Interplay of hydrogen bonds, iodo⋯nitro interactions and aromatic π⋯π stacking interactions in iodo-nitroanilines

Garden, S.J.; Fontes, S.P.; Wardell, J.L.; Skakle, J.M.S.; Low, J.N.; Glidewell, C.

doi:10.1107/S0108768102007978

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Interplay of hydrogen bonds, iodonitro interactions and aromatic ππ stacking interactions in iodo-nitroanilines

S. J. Garden, S. P. Fontes, J. L. Wardell, J. M. S. Skakle, J. N. Low and C. Glidewell

Molecules of 2-iodo-5-nitroaniline (I) are linked by N—H

O hydrogen bonds into centrosymmetric dimers and by asymmetric three-centre iodo

nitro interactions into chains, so forming chains of fused centrosymmetric rings: these chains are linked by aromatic π

π stacking interactions to form a three-dimensional structure. In the isomeric 4-iodo-2-nitroaniline (II), each of the two independent molecules forms hydrogen-bonded chains that are linked by two-centre iodo

nitro interactions into sheets of two types, each containing only a single type of molecule: π

π stacking interactions are absent. In 2,4-diiodo-3-nitroaniline (III), where the nitro group is almost orthogonal to the aryl ring, a combination of N—H

O hydrogen bonds and two distinct two-centre iodo

nitro interactions links the molecules into a three-dimensional framework that is reinforced by aromatic π

π stacking interactions. Bond lengths and conformations are discussed and comparisons are drawn with related compounds.

Keywords: iodo

nitro interactions; π

π stacking interactions; 2-iodo-5-nitroaniline; 4-iodo-2-nitroaniline; 2,4-diiodo-3-nitroaniline.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768102007978/na0135sup1.cif Contains datablocks global, I, II, III
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102007978/na0135Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102007978/na0135IIsup3.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102007978/na0135IIIsup4.hkl Contains datablock III

CCDC references: 193585; 193586; 193587

Comment top

In full text version

Experimental top

In full text version

Structure description top

In full text version

Computing details top

Data collection: SMART (Bruker, 1997) for (I); Kappa-CCD server software (Nonius, 1997) for (II), (III). Cell refinement: SMART (Bruker, 1997) for (I); DENZO-SMN (Otwinowski & Minor, 1997) for (II), (III). Data reduction: SHELXTL (Bruker, 1997) for (I); DENZO-SMN (Otwinowski & Minor, 1997) for (II), (III). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Figures top

In full text version

(I) 2-Iodo-5-nitro-aniline top

Crystal data top

C₆H₅IN₂O₂	Z = 2
M_r = 264.02	F(000) = 248
Triclinic, P1	D_x = 2.326 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4236 (15) Å	Cell parameters from 1674 reflections
b = 7.4979 (18) Å	θ = 2.6–28.4°
c = 8.293 (2) Å	µ = 4.20 mm⁻¹
α = 71.422 (4)°	T = 120 K
β = 85.285 (4)°	Plate, orange
γ = 86.125 (4)°	0.24 × 0.12 × 0.04 mm
V = 376.98 (16) Å³

Data collection top

Kappa-CCD diffractometer	1674 independent reflections
Radiation source: fine-focus sealed X-ray tube	1620 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ scans, and ω scans with κ offsets	θ_max = 28.4°, θ_min = 2.6°
Absorption correction: multi-scan SADABS (Bruker, 1997)	h = −8→7
T_min = 0.434, T_max = 0.850	k = −10→9
2274 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0823P)² + 0.6322P] where P = (F_o² + 2F_c²)/3
1674 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 1.29 e Å⁻³
0 restraints	Δρ_min = −1.86 e Å⁻³

Crystal data top

C₆H₅IN₂O₂	γ = 86.125 (4)°
M_r = 264.02	V = 376.98 (16) Å³
Triclinic, P1	Z = 2
a = 6.4236 (15) Å	Mo Kα radiation
b = 7.4979 (18) Å	µ = 4.20 mm⁻¹
c = 8.293 (2) Å	T = 120 K
α = 71.422 (4)°	0.24 × 0.12 × 0.04 mm
β = 85.285 (4)°

Data collection top

Kappa-CCD diffractometer	1674 independent reflections
Absorption correction: multi-scan SADABS (Bruker, 1997)	1620 reflections with I > 2σ(I)
T_min = 0.434, T_max = 0.850	R_int = 0.025
2274 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.07	Δρ_max = 1.29 e Å⁻³
1674 reflections	Δρ_min = −1.86 e Å⁻³
100 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.4449 (7)	0.3288 (6)	0.3513 (6)	0.0159 (8)
N1	0.3913 (6)	0.4158 (6)	0.1884 (5)	0.0219 (8)
C2	0.6412 (7)	0.2368 (6)	0.3906 (6)	0.0173 (8)
I2	0.85816 (4)	0.22346 (3)	0.19084 (3)	0.01932 (15)
C3	0.6972 (7)	0.1579 (6)	0.5580 (6)	0.0204 (9)
C4	0.5607 (7)	0.1669 (6)	0.6939 (6)	0.0200 (8)
C5	0.3661 (7)	0.2556 (6)	0.6540 (6)	0.0176 (8)
N5	0.2134 (7)	0.2636 (5)	0.7936 (5)	0.0205 (8)
O51	0.0377 (6)	0.3326 (6)	0.7592 (5)	0.0282 (8)
O52	0.2667 (6)	0.1987 (6)	0.9413 (4)	0.0283 (8)
C6	0.3051 (7)	0.3348 (6)	0.4907 (6)	0.0180 (8)
H1A	0.4812	0.4160	0.1024	0.026*
H1B	0.2668	0.4719	0.1692	0.026*
H3	0.8312	0.0968	0.5795	0.025*
H4	0.5982	0.1150	0.8086	0.024*
H6	0.1696	0.3934	0.4714	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.018 (2)	0.0155 (19)	0.0126 (19)	−0.0095 (15)	0.0021 (16)	−0.0016 (15)
N1	0.0179 (17)	0.029 (2)	0.0154 (17)	−0.0018 (15)	0.0001 (14)	−0.0024 (15)
C2	0.0178 (19)	0.0142 (18)	0.019 (2)	−0.0031 (15)	0.0049 (16)	−0.0055 (15)
I2	0.0192 (2)	0.0186 (2)	0.0180 (2)	−0.00292 (12)	0.00588 (13)	−0.00399 (14)
C3	0.019 (2)	0.019 (2)	0.021 (2)	−0.0011 (16)	0.0005 (18)	−0.0029 (17)
C4	0.023 (2)	0.020 (2)	0.015 (2)	−0.0029 (16)	−0.0009 (17)	−0.0016 (16)
C5	0.022 (2)	0.0138 (17)	0.0153 (18)	−0.0068 (15)	0.0061 (15)	−0.0029 (15)
N5	0.029 (2)	0.0177 (18)	0.0151 (18)	−0.0066 (14)	0.0046 (15)	−0.0052 (15)
O51	0.0228 (17)	0.035 (2)	0.0239 (19)	0.0037 (15)	0.0051 (15)	−0.0083 (16)
O52	0.036 (2)	0.036 (2)	0.0109 (16)	−0.0048 (16)	0.0040 (14)	−0.0048 (14)
C6	0.020 (2)	0.0171 (19)	0.016 (2)	−0.0039 (16)	0.0027 (16)	−0.0040 (15)

Geometric parameters (Å, º) top

C1—C2	1.406 (6)	N5—O51	1.226 (6)
C2—C3	1.392 (6)	N5—O52	1.233 (5)
C3—C4	1.387 (7)	C2—I2	2.099 (4)
C4—C5	1.389 (6)	N1—H1A	0.8800
C5—C6	1.372 (6)	N1—H1B	0.8800
C6—C1	1.415 (6)	C3—H3	0.9500
C1—N1	1.361 (6)	C4—H4	0.9500
C5—N5	1.469 (6)	C6—H6	0.9500

N1—C1—C2	122.8 (4)	C3—C4—C5	116.6 (4)
N1—C1—C6	120.4 (4)	C3—C4—H4	121.7
C2—C1—C6	116.7 (4)	C5—C4—H4	121.7
C1—N1—H1A	120.0	C6—C5—C4	124.0 (4)
C1—N1—H1B	120.0	C6—C5—N5	117.3 (4)
H1A—N1—H1B	120.0	C4—C5—N5	118.7 (4)
C3—C2—C1	121.9 (4)	O51—N5—O52	122.6 (5)
C3—C2—I2	119.1 (3)	O51—N5—C5	118.9 (4)
C1—C2—I2	119.0 (3)	O52—N5—C5	118.5 (4)
C4—C3—C2	121.1 (4)	C5—C6—C1	119.7 (4)
C4—C3—H3	119.5	C5—C6—H6	120.1
C2—C3—H3	119.5	C1—C6—H6	120.1

C4—C5—N5—O51	−176.1 (5)	C6—C5—N5—O51	3.0 (7)
C4—C5—N5—O52	3.2 (7)	C6—C5—N5—O52	−177.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I2	0.88	2.76	3.237 (4)	115
N1—H1A···N1ⁱ	0.88	2.44	3.212 (6)	147
N1—H1B···O51ⁱⁱ	0.88	2.51	3.311 (6)	152

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

(II) 4-Iodo-2-nitroaniline top

Crystal data top

C₆H₅IN₂O₂	F(000) = 1984
M_r = 264.02	D_x = 2.325 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3426 reflections
a = 26.5541 (9) Å	θ = 3.0–27.5°
b = 7.0445 (2) Å	µ = 4.19 mm⁻¹
c = 16.4416 (5) Å	T = 120 K
β = 101.1548 (16)°	Plate, orange
V = 3017.47 (16) Å³	0.25 × 0.20 × 0.05 mm
Z = 16

Data collection top

Kappa-CCD diffractometer	3426 independent reflections
Radiation source: fine-focus sealed X-ray tube	2696 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
φ scans, and ω scans with κ offsets	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −34→33
T_min = 0.380, T_max = 0.811	k = −8→9
10470 measured reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: Patterson
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0372P)² + 3.2146P] where P = (F_o² + 2F_c²)/3
3426 reflections	(Δ/σ)_max = 0.001
193 parameters	Δρ_max = 1.22 e Å⁻³
0 restraints	Δρ_min = −1.55 e Å⁻³

Crystal data top

C₆H₅IN₂O₂	V = 3017.47 (16) Å³
M_r = 264.02	Z = 16
Monoclinic, C2/c	Mo Kα radiation
a = 26.5541 (9) Å	µ = 4.19 mm⁻¹
b = 7.0445 (2) Å	T = 120 K
c = 16.4416 (5) Å	0.25 × 0.20 × 0.05 mm
β = 101.1548 (16)°

Data collection top

Kappa-CCD diffractometer	3426 independent reflections
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	2696 reflections with I > 2σ(I)
T_min = 0.380, T_max = 0.811	R_int = 0.056
10470 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.05	Δρ_max = 1.22 e Å⁻³
3426 reflections	Δρ_min = −1.55 e Å⁻³
193 parameters

Special details top

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used.

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

	x	y	z	U_iso*/U_eq
N11	0.68796 (13)	0.1809 (5)	−0.1364 (2)	0.0198 (8)
C11	0.68831 (15)	0.0538 (5)	−0.0754 (2)	0.0119 (8)
C12	0.68395 (15)	−0.1455 (5)	−0.0880 (2)	0.0124 (8)
N12	0.67958 (13)	−0.2279 (4)	−0.16873 (18)	0.0153 (7)
O11	0.68253 (14)	−0.4017 (4)	−0.17493 (18)	0.0258 (8)
O12	0.67287 (12)	−0.1245 (3)	−0.23131 (16)	0.0188 (7)
C13	0.68352 (15)	−0.2708 (5)	−0.0221 (2)	0.0120 (8)
C14	0.68856 (15)	−0.2026 (5)	0.0571 (2)	0.0133 (8)
I14	0.685502 (10)	−0.39196 (3)	0.154272 (15)	0.01541 (10)
C15	0.69470 (15)	−0.0077 (5)	0.0717 (2)	0.0130 (6)
C16	0.69464 (16)	0.1149 (5)	0.0072 (2)	0.0134 (9)
N21	0.56163 (13)	0.1718 (5)	0.71651 (19)	0.0189 (8)
C21	0.56160 (16)	0.0452 (6)	0.6553 (2)	0.0137 (8)
C22	0.56084 (16)	−0.1527 (5)	0.6649 (2)	0.0130 (8)
N22	0.56014 (13)	−0.2378 (4)	0.74340 (18)	0.0158 (7)
O21	0.56090 (14)	−0.4123 (4)	0.74901 (17)	0.0278 (8)
O22	0.55858 (12)	−0.1370 (4)	0.80485 (16)	0.0191 (7)
C23	0.56147 (14)	−0.2773 (5)	0.5981 (2)	0.0125 (8)
C24	0.56281 (15)	−0.2051 (5)	0.5220 (2)	0.0120 (8)
I24	0.562716 (10)	−0.39239 (3)	0.422623 (14)	0.01538 (10)
C25	0.56393 (15)	−0.0091 (5)	0.5095 (2)	0.0130 (6)
C26	0.56319 (16)	0.1112 (5)	0.5744 (2)	0.0134 (9)
H11A	0.6917	0.3025	−0.1245	0.024*
H11B	0.6840	0.1426	−0.1882	0.024*
H13	0.6797	−0.4033	−0.0323	0.014*
H15	0.6989	0.0398	0.1266	0.016*
H16	0.6990	0.2466	0.0188	0.016*
H21A	0.5621	0.2942	0.7060	0.023*
H21B	0.5611	0.1322	0.7671	0.023*
H23	0.5610	−0.4108	0.6062	0.015*
H25	0.5652	0.0403	0.4562	0.016*
H26	0.5638	0.2442	0.5650	0.016*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N11	0.037 (2)	0.0105 (16)	0.0134 (17)	0.0012 (15)	0.0078 (16)	0.0014 (14)
C11	0.020 (2)	0.0088 (18)	0.0087 (18)	−0.0004 (16)	0.0071 (16)	0.0033 (15)
C12	0.017 (2)	0.014 (2)	0.0070 (18)	0.0009 (15)	0.0042 (15)	−0.0018 (15)
N12	0.023 (2)	0.0151 (18)	0.0080 (16)	−0.0010 (14)	0.0039 (14)	0.0004 (13)
O11	0.054 (2)	0.0094 (15)	0.0140 (15)	−0.0014 (13)	0.0078 (15)	−0.0025 (12)
O12	0.0311 (18)	0.0186 (15)	0.0069 (13)	0.0003 (12)	0.0042 (12)	0.0022 (11)
C13	0.017 (2)	0.0091 (18)	0.0102 (18)	0.0006 (15)	0.0024 (15)	0.0022 (15)
C14	0.019 (2)	0.014 (2)	0.0074 (18)	−0.0022 (16)	0.0036 (16)	0.0034 (15)
I14	0.02537 (19)	0.01421 (16)	0.00771 (15)	0.00093 (10)	0.00583 (12)	0.00265 (9)
C15	0.0202 (16)	0.0138 (15)	0.0062 (13)	0.0003 (11)	0.0056 (11)	0.0003 (11)
C16	0.018 (2)	0.0072 (19)	0.016 (2)	−0.0005 (15)	0.0057 (17)	−0.0019 (16)
N21	0.039 (2)	0.0094 (15)	0.0096 (16)	−0.0020 (16)	0.0078 (15)	−0.0029 (14)
C21	0.020 (2)	0.0130 (18)	0.0092 (19)	−0.0015 (17)	0.0043 (16)	−0.0017 (16)
C22	0.021 (2)	0.0091 (17)	0.0094 (18)	0.0004 (16)	0.0037 (16)	0.0021 (15)
N22	0.028 (2)	0.0099 (16)	0.0097 (16)	−0.0020 (14)	0.0045 (14)	0.0007 (13)
O21	0.068 (3)	0.0078 (14)	0.0084 (14)	−0.0022 (14)	0.0108 (15)	0.0024 (11)
O22	0.0351 (19)	0.0162 (15)	0.0070 (14)	0.0010 (12)	0.0068 (13)	−0.0043 (11)
C23	0.017 (2)	0.0100 (19)	0.0108 (19)	0.0022 (15)	0.0028 (16)	0.0002 (15)
C24	0.018 (2)	0.0103 (19)	0.0081 (18)	0.0004 (15)	0.0034 (15)	−0.0031 (14)
I24	0.02791 (19)	0.01243 (16)	0.00651 (15)	0.00078 (10)	0.00514 (12)	−0.00251 (9)
C25	0.0202 (16)	0.0138 (15)	0.0062 (13)	0.0003 (11)	0.0056 (11)	0.0003 (11)
C26	0.021 (2)	0.0096 (19)	0.010 (2)	−0.0011 (16)	0.0046 (17)	0.0012 (15)

Geometric parameters (Å, º) top

C11—C12	1.421 (5)	C21—C22	1.404 (5)
C12—C13	1.399 (5)	C22—C23	1.409 (5)
C13—C14	1.370 (5)	C23—C24	1.357 (5)
C14—C15	1.398 (5)	C24—C25	1.397 (5)
C15—C16	1.366 (5)	C25—C26	1.366 (5)
C16—C11	1.405 (5)	C26—C21	1.417 (6)
C11—N11	1.343 (5)	C21—N21	1.344 (5)
C12—N12	1.433 (5)	C22—N22	1.426 (5)
N12—O11	1.232 (4)	N22—O21	1.233 (4)
N12—O12	1.245 (4)	N22—O22	1.242 (4)
C14—I14	2.095 (4)	C24—I24	2.099 (4)
N11—H11A	0.8800	N21—H21A	0.8800
N11—H11B	0.8800	N21—H21B	0.8800
C13—H13	0.9500	C23—H23	0.9500
C15—H15	0.9500	C25—H25	0.9500
C16—H16	0.9500	C26—H26	0.9500

C11—N11—H11A	120.0	C21—N21—H21A	120.0
C11—N11—H11B	120.0	C21—N21—H21B	120.0
H11A—N11—H11B	120.0	H21A—N21—H21B	120.0
N11—C11—C12	124.2 (4)	N21—C21—C22	124.9 (4)
N11—C11—C16	120.0 (4)	N21—C21—C26	119.3 (4)
C12—C11—C16	115.8 (3)	C22—C21—C26	115.8 (3)
C13—C12—C11	121.6 (3)	C21—C22—C23	121.9 (3)
C13—C12—N12	116.8 (3)	C21—C22—N22	121.5 (3)
C11—C12—N12	121.6 (3)	C23—C22—N22	116.6 (3)
O11—N12—O12	120.9 (3)	O21—N22—O22	120.8 (3)
O11—N12—C12	118.9 (3)	O21—N22—C22	118.9 (3)
O12—N12—C12	120.1 (3)	O22—N22—C22	120.2 (3)
C14—C13—C12	120.0 (3)	C24—C23—C22	119.5 (3)
C14—C13—H13	120.0	C24—C23—H23	120.3
C12—C13—H13	120.0	C22—C23—H23	120.3
C13—C14—C15	119.6 (3)	C23—C24—C25	120.7 (3)
C13—C14—I14	119.4 (3)	C23—C24—I24	119.0 (3)
C15—C14—I14	121.0 (2)	C25—C24—I24	120.3 (3)
C16—C15—C14	120.3 (3)	C26—C25—C24	119.7 (3)
C16—C15—H15	119.8	C26—C25—H25	120.2
C14—C15—H15	119.8	C24—C25—H25	120.2
C15—C16—C11	122.6 (3)	C25—C26—C21	122.5 (3)
C15—C16—H16	118.7	C25—C26—H26	118.8
C11—C16—H16	118.7	C21—C26—H26	118.8

C11—C12—N12—O11	170.8 (4)	C21—C22—N22—O21	−178.0 (4)
C11—C12—N12—O12	−9.3 (6)	C21—C22—N22—O22	2.2 (6)
C13—C12—N12—O11	−9.5 (6)	C23—C22—N22—O21	1.1 (6)
C13—C12—N12—O12	170.5 (4)	C23—C22—N22—O22	−178.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O11ⁱ	0.88	2.24	3.005 (5)	146
N11—H11B···O12	0.88	2.01	2.642 (4)	128
N21—H21A···O21ⁱ	0.88	2.19	2.979 (5)	149
N21—H21B···O22	0.88	2.00	2.626 (4)	127
C25—H25···O22ⁱⁱ	0.95	2.55	3.495 (4)	172

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

(III) 2,4-Diiodo-3-nitroaniline top

Crystal data top

C₆H₄I₂N₂O₂	F(000) = 704
M_r = 389.91	D_x = 2.752 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2144 reflections
a = 7.6069 (3) Å	θ = 3.2–27.5°
b = 12.5917 (4) Å	µ = 6.65 mm⁻¹
c = 10.2546 (3) Å	T = 120 K
β = 106.6693 (16)°	Plate, colourless
V = 940.95 (6) Å³	0.28 × 0.24 × 0.08 mm
Z = 4

Data collection top

Kappa-CCD diffractometer	2144 independent reflections
Radiation source: fine-focus sealed X-ray tube	1950 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.104
φ scans, and ω scans with κ offsets	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −9→8
T_min = 0.180, T_max = 0.618	k = −14→16
8456 measured reflections	l = −13→13

Refinement top

Refinement on F²	Secondary 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) = 0.122	w = 1/[σ²(F_o²) + (0.0534P)² + 3.8878P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max = 0.001
2144 reflections	Δρ_max = 2.36 e Å⁻³
110 parameters	Δρ_min = −2.26 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0044 (5)

Crystal data top

C₆H₄I₂N₂O₂	V = 940.95 (6) Å³
M_r = 389.91	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6069 (3) Å	µ = 6.65 mm⁻¹
b = 12.5917 (4) Å	T = 120 K
c = 10.2546 (3) Å	0.28 × 0.24 × 0.08 mm
β = 106.6693 (16)°

Data collection top

Kappa-CCD diffractometer	2144 independent reflections
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	1950 reflections with I > 2σ(I)
T_min = 0.180, T_max = 0.618	R_int = 0.104
8456 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.13	Δρ_max = 2.36 e Å⁻³
2144 reflections	Δρ_min = −2.26 e Å⁻³
110 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
N1	1.1845 (9)	0.7118 (4)	1.0887 (5)	0.0243 (12)
C1	1.0924 (10)	0.6510 (5)	0.9783 (6)	0.0196 (12)
C2	0.9004 (9)	0.6434 (4)	0.9321 (6)	0.0181 (12)
I2	0.74257 (6)	0.72632 (3)	1.03612 (4)	0.02391 (19)
C3	0.8187 (9)	0.5795 (4)	0.8200 (5)	0.0140 (11)
N3	0.6156 (8)	0.5717 (4)	0.7755 (5)	0.0193 (11)
O131	0.5473 (7)	0.4924 (4)	0.8106 (5)	0.0272 (10)
O132	0.5278 (7)	0.6435 (4)	0.7058 (5)	0.0256 (10)
C4	0.9182 (9)	0.5253 (4)	0.7479 (5)	0.0174 (12)
I4	0.79798 (6)	0.42775 (3)	0.58144 (4)	0.02460 (19)
C5	1.1090 (9)	0.5363 (5)	0.7901 (6)	0.0198 (12)
C6	1.1913 (9)	0.5982 (5)	0.9006 (6)	0.0198 (12)
H1A	1.1226	0.7482	1.1341	0.029*
H1B	1.3052	0.7141	1.1138	0.029*
H5	1.1817	0.5009	0.7421	0.024*
H6	1.3210	0.6059	0.9261	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.028 (3)	0.023 (3)	0.019 (2)	−0.004 (2)	0.001 (2)	−0.001 (2)
C1	0.030 (3)	0.013 (2)	0.015 (2)	−0.002 (2)	0.006 (2)	0.004 (2)
C2	0.026 (3)	0.010 (2)	0.017 (3)	0.001 (2)	0.005 (2)	0.000 (2)
I2	0.0295 (3)	0.0187 (3)	0.0244 (3)	0.00087 (15)	0.0092 (2)	−0.00817 (15)
C3	0.017 (3)	0.010 (2)	0.014 (2)	0.0006 (19)	0.003 (2)	0.0049 (19)
N3	0.026 (3)	0.014 (2)	0.018 (2)	−0.001 (2)	0.006 (2)	−0.0029 (18)
O131	0.025 (3)	0.025 (2)	0.034 (2)	−0.005 (2)	0.011 (2)	0.0041 (19)
O132	0.023 (2)	0.023 (2)	0.027 (2)	0.0044 (19)	0.0006 (19)	0.0063 (18)
C4	0.027 (3)	0.012 (3)	0.013 (2)	0.000 (2)	0.007 (2)	0.001 (2)
I4	0.0378 (3)	0.0208 (3)	0.0164 (3)	−0.00668 (16)	0.0098 (2)	−0.00600 (14)
C5	0.023 (3)	0.020 (3)	0.017 (3)	0.004 (2)	0.008 (2)	0.002 (2)
C6	0.016 (3)	0.024 (3)	0.020 (3)	0.003 (2)	0.006 (2)	0.003 (2)

Geometric parameters (Å, º) top

N1—H1A	0.8800	C1—N1	1.380 (8)
N1—H1B	0.8800	C2—I2	2.099 (6)
C1—C2	1.404 (10)	C3—N3	1.484 (8)
C2—C3	1.394 (8)	N3—O131	1.225 (7)
C3—C4	1.380 (8)	N3—O132	1.225 (7)
C4—C5	1.398 (9)	C4—I4	2.089 (6)
C5—C6	1.370 (9)	C5—H5	0.9500
C6—C1	1.409 (9)	C6—H6	0.9500

C1—N1—H1A	120.0	O132—N3—O131	124.5 (6)
C1—N1—H1B	120.0	O132—N3—C3	118.4 (5)
H1A—N1—H1B	120.0	O131—N3—C3	117.1 (5)
N1—C1—C2	123.4 (6)	C3—C4—C5	117.7 (5)
N1—C1—C6	119.8 (6)	C3—C4—I4	123.4 (5)
C2—C1—C6	116.7 (6)	C5—C4—I4	118.9 (4)
C3—C2—C1	119.5 (6)	C6—C5—C4	120.0 (6)
C3—C2—I2	121.4 (5)	C6—C5—H5	120.0
C1—C2—I2	119.1 (4)	C4—C5—H5	120.0
C4—C3—C2	122.9 (6)	C5—C6—C1	123.0 (6)
C4—C3—N3	119.0 (5)	C5—C6—H6	118.5
C2—C3—N3	118.0 (5)	C1—C6—H6	118.5

N1—C1—C2—C3	−179.6 (5)	C2—C3—N3—O131	−100.3 (6)
C6—C1—C2—C3	4.4 (8)	C2—C3—C4—C5	−0.3 (8)
N1—C1—C2—I2	−0.8 (8)	N3—C3—C4—C5	178.4 (5)
C6—C1—C2—I2	−176.8 (4)	C2—C3—C4—I4	179.2 (4)
C1—C2—C3—C4	−2.4 (8)	N3—C3—C4—I4	−2.1 (7)
I2—C2—C3—C4	178.9 (4)	C3—C4—C5—C6	0.8 (9)
C1—C2—C3—N3	178.9 (5)	I4—C4—C5—C6	−178.7 (4)
I2—C2—C3—N3	0.1 (7)	C4—C5—C6—C1	1.5 (9)
C4—C3—N3—O132	−98.4 (6)	N1—C1—C6—C5	179.8 (6)
C2—C3—N3—O132	80.4 (7)	C2—C1—C6—C5	−4.1 (9)
C4—C3—N3—O131	81.0 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O132ⁱ	0.88	2.46	3.128 (8)	133

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

Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₆H₅IN₂O₂	C₆H₅IN₂O₂	C₆H₄I₂N₂O₂
M_r	264.02	264.02	389.91
Crystal system, space group	Triclinic, P1	Monoclinic, C2/c	Monoclinic, P2₁/c
Temperature (K)	120	120	120
a, b, c (Å)	6.4236 (15), 7.4979 (18), 8.293 (2)	26.5541 (9), 7.0445 (2), 16.4416 (5)	7.6069 (3), 12.5917 (4), 10.2546 (3)
α, β, γ (°)	71.422 (4), 85.285 (4), 86.125 (4)	90, 101.1548 (16), 90	90, 106.6693 (16), 90
V (Å³)	376.98 (16)	3017.47 (16)	940.95 (6)
Z	2	16	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	4.20	4.19	6.65
Crystal size (mm)	0.24 × 0.12 × 0.04	0.25 × 0.20 × 0.05	0.28 × 0.24 × 0.08

Data collection
Diffractometer	Kappa-CCD	Kappa-CCD	Kappa-CCD
Absorption correction	Multi-scan SADABS (Bruker, 1997)	Multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	Multi-scan DENZO-SMN (Otwinowski & Minor, 1997)
T_min, T_max	0.434, 0.850	0.380, 0.811	0.180, 0.618
No. of measured, independent and observed [I > 2σ(I)] reflections	2274, 1674, 1620	10470, 3426, 2696	8456, 2144, 1950
R_int	0.025	0.056	0.104
(sin θ/λ)_max (Å⁻¹)	0.670	0.649	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.102, 1.07	0.032, 0.082, 1.05	0.045, 0.122, 1.13
No. of reflections	1674	3426	2144
No. of parameters	100	193	110
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.29, −1.86	1.22, −1.55	2.36, −2.26

Computer programs: SMART (Bruker, 1997), Kappa-CCD server software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2002), SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) for (I) top

C1—C2	1.406 (6)	C1—N1	1.361 (6)
C2—C3	1.392 (6)	C5—N5	1.469 (6)
C3—C4	1.387 (7)	N5—O51	1.226 (6)
C4—C5	1.389 (6)	N5—O52	1.233 (5)
C5—C6	1.372 (6)	C2—I2	2.099 (4)
C6—C1	1.415 (6)

C4—C5—N5—O52	3.2 (7)	C6—C5—N5—O51	3.0 (7)

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I2	0.88	2.76	3.237 (4)	115
N1—H1A···N1ⁱ	0.88	2.44	3.212 (6)	147
N1—H1B···O51ⁱⁱ	0.88	2.51	3.311 (6)	152

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

Selected geometric parameters (Å, º) for (II) top

C11—C12	1.421 (5)	C21—C22	1.404 (5)
C12—C13	1.399 (5)	C22—C23	1.409 (5)
C13—C14	1.370 (5)	C23—C24	1.357 (5)
C14—C15	1.398 (5)	C24—C25	1.397 (5)
C15—C16	1.366 (5)	C25—C26	1.366 (5)
C16—C11	1.405 (5)	C26—C21	1.417 (6)
C11—N11	1.343 (5)	C21—N21	1.344 (5)
C12—N12	1.433 (5)	C22—N22	1.426 (5)
N12—O11	1.232 (4)	N22—O21	1.233 (4)
N12—O12	1.245 (4)	N22—O22	1.242 (4)
C14—I14	2.095 (4)	C24—I24	2.099 (4)

N11—C11—C12	124.2 (4)	N21—C21—C22	124.9 (4)
N11—C11—C16	120.0 (4)	N21—C21—C26	119.3 (4)
C12—C11—C16	115.8 (3)	C22—C21—C26	115.8 (3)

C11—C12—N12—O12	−9.3 (6)	C21—C22—N22—O22	2.2 (6)
C13—C12—N12—O11	−9.5 (6)	C23—C22—N22—O21	1.1 (6)

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O11ⁱ	0.88	2.24	3.005 (5)	146
N11—H11B···O12	0.88	2.01	2.642 (4)	128
N21—H21A···O21ⁱ	0.88	2.19	2.979 (5)	149
N21—H21B···O22	0.88	2.00	2.626 (4)	127
C25—H25···O22ⁱⁱ	0.95	2.55	3.495 (4)	172

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

Selected geometric parameters (Å, º) for (III) top

C1—C2	1.404 (10)	C1—N1	1.380 (8)
C2—C3	1.394 (8)	C2—I2	2.099 (6)
C3—C4	1.380 (8)	C3—N3	1.484 (8)
C4—C5	1.398 (9)	N3—O131	1.225 (7)
C5—C6	1.370 (9)	N3—O132	1.225 (7)
C6—C1	1.409 (9)	C4—I4	2.089 (6)

N1—C1—C2	123.4 (6)	C4—C3—C2	122.9 (6)
N1—C1—C6	119.8 (6)	C4—C3—N3	119.0 (5)
C2—C1—C6	116.7 (6)	C2—C3—N3	118.0 (5)
C3—C2—C1	119.5 (6)	C3—C4—C5	117.7 (5)
C3—C2—I2	121.4 (5)	C3—C4—I4	123.4 (5)
C1—C2—I2	119.1 (4)	C5—C4—I4	118.9 (4)

C2—C3—N3—O132	80.4 (7)	C2—C3—N3—O131	−100.3 (6)

Hydrogen-bond geometry (Å, º) for (III) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O132ⁱ	0.88	2.46	3.128 (8)	133

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

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