The 1:2 adduct N,N-di­methyl­ethyl­enedi­amine-1,4-diium bis(2,4-di­nitro­phenolate)

In the title salt, C₄H₁₄N₂²⁺·2C₆H₃N₂O₅^-, the dication acts as a hydrogen donor with all its N-H bonds involved in hydrogen bonds to the O atoms of the phenolate and nitro groups, and with six of its eight C-H bonds involved in interactions with the O atoms of the nitro groups of the surrounding 2,4-di­nitro­phenolates. The packing structure is stabilized by these hydrogen-bonding interactions.

Key indicators

• Single-crystal X-ray study
• T = 183 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.058
• wR factor = 0.138
• Data-to-parameter ratio = 11.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_353  Alert C Long  N-H Bond (0.87A)     N(6)   -   H(6)   =       1.01 Ang.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

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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).

(I)

Crystal data

C4H14N2^+·2C6H3N2O5^−	F(000) = 952
Mr = 456.38	Dx = 1.527 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.3777 (3) Å	Cell parameters from 3306 reflections
b = 7.3596 (2) Å	θ = 2.9–28.3°
c = 22.0064 (1) Å	µ = 0.13 mm^−1
β = 97.886 (2)°	T = 183 K
V = 1985.71 (7) Å^3	Block, yellow
Z = 4	0.28 × 0.28 × 0.10 mm

Data collection

Siemens SMART CCD area-detector diffractometer	3427 independent reflections
Radiation source: fine-focus sealed tube	1790 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
Detector resolution: 8.33 pixels mm^-1	θmax = 25.0°, θmin = 2.9°
ω scans	h = −14→14
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −8→8
Tmin = 0.965, Tmax = 0.987	l = −26→17
9040 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)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.0449P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.87	(Δ/σ)max < 0.001
3427 reflections	Δρmax = 0.25 e Å^−3
304 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: 0.0120 (13)

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 10 s covered 0.3° in ω. The crystal-to-detector distance was 5 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	0.8426 (2)	0.4659 (4)	0.67139 (12)	0.0607 (9)
O2	0.9524 (2)	0.6303 (4)	0.62746 (12)	0.0544 (8)
O3	0.9231 (2)	0.6909 (4)	0.41268 (12)	0.0520 (8)
O4	0.79282 (19)	0.5594 (4)	0.35321 (11)	0.0450 (8)
O5	0.64990 (19)	0.3831 (4)	0.60616 (10)	0.0422 (7)
O6	0.35296 (19)	0.1963 (4)	0.31157 (11)	0.0511 (8)
O7	0.46995 (19)	0.2267 (4)	0.39199 (11)	0.0476 (8)
O8	0.3867 (3)	0.1096 (4)	0.59010 (12)	0.0696 (10)
O9	0.2509 (3)	−0.0628 (5)	0.60299 (13)	0.0723 (11)
O10	0.17025 (16)	0.0135 (3)	0.31847 (9)	0.0247 (6)
N1	0.8697 (3)	0.5352 (4)	0.62518 (14)	0.0365 (8)
N2	0.8393 (2)	0.5987 (4)	0.40519 (13)	0.0342 (8)
N3	0.3792 (2)	0.1771 (4)	0.36686 (13)	0.0275 (7)
N4	0.3044 (3)	0.0233 (5)	0.56998 (15)	0.0470 (9)
N5	0.6660 (2)	0.2549 (4)	0.71889 (13)	0.0290 (7)
H5B	0.6825	0.3281	0.6853	0.035*
H5A	0.682 (3)	0.325 (5)	0.7566 (16)	0.047 (11)*
H5C	0.711 (3)	0.148 (6)	0.7220 (16)	0.055 (12)*
N6	0.4632 (2)	0.4872 (4)	0.75961 (12)	0.0343 (8)
H6	0.535 (3)	0.489 (5)	0.7877 (18)	0.068 (13)*
C1	0.8053 (3)	0.5052 (5)	0.56617 (14)	0.0242 (8)
C2	0.8505 (3)	0.5606 (4)	0.51506 (15)	0.0257 (8)
H2	0.9189	0.6152	0.5196	0.031*
C3	0.7940 (3)	0.5347 (4)	0.45791 (14)	0.0240 (8)
C4	0.6896 (3)	0.4571 (4)	0.45037 (14)	0.0239 (8)
H4	0.6520	0.4385	0.4113	0.029*
C5	0.6440 (3)	0.4094 (5)	0.50055 (14)	0.0265 (8)
H5	0.5737	0.3619	0.4948	0.032*
C6	0.6979 (3)	0.4284 (5)	0.56168 (15)	0.0268 (8)
C7	0.3052 (3)	0.0949 (4)	0.40386 (14)	0.0217 (8)
C8	0.3371 (3)	0.0940 (4)	0.46648 (15)	0.0268 (8)
H8	0.4042	0.1426	0.4828	0.032*
C9	0.2698 (3)	0.0215 (5)	0.50446 (14)	0.0273 (8)
C10	0.1686 (3)	−0.0506 (5)	0.48069 (15)	0.0322 (9)
H10	0.1230	−0.0990	0.5069	0.039*
C11	0.1368 (3)	−0.0497 (5)	0.41908 (15)	0.0277 (8)
H11	0.0688	−0.0972	0.4041	0.033*
C12	0.2031 (2)	0.0207 (4)	0.37636 (14)	0.0208 (8)
C13	0.5468 (3)	0.2205 (5)	0.71083 (15)	0.0344 (9)
H13A	0.5282	0.1572	0.7466	0.041*
H13B	0.5275	0.1424	0.6755	0.041*
C14	0.4814 (3)	0.3925 (5)	0.70195 (14)	0.0277 (9)
H14A	0.5184	0.4755	0.6774	0.033*
H14B	0.4110	0.3643	0.6788	0.033*
C15	0.3853 (3)	0.3901 (7)	0.79323 (19)	0.0720 (16)
H15A	0.3832	0.4478	0.8322	0.108*
H15B	0.4081	0.2661	0.7996	0.108*
H15C	0.3140	0.3935	0.7698	0.108*
C16	0.4250 (3)	0.6776 (6)	0.74666 (18)	0.0505 (12)
H16A	0.4798	0.7443	0.7291	0.076*
H16B	0.4119	0.7347	0.7842	0.076*
H16C	0.3587	0.6761	0.7183	0.076*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.072 (2)	0.084 (2)	0.0219 (16)	−0.0150 (17)	−0.0115 (14)	−0.0012 (15)
O2	0.0475 (19)	0.059 (2)	0.0493 (18)	−0.0120 (15)	−0.0198 (14)	−0.0128 (14)
O3	0.0389 (17)	0.063 (2)	0.0550 (18)	−0.0244 (15)	0.0087 (13)	0.0092 (15)
O4	0.0360 (16)	0.073 (2)	0.0246 (15)	−0.0043 (13)	−0.0004 (12)	0.0107 (13)
O5	0.0270 (15)	0.074 (2)	0.0253 (15)	0.0087 (13)	0.0039 (11)	0.0041 (13)
O6	0.0356 (16)	0.090 (2)	0.0246 (16)	−0.0257 (15)	−0.0056 (12)	0.0125 (14)
O7	0.0317 (16)	0.061 (2)	0.0456 (17)	−0.0184 (14)	−0.0101 (12)	0.0038 (14)
O8	0.100 (3)	0.064 (2)	0.0346 (18)	−0.0075 (19)	−0.0280 (17)	−0.0052 (15)
O9	0.075 (2)	0.118 (3)	0.0262 (17)	0.013 (2)	0.0142 (15)	0.0082 (17)
O10	0.0220 (13)	0.0348 (15)	0.0157 (13)	−0.0025 (10)	−0.0024 (9)	0.0012 (10)
N1	0.039 (2)	0.037 (2)	0.030 (2)	0.0062 (16)	−0.0066 (15)	−0.0108 (16)
N2	0.0277 (19)	0.043 (2)	0.032 (2)	−0.0006 (15)	0.0061 (15)	0.0100 (15)
N3	0.0214 (17)	0.0283 (18)	0.0309 (18)	−0.0021 (13)	−0.0034 (14)	0.0014 (13)
N4	0.068 (3)	0.047 (2)	0.026 (2)	0.016 (2)	0.0021 (19)	0.0002 (17)
N5	0.0368 (19)	0.028 (2)	0.0206 (17)	0.0089 (15)	0.0000 (13)	−0.0026 (14)
N6	0.0162 (17)	0.069 (3)	0.0175 (16)	0.0037 (16)	0.0014 (13)	−0.0015 (15)
C1	0.0259 (19)	0.026 (2)	0.0189 (19)	0.0082 (16)	−0.0042 (14)	−0.0061 (15)
C2	0.0208 (19)	0.021 (2)	0.033 (2)	0.0012 (15)	−0.0024 (15)	−0.0021 (16)
C3	0.0219 (19)	0.026 (2)	0.0239 (19)	0.0019 (15)	0.0028 (15)	0.0025 (15)
C4	0.0231 (19)	0.027 (2)	0.0197 (19)	0.0012 (15)	−0.0046 (14)	0.0037 (15)
C5	0.0204 (19)	0.038 (2)	0.020 (2)	0.0005 (16)	−0.0021 (15)	0.0023 (15)
C6	0.024 (2)	0.035 (2)	0.023 (2)	0.0095 (16)	0.0065 (16)	−0.0011 (16)
C7	0.0221 (19)	0.019 (2)	0.0227 (19)	−0.0005 (15)	−0.0013 (14)	−0.0013 (14)
C8	0.029 (2)	0.022 (2)	0.026 (2)	0.0034 (16)	−0.0071 (16)	−0.0076 (15)
C9	0.036 (2)	0.028 (2)	0.0166 (19)	0.0056 (17)	−0.0009 (16)	−0.0022 (16)
C10	0.039 (2)	0.037 (2)	0.023 (2)	0.0047 (18)	0.0113 (16)	0.0047 (17)
C11	0.024 (2)	0.030 (2)	0.030 (2)	−0.0040 (16)	0.0046 (15)	0.0006 (16)
C12	0.0213 (18)	0.016 (2)	0.025 (2)	0.0022 (14)	0.0020 (15)	−0.0021 (14)
C13	0.037 (2)	0.035 (2)	0.027 (2)	0.0004 (18)	−0.0112 (16)	0.0023 (17)
C14	0.029 (2)	0.035 (2)	0.0166 (18)	0.0005 (17)	−0.0049 (15)	0.0055 (15)
C15	0.026 (2)	0.138 (5)	0.057 (3)	0.015 (3)	0.023 (2)	0.047 (3)
C16	0.037 (2)	0.063 (3)	0.054 (3)	0.012 (2)	0.013 (2)	−0.017 (2)

Geometric parameters (Å, º)

O1—N1	1.225 (4)	C3—C4	1.402 (4)
O2—N1	1.235 (4)	C4—C5	1.354 (4)
O3—N2	1.232 (3)	C4—H4	0.9300
O4—N2	1.242 (3)	C5—C6	1.424 (4)
O5—C6	1.258 (4)	C5—H5	0.9300
O6—N3	1.224 (3)	C7—C8	1.380 (4)
O7—N3	1.237 (3)	C7—C12	1.432 (4)
O8—N4	1.229 (4)	C8—C9	1.366 (5)
O9—N4	1.225 (4)	C8—H8	0.9300
O10—C12	1.284 (3)	C9—C10	1.395 (5)
N1—C1	1.444 (4)	C10—C11	1.359 (4)
N2—C3	1.435 (4)	C10—H10	0.9300
N3—C7	1.440 (4)	C11—C12	1.427 (4)
N4—C9	1.447 (4)	C11—H11	0.9300
N5—C13	1.484 (4)	C13—C14	1.500 (4)
N5—H5B	0.9599	C13—H13A	0.9700
N5—H5A	0.97 (4)	C13—H13B	0.9700
N5—H5C	0.97 (4)	C14—H14A	0.9700
N6—C15	1.477 (5)	C14—H14B	0.9700
N6—C14	1.492 (4)	C15—H15A	0.9600
N6—C16	1.494 (5)	C15—H15B	0.9600
N6—H6	1.01 (4)	C15—H15C	0.9600
C1—C2	1.384 (4)	C16—H16A	0.9600
C1—C6	1.436 (4)	C16—H16B	0.9600
C2—C3	1.366 (4)	C16—H16C	0.9600
C2—H2	0.9300
O1—N1—O2	121.4 (3)	C8—C7—C12	122.4 (3)
O1—N1—C1	120.2 (3)	C8—C7—N3	116.7 (3)
O2—N1—C1	118.3 (3)	C12—C7—N3	121.0 (3)
O3—N2—O4	121.8 (3)	C9—C8—C7	119.8 (3)
O3—N2—C3	119.2 (3)	C9—C8—H8	120.1
O4—N2—C3	119.0 (3)	C7—C8—H8	120.1
O6—N3—O7	120.8 (3)	C8—C9—C10	120.7 (3)
O6—N3—C7	120.5 (3)	C8—C9—N4	119.0 (3)
O7—N3—C7	118.7 (3)	C10—C9—N4	120.3 (3)
O9—N4—O8	122.8 (4)	C11—C10—C9	119.6 (3)
O9—N4—C9	118.4 (4)	C11—C10—H10	120.2
O8—N4—C9	118.7 (4)	C9—C10—H10	120.2
C13—N5—H5B	108.5	C10—C11—C12	123.1 (3)
C13—N5—H5A	106 (2)	C10—C11—H11	118.5
H5B—N5—H5A	108.8	C12—C11—H11	118.5
C13—N5—H5C	116 (2)	O10—C12—C11	120.4 (3)
H5B—N5—H5C	109.2	O10—C12—C7	125.2 (3)
H5A—N5—H5C	109 (3)	C11—C12—C7	114.4 (3)
C15—N6—C14	112.7 (3)	N5—C13—C14	112.4 (3)
C15—N6—C16	109.7 (3)	N5—C13—H13A	109.1
C14—N6—C16	110.9 (3)	C14—C13—H13A	109.1
C15—N6—H6	106 (2)	N5—C13—H13B	109.1
C14—N6—H6	108 (2)	C14—C13—H13B	109.1
C16—N6—H6	110 (2)	H13A—C13—H13B	107.9
C2—C1—C6	122.2 (3)	N6—C14—C13	115.2 (3)
C2—C1—N1	116.8 (3)	N6—C14—H14A	108.5
C6—C1—N1	120.9 (3)	C13—C14—H14A	108.5
C3—C2—C1	119.7 (3)	N6—C14—H14B	108.5
C3—C2—H2	120.2	C13—C14—H14B	108.5
C1—C2—H2	120.2	H14A—C14—H14B	107.5
C2—C3—C4	120.8 (3)	N6—C15—H15A	109.5
C2—C3—N2	119.4 (3)	N6—C15—H15B	109.5
C4—C3—N2	119.6 (3)	H15A—C15—H15B	109.5
C5—C4—C3	119.3 (3)	N6—C15—H15C	109.5
C5—C4—H4	120.3	H15A—C15—H15C	109.5
C3—C4—H4	120.3	H15B—C15—H15C	109.5
C4—C5—C6	123.4 (3)	N6—C16—H16A	109.5
C4—C5—H5	118.3	N6—C16—H16B	109.5
C6—C5—H5	118.3	H16A—C16—H16B	109.5
O5—C6—C5	119.9 (3)	N6—C16—H16C	109.5
O5—C6—C1	125.6 (3)	H16A—C16—H16C	109.5
C5—C6—C1	114.4 (3)	H16B—C16—H16C	109.5
O1—N1—C1—C2	−169.0 (3)	O6—N3—C7—C12	5.1 (5)
O2—N1—C1—C2	10.2 (5)	O7—N3—C7—C12	−174.5 (3)
O1—N1—C1—C6	13.5 (5)	C12—C7—C8—C9	−0.5 (5)
O2—N1—C1—C6	−167.2 (3)	N3—C7—C8—C9	178.7 (3)
C6—C1—C2—C3	−3.1 (5)	C7—C8—C9—C10	−0.5 (5)
N1—C1—C2—C3	179.5 (3)	C7—C8—C9—N4	−179.5 (3)
C1—C2—C3—C4	1.7 (5)	O9—N4—C9—C8	−170.4 (3)
C1—C2—C3—N2	177.6 (3)	O8—N4—C9—C8	8.9 (5)
O3—N2—C3—C2	−6.9 (5)	O9—N4—C9—C10	10.6 (5)
O4—N2—C3—C2	173.1 (3)	O8—N4—C9—C10	−170.1 (3)
O3—N2—C3—C4	169.1 (3)	C8—C9—C10—C11	0.4 (5)
O4—N2—C3—C4	−10.9 (5)	N4—C9—C10—C11	179.4 (3)
C2—C3—C4—C5	0.8 (5)	C9—C10—C11—C12	0.6 (5)
N2—C3—C4—C5	−175.1 (3)	C10—C11—C12—O10	178.1 (3)
C3—C4—C5—C6	−2.1 (5)	C10—C11—C12—C7	−1.5 (5)
C4—C5—C6—O5	179.2 (3)	C8—C7—C12—O10	−178.1 (3)
C4—C5—C6—C1	0.8 (5)	N3—C7—C12—O10	2.7 (5)
C2—C1—C6—O5	−176.5 (3)	C8—C7—C12—C11	1.4 (4)
N1—C1—C6—O5	0.9 (5)	N3—C7—C12—C11	−177.7 (3)
C2—C1—C6—C5	1.8 (5)	C15—N6—C14—C13	−71.9 (4)
N1—C1—C6—C5	179.1 (3)	C16—N6—C14—C13	164.7 (3)
O6—N3—C7—C8	−174.1 (3)	N5—C13—C14—N6	−84.6 (4)
O7—N3—C7—C8	6.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O6^i	0.97 (4)	2.29 (4)	2.889 (4)	119 (3)
N5—H5A···O10^i	0.97 (4)	1.83 (4)	2.771 (4)	162 (3)
N5—H5B···O1	0.96	2.28	2.985 (4)	129
N5—H5B···O5	0.96	1.78	2.636 (4)	147
N5—H5C···O10^ii	0.96 (4)	2.17 (4)	3.024 (3)	147 (3)
N6—H6···O10^i	1.01 (4)	1.72 (4)	2.708 (3)	166 (3)
C11—H11···O3^iii	0.93	2.41	3.249 (5)	150
C13—H13B···O8	0.97	2.39	3.195 (5)	140
C14—H14A···O5	0.97	2.50	3.163 (4)	125
C14—H14B···O4^iv	0.97	2.59	3.462 (4)	150
C15—H15A···O9^v	0.96	2.33	3.039 (5)	130
C15—H15B···O2^vi	0.96	2.41	3.127 (5)	131
C16—H16A···O6^iv	0.96	2.41	3.320 (5)	159

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