1,4-Di­aza­bi­cyclo­[2.2.2]­octanium 2,4-di­nitro­phenolate

In the title salt, C₆H₁₃N₂⁺·C₆H₃N₂O₅⁻, the cation acts as a donor for the bifurcated intermolecular N—H...O hydrogen bonding interactions with the O atoms of the phenolate and one of the nitro groups of the 2,4-di­nitro­phenolate. The crystal packing structure is built from molecular ribbons of 2,4-di­nitro­phenolates parallel to the c axis, with the cation linking them by four intermolecular C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 203 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.054
• wR factor = 0.131
• Data-to-parameter ratio = 12.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

1,4-Diazabicyclo[2.2.2]octanium 2,4-dinitrophenolate

Crystal data

C6H13N2^+·C6H3N2O5^−	F(000) = 1248
Mr = 296.29	Dx = 1.472 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.6934 (4) Å	Cell parameters from 4593 reflections
b = 6.4529 (2) Å	θ = 3.3–28.3°
c = 19.1830 (5) Å	µ = 0.12 mm^−1
β = 114.247 (1)°	T = 203 K
V = 2674.2 (1) Å^3	Block, yellow
Z = 8	0.38 × 0.32 × 0.18 mm

Data collection

Siemens SMART CCD area-detector diffractometer	3218 independent reflections
Radiation source: fine-focus sealed tube	1908 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 3.3°
ω scans	h = −31→22
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −8→8
Tmin = 0.957, Tmax = 0.979	l = −23→25
7527 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
S = 0.83	(Δ/σ)max < 0.001
3218 reflections	Δρmax = 0.31 e Å^−3
255 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0057 (7)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different φ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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
O1	0.58574 (6)	0.2148 (2)	0.35135 (7)	0.0321 (3)
O2	0.68051 (7)	0.2464 (3)	0.49008 (9)	0.0491 (4)
O3	0.66161 (7)	0.2203 (3)	0.58905 (8)	0.0576 (5)
O4	0.46233 (8)	0.2815 (2)	0.58209 (9)	0.0450 (4)
O5	0.38135 (8)	0.2617 (3)	0.47485 (11)	0.0548 (5)
N3	0.64354 (7)	0.2343 (2)	0.51945 (9)	0.0280 (4)
N4	0.43802 (8)	0.2637 (2)	0.51176 (11)	0.0330 (4)
C7	0.55361 (8)	0.2205 (2)	0.39046 (9)	0.0213 (4)
C8	0.57792 (7)	0.2348 (2)	0.47266 (9)	0.0185 (4)
C9	0.53986 (8)	0.2490 (2)	0.51128 (10)	0.0203 (4)
C10	0.47674 (8)	0.2462 (2)	0.47097 (10)	0.0221 (4)
C11	0.45001 (9)	0.2236 (3)	0.39123 (11)	0.0276 (4)
C12	0.48719 (9)	0.2099 (3)	0.35305 (11)	0.0266 (4)
H9	0.5566 (9)	0.265 (3)	0.5642 (12)	0.032 (5)*
H11	0.4071 (10)	0.211 (3)	0.3667 (11)	0.035 (6)*
H12	0.4715 (9)	0.192 (3)	0.2992 (12)	0.029 (5)*
N2	0.70352 (8)	0.8253 (2)	0.29971 (9)	0.0314 (4)
N1	0.65687 (7)	0.5294 (2)	0.34453 (8)	0.0244 (4)
C6	0.72565 (12)	0.6282 (4)	0.28377 (15)	0.0415 (6)
C5	0.69363 (10)	0.4447 (3)	0.30379 (12)	0.0315 (5)
C4	0.72097 (13)	0.8416 (4)	0.38215 (12)	0.0406 (6)
C3	0.69868 (10)	0.6522 (3)	0.41216 (10)	0.0312 (5)
C2	0.63628 (11)	0.8327 (3)	0.26148 (12)	0.0371 (5)
C1	0.60612 (9)	0.6663 (4)	0.29156 (13)	0.0349 (5)
H6A	0.7171 (11)	0.618 (4)	0.2322 (14)	0.058 (7)*
H6B	0.7754 (15)	0.613 (5)	0.3194 (16)	0.097 (10)*
H5A	0.6642 (11)	0.375 (4)	0.2609 (13)	0.053 (7)*
H5B	0.7264 (11)	0.351 (3)	0.3416 (12)	0.045 (6)*
H4A	0.7015 (11)	0.976 (4)	0.3895 (13)	0.058 (7)*
H4B	0.7636 (16)	0.842 (4)	0.4022 (16)	0.083 (10)*
H3A	0.6742 (12)	0.690 (3)	0.4419 (14)	0.055 (7)*
H3B	0.7320 (12)	0.557 (4)	0.4417 (13)	0.063 (7)*
H2A	0.6235 (11)	0.983 (4)	0.2713 (12)	0.059 (7)*
H2B	0.6267 (11)	0.810 (3)	0.2091 (14)	0.053 (7)*
H1A	0.5844 (13)	0.719 (4)	0.3250 (15)	0.066 (8)*
H1B	0.5785 (11)	0.579 (4)	0.2516 (13)	0.057 (7)*
H1N1	0.6332 (11)	0.416 (4)	0.3555 (12)	0.057 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0347 (8)	0.0383 (8)	0.0304 (7)	−0.0129 (6)	0.0205 (6)	−0.0063 (6)
O2	0.0207 (7)	0.0819 (12)	0.0471 (9)	−0.0017 (7)	0.0163 (7)	0.0097 (8)
O3	0.0320 (9)	0.1068 (14)	0.0234 (7)	−0.0008 (9)	0.0005 (6)	0.0050 (8)
O4	0.0687 (12)	0.0349 (8)	0.0531 (10)	0.0032 (7)	0.0468 (9)	0.0014 (7)
O5	0.0323 (9)	0.0557 (10)	0.0895 (13)	0.0058 (8)	0.0385 (9)	0.0000 (8)
N3	0.0210 (8)	0.0312 (9)	0.0294 (8)	−0.0012 (7)	0.0080 (7)	0.0027 (6)
N4	0.0401 (10)	0.0166 (8)	0.0572 (12)	0.0019 (7)	0.0352 (9)	0.0018 (7)
C7	0.0269 (9)	0.0148 (8)	0.0240 (9)	−0.0043 (7)	0.0121 (7)	−0.0007 (6)
C8	0.0161 (8)	0.0153 (8)	0.0231 (8)	−0.0002 (6)	0.0071 (7)	0.0015 (6)
C9	0.0292 (10)	0.0122 (8)	0.0212 (9)	−0.0004 (7)	0.0122 (7)	0.0011 (6)
C10	0.0243 (9)	0.0117 (8)	0.0366 (10)	0.0014 (7)	0.0188 (8)	0.0011 (7)
C11	0.0177 (9)	0.0237 (9)	0.0372 (10)	−0.0005 (8)	0.0071 (8)	0.0033 (8)
C12	0.0270 (10)	0.0267 (10)	0.0228 (9)	−0.0052 (8)	0.0070 (7)	−0.0003 (7)
N2	0.0373 (10)	0.0283 (9)	0.0343 (9)	−0.0004 (7)	0.0206 (8)	0.0063 (7)
N1	0.0223 (8)	0.0265 (8)	0.0275 (8)	−0.0028 (7)	0.0134 (6)	0.0017 (6)
C6	0.0493 (15)	0.0413 (13)	0.0518 (14)	0.0103 (11)	0.0388 (12)	0.0090 (10)
C5	0.0307 (11)	0.0269 (10)	0.0392 (11)	0.0036 (9)	0.0168 (9)	−0.0051 (9)
C4	0.0446 (14)	0.0381 (13)	0.0344 (11)	−0.0135 (11)	0.0112 (10)	−0.0016 (9)
C3	0.0327 (11)	0.0399 (12)	0.0203 (9)	−0.0037 (9)	0.0103 (8)	−0.0010 (8)
C2	0.0434 (13)	0.0372 (12)	0.0296 (11)	0.0110 (10)	0.0138 (9)	0.0085 (9)
C1	0.0198 (10)	0.0455 (13)	0.0372 (11)	0.0081 (9)	0.0094 (9)	−0.0005 (10)

Geometric parameters (Å, º)

O1—C7	1.270 (2)	N1—C5	1.492 (2)
O2—N3	1.223 (2)	N1—C3	1.496 (2)
O3—N3	1.227 (2)	N1—C1	1.502 (2)
O4—N4	1.236 (2)	N1—H1N1	1.00 (3)
O5—N4	1.234 (2)	C2—C1	1.528 (3)
N3—C8	1.441 (2)	C4—C3	1.534 (3)
N4—C10	1.434 (2)	C6—C5	1.538 (3)
C7—C12	1.438 (3)	C6—H6A	0.93 (2)
C7—C8	1.442 (2)	C6—H6B	1.10 (3)
C8—C9	1.385 (2)	C5—H5A	0.95 (2)
C9—C10	1.373 (3)	C5—H5B	1.02 (2)
C9—H9	0.93 (2)	C4—H4A	1.02 (3)
C10—C11	1.402 (3)	C4—H4B	0.92 (3)
C11—C12	1.360 (3)	C3—H3A	1.00 (3)
C11—H11	0.93 (2)	C3—H3B	0.98 (3)
C12—H12	0.950 (19)	C2—H2A	1.06 (2)
N2—C6	1.455 (3)	C2—H2B	0.95 (2)
N2—C2	1.456 (3)	C1—H1A	1.03 (3)
N2—C4	1.465 (3)	C1—H1B	0.96 (2)
O2—N3—O3	120.67 (16)	C5—C6—H6A	107.4 (16)
O2—N3—C8	120.43 (15)	N2—C6—H6B	109.4 (16)
O3—N3—C8	118.90 (16)	C5—C6—H6B	107.0 (16)
O5—N4—O4	122.47 (18)	H6A—C6—H6B	111 (2)
O5—N4—C10	118.36 (18)	N1—C5—C6	107.63 (16)
O4—N4—C10	119.16 (17)	N1—C5—H5A	104.5 (14)
O1—C7—C12	120.15 (16)	C6—C5—H5A	114.4 (14)
O1—C7—C8	125.48 (16)	N1—C5—H5B	106.4 (13)
C12—C7—C8	114.36 (16)	C6—C5—H5B	109.0 (13)
C9—C8—N3	116.09 (15)	H5A—C5—H5B	114.3 (19)
C9—C8—C7	122.24 (16)	N2—C4—C3	111.08 (17)
N3—C8—C7	121.68 (16)	N2—C4—H4A	105.5 (13)
C10—C9—C8	119.71 (16)	C3—C4—H4A	112.4 (14)
C10—C9—H9	119.5 (12)	N2—C4—H4B	103.1 (18)
C8—C9—H9	120.7 (12)	C3—C4—H4B	109.3 (18)
C9—C10—C11	121.02 (17)	H4A—C4—H4B	115 (2)
C9—C10—N4	118.99 (17)	N1—C3—C4	107.69 (15)
C11—C10—N4	119.98 (17)	N1—C3—H3A	107.0 (14)
C12—C11—C10	119.45 (17)	C4—C3—H3A	113.0 (13)
C12—C11—H11	122.4 (12)	N1—C3—H3B	104.9 (14)
C10—C11—H11	118.0 (12)	C4—C3—H3B	113.5 (15)
C11—C12—C7	123.10 (17)	H3A—C3—H3B	110.2 (18)
C11—C12—H12	122.9 (12)	N2—C2—C1	111.81 (16)
C7—C12—H12	114.0 (12)	N2—C2—H2A	106.0 (13)
C6—N2—C2	109.70 (17)	C1—C2—H2A	111.4 (13)
C6—N2—C4	108.87 (18)	N2—C2—H2B	105.4 (15)
C2—N2—C4	107.87 (18)	C1—C2—H2B	110.2 (14)
C5—N1—C3	109.11 (15)	H2A—C2—H2B	111.9 (19)
C5—N1—C1	109.78 (15)	N1—C1—C2	107.47 (16)
C3—N1—C1	109.65 (16)	N1—C1—H1A	103.7 (14)
C5—N1—H1N1	109.9 (14)	C2—C1—H1A	115.8 (14)
C3—N1—H1N1	115.8 (13)	N1—C1—H1B	106.7 (14)
C1—N1—H1N1	102.3 (14)	C2—C1—H1B	112.5 (13)
N2—C6—C5	111.29 (17)	H1A—C1—H1B	110 (2)
N2—C6—H6A	110.3 (16)
O2—N3—C8—C9	−171.51 (16)	C10—C11—C12—C7	−0.9 (3)
O3—N3—C8—C9	8.9 (2)	O1—C7—C12—C11	−177.27 (17)
O2—N3—C8—C7	8.7 (3)	C8—C7—C12—C11	3.4 (3)
O3—N3—C8—C7	−170.88 (16)	C2—N2—C6—C5	−53.5 (2)
O1—C7—C8—C9	177.25 (16)	C4—N2—C6—C5	64.3 (2)
C12—C7—C8—C9	−3.5 (2)	C3—N1—C5—C6	−55.6 (2)
O1—C7—C8—N3	−3.0 (3)	C1—N1—C5—C6	64.6 (2)
C12—C7—C8—N3	176.26 (15)	N2—C6—C5—N1	−8.5 (3)
N3—C8—C9—C10	−178.70 (14)	C6—N2—C4—C3	−53.6 (3)
C7—C8—C9—C10	1.1 (2)	C2—N2—C4—C3	65.4 (2)
C8—C9—C10—C11	1.7 (2)	C5—N1—C3—C4	65.8 (2)
C8—C9—C10—N4	−179.23 (14)	C1—N1—C3—C4	−54.5 (2)
O5—N4—C10—C9	179.78 (15)	N2—C4—C3—N1	−9.5 (3)
O4—N4—C10—C9	0.3 (2)	C6—N2—C2—C1	63.1 (2)
O5—N4—C10—C11	−1.2 (2)	C4—N2—C2—C1	−55.3 (2)
O4—N4—C10—C11	179.31 (15)	C5—N1—C1—C2	−55.7 (2)
C9—C10—C11—C12	−1.8 (3)	C3—N1—C1—C2	64.2 (2)
N4—C10—C11—C12	179.15 (16)	N2—C2—C1—N1	−7.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···O1	1.00 (3)	1.70 (3)	2.676 (2)	166 (2)
N1—H11N···O2	1.00 (3)	2.60 (2)	3.187 (2)	118 (2)
C1—H1A···O4^i	1.03 (3)	2.45 (3)	3.442 (3)	160 (2)
C2—H2A···O1^ii	1.06 (3)	2.55 (3)	3.490 (3)	147 (2)
C3—H3A···O5^i	1.00 (3)	2.47 (3)	3.461 (3)	172 (2)
C5—H5B···O3^iii	1.02 (2)	2.47 (3)	3.366 (3)	146 (2)

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