Role of secondary inter­actions in a series of 2:1 halogen-bonded cocrystals formed between 4-(di­methyl­amino)­pyridine and ditopic halogen-bond donors

Bosch, E.; Bowling, N.P.

doi:10.1107/S205322962400771X

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Role of secondary interactions in a series of 2:1 halogen-bonded cocrystals formed between 4-(dimethylamino)pyridine and ditopic halogen-bond donors

E. Bosch and N. P. Bowling

The structures of a series of 2:1 cocrystals formed between 4-(dimethylamino)pyridine and each of 1,2,4,5-tetrachloro-3,6-diiodobenzene, 2C₇H₁₀N₂·C₆Cl₄I₂, 1,2,4,5-tetrabromo-3,6-diiodobenzene, 2C₇H₁₀N₂·C₆Br₄I₂, 1-bromo-4-iodo-2,3,5,6-tetrafluorobenzene, 2C₇H₁₀N₂·C₆BrF₄I, and 1,2-dibromo-4,5-difluoro-3,6-diiodobenzene, 2C₇H₁₀N₂·C₆Br₂F₂I₂, are reported. In all five structures, the core halogen-bonded 2:1 trimolecular units have geometrically similar parameters, with the central halogen-bond donor flanked by two pyridine halogen-bond acceptors twisted with respect to the central halogen-bond donor at angles ranging from 76 to 86°. The I

N halogen-bond separations are all short, ranging from 73.3 to 76.7% of the sum of the van der Waals radii, while the C—I

N bond angles are essentially linear. The Br

N halogen-bond separation in the cocrystal formed with 1-bromo-4-iodo-2,3,5,6-tetrafluorobenzene is 80.4% of the sum of the van der Waals radii. Subtle differences in the crystal packings are attributed to the role of secondary C—H

π and weak π-type interactions with chloro and bromo substituents. The cocrystals 2C₇H₁₀N₂·C₆Cl₄I₂ and 2C₇H₁₀N₂·C₆Br₄I₂ are isomorphous.

Keywords: crystal structure; halogen bonding; 1,4-diiodotetrahalobenzene; C—Cl

π; C—Br

π; C—H

π.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S205322962400771X/vp3039sup1.cif Contains datablocks 2DMAP.DITCB, 2DMAP.DITBB, 2DMAP.IBTFB, 2DMAP.DIBFB, global
	Structure factor file (CIF format) https://doi.org/10.1107/S205322962400771X/vp30392DMAP.DITCBsup2.hkl Contains datablock 2DMAP.DITCB
	Structure factor file (CIF format) https://doi.org/10.1107/S205322962400771X/vp30392DMAP.DITBBsup3.hkl Contains datablock 2DMAP.DITBB
	Structure factor file (CIF format) https://doi.org/10.1107/S205322962400771X/vp30392DMAP.IBTFBsup4.hkl Contains datablock 2DMAP.IBTFB
	Structure factor file (CIF format) https://doi.org/10.1107/S205322962400771X/vp30392DMAP.DIBFBsup5.hkl Contains datablock 2DMAP.DIBFB
	Chemical Markup Language (CML) file https://doi.org/10.1107/S205322962400771X/vp30392DMAP.DITCBsup6.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S205322962400771X/vp30392DMAP.DITBBsup7.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S205322962400771X/vp30392DMAP.IBTFBsup8.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S205322962400771X/vp30392DMAP.DIBFBsup9.cml Supplementary material

CCDC references: 2375541; 2375540; 2375539; 2375538

Computing details top

4-(Dimethylamino)pyridine–1,2,4,5-tetrachloro-3,6-diiodobenzene (2/1) (2DMAP.DITCB) top

Crystal data top

2C₇H₁₀N₂·C₆Cl₄I₂	Z = 1
M_r = 712.03	F(000) = 344.569
Triclinic, P1	D_x = 1.987 Mg m⁻³
a = 8.1680 (3) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.1290 (4) Å	Cell parameters from 5533 reflections
c = 9.8118 (3) Å	θ = 5.2–76.7°
α = 103.727 (3)°	µ = 25.03 mm⁻¹
β = 107.165 (3)°	T = 100 K
γ = 112.180 (4)°	Block, colourless
V = 594.91 (5) Å³	0.14 × 0.1 × 0.03 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	2500 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2413 reflections with I ≥ 2u(I)
Mirror monochromator	R_int = 0.063
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.8°, θ_min = 5.1°
ω scans	h = −8→10
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2023)	k = −11→11
T_min = 0.104, T_max = 0.510	l = −12→10
8921 measured reflections

Refinement top

Refinement on F²	16 constraints
Least-squares matrix: full	Primary atom site location: dual
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0833P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = −0.0004
2500 reflections	Δρ_max = 1.33 e Å⁻³
138 parameters	Δρ_min = −1.51 e Å⁻³
0 restraints

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

	x	y	z	U_iso*/U_eq
I1	0.66832 (3)	0.55170 (3)	0.83016 (2)	0.02027 (14)
Cl1	0.55433 (14)	0.87164 (13)	0.82188 (12)	0.0244 (2)
Cl2	0.84204 (14)	1.25822 (12)	0.96798 (12)	0.0236 (2)
N1	0.4176 (6)	0.2104 (5)	0.6920 (5)	0.0256 (8)
N2	−0.0264 (6)	−0.3045 (5)	0.4505 (5)	0.0265 (8)
C10	0.9318 (6)	1.1168 (5)	0.9868 (5)	0.0191 (7)
C2	0.3727 (6)	0.1184 (6)	0.5449 (5)	0.0250 (8)
H2	0.4439 (6)	0.1742 (6)	0.4948 (5)	0.0299 (10)*
C5	0.1183 (6)	−0.1363 (5)	0.5291 (5)	0.0206 (8)
C9	0.8010 (6)	0.9401 (5)	0.9196 (5)	0.0197 (7)
C1	0.2313 (6)	−0.0503 (6)	0.4621 (5)	0.0246 (8)
H1	0.2100 (6)	−0.1089 (6)	0.3594 (5)	0.0295 (10)*
C3	0.3125 (6)	0.1261 (5)	0.7584 (5)	0.0240 (8)
H3	0.3424 (6)	0.1869 (5)	0.8631 (5)	0.0287 (10)*
C8	0.8668 (6)	0.8202 (5)	0.9319 (5)	0.0197 (8)
C4	0.1660 (6)	−0.0410 (6)	0.6849 (5)	0.0233 (8)
H4	0.0967 (6)	−0.0928 (6)	0.7379 (5)	0.0280 (10)*
C6	−0.1438 (7)	−0.3878 (6)	0.5229 (6)	0.0297 (9)
H6a	−0.0579 (8)	−0.381 (4)	0.621 (2)	0.0445 (14)*
H6b	−0.218 (4)	−0.330 (3)	0.544 (4)	0.0445 (14)*
H6c	−0.234 (4)	−0.5088 (14)	0.453 (2)	0.0445 (14)*
C7	−0.0832 (7)	−0.3915 (6)	0.2866 (5)	0.0287 (9)
H7a	−0.119 (5)	−0.325 (3)	0.2303 (8)	0.0431 (13)*
H7b	0.027 (2)	−0.402 (4)	0.2728 (6)	0.0431 (13)*
H7c	−0.195 (4)	−0.5064 (19)	0.2461 (12)	0.0431 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01750 (18)	0.01770 (19)	0.02180 (19)	0.00611 (13)	0.00822 (13)	0.00595 (13)
Cl1	0.0153 (4)	0.0225 (5)	0.0289 (5)	0.0072 (4)	0.0055 (4)	0.0081 (4)
Cl2	0.0205 (5)	0.0205 (5)	0.0285 (5)	0.0109 (4)	0.0086 (4)	0.0084 (4)
N1	0.0211 (18)	0.0238 (18)	0.0272 (19)	0.0105 (15)	0.0079 (15)	0.0063 (16)
N2	0.0226 (18)	0.0239 (18)	0.0230 (18)	0.0053 (15)	0.0093 (15)	0.0040 (15)
C10	0.0201 (19)	0.0204 (18)	0.0195 (18)	0.0102 (16)	0.0113 (16)	0.0082 (15)
C2	0.021 (2)	0.029 (2)	0.029 (2)	0.0129 (18)	0.0130 (18)	0.0147 (18)
C5	0.0157 (19)	0.0203 (19)	0.024 (2)	0.0101 (16)	0.0052 (16)	0.0067 (16)
C9	0.0153 (17)	0.0236 (19)	0.0149 (18)	0.0065 (15)	0.0051 (14)	0.0054 (15)
C1	0.022 (2)	0.025 (2)	0.025 (2)	0.0124 (17)	0.0097 (17)	0.0058 (17)
C3	0.0191 (19)	0.023 (2)	0.026 (2)	0.0087 (17)	0.0091 (17)	0.0068 (17)
C8	0.0178 (19)	0.0172 (18)	0.021 (2)	0.0058 (16)	0.0089 (16)	0.0066 (16)
C4	0.0199 (19)	0.026 (2)	0.024 (2)	0.0120 (17)	0.0096 (17)	0.0097 (17)
C6	0.027 (2)	0.027 (2)	0.032 (2)	0.0087 (19)	0.013 (2)	0.014 (2)
C7	0.025 (2)	0.021 (2)	0.025 (2)	0.0063 (17)	0.0052 (18)	0.0006 (17)

Geometric parameters (Å, º) top

I1—C8	2.125 (4)	C5—C4	1.417 (6)
Cl1—C9	1.730 (4)	C9—C8	1.405 (6)
Cl2—C10	1.728 (4)	C1—H1	0.9500
N1—C2	1.343 (6)	C3—H3	0.9500
N1—C3	1.350 (6)	C3—C4	1.367 (6)
N2—C5	1.371 (6)	C4—H4	0.9500
N2—C6	1.453 (6)	C6—H6a	0.9800
N2—C7	1.451 (6)	C6—H6b	0.9800
C10—C9	1.398 (6)	C6—H6c	0.9800
C10—C8ⁱ	1.402 (6)	C7—H7a	0.9800
C2—H2	0.9500	C7—H7b	0.9800
C2—C1	1.370 (6)	C7—H7c	0.9800
C5—C1	1.398 (6)

C3—N1—C2	115.7 (4)	C4—C3—N1	124.3 (4)
C6—N2—C5	120.4 (4)	C4—C3—H3	117.8 (3)
C7—N2—C5	119.7 (4)	C10ⁱ—C8—I1	121.0 (3)
C7—N2—C6	119.2 (4)	C9—C8—I1	121.2 (3)
C9—C10—Cl2	119.0 (3)	C9—C8—C10ⁱ	117.8 (4)
C8ⁱ—C10—Cl2	119.9 (3)	C3—C4—C5	119.5 (4)
C8ⁱ—C10—C9	121.1 (4)	H4—C4—C5	120.3 (2)
H2—C2—N1	117.8 (2)	H4—C4—C3	120.3 (3)
C1—C2—N1	124.4 (4)	H6a—C6—N2	109.5
C1—C2—H2	117.8 (3)	H6b—C6—N2	109.5
C1—C5—N2	122.1 (4)	H6b—C6—H6a	109.5
C4—C5—N2	121.8 (4)	H6c—C6—N2	109.5
C4—C5—C1	116.1 (4)	H6c—C6—H6a	109.5
C10—C9—Cl1	118.5 (3)	H6c—C6—H6b	109.5
C8—C9—Cl1	120.4 (3)	H7a—C7—N2	109.5
C8—C9—C10	121.1 (4)	H7b—C7—N2	109.5
C5—C1—C2	119.9 (4)	H7b—C7—H7a	109.5
H1—C1—C2	120.1 (3)	H7c—C7—N2	109.5
H1—C1—C5	120.1 (2)	H7c—C7—H7a	109.5
H3—C3—N1	117.8 (3)	H7c—C7—H7b	109.5

I1—C8—C10ⁱ—Cl2ⁱ	−0.2 (3)	Cl2—C10—C8ⁱ—C9ⁱ	179.9 (3)
I1—C8—C10ⁱ—C9ⁱ	−179.9 (3)	N1—C2—C1—C5	2.1 (5)
I1—C8—C9—Cl1	0.6 (3)	N1—C3—C4—C5	0.5 (5)
I1—C8—C9—C10	179.9 (3)	N2—C5—C1—C2	179.3 (4)
Cl1—C9—C10—Cl2	−0.6 (3)	N2—C5—C4—C3	179.5 (4)
Cl1—C9—C10—C8ⁱ	179.7 (3)	C10—C9—C8—C10ⁱ	−0.4 (4)
Cl1—C9—C8—C10ⁱ	−179.7 (3)	C10ⁱ—C8—C9—C10	−0.4 (4)
Cl2—C10—C9—C8	−179.9 (3)	C2—C1—C5—C4	−2.6 (5)

Symmetry code: (i) −x+2, −y+2, −z+2.

4-(Dimethylamino)pyridine–1,2,4,5-tetrabromo-3,6-diiodobenzene (2/1) (2DMAP.DITBB) top

Crystal data top

2C₇H₁₀N₂·C₆Br₄I₂	Z = 1
M_r = 889.83	F(000) = 412.446
Triclinic, P1	D_x = 2.411 Mg m⁻³
a = 8.3361 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.3089 (3) Å	Cell parameters from 8887 reflections
c = 9.8204 (2) Å	θ = 5.1–76.2°
α = 102.484 (2)°	µ = 27.92 mm⁻¹
β = 108.399 (2)°	T = 100 K
γ = 113.064 (2)°	Irregular, clear colourless
V = 612.84 (4) Å³	0.21 × 0.17 × 0.08 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	2446 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2429 reflections with I ≥ 2u(I)
Mirror monochromator	R_int = 0.055
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.1°, θ_min = 5.2°
ω scans	h = −10→10
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2023)	k = −8→11
T_min = 0.011, T_max = 0.146	l = −12→11
11315 measured reflections

Refinement top

Refinement on F²	16 constraints
Least-squares matrix: full	Primary atom site location: dual
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0862P)² + 0.8994P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2446 reflections	Δρ_max = 1.81 e Å⁻³
138 parameters	Δρ_min = −1.59 e Å⁻³
0 restraints

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

	x	y	z	U_iso*/U_eq
I1	0.66402 (4)	0.55739 (3)	0.82970 (3)	0.02993 (15)
Br1	1.15967 (7)	0.73203 (6)	1.03222 (6)	0.03016 (17)
Br2	1.46760 (7)	1.13485 (6)	1.18536 (6)	0.03136 (17)
N1	0.4123 (7)	0.2193 (6)	0.6942 (6)	0.0353 (10)
N2	−0.0154 (7)	−0.2952 (6)	0.4640 (6)	0.0353 (10)
C9	1.0645 (7)	0.8856 (6)	1.0133 (6)	0.0272 (9)
C10	1.1981 (7)	1.0596 (6)	1.0791 (6)	0.0275 (9)
C3	0.1231 (7)	−0.1283 (6)	0.5382 (6)	0.0288 (10)
C8	0.8650 (7)	0.8220 (6)	0.9320 (6)	0.0276 (10)
C2	0.1625 (8)	−0.0294 (7)	0.6879 (6)	0.0326 (10)
H2	0.0909 (8)	−0.0788 (7)	0.7395 (6)	0.0391 (12)*
C4	0.2372 (8)	−0.0440 (7)	0.4711 (6)	0.0331 (10)
H4	0.2183 (8)	−0.1031 (7)	0.3705 (6)	0.0398 (12)*
C5	0.3767 (8)	0.1251 (7)	0.5530 (6)	0.0318 (10)
H5	0.4529 (8)	0.1783 (7)	0.5058 (6)	0.0381 (12)*
C1	0.3051 (8)	0.1395 (6)	0.7594 (6)	0.0313 (10)
H1	0.3289 (8)	0.2028 (6)	0.8605 (6)	0.0375 (12)*
C6	−0.1347 (9)	−0.3752 (7)	0.5351 (7)	0.0389 (12)
H6a	−0.0505 (9)	−0.362 (6)	0.638 (3)	0.0583 (18)*
H6b	−0.213 (6)	−0.322 (4)	0.546 (6)	0.0583 (18)*
H6c	−0.221 (5)	−0.4962 (15)	0.469 (3)	0.0583 (18)*
C7	−0.0661 (9)	−0.3860 (7)	0.3027 (7)	0.0415 (13)
H7a	−0.103 (7)	−0.326 (4)	0.2392 (13)	0.0623 (19)*
H7b	0.046 (3)	−0.392 (6)	0.2968 (11)	0.0623 (19)*
H7c	−0.175 (5)	−0.501 (2)	0.264 (2)	0.0623 (19)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0289 (2)	0.0298 (2)	0.0321 (2)	0.01458 (16)	0.01462 (16)	0.01236 (15)
Br1	0.0299 (3)	0.0301 (3)	0.0361 (3)	0.0184 (2)	0.0154 (2)	0.0147 (2)
Br2	0.0245 (3)	0.0328 (3)	0.0362 (3)	0.0150 (2)	0.0118 (2)	0.0135 (2)
N1	0.032 (2)	0.034 (2)	0.035 (2)	0.0144 (19)	0.0144 (19)	0.0111 (19)
N2	0.036 (2)	0.037 (2)	0.032 (2)	0.016 (2)	0.018 (2)	0.0133 (19)
C9	0.029 (2)	0.031 (2)	0.029 (2)	0.0178 (19)	0.016 (2)	0.0135 (18)
C10	0.025 (2)	0.031 (2)	0.028 (2)	0.0134 (18)	0.0143 (19)	0.0132 (18)
C3	0.026 (2)	0.030 (2)	0.031 (2)	0.0150 (19)	0.012 (2)	0.0119 (19)
C8	0.031 (2)	0.028 (2)	0.025 (2)	0.0141 (19)	0.014 (2)	0.0108 (18)
C2	0.029 (2)	0.040 (3)	0.035 (3)	0.020 (2)	0.016 (2)	0.018 (2)
C4	0.031 (2)	0.041 (3)	0.032 (2)	0.020 (2)	0.015 (2)	0.015 (2)
C5	0.031 (2)	0.036 (2)	0.037 (3)	0.019 (2)	0.020 (2)	0.019 (2)
C1	0.033 (3)	0.031 (2)	0.032 (2)	0.017 (2)	0.016 (2)	0.011 (2)
C6	0.034 (3)	0.037 (3)	0.039 (3)	0.013 (2)	0.014 (2)	0.015 (2)
C7	0.042 (3)	0.034 (3)	0.038 (3)	0.014 (2)	0.017 (3)	0.006 (2)

Geometric parameters (Å, º) top

I1—C8	2.126 (5)	C2—H2	0.9500
Br1—C9	1.902 (5)	C2—C1	1.382 (8)
Br2—C10	1.897 (5)	C4—H4	0.9500
N1—C5	1.338 (7)	C4—C5	1.380 (8)
N1—C1	1.345 (7)	C5—H5	0.9500
N2—C3	1.361 (7)	C1—H1	0.9500
N2—C6	1.454 (8)	C6—H6a	0.9800
N2—C7	1.457 (7)	C6—H6b	0.9800
C9—C10	1.400 (7)	C6—H6c	0.9800
C9—C8	1.393 (7)	C7—H7a	0.9800
C10—C8ⁱ	1.404 (7)	C7—H7b	0.9800
C3—C2	1.411 (8)	C7—H7c	0.9800
C3—C4	1.410 (7)

C1—N1—C5	116.3 (5)	C5—C4—C3	119.4 (5)
C6—N2—C3	120.3 (5)	C5—C4—H4	120.3 (3)
C7—N2—C3	119.5 (5)	C4—C5—N1	124.6 (5)
C7—N2—C6	119.4 (5)	H5—C5—N1	117.7 (3)
C10—C9—Br1	118.8 (4)	H5—C5—C4	117.7 (3)
C8—C9—Br1	119.3 (4)	C2—C1—N1	123.7 (5)
C8—C9—C10	121.9 (5)	H1—C1—N1	118.1 (3)
C9—C10—Br2	119.1 (4)	H1—C1—C2	118.1 (3)
C8ⁱ—C10—Br2	120.0 (4)	H6a—C6—N2	109.5
C8ⁱ—C10—C9	121.0 (5)	H6b—C6—N2	109.5
C2—C3—N2	121.9 (5)	H6b—C6—H6a	109.5
C4—C3—N2	122.2 (5)	H6c—C6—N2	109.5
C4—C3—C2	115.9 (5)	H6c—C6—H6a	109.5
C9—C8—I1	121.5 (4)	H6c—C6—H6b	109.5
C10ⁱ—C8—I1	121.3 (4)	H7a—C7—N2	109.5
C10ⁱ—C8—C9	117.1 (5)	H7b—C7—N2	109.5
H2—C2—C3	120.0 (3)	H7b—C7—H7a	109.5
C1—C2—C3	120.1 (5)	H7c—C7—N2	109.5
C1—C2—H2	120.0 (3)	H7c—C7—H7a	109.5
H4—C4—C3	120.3 (3)	H7c—C7—H7b	109.5

I1—C8—C9—Br1	0.3 (4)	Br2—C10—C8ⁱ—C9ⁱ	179.2 (4)
I1—C8—C9—C10	179.1 (4)	N1—C5—C4—C3	−0.9 (7)
I1—C8—C10ⁱ—Br2ⁱ	0.6 (4)	N1—C1—C2—C3	0.4 (7)
I1—C8—C10ⁱ—C9ⁱ	−179.1 (4)	N2—C3—C2—C1	179.7 (5)
Br1—C9—C10—Br2	−0.4 (4)	N2—C3—C4—C5	−179.4 (5)
Br1—C9—C10—C8ⁱ	179.9 (4)	C9—C10—C8ⁱ—C9ⁱ	−1.1 (4)
Br1—C9—C8—C10ⁱ	−179.9 (4)	C9—C8—C10ⁱ—C9ⁱ	1.1 (4)
Br2—C10—C9—C8	−179.2 (4)

Symmetry code: (i) −x+2, −y+2, −z+2.

4-(Dimethylamino)pyridine–1-bromo-4-iodo-2,3,5,6-tetrafluorobenzene (2/1) (2DMAP.IBTFB) top

Crystal data top

2C₇H₁₀N₂·C₆BrF₄I	F(000) = 584.861
M_r = 599.21	D_x = 1.837 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 7.3898 (1) Å	Cell parameters from 6158 reflections
b = 16.2120 (2) Å	θ = 2.7–77.2°
c = 9.4236 (1) Å	µ = 14.21 mm⁻¹
β = 106.304 (2)°	T = 100 K
V = 1083.58 (3) Å³	Irregular, clear colourless
Z = 2	0.12 × 0.08 × 0.05 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	2300 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2252 reflections with I ≥ 2u(I)
Mirror monochromator	R_int = 0.042
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.8°, θ_min = 5.5°
ω scans	h = −9→8
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2023)	k = −20→20
T_min = 0.357, T_max = 0.595	l = −11→11
10454 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.034	w = 1/[σ²(F_o²) + (0.P)² + 7.3962P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.080	(Δ/σ)_max = −0.0003
S = 1.00	Δρ_max = 0.75 e Å⁻³
2300 reflections	Δρ_min = −0.58 e Å⁻³
142 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.00052 (12)
17 constraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.5971 (11)	0.1994 (3)	0.5192 (9)	0.0152 (3)	0.500000
F1	0.8516 (3)	0.05177 (14)	0.5086 (3)	0.0208 (5)
F2	0.7755 (3)	−0.10968 (14)	0.4932 (3)	0.0225 (5)
N2	0.8291 (5)	0.6174 (2)	0.5179 (4)	0.0232 (7)
N1	0.6838 (5)	0.3679 (2)	0.5376 (4)	0.0223 (7)
C9	0.6759 (5)	0.0271 (2)	0.5040 (4)	0.0166 (7)
C8	0.5400 (5)	0.0856 (2)	0.5067 (4)	0.0165 (7)
C3	0.7814 (5)	0.5370 (2)	0.5251 (4)	0.0182 (7)
C4	0.8329 (5)	0.4914 (2)	0.6585 (4)	0.0196 (8)
H4	0.9035 (5)	0.5168 (2)	0.7478 (4)	0.0236 (9)*
C10	0.6374 (5)	−0.0562 (2)	0.4966 (4)	0.0171 (7)
C1	0.6320 (6)	0.4122 (3)	0.4111 (4)	0.0220 (8)
H1	0.5583 (6)	0.3852 (3)	0.3247 (4)	0.0264 (10)*
C5	0.7796 (6)	0.4098 (3)	0.6572 (5)	0.0215 (8)
H5	0.8137 (6)	0.3811 (3)	0.7488 (5)	0.0258 (10)*
C2	0.6781 (6)	0.4934 (2)	0.3983 (4)	0.0200 (8)
H2	0.6407 (6)	0.5202 (2)	0.3049 (4)	0.0241 (9)*
C6	0.7750 (6)	0.6616 (3)	0.3788 (5)	0.0255 (9)
H6a	0.826 (4)	0.6332 (11)	0.3067 (12)	0.0383 (13)*
H6b	0.6371 (6)	0.6635 (18)	0.3418 (19)	0.0383 (13)*
H6c	0.825 (4)	0.7179 (7)	0.3937 (9)	0.0383 (13)*
C7	0.9279 (7)	0.6620 (3)	0.6521 (5)	0.0289 (9)
H7a	0.853 (2)	0.6603 (19)	0.7228 (16)	0.0433 (14)*
H7b	1.051 (2)	0.6362 (13)	0.696 (2)	0.0433 (14)*
H7c	0.946 (4)	0.7195 (6)	0.6272 (8)	0.0433 (14)*
I1	0.6049 (7)	0.21223 (17)	0.5197 (5)	0.0152 (3)	0.500000

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0184 (4)	0.0075 (9)	0.01871 (18)	−0.0009 (7)	0.0037 (2)	−0.0006 (7)
F1	0.0143 (10)	0.0228 (12)	0.0258 (12)	−0.0028 (9)	0.0063 (9)	−0.0008 (9)
F2	0.0177 (11)	0.0188 (11)	0.0314 (13)	0.0042 (9)	0.0077 (9)	−0.0014 (9)
N2	0.0305 (18)	0.0171 (16)	0.0202 (17)	−0.0049 (14)	0.0042 (14)	0.0000 (13)
N1	0.0174 (15)	0.0232 (18)	0.0257 (18)	0.0008 (13)	0.0051 (13)	0.0012 (14)
C9	0.0152 (16)	0.0190 (19)	0.0140 (17)	−0.0041 (14)	0.0015 (13)	0.0014 (14)
C8	0.0175 (17)	0.0146 (17)	0.0170 (18)	−0.0014 (14)	0.0042 (14)	−0.0003 (14)
C3	0.0187 (17)	0.0188 (18)	0.0191 (18)	−0.0002 (15)	0.0086 (15)	−0.0031 (15)
C4	0.0200 (18)	0.0194 (19)	0.0197 (19)	0.0003 (15)	0.0058 (15)	−0.0010 (15)
C10	0.0177 (17)	0.0175 (18)	0.0167 (18)	0.0023 (14)	0.0057 (14)	0.0005 (14)
C1	0.0222 (19)	0.026 (2)	0.0180 (19)	0.0003 (16)	0.0055 (15)	−0.0035 (16)
C5	0.0233 (19)	0.022 (2)	0.0194 (19)	0.0020 (16)	0.0062 (15)	0.0009 (15)
C2	0.0239 (19)	0.0200 (19)	0.0154 (18)	−0.0003 (15)	0.0041 (15)	0.0006 (15)
C6	0.033 (2)	0.019 (2)	0.025 (2)	0.0001 (17)	0.0101 (18)	0.0021 (16)
C7	0.036 (2)	0.020 (2)	0.027 (2)	−0.0085 (18)	0.0041 (19)	−0.0047 (17)
I1	0.0184 (4)	0.0075 (9)	0.01871 (18)	−0.0009 (7)	0.0037 (2)	−0.0006 (7)

Geometric parameters (Å, º) top

Br1—C8	1.888 (6)	C3—C2	1.413 (5)
Br1—I1	0.216 (8)	C4—H4	0.9500
F1—C9	1.348 (4)	C4—C5	1.380 (6)
F2—C10	1.346 (4)	C1—H1	0.9500
N2—C3	1.358 (5)	C1—C2	1.373 (6)
N2—C6	1.448 (5)	C5—H5	0.9500
N2—C7	1.462 (5)	C2—H2	0.9500
N1—C1	1.352 (5)	C6—H6a	0.9800
N1—C5	1.336 (5)	C6—H6b	0.9800
C9—C8	1.388 (5)	C6—H6c	0.9800
C9—C10	1.377 (5)	C7—H7a	0.9800
C8—C10ⁱ	1.387 (5)	C7—H7b	0.9800
C8—I1	2.103 (5)	C7—H7c	0.9800
C3—C4	1.415 (6)

C6—N2—C3	120.7 (3)	H1—C1—N1	117.6 (2)
C7—N2—C3	120.4 (3)	C2—C1—N1	124.8 (4)
C7—N2—C6	118.8 (3)	C2—C1—H1	117.6 (2)
C5—N1—C1	115.2 (4)	C4—C5—N1	125.2 (4)
C8—C9—F1	119.4 (3)	H5—C5—N1	117.4 (2)
C10—C9—F1	118.4 (3)	H5—C5—C4	117.4 (2)
C10—C9—C8	122.1 (3)	C1—C2—C3	119.5 (4)
C9—C8—Br1	121.3 (4)	H2—C2—C3	120.2 (2)
C10ⁱ—C8—Br1	122.1 (4)	H2—C2—C1	120.2 (2)
C10ⁱ—C8—C9	116.6 (3)	H6a—C6—N2	109.5
I1—C8—C9	121.0 (3)	H6b—C6—N2	109.5
I1—C8—C10ⁱ	122.4 (3)	H6b—C6—H6a	109.5
C4—C3—N2	122.4 (4)	H6c—C6—N2	109.5
C2—C3—N2	121.6 (4)	H6c—C6—H6a	109.5
C2—C3—C4	115.9 (4)	H6c—C6—H6b	109.5
H4—C4—C3	120.4 (2)	H7a—C7—N2	109.5
C5—C4—C3	119.2 (4)	H7b—C7—N2	109.5
C5—C4—H4	120.4 (2)	H7b—C7—H7a	109.5
C9—C10—F2	119.0 (3)	H7c—C7—N2	109.5
C8ⁱ—C10—F2	119.7 (3)	H7c—C7—H7a	109.5
C8ⁱ—C10—C9	121.2 (4)	H7c—C7—H7b	109.5

Br1—C8—C9—F1	−0.8 (4)	F2—C10—C8ⁱ—C9ⁱ	−179.6 (3)
Br1—C8—C9—C10	179.3 (4)	F2—C10—C8ⁱ—I1ⁱ	−0.8 (4)
Br1—C8—C10ⁱ—F2ⁱ	1.1 (5)	N2—C3—C4—C5	−179.9 (4)
Br1—C8—C10ⁱ—C9ⁱ	−179.2 (4)	N2—C3—C2—C1	−179.6 (4)
F1—C9—C8—C10ⁱ	−179.3 (3)	N1—C1—C2—C3	−2.4 (5)
F1—C9—C8—I1	−0.5 (4)	N1—C5—C4—C3	1.4 (5)
F1—C9—C10—F2	−0.5 (4)	C9—C8—C10ⁱ—C9ⁱ	−0.7 (3)
F1—C9—C10—C8ⁱ	179.2 (3)	C9—C10—C8ⁱ—C9ⁱ	0.7 (4)
F2—C10—C9—C8	179.5 (3)	C9—C10—C8ⁱ—I1ⁱ	179.5 (3)

Symmetry code: (i) −x+1, −y, −z+1.

4-(Dimethylamino)pyridine–1,2-dibromo-4,5-difluoro-3,6-diiodobenzene (2/1) (2DMAP.DIBFB) top

Crystal data top

2C₇H₁₀N₂·C₆Br₂F₂I₂	Z = 2
M_r = 768.02	F(000) = 723.788
Triclinic, P1	D_x = 2.169 Mg m⁻³
a = 9.6158 (4) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.7518 (4) Å	Cell parameters from 12656 reflections
c = 14.8423 (7) Å	θ = 3.1–77.0°
α = 74.473 (4)°	µ = 25.26 mm⁻¹
β = 85.820 (4)°	T = 100 K
γ = 61.476 (4)°	Plate, clear colourless
V = 1175.73 (10) Å³	0.23 × 0.1 × 0.04 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	4962 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	4694 reflections with I ≥ 2u(I)
Mirror monochromator	R_int = 0.063
Detector resolution: 10.0000 pixels mm^-1	θ_max = 78.5°, θ_min = 3.1°
ω scans	h = −11→12
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2023)	k = −12→12
T_min = 0.055, T_max = 0.441	l = −18→18
22021 measured reflections

Refinement top

Refinement on F²	32 constraints
Least-squares matrix: full	Primary atom site location: dual
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.1145P)² + 0.3489P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = −0.0004
4962 reflections	Δρ_max = 3.00 e Å⁻³
275 parameters	Δρ_min = −1.94 e Å⁻³
0 restraints

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

	x	y	z	U_iso*/U_eq
I1	0.40062 (3)	0.97911 (4)	0.70655 (2)	0.02939 (14)
I2	0.79056 (4)	0.12383 (4)	0.81263 (2)	0.03182 (14)
Br2	0.54649 (6)	0.76869 (6)	0.53272 (3)	0.02882 (15)
Br1	0.72000 (6)	0.37330 (6)	0.58100 (4)	0.03075 (16)
F1	0.4850 (4)	0.6969 (4)	0.8923 (2)	0.0365 (7)
F2	0.6273 (4)	0.3785 (4)	0.9317 (2)	0.0396 (7)
N1	0.2482 (6)	1.3018 (6)	0.6717 (4)	0.0349 (10)
N2	0.0075 (6)	1.8081 (7)	0.6108 (4)	0.0360 (10)
N3	0.9490 (6)	−0.2038 (6)	0.8602 (4)	0.0376 (10)
N4	1.1802 (6)	−0.7074 (7)	0.9133 (4)	0.0392 (11)
C12	0.6494 (5)	0.4759 (6)	0.6795 (3)	0.0257 (9)
C8	0.5171 (6)	0.7235 (6)	0.7292 (4)	0.0262 (9)
C1	0.2447 (6)	1.5495 (7)	0.6697 (4)	0.0290 (10)
C5	0.0864 (6)	1.6428 (7)	0.6311 (3)	0.0272 (9)
C13	0.5739 (5)	0.6440 (6)	0.6585 (3)	0.0251 (9)
C11	0.6720 (6)	0.3808 (6)	0.7722 (4)	0.0267 (10)
C3	0.0972 (6)	1.3892 (7)	0.6354 (4)	0.0336 (11)
C9	0.5373 (6)	0.6278 (7)	0.8202 (4)	0.0311 (10)
C4	0.0143 (6)	1.5545 (7)	0.6148 (4)	0.0313 (10)
C2	0.3179 (6)	1.3846 (7)	0.6872 (4)	0.0334 (11)
C10	0.6122 (6)	0.4623 (7)	0.8411 (4)	0.0321 (10)
C17	0.9472 (6)	−0.4472 (7)	0.8581 (4)	0.0347 (11)
C16	0.8784 (7)	−0.2829 (8)	0.8424 (4)	0.0380 (12)
C15	1.1001 (7)	−0.2938 (7)	0.8956 (4)	0.0352 (11)
C18	1.1063 (6)	−0.5444 (7)	0.8958 (4)	0.0304 (10)
C14	1.1818 (6)	−0.4598 (7)	0.9140 (4)	0.0333 (11)
C6	−0.1606 (6)	1.8945 (7)	0.5886 (5)	0.0383 (12)
C7	0.0866 (6)	1.8924 (7)	0.6323 (4)	0.0352 (11)
C19	1.0981 (8)	−0.7907 (8)	0.8951 (5)	0.0424 (13)
C20	1.3464 (8)	−0.8058 (8)	0.9470 (6)	0.0496 (16)
H1	0.2999 (6)	1.6011 (7)	0.6834 (4)	0.0348 (12)*
H4	−0.0923 (6)	1.6100 (7)	0.5894 (4)	0.0376 (12)*
H14	1.2888 (6)	−0.5176 (7)	0.9388 (4)	0.0400 (13)*
H17	0.8890 (6)	−0.4956 (7)	0.8438 (4)	0.0417 (13)*
H6a	−0.1829 (7)	1.887 (6)	0.5273 (18)	0.0575 (18)*
H6b	−0.2125 (9)	1.847 (4)	0.637 (2)	0.0575 (18)*
H6c	−0.2011 (12)	2.0085 (15)	0.587 (4)	0.0575 (18)*
H7a	0.101 (6)	1.869 (5)	0.7005 (4)	0.0529 (17)*
H7b	0.190 (3)	1.856 (5)	0.605 (3)	0.0529 (17)*
H7c	0.021 (3)	2.0093 (8)	0.606 (3)	0.0529 (17)*
H19a	1.002 (4)	−0.763 (6)	0.930 (3)	0.0636 (19)*
H19b	1.069 (6)	−0.758 (5)	0.8279 (7)	0.0636 (19)*
H19c	1.168 (3)	−0.9079 (8)	0.915 (4)	0.0636 (19)*
H20a	1.4084 (14)	−0.757 (4)	0.910 (3)	0.074 (2)*
H20b	1.3569 (12)	−0.811 (7)	1.0132 (14)	0.074 (2)*
H20c	1.386 (2)	−0.915 (2)	0.940 (4)	0.074 (2)*
H3	0.0454 (6)	1.3331 (7)	0.6235 (4)	0.0403 (13)*
H2	0.4250 (6)	1.3250 (7)	0.7119 (4)	0.0400 (13)*
H15	1.1535 (7)	−0.2400 (7)	0.9087 (4)	0.0422 (13)*
H16	0.7718 (7)	−0.2206 (8)	0.8168 (4)	0.0456 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0264 (2)	0.0275 (2)	0.0354 (2)	−0.01116 (15)	−0.00138 (12)	−0.01253 (14)
I2	0.0300 (2)	0.0277 (2)	0.0357 (2)	−0.01197 (16)	−0.00371 (13)	−0.00713 (14)
Br2	0.0297 (3)	0.0295 (3)	0.0269 (3)	−0.0135 (2)	−0.00174 (18)	−0.0074 (2)
Br1	0.0323 (3)	0.0306 (3)	0.0308 (3)	−0.0132 (2)	0.00128 (19)	−0.0139 (2)
F1	0.0482 (17)	0.0334 (16)	0.0300 (14)	−0.0177 (14)	0.0055 (12)	−0.0162 (12)
F2	0.0489 (17)	0.0399 (18)	0.0280 (14)	−0.0198 (15)	0.0013 (12)	−0.0080 (13)
N1	0.033 (2)	0.034 (3)	0.038 (2)	−0.013 (2)	−0.0033 (18)	−0.013 (2)
N2	0.028 (2)	0.037 (3)	0.044 (3)	−0.013 (2)	−0.0039 (18)	−0.017 (2)
N3	0.038 (2)	0.030 (2)	0.042 (3)	−0.015 (2)	−0.0056 (19)	−0.0049 (19)
N4	0.035 (2)	0.034 (3)	0.043 (3)	−0.011 (2)	−0.009 (2)	−0.010 (2)
C12	0.024 (2)	0.026 (2)	0.032 (2)	−0.0121 (18)	0.0011 (16)	−0.0142 (19)
C8	0.0194 (19)	0.026 (2)	0.033 (2)	−0.0094 (19)	−0.0002 (16)	−0.0105 (19)
C1	0.028 (2)	0.035 (3)	0.031 (2)	−0.019 (2)	0.0023 (18)	−0.013 (2)
C5	0.024 (2)	0.028 (2)	0.027 (2)	−0.0095 (19)	0.0007 (16)	−0.0100 (19)
C13	0.027 (2)	0.027 (2)	0.0214 (19)	−0.0140 (19)	−0.0010 (15)	−0.0037 (17)
C11	0.026 (2)	0.021 (2)	0.034 (2)	−0.0109 (19)	0.0000 (18)	−0.0077 (19)
C3	0.029 (2)	0.038 (3)	0.039 (3)	−0.017 (2)	−0.0026 (19)	−0.016 (2)
C9	0.030 (2)	0.037 (3)	0.032 (2)	−0.015 (2)	0.0013 (18)	−0.019 (2)
C4	0.024 (2)	0.034 (3)	0.037 (2)	−0.013 (2)	−0.0007 (18)	−0.012 (2)
C2	0.025 (2)	0.036 (3)	0.040 (3)	−0.013 (2)	−0.0026 (19)	−0.014 (2)
C10	0.034 (2)	0.039 (3)	0.026 (2)	−0.020 (2)	−0.0008 (18)	−0.006 (2)
C17	0.030 (2)	0.037 (3)	0.037 (3)	−0.016 (2)	0.000 (2)	−0.008 (2)
C16	0.032 (2)	0.039 (3)	0.037 (3)	−0.013 (2)	−0.005 (2)	−0.006 (2)
C15	0.038 (3)	0.034 (3)	0.035 (2)	−0.018 (2)	−0.001 (2)	−0.009 (2)
C18	0.030 (2)	0.031 (3)	0.026 (2)	−0.010 (2)	−0.0016 (18)	−0.009 (2)
C14	0.029 (2)	0.034 (3)	0.035 (2)	−0.013 (2)	−0.0021 (19)	−0.010 (2)
C6	0.027 (2)	0.030 (3)	0.051 (3)	−0.007 (2)	−0.003 (2)	−0.012 (2)
C7	0.031 (2)	0.030 (3)	0.048 (3)	−0.013 (2)	0.002 (2)	−0.017 (2)
C19	0.043 (3)	0.037 (3)	0.048 (3)	−0.017 (3)	0.002 (2)	−0.016 (3)
C20	0.037 (3)	0.031 (3)	0.069 (4)	−0.002 (2)	−0.009 (3)	−0.016 (3)

Geometric parameters (Å, º) top

I1—C8	2.127 (5)	C3—C4	1.368 (8)
I2—C11	2.123 (5)	C3—H3	0.9500
Br2—C13	1.894 (5)	C9—C10	1.369 (8)
Br1—C12	1.894 (5)	C4—H4	0.9500
F1—C9	1.354 (6)	C2—H2	0.9500
F2—C10	1.351 (6)	C17—C16	1.367 (9)
N1—C3	1.346 (7)	C17—C18	1.417 (7)
N1—C2	1.338 (8)	C17—H17	0.9500
N2—C5	1.368 (8)	C16—H16	0.9500
N2—C6	1.435 (7)	C15—C14	1.375 (8)
N2—C7	1.459 (8)	C15—H15	0.9500
N3—C16	1.327 (8)	C18—C14	1.414 (8)
N3—C15	1.343 (8)	C14—H14	0.9500
N4—C18	1.352 (8)	C6—H6a	0.9800
N4—C19	1.455 (8)	C6—H6b	0.9800
N4—C20	1.456 (8)	C6—H6c	0.9800
C12—C13	1.391 (7)	C7—H7a	0.9800
C12—C11	1.403 (7)	C7—H7b	0.9800
C8—C13	1.394 (7)	C7—H7c	0.9800
C8—C9	1.388 (8)	C19—H19a	0.9800
C1—C5	1.414 (7)	C19—H19b	0.9800
C1—C2	1.368 (8)	C19—H19c	0.9800
C1—H1	0.9500	C20—H20a	0.9800
C5—C4	1.409 (8)	C20—H20b	0.9800
C11—C10	1.385 (8)	C20—H20c	0.9800

C2—N1—C3	116.7 (5)	C9—C10—C11	121.8 (5)
C6—N2—C5	119.9 (5)	C18—C17—C16	119.2 (5)
C7—N2—C5	119.3 (5)	H17—C17—C16	120.4 (3)
C7—N2—C6	119.3 (5)	H17—C17—C18	120.4 (3)
C15—N3—C16	116.6 (5)	C17—C16—N3	125.1 (5)
C19—N4—C18	121.0 (5)	H16—C16—N3	117.5 (3)
C20—N4—C18	121.5 (5)	H16—C16—C17	117.5 (3)
C20—N4—C19	117.4 (5)	C14—C15—N3	123.5 (5)
C13—C12—Br1	119.5 (4)	H15—C15—N3	118.2 (3)
C11—C12—Br1	119.3 (4)	H15—C15—C14	118.2 (3)
C11—C12—C13	121.2 (5)	C17—C18—N4	121.8 (5)
C13—C8—I1	124.6 (4)	C14—C18—N4	122.5 (5)
C9—C8—I1	118.2 (4)	C14—C18—C17	115.7 (5)
C9—C8—C13	117.1 (5)	C18—C14—C15	119.9 (5)
C2—C1—C5	119.7 (5)	H14—C14—C15	120.0 (3)
H1—C1—C5	120.2 (3)	H14—C14—C18	120.0 (3)
H1—C1—C2	120.2 (3)	H6a—C6—N2	109.5
C1—C5—N2	122.4 (5)	H6b—C6—N2	109.5
C4—C5—N2	121.9 (5)	H6b—C6—H6a	109.5
C4—C5—C1	115.7 (5)	H6c—C6—N2	109.5
C12—C13—Br2	120.1 (4)	H6c—C6—H6a	109.5
C8—C13—Br2	118.9 (4)	H6c—C6—H6b	109.5
C8—C13—C12	120.9 (4)	H7a—C7—N2	109.5
C12—C11—I2	124.4 (4)	H7b—C7—N2	109.5
C10—C11—I2	118.7 (4)	H7b—C7—H7a	109.5
C10—C11—C12	116.9 (5)	H7c—C7—N2	109.5
C4—C3—N1	123.5 (5)	H7c—C7—H7a	109.5
H3—C3—N1	118.3 (3)	H7c—C7—H7b	109.5
H3—C3—C4	118.3 (3)	H19a—C19—N4	109.5
C8—C9—F1	120.3 (5)	H19b—C19—N4	109.5
C10—C9—F1	117.7 (5)	H19b—C19—H19a	109.5
C10—C9—C8	122.0 (5)	H19c—C19—N4	109.5
C3—C4—C5	120.2 (5)	H19c—C19—H19a	109.5
H4—C4—C5	119.9 (3)	H19c—C19—H19b	109.5
H4—C4—C3	119.9 (3)	H20a—C20—N4	109.5
C1—C2—N1	124.2 (5)	H20b—C20—N4	109.5
H2—C2—N1	117.9 (3)	H20b—C20—H20a	109.5
H2—C2—C1	117.9 (3)	H20c—C20—N4	109.5
C11—C10—F2	120.1 (5)	H20c—C20—H20a	109.5
C9—C10—F2	118.1 (5)	H20c—C20—H20b	109.5

I1—C8—C13—Br2	−0.3 (4)	F2—C10—C11—C12	178.9 (5)
I1—C8—C13—C12	179.7 (4)	F2—C10—C9—C8	179.7 (4)
I1—C8—C9—F1	−0.7 (4)	N1—C3—C4—C5	0.2 (7)
I1—C8—C9—C10	−179.4 (4)	N1—C2—C1—C5	−1.3 (7)
I2—C11—C12—Br1	2.7 (4)	N2—C5—C1—C2	−179.1 (5)
I2—C11—C12—C13	−178.4 (4)	N2—C5—C4—C3	179.6 (5)
I2—C11—C10—F2	−1.2 (4)	N3—C16—C17—C18	−0.3 (7)
I2—C11—C10—C9	178.7 (4)	N3—C15—C14—C18	−0.2 (7)
Br2—C13—C12—Br1	−1.5 (4)	N4—C18—C17—C16	179.6 (6)
Br2—C13—C12—C11	179.6 (4)	N4—C18—C14—C15	−179.3 (6)
Br2—C13—C8—C9	179.0 (4)	C12—C13—C8—C9	−1.0 (5)
Br1—C12—C13—C8	178.5 (3)	C12—C11—C10—C9	−1.3 (6)
Br1—C12—C11—C10	−177.4 (4)	C8—C9—C10—C11	−0.2 (6)
F1—C9—C8—C13	180.0 (5)	C1—C5—C4—C3	−0.5 (6)
F1—C9—C10—F2	1.0 (5)	C17—C18—C14—C15	0.5 (6)
F1—C9—C10—C11	−178.9 (4)

Geometric parameters (Å, °) for the cocrystals in this study top

Perhalobenzene	DITFB^a	DITCB	DITBB	IBTFB	DIBFB
N···I	2.6622 (4)	2.698 (4)	2.708 (5)	2.588 (5) I	2.675 (5)
				2.797 (6) Br	2.707 (5)
C—-I···N	179.323 (14)	178.08 (13)	178.48 (16)	179.5 (3)	178.11 (18)
					177.71 (18)
Cp—N···I^b	172.92 (2)	172.67 (17)	174.9 (2)	173.2 (2)	175.5 (3)
					175.5 (3)
CX₆···DMAP	79.17 (2)	86.6 (16)	82.4 (5)	78.6 (4)	76.59 (19)
					76.3 (2)

Notes: (a) data from CSD refcode RUYHID02 collected at 100 K (Wang et al., 2018); (b) C_p is the pyridyl C atom para to the pyridyl N atom.

Hirshfeld analysis of the DMAP molecule in each 2:1 (DMAP)₂•CI₂X₄ cocrystal with an element-by-element delineation of the % contribution top

XB donor	H···H^a^,^b	C···X^a	C···C^a	H···C^a^,^b	H···X^a	H···I^a	N···I^a
DITCB	35.5	3.3	3.4	20.9	17.6	7.7	3.0
DITBB	37.0	4.0	3.3	20.2	16.4	7.6	3.0
DIBFB	35.8	4.5 (Br)	3.4	20.3	16.0 (Br)	8.2	3.1
		0.0 (F)			0.0 (F)
DITFB	34.3	0.0	5.3	21.3	17.5	8.2	3.0

Notes: (a) the first element listed corresponds to the DMAP molecule, while the second element is an element with a close contact from outside the DMAP molecule. (b) Includes reciprocal contacts. Part corresponds to a DMAP methyl–H contact with the C atom of a π-stacked DMAP molecule and part corresponds to the DMAP pyridyl–H contact to a C atom of C₆X₆.

Hirshfeld analysis of the perhalobenzene molecule in each 2:1 (DMAP)₂•CI₂X₄ cocrystal with an element-by-element delineation of the % contribution top

XB donor	X···H^a	I···H	C···H	X···X	I···X^b	I···N
DITCB	37.2	26.5	16.0	4.3	3.9	5.3
DITBB	36.0	25.1	15.9	5.8	3.9	5.0
DIBFB	19.0 (Br)	29.9	16.0	3.8 (Br)	2.1 (Br)	5.4
	15.5 (F)			3.3 (F)	0.0 (F)
DITFB	34.6	35.1	16.6	7.4	0.0	6.2

Notes: (a) the first element listed corresponds to the CI₂X₄ molecule, while the second is an element with a close contact from outside the CI₂X₄ molecule; (b) includes reciprocal contacts.

Major intermolecular interaction energies between interacting molecules within each cocrystal listed according to the major interaction type for each pair of molecules top

Halobenzene major interaction	DITCB	DITBB	DIBFB
DMAP π–π stacking^a	-36.8	-36.9	-37.0, -36.9^d
DMAP offset π–π stacked^b	-15.4	-13.8	-12.8
Halogen bond (N···I)^c	-29.9 (76.4)	-29.5 (76.7)	-32.2 (75.8, 76.6)
C—H···π (C₆X₆)	-19.7	-22.0	-21.1
C—X···π (DMAP)	-9.6	-15.4	-15.9 (X = Br)

Notes: (a) corresponds to pairs of DMAP molecules with maximum π–π overlap. (b) Mainly methyl–methyl interactions. (c) N···I separation as a % of the van der Waals radii in parentheses. (d) The second value corresponds to the inner two DMAP molecules, labeled `y2' in Fig. 6(b).

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Role of secondary inter­actions in a series of 2:1 halogen-bonded cocrystals formed between 4-(di­methyl­amino)­pyridine and ditopic halogen-bond donors

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Role of secondary interactions in a series of 2:1 halogen-bonded cocrystals formed between 4-(dimethylamino)pyridine and ditopic halogen-bond donors