Concomitant polymorphic forms of 3-cyclo­propyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxa­diazole

Shishkina, S.V.; Konovalova, I.S.; Karpina, V.R.; Kovalenko, S.S.; Kovalenko, S.M.; Bunyatyan, N.D.

doi:10.1107/S2053229620010414

Concomitant polymorphic forms of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole

S. V. Shishkina, I. S. Konovalova, V. R. Karpina, S. S. Kovalenko, S. M. Kovalenko and N. D. Bunyatyan

The dipharmacophore compound 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole, C₁₀H₁₁N₅O, was studied on the assumption of its potential biological activity. Two concomitant polymorphs were obtained on crystallization from isopropanol solution and these were thoroughly studied. Identical conformations of the molecules are found in both structures despite the low difference in energy between the four possible conformers. The two polymorphs differ crucially with respect to their crystal structures. A centrosymmetric dimer formed due to both stacking interactions of the `head-to-tail' type and N—H

N(π) hydrogen bonds is the building unit in the triclinic structure. The dimeric building units form an isotropic packing. In the orthorhombic polymorphic structure, the molecules form stacking interactions of the `head-to-head' type, which results in their organization in a column as the primary basic structural motif. The formation of N—H

N(lone pair) hydrogen bonds between two neighbouring columns allows the formation of a double column as the main structural motif. The correct packing motifs in the two polymorphs could not be identified without calculations of the pairwise interaction energies. The triclinic structure has a higher density and a lower (by 0.60 kcal mol⁻¹) lattice energy according to periodic calculations compared to the orthorhombic structure. This allows us to presume that the triclinic form of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole is the more stable.

Keywords: cyclopropyl; pyridine; 1,2,4-oxadiazole; dipharmacophore; concomitant polymorphs; crystal structure; pairwise interaction energies; periodic calculations.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229620010414/ku3265sup1.cif Contains datablocks 1t, 1r, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620010414/ku32651tsup2.hkl Contains datablock 1t
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620010414/ku32651rsup3.hkl Contains datablock 1r
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229620010414/ku32651rsup4.cml Supplementary material
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229620010414/ku3265sup5.pdf Additional packing and energy-vector diagrams, plus interaction energy tables

CCDC references: 2015686; 2015685

Computing details top

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).

3-Cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole (1t) top

Crystal data top

C₁₀H₁₁N₅O	Z = 2
M_r = 217.24	F(000) = 228
Triclinic, P1	D_x = 1.407 Mg m⁻³
a = 8.4476 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5662 (8) Å	Cell parameters from 846 reflections
c = 8.6125 (8) Å	θ = 4.2–25.7°
α = 110.812 (9)°	µ = 0.10 mm⁻¹
β = 115.048 (11)°	T = 293 K
γ = 92.854 (9)°	Block, colorless
V = 512.82 (10) Å³	0.20 × 0.17 × 0.10 mm

Data collection top

Rigaku Xcalibur Sapphire3 diffractometer	1795 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1337 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	R_int = 0.043
ω scans	θ_max = 25.0°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −5→10
T_min = 0.188, T_max = 1.000	k = −10→10
3563 measured reflections	l = −10→9

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.164	w = 1/[σ²(F_o²) + (0.0858P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1795 reflections	Δρ_max = 0.20 e Å⁻³
157 parameters	Δρ_min = −0.21 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
O1	0.6672 (2)	0.56003 (19)	0.9056 (2)	0.0672 (5)
N1	0.8289 (3)	0.6863 (3)	0.9853 (3)	0.0741 (6)
N2	0.7711 (2)	0.4883 (2)	0.7013 (2)	0.0554 (5)
N3	0.3083 (2)	0.0515 (2)	0.3385 (3)	0.0597 (5)
N4	0.5318 (3)	0.2269 (2)	0.3501 (3)	0.0604 (5)
H4	0.637 (4)	0.302 (3)	0.409 (4)	0.086 (8)*
N5	0.4945 (3)	0.1157 (3)	0.1664 (3)	0.0686 (6)
H5NA	0.479 (4)	0.005 (4)	0.162 (4)	0.106 (10)*
H5NB	0.382 (4)	0.125 (3)	0.088 (4)	0.089 (9)*
C1	0.6453 (3)	0.4486 (3)	0.7380 (3)	0.0521 (5)
C2	0.8817 (3)	0.6343 (3)	0.8581 (3)	0.0612 (6)
C3	1.0478 (3)	0.7243 (3)	0.8816 (3)	0.0697 (7)
H3	1.115238	0.830316	0.996389	0.084*
C4	1.0535 (3)	0.7184 (3)	0.7084 (4)	0.0739 (7)
H4A	0.946671	0.655610	0.588201	0.089*
H4B	1.120473	0.819869	0.718224	0.089*
C5	1.1560 (3)	0.6188 (3)	0.8065 (4)	0.0762 (7)
H5A	1.285910	0.659122	0.876536	0.091*
H5B	1.112103	0.494859	0.746510	0.091*
C6	0.4923 (3)	0.3020 (2)	0.6283 (3)	0.0515 (5)
C7	0.3911 (3)	0.2607 (3)	0.7049 (3)	0.0583 (6)
H7	0.416969	0.330972	0.827516	0.070*
C8	0.2524 (3)	0.1164 (3)	0.6011 (3)	0.0632 (6)
H8	0.183345	0.087335	0.651314	0.076*
C9	0.2187 (3)	0.0162 (3)	0.4206 (4)	0.0656 (6)
H9	0.126635	−0.083141	0.351538	0.079*
C10	0.4442 (3)	0.1922 (3)	0.4374 (3)	0.0507 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0811 (11)	0.0626 (10)	0.0438 (9)	−0.0021 (8)	0.0312 (9)	0.0077 (8)
N1	0.0835 (14)	0.0646 (12)	0.0472 (11)	−0.0130 (10)	0.0275 (11)	0.0031 (10)
N2	0.0577 (10)	0.0510 (10)	0.0413 (10)	−0.0015 (8)	0.0205 (9)	0.0077 (9)
N3	0.0547 (11)	0.0542 (11)	0.0527 (12)	0.0004 (8)	0.0217 (9)	0.0102 (9)
N4	0.0652 (12)	0.0581 (11)	0.0421 (10)	−0.0048 (9)	0.0278 (9)	0.0035 (9)
N5	0.0751 (14)	0.0660 (14)	0.0453 (11)	−0.0041 (11)	0.0318 (11)	0.0012 (10)
C1	0.0612 (12)	0.0481 (11)	0.0360 (11)	0.0070 (9)	0.0197 (10)	0.0108 (9)
C2	0.0649 (14)	0.0553 (13)	0.0425 (12)	−0.0017 (10)	0.0160 (11)	0.0119 (11)
C3	0.0700 (15)	0.0609 (14)	0.0532 (14)	−0.0094 (11)	0.0201 (12)	0.0119 (12)
C4	0.0705 (15)	0.0751 (16)	0.0703 (17)	0.0012 (12)	0.0265 (13)	0.0345 (14)
C5	0.0598 (14)	0.0802 (17)	0.0783 (18)	0.0061 (12)	0.0232 (13)	0.0350 (15)
C6	0.0535 (12)	0.0509 (12)	0.0442 (12)	0.0089 (9)	0.0210 (10)	0.0169 (10)
C7	0.0649 (13)	0.0648 (13)	0.0479 (13)	0.0142 (11)	0.0299 (11)	0.0224 (11)
C8	0.0560 (12)	0.0696 (15)	0.0637 (15)	0.0049 (11)	0.0281 (11)	0.0290 (13)
C9	0.0590 (13)	0.0597 (14)	0.0674 (16)	−0.0012 (11)	0.0293 (12)	0.0177 (13)
C10	0.0508 (11)	0.0511 (12)	0.0441 (12)	0.0081 (9)	0.0203 (10)	0.0166 (10)

Geometric parameters (Å, º) top

O1—C1	1.344 (2)	C3—C5	1.496 (4)
O1—N1	1.428 (2)	C3—H3	0.9800
N1—C2	1.299 (3)	C4—C5	1.469 (3)
N2—C1	1.293 (3)	C4—H4A	0.9700
N2—C2	1.369 (3)	C4—H4B	0.9700
N3—C9	1.322 (3)	C5—H5A	0.9700
N3—C10	1.342 (3)	C5—H5B	0.9700
N4—C10	1.344 (3)	C6—C7	1.381 (3)
N4—N5	1.410 (3)	C6—C10	1.432 (3)
N4—H4	0.89 (3)	C7—C8	1.372 (3)
N5—H5NA	0.94 (3)	C7—H7	0.9300
N5—H5NB	0.93 (3)	C8—C9	1.373 (3)
C1—C6	1.449 (3)	C8—H8	0.9300
C2—C3	1.465 (3)	C9—H9	0.9300
C3—C4	1.495 (3)

C1—O1—N1	105.88 (15)	C5—C4—H4B	117.7
C2—N1—O1	102.95 (18)	C3—C4—H4B	117.7
C1—N2—C2	103.20 (17)	H4A—C4—H4B	114.8
C9—N3—C10	118.7 (2)	C4—C5—C3	60.58 (16)
C10—N4—N5	122.60 (18)	C4—C5—H5A	117.7
C10—N4—H4	124.1 (18)	C3—C5—H5A	117.7
N5—N4—H4	111.1 (18)	C4—C5—H5B	117.7
N4—N5—H5NA	105.2 (19)	C3—C5—H5B	117.7
N4—N5—H5NB	105.1 (17)	H5A—C5—H5B	114.8
H5NA—N5—H5NB	106 (3)	C7—C6—C10	117.7 (2)
N2—C1—O1	113.07 (18)	C7—C6—C1	121.45 (19)
N2—C1—C6	129.37 (18)	C10—C6—C1	120.79 (18)
O1—C1—C6	117.54 (17)	C8—C7—C6	120.3 (2)
N1—C2—N2	114.88 (19)	C8—C7—H7	119.8
N1—C2—C3	122.4 (2)	C6—C7—H7	119.8
N2—C2—C3	122.7 (2)	C7—C8—C9	117.93 (18)
C2—C3—C4	117.8 (2)	C7—C8—H8	121.0
C2—C3—C5	118.1 (2)	C9—C8—H8	121.0
C4—C3—C5	58.81 (16)	N3—C9—C8	124.3 (2)
C2—C3—H3	116.6	N3—C9—H9	117.8
C4—C3—H3	116.6	C8—C9—H9	117.8
C5—C3—H3	116.6	N3—C10—N4	117.64 (19)
C5—C4—C3	60.61 (17)	N3—C10—C6	120.90 (18)
C5—C4—H4A	117.7	N4—C10—C6	121.46 (19)
C3—C4—H4A	117.7

C1—O1—N1—C2	−0.3 (2)	O1—C1—C6—C7	−11.2 (3)
C2—N2—C1—O1	0.8 (2)	N2—C1—C6—C10	−11.5 (3)
C2—N2—C1—C6	−177.3 (2)	O1—C1—C6—C10	170.48 (17)
N1—O1—C1—N2	−0.3 (2)	C10—C6—C7—C8	1.6 (3)
N1—O1—C1—C6	177.99 (17)	C1—C6—C7—C8	−176.74 (18)
O1—N1—C2—N2	0.9 (3)	C6—C7—C8—C9	0.0 (3)
O1—N1—C2—C3	−178.65 (19)	C10—N3—C9—C8	1.5 (4)
C1—N2—C2—N1	−1.1 (3)	C7—C8—C9—N3	−1.6 (4)
C1—N2—C2—C3	178.5 (2)	C9—N3—C10—N4	−179.08 (19)
N1—C2—C3—C4	−149.0 (2)	C9—N3—C10—C6	0.3 (3)
N2—C2—C3—C4	31.5 (3)	N5—N4—C10—N3	−4.6 (3)
N1—C2—C3—C5	143.4 (3)	N5—N4—C10—C6	176.1 (2)
N2—C2—C3—C5	−36.1 (3)	C7—C6—C10—N3	−1.8 (3)
C2—C3—C4—C5	−107.6 (3)	C1—C6—C10—N3	176.59 (18)
C2—C3—C5—C4	107.2 (2)	C7—C6—C10—N4	177.56 (19)
N2—C1—C6—C7	166.7 (2)	C1—C6—C10—N4	−4.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N2	0.89 (3)	2.17 (3)	2.795 (3)	127 (2)
N5—H5NA···C8ⁱ	0.94 (3)	2.87 (3)	3.487 (3)	125 (2)
N5—H5NB···N1ⁱⁱ	0.93 (3)	2.50 (3)	3.325 (4)	148 (2)
N5—H5NA···N3	0.94 (3)	2.45 (3)	2.728 (2)	97 (2)

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

3-Cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole (1r) top

Crystal data top

C₁₀H₁₁N₅O	D_x = 1.364 Mg m⁻³
M_r = 217.24	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 655 reflections
a = 4.8240 (11) Å	θ = 4.0–20.0°
b = 8.2685 (19) Å	µ = 0.10 mm⁻¹
c = 26.527 (10) Å	T = 293 K
V = 1058.1 (5) Å³	Stick, colourless
Z = 4	0.20 × 0.05 × 0.05 mm
F(000) = 456

Data collection top

Rigaku Xcalibur Sapphire3 diffractometer	1859 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1194 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	R_int = 0.080
ω scans	θ_max = 25.0°, θ_min = 3.4°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −5→5
T_min = 0.176, T_max = 1.000	k = −9→9
7941 measured reflections	l = −31→31

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0373P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.051	(Δ/σ)_max < 0.001
wR(F²) = 0.119	Δρ_max = 0.14 e Å⁻³
S = 0.99	Δρ_min = −0.13 e Å⁻³
1859 reflections	Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
158 parameters	Extinction coefficient: 0.007 (3)
0 restraints	Absolute structure: Flack x determined using 320 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Hydrogen site location: mixed	Absolute structure parameter: −0.7 (10)

Special details top

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

	x	y	z	U_iso*/U_eq
O1	0.3081 (6)	0.5574 (4)	0.66612 (13)	0.0744 (10)
N1	0.1474 (7)	0.6666 (5)	0.69605 (17)	0.0774 (11)
N2	0.4560 (6)	0.8019 (4)	0.64848 (14)	0.0577 (9)
N3	1.0284 (7)	0.5842 (4)	0.54210 (14)	0.0650 (10)
N4	0.8594 (7)	0.8191 (4)	0.57554 (15)	0.0627 (10)
H4N	0.733 (8)	0.878 (5)	0.6013 (18)	0.078 (14)*
N5	1.0260 (11)	0.9131 (5)	0.5430 (2)	0.0726 (12)
H5NA	1.190 (10)	0.871 (6)	0.5497 (18)	0.082 (18)*
H5NB	0.960 (10)	0.900 (6)	0.514 (2)	0.10 (2)*
C1	0.4820 (8)	0.6484 (5)	0.63948 (16)	0.0568 (11)
C2	0.2470 (7)	0.8070 (6)	0.68382 (18)	0.0630 (12)
C3	0.1501 (8)	0.9554 (6)	0.70658 (19)	0.0690 (13)
H3	0.003885	0.944058	0.731985	0.083*
C4	0.1412 (10)	1.1041 (6)	0.6759 (2)	0.0820 (15)
H4A	0.201476	1.096713	0.641069	0.098*
H4B	−0.010220	1.178923	0.681769	0.098*
C5	0.3504 (9)	1.0890 (6)	0.7148 (2)	0.0913 (18)
H5A	0.328856	1.154211	0.744962	0.110*
H5B	0.540637	1.071967	0.704246	0.110*
C6	0.6711 (8)	0.5670 (5)	0.60523 (17)	0.0530 (11)
C7	0.6770 (9)	0.4014 (5)	0.6022 (2)	0.0677 (13)
H7	0.558548	0.339649	0.622056	0.081*
C8	0.8581 (10)	0.3271 (6)	0.5697 (2)	0.0782 (15)
H8	0.866570	0.214969	0.567491	0.094*
C9	1.0241 (10)	0.4218 (6)	0.5411 (2)	0.0744 (14)
H9	1.144768	0.370362	0.518949	0.089*
C10	0.8517 (8)	0.6557 (5)	0.57396 (17)	0.0541 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0751 (18)	0.0711 (19)	0.077 (2)	−0.0089 (17)	0.0060 (18)	0.0124 (19)
N1	0.066 (2)	0.090 (3)	0.076 (3)	−0.002 (2)	0.011 (2)	0.011 (3)
N2	0.0500 (17)	0.063 (2)	0.060 (2)	0.0007 (17)	0.0040 (18)	0.002 (2)
N3	0.071 (2)	0.066 (2)	0.057 (3)	0.0128 (19)	−0.004 (2)	−0.009 (2)
N4	0.070 (2)	0.055 (2)	0.063 (3)	−0.001 (2)	0.017 (2)	−0.003 (2)
N5	0.086 (3)	0.064 (2)	0.068 (3)	−0.003 (2)	0.017 (3)	0.001 (3)
C1	0.049 (2)	0.067 (3)	0.055 (3)	−0.006 (2)	−0.005 (2)	0.012 (2)
C2	0.048 (2)	0.084 (3)	0.057 (3)	0.000 (2)	0.000 (2)	0.005 (3)
C3	0.053 (2)	0.092 (3)	0.063 (3)	0.010 (3)	0.013 (2)	0.002 (3)
C4	0.074 (3)	0.086 (3)	0.086 (4)	0.004 (3)	0.008 (3)	−0.002 (3)
C5	0.056 (2)	0.119 (4)	0.099 (5)	0.003 (3)	0.002 (3)	−0.039 (4)
C6	0.051 (2)	0.053 (2)	0.055 (3)	0.002 (2)	−0.010 (2)	−0.001 (2)
C7	0.079 (3)	0.053 (2)	0.072 (3)	−0.003 (3)	−0.012 (3)	−0.001 (3)
C8	0.102 (3)	0.052 (2)	0.080 (4)	0.013 (3)	−0.019 (3)	−0.013 (3)
C9	0.088 (3)	0.070 (3)	0.066 (3)	0.021 (3)	−0.012 (3)	−0.018 (3)
C10	0.056 (2)	0.056 (2)	0.050 (3)	0.002 (2)	−0.007 (2)	−0.002 (2)

Geometric parameters (Å, º) top

O1—C1	1.330 (5)	C3—C5	1.484 (6)
O1—N1	1.431 (5)	C3—H3	0.9800
N1—C2	1.297 (5)	C4—C5	1.449 (7)
N2—C1	1.298 (5)	C4—H4A	0.9700
N2—C2	1.377 (5)	C4—H4B	0.9700
N3—C10	1.338 (5)	C5—H5A	0.9700
N3—C9	1.343 (5)	C5—H5B	0.9700
N4—C10	1.352 (5)	C6—C7	1.372 (5)
N4—N5	1.413 (5)	C6—C10	1.409 (6)
N4—H4N	1.04 (4)	C7—C8	1.371 (6)
N5—H5NA	0.88 (5)	C7—H7	0.9300
N5—H5NB	0.84 (5)	C8—C9	1.354 (6)
C1—C6	1.453 (6)	C8—H8	0.9300
C2—C3	1.445 (6)	C9—H9	0.9300
C3—C4	1.475 (6)

C1—O1—N1	106.2 (3)	C5—C4—H4B	117.7
C2—N1—O1	103.0 (3)	C3—C4—H4B	117.7
C1—N2—C2	103.0 (4)	H4A—C4—H4B	114.8
C10—N3—C9	116.4 (4)	C4—C5—C3	60.4 (3)
C10—N4—N5	123.1 (4)	C4—C5—H5A	117.7
C10—N4—H4N	118 (2)	C3—C5—H5A	117.7
N5—N4—H4N	119 (2)	C4—C5—H5B	117.7
N4—N5—H5NA	100 (3)	C3—C5—H5B	117.7
N4—N5—H5NB	106 (4)	H5A—C5—H5B	114.9
H5NA—N5—H5NB	118 (5)	C7—C6—C10	118.2 (4)
N2—C1—O1	113.3 (4)	C7—C6—C1	120.8 (4)
N2—C1—C6	129.0 (4)	C10—C6—C1	121.0 (4)
O1—C1—C6	117.8 (4)	C8—C7—C6	119.8 (5)
N1—C2—N2	114.5 (4)	C8—C7—H7	120.1
N1—C2—C3	122.4 (4)	C6—C7—H7	120.1
N2—C2—C3	123.2 (4)	C9—C8—C7	118.0 (4)
C2—C3—C4	119.1 (4)	C9—C8—H8	121.0
C2—C3—C5	118.9 (4)	C7—C8—H8	121.0
C4—C3—C5	58.6 (3)	N3—C9—C8	125.2 (5)
C2—C3—H3	116.0	N3—C9—H9	117.4
C4—C3—H3	116.0	C8—C9—H9	117.4
C5—C3—H3	116.0	N3—C10—N4	116.4 (4)
C5—C4—C3	61.0 (3)	N3—C10—C6	122.4 (4)
C5—C4—H4A	117.7	N4—C10—C6	121.3 (4)
C3—C4—H4A	117.7

C1—O1—N1—C2	−0.5 (4)	O1—C1—C6—C7	−2.6 (6)
C2—N2—C1—O1	−0.1 (5)	N2—C1—C6—C10	−3.3 (7)
C2—N2—C1—C6	−180.0 (4)	O1—C1—C6—C10	176.8 (4)
N1—O1—C1—N2	0.4 (5)	C10—C6—C7—C8	0.8 (7)
N1—O1—C1—C6	−179.7 (3)	C1—C6—C7—C8	−179.7 (4)
O1—N1—C2—N2	0.5 (5)	C6—C7—C8—C9	−0.8 (7)
O1—N1—C2—C3	−178.0 (4)	C10—N3—C9—C8	−0.5 (7)
C1—N2—C2—N1	−0.3 (5)	C7—C8—C9—N3	0.7 (8)
C1—N2—C2—C3	178.2 (4)	C9—N3—C10—N4	179.0 (4)
N1—C2—C3—C4	−146.1 (5)	C9—N3—C10—C6	0.4 (6)
N2—C2—C3—C4	35.5 (6)	N5—N4—C10—N3	5.0 (7)
N1—C2—C3—C5	145.8 (5)	N5—N4—C10—C6	−176.4 (4)
N2—C2—C3—C5	−32.5 (7)	C7—C6—C10—N3	−0.6 (6)
C2—C3—C4—C5	−107.9 (5)	C1—C6—C10—N3	179.9 (4)
C2—C3—C5—C4	108.3 (5)	C7—C6—C10—N4	−179.1 (4)
N2—C1—C6—C7	177.2 (4)	C1—C6—C10—N4	1.4 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···N2	1.04 (4)	1.93 (4)	2.748 (5)	133 (3)
N5—H5NB···N3ⁱ	0.84 (5)	2.56 (5)	3.295 (7)	146 (5)
N5—H5NA···N3	0.88 (5)	2.51 (5)	2.720 (6)	94 (3)

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

Selected geometric parameters for molecule 1 in triclinic and orthorhombic polymorphic crystals top

Parameter	Structure 1t	Structure 1r
Bond lengths (Å)
C1—C6	1.450 (3)	1.453 (6)
N4—N5	1.410 (3)	1.412 (6)
N4—C10	1.345 (4)	1.352 (5)
C2—C3	1.465 (4)	1.445 (7)

Torsion angles (°)
C7—C6—C1—O1	-11.2 (4)	-2.7 (6)
N1—C2—C3—H3	-3.0	0.0
N3—C10—N4—N5	-4.6 (4)	5.0 (6)

Intramolecular hydrogen bonds (Å, °)
N4—H···N2
H···N	2.17 (3)	1.94 (4)
N—-H···N	127 (2)	133 (3)
N5–H···N3
H···N	2.45 (3)	2.50 (5)
N—H···N	97 (2)	94 (3)

Geometric characteristics of the intermolecular hydrogen bonds and stacking interactions in different polymorphic crystals of compound 1 top

Interaction	Symmetry operation	Geometric characteristics
		H···A (Å)	D—H···A (°)
Polymorph 1t
N5—H5NA···C8(π)	-x+1, -y, -z+1	2.87 (3)	125 (3)
N5—H5NB···N1(π)	-x+1, -y+1, -z+1	2.50 (3)	148 (3)
C3—H3···N3(lp)	x+1, y+1, z+1	2.57	165
Stacking mol–mol	-x+1, -y+1, -z+1	Distance between mean planes is 3.56 Å Plane-to-plane shift is 2.709 Å Plane-to-plane twist angle is 0.0°
Stacking pyr–pyr	-x+1, -y, -z+1	Distance between mean planes is 3.41 Å Plane-to-plane shift is 1.669 Å Plane-to-plane twist angle is 0.0°
Polymorph 1r
N5—H5NB···N3(lp)	x-1/2, -y+3/2, -z+1	2.56 (5)	146 (4)
C8—H8···N5(lp)	x, y-1, z	2.69	162
Stacking oxadiaz–pyr	x+1, y, z	Distance between mean planes is 3.36 Å Plane-to-plane shift is 1.761 Å Plane-to-plane twist angle is 3.3°

Symmetry codes, interaction energies of the basic unit with neighbouring units (E_int, kcal mol^-1) with the highest values (more than 5% of the total interaction energy) and the contribution of this energy to the total interaction energy (%) in polymorphic crystals 1t (for full list of dimers, see Tables S1 and S2 in the supporting information) top

Dimer	Symmetry operation	E_int (kcal mol^-1)	Contribution to the total interaction energy (%)	Type of interaction
Building unit is a molecule
1t_m1	-x+1, -y+1, -z+1	-14.07	23.6	stacking, N—H···π
1t_m2	-x+1, -y, -z+1	-9.41	15.8	stacking, N—H···π
1t_m3	-x+2, -y+1, -z+1	-6.38	10.7	dispersion
1t_m4	-x+2, -y+1, -z+2	-5.74	9.6	dispersion
1t_m5	-x+1, -y+1, -z+2	-4.78	8.0	C—H···O
1t_m6	x+1, y+1, z+1	-4.15	7.0	C—H···N(pyr)
1t_m7	x-1, y-1, z-1	-4.15	7.0	C—H···N(pyr)

Building unit is a dimer (symmetry operation -x+1, -y+1, -z+1)
1t_d1	x+1, y, z	-10.84	11.1	dispersion
1t_d2	x-1, y, z	-10.84	11.1	dispersion
1t_d3	x+1, y+1, z+1	-10.47	10.7	C—H···N(pyr)
1t_d4	x-1, y-1, z-1	-10.47	10.7	C—H···N(pyr)
1t_d5	x, y-1, z	-10.12	10.3	stacking pyr–pyr
1t_d6	x, y+1, z	-10.12	10.3	stacking pyr–pyr
1t_d7	x, y, z-1	-6.48	6.6	C—H···.O (2)
1t_d8	x, y,, z+1	-6.48	6.6	C—H···.O (2)
1t_d9	x-1,, z-1	-6.19	6.3	dispersion
1t_d10	x+1, y, z+1	-6.19	6.3	dispersion

Symmetry codes, interaction energies of the basic molecule with neighbouring molecules (E_int, kcal mol^-1) with the highest values (more than 5% of the total interaction energy) and the contribution of this energy to the total interaction energy (%) in polymorphic crystals 1r (for full list of dimers, see Table S3 in the supporting information) top

Dimer	Symmetry operation	E_int (kcal mol^-1)	Contribution to the total interaction energy (%)	Type of interaction
1r_m1	x+1, y, z	-10.46	17.4	stacking oxadiaz–hydrazine
1r_m2	x-1, y, z	-10.46	17.4	stacking oxadiaz–hydrazine
1r_m3	x+1/2, -y+3/2, -z+1	-6.99	11.7	N—H···N(pyr)
1r_m4	x-1/2, -y+3/2, -z+1	-6.99	11.7	N—H···N(pyr)
1r_m5	x, y-1, z	-3.96	6.6	C—H···N(lp)
1r_m6	x, y+1, z	-3.96	6.6	C—H···N(lp)
1r_m7	-x, y+1/2, -z+3/2	-3.14	5.2	dispersion
1r_m8	-x, y-1/2, -z+3/2	-3.14	5.2	dispersion

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Concomitant polymorphic forms of 3-cyclo­propyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxa­diazole

Supporting information

Concomitant polymorphic forms of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole