N′-[6-(3,5-Dimethylpyrazol-1-yl)-1,2,4,5-tetrazin-3-yl]propanohydrazide

In the title compound, C₁₀H₁₄N₈O, the tetra­zine and pyrazole rings form a dihedral angle of 48.81 (2)°. In the crystal, inter­molecular N—H...N and N—H...O hydrogen bonds link the mol­ecules into layers parallel to (101).

Key indicators

• Single-crystal X-ray study
• T = 103 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.097
• Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         19
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          2

Alert level G
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

1,2,4,5-Tetrazine derivatives have high potential for biological activity, possessing a wide spectrum of antiviral and antitumor properties. They have been widely used in pesticides and herbicides (Sauer,1996). In continuation of our study of the structure-activity relationships of 1,2,4,5-tetrazine derivatives (Hu et al., 2004; Xu et al., 2010), we present here the crystal structure of the title compound (I).

In (I) (Fig. 1), the essentially planar tetrazine ring forms a dihedral angle of 48.81 (2)° with the pyrazole ring. The N14/N15/C16/O17 and C16/C18/C19 planes form dihedral angles of 79.07 (2)° and 53.51 (2)°, respectively, with the tetrazine ring. In the crystal structure, intermolecular N—H···N and N—H···O hydrogen bonds (Table 1) link the molecules into layers parallel to the plane (101) (Fig. 2).

Related literature

For related structures, see: Hu et al. (2004); Xu et al. (2010). For applications of 1,2,4,5-tetrazine derivatives, see: Sauer (1996).

S2. Experimental

3,6-Di(3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazine (3.0 mmol), chloroform (10 ml) and pyridine(0.25 ml,3.1 mmol) were mixed. Propionyl chloride(3.0 mmol) in chloroform (10 ml) was added dropwise with stirring at room temperature. After the starting 1,2,4,5-tetrazine was completely consumed (the reaction courses was monitored by TLC, ethyl acetate system), evaporation of the chloroform, crude product was obtained and purified by preparative thin-layer chromatography over silica gel GF254(2 mm) (dichloromethane: petroleum ether=1:1). The solution of the compound in anhydrous ethanol was concentrated gradually at room temperature to afford single crystals, which was suitable for X-ray diffraction.

S3. Refinement

C-bound H atoms were placed in calculated positions with C—H = 0.93 (aromatic) and 0.96 Å (methyl), and refined as riding, with U_iso(H) = 1.2U_eq(C). Amino H atoms were located on a difference map and isotropically refined.

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2008); cell refinement: CrystalClear (Rigaku/MSC, 2008); data reduction: CrystalClear (Rigaku/MSC, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (I), shown with 30% probability displacement ellipsoids.
	Fig. 2. A portion of the crystal packing of (I), viewed down the b axis (N—H···O and N—H···N hydrogen bonds shown as dashed lines).

N'-[6-(3,5-Dimethylpyrazol-1-yl)-1,2,4,5-tetrazin-3-yl]propanohydrazide

Crystal data

C10H14N8O	F(000) = 552
Mr = 262.29	Dx = 1.370 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3481 reflections
a = 10.896 (3) Å	θ = 3.1–27.5°
b = 8.0354 (18) Å	µ = 0.10 mm^−1
c = 14.805 (3) Å	T = 103 K
β = 101.243 (3)°	Block, red
V = 1271.3 (5) Å^3	0.43 × 0.43 × 0.40 mm
Z = 4

Data collection

Rigaku AFC10/Saturn724+ diffractometer	2449 reflections with I > 2σ(I)
Radiation source: Rotating Anode	Rint = 0.026
Graphite monochromator	θmax = 27.5°, θmin = 3.2°
Detector resolution: 28.5714 pixels mm^-1	h = −14→14
phi and ω scans	k = −10→9
11006 measured reflections	l = −19→15
2889 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 0.356P] where P = (Fo^2 + 2Fc^2)/3
2889 reflections	(Δ/σ)max = 0.001
183 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O17	0.65146 (8)	0.86367 (11)	0.70314 (6)	0.0179 (2)
N1	0.36485 (9)	0.55187 (13)	0.58619 (7)	0.0181 (2)
N2	0.48288 (9)	0.59455 (13)	0.59073 (7)	0.0178 (2)
N4	0.54093 (9)	0.41800 (13)	0.72319 (7)	0.0178 (2)
N5	0.42231 (9)	0.37460 (13)	0.71646 (7)	0.0180 (2)
N7	0.21537 (9)	0.38630 (13)	0.63454 (7)	0.0153 (2)
N8	0.15710 (9)	0.34258 (13)	0.54720 (7)	0.0162 (2)
N14	0.69045 (9)	0.54690 (13)	0.65843 (7)	0.0150 (2)
N15	0.72507 (9)	0.68179 (12)	0.61051 (7)	0.0143 (2)
C3	0.56793 (11)	0.51973 (14)	0.65674 (8)	0.0141 (2)
C6	0.34064 (11)	0.43941 (15)	0.64680 (8)	0.0144 (2)
C9	0.04184 (11)	0.30101 (15)	0.55470 (9)	0.0160 (3)
C10	0.02513 (11)	0.31991 (16)	0.64640 (9)	0.0182 (3)
H10	−0.0491	0.2986	0.6691	0.022*
C11	0.13712 (11)	0.37494 (15)	0.69613 (8)	0.0162 (3)
C12	0.17476 (12)	0.42513 (18)	0.79463 (9)	0.0225 (3)
H12A	0.1010	0.4254	0.8234	0.027*
H12B	0.2114	0.5369	0.7983	0.027*
H12C	0.2366	0.3461	0.8269	0.027*
C13	−0.04989 (11)	0.24561 (17)	0.47157 (9)	0.0202 (3)
H13A	−0.0168	0.2705	0.4161	0.024*
H13B	−0.1293	0.3045	0.4689	0.024*
H13C	−0.0637	0.1255	0.4752	0.024*
C16	0.70060 (10)	0.83713 (14)	0.63648 (8)	0.0138 (2)
C18	0.73811 (12)	0.97462 (16)	0.57793 (9)	0.0204 (3)
H18A	0.8278	1.0008	0.5999	0.024*
H18B	0.7275	0.9354	0.5135	0.024*
C19	0.66242 (18)	1.13003 (19)	0.58044 (13)	0.0396 (4)
H19A	0.5744	1.1071	0.5539	0.048*
H19B	0.6936	1.2175	0.5447	0.048*
H19C	0.6698	1.1669	0.6444	0.048*
H14N	0.7449 (16)	0.507 (2)	0.7030 (12)	0.032 (5)*
H15N	0.7596 (16)	0.663 (2)	0.5615 (12)	0.032 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O17	0.0174 (4)	0.0197 (5)	0.0189 (4)	−0.0030 (3)	0.0092 (3)	−0.0036 (4)
N1	0.0153 (5)	0.0192 (5)	0.0195 (5)	−0.0025 (4)	0.0025 (4)	0.0026 (4)
N2	0.0153 (5)	0.0183 (5)	0.0196 (5)	−0.0022 (4)	0.0025 (4)	0.0032 (4)
N4	0.0142 (5)	0.0190 (5)	0.0207 (5)	−0.0005 (4)	0.0045 (4)	0.0042 (4)
N5	0.0161 (5)	0.0184 (5)	0.0203 (5)	−0.0011 (4)	0.0057 (4)	0.0033 (4)
N7	0.0141 (5)	0.0190 (5)	0.0133 (5)	−0.0019 (4)	0.0040 (4)	−0.0007 (4)
N8	0.0158 (5)	0.0187 (5)	0.0147 (5)	−0.0018 (4)	0.0042 (4)	−0.0018 (4)
N14	0.0139 (5)	0.0135 (5)	0.0177 (5)	−0.0003 (4)	0.0034 (4)	0.0048 (4)
N15	0.0170 (5)	0.0132 (5)	0.0146 (5)	−0.0019 (4)	0.0077 (4)	0.0014 (4)
C3	0.0164 (5)	0.0115 (5)	0.0151 (6)	−0.0001 (4)	0.0051 (4)	−0.0015 (4)
C6	0.0138 (5)	0.0148 (6)	0.0156 (6)	−0.0012 (4)	0.0050 (4)	−0.0013 (4)
C9	0.0143 (5)	0.0151 (6)	0.0194 (6)	−0.0003 (4)	0.0054 (5)	0.0012 (5)
C10	0.0162 (5)	0.0200 (6)	0.0202 (6)	−0.0010 (5)	0.0077 (5)	0.0011 (5)
C11	0.0172 (6)	0.0158 (6)	0.0177 (6)	0.0010 (4)	0.0084 (5)	0.0024 (5)
C12	0.0227 (6)	0.0285 (7)	0.0178 (6)	−0.0022 (5)	0.0075 (5)	−0.0005 (5)
C13	0.0171 (6)	0.0221 (6)	0.0217 (6)	−0.0034 (5)	0.0042 (5)	−0.0009 (5)
C16	0.0105 (5)	0.0148 (6)	0.0160 (6)	−0.0013 (4)	0.0026 (4)	0.0000 (4)
C18	0.0224 (6)	0.0167 (6)	0.0241 (7)	−0.0016 (5)	0.0096 (5)	0.0034 (5)
C19	0.0561 (10)	0.0238 (8)	0.0457 (10)	0.0138 (7)	0.0269 (8)	0.0154 (7)

Geometric parameters (Å, º)

O17—C16	1.2297 (15)	C9—C13	1.4940 (17)
N1—N2	1.3200 (14)	C10—C11	1.3698 (17)
N1—C6	1.3355 (16)	C10—H10	0.9500
N2—C3	1.3499 (16)	C11—C12	1.4914 (18)
N4—N5	1.3235 (14)	C12—H12A	0.9800
N4—C3	1.3547 (16)	C12—H12B	0.9800
N5—C6	1.3300 (16)	C12—H12C	0.9800
N7—C11	1.3675 (15)	C13—H13A	0.9800
N7—N8	1.3705 (14)	C13—H13B	0.9800
N7—C6	1.4076 (15)	C13—H13C	0.9800
N8—C9	1.3249 (15)	C16—C18	1.5091 (17)
N14—C3	1.3480 (15)	C18—C19	1.501 (2)
N14—N15	1.3874 (14)	C18—H18A	0.9900
N14—H14N	0.860 (18)	C18—H18B	0.9900
N15—C16	1.3480 (16)	C19—H19A	0.9800
N15—H15N	0.893 (19)	C19—H19B	0.9800
C9—C10	1.4128 (17)	C19—H19C	0.9800
N2—N1—C6	117.36 (10)	C10—C11—C12	131.24 (11)
N1—N2—C3	116.47 (10)	C11—C12—H12A	109.5
N5—N4—C3	116.84 (10)	C11—C12—H12B	109.5
N4—N5—C6	116.81 (10)	H12A—C12—H12B	109.5
C11—N7—N8	112.19 (10)	C11—C12—H12C	109.5
C11—N7—C6	130.48 (10)	H12A—C12—H12C	109.5
N8—N7—C6	117.30 (9)	H12B—C12—H12C	109.5
C9—N8—N7	104.95 (10)	C9—C13—H13A	109.5
C3—N14—N15	118.95 (10)	C9—C13—H13B	109.5
C3—N14—H14N	119.1 (12)	H13A—C13—H13B	109.5
N15—N14—H14N	118.1 (12)	C9—C13—H13C	109.5
C16—N15—N14	119.27 (10)	H13A—C13—H13C	109.5
C16—N15—H15N	122.0 (11)	H13B—C13—H13C	109.5
N14—N15—H15N	118.7 (11)	O17—C16—N15	122.06 (11)
N14—C3—N2	118.61 (11)	O17—C16—C18	122.90 (11)
N14—C3—N4	116.02 (10)	N15—C16—C18	115.04 (11)
N2—C3—N4	125.37 (11)	C19—C18—C16	112.53 (11)
N5—C6—N1	126.59 (11)	C19—C18—H18A	109.1
N5—C6—N7	117.82 (11)	C16—C18—H18A	109.1
N1—C6—N7	115.60 (10)	C19—C18—H18B	109.1
N8—C9—C10	110.81 (11)	C16—C18—H18B	109.1
N8—C9—C13	119.93 (11)	H18A—C18—H18B	107.8
C10—C9—C13	129.25 (11)	C18—C19—H19A	109.5
C11—C10—C9	106.44 (11)	C18—C19—H19B	109.5
C11—C10—H10	126.8	H19A—C19—H19B	109.5
C9—C10—H10	126.8	C18—C19—H19C	109.5
N7—C11—C10	105.61 (11)	H19A—C19—H19C	109.5
N7—C11—C12	123.07 (11)	H19B—C19—H19C	109.5
C6—N1—N2—C3	−0.04 (16)	C11—N7—C6—N1	−130.25 (13)
C3—N4—N5—C6	−2.11 (16)	N8—N7—C6—N1	47.37 (15)
C11—N7—N8—C9	−0.96 (13)	N7—N8—C9—C10	0.78 (13)
C6—N7—N8—C9	−179.01 (10)	N7—N8—C9—C13	−179.96 (10)
C3—N14—N15—C16	64.25 (15)	N8—C9—C10—C11	−0.34 (14)
N15—N14—C3—N2	17.35 (16)	C13—C9—C10—C11	−179.53 (12)
N15—N14—C3—N4	−162.40 (10)	N8—N7—C11—C10	0.75 (13)
N1—N2—C3—N14	173.64 (10)	C6—N7—C11—C10	178.47 (12)
N1—N2—C3—N4	−6.63 (18)	N8—N7—C11—C12	−176.21 (11)
N5—N4—C3—N14	−172.47 (10)	C6—N7—C11—C12	1.5 (2)
N5—N4—C3—N2	7.79 (18)	C9—C10—C11—N7	−0.25 (13)
N4—N5—C6—N1	−4.45 (19)	C9—C10—C11—C12	176.37 (13)
N4—N5—C6—N7	175.75 (10)	N14—N15—C16—O17	2.05 (17)
N2—N1—C6—N5	5.63 (19)	N14—N15—C16—C18	−178.04 (10)
N2—N1—C6—N7	−174.57 (10)	O17—C16—C18—C19	−25.57 (18)
C11—N7—C6—N5	49.57 (18)	N15—C16—C18—C19	154.53 (13)
N8—N7—C6—N5	−132.81 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N14—H14N···O17^i	0.859 (17)	1.980 (17)	2.821 (2)	166 (2)
N15—H15N···N8^ii	0.893 (18)	1.996 (18)	2.882 (2)	171 (2)

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+1, −y+1, −z+1.