Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030631/wn6382sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030631/wn6382Isup2.hkl |
CCDC reference: 287750
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (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
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.
All H atoms were positioned geometrically and refined as riding, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
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.
C14H10N4O4 | F(000) = 308 |
Mr = 298.26 | Dx = 1.447 Mg m−3 |
Monoclinic, P21/n | Melting point = 469–470 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9694 (19) Å | Cell parameters from 1134 reflections |
b = 7.833 (2) Å | θ = 3.0–26.1° |
c = 12.990 (4) Å | µ = 0.11 mm−1 |
β = 105.175 (4)° | T = 294 K |
V = 684.4 (3) Å3 | Block, light yellow |
Z = 2 | 0.34 × 0.30 × 0.14 mm |
Bruker SMART 1000 CCD area-detector diffractometer | 1204 independent reflections |
Radiation source: fine-focus sealed tube | 814 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ϕ and ω scans | θmax = 25.0°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.962, Tmax = 1.000 | k = −7→9 |
3318 measured reflections | l = −15→15 |
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)] = 0.038 | H-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 reflections | Δρmax = 0.12 e Å−3 |
101 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.094 (9) |
C14H10N4O4 | V = 684.4 (3) Å3 |
Mr = 298.26 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.9694 (19) Å | µ = 0.11 mm−1 |
b = 7.833 (2) Å | T = 294 K |
c = 12.990 (4) Å | 0.34 × 0.30 × 0.14 mm |
β = 105.175 (4)° |
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 = 1.000 | Rint = 0.035 |
3318 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.12 e Å−3 |
1204 reflections | Δρmin = −0.18 e Å−3 |
101 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.6567 (2) | 0.8906 (2) | 1.09525 (13) | 0.0816 (5) | |
O2 | 0.8984 (2) | 0.7322 (2) | 1.17929 (11) | 0.0769 (5) | |
N1 | 0.8070 (2) | 0.8074 (2) | 1.09941 (14) | 0.0562 (5) | |
N2 | 1.4133 (2) | 0.53887 (19) | 1.00720 (13) | 0.0530 (5) | |
C1 | 1.3163 (3) | 0.6158 (2) | 0.92344 (15) | 0.0504 (5) | |
H1 | 1.3649 | 0.6158 | 0.8632 | 0.060* | |
C2 | 1.1288 (2) | 0.7046 (2) | 0.92005 (14) | 0.0461 (5) | |
C3 | 1.0230 (3) | 0.7846 (2) | 0.82660 (15) | 0.0578 (6) | |
H3 | 1.0708 | 0.7805 | 0.7662 | 0.069* | |
C4 | 0.8475 (3) | 0.8700 (3) | 0.82294 (16) | 0.0632 (6) | |
H4 | 0.7788 | 0.9232 | 0.7601 | 0.076* | |
C5 | 0.7733 (3) | 0.8773 (2) | 0.91120 (16) | 0.0566 (5) | |
H5 | 0.6550 | 0.9340 | 0.9090 | 0.068* | |
C6 | 0.8800 (2) | 0.7978 (2) | 1.00290 (14) | 0.0465 (5) | |
C7 | 1.0551 (2) | 0.7121 (2) | 1.00964 (13) | 0.0458 (5) | |
H7 | 1.1231 | 0.6599 | 1.0730 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0668 (10) | 0.0918 (12) | 0.0978 (12) | 0.0211 (9) | 0.0419 (8) | −0.0015 (9) |
O2 | 0.0742 (10) | 0.1063 (12) | 0.0551 (9) | 0.0186 (9) | 0.0256 (8) | 0.0065 (9) |
N1 | 0.0505 (10) | 0.0588 (11) | 0.0645 (11) | −0.0021 (8) | 0.0239 (8) | −0.0091 (8) |
N2 | 0.0480 (9) | 0.0547 (10) | 0.0627 (10) | 0.0028 (7) | 0.0259 (8) | 0.0010 (8) |
C1 | 0.0525 (11) | 0.0496 (11) | 0.0551 (11) | −0.0037 (9) | 0.0250 (9) | −0.0024 (9) |
C2 | 0.0472 (10) | 0.0450 (10) | 0.0486 (10) | −0.0051 (8) | 0.0171 (8) | −0.0033 (8) |
C3 | 0.0608 (12) | 0.0684 (13) | 0.0459 (11) | −0.0046 (10) | 0.0170 (9) | −0.0034 (9) |
C4 | 0.0570 (12) | 0.0738 (14) | 0.0519 (12) | 0.0032 (11) | 0.0021 (10) | 0.0028 (10) |
C5 | 0.0428 (10) | 0.0584 (12) | 0.0649 (13) | 0.0020 (9) | 0.0074 (9) | −0.0053 (10) |
C6 | 0.0430 (10) | 0.0460 (10) | 0.0516 (11) | −0.0055 (8) | 0.0143 (8) | −0.0049 (8) |
C7 | 0.0456 (11) | 0.0445 (10) | 0.0487 (11) | −0.0012 (8) | 0.0146 (8) | 0.0014 (8) |
O1—N1 | 1.223 (2) | C3—C4 | 1.385 (3) |
O2—N1 | 1.2181 (19) | C3—H3 | 0.9300 |
N1—C6 | 1.473 (2) | C4—C5 | 1.377 (3) |
N2—C1 | 1.272 (2) | C4—H4 | 0.9300 |
N2—N2i | 1.409 (3) | C5—C6 | 1.377 (3) |
C1—C2 | 1.471 (2) | C5—H5 | 0.9300 |
C1—H1 | 0.9300 | C6—C7 | 1.375 (2) |
C2—C7 | 1.391 (2) | C7—H7 | 0.9300 |
C2—C3 | 1.393 (3) | ||
O2—N1—O1 | 123.11 (17) | C5—C4—C3 | 120.83 (18) |
O2—N1—C6 | 118.68 (16) | C5—C4—H4 | 119.6 |
O1—N1—C6 | 118.20 (17) | C3—C4—H4 | 119.6 |
C1—N2—N2i | 111.9 (2) | C4—C5—C6 | 117.78 (18) |
N2—C1—C2 | 121.24 (17) | C4—C5—H5 | 121.1 |
N2—C1—H1 | 119.4 | C6—C5—H5 | 121.1 |
C2—C1—H1 | 119.4 | C7—C6—C5 | 123.04 (18) |
C7—C2—C3 | 118.88 (17) | C7—C6—N1 | 117.99 (16) |
C7—C2—C1 | 120.98 (16) | C5—C6—N1 | 118.96 (16) |
C3—C2—C1 | 120.15 (17) | C6—C7—C2 | 118.89 (17) |
C4—C3—C2 | 120.58 (19) | C6—C7—H7 | 120.6 |
C4—C3—H3 | 119.7 | C2—C7—H7 | 120.6 |
C2—C3—H3 | 119.7 | ||
N2i—N2—C1—C2 | 179.36 (17) | O2—N1—C6—C7 | −3.7 (2) |
N2—C1—C2—C7 | 2.2 (3) | O1—N1—C6—C7 | 176.48 (16) |
N2—C1—C2—C3 | −178.53 (17) | O2—N1—C6—C5 | 177.64 (16) |
C7—C2—C3—C4 | 0.0 (3) | O1—N1—C6—C5 | −2.2 (2) |
C1—C2—C3—C4 | −179.32 (17) | C5—C6—C7—C2 | 0.0 (3) |
C2—C3—C4—C5 | −0.3 (3) | N1—C6—C7—C2 | −178.63 (15) |
C3—C4—C5—C6 | 0.4 (3) | C3—C2—C7—C6 | 0.1 (2) |
C4—C5—C6—C7 | −0.2 (3) | C1—C2—C7—C6 | 179.47 (15) |
C4—C5—C6—N1 | 178.36 (17) |
Symmetry code: (i) −x+3, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1ii | 0.93 | 2.56 | 3.487 (3) | 176 |
Symmetry code: (ii) −x+1, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C14H10N4O4 |
Mr | 298.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 6.9694 (19), 7.833 (2), 12.990 (4) |
β (°) | 105.175 (4) |
V (Å3) | 684.4 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.34 × 0.30 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.962, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3318, 1204, 814 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.116, 1.03 |
No. of reflections | 1204 |
No. of parameters | 101 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.12, −0.18 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
O1—N1 | 1.223 (2) | N2—C1 | 1.272 (2) |
O2—N1 | 1.2181 (19) | N2—N2i | 1.409 (3) |
N1—C6 | 1.473 (2) | ||
O2—N1—O1 | 123.11 (17) | O1—N1—C6 | 118.20 (17) |
O2—N1—C6 | 118.68 (16) | C1—N2—N2i | 111.9 (2) |
Symmetry code: (i) −x+3, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1ii | 0.93 | 2.56 | 3.487 (3) | 176 |
Symmetry code: (ii) −x+1, −y+2, −z+2. |
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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 C═N—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 C═N 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).