2-Nitro­benzaldehyde 2-iodo­benzoyl­hydrazone

Glidewell, C.; Low, J.N.; Wardell, J.L.

doi:10.1107/S1600536805021355

organic compounds

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ISSN: 2056-9890

Volume 61| Part 8| August 2005| Pages o2438-o2440

https://doi.org/10.1107/S1600536805021355

2-Nitrobenzaldehyde 2-iodobenzoylhydrazone

Christopher Glidewell,^a ^* John N. Low ^b and James L. Wardell ^c

^aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 1 July 2005; accepted 5 July 2005; online 9 July 2005)

Molecules of the title compound, C₁₄H₁₀IN₃O₃, are linked into sheets by a combination of N—H⋯O and C—H⋯O hydrogen bonds.

Comment

The title compound, (I), was prepared as part of our study of the supramolecular arrangements of imine and amido compounds.

In the molecules of (I) (Fig. 1), the bond distances (Table 1) in the acyclic acylhydrazone fragment C11–C21 are all standard (Allen et al., 1987 ), and there is no evidence for any bond fixation within the aryl rings. Hence, the conventional representation (I) is entirely appropriate. This central spacer unit is nearly planar, as shown by the key torsional angles, with a trans planar H—N—C=O fragment, as expected, and an E configuration at the C1=N1 bond. However, the aryl rings are both twisted out of this plane, making dihedral angles of 38.9 (2) and 43.3 (2)°, while the nitro group is twisted out of the plane of the adjacent aryl ring by 33.7 (2)°. Within the spacer unit C11–C21, the intrachain bond angles are all less than 120°.

The molecules of (I) are linked into sheets by one N—H⋯O hydrogen bond and two C—H⋯O hydrogen bonds, one of which utilizes the carbonyl O atom as acceptor, while the other utilizes a nitro O atom. Hydrazone atom N2 and methine atom C1 in the molecule at (x, y, z) both act as hydrogen-bond donors to carbonyl atom O2 in the molecule at (x, −1 + y, z), thus generating by translation a C(4)C(6)[R₂¹(6)] chain of rings (Bernstein et al., 1995 ) running parallel to the [010] direction (Fig. 2). It may be noted here that analogous C(4) motifs are rather common in both carboxamides and sulfonamides.

In addition, aryl atom C26 in the molecule at (x, y, z) acts as hydrogen-bond donor to nitro atom O22 in the molecule at (1 − x, −y, − $[{1\over 2}]$ + z), thereby forming a C(11) chain, generated by the 2₁ screw axis along ( $[{1\over 2}]$ , 0, z) and running parallel to the [001] direction (Fig. 3). The combination of the simple [001] chains and the [010] chains of rings then generates a complex (100) sheet (Fig. 4). This sheet lies in the domain 0.21 < x < 0.79 and a second such sheet, related to the first by the action of the glide planes, lies in the domain 0.71 < x < 1.29. However, there are no direction-specific interactions between adjacent sheets: in particular, C—H⋯π(arene) hydrogen bonds, aromatic π–π stacking interactions, and iodo–nitro interactions are all absent.

Figure 1
The molecule of compound (I)

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

Figure 2
Part of the crystal structure of compound (I)

, showing the formation of a C(4)C(6)[R₂¹(6)] chain of rings along [010]. For the sake of clarity, the H atoms on the aryl rings have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, −1 + y, z) and (x, 1 + y, z), respectively.

Figure 3
Part of the crystal structure of compound (I)

, showing the formation of a C(11) chain along [001]. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#) or an ampersand (&) are at the symmetry positions (1 − x, −y, − $[{1\over 2}]$ + z), (1 − x, −y, $[{1\over 2}]$ + z) and (x, y, 1 + z), respectively.

Figure 4
Stereoview of part of the crystal structure of compound (I)

, showing the formation of a (100) sheet. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.

Experimental

The title compound was prepared by reaction of 2-nitrobenzaldehyde hydrazone with 2-iodobenzoyl chloride. A solution containg 2 mmol of each reactant in 1,2-dichloroethane (20 ml) was heated under reflux for 1 h; the mixture was cooled and the solvent was removed under reduced pressure. The solid residue was crystallized initially from ethanol, and crystals suitable for single-crystal X-ray diffraction were obtained by slow evaporation of a solution in ethanol and 2-propanol [1/1 (v/v), m.p. > 520 K]. IR (KBr disk): 1680 cm⁻¹.

Crystal data

C₁₄H₁₀IN₃O₃
M_r = 395.15
Orthorhombic, P c a 2₁
a = 21.6122 (8) Å
b = 5.0393 (2) Å
c = 12.7868 (5) Å
V = 1392.62 (9) Å³
Z = 4
D_x = 1.885 Mg m⁻³
Mo Kα radiation
Cell parameters from 2783 reflections
θ = 3.7–27.5°
μ = 2.31 mm⁻¹
T = 120 (2) K
Plate, green
0.28 × 0.08 × 0.05 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.564, T_max = 0.893
12100 measured reflections
2783 independent reflections
2579 reflections with I > 2σ(I)
R_int = 0.036
θ_max = 27.5°
h = −27 → 25
k = −6 → 6
l = −16 → 14

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.054
S = 1.05
2783 reflections
190 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0068P)² + 2.6684P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.64 e Å⁻³
Absolute structure: Flack (1983 ), 1119 Friedel pairs
Flack parameter: −0.01 (2)

Table 1
Selected geometric parameters (Å, °)

C11—C1	1.476 (5)
C1—N1	1.286 (5)
N1—N2	1.396 (5)
N2—C2	1.358 (6)
C2—O2	1.233 (5)
C2—C21	1.482 (5)
C22—I22	2.107 (4)

C11—C1—N1	118.3 (3)
C1—N1—N2	113.2 (3)
N1—N2—C2	119.1 (4)
N2—C2—O2	123.5 (4)
O2—C2—C21	122.2 (4)
N2—C2—C21	114.2 (3)

C12—C11—C1—N1	−151.3 (4)
C11—C1—N1—N2	−175.4 (3)
C1—N1—N2—C2	−174.4 (4)
N1—N2—C2—C21	176.2 (3)
N2—C2—C21—C22	138.2 (4)
C11—C12—N12—O11	18.6 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.88	1.98	2.820 (5)	159
C1—H1⋯O2ⁱ	0.95	2.27	3.082 (5)	142
C26—H26⋯O22ⁱⁱ	0.95	2.39	3.169 (6)	139
Symmetry codes: (i) x, y-1, z; (ii) $[-x+1, -y, z-{\script{1\over 2}}]$ .

All H atoms were located in difference maps and subsequently treated as riding atoms, with distances C—H = 0.95 Å and N—H = 0.88 Å, and with U_iso(H) = 1.2U_eq(C,N). The correct orientation of the structure with respect to the polar-axis direction c (Jones, 1986 ) was established using the Flack (1983) parameter.

Data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805021355/lh6467sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805021355/lh6467Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

2-Nitrobenzaldehyde 2-iodobenzoylhydrazone top

Crystal data top

C₁₄H₁₀IN₃O₃	F(000) = 768
M_r = 395.15	D_x = 1.885 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2783 reflections
a = 21.6122 (8) Å	θ = 3.7–27.5°
b = 5.0393 (2) Å	µ = 2.31 mm⁻¹
c = 12.7868 (5) Å	T = 120 K
V = 1392.62 (9) Å³	Plate, green
Z = 4	0.28 × 0.08 × 0.05 mm

Data collection top

Bruker-Nonius 95mm CCD camera on κ goniostat diffractometer	2783 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	2579 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.7°
φ and ω scans	h = −27→25
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −6→6
T_min = 0.564, T_max = 0.893	l = −16→14
12100 measured reflections

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)] = 0.026	H-atom parameters constrained
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0068P)² + 2.6684P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2783 reflections	Δρ_max = 0.62 e Å⁻³
190 parameters	Δρ_min = −0.64 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1119 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (2)

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

	x	y	z	U_iso*/U_eq
I22	0.218672 (9)	1.14431 (4)	0.18746 (3)	0.01788 (7)
O2	0.35439 (14)	1.0376 (5)	0.2880 (2)	0.0213 (7)
O11	0.51157 (14)	0.1203 (6)	0.4398 (2)	0.0247 (7)
O22	0.53559 (14)	−0.1309 (6)	0.5706 (3)	0.0266 (7)
N1	0.39015 (15)	0.6282 (6)	0.4133 (2)	0.0130 (7)
N2	0.36433 (19)	0.5915 (8)	0.3143 (3)	0.0133 (8)
N12	0.50990 (15)	0.0622 (7)	0.5329 (3)	0.0159 (7)
C1	0.40790 (17)	0.4105 (8)	0.4563 (3)	0.0130 (8)
C2	0.34859 (19)	0.8076 (8)	0.2566 (3)	0.0122 (8)
C11	0.43163 (19)	0.4209 (8)	0.5645 (3)	0.0113 (8)
C12	0.47550 (18)	0.2408 (8)	0.6041 (3)	0.0114 (8)
C13	0.49059 (18)	0.2288 (8)	0.7098 (3)	0.0148 (10)
C14	0.4634 (2)	0.4062 (9)	0.7785 (3)	0.0186 (9)
C16	0.4064 (2)	0.5965 (12)	0.6355 (4)	0.0159 (12)
C15	0.4210 (3)	0.5966 (12)	0.7408 (4)	0.0187 (12)
C21	0.32548 (19)	0.7445 (8)	0.1504 (3)	0.0107 (8)
C22	0.27457 (17)	0.8738 (7)	0.1046 (3)	0.0130 (8)
C23	0.2557 (2)	0.8143 (8)	0.0036 (3)	0.0191 (9)
C24	0.2873 (2)	0.6247 (9)	−0.0540 (3)	0.0218 (9)
C25	0.3375 (2)	0.4930 (8)	−0.0110 (3)	0.0186 (9)
C26	0.3569 (2)	0.5553 (10)	0.0908 (4)	0.0150 (10)
H1	0.4058	0.2471	0.4194	0.016*
H2	0.3583	0.4305	0.2896	0.016*
H13	0.5192	0.1003	0.7345	0.018*
H14	0.4733	0.3999	0.8508	0.022*
H16	0.3774	0.7238	0.6107	0.019*
H15	0.4029	0.7225	0.7868	0.022*
H23	0.2211	0.9033	−0.0260	0.023*
H24	0.2744	0.5849	−0.1233	0.026*
H25	0.3587	0.3613	−0.0503	0.022*
H26	0.3919	0.4676	0.1196	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I22	0.01464 (11)	0.01349 (11)	0.02551 (12)	0.00233 (9)	−0.00086 (18)	−0.0044 (2)
O2	0.0360 (19)	0.0091 (14)	0.0188 (15)	0.0015 (12)	−0.0124 (13)	−0.0027 (12)
O11	0.0323 (18)	0.0245 (17)	0.0174 (15)	0.0082 (14)	0.0042 (13)	0.0018 (13)
O22	0.0232 (17)	0.0221 (17)	0.0346 (18)	0.0128 (13)	0.0019 (14)	0.0032 (15)
N1	0.0157 (17)	0.0146 (17)	0.0088 (15)	0.0010 (13)	−0.0025 (13)	−0.0002 (13)
N2	0.019 (2)	0.0101 (17)	0.0102 (18)	0.0024 (15)	−0.0033 (15)	−0.0032 (15)
N12	0.0131 (17)	0.0135 (17)	0.0209 (19)	−0.0012 (14)	−0.0007 (14)	0.0057 (14)
C1	0.0135 (19)	0.0125 (19)	0.0131 (19)	−0.0008 (15)	−0.0029 (15)	−0.0001 (15)
C2	0.012 (2)	0.011 (2)	0.014 (2)	0.0020 (16)	−0.0019 (16)	0.0008 (16)
C11	0.011 (2)	0.0107 (19)	0.012 (2)	−0.0043 (16)	−0.0005 (15)	0.0024 (15)
C12	0.013 (2)	0.010 (2)	0.011 (2)	−0.0022 (16)	0.0010 (16)	0.0021 (17)
C13	0.0156 (18)	0.0139 (18)	0.015 (3)	−0.0013 (15)	−0.0053 (16)	0.0038 (16)
C14	0.022 (3)	0.022 (2)	0.012 (2)	−0.004 (2)	−0.0054 (18)	−0.0009 (18)
C16	0.021 (3)	0.011 (2)	0.016 (3)	0.0017 (19)	−0.0014 (19)	0.0004 (19)
C15	0.024 (3)	0.020 (3)	0.012 (3)	−0.003 (2)	0.0011 (19)	−0.005 (2)
C21	0.0132 (19)	0.0087 (19)	0.0101 (19)	−0.0025 (16)	0.0011 (14)	0.0027 (14)
C22	0.0142 (19)	0.0102 (19)	0.0146 (19)	−0.0005 (15)	−0.0004 (15)	0.0017 (15)
C23	0.020 (2)	0.019 (2)	0.019 (2)	0.0017 (17)	−0.0044 (17)	0.0001 (17)
C24	0.028 (2)	0.026 (2)	0.012 (2)	0.0002 (19)	−0.0025 (17)	−0.0032 (17)
C25	0.022 (2)	0.017 (2)	0.017 (2)	0.0014 (17)	0.0014 (17)	−0.0042 (16)
C26	0.013 (2)	0.014 (2)	0.018 (2)	0.0009 (17)	0.0021 (18)	−0.0048 (19)

Geometric parameters (Å, º) top

C11—C1	1.476 (5)	C14—C15	1.411 (7)
C1—N1	1.286 (5)	C14—H14	0.95
C1—H1	0.95	C16—C15	1.383 (5)
N1—N2	1.396 (5)	C16—H16	0.95
N2—C2	1.358 (6)	C15—H15	0.95
N2—H2	0.88	C21—C26	1.397 (7)
C2—O2	1.233 (5)	C21—C22	1.407 (5)
C2—C21	1.482 (5)	C22—C23	1.387 (6)
C11—C16	1.381 (7)	C22—I22	2.107 (4)
C11—C12	1.407 (6)	C23—C24	1.386 (6)
C12—C13	1.391 (6)	C23—H23	0.95
C12—N12	1.481 (5)	C24—C25	1.386 (6)
N12—O22	1.220 (4)	C24—H24	0.95
N12—O11	1.227 (4)	C25—C26	1.403 (6)
C13—C14	1.384 (6)	C25—H25	0.95
C13—H13	0.95	C26—H26	0.95

C11—C1—N1	118.3 (3)	C11—C16—C15	123.3 (6)
N1—C1—H1	120.9	C11—C16—H16	118.3
C11—C1—H1	120.9	C15—C16—H16	118.3
C1—N1—N2	113.2 (3)	C16—C15—C14	118.7 (6)
N1—N2—C2	119.1 (4)	C16—C15—H15	120.6
C2—N2—H2	120.5	C14—C15—H15	120.6
N1—N2—H2	120.5	C26—C21—C22	118.0 (4)
N2—C2—O2	123.5 (4)	C26—C21—C2	118.9 (4)
O2—C2—C21	122.2 (4)	C22—C21—C2	123.1 (4)
N2—C2—C21	114.2 (3)	C23—C22—C21	121.2 (4)
C16—C11—C12	116.3 (4)	C23—C22—I22	116.1 (3)
C16—C11—C1	120.1 (4)	C21—C22—I22	122.6 (3)
C12—C11—C1	123.3 (4)	C24—C23—C22	120.0 (4)
C13—C12—C11	122.4 (4)	C24—C23—H23	120.0
C13—C12—N12	117.0 (3)	C22—C23—H23	120.0
C11—C12—N12	120.6 (4)	C25—C24—C23	120.3 (4)
O22—N12—O11	124.1 (4)	C25—C24—H24	119.8
O22—N12—C12	118.0 (3)	C23—C24—H24	119.8
O11—N12—C12	117.8 (3)	C24—C25—C26	119.6 (4)
C14—C13—C12	119.3 (4)	C24—C25—H25	120.2
C14—C13—H13	120.4	C26—C25—H25	120.2
C12—C13—H13	120.4	C21—C26—C25	120.9 (4)
C13—C14—C15	119.8 (4)	C21—C26—H26	119.5
C13—C14—H14	120.1	C25—C26—H26	119.5
C15—C14—H14	120.1

C12—C11—C1—N1	−151.3 (4)	C12—C11—C16—C15	−1.6 (8)
C11—C1—N1—N2	−175.4 (3)	C1—C11—C16—C15	172.2 (5)
C1—N1—N2—C2	−174.4 (4)	C11—C16—C15—C14	−0.8 (10)
N1—N2—C2—O2	−1.9 (6)	C13—C14—C15—C16	1.7 (8)
N1—N2—C2—C21	176.2 (3)	O2—C2—C21—C26	133.7 (5)
N2—C2—C21—C22	138.2 (4)	N2—C2—C21—C26	−44.4 (5)
N1—C1—C11—C16	35.3 (6)	O2—C2—C21—C22	−43.7 (6)
C16—C11—C12—C13	3.3 (6)	C26—C21—C22—C23	0.5 (6)
C1—C11—C12—C13	−170.4 (4)	C2—C21—C22—C23	178.0 (4)
C16—C11—C12—N12	−173.9 (4)	C26—C21—C22—I22	175.7 (3)
C1—C11—C12—N12	12.4 (6)	C2—C21—C22—I22	−6.9 (5)
C13—C12—N12—O22	20.2 (5)	C21—C22—C23—C24	−0.1 (6)
C11—C12—N12—O22	−162.5 (4)	I22—C22—C23—C24	−175.6 (3)
C13—C12—N12—O11	−158.7 (4)	C22—C23—C24—C25	0.4 (6)
C11—C12—N12—O11	18.6 (5)	C23—C24—C25—C26	−0.9 (6)
C11—C12—C13—C14	−2.5 (6)	C22—C21—C26—C25	−1.1 (7)
N12—C12—C13—C14	174.8 (4)	C2—C21—C26—C25	−178.7 (4)
C12—C13—C14—C15	−0.1 (6)	C24—C25—C26—C21	1.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.88	1.98	2.820 (5)	159
C1—H1···O2ⁱ	0.95	2.27	3.082 (5)	142
C26—H26···O22ⁱⁱ	0.95	2.39	3.169 (6)	139

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

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England. The authors thank the staff for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

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