A hydrogen-bonded C(6) chain in glyoxal 3-nitro­phenyl­hydrazone

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

doi:10.1107/S160053680601186X

organic compounds

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ISSN: 2056-9890

Volume 62| Part 5| May 2006| Pages o1816-o1818

https://doi.org/10.1107/S160053680601186X

A hydrogen-bonded C(6) chain in glyoxal 3-nitrophenylhydrazone

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

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

(Received 31 March 2006; accepted 31 March 2006; online 11 April 2006)

The molecules of the title compound, C₈H₇N₃O₃, which are nearly planar, are linked into simple C(6) chains by an N—H⋯O hydrogen bond.

Comment

The title compound, (I), was prepared as part of our continuing study of the supramolecular arrangements of N-(nitropheny)imide and hydrazone derivatives. We have recently reported the supramolecular structure of the isomeric compound glyoxal 4-nitrophenylhydrazone, (II), in which triple helices enclose two types of channel lying respectively along $[\overline{4}]$ , and 4₁ or 4₃ axes in space group I4₁/a (Glidewell et al., 2005 ): the supramolecular structure of (I), by contrast, is very simple.

The molecules of compound (I) (Fig. 1) are almost planar, as shown by the leading torsion angles (Table 1); the side chain between atoms N1 and O1 adopts a planar all-trans conformation, and the nitro group is nearly coplanar with the aryl ring. There is strong bond fixation in the side chain with very short N2—C11 and C12—O1 bonds, with no evidence for bond polarization in this fragment.

A single hydrogen bond (Table 2) links the molecules into chains; atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O1 in the molecule at (− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z), forming a C(6) chain running parallel to the [10 $[\overline{1}]$ ] direction and generated by the n-glide plane at y = 0.25 (Fig. 2). Two such chains pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

Figure 1
A 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(6) hydrogen-bonded chain along [10 $[\overline{1}]$ ]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z) and ( $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z), respectively.

Experimental

Compound (I) was prepared by heating under reflux for 1 h a solution of glyoxal (1 mmol as a 40% aqueous solution) and 3-nitrophenylhydrazine (1 mmol) in methanol (40 ml). The mixture was cooled to ambient temperature and the solvent was removed under reduced pressure. The residue was crystallized from ethanol to yield crystals suitable for single-crystal X-ray diffraction.

Crystal data

C₈H₇N₃O₃
M_r = 193.17
Monoclinic, C c
a = 7.4737 (4) Å
b = 19.7711 (13) Å
c = 6.0262 (4) Å
β = 107.080 (4)°
V = 851.18 (9) Å³
Z = 4
D_x = 1.507 Mg m⁻³
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 120 (2) K
Lath, yellow
0.16 × 0.08 × 0.02 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.961, T_max = 0.998
7928 measured reflections
987 independent reflections
871 reflections with I > 2σ(I)
R_int = 0.063
θ_max = 27.6°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.098
S = 1.08
987 reflections
127 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0568P)² + 0.1446P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—N1	1.395 (3)
N1—N2	1.331 (3)
N2—C11	1.294 (3)
C11—C12	1.445 (4)
C12—O1	1.224 (3)

C2—C1—N1—N2	−3.6 (4)
C1—N1—N2—C11	−175.8 (2)
N1—N2—C11—C12	−179.1 (2)
N2—C11—C12—O1	−177.1 (3)
C2—C3—N3—O31	6.7 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88	2.15	2.940 (3)	149
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 Å and N—H = 0.88 Å, and with U_iso(H) = 1.2U_eq(C,N). In the absence of significant anomalous dispersion the Flack (1983 ) parameter was indeterminate and it was not possible to determine the correct orientation of the structure with respect to the polar axis directions. Accordingly, the Friedel-equivalent reflections were merged prior to the final refinement.

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/S160053680601186X/lh2037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680601186X/lh2037Isup2.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).

Glyoxal 3-nitrophenylhydrazone top

Crystal data top

C₈H₇N₃O₃	F(000) = 400
M_r = 193.17	D_x = 1.507 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 987 reflections
a = 7.4737 (4) Å	θ = 3.0–27.6°
b = 19.7711 (13) Å	µ = 0.12 mm⁻¹
c = 6.0262 (4) Å	T = 120 K
β = 107.080 (4)°	Lath, yellow
V = 851.18 (9) Å³	0.16 × 0.08 × 0.02 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD diffractometer	987 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	871 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.0°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −25→25
T_min = 0.961, T_max = 0.998	l = −7→7
7928 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0568P)² + 0.1446P] where P = (F_o² + 2F_c²)/3
987 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.17 e Å⁻³
2 restraints	Δρ_min = −0.26 e Å⁻³

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

	x	y	z	U_iso*/U_eq
N1	0.2050 (3)	0.15679 (11)	0.1679 (3)	0.0221 (5)
N2	0.3161 (3)	0.19066 (11)	0.0702 (4)	0.0221 (5)
C11	0.2384 (4)	0.22429 (13)	−0.1177 (5)	0.0237 (6)
C12	0.3675 (4)	0.25897 (14)	−0.2160 (5)	0.0249 (6)
O1	0.3218 (3)	0.29536 (11)	−0.3877 (3)	0.0327 (5)
C1	0.2813 (4)	0.12344 (13)	0.3786 (4)	0.0219 (5)
C2	0.4747 (4)	0.12149 (13)	0.4849 (4)	0.0228 (6)
C3	0.5377 (4)	0.08816 (14)	0.6942 (4)	0.0240 (6)
N3	0.7413 (4)	0.08596 (12)	0.8066 (4)	0.0295 (6)
O31	0.8425 (3)	0.11907 (12)	0.7197 (3)	0.0346 (5)
O32	0.8008 (3)	0.05119 (12)	0.9815 (4)	0.0415 (6)
C4	0.4212 (4)	0.05643 (14)	0.8030 (5)	0.0270 (6)
C5	0.2295 (4)	0.05803 (13)	0.6913 (5)	0.0276 (6)
C6	0.1600 (4)	0.09135 (13)	0.4822 (5)	0.0232 (5)
H1	0.0830	0.1607	0.1044	0.027*
H11	0.1066	0.2260	−0.1859	0.028*
H12	0.4975	0.2531	−0.1418	0.030*
H2	0.5594	0.1424	0.4154	0.027*
H4	0.4702	0.0344	0.9484	0.032*
H5	0.1458	0.0360	0.7596	0.033*
H6	0.0289	0.0924	0.4085	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0188 (10)	0.0265 (11)	0.0201 (11)	−0.0011 (9)	0.0042 (9)	0.0022 (9)
N2	0.0209 (11)	0.0241 (11)	0.0216 (11)	−0.0011 (9)	0.0067 (9)	−0.0015 (8)
C11	0.0233 (12)	0.0261 (13)	0.0194 (12)	0.0017 (10)	0.0029 (10)	0.0004 (11)
C12	0.0193 (12)	0.0315 (14)	0.0220 (14)	−0.0021 (11)	0.0030 (10)	0.0021 (12)
O1	0.0271 (10)	0.0389 (11)	0.0288 (11)	−0.0020 (9)	0.0031 (8)	0.0096 (9)
C1	0.0236 (13)	0.0211 (13)	0.0208 (12)	0.0004 (9)	0.0064 (11)	−0.0017 (10)
C2	0.0236 (14)	0.0227 (13)	0.0225 (13)	−0.0007 (10)	0.0073 (11)	−0.0024 (11)
C3	0.0215 (15)	0.0277 (14)	0.0203 (13)	0.0023 (10)	0.0022 (11)	−0.0019 (10)
N3	0.0276 (13)	0.0323 (13)	0.0257 (12)	0.0039 (10)	0.0035 (10)	−0.0043 (10)
O31	0.0230 (10)	0.0507 (14)	0.0297 (11)	0.0021 (9)	0.0072 (9)	−0.0021 (10)
O32	0.0348 (13)	0.0468 (14)	0.0330 (11)	0.0074 (10)	−0.0055 (10)	0.0090 (10)
C4	0.0368 (16)	0.0230 (14)	0.0223 (13)	0.0083 (11)	0.0103 (12)	0.0045 (11)
C5	0.0339 (16)	0.0228 (13)	0.0298 (15)	0.0014 (11)	0.0150 (13)	0.0016 (11)
C6	0.0220 (13)	0.0231 (13)	0.0249 (13)	0.0016 (10)	0.0076 (10)	−0.0021 (11)

Geometric parameters (Å, º) top

C1—N1	1.395 (3)	C2—H2	0.95
N1—N2	1.331 (3)	C3—C4	1.384 (4)
N1—H1	0.88	C3—N3	1.473 (3)
N2—C11	1.294 (3)	N3—O32	1.227 (3)
C11—C12	1.445 (4)	N3—O31	1.228 (3)
C11—H11	0.95	C4—C5	1.393 (4)
C12—O1	1.224 (3)	C4—H4	0.95
C12—H12	0.95	C5—C6	1.381 (4)
C1—C6	1.395 (4)	C5—H5	0.95
C1—C2	1.399 (4)	C6—H6	0.95
C2—C3	1.378 (4)

N2—N1—C1	119.9 (2)	C2—C3—C4	123.8 (2)
N2—N1—H1	117.6	C2—C3—N3	117.6 (2)
C1—N1—H1	122.0	C4—C3—N3	118.5 (2)
C11—N2—N1	117.9 (2)	O32—N3—O31	123.5 (3)
N2—C11—C12	114.9 (2)	O32—N3—C3	118.4 (2)
N2—C11—H11	122.6	O31—N3—C3	118.1 (2)
C12—C11—H11	122.6	C3—C4—C5	117.5 (2)
O1—C12—C11	124.8 (2)	C3—C4—H4	121.3
O1—C12—H12	117.6	C5—C4—H4	121.3
C11—C12—H12	117.6	C6—C5—C4	120.7 (3)
C6—C1—N1	118.4 (2)	C6—C5—H5	119.7
C6—C1—C2	120.2 (2)	C4—C5—H5	119.7
N1—C1—C2	121.4 (2)	C5—C6—C1	120.3 (2)
C3—C2—C1	117.5 (2)	C5—C6—H6	119.8
C3—C2—H2	121.3	C1—C6—H6	119.8
C1—C2—H2	121.3

C2—C1—N1—N2	−3.6 (4)	C4—C3—N3—O32	6.3 (4)
C1—N1—N2—C11	−175.8 (2)	C2—C3—N3—O31	6.7 (4)
N1—N2—C11—C12	−179.1 (2)	C4—C3—N3—O31	−173.8 (2)
N2—C11—C12—O1	−177.1 (3)	C2—C3—C4—C5	0.7 (4)
N2—N1—C1—C6	176.8 (2)	N3—C3—C4—C5	−178.8 (2)
C6—C1—C2—C3	−1.2 (3)	C3—C4—C5—C6	−1.3 (4)
N1—C1—C2—C3	179.2 (2)	C4—C5—C6—C1	0.6 (4)
C1—C2—C3—C4	0.5 (4)	N1—C1—C6—C5	−179.7 (2)
C1—C2—C3—N3	180.0 (2)	C2—C1—C6—C5	0.7 (4)
C2—C3—N3—O32	−173.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88	2.15	2.940 (3)	149

Symmetry code: (i) x−1/2, −y+1/2, 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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