Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, C14H10N4O4, was synthesized by the reaction of 3-nitro­benzaldehyde with hydrazine hydrate. The mol­ecule possesses a crystallographically imposed center of symmetry and is essentially planar; the dihedral angle between the nitro group and the benzene ring is 3.4 (2)°. Inter­molecular C—H...O hydrogen bonds link the mol­ecules into an infinite chain.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030631/wn6382sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030631/wn6382Isup2.hkl
Contains datablock I

CCDC reference: 287750

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.038
  • wR factor = 0.116
  • Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.99 PLAT230_ALERT_2_C Hirshfeld Test Diff for O2 - N1 .. 5.59 su PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C14 H10 N4 O4 PLAT804_ALERT_4_C ARU-Pack Problem in PLATON Analysis ............ !
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Recently, a number of azine compounds containing both a diimine linkage and N—N bonding have been investigated in terms of their crystallography and coordination chemistry (Zheng et al., 2005; Kundu et al., 2005; Kesslen & Euler, 1999; Armstrong et al., 1998; Xu et al., 1997). We report here the crystal structure of the title compound, (I), where two 3-nitrobenzylidene units are directly linked through the imine N atoms.

The title molecule crystallizes in an E,E configuration, possessing a crystallographically imposed center of symmetry at the mid-point of the N—N bond (Fig. 1). This configuration agrees with that commonly found in a number of azine compounds (Zheng et al., 2005, Şengül et al., 2004, Liu et al., 2004). The N—N bond length of 1.409 (3) Å (Table 1) is somewhat longer than that observed in related azine compounds (Xu et al., 2005; Şengül et al., 2004). The CN—N angle [111.9 (2)°] is similar to that in N,N'-bis(4-chlorobenzylidene)hydrazine (Zheng et al., 2005), but significantly smaller than the ideal sp2 value of 120°, as a consequence of repulsion between the nitrogen lone pairs and the adjacent CN bond. The dihedral angle between the nitro group and the benzene ring is 3.4 (2)°. The bis-benzylidenehydrazine backbone assumes a planar structure, with an r.m.s. deviation of 0.012 (2) Å.

In the crystal structure, a weak intermolecular C—H···O hydrogen bond (Table 2) leads to a ten-membered ring, described by the graph-set descriptor R22(10), linking the molecules into an infinite chain (Fig. 2).

Experimental top

The title compound was synthesized by the reaction of 3-nitrobenzaldehyde with hydrazine hydrate in refluxing ethanol (Liu et al., 2004). Single crystals suitable for X-ray analysis were obtained by slow evaporation of a tetrahydrofuran solution.

Refinement top

All H atoms were positioned geometrically and refined as riding, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of the molecule of (I), with displacement ellipsoids drawn at the 30% probability level. The suffix A corresponds to symmetry code (3 − x, 1 − y, 2 − z).
[Figure 2] Fig. 2. The packing of (I), viewed down the a axis, showing the intermolecular hydrogen-bonding (dashed lines) extended network.
N,N'-Bis(3-nitrobenzylidene)hydrazine top
Crystal data top
C14H10N4O4F(000) = 308
Mr = 298.26Dx = 1.447 Mg m3
Monoclinic, P21/nMelting point = 469–470 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 6.9694 (19) ÅCell parameters from 1134 reflections
b = 7.833 (2) Åθ = 3.0–26.1°
c = 12.990 (4) ŵ = 0.11 mm1
β = 105.175 (4)°T = 294 K
V = 684.4 (3) Å3Block, light yellow
Z = 20.34 × 0.30 × 0.14 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
1204 independent reflections
Radiation source: fine-focus sealed tube814 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ϕ and ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.962, Tmax = 1.000k = 79
3318 measured reflectionsl = 1515
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.116 w = 1/[σ2(Fo2) + (0.061P)2 + 0.0625P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1204 reflectionsΔρmax = 0.12 e Å3
101 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.094 (9)
Crystal data top
C14H10N4O4V = 684.4 (3) Å3
Mr = 298.26Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.9694 (19) ŵ = 0.11 mm1
b = 7.833 (2) ÅT = 294 K
c = 12.990 (4) Å0.34 × 0.30 × 0.14 mm
β = 105.175 (4)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
1204 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
814 reflections with I > 2σ(I)
Tmin = 0.962, Tmax = 1.000Rint = 0.035
3318 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.03Δρmax = 0.12 e Å3
1204 reflectionsΔρmin = 0.18 e Å3
101 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.6567 (2)0.8906 (2)1.09525 (13)0.0816 (5)
O20.8984 (2)0.7322 (2)1.17929 (11)0.0769 (5)
N10.8070 (2)0.8074 (2)1.09941 (14)0.0562 (5)
N21.4133 (2)0.53887 (19)1.00720 (13)0.0530 (5)
C11.3163 (3)0.6158 (2)0.92344 (15)0.0504 (5)
H11.36490.61580.86320.060*
C21.1288 (2)0.7046 (2)0.92005 (14)0.0461 (5)
C31.0230 (3)0.7846 (2)0.82660 (15)0.0578 (6)
H31.07080.78050.76620.069*
C40.8475 (3)0.8700 (3)0.82294 (16)0.0632 (6)
H40.77880.92320.76010.076*
C50.7733 (3)0.8773 (2)0.91120 (16)0.0566 (5)
H50.65500.93400.90900.068*
C60.8800 (2)0.7978 (2)1.00290 (14)0.0465 (5)
C71.0551 (2)0.7121 (2)1.00964 (13)0.0458 (5)
H71.12310.65991.07300.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0668 (10)0.0918 (12)0.0978 (12)0.0211 (9)0.0419 (8)0.0015 (9)
O20.0742 (10)0.1063 (12)0.0551 (9)0.0186 (9)0.0256 (8)0.0065 (9)
N10.0505 (10)0.0588 (11)0.0645 (11)0.0021 (8)0.0239 (8)0.0091 (8)
N20.0480 (9)0.0547 (10)0.0627 (10)0.0028 (7)0.0259 (8)0.0010 (8)
C10.0525 (11)0.0496 (11)0.0551 (11)0.0037 (9)0.0250 (9)0.0024 (9)
C20.0472 (10)0.0450 (10)0.0486 (10)0.0051 (8)0.0171 (8)0.0033 (8)
C30.0608 (12)0.0684 (13)0.0459 (11)0.0046 (10)0.0170 (9)0.0034 (9)
C40.0570 (12)0.0738 (14)0.0519 (12)0.0032 (11)0.0021 (10)0.0028 (10)
C50.0428 (10)0.0584 (12)0.0649 (13)0.0020 (9)0.0074 (9)0.0053 (10)
C60.0430 (10)0.0460 (10)0.0516 (11)0.0055 (8)0.0143 (8)0.0049 (8)
C70.0456 (11)0.0445 (10)0.0487 (11)0.0012 (8)0.0146 (8)0.0014 (8)
Geometric parameters (Å, º) top
O1—N11.223 (2)C3—C41.385 (3)
O2—N11.2181 (19)C3—H30.9300
N1—C61.473 (2)C4—C51.377 (3)
N2—C11.272 (2)C4—H40.9300
N2—N2i1.409 (3)C5—C61.377 (3)
C1—C21.471 (2)C5—H50.9300
C1—H10.9300C6—C71.375 (2)
C2—C71.391 (2)C7—H70.9300
C2—C31.393 (3)
O2—N1—O1123.11 (17)C5—C4—C3120.83 (18)
O2—N1—C6118.68 (16)C5—C4—H4119.6
O1—N1—C6118.20 (17)C3—C4—H4119.6
C1—N2—N2i111.9 (2)C4—C5—C6117.78 (18)
N2—C1—C2121.24 (17)C4—C5—H5121.1
N2—C1—H1119.4C6—C5—H5121.1
C2—C1—H1119.4C7—C6—C5123.04 (18)
C7—C2—C3118.88 (17)C7—C6—N1117.99 (16)
C7—C2—C1120.98 (16)C5—C6—N1118.96 (16)
C3—C2—C1120.15 (17)C6—C7—C2118.89 (17)
C4—C3—C2120.58 (19)C6—C7—H7120.6
C4—C3—H3119.7C2—C7—H7120.6
C2—C3—H3119.7
N2i—N2—C1—C2179.36 (17)O2—N1—C6—C73.7 (2)
N2—C1—C2—C72.2 (3)O1—N1—C6—C7176.48 (16)
N2—C1—C2—C3178.53 (17)O2—N1—C6—C5177.64 (16)
C7—C2—C3—C40.0 (3)O1—N1—C6—C52.2 (2)
C1—C2—C3—C4179.32 (17)C5—C6—C7—C20.0 (3)
C2—C3—C4—C50.3 (3)N1—C6—C7—C2178.63 (15)
C3—C4—C5—C60.4 (3)C3—C2—C7—C60.1 (2)
C4—C5—C6—C70.2 (3)C1—C2—C7—C6179.47 (15)
C4—C5—C6—N1178.36 (17)
Symmetry code: (i) x+3, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O1ii0.932.563.487 (3)176
Symmetry code: (ii) x+1, y+2, z+2.

Experimental details

Crystal data
Chemical formulaC14H10N4O4
Mr298.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)294
a, b, c (Å)6.9694 (19), 7.833 (2), 12.990 (4)
β (°) 105.175 (4)
V3)684.4 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.34 × 0.30 × 0.14
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.962, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
3318, 1204, 814
Rint0.035
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.116, 1.03
No. of reflections1204
No. of parameters101
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.12, 0.18

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
O1—N11.223 (2)N2—C11.272 (2)
O2—N11.2181 (19)N2—N2i1.409 (3)
N1—C61.473 (2)
O2—N1—O1123.11 (17)O1—N1—C6118.20 (17)
O2—N1—C6118.68 (16)C1—N2—N2i111.9 (2)
Symmetry code: (i) x+3, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O1ii0.932.563.487 (3)176
Symmetry code: (ii) x+1, y+2, z+2.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds