6,6′-Di­nitro-1,1′-(ethane-1,2-di­yl)di(1H-indazole)

Kouakou, A.; Rakib, E.M.; El Malki, A.; Saadi, M.; El Ammari, L.

doi:10.1107/S1600536814004516

6,6′-Dinitro-1,1′-(ethane-1,2-diyl)di(1H-indazole)

A. Kouakou, E. M. Rakib, A. El Malki, M. Saadi and L. El Ammari

The molecule of the title compound, C₁₆H₁₂N₆O₄, is built up from two fused five- and six-membered rings linked by an ethylene group. The dihedral angle between the planes through the indazole ring systems is 39.74 (5)°. The nitro groups are tilted by 7.2 (2) and 8.5 (2)° with respect to planes of the fused-ring systems. In the crystal, molecules are linked by C—H

N and C—H

O hydrogen bonds into chains running parallel to the c axis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536814004516/rz5107sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536814004516/rz5107Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536814004516/rz5107Isup3.cml Supplementary material

CCDC reference: 988920

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.002 Å
R factor = 0.039
wR factor = 0.111
Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......      3.300 Sigma
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     --  N1      ..        6.3 su

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT128_ALERT_4_G Alternate Setting for Input Space-Group  P21/c        P21/n Note
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          2 Why ?

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   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
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Indazole moiety have been nucleus is a pharmaceutically important and emerging heterocycle with a broad spectrum of activities including anti-microbial1, anti-cancer, anti-inflammatory, anti- platelet, and selective 5-HT6 antagonists (Ali et al., 2012; Abbassi et al., 2012; Plescia et al., 2010; Lee et al., 2001; Liu et al., 2011). The present work is a continuation of the investigation on the indazole derivatives published recently by our team (Kouakou et al., 2013; Chicha et al., 2013).

The molecule of the title compound is formed by two fused five- and six-membered rings linked by an ethylene group and connected to two nitro groups as shown in Fig. 1. The two fused ring systems (N2/N3/C1–C7 and N4/N5C10–C16) make dihedral angles of 7.2 (2)° and 8.5 (2)° with the planes through the attached nitro groups (N1/O1/O2 and N6/O3(O4), respectively. The dihedral angle between the indazole ring systems is 39.74 (5)°. In the crystal, molecules are linked by C7—H7···N5 and C15—H15···O1 hydrogen interactions (Table 1) into chains running parallel to the [0 0 1] direction as shown in Fig. 2.

Related literature top

For biological activities of the indazole moiety, see: Ali et al. (2012); Abbassi et al. (2012); Plescia et al. (2010); Lee et al. (2001); Liu et al. (2011). For related compounds, see: Kouakou et al. (2013); Chicha et al. (2013).

Experimental top

A solution of 6-nitroindazole (0.5 g, 3.06 mmol) and KOH (0.17 g, 3.08 mmol) in EtOH (15 ml) was heated under reflux for 48 h. The mixture was cooled and the solvent removed from the filtrate in vacuo. The formed 6-nitroindazole potassium salt and 1,2-ethylene dibromide (0.27 ml, 1.48 mmol) was heated in dimethylformamide (5 ml) under reflux for 3 h. The mixture was then cooled, all volatiles were removed in vacuo and water was added. The precipitate was filtered and was purified by column chromatography (EtOAc/hexane 2:8 v/v). The title compound was recrystallized from acetone (yield: 35%; m. p.: 468 K).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are represented as small circles.
	Fig. 2. Partial crystal packing of the title compound showing a chain of molecules linked by hydrogen bonds (dashed lines).

6,6'-Dinitro-1,1'-(ethane-1,2-diyl)di(1H-indazole) top

Crystal data top

C₁₆H₁₂N₆O₄	F(000) = 728
M_r = 352.32	D_x = 1.473 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3672 reflections
a = 9.410 (5) Å	θ = 1.5–27.1°
b = 12.064 (5) Å	µ = 0.11 mm⁻¹
c = 14.804 (4) Å	T = 296 K
β = 109.01 (2)°	Block, colourless
V = 1588.9 (12) Å³	0.37 × 0.32 × 0.26 mm
Z = 4

Data collection top

Bruker X8 APEX diffractometer	2667 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 27.1°, θ_min = 2.8°
ϕ and ω scans	h = −12→12
16446 measured reflections	k = −15→15
3503 independent reflections	l = −18→18

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)] = 0.039	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0493P)² + 0.3594P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3503 reflections	Δρ_max = 0.20 e Å⁻³
236 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0033 (10)

Crystal data top

C₁₆H₁₂N₆O₄	V = 1588.9 (12) Å³
M_r = 352.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.410 (5) Å	µ = 0.11 mm⁻¹
b = 12.064 (5) Å	T = 296 K
c = 14.804 (4) Å	0.37 × 0.32 × 0.26 mm
β = 109.01 (2)°

Data collection top

Bruker X8 APEX diffractometer	2667 reflections with I > 2σ(I)
16446 measured reflections	R_int = 0.033
3503 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.03	Δρ_max = 0.20 e Å⁻³
3503 reflections	Δρ_min = −0.19 e Å⁻³
236 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

	x	y	z	U_iso*/U_eq
O1	0.72668 (16)	0.44512 (14)	0.20575 (10)	0.0753 (4)
O2	0.8642 (2)	0.57503 (14)	0.28985 (14)	0.1037 (6)
O3	1.06798 (18)	0.14604 (14)	0.75890 (9)	0.0817 (5)
O4	1.28535 (16)	0.17800 (15)	0.74730 (11)	0.0990 (6)
N1	0.78171 (17)	0.49484 (13)	0.28105 (13)	0.0617 (4)
N2	0.53003 (16)	0.25102 (14)	0.54188 (9)	0.0580 (4)
N3	0.54014 (13)	0.24766 (11)	0.45233 (8)	0.0435 (3)
N4	0.74940 (12)	0.09097 (10)	0.40649 (8)	0.0384 (3)
N5	0.74567 (15)	0.09998 (12)	0.31430 (8)	0.0487 (3)
N6	1.15060 (18)	0.16124 (12)	0.71175 (11)	0.0612 (4)
C1	0.74301 (17)	0.45822 (13)	0.36515 (12)	0.0474 (4)
C2	0.7928 (2)	0.52228 (15)	0.44873 (15)	0.0630 (5)
H2	0.8535	0.5839	0.4515	0.076*
C3	0.7517 (2)	0.49382 (17)	0.52569 (14)	0.0669 (5)
H3	0.7817	0.5367	0.5809	0.080*
C4	0.66362 (18)	0.39900 (15)	0.52037 (11)	0.0504 (4)
C5	0.62089 (15)	0.33505 (12)	0.43641 (10)	0.0386 (3)
C6	0.65760 (16)	0.36455 (12)	0.35590 (10)	0.0407 (3)
H6	0.6263	0.3234	0.2997	0.049*
C7	0.6008 (2)	0.34107 (18)	0.58152 (12)	0.0645 (5)
H7	0.6090	0.3644	0.6429	0.077*
C8	0.49431 (15)	0.14827 (13)	0.39587 (11)	0.0439 (4)
H8A	0.4747	0.1659	0.3290	0.053*
H8B	0.4017	0.1208	0.4030	0.053*
C9	0.61375 (15)	0.05839 (13)	0.42568 (11)	0.0443 (4)
H9A	0.6375	0.0436	0.4934	0.053*
H9B	0.5748	−0.0094	0.3912	0.053*
C10	0.87881 (19)	0.13663 (14)	0.31726 (11)	0.0505 (4)
H10	0.9067	0.1501	0.2635	0.061*
C11	0.97408 (16)	0.15298 (12)	0.41201 (10)	0.0401 (3)
C12	1.12332 (17)	0.18656 (13)	0.45625 (13)	0.0511 (4)
H12	1.1830	0.2074	0.4199	0.061*
C13	1.17921 (16)	0.18815 (13)	0.55331 (13)	0.0520 (4)
H13	1.2785	0.2087	0.5841	0.062*
C14	1.08659 (16)	0.15870 (12)	0.60685 (11)	0.0433 (4)
C15	0.93939 (15)	0.12611 (12)	0.56797 (10)	0.0375 (3)
H15	0.8802	0.1076	0.6052	0.045*
C16	0.88544 (14)	0.12277 (11)	0.46851 (9)	0.0337 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0816 (9)	0.0892 (11)	0.0650 (9)	0.0071 (8)	0.0377 (7)	0.0152 (8)
O2	0.1124 (13)	0.0726 (11)	0.1501 (16)	−0.0232 (10)	0.0756 (12)	0.0175 (10)
O3	0.0884 (10)	0.1023 (12)	0.0437 (7)	0.0028 (9)	0.0066 (7)	−0.0094 (7)
O4	0.0647 (9)	0.1077 (13)	0.0874 (11)	−0.0184 (8)	−0.0262 (8)	−0.0118 (9)
N1	0.0585 (9)	0.0505 (9)	0.0863 (12)	0.0087 (7)	0.0376 (8)	0.0203 (8)
N2	0.0521 (8)	0.0823 (11)	0.0423 (8)	0.0015 (8)	0.0193 (6)	0.0077 (7)
N3	0.0397 (6)	0.0518 (8)	0.0396 (7)	−0.0015 (6)	0.0139 (5)	0.0034 (5)
N4	0.0345 (6)	0.0445 (7)	0.0350 (6)	−0.0009 (5)	0.0096 (5)	0.0047 (5)
N5	0.0539 (8)	0.0556 (8)	0.0348 (7)	0.0022 (6)	0.0122 (5)	0.0045 (6)
N6	0.0602 (9)	0.0482 (9)	0.0565 (9)	−0.0003 (7)	−0.0065 (7)	−0.0092 (7)
C1	0.0448 (8)	0.0398 (9)	0.0594 (10)	0.0049 (7)	0.0195 (7)	0.0067 (7)
C2	0.0607 (11)	0.0428 (10)	0.0824 (13)	−0.0098 (8)	0.0189 (9)	−0.0067 (9)
C3	0.0704 (12)	0.0604 (12)	0.0614 (12)	−0.0067 (9)	0.0098 (9)	−0.0233 (9)
C4	0.0484 (8)	0.0589 (11)	0.0403 (8)	0.0030 (8)	0.0096 (7)	−0.0072 (7)
C5	0.0340 (7)	0.0411 (8)	0.0386 (7)	0.0026 (6)	0.0088 (6)	0.0006 (6)
C6	0.0425 (8)	0.0388 (8)	0.0402 (8)	0.0044 (6)	0.0126 (6)	0.0003 (6)
C7	0.0645 (11)	0.0929 (15)	0.0362 (9)	0.0050 (10)	0.0164 (8)	−0.0053 (9)
C8	0.0307 (7)	0.0476 (9)	0.0490 (8)	−0.0051 (6)	0.0068 (6)	0.0043 (7)
C9	0.0341 (7)	0.0446 (9)	0.0510 (9)	−0.0058 (6)	0.0095 (6)	0.0098 (7)
C10	0.0589 (10)	0.0556 (10)	0.0445 (9)	0.0084 (8)	0.0272 (7)	0.0085 (7)
C11	0.0410 (7)	0.0369 (8)	0.0481 (8)	0.0058 (6)	0.0221 (6)	0.0066 (6)
C12	0.0387 (8)	0.0456 (9)	0.0772 (12)	0.0017 (7)	0.0300 (8)	0.0100 (8)
C13	0.0307 (7)	0.0395 (9)	0.0805 (12)	−0.0024 (6)	0.0110 (7)	0.0025 (8)
C14	0.0396 (7)	0.0328 (8)	0.0494 (9)	0.0009 (6)	0.0035 (6)	−0.0035 (6)
C15	0.0376 (7)	0.0354 (7)	0.0399 (7)	0.0015 (6)	0.0132 (6)	0.0017 (6)
C16	0.0304 (6)	0.0311 (7)	0.0397 (7)	0.0020 (5)	0.0117 (5)	0.0027 (5)

Geometric parameters (Å, º) top

O1—N1	1.223 (2)	C4—C7	1.416 (3)
O2—N1	1.220 (2)	C5—C6	1.391 (2)
O3—N6	1.216 (2)	C6—H6	0.9300
O4—N6	1.221 (2)	C7—H7	0.9300
N1—C1	1.474 (2)	C8—C9	1.520 (2)
N2—C7	1.309 (3)	C8—H8A	0.9700
N2—N3	1.3603 (18)	C8—H8B	0.9700
N3—C5	1.3643 (19)	C9—H9A	0.9700
N3—C8	1.445 (2)	C9—H9B	0.9700
N4—N5	1.3581 (17)	C10—C11	1.411 (2)
N4—C16	1.3650 (18)	C10—H10	0.9300
N4—C9	1.4494 (19)	C11—C12	1.402 (2)
N5—C10	1.316 (2)	C11—C16	1.4082 (19)
N6—C14	1.472 (2)	C12—C13	1.360 (2)
C1—C6	1.367 (2)	C12—H12	0.9300
C1—C2	1.404 (2)	C13—C14	1.401 (2)
C2—C3	1.361 (3)	C13—H13	0.9300
C2—H2	0.9300	C14—C15	1.373 (2)
C3—C4	1.400 (3)	C15—C16	1.3929 (19)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.406 (2)

O2—N1—O1	123.51 (18)	C4—C7—H7	123.8
O2—N1—C1	118.09 (18)	N3—C8—C9	111.77 (12)
O1—N1—C1	118.37 (15)	N3—C8—H8A	109.3
C7—N2—N3	105.94 (14)	C9—C8—H8A	109.3
N2—N3—C5	111.41 (13)	N3—C8—H8B	109.3
N2—N3—C8	119.09 (13)	C9—C8—H8B	109.3
C5—N3—C8	128.28 (12)	H8A—C8—H8B	107.9
N5—N4—C16	111.41 (11)	N4—C9—C8	111.39 (12)
N5—N4—C9	118.85 (11)	N4—C9—H9A	109.3
C16—N4—C9	129.58 (12)	C8—C9—H9A	109.3
C10—N5—N4	106.31 (12)	N4—C9—H9B	109.3
O3—N6—O4	123.09 (18)	C8—C9—H9B	109.3
O3—N6—C14	118.95 (15)	H9A—C9—H9B	108.0
O4—N6—C14	117.96 (18)	N5—C10—C11	111.71 (13)
C6—C1—C2	124.04 (16)	N5—C10—H10	124.1
C6—C1—N1	117.51 (15)	C11—C10—H10	124.1
C2—C1—N1	118.44 (16)	C12—C11—C16	119.62 (14)
C3—C2—C1	119.66 (17)	C12—C11—C10	136.07 (14)
C3—C2—H2	120.2	C16—C11—C10	104.29 (13)
C1—C2—H2	120.2	C13—C12—C11	118.78 (14)
C2—C3—C4	118.92 (16)	C13—C12—H12	120.6
C2—C3—H3	120.5	C11—C12—H12	120.6
C4—C3—H3	120.5	C12—C13—C14	119.75 (14)
C3—C4—C5	119.45 (16)	C12—C13—H13	120.1
C3—C4—C7	136.90 (17)	C14—C13—H13	120.1
C5—C4—C7	103.63 (16)	C15—C14—C13	124.32 (15)
N3—C5—C6	130.81 (13)	C15—C14—N6	117.30 (15)
N3—C5—C4	106.64 (13)	C13—C14—N6	118.38 (14)
C6—C5—C4	122.54 (15)	C14—C15—C16	114.97 (13)
C1—C6—C5	115.31 (14)	C14—C15—H15	122.5
C1—C6—H6	122.3	C16—C15—H15	122.5
C5—C6—H6	122.3	N4—C16—C15	131.16 (12)
N2—C7—C4	112.36 (15)	N4—C16—C11	106.28 (12)
N2—C7—H7	123.8	C15—C16—C11	122.54 (13)

C7—N2—N3—C5	1.38 (17)	C5—N3—C8—C9	87.72 (18)
C7—N2—N3—C8	169.77 (14)	N5—N4—C9—C8	−68.45 (17)
C16—N4—N5—C10	0.40 (17)	C16—N4—C9—C8	106.61 (16)
C9—N4—N5—C10	176.31 (14)	N3—C8—C9—N4	−65.19 (17)
O2—N1—C1—C6	−176.34 (16)	N4—N5—C10—C11	−0.10 (18)
O1—N1—C1—C6	5.4 (2)	N5—C10—C11—C12	177.90 (17)
O2—N1—C1—C2	5.0 (2)	N5—C10—C11—C16	−0.21 (18)
O1—N1—C1—C2	−173.22 (15)	C16—C11—C12—C13	0.6 (2)
C6—C1—C2—C3	−2.2 (3)	C10—C11—C12—C13	−177.33 (17)
N1—C1—C2—C3	176.39 (16)	C11—C12—C13—C14	−1.3 (2)
C1—C2—C3—C4	1.7 (3)	C12—C13—C14—C15	0.8 (2)
C2—C3—C4—C5	0.6 (3)	C12—C13—C14—N6	179.97 (14)
C2—C3—C4—C7	178.7 (2)	O3—N6—C14—C15	−7.5 (2)
N2—N3—C5—C6	−179.39 (14)	O4—N6—C14—C15	172.00 (16)
C8—N3—C5—C6	13.6 (2)	O3—N6—C14—C13	173.18 (16)
N2—N3—C5—C4	−0.72 (16)	O4—N6—C14—C13	−7.3 (2)
C8—N3—C5—C4	−167.77 (13)	C13—C14—C15—C16	0.6 (2)
C3—C4—C5—N3	178.52 (15)	N6—C14—C15—C16	−178.62 (12)
C7—C4—C5—N3	−0.18 (17)	N5—N4—C16—C15	−179.32 (14)
C3—C4—C5—C6	−2.7 (2)	C9—N4—C16—C15	5.3 (3)
C7—C4—C5—C6	178.62 (14)	N5—N4—C16—C11	−0.53 (15)
C2—C1—C6—C5	0.2 (2)	C9—N4—C16—C11	−175.88 (14)
N1—C1—C6—C5	−178.41 (12)	C14—C15—C16—N4	177.23 (14)
N3—C5—C6—C1	−179.27 (14)	C14—C15—C16—C11	−1.4 (2)
C4—C5—C6—C1	2.2 (2)	C12—C11—C16—N4	−178.06 (13)
N3—N2—C7—C4	−1.5 (2)	C10—C11—C16—N4	0.43 (15)
C3—C4—C7—N2	−177.3 (2)	C12—C11—C16—C15	0.9 (2)
C5—C4—C7—N2	1.1 (2)	C10—C11—C16—C15	179.35 (13)
N2—N3—C8—C9	−78.47 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N5ⁱ	0.93	2.48	3.344 (2)	154
C15—H15···O1ⁱ	0.93	2.47	3.401 (2)	179

Symmetry code: (i) x, −y+1/2, z+1/2.