Bulk polarity of 3,5,7-tri­nitro-1-aza­adam­an­tane mediated by asymmetric NO2(lone pair)⋯NO2(π-hole) supra­molecular bonding

Domasevitch, K.V.; Senchyk, G.A.; Krautscheid, H.

doi:10.1107/S2053229620006762

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO₂(lone pair)NO₂(π-hole) supramolecular bonding

K. V. Domasevitch, G. A. Senchyk and H. Krautscheid

Molecular crystals exhibiting polar symmetry are important paradigms for developing new electrooptical materials. Though accessing bulk polarity still presents a significant challenge, in some cases it may be rationalized as being associated with the specific molecular shapes and symmetries and subtle features of supramolecular interactions. In the crystal structure of 3,5,7-trinitro-1-azaadamantane, C₉H₁₂N₄O₆, the polar symmetry of the molecular arrangement is a result of complementary prerequisites, namely the C_3v symmetry of the molecules is suited to the generation of polar stacks and the inherent asymmetry of the principal supramolecular bonding, as is provided by NO₂(lone pair)

NO₂(π-hole) interactions. These bonds arrange the molecules into a trigonal network. In spite of the apparent simplicity, the structure comprises three unique molecules (Z′ = $1 \over 3$ + $1 \over 3$ + $1 \over 3$ ), two of which are donors and acceptors of three N

O interactions and the third being primarily important for weak C—H

O hydrogen bonding. These distinct structural roles agree with the results of Hirshfeld surface analysis. A set of weak C—H

O and C—H

N hydrogen bonds yields three kinds of stacks. The orientation of the stacks is identical and therefore the polarity of each molecule contributes additively to the net dipole moment of the crystal. This suggests a special potential of asymmetric NO₂(lone pair)

NO₂(π-hole) interactions for the supramolecular synthesis of acentric materials.

Keywords: acentric crystals; π-hole interactions; crystal structure; high Z′ structures; twinning; Hirschfeld surface analysis; azaadamantane; trinitro.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229620006762/vp3006sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620006762/vp3006Isup2.hkl Contains datablock I

CCDC reference: 2004782

Computing details top

Data collection: IPDS (Stoe & Cie, 2000); cell refinement: IPDS (Stoe & Cie, 2000); data reduction: IPDS (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

2,5,7-Trinitro-1-azatricyclo[3.3.1.13.7]decane top

Crystal data top

C₉H₁₂N₄O₆	D_x = 1.622 Mg m⁻³
M_r = 272.23	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3	Cell parameters from 5172 reflections
a = 12.7917 (14) Å	θ = 3.2–29.2°
c = 5.8996 (6) Å	µ = 0.14 mm⁻¹
V = 836.0 (2) Å³	T = 200 K
Z = 3	Prism, colorless
F(000) = 426	0.22 × 0.20 × 0.17 mm

Data collection top

Stoe Image plate diffraction system IPDS-2T diffractometer	2451 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
φ oscillation scans	θ_max = 29.2°, θ_min = 3.2°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −17→16
T_min = 0.654, T_max = 0.792	k = −17→15
5172 measured reflections	l = −8→8
2961 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: difference Fourier map
wR(F²) = 0.063	All H-atom parameters refined
S = 0.92	w = 1/[σ²(F_o²) + (0.033P)²] where P = (F_o² + 2F_c²)/3
2961 reflections	(Δ/σ)_max < 0.001
221 parameters	Δρ_max = 0.14 e Å⁻³
1 restraint	Δρ_min = −0.19 e Å⁻³

Special details top

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

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq
O1A	0.2573 (3)	0.2891 (2)	−0.2900 (6)	0.0475 (7)
O2A	0.3275 (2)	0.1737 (3)	−0.1919 (5)	0.0413 (6)
N1A	0.000000	0.000000	0.1998 (7)	0.0183 (9)
N2A	0.2452 (3)	0.1945 (3)	−0.2164 (4)	0.0267 (6)
C1A	0.1201 (3)	0.0952 (3)	0.1220 (5)	0.0205 (6)
C2A	0.1207 (3)	0.0967 (3)	−0.1406 (5)	0.0196 (6)
C3A	0.0253 (3)	0.1249 (3)	−0.2281 (5)	0.0203 (6)
H1A	0.182 (3)	0.077 (3)	0.183 (5)	0.019 (8)*
H2A	0.131 (3)	0.167 (4)	0.173 (6)	0.017 (8)*
H3A	0.039 (3)	0.197 (4)	−0.180 (5)	0.011 (8)*
H4A	0.024 (3)	0.118 (3)	−0.396 (6)	0.018 (8)*
O1B	0.3760 (2)	0.3259 (3)	0.2319 (5)	0.0362 (6)
O2B	0.5076 (3)	0.4797 (3)	0.0412 (6)	0.0488 (8)
N1B	0.666667	0.333333	0.5825 (7)	0.0224 (10)
N2B	0.4789 (3)	0.3926 (3)	0.1637 (4)	0.0259 (6)
C1B	0.5760 (3)	0.3643 (3)	0.5048 (5)	0.0241 (6)
C2B	0.5754 (3)	0.3651 (3)	0.2425 (5)	0.0178 (6)
C3B	0.5402 (3)	0.2387 (3)	0.1525 (5)	0.0183 (6)
H1B	0.599 (3)	0.443 (4)	0.554 (5)	0.016 (8)*
H2B	0.506 (3)	0.312 (3)	0.567 (5)	0.008 (7)*
H3B	0.466 (3)	0.182 (3)	0.207 (5)	0.012 (8)*
H4B	0.549 (4)	0.243 (3)	−0.006 (6)	0.024 (9)*
O1C	0.1491 (3)	0.3784 (3)	0.2511 (5)	0.0462 (7)
O2C	0.0360 (3)	0.3839 (3)	0.5158 (6)	0.0521 (9)
N1C	0.333333	0.666667	0.8362 (8)	0.0264 (11)
N2C	0.1322 (3)	0.4261 (2)	0.4153 (5)	0.0264 (6)
C1C	0.2356 (3)	0.5486 (3)	0.7592 (5)	0.0248 (7)
C2C	0.2346 (3)	0.5470 (3)	0.4983 (5)	0.0201 (6)
C3C	0.3551 (3)	0.5649 (3)	0.4084 (5)	0.0205 (6)
H1C	0.160 (4)	0.543 (3)	0.807 (6)	0.025 (9)*
H2C	0.245 (4)	0.484 (4)	0.813 (6)	0.024 (9)*
H3C	0.347 (3)	0.562 (3)	0.242 (5)	0.010 (8)*
H4C	0.370 (3)	0.504 (3)	0.463 (5)	0.014 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.0353 (15)	0.0306 (15)	0.0659 (16)	0.0084 (12)	0.0138 (14)	0.0198 (14)
O2A	0.0191 (13)	0.0453 (16)	0.0532 (15)	0.0113 (12)	0.0059 (11)	0.0085 (13)
N1A	0.0182 (14)	0.0182 (14)	0.019 (2)	0.0091 (7)	0.000	0.000
N2A	0.0199 (14)	0.0239 (14)	0.0246 (13)	0.0022 (12)	0.0032 (10)	0.0011 (11)
C1A	0.0189 (16)	0.0209 (16)	0.0188 (13)	0.0078 (13)	−0.0014 (12)	−0.0020 (12)
C2A	0.0191 (15)	0.0211 (15)	0.0188 (12)	0.0102 (13)	−0.0002 (12)	0.0010 (11)
C3A	0.0226 (15)	0.0201 (16)	0.0194 (15)	0.0116 (13)	0.0018 (11)	0.0028 (12)
O1B	0.0184 (12)	0.0408 (15)	0.0510 (15)	0.0161 (12)	0.0015 (10)	−0.0020 (12)
O2B	0.0373 (17)	0.0530 (19)	0.0662 (17)	0.0300 (15)	0.0032 (13)	0.0265 (15)
N1B	0.0256 (16)	0.0256 (16)	0.016 (2)	0.0128 (8)	0.000	0.000
N2B	0.0243 (15)	0.0290 (16)	0.0296 (14)	0.0173 (12)	−0.0024 (11)	−0.0039 (12)
C1B	0.0257 (18)	0.0283 (17)	0.0197 (13)	0.0146 (15)	0.0058 (12)	0.0023 (13)
C2B	0.0150 (14)	0.0193 (14)	0.0208 (13)	0.0099 (12)	−0.0022 (10)	−0.0019 (11)
C3B	0.0164 (15)	0.0180 (15)	0.0197 (14)	0.0079 (12)	−0.0014 (11)	−0.0011 (12)
O1C	0.0374 (16)	0.0329 (15)	0.0592 (17)	0.0107 (14)	−0.0005 (13)	−0.0216 (13)
O2C	0.0251 (15)	0.0407 (19)	0.067 (2)	−0.0013 (14)	0.0101 (13)	−0.0094 (15)
N1C	0.0315 (17)	0.0315 (17)	0.016 (2)	0.0157 (9)	0.000	0.000
N2C	0.0235 (15)	0.0186 (14)	0.0358 (15)	0.0094 (13)	−0.0017 (12)	0.0001 (11)
C1C	0.0251 (18)	0.0264 (18)	0.0221 (15)	0.0123 (14)	0.0047 (13)	0.0051 (12)
C2C	0.0171 (16)	0.0156 (15)	0.0236 (15)	0.0052 (12)	0.0005 (12)	−0.0008 (11)
C3C	0.0201 (15)	0.0191 (15)	0.0230 (14)	0.0103 (13)	0.0018 (12)	0.0012 (11)

Geometric parameters (Å, º) top

O1A—N2A	1.220 (4)	C1B—H1B	0.94 (4)
O2A—N2A	1.217 (4)	C1B—H2B	0.89 (3)
N1A—C1Aⁱ	1.478 (3)	C2B—C3B^iv	1.523 (4)
N1A—C1Aⁱⁱ	1.478 (3)	C2B—C3B	1.540 (4)
N1A—C1A	1.478 (3)	C3B—H3B	0.92 (3)
N2A—C2A	1.519 (4)	C3B—H4B	0.94 (4)
C1A—C2A	1.549 (4)	O1C—N2C	1.220 (4)
C1A—H1A	1.00 (4)	O2C—N2C	1.222 (4)
C1A—H2A	0.91 (4)	N1C—C1C	1.470 (4)
C2A—C3A	1.525 (5)	N1C—C1C^v	1.470 (4)
C2A—C3Aⁱ	1.534 (4)	N1C—C1C^vi	1.470 (4)
C3A—H3A	0.89 (4)	N2C—C2C	1.524 (4)
C3A—H4A	0.99 (3)	C1C—C2C	1.539 (4)
O1B—N2B	1.225 (4)	C1C—H1C	0.97 (4)
O2B—N2B	1.219 (4)	C1C—H2C	0.95 (4)
N1B—C1Bⁱⁱⁱ	1.473 (4)	C2C—C3C^v	1.532 (4)
N1B—C1B^iv	1.473 (4)	C2C—C3C	1.535 (5)
N1B—C1B	1.473 (4)	C3C—H3C	0.99 (3)
N2B—C2B	1.517 (4)	C3C—H4C	0.94 (4)
C1B—C2B	1.548 (4)

C1Aⁱ—N1A—C1Aⁱⁱ	110.82 (19)	N2B—C2B—C3B^iv	110.2 (2)
C1Aⁱ—N1A—C1A	110.82 (19)	N2B—C2B—C3B	107.1 (2)
C1Aⁱⁱ—N1A—C1A	110.82 (19)	C3B^iv—C2B—C3B	111.0 (3)
O2A—N2A—O1A	124.4 (3)	N2B—C2B—C1B	108.4 (2)
O2A—N2A—C2A	116.7 (3)	C3B^iv—C2B—C1B	110.3 (2)
O1A—N2A—C2A	118.9 (3)	C3B—C2B—C1B	109.7 (3)
N1A—C1A—C2A	108.5 (3)	C2Bⁱⁱⁱ—C3B—C2B	106.2 (3)
N1A—C1A—H1A	108 (2)	C2Bⁱⁱⁱ—C3B—H3B	109 (2)
C2A—C1A—H1A	111.4 (19)	C2B—C3B—H3B	110 (2)
N1A—C1A—H2A	107 (2)	C2Bⁱⁱⁱ—C3B—H4B	106 (2)
C2A—C1A—H2A	109 (2)	C2B—C3B—H4B	108 (2)
H1A—C1A—H2A	112 (3)	H3B—C3B—H4B	116 (3)
N2A—C2A—C3A	109.8 (3)	C1C—N1C—C1C^v	110.9 (2)
N2A—C2A—C3Aⁱ	108.5 (3)	C1C—N1C—C1C^vi	110.9 (2)
C3A—C2A—C3Aⁱ	111.8 (3)	C1C^v—N1C—C1C^vi	110.9 (2)
N2A—C2A—C1A	107.5 (2)	O1C—N2C—O2C	123.7 (3)
C3A—C2A—C1A	110.0 (3)	O1C—N2C—C2C	119.1 (3)
C3Aⁱ—C2A—C1A	109.1 (3)	O2C—N2C—C2C	117.2 (3)
C2A—C3A—C2Aⁱⁱ	106.6 (3)	N1C—C1C—C2C	108.7 (3)
C2A—C3A—H3A	112 (2)	N1C—C1C—H1C	107 (2)
C2Aⁱⁱ—C3A—H3A	111 (2)	C2C—C1C—H1C	107 (2)
C2A—C3A—H4A	107 (2)	N1C—C1C—H2C	112 (2)
C2Aⁱⁱ—C3A—H4A	107.5 (19)	C2C—C1C—H2C	109 (2)
H3A—C3A—H4A	113 (3)	H1C—C1C—H2C	113 (3)
C1Bⁱⁱⁱ—N1B—C1B^iv	110.8 (2)	N2C—C2C—C3C^v	107.1 (2)
C1Bⁱⁱⁱ—N1B—C1B	110.8 (2)	N2C—C2C—C3C	109.2 (3)
C1B^iv—N1B—C1B	110.8 (2)	C3C^v—C2C—C3C	111.1 (3)
O2B—N2B—O1B	124.0 (3)	N2C—C2C—C1C	109.4 (3)
O2B—N2B—C2B	119.0 (3)	C3C^v—C2C—C1C	109.8 (2)
O1B—N2B—C2B	117.0 (3)	C3C—C2C—C1C	110.0 (3)
N1B—C1B—C2B	108.7 (3)	C2C^vi—C3C—C2C	106.2 (3)
N1B—C1B—H1B	109 (2)	C2C^vi—C3C—H3C	113 (2)
C2B—C1B—H1B	107.5 (19)	C2C—C3C—H3C	104.9 (18)
N1B—C1B—H2B	108 (2)	C2C^vi—C3C—H4C	109 (2)
C2B—C1B—H2B	114.3 (19)	C2C—C3C—H4C	111 (2)
H1B—C1B—H2B	109 (3)	H3C—C3C—H4C	112 (3)

C1Aⁱ—N1A—C1A—C2A	62.2 (3)	O1B—N2B—C2B—C1B	−56.3 (4)
C1Aⁱⁱ—N1A—C1A—C2A	−61.3 (3)	N1B—C1B—C2B—N2B	178.0 (2)
O2A—N2A—C2A—C3A	−168.0 (3)	N1B—C1B—C2B—C3B^iv	−61.2 (3)
O1A—N2A—C2A—C3A	14.4 (4)	N1B—C1B—C2B—C3B	61.4 (3)
O2A—N2A—C2A—C3Aⁱ	−45.5 (4)	N2B—C2B—C3B—C2Bⁱⁱⁱ	−177.4 (2)
O1A—N2A—C2A—C3Aⁱ	136.9 (3)	C3B^iv—C2B—C3B—C2Bⁱⁱⁱ	62.2 (4)
O2A—N2A—C2A—C1A	72.4 (4)	C1B—C2B—C3B—C2Bⁱⁱⁱ	−60.0 (3)
O1A—N2A—C2A—C1A	−105.2 (4)	C1C^v—N1C—C1C—C2C	62.0 (3)
N1A—C1A—C2A—N2A	−179.6 (2)	C1C^vi—N1C—C1C—C2C	−61.7 (3)
N1A—C1A—C2A—C3A	60.9 (3)	O1C—N2C—C2C—C3C^v	100.4 (3)
N1A—C1A—C2A—C3Aⁱ	−62.1 (3)	O2C—N2C—C2C—C3C^v	−77.8 (4)
N2A—C2A—C3A—C2Aⁱⁱ	−178.8 (2)	O1C—N2C—C2C—C3C	−20.1 (4)
C3Aⁱ—C2A—C3A—C2Aⁱⁱ	60.7 (4)	O2C—N2C—C2C—C3C	161.7 (3)
C1A—C2A—C3A—C2Aⁱⁱ	−60.7 (3)	O1C—N2C—C2C—C1C	−140.6 (3)
C1Bⁱⁱⁱ—N1B—C1B—C2B	−61.9 (3)	O2C—N2C—C2C—C1C	41.2 (4)
C1B^iv—N1B—C1B—C2B	61.4 (3)	N1C—C1C—C2C—N2C	−178.9 (2)
O2B—N2B—C2B—C3B^iv	1.6 (4)	N1C—C1C—C2C—C3C^v	−61.6 (3)
O1B—N2B—C2B—C3B^iv	−177.1 (3)	N1C—C1C—C2C—C3C	61.1 (3)
O2B—N2B—C2B—C3B	−119.2 (3)	N2C—C2C—C3C—C2C^vi	180.0 (2)
O1B—N2B—C2B—C3B	62.0 (3)	C3C^v—C2C—C3C—C2C^vi	62.0 (4)
O2B—N2B—C2B—C1B	122.4 (3)	C1C—C2C—C3C—C2C^vi	−59.9 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1A—H2A···O1C	0.90 (4)	2.64 (4)	3.536 (5)	170 (3)
C3A—H4A···N1A^vii	0.99 (3)	2.76 (3)	3.678 (5)	154 (3)
C1B—H1B···O2C^vi	0.94 (4)	2.58 (4)	3.455 (5)	154 (3)
C1B—H2B···O2A^viii	0.89 (3)	2.51 (3)	3.392 (4)	170 (2)
C3B—H4B···N1B^vii	0.94 (4)	2.79 (4)	3.664 (5)	156 (3)
C1C—H1C···O2B	0.98 (4)	2.56 (4)	3.496 (4)	161 (3)
C1C—H2C···O1A^viii	0.96 (4)	2.64 (4)	3.479 (5)	147 (3)
C3C—H4C···O1A^viii	0.94 (4)	2.80 (3)	3.574 (4)	140 (3)
C3C—H4C···O1B	0.94 (4)	2.69 (3)	3.365 (4)	129 (2)
C3C—H3C···N1C^vii	0.98 (3)	2.79 (3)	3.678 (5)	150 (3)

Symmetry codes: (vi) −y+1, x−y+1, z; (vii) x, y, z−1; (viii) x, y, z+1.

Calculated interaction energies (kJ mol^-1). top

Type^a	Path	R (Å)	E_ele	E_pol	E_dis	E_rep	E_tot
Type 1	A···B	7.72	-9.4	-2.2	-18.7	13.4	-19.7
Type 2	A···B^vii	8.23	-9.3	-1.8	-10.9	11.9	-13.3
	A···C	8.27	-8.1	-1.6	-9.1	6.1	-13.9
	B···C^vii	8.60	-7.0	-1.1	-7.1	5.3	-11.1
Type 3	A···C^vii	7.70	-8.8	-2.2	-16.5	9.0	-19.7
	B···C	7.53	-8.4	-2.9	-21.3	14.4	-20.7
Type 4	A···A^vii	5.90	-5.7	-5.3	-32.6	18.8	-26.7
	B···B^vii	5.90	-9.0	-5.3	-34.6	20.8	-30.8
	C···C^vii	5.90	-11.6	-4.0	-35.8	22.0	-32.8

Interaction energies were calculated employing the CE-B3LYP/6-31G(d,p) functional/basis set combination. The scale factors used to determine E_tot: k_ele = 1.057, k_pol = 0.740, k_dis = 0.871 and k_rep = 0.618 (Mackenzie et al., 2017). Note: (a) for details of the interaction modes, See Fig. 6; R is the distance between the centroids of interacting molecules. [Symmetry code: (vii) x, y, z-1.]

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

Bulk polarity of 3,5,7-tri­nitro-1-aza­adam­an­tane mediated by asymmetric NO2(lone pair)NO2(π-hole) supra­molecular bonding

Supporting information

Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO₂(lone pair)NO₂(π-hole) supramolecular bonding