Chemical bonding and intermolecular interactions in energetic materials: 1,3,4-trinitro-7,8-diazapentalene

Chen, Y.-S.; Stash, A.I.; Pinkerton, A.A.

doi:10.1107/S010876810700242X

Chemical bonding and intermolecular interactions in energetic materials: 1,3,4-trinitro-7,8-diazapentalene

Y.-S. Chen, A. I. Stash and A. A. Pinkerton

The electron density and related properties of the red-colored energetic material 1,3,4-trinitro-7,8-diazapentalene (space group Pca2₁) have been determined from a low-temperature [90.0 (1) K] X-ray diffraction experiment. Intensity data were measured with a 2 K CCD Bruker diffractometer using Ag Kα radiation. One detector setting, several φ settings, 0.15° ω scans and 96 s exposure time per frame gave R_int = 0.0188 for 31 952 (10 283 unique) reflections and (sin θ/λ)_max = 1.15 Å⁻¹. The electron density was modeled using the Hansen–Coppens [(1978), Acta Cryst. A34, 909–921] multipole model and refined to R = 0.026 for 9455 unique observed reflections. The electron density, Laplacian and electrostatic potential distributions are reported and discussed. The properties of the bond (3,−1) critical points are analyzed. All results are indicative of multiple bonds in the five-membered rings. In addition, a significant number of weak intermolecular interactions (O

H, O

O, O

N, O

C) have also been characterized by the properties of their critical points. A comparison of experimental results with those obtained from theoretical calculations (periodic, CRYSTAL98; single molecule, GAUSSIAN98) is also reported.

Keywords: energetic materials; electron density; critical points.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S010876810700242X/bs5038sup1.cif Contains datablock TNDP
	Structure factor file (CIF format) https://doi.org/10.1107/S010876810700242X/bs5038TNDPsup2.hkl Contains datablock TNDP

CCDC reference: 644713

Computing details top

Data collection: Siemens (1996a); cell refinement: Siemens (1996b); data reduction: Siemens (1996b); program(s) used to solve structure: Sheldrick (1997); program(s) used to refine structure: Koritsanszky et al., (2003); molecular graphics: Koritsanszky et al., (2003); software used to prepare material for publication: Koritsanszky et al., (2003).

Figures top

(TNDP) top

Crystal data top

C₆H₃N₅O₆	D_x = 1.837 Mg m⁻³
M_r = 241.13	Ag Kα radiation, λ = 0.56083 Å
Orthorhombic, Pca2₁	Cell parameters from 31952 reflections
a = 13.3229 (3) Å	θ = 2.0–40.1°
b = 7.0005 (1) Å	µ = 0.10 mm⁻¹
c = 9.3471 (2) Å	T = 90 K
V = 871.78 (3) Å³	Prism, red
Z = 4	0.30 × 0.25 × 0.21 mm

Data collection top

Smart CCD2000 diffractometer	R_int = 0.019
w scans	θ_max = 40.1°
31952 measured reflections	h = −30→30
10283 independent reflections	k = −16→16
9455 reflections with I > 3σ	l = −20→20

Refinement top

Refinement on F²	w = 1/[s²(Fsqd)]
R[F² > 2σ(F²)] = 0.026	(Δ/σ)_max < 0.001
wR(F²) = 0.023	Δρ_max = 0.16 e Å⁻³
S = 1.44	Δρ_min = −0.12 e Å⁻³
9455 reflections	Extinction correction: B-C type 1 Gaussian isotropic
452 parameters	Extinction coefficient: 0.1188
All H-atom parameters refined

Crystal data top

C₆H₃N₅O₆	V = 871.78 (3) Å³
M_r = 241.13	Z = 4
Orthorhombic, Pca2₁	Ag Kα radiation, λ = 0.56083 Å
a = 13.3229 (3) Å	µ = 0.10 mm⁻¹
b = 7.0005 (1) Å	T = 90 K
c = 9.3471 (2) Å	0.30 × 0.25 × 0.21 mm

Data collection top

Smart CCD2000 diffractometer	9455 reflections with I > 3σ
31952 measured reflections	R_int = 0.019
10283 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	452 parameters
wR(F²) = 0.023	All H-atom parameters refined
S = 1.44	Δρ_max = 0.16 e Å⁻³
9455 reflections	Δρ_min = −0.12 e Å⁻³

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

	x	y	z	U_iso*/U_eq
O(11)	−0.06192 (3)	0.05935 (8)	0.12282 (7)	0.019
O(12)	0.00331 (4)	−0.22572 (7)	0.14310 (6)	0.017
O(31)	0.36238 (4)	−0.08134 (9)	0.42410 (7)	0.020
O(32)	0.36351 (3)	0.23008 (9)	0.41676 (8)	0.020
O(41)	0.25749 (4)	0.33833 (8)	0.62907 (6)	0.018
O(42)	0.20362 (4)	0.63138 (8)	0.60706 (9)	0.022
N(1)	0.00159 (3)	−0.05335 (6)	0.16855 (5)	0.012
N(3)	0.32045 (2)	0.07450 (7)	0.41031 (6)	0.012
N(4)	0.20885 (3)	0.46351 (6)	0.56789 (6)	0.012
N(7)	0.07328 (2)	0.20378 (5)	0.31030	0.009
N(8)	0.15749 (2)	0.23261 (5)	0.38999 (5)	0.008
C(1)	0.07771 (3)	0.01974 (6)	0.25684 (6)	0.010
C(2)	0.16689 (3)	−0.06434 (6)	0.29878 (6)	0.011
C(3)	0.21711 (2)	0.07167 (6)	0.37970 (5)	0.009
C(4)	0.15046 (3)	0.41044 (6)	0.44878 (5)	0.009
C(5)	0.06152 (3)	0.49517 (6)	0.40056 (6)	0.011
C(6)	0.01383 (3)	0.36330 (6)	0.31433 (6)	0.011
H(2)	0.19761	−0.19946	0.26425	0.035 (2)
H(5)	0.03234	0.63197	0.43406	0.033 (2)
H(6)	−0.05770	0.36826	0.26008	0.035 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O(11)	0.0153 (1)	0.0225 (2)	0.0198 (1)	0.0027 (1)	−0.0086 (1)	−0.0052 (1)
O(12)	0.0203 (1)	0.0146 (1)	0.0156 (1)	−0.0055 (1)	−0.0025 (1)	−0.0034 (1)
O(31)	0.0150 (1)	0.0236 (2)	0.0227 (2)	0.0108 (1)	−0.0046 (1)	−0.0046 (1)
O(32)	0.00985 (9)	0.02393 (17)	0.0266 (2)	−0.0041 (1)	−0.0025 (1)	−0.00053 (15)
O(41)	0.0213 (1)	0.0192 (1)	0.0128 (1)	0.0016 (1)	−0.0073 (1)	0.0004 (1)
O(42)	0.0210 (1)	0.0164 (1)	0.0278 (2)	0.0016 (1)	−0.0069 (1)	−0.0113 (1)
N(1)	0.01107 (9)	0.01508 (12)	0.01028 (9)	−0.00242 (8)	−0.00165 (8)	−0.00247 (9)
N(3)	0.00775 (7)	0.01766 (13)	0.01193 (10)	0.00246 (8)	−0.00090 (7)	−0.00189 (9)
N(4)	0.01179 (9)	0.01249 (11)	0.01057 (9)	−0.00018 (8)	−0.00158 (8)	−0.00267 (9)
N(7)	0.00750 (7)	0.00979 (9)	0.00903 (8)	−0.00009 (6)	−0.00136 (6)	−0.00008 (7)
N(8)	0.00703 (6)	0.00889 (8)	0.00800 (8)	0.00033 (6)	−0.00073 (6)	−0.00030 (7)
C(1)	0.00927 (9)	0.01090 (11)	0.0102 (1)	−0.00079 (8)	−0.00144 (8)	−0.00148 (9)
C(2)	0.01065 (9)	0.01061 (11)	0.01076 (11)	0.00113 (8)	−0.00012 (8)	−0.00172 (9)
C(3)	0.00759 (8)	0.01075 (10)	0.00962 (10)	0.00127 (7)	−0.00034 (7)	−0.00061 (8)
C(4)	0.00930 (9)	0.00911 (10)	0.0095 (1)	−0.00006 (7)	−0.00084 (7)	−0.00013 (8)
C(5)	0.01104 (9)	0.00910 (10)	0.01388 (12)	0.00137 (8)	−0.00116 (9)	0.00091 (9)
C(6)	0.00914 (9)	0.01138 (11)	0.01278 (11)	0.00117 (8)	−0.00227 (8)	0.00139 (10)

Geometric parameters (Å, º) top

O(11)—N(1)	1.2333 (6)	N(7)—C(6)	1.3696 (5)
O(12)—N(1)	1.2301 (6)	N(8)—C(3)	1.3818 (5)
O(31)—N(3)	1.2324 (7)	N(8)—C(4)	1.3640 (5)
O(32)—N(3)	1.2324 (7)	C(1)—C(2)	1.3827 (5)
O(41)—N(4)	1.2308 (6)	C(2)—C(3)	1.3879 (5)
O(42)—N(4)	1.2329 (6)	C(2)—H(2)	1.0800 (4)
N(1)—C(1)	1.4040 (5)	C(4)—C(5)	1.3997 (5)
N(3)—C(3)	1.4064 (5)	C(5)—C(6)	1.3804 (6)
N(4)—C(4)	1.4080 (5)	C(5)—H(5)	1.0800 (4)
N(7)—N(8)	1.3617 (4)	C(6)—H(6)	1.0800 (4)
N(7)—C(1)	1.3832 (5)

O(11)—N(1)—O(12)	124.98 (4)	N(7)—C(1)—C(2)	109.31 (3)
O(11)—N(1)—C(1)	117.79 (4)	C(1)—C(2)—C(3)	106.06 (3)
O(12)—N(1)—C(1)	117.23 (4)	C(1)—C(2)—H(2)	127.86 (4)
O(31)—N(3)—O(32)	124.49 (4)	C(3)—C(2)—H(2)	125.53 (3)
O(31)—N(3)—C(3)	116.91 (5)	N(3)—C(3)—N(8)	122.48 (4)
O(32)—N(3)—C(3)	118.56 (4)	N(3)—C(3)—C(2)	126.33 (4)
O(41)—N(4)—O(42)	124.78 (5)	N(8)—C(3)—C(2)	108.68 (3)
O(41)—N(4)—C(4)	118.06 (4)	N(4)—C(4)—N(8)	121.43 (3)
O(42)—N(4)—C(4)	117.07 (4)	N(4)—C(4)—C(5)	127.63 (4)
N(8)—N(7)—C(1)	107.49 (3)	N(8)—C(4)—C(5)	108.37 (3)
N(8)—N(7)—C(6)	109.92 (3)	C(4)—C(5)—C(6)	107.12 (3)
C(1)—N(7)—C(6)	142.57 (3)	C(4)—C(5)—H(5)	125.96 (4)
N(7)—N(8)—C(3)	108.34 (3)	C(6)—C(5)—H(5)	126.62 (4)
N(7)—N(8)—C(4)	107.40 (3)	N(7)—C(6)—C(5)	107.16 (3)
C(3)—N(8)—C(4)	144.26 (3)	N(7)—C(6)—H(6)	121.57 (4)
N(1)—C(1)—N(7)	121.40 (4)	C(5)—C(6)—H(6)	131.21 (4)
N(1)—C(1)—C(2)	129.22 (4)

Experimental details

Crystal data
Chemical formula	C₆H₃N₅O₆
M_r	241.13
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	90
a, b, c (Å)	13.3229 (3), 7.0005 (1), 9.3471 (2)
V (Å³)	871.78 (3)
Z	4
Radiation type	Ag Kα, λ = 0.56083 Å
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.25 × 0.21

Data collection
Diffractometer	Smart CCD2000 diffractometer
Absorption correction	–
No. of measured, independent and observed (I > 3σ) reflections	31952, 10283, 9455
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	1.149

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.023, 1.44
No. of reflections	9455
No. of parameters	452
No. of restraints	?
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.12

Computer programs: Siemens (1996a), Siemens (1996b), Sheldrick (1997), Koritsanszky et al., (2003).

Selected geometric parameters (Å, º) top

O(11)—N(1)	1.2333 (6)	N(7)—C(6)	1.3696 (5)
O(12)—N(1)	1.2301 (6)	N(8)—C(3)	1.3818 (5)
O(31)—N(3)	1.2324 (7)	N(8)—C(4)	1.3640 (5)
O(32)—N(3)	1.2324 (7)	C(1)—C(2)	1.3827 (5)
O(41)—N(4)	1.2308 (6)	C(2)—C(3)	1.3879 (5)
O(42)—N(4)	1.2329 (6)	C(2)—H(2)	1.0800 (4)
N(1)—C(1)	1.4040 (5)	C(4)—C(5)	1.3997 (5)
N(3)—C(3)	1.4064 (5)	C(5)—C(6)	1.3804 (6)
N(4)—C(4)	1.4080 (5)	C(5)—H(5)	1.0800 (4)
N(7)—N(8)	1.3617 (4)	C(6)—H(6)	1.0800 (4)
N(7)—C(1)	1.3832 (5)

O(11)—N(1)—O(12)	124.98 (4)	N(7)—C(1)—C(2)	109.31 (3)
O(11)—N(1)—C(1)	117.79 (4)	C(1)—C(2)—C(3)	106.06 (3)
O(12)—N(1)—C(1)	117.23 (4)	C(1)—C(2)—H(2)	127.86 (4)
O(31)—N(3)—O(32)	124.49 (4)	C(3)—C(2)—H(2)	125.53 (3)
O(31)—N(3)—C(3)	116.91 (5)	N(3)—C(3)—N(8)	122.48 (4)
O(32)—N(3)—C(3)	118.56 (4)	N(3)—C(3)—C(2)	126.33 (4)
O(41)—N(4)—O(42)	124.78 (5)	N(8)—C(3)—C(2)	108.68 (3)
O(41)—N(4)—C(4)	118.06 (4)	N(4)—C(4)—N(8)	121.43 (3)
O(42)—N(4)—C(4)	117.07 (4)	N(4)—C(4)—C(5)	127.63 (4)
N(8)—N(7)—C(1)	107.49 (3)	N(8)—C(4)—C(5)	108.37 (3)
N(8)—N(7)—C(6)	109.92 (3)	C(4)—C(5)—C(6)	107.12 (3)
C(1)—N(7)—C(6)	142.57 (3)	C(4)—C(5)—H(5)	125.96 (4)
N(7)—N(8)—C(3)	108.34 (3)	C(6)—C(5)—H(5)	126.62 (4)
N(7)—N(8)—C(4)	107.40 (3)	N(7)—C(6)—C(5)	107.16 (3)
C(3)—N(8)—C(4)	144.26 (3)	N(7)—C(6)—H(6)	121.57 (4)
N(1)—C(1)—N(7)	121.40 (4)	C(5)—C(6)—H(6)	131.21 (4)
N(1)—C(1)—C(2)	129.22 (4)

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