1,4-Diazo-niabicyclo-[2.2.2]octane bis-(2,4,6-trinitro-phenolate).

In the title compound, C(6)H(14)N(2) (2+)·2C(6)H(2)N(3)O(7) (-), the cation possesses crystallographically imposed twofold rotation symmetry. In the crystal structure, the cation and anions are linked into a trimeric aggregate by inter-molecular N-H⋯O hydrogen bonds. The trimeric units are further connected by π-π inter-actions [centroid-centroid distances = 3.507 (2)-3.660 (3) Å], forming layers parallel to the bc plane.

Related literature

For a discussion on hydrogen bonding in in the title crystal, see: Kumai et al. (2007 ▶); Horiuchi et al. (2005 ▶). For related structures, see: Dabros et al. (2007 ▶); Jin et al. (2004 ▶); Glidewell et al. (1999 ▶); Chen et al. (2009 ▶).

Experimental

Crystal data

C6H14N2 2+·2C6n class="Species">H2N3O7 −

M = 570.40

Monoclinic,

a = 15.3808 (11) Å

b = 7.1520 (5) Å

c = 25.3527 (14) Å

β = 125.496 (2)°

V = 2270.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.15 mm−1

T = 93 K

0.1 × 0.1 × 0.1 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.857, T max = 1.000

10700 measured reflections

2590 independent reflections

2218 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.098

S = 1.07

2590 reflections

181 parameters

H-atom parameters constrained

Δρmax = 0.54 e Å−3

Δρmin = −0.59 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear (Rigaku, 2005 ▶); data reduction: CrystalClear (Rigaku, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021021/rz2442sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021021/rz2442Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H14N22+·2C6H2N3O7−	F(000) = 1176
Mr = 570.40	Dx = 1.669 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -C 2yc	Cell parameters from 4042 reflections
a = 15.3808 (11) Å	θ = 3.5–27.6°
b = 7.1520 (5) Å	µ = 0.15 mm−1
c = 25.3527 (14) Å	T = 93 K
β = 125.496 (2)°	Prism, yellow
V = 2270.6 (3) Å3	0.1 × 0.1 × 0.1 mm
Z = 4

Rigaku SCXmini diffractometer	2590 independent reflections
Radiation source: fine-focus sealed tube	2218 reflections with I > 2σ(I)
graphite	Rint = 0.028
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −19→18
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.857, Tmax = 1.000	l = −32→32
10700 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0406P)2 + 3.4753P] where P = (Fo2 + 2Fc2)/3
2590 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.59 e Å−3

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. 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.

	x	y	z	Uiso*/Ueq
O1	0.06908 (8)	0.27695 (17)	0.12769 (5)	0.0196 (2)
O2	−0.12313 (9)	0.44433 (16)	0.07242 (5)	0.0189 (2)
O3	−0.23908 (8)	0.41893 (16)	−0.03110 (5)	0.0192 (2)
O4	−0.13536 (9)	0.27577 (18)	−0.16941 (5)	0.0248 (3)
O5	0.01746 (9)	0.14572 (17)	−0.13108 (5)	0.0241 (3)
O6	0.28037 (11)	0.2978 (2)	0.13599 (8)	0.0563 (5)
O7	0.23717 (10)	0.01540 (18)	0.13396 (7)	0.0404 (4)
N1	−0.14821 (10)	0.39809 (17)	0.01833 (6)	0.0135 (3)
N2	−0.04785 (10)	0.21799 (18)	−0.12408 (6)	0.0167 (3)
N3	0.21729 (10)	0.17069 (18)	0.11151 (6)	0.0156 (3)
N4	0.00848 (9)	0.28214 (18)	0.20398 (6)	0.0136 (3)
H4A	0.0147	0.2825	0.1696	0.016*
C1	0.03700 (11)	0.2720 (2)	0.06954 (7)	0.0135 (3)
C2	−0.06664 (11)	0.3209 (2)	0.01256 (7)	0.0129 (3)
C3	−0.09268 (11)	0.30461 (19)	−0.04961 (7)	0.0133 (3)
H3A	−0.1616	0.3403	−0.0859	0.016*
C4	−0.01856 (12)	0.2367 (2)	−0.05864 (7)	0.0143 (3)
C5	0.08530 (12)	0.1875 (2)	−0.00629 (7)	0.0141 (3)
H5A	0.1364	0.1409	−0.0126	0.017*
C6	0.10876 (11)	0.2103 (2)	0.05401 (7)	0.0137 (3)
C7	0.01049 (12)	0.4793 (2)	0.22402 (7)	0.0163 (3)
H7A	−0.0450	0.5536	0.1862	0.020*
H7B	0.0809	0.5363	0.2414	0.020*
C8	0.10044 (12)	0.1762 (2)	0.25921 (7)	0.0182 (3)
H8A	0.1687	0.2302	0.2707	0.022*
H8B	0.0973	0.0438	0.2468	0.022*
C9	−0.09404 (11)	0.1889 (2)	0.18263 (7)	0.0149 (3)
H9A	−0.0970	0.0621	0.1660	0.018*
H9B	−0.1552	0.2620	0.1474	0.018*

	U11	U22	U33	U12	U13	U23
O1	0.0162 (5)	0.0311 (6)	0.0120 (5)	0.0027 (5)	0.0085 (4)	0.0029 (4)
O2	0.0207 (5)	0.0237 (6)	0.0143 (5)	0.0014 (4)	0.0113 (5)	−0.0021 (4)
O3	0.0138 (5)	0.0258 (6)	0.0153 (5)	0.0029 (4)	0.0069 (4)	0.0023 (4)
O4	0.0198 (6)	0.0389 (7)	0.0128 (5)	−0.0009 (5)	0.0078 (5)	0.0008 (5)
O5	0.0306 (6)	0.0267 (6)	0.0222 (6)	0.0043 (5)	0.0194 (5)	−0.0029 (5)
O6	0.0256 (7)	0.0389 (9)	0.0517 (9)	−0.0181 (6)	−0.0076 (7)	0.0214 (7)
O7	0.0271 (7)	0.0164 (6)	0.0401 (8)	0.0023 (5)	−0.0020 (6)	0.0064 (5)
N1	0.0144 (6)	0.0126 (6)	0.0138 (6)	−0.0010 (5)	0.0083 (5)	0.0008 (4)
N2	0.0201 (6)	0.0165 (6)	0.0153 (6)	−0.0040 (5)	0.0114 (5)	−0.0029 (5)
N3	0.0138 (6)	0.0181 (6)	0.0164 (6)	0.0000 (5)	0.0096 (5)	0.0013 (5)
N4	0.0142 (6)	0.0167 (6)	0.0113 (5)	0.0000 (5)	0.0082 (5)	0.0000 (4)
C1	0.0150 (7)	0.0125 (7)	0.0137 (6)	−0.0023 (5)	0.0087 (6)	0.0003 (5)
C2	0.0138 (7)	0.0118 (6)	0.0147 (6)	−0.0013 (5)	0.0092 (6)	−0.0003 (5)
C3	0.0140 (6)	0.0108 (6)	0.0137 (6)	−0.0028 (5)	0.0073 (6)	−0.0002 (5)
C4	0.0192 (7)	0.0118 (7)	0.0133 (6)	−0.0034 (5)	0.0103 (6)	−0.0018 (5)
C5	0.0168 (7)	0.0105 (7)	0.0182 (7)	−0.0008 (5)	0.0120 (6)	−0.0006 (5)
C6	0.0129 (6)	0.0118 (6)	0.0156 (7)	−0.0006 (5)	0.0078 (6)	0.0024 (5)
C7	0.0199 (7)	0.0155 (7)	0.0142 (7)	−0.0031 (6)	0.0102 (6)	−0.0015 (5)
C8	0.0142 (7)	0.0256 (8)	0.0141 (7)	0.0063 (6)	0.0077 (6)	0.0023 (6)
C9	0.0137 (6)	0.0167 (7)	0.0127 (6)	−0.0030 (5)	0.0067 (6)	−0.0027 (5)

O1—C1	1.2543 (17)	C2—C3	1.3876 (19)
O2—N1	1.2348 (16)	C3—C4	1.375 (2)
O3—N1	1.2297 (16)	C3—H3A	0.9500
O4—N2	1.2274 (17)	C4—C5	1.405 (2)
O5—N2	1.2307 (17)	C5—C6	1.361 (2)
O6—N3	1.2054 (19)	C5—H5A	0.9500
O7—N3	1.2037 (18)	C7—C7i	1.528 (3)
N1—C2	1.4535 (18)	C7—H7A	0.9900
N2—C4	1.4510 (18)	C7—H7B	0.9900
N3—C6	1.4718 (18)	C8—C9i	1.536 (2)
N4—C7	1.4930 (19)	C8—H8A	0.9900
N4—C9	1.4942 (18)	C8—H8B	0.9900
N4—C8	1.4952 (18)	C9—C8i	1.536 (2)
N4—H4A	0.9300	C9—H9A	0.9900
C1—C6	1.440 (2)	C9—H9B	0.9900
C1—C2	1.4409 (19)
O3—N1—O2	122.45 (12)	C5—C4—N2	119.00 (13)
O3—N1—C2	118.70 (12)	C6—C5—C4	116.45 (13)
O2—N1—C2	118.83 (12)	C6—C5—H5A	121.8
O4—N2—O5	123.34 (12)	C4—C5—H5A	121.8
O4—N2—C4	118.88 (12)	C5—C6—C1	126.76 (13)
O5—N2—C4	117.78 (12)	C5—C6—N3	119.86 (13)
O7—N3—O6	123.01 (14)	C1—C6—N3	113.38 (12)
O7—N3—C6	118.46 (12)	N4—C7—C7i	108.68 (7)
O6—N3—C6	118.41 (13)	N4—C7—H7A	110.0
C7—N4—C9	110.72 (11)	C7i—C7—H7A	110.0
C7—N4—C8	109.79 (11)	N4—C7—H7B	110.0
C9—N4—C8	109.80 (12)	C7i—C7—H7B	110.0
C7—N4—H4A	108.8	H7A—C7—H7B	108.3
C9—N4—H4A	108.8	N4—C8—C9i	108.41 (11)
C8—N4—H4A	108.8	N4—C8—H8A	110.0
O1—C1—C6	119.29 (13)	C9i—C8—H8A	110.0
O1—C1—C2	128.51 (14)	N4—C8—H8B	110.0
C6—C1—C2	112.20 (12)	C9i—C8—H8B	110.0
C3—C2—C1	122.68 (13)	H8A—C8—H8B	108.4
C3—C2—N1	116.72 (12)	N4—C9—C8i	108.72 (11)
C1—C2—N1	120.56 (12)	N4—C9—H9A	109.9
C4—C3—C2	119.91 (13)	C8i—C9—H9A	109.9
C4—C3—H3A	120.0	N4—C9—H9B	109.9
C2—C3—H3A	120.0	C8i—C9—H9B	109.9
C3—C4—C5	121.92 (13)	H9A—C9—H9B	108.3
C3—C4—N2	119.08 (13)
O1—C1—C2—C3	−178.37 (14)	N2—C4—C5—C6	179.14 (13)
C6—C1—C2—C3	1.4 (2)	C4—C5—C6—C1	2.8 (2)
O1—C1—C2—N1	4.2 (2)	C4—C5—C6—N3	−177.06 (12)
C6—C1—C2—N1	−175.98 (12)	O1—C1—C6—C5	176.35 (14)
O3—N1—C2—C3	10.33 (19)	C2—C1—C6—C5	−3.5 (2)
O2—N1—C2—C3	−167.99 (13)	O1—C1—C6—N3	−3.80 (19)
O3—N1—C2—C1	−172.10 (13)	C2—C1—C6—N3	176.37 (12)
O2—N1—C2—C1	9.59 (19)	O7—N3—C6—C5	−90.91 (18)
C1—C2—C3—C4	1.0 (2)	O6—N3—C6—C5	93.1 (2)
N1—C2—C3—C4	178.54 (12)	O7—N3—C6—C1	89.23 (18)
C2—C3—C4—C5	−1.9 (2)	O6—N3—C6—C1	−86.80 (19)
C2—C3—C4—N2	179.07 (13)	C9—N4—C7—C7i	55.03 (18)
O4—N2—C4—C3	5.2 (2)	C8—N4—C7—C7i	−66.36 (18)
O5—N2—C4—C3	−175.42 (13)	C7—N4—C8—C9i	56.78 (15)
O4—N2—C4—C5	−173.87 (13)	C9—N4—C8—C9i	−65.17 (13)
O5—N2—C4—C5	5.5 (2)	C7—N4—C9—C8i	−64.33 (15)
C3—C4—C5—C6	0.1 (2)	C8—N4—C9—C8i	57.06 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1	0.93	1.69	2.589 (2)	161
N4—H4A···O2	0.93	2.42	2.954 (2)	117

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O1	0.93	1.69	2.589 (2)	161
N4—H4A⋯O2	0.93	2.42	2.954 (2)	117