C4—C5—C6	−2.6 (3)	C7—N9—C10—C11	144.61 (18)
C3—C4—C5—I15	177.16 (14)	C14—N9—C10—C11	−52.8 (2)
C2—C1—C6—C5	0.7 (3)	N9—C10—C11—O12	55.7 (2)
C4—C5—C6—C1	1.7 (3)	C10—C11—O12—C13	−60.2 (2)
I15—C5—C6—C1	−178.08 (15)	C11—O12—C13—C14	60.2 (2)
C14—N9—C7—O8	−158.05 (19)	C7—N9—C14—C13	−145.47 (19)
C10—N9—C7—O8	2.0 (3)	C10—N9—C14—C13	53.6 (2)
C14—N9—C7—C2	23.8 (3)	O12—C13—C14—N9	−56.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···O8ⁱ	0.97 (2)	2.52 (2)	3.480 (3)	171.7 (18)
C14—H14B···O8ⁱⁱ	0.96 (2)	2.41 (2)	3.069 (2)	125.6 (18)

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

4-[(4-Bromophenyl)carbonyl]morpholine (BD144_a) top

Crystal data top

C₁₁H₁₂BrNO₂	D_x = 1.596 Mg m⁻³
M_r = 270.13	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁	Cell parameters from 5805 reflections
a = 9.9577 (2) Å	θ = 3.1–26.0°
c = 9.8213 (2) Å	µ = 3.64 mm⁻¹
V = 843.37 (4) Å³	T = 100 K
Z = 3	Plate, colourless
F(000) = 408	0.5 × 0.45 × 0.4 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	2180 independent reflections
Radiation source: fine-focus sealed tube	2129 reflections with I > 2σ(I)
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	R_int = 0.046
ω–scan	θ_max = 26.0°, θ_min = 3.1°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	h = −10→12
T_min = 0.776, T_max = 1.000	k = −12→10
5805 measured reflections	l = −12→11

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.023	w = 1/[σ²(F_o²) + (0.0358P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.057	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.32 e Å⁻³
2180 reflections	Δρ_min = −0.38 e Å⁻³
150 parameters	Absolute structure: Flack x determined using 1007 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.007 (9)

Special details top

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

	x	y	z	U_iso*/U_eq
Br1	0.42153 (4)	0.07632 (4)	0.08969 (4)	0.02375 (13)
N1	0.2551 (4)	0.3767 (4)	0.6554 (3)	0.0185 (6)
O1	0.4186 (3)	0.5968 (3)	0.5427 (3)	0.0229 (6)
C1	0.3508 (4)	0.4544 (4)	0.5518 (4)	0.0171 (7)
C3	0.1615 (4)	0.2074 (4)	0.6681 (4)	0.0199 (8)
H3A	0.197 (4)	0.165 (4)	0.605 (4)	0.027 (12)*
H3B	0.0542	0.1797	0.6511	0.023 (11)*
C2	0.2206 (5)	0.4597 (4)	0.7606 (4)	0.0208 (8)
H2B	0.287 (4)	0.571 (4)	0.753 (3)	0.023 (11)*
H2A	0.1098	0.4456	0.7443	0.025 (12)*
O2	0.1320 (3)	0.2354 (3)	0.9102 (3)	0.0235 (6)
C5	0.1773 (5)	0.1614 (5)	0.8105 (4)	0.0233 (8)
H5A	0.1134	0.0498	0.8200	0.028*
H5B	0.2842	0.1889	0.8263	0.028*
C4	0.2289 (5)	0.4002 (4)	0.9003 (4)	0.0233 (8)
H4A	0.3353	0.4283	0.9195	0.028*
H4B	0.1970	0.4495	0.9682	0.028*
C1P	0.3722 (4)	0.3616 (4)	0.4415 (4)	0.0159 (7)
C2P	0.3019 (4)	0.3508 (4)	0.3160 (4)	0.0180 (7)
H2P	0.2437	0.3992	0.3029	0.022*
C3P	0.3188 (4)	0.2680 (4)	0.2109 (4)	0.0185 (7)
H3P	0.264 (5)	0.251 (5)	0.123 (5)	0.023 (11)*
C4P	0.4098 (4)	0.1999 (4)	0.2318 (4)	0.0172 (7)
C5P	0.4841 (4)	0.2142 (4)	0.3525 (4)	0.0210 (8)
H5P	0.5472	0.1707	0.3633	0.025*
C6P	0.4641 (4)	0.2949 (4)	0.4593 (4)	0.0207 (8)
H6P	0.5125	0.3038	0.5425	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0271 (2)	0.0240 (2)	0.02284 (19)	0.01485 (18)	0.00566 (16)	−0.00278 (16)
N1	0.0232 (16)	0.0136 (15)	0.0186 (16)	0.0090 (13)	−0.0002 (13)	−0.0014 (11)
O1	0.0305 (14)	0.0128 (13)	0.0226 (14)	0.0086 (11)	−0.0015 (11)	0.0001 (10)
C1	0.0193 (17)	0.0191 (18)	0.0144 (17)	0.0108 (15)	−0.0054 (14)	−0.0021 (14)
C3	0.0192 (19)	0.0145 (19)	0.024 (2)	0.0067 (16)	−0.0013 (15)	−0.0038 (15)
C2	0.024 (2)	0.0190 (18)	0.021 (2)	0.0116 (16)	0.0002 (14)	−0.0043 (15)
O2	0.0246 (14)	0.0191 (12)	0.0224 (15)	0.0077 (11)	0.0034 (11)	0.0007 (11)
C5	0.028 (2)	0.0167 (18)	0.024 (2)	0.0102 (17)	0.0019 (16)	0.0007 (16)
C4	0.022 (2)	0.0205 (18)	0.0227 (19)	0.0075 (15)	−0.0004 (15)	−0.0037 (16)
C1P	0.0160 (17)	0.0110 (16)	0.0173 (18)	0.0041 (13)	0.0015 (14)	0.0016 (13)
C2P	0.0187 (17)	0.0208 (18)	0.0190 (19)	0.0133 (15)	0.0007 (14)	0.0039 (14)
C3P	0.0199 (18)	0.0214 (18)	0.0155 (18)	0.0112 (15)	−0.0003 (14)	0.0019 (14)
C4P	0.0180 (17)	0.0125 (16)	0.0186 (18)	0.0058 (13)	0.0070 (14)	0.0016 (14)
C5P	0.0145 (17)	0.0181 (18)	0.033 (2)	0.0098 (15)	−0.0018 (15)	−0.0009 (15)
C6P	0.0206 (19)	0.0197 (17)	0.022 (2)	0.0104 (16)	−0.0080 (15)	−0.0032 (15)

Geometric parameters (Å, º) top

Br1—C4P	1.902 (4)	C5—H5A	0.9700
N1—C1	1.344 (5)	C5—H5B	0.9700
N1—C2	1.467 (5)	C4—H4A	0.9700
N1—C3	1.468 (5)	C4—H4B	0.9700
O1—C1	1.231 (5)	C1P—C6P	1.386 (5)
C1—C1P	1.506 (5)	C1P—C2P	1.395 (5)
C3—C5	1.505 (5)	C2P—C3P	1.383 (5)
C3—H3A	0.92 (4)	C2P—H2P	0.9300
C3—H3B	0.9750	C3P—C4P	1.393 (5)
C2—C4	1.513 (6)	C3P—H3P	0.99 (5)
C2—H2B	0.96 (4)	C4P—C5P	1.367 (5)
C2—H2A	1.0517	C5P—C6P	1.395 (6)
O2—C5	1.428 (5)	C5P—H5P	0.9300
O2—C4	1.432 (4)	C6P—H6P	0.9300

C1—N1—C2	120.5 (3)	O2—C4—C2	111.9 (3)
C1—N1—C3	125.9 (3)	O2—C4—H4A	109.2
C2—N1—C3	113.2 (3)	C2—C4—H4A	109.2
O1—C1—N1	122.7 (3)	O2—C4—H4B	109.2
O1—C1—C1P	119.3 (3)	C2—C4—H4B	109.2
N1—C1—C1P	117.9 (3)	H4A—C4—H4B	107.9
N1—C3—C5	109.0 (3)	C6P—C1P—C2P	120.0 (3)
N1—C3—H3A	108 (2)	C6P—C1P—C1	122.3 (3)
C5—C3—H3A	111 (2)	C2P—C1P—C1	117.7 (3)
N1—C3—H3B	106.7	C3P—C2P—C1P	120.1 (3)
C5—C3—H3B	109.9	C3P—C2P—H2P	120.0
H3A—C3—H3B	112.2	C1P—C2P—H2P	120.0
N1—C2—C4	110.2 (3)	C2P—C3P—C4P	118.9 (3)
N1—C2—H2B	112 (2)	C2P—C3P—H3P	122 (3)
C4—C2—H2B	112 (2)	C4P—C3P—H3P	119 (3)
N1—C2—H2A	110.0	C5P—C4P—C3P	121.8 (4)
C4—C2—H2A	110.2	C5P—C4P—Br1	119.9 (3)
H2B—C2—H2A	102.3	C3P—C4P—Br1	118.2 (3)
C5—O2—C4	109.9 (3)	C4P—C5P—C6P	119.1 (3)
O2—C5—C3	111.8 (3)	C4P—C5P—H5P	120.4
O2—C5—H5A	109.2	C6P—C5P—H5P	120.4
C3—C5—H5A	109.2	C1P—C6P—C5P	120.0 (4)
O2—C5—H5B	109.2	C1P—C6P—H6P	120.0
C3—C5—H5B	109.2	C5P—C6P—H6P	120.0
H5A—C5—H5B	107.9

C2—N1—C1—O1	3.1 (5)	N1—C1—C1P—C6P	−76.6 (4)
C3—N1—C1—O1	175.1 (3)	O1—C1—C1P—C2P	−72.1 (4)
C2—N1—C1—C1P	−175.5 (3)	N1—C1—C1P—C2P	106.6 (4)
C3—N1—C1—C1P	−3.5 (5)	C6P—C1P—C2P—C3P	2.6 (5)
C1—N1—C3—C5	134.4 (4)	C1—C1P—C2P—C3P	179.5 (3)
C2—N1—C3—C5	−53.1 (4)	C1P—C2P—C3P—C4P	−1.7 (5)
C1—N1—C2—C4	−135.3 (3)	C2P—C3P—C4P—C5P	−0.7 (5)
C3—N1—C2—C4	51.7 (4)	C2P—C3P—C4P—Br1	176.3 (3)
C4—O2—C5—C3	−60.8 (4)	C3P—C4P—C5P—C6P	2.2 (6)
N1—C3—C5—O2	57.4 (4)	Br1—C4P—C5P—C6P	−174.9 (3)
C5—O2—C4—C2	58.7 (4)	C2P—C1P—C6P—C5P	−1.2 (6)
N1—C2—C4—O2	−53.9 (4)	C1—C1P—C6P—C5P	−177.9 (3)
O1—C1—C1P—C6P	104.7 (4)	C4P—C5P—C6P—C1P	−1.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O2ⁱ	0.92 (4)	2.63 (3)	3.257 (4)	126 (3)
C2—H2B···O1ⁱⁱ	0.96 (4)	2.48 (4)	3.322 (5)	146 (3)
C3P—H3P···O2ⁱⁱⁱ	0.99 (5)	2.43 (5)	3.417 (5)	174 (4)

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

4-[(4-Chlorophenyl)carbonyl]morpholine (BD138_1_a) top

Crystal data top

C₁₁H₁₂ClNO₂	D_x = 1.359 Mg m⁻³
M_r = 225.67	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁	Cell parameters from 5673 reflections
a = 9.9808 (3) Å	θ = 3.2–26.0°
c = 9.5853 (3) Å	µ = 0.33 mm⁻¹
V = 826.93 (6) Å³	T = 100 K
Z = 3	Plate, colourless
F(000) = 354	0.5 × 0.45 × 0.4 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	1590 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω–scan	h = −12→12
5673 measured reflections	k = −12→11
1680 independent reflections	l = −11→8

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0396P)² + 0.0699P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.068	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 0.27 e Å⁻³
1680 reflections	Δρ_min = −0.45 e Å⁻³
185 parameters	Absolute structure: Flack x determined using 505 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.00 (2)

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.3163 (3)	0.2866 (3)	0.4498 (3)	0.0226 (5)
C2	0.1564 (3)	0.1932 (3)	0.4573 (3)	0.0256 (5)
H2	0.1106	0.1392	0.5389	0.031*
C3	0.0650 (3)	0.1804 (3)	0.3433 (3)	0.0290 (6)
H3	−0.0418	0.1167	0.3472	0.035*
C4	0.1349 (3)	0.2634 (3)	0.2245 (3)	0.0293 (6)
C5	0.2943 (3)	0.3562 (3)	0.2143 (3)	0.0300 (6)
H5	0.335 (4)	0.407 (4)	0.137 (4)	0.035 (8)*
C6	0.3843 (3)	0.3654 (3)	0.3272 (3)	0.0267 (5)
H6	0.4915	0.4249	0.3211	0.032*
C7	0.4210 (3)	0.2962 (3)	0.5668 (3)	0.0263 (6)
O8	0.5048 (2)	0.2403 (2)	0.55140 (19)	0.0288 (4)
O12	0.4569 (2)	0.5489 (2)	0.9185 (2)	0.0339 (5)
Cl15	0.02234 (9)	0.25628 (8)	0.08276 (8)	0.0463 (2)
N9B	0.4023 (5)	0.3476 (5)	0.6961 (4)	0.0228 (8)	0.65
C10A	0.4949 (5)	0.3523 (5)	0.8162 (4)	0.0252 (8)	0.65
H10A	0.5720	0.3263	0.7866	0.030*	0.65
H10B	0.4287	0.2763	0.8846	0.030*	0.65
C11A	0.5737 (6)	0.5102 (6)	0.8814 (5)	0.0267 (9)	0.65
H11A	0.6301	0.5107	0.9640	0.032*	0.65
H11B	0.6465	0.5857	0.8161	0.032*	0.65
C13A	0.3819 (7)	0.5609 (7)	0.7974 (6)	0.0294 (11)	0.65
H13A	0.4577	0.6354	0.7333	0.035*	0.65
H13B	0.3104	0.5960	0.8227	0.035*	0.65
C14A	0.2949 (4)	0.4031 (4)	0.7284 (4)	0.0228 (7)	0.65
H14A	0.2144	0.3306	0.7904	0.027*	0.65
H14B	0.2463	0.4103	0.6432	0.027*	0.65
N9A	0.4587 (9)	0.4097 (9)	0.6589 (8)	0.0210 (15)	0.35
C10B	0.5752 (9)	0.4401 (10)	0.7686 (8)	0.0259 (15)	0.35
H10C	0.6647	0.5420	0.7552	0.031*	0.35
H10D	0.6088	0.3644	0.7623	0.031*	0.35
C11B	0.5065 (10)	0.4310 (11)	0.9087 (9)	0.0248 (16)	0.35
H11C	0.5822	0.4496	0.9807	0.030*	0.35
H11D	0.4181	0.3285	0.9229	0.030*	0.35
C13B	0.3236 (12)	0.4895 (13)	0.8160 (11)	0.029 (2)	0.35
H13C	0.2496	0.3819	0.8356	0.035*	0.35
H13D	0.2713	0.5489	0.8246	0.035*	0.35
C14B	0.3855 (9)	0.5048 (8)	0.6735 (9)	0.0257 (16)	0.35
H14C	0.3023	0.4718	0.6062	0.031*	0.35
H14D	0.4608	0.6122	0.6549	0.031*	0.35

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0256 (12)	0.0226 (11)	0.0227 (13)	0.0144 (10)	−0.0026 (10)	−0.0042 (10)
C2	0.0264 (12)	0.0252 (12)	0.0246 (13)	0.0124 (10)	0.0016 (10)	0.0031 (10)
C3	0.0246 (12)	0.0220 (12)	0.0389 (15)	0.0104 (10)	−0.0063 (11)	−0.0034 (11)
C4	0.0388 (14)	0.0262 (13)	0.0290 (14)	0.0209 (11)	−0.0151 (12)	−0.0094 (11)
C5	0.0406 (15)	0.0267 (13)	0.0256 (15)	0.0190 (12)	0.0014 (12)	0.0012 (11)
C6	0.0251 (12)	0.0256 (12)	0.0285 (14)	0.0120 (10)	0.0006 (11)	−0.0034 (10)
C7	0.0267 (13)	0.0251 (12)	0.0285 (14)	0.0141 (11)	−0.0063 (10)	−0.0041 (11)
O8	0.0304 (9)	0.0374 (10)	0.0270 (11)	0.0232 (8)	0.0010 (8)	0.0016 (8)
O12	0.0464 (11)	0.0405 (11)	0.0245 (10)	0.0290 (9)	−0.0079 (8)	−0.0068 (8)
Cl15	0.0606 (5)	0.0449 (4)	0.0396 (4)	0.0311 (4)	−0.0285 (4)	−0.0107 (4)
N9B	0.026 (2)	0.025 (2)	0.021 (2)	0.0159 (17)	−0.0027 (16)	0.0002 (16)
C10A	0.031 (2)	0.024 (2)	0.023 (2)	0.0159 (18)	−0.0050 (18)	0.0013 (18)
C11A	0.024 (2)	0.024 (2)	0.027 (2)	0.0087 (19)	−0.0026 (18)	0.002 (2)
C13A	0.040 (3)	0.024 (3)	0.029 (3)	0.019 (2)	−0.008 (2)	−0.005 (2)
C14A	0.0247 (18)	0.025 (2)	0.0214 (19)	0.0146 (17)	−0.0008 (16)	−0.0038 (17)
N9A	0.025 (4)	0.026 (4)	0.016 (4)	0.016 (3)	−0.002 (3)	0.001 (3)
C10B	0.026 (4)	0.031 (4)	0.022 (4)	0.016 (3)	−0.009 (3)	−0.003 (3)
C11B	0.027 (4)	0.020 (4)	0.024 (4)	0.010 (4)	−0.005 (3)	0.001 (4)
C13B	0.030 (5)	0.025 (5)	0.033 (5)	0.014 (4)	−0.006 (4)	−0.002 (5)
C14B	0.030 (4)	0.018 (3)	0.033 (4)	0.015 (3)	−0.007 (3)	−0.003 (3)

Geometric parameters (Å, º) top

C1—C6	1.388 (4)	C10A—H10A	0.9700
C1—C2	1.391 (3)	C10A—H10B	0.9700
C1—C7	1.503 (3)	C11A—H11A	0.9700
C2—C3	1.388 (4)	C11A—H11B	0.9700
C2—H2	0.9300	C13A—C14A	1.518 (6)
C3—C4	1.375 (4)	C13A—H13A	0.9700
C3—H3	0.9300	C13A—H13B	0.9700
C4—C5	1.387 (4)	C14A—H14A	0.9700
C4—Cl15	1.741 (3)	C14A—H14B	0.9700
C5—C6	1.380 (4)	N9A—C14B	1.465 (10)
C5—H5	0.88 (3)	N9A—C10B	1.482 (10)
C6—H6	0.9300	C10B—C11B	1.490 (12)
C7—O8	1.224 (3)	C10B—H10C	0.9700
C7—N9A	1.334 (8)	C10B—H10D	0.9700
C7—N9B	1.389 (5)	C11B—H11C	0.9700
O12—C13A	1.418 (6)	C11B—H11D	0.9700
O12—C11A	1.444 (5)	C13B—C14B	1.475 (14)
O12—C11B	1.490 (8)	C13B—H13C	0.9700
O12—C13B	1.516 (10)	C13B—H13D	0.9700
N9B—C10A	1.463 (5)	C14B—H14C	0.9700
N9B—C14A	1.465 (6)	C14B—H14D	0.9700
C10A—C11A	1.501 (6)

C6—C1—C2	119.8 (2)	O12—C13A—C14A	108.7 (4)
C6—C1—C7	117.9 (2)	O12—C13A—H13A	109.9
C2—C1—C7	122.2 (2)	C14A—C13A—H13A	109.9
C3—C2—C1	120.1 (3)	O12—C13A—H13B	109.9
C3—C2—H2	119.9	C14A—C13A—H13B	109.9
C1—C2—H2	119.9	H13A—C13A—H13B	108.3
C4—C3—C2	119.0 (2)	N9B—C14A—C13A	109.7 (4)
C4—C3—H3	120.5	N9B—C14A—H14A	109.7
C2—C3—H3	120.5	C13A—C14A—H14A	109.7
C3—C4—C5	121.8 (3)	N9B—C14A—H14B	109.7
C3—C4—Cl15	119.9 (2)	C13A—C14A—H14B	109.7
C5—C4—Cl15	118.3 (2)	H14A—C14A—H14B	108.2
C6—C5—C4	118.7 (3)	C7—N9A—C14B	126.4 (6)
C6—C5—H5	122 (2)	C7—N9A—C10B	120.2 (6)
C4—C5—H5	119 (2)	C14B—N9A—C10B	113.2 (6)
C5—C6—C1	120.5 (2)	N9A—C10B—C11B	109.7 (6)
C5—C6—H6	119.7	N9A—C10B—H10C	109.7
C1—C6—H6	119.7	C11B—C10B—H10C	109.7
O8—C7—N9A	120.0 (4)	N9A—C10B—H10D	109.7
O8—C7—N9B	121.6 (3)	C11B—C10B—H10D	109.7
O8—C7—C1	119.5 (2)	H10C—C10B—H10D	108.2
N9A—C7—C1	116.1 (4)	C10B—C11B—O12	109.5 (6)
N9B—C7—C1	118.1 (2)	C10B—C11B—H11C	109.8
C13A—O12—C11A	110.6 (3)	O12—C11B—H11C	109.8
C11B—O12—C13B	102.9 (5)	C10B—C11B—H11D	109.8
C7—N9B—C10A	121.0 (3)	O12—C11B—H11D	109.8
C7—N9B—C14A	126.0 (3)	H11C—C11B—H11D	108.2
C10A—N9B—C14A	113.0 (4)	C14B—C13B—O12	108.7 (7)
N9B—C10A—C11A	110.6 (3)	C14B—C13B—H13C	110.0
N9B—C10A—H10A	109.5	O12—C13B—H13C	110.0
C11A—C10A—H10A	109.5	C14B—C13B—H13D	110.0
N9B—C10A—H10B	109.5	O12—C13B—H13D	110.0
C11A—C10A—H10B	109.5	H13C—C13B—H13D	108.3
H10A—C10A—H10B	108.1	N9A—C14B—C13B	109.9 (7)
O12—C11A—C10A	108.3 (3)	N9A—C14B—H14C	109.7
O12—C11A—H11A	110.0	C13B—C14B—H14C	109.7
C10A—C11A—H11A	110.0	N9A—C14B—H14D	109.7
O12—C11A—H11B	110.0	C13B—C14B—H14D	109.7
C10A—C11A—H11B	110.0	H14C—C14B—H14D	108.2
H11A—C11A—H11B	108.4

C6—C1—C2—C3	−0.9 (4)	C7—N9B—C10A—C11A	126.9 (4)
C7—C1—C2—C3	−175.9 (2)	C14A—N9B—C10A—C11A	−52.4 (5)
C1—C2—C3—C4	−1.1 (4)	C13A—O12—C11A—C10A	−64.4 (5)
C2—C3—C4—C5	1.7 (4)	N9B—C10A—C11A—O12	56.5 (5)
C2—C3—C4—Cl15	−177.11 (19)	C11A—O12—C13A—C14A	64.7 (5)
C3—C4—C5—C6	−0.3 (4)	C7—N9B—C14A—C13A	−127.2 (4)
Cl15—C4—C5—C6	178.54 (19)	C10A—N9B—C14A—C13A	52.0 (5)
C4—C5—C6—C1	−1.7 (4)	O12—C13A—C14A—N9B	−57.1 (5)
C2—C1—C6—C5	2.3 (4)	O8—C7—N9A—C14B	169.4 (6)
C7—C1—C6—C5	177.5 (2)	C1—C7—N9A—C14B	13.0 (10)
C6—C1—C7—O8	−64.8 (3)	O8—C7—N9A—C10B	−16.6 (9)
C2—C1—C7—O8	110.2 (3)	C1—C7—N9A—C10B	−173.0 (6)
C6—C1—C7—N9A	91.7 (5)	C7—N9A—C10B—C11B	−123.5 (8)
C2—C1—C7—N9A	−93.3 (5)	C14B—N9A—C10B—C11B	51.1 (9)
C6—C1—C7—N9B	124.7 (3)	N9A—C10B—C11B—O12	−60.1 (8)
C2—C1—C7—N9B	−60.2 (3)	C13B—O12—C11B—C10B	67.8 (8)
O8—C7—N9B—C10A	6.6 (5)	C11B—O12—C13B—C14B	−68.7 (8)
C1—C7—N9B—C10A	176.9 (3)	C7—N9A—C14B—C13B	121.7 (9)
O8—C7—N9B—C14A	−174.2 (3)	C10B—N9A—C14B—C13B	−52.6 (9)
C1—C7—N9B—C14A	−3.9 (5)	O12—C13B—C14B—N9A	62.0 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O12ⁱ	0.88 (3)	2.48 (4)	3.354 (4)	178 (3)
C10A—H10A···O8ⁱⁱ	0.97	2.43	3.240 (4)	140
C10A—H10B···Cl15ⁱⁱⁱ	0.97	2.92	3.382 (4)	110
C14A—H14B···O12^iv	0.97	2.55	3.282 (4)	133
C10B—H10D···O8ⁱⁱ	0.97	2.48	3.306 (7)	143
C11B—H11C···O8^v	0.97	2.65	3.601 (8)	166
C14B—H14C···O12^iv	0.97	2.54	3.251 (7)	130

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

4-[(4-Fluorophenyl)carbonyl]morpholine (BD264_a) top

Crystal data top

C₁₁H₁₂FNO₂	D_x = 1.377 Mg m⁻³
M_r = 209.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 12441 reflections
a = 7.3584 (5) Å	θ = 3.0–26.0°
b = 7.2979 (5) Å	µ = 0.11 mm⁻¹
c = 37.576 (2) Å	T = 100 K
V = 2017.9 (2) Å³	Plate, colourless
Z = 8	0.2 × 0.15 × 0.1 mm
F(000) = 880

Data collection top

Oxford Diffraction Xcalibur diffractometer	1193 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.092
Graphite monochromator	θ_max = 26.0°, θ_min = 3.0°
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	h = −9→9
ω–scan	k = −9→8
12441 measured reflections	l = −38→46
1977 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0327P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max < 0.001
1977 reflections	Δρ_max = 0.19 e Å⁻³
152 parameters	Δρ_min = −0.23 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
C1	0.5048 (3)	0.3731 (3)	0.39818 (5)	0.0150 (5)
C2	0.6167 (3)	0.2327 (3)	0.41019 (5)	0.0212 (5)
H2	0.6961	0.1756	0.3944	0.025*
C3	0.6111 (3)	0.1773 (3)	0.44536 (5)	0.0225 (5)
H3	0.6859	0.0835	0.4535	0.027*
C4	0.4926 (3)	0.2638 (3)	0.46790 (5)	0.0207 (5)
C5	0.3829 (3)	0.4048 (3)	0.45731 (5)	0.0222 (5)
H5	0.3045	0.4613	0.4733	0.027*
C6	0.3916 (3)	0.4614 (3)	0.42214 (5)	0.0193 (5)
H6	0.3208	0.5595	0.4146	0.023*
O8	0.54816 (18)	0.60234 (18)	0.35425 (3)	0.0189 (4)
C7	0.5118 (3)	0.4402 (3)	0.36044 (5)	0.0147 (5)
N9	0.4773 (2)	0.3185 (2)	0.33405 (4)	0.0142 (4)
C10	0.4901 (3)	0.3736 (3)	0.29649 (5)	0.0161 (5)
H10A	0.5498	0.4918	0.2947	0.019*
H10B	0.3692	0.3849	0.2864	0.019*
C11	0.5973 (3)	0.2316 (3)	0.27605 (5)	0.0189 (5)
H11A	0.5949 (18)	0.2614 (17)	0.2498 (4)	0.015 (5)*
H11B	0.7269	0.2305	0.2847	0.018*
O12	0.52018 (19)	0.05262 (17)	0.27991 (3)	0.0201 (4)
C13	0.5174 (3)	0.0010 (3)	0.31667 (5)	0.0177 (5)
H13A	0.647 (3)	−0.001 (2)	0.3263 (5)	0.022 (6)*
H13B	0.464 (2)	−0.125 (3)	0.3176 (5)	0.020 (5)*
C14	0.4050 (3)	0.1331 (3)	0.33829 (5)	0.0165 (5)
H14A	0.2806 (17)	0.1330 (17)	0.3295 (3)	0.010 (5)*
H14B	0.4053	0.0938	0.3642	0.012*
F15	0.48309 (18)	0.20748 (16)	0.50252 (3)	0.0315 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0138 (11)	0.0155 (11)	0.0157 (11)	−0.0022 (10)	0.0001 (9)	−0.0014 (8)
C2	0.0235 (13)	0.0223 (13)	0.0179 (12)	0.0050 (11)	0.0021 (9)	−0.0023 (10)
C3	0.0291 (14)	0.0201 (12)	0.0182 (12)	0.0080 (11)	−0.0045 (10)	0.0034 (10)
C4	0.0300 (14)	0.0215 (11)	0.0107 (11)	−0.0033 (12)	0.0001 (10)	0.0010 (9)
C5	0.0248 (13)	0.0242 (13)	0.0176 (12)	0.0017 (11)	0.0038 (10)	−0.0038 (10)
C6	0.0209 (12)	0.0191 (12)	0.0179 (12)	0.0031 (10)	−0.0027 (9)	−0.0010 (10)
O8	0.0240 (8)	0.0132 (8)	0.0196 (8)	−0.0015 (7)	−0.0025 (6)	−0.0003 (6)
C7	0.0093 (11)	0.0174 (11)	0.0175 (11)	0.0019 (9)	0.0001 (9)	−0.0004 (9)
N9	0.0174 (10)	0.0139 (9)	0.0115 (9)	−0.0028 (8)	0.0005 (8)	0.0016 (7)
C10	0.0197 (12)	0.0170 (11)	0.0116 (11)	−0.0016 (11)	−0.0026 (9)	0.0019 (8)
C11	0.0248 (13)	0.0156 (12)	0.0164 (12)	−0.0024 (10)	0.0018 (10)	0.0003 (9)
O12	0.0301 (9)	0.0148 (7)	0.0154 (7)	−0.0025 (7)	0.0010 (7)	−0.0009 (6)
C13	0.0210 (14)	0.0155 (12)	0.0167 (11)	−0.0022 (11)	−0.0009 (11)	0.0028 (9)
C14	0.0193 (12)	0.0155 (11)	0.0148 (11)	−0.0035 (10)	−0.0001 (10)	0.0012 (10)
F15	0.0487 (9)	0.0319 (8)	0.0137 (6)	0.0032 (7)	0.0018 (6)	0.0047 (5)

Geometric parameters (Å, º) top

C1—C6	1.385 (3)	N9—C14	1.463 (2)
C1—C2	1.390 (3)	N9—C10	1.470 (2)
C1—C7	1.501 (3)	C10—C11	1.512 (3)
C2—C3	1.382 (3)	C10—H10A	0.9700
C2—H2	0.9300	C10—H10B	0.9700
C3—C4	1.370 (3)	C11—O12	1.431 (2)
C3—H3	0.9300	C11—H11A	1.010 (14)
C4—F15	1.366 (2)	C11—H11B	1.0073
C4—C5	1.366 (3)	O12—C13	1.432 (2)
C5—C6	1.386 (3)	C13—C14	1.508 (3)
C5—H5	0.9300	C13—H13A	1.02 (2)
C6—H6	0.9300	C13—H13B	1.001 (19)
O8—C7	1.235 (2)	C14—H14A	0.974 (13)
C7—N9	1.355 (2)	C14—H14B	1.0138

C6—C1—C2	119.23 (18)	N9—C10—H10A	109.8
C6—C1—C7	118.86 (18)	C11—C10—H10A	109.8
C2—C1—C7	121.79 (18)	N9—C10—H10B	109.8
C3—C2—C1	120.5 (2)	C11—C10—H10B	109.8
C3—C2—H2	119.7	H10A—C10—H10B	108.2
C1—C2—H2	119.7	O12—C11—C10	111.53 (16)
C4—C3—C2	118.4 (2)	O12—C11—H11A	106.8 (8)
C4—C3—H3	120.8	C10—C11—H11A	109.8 (8)
C2—C3—H3	120.8	O12—C11—H11B	109.6
F15—C4—C5	118.27 (19)	C10—C11—H11B	109.6
F15—C4—C3	118.85 (19)	H11A—C11—H11B	109.4
C5—C4—C3	122.88 (19)	C11—O12—C13	110.11 (15)
C4—C5—C6	118.3 (2)	O12—C13—C14	111.05 (17)
C4—C5—H5	120.8	O12—C13—H13A	109.4 (11)
C6—C5—H5	120.8	C14—C13—H13A	109.5 (11)
C1—C6—C5	120.6 (2)	O12—C13—H13B	106.2 (10)
C1—C6—H6	119.7	C14—C13—H13B	110.7 (11)
C5—C6—H6	119.7	H13A—C13—H13B	109.9 (15)
O8—C7—N9	122.02 (17)	N9—C14—C13	109.46 (16)
O8—C7—C1	119.86 (18)	N9—C14—H14A	107.8 (8)
N9—C7—C1	118.12 (17)	C13—C14—H14A	109.4 (7)
C7—N9—C14	126.47 (16)	N9—C14—H14B	111.4
C7—N9—C10	120.76 (16)	C13—C14—H14B	109.5
C14—N9—C10	112.38 (15)	H14A—C14—H14B	109.2
N9—C10—C11	109.49 (16)

C6—C1—C2—C3	2.2 (3)	C2—C1—C7—N9	59.3 (3)
C7—C1—C2—C3	178.1 (2)	O8—C7—N9—C14	−169.47 (18)
C1—C2—C3—C4	0.1 (3)	C1—C7—N9—C14	10.5 (3)
C2—C3—C4—F15	178.61 (19)	O8—C7—N9—C10	2.8 (3)
C2—C3—C4—C5	−1.5 (3)	C1—C7—N9—C10	−177.22 (17)
F15—C4—C5—C6	−179.61 (19)	C7—N9—C10—C11	133.04 (19)
C3—C4—C5—C6	0.4 (3)	C14—N9—C10—C11	−53.7 (2)
C2—C1—C6—C5	−3.2 (3)	N9—C10—C11—O12	55.7 (2)
C7—C1—C6—C5	−179.26 (19)	C10—C11—O12—C13	−59.5 (2)
C4—C5—C6—C1	1.9 (3)	C11—O12—C13—C14	60.3 (2)
C6—C1—C7—O8	55.2 (3)	C7—N9—C14—C13	−132.5 (2)
C2—C1—C7—O8	−120.7 (2)	C10—N9—C14—C13	54.7 (2)
C6—C1—C7—N9	−124.8 (2)	O12—C13—C14—N9	−57.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O12ⁱ	1.010 (14)	2.546 (13)	3.265 (2)	127.9 (9)
C13—H13A···O8ⁱⁱ	1.02 (2)	2.59 (2)	3.572 (3)	161.5 (14)
C13—H13B···O8ⁱⁱⁱ	1.001 (19)	2.499 (18)	3.242 (2)	130.7 (14)
C14—H14A···O8^iv	0.974 (13)	2.601 (12)	3.395 (2)	138.8 (10)

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

Summary of hydrogen-bond geometry (Å, °) for 1a–1d top

D—H···A	D—H (Å)	H···A (Å)	D···A (Å)	D—H···A (°)
1a
C14—H14A···O8ⁱ	0.97 (2)	2.52 (2)	3.480 (3)	171.7 (18)
C14—H14B···O8ⁱⁱ	0.96 (2)	2.41 (2)	3.069 (2)	125.6 (18)

1b
C3—H3A···O2ⁱⁱⁱ	0.92 (4)	2.63 (4)	3.257 (4)	126 (3)
C2—H2B···O1^iv	0.96 (4)	2.48 (4)	3.322 (5)	146 (3)
C3P—H3P···O2^v	0.99 (5)	2.43 (5)	3.417 (5)	174 (4)

1c
C5—H5···O12^v	0.88 (3)	2.48 (4)	3.353 (4)	178 (3)
C10A—H10A···O8^vi	0.97	2.43	3.240 (4)	140.3
C10A—H10B···Cl15^vii	0.97	2.92	3.382 (4)	110.1
C14A—H14B···O12^viii	0.97	2.55	3.281 (4)	132.6
C10B—H10D···O8^vi	0.97	2.48	3.307 (7)	143.2
C11B—H11C···O8^ix	0.97	2.65	3.601 (8)	166.1
C14B—H14C···O12^viii	0.97	2.54	3.250 (7)	130.2

1d
C11—H11A···O12^x	1.010 (14)	2.546 (13)	3.265 (2)	127.9 (9)
C13—H13A···O8^xi	1.02 (2)	2.59 (2)	3.572 (2)	161.5 (14)
C13—H13B···O8^xii	1.001 (19)	2.499 (18)	3.242 (2)	130.7 (14)
C14—H14A···O8^xiii	0.974 (13)	2.601 (12)	3.395 (2)	138.8 (10)

Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, y-1/2, -z+1/2; (iii) -x+y, -x, z-1/3; (iv) -y+1, x-y+1, z+1/3; (v) x, y, z-1; (vi) -y+1, x-y, z+1/3; (vii) -x+y, -x, z+2/3; (viii) -x+y, -x+1, z-1/3; (ix) -x+y+1, -x+1, z+2/3; (x) -x+1, y+1/2, -z+1/2; (xi) -x+3/2, y-1/2, z; (xii) x, y-1, z; (xiii) -x+1/2, y-1/2, z.

Selected crystallographic structural parameters (Å, °) of 4-halobenzamides 1a–1d top

Entry	Amide	N—C(O)	C═O	NC(O) τ	NC(O) χ_N	CC(O) τ
1	1a (R = I)	1.357	1.234	12.90	19.99	43.77
2	1b (R = Br)	1.345	1.230	0.18	8.28	74.30
3	1c (R = Cl)	1.389	1.224	1.35	0.89	62.54
4	1d (R = F)	1.354	1.236	6.69	7.81	57.28
5	Benzamide	1.342	1.265	0.02	0.07	25.66
6	Formamide	1.349	1.193	0.0	0.0	0.0

Entries 1–4 are from this study and are X-ray structures, entry 5 is from Johansson & van de Streek (2016) and is an X-ray structure, and entry 6 is from Greenberg & Venanzi (1993) and are calculated values.

Resonance energies of amides 1a–1e calculated using the COSNAR method^a top

Entry	1	E_R (kcal mol^-1)
1	1a (R = I)	15.3
2	1b (R = Br)	15.2
3	1c (R = Cl)	15.2
4	1d (R = F)	15.0
5	1e (R = H)	15.3

Note: (a) representative data on twisted amides: Szostak et al. (2016); representative data on bridged lactams: Greenberg et al. (1996) and Szostak et al. (2015).

Resonance energies of amides 2a–2e calculated using the COSNAR method^a top

Entry	2	E_R (kcal mol^-1)
1	2a (R = I)	15.5
2	2b (R = Br)	15.4
3	2c (R = Cl)	15.5
4	2d (R = F)	15.1
5	2e (R = H)	15.5

Note: (a) representative data on twisted amides: Szostak et al. (2016); representative data on bridged lactams: Greenberg et al. (1996) and Szostak et al. (2015).

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Structures and energetic properties of 4-halo­benzamides

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Structures and energetic properties of 4-halobenzamides