Diethyl­aminium 3,5-dinitro­salicylate at 130 K

The low-temperature (130 K) crystal structure of the 1:1 proton-transfer compound of 3,5-dinitro­salicylic acid (DNSA) with diethyl­amine, viz. diethyl­aminium 3,5-dinitro­salicylate, C₄H₁₂N⁺·C₇H₃N₂O₇⁻, shows the presence of conformationally extended diethyl­aminium cations in which both H atoms of the aminium centres participate in three-centre hydrogen-bonding associations [one R₁²(4) and the other R₁²(6)] with carbox­yl, phenol and nitro O-atom acceptors of two separate DNSA anion species [N...O = 2.813 (3)–3.320 (3) Å]. These result in 12-membered cyclic R₆⁴(12) associations linking the two sets of hetero-species into discrete centrosymmetric tetra­mers which have no significant peripheral extensions.

Key indicators

• Single-crystal X-ray study
• T = 130 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.065
• wR factor = 0.195
• Data-to-parameter ratio = 11.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O51    -   N5      ..       5.91 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        N11
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O72    -   H72    ...       1.05 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Diethylaminium 3,5-dinitrosalicylate

Crystal data

C4H12N^+·C7H3N2O7^−	Z = 2
Mr = 301.26	F(000) = 316
Triclinic, P1	Dx = 1.441 Mg m^−3
Hall symbol: -P 1	Melting point = 431.8–433.6 K
a = 7.329 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.168 (5) Å	Cell parameters from 1831 reflections
c = 10.660 (5) Å	θ = 2.3–27.5°
α = 67.126 (5)°	µ = 0.12 mm^−1
β = 80.663 (8)°	T = 130 K
γ = 71.700 (8)°	Block, yellow
V = 694.1 (5) Å^3	0.40 × 0.40 × 0.35 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1886 reflections with F^2 > 2σ(F^2)
Radiation source: sealed tube	Rint = 0.071
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
φ and ω scans	h = −6→8
3502 measured reflections	k = −8→12
2395 independent reflections	l = −11→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.195	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.119P)^2 + 0.1544P] where P = (Fo^2 + 2Fc^2)/3
2395 reflections	(Δ/σ)max = 0.002
204 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O2	0.2468 (3)	0.25042 (18)	0.39944 (16)	0.0475 (6)
O31	0.1139 (4)	0.4801 (2)	0.1764 (2)	0.0857 (9)
O32	0.0404 (4)	0.6972 (2)	0.1781 (2)	0.0687 (8)
O51	0.2144 (3)	0.8094 (2)	0.5220 (2)	0.0688 (8)
O52	0.3207 (3)	0.6354 (3)	0.7101 (2)	0.0699 (8)
O71	0.4588 (3)	0.1159 (2)	0.77125 (18)	0.0598 (7)
O72	0.3836 (3)	0.0539 (2)	0.61495 (19)	0.0615 (7)
N3	0.1102 (3)	0.5648 (2)	0.2317 (2)	0.0418 (6)
N5	0.2633 (3)	0.6788 (3)	0.5958 (3)	0.0531 (9)
C1	0.3190 (3)	0.3118 (3)	0.5736 (2)	0.0367 (7)
C2	0.2502 (3)	0.3509 (2)	0.4410 (2)	0.0357 (7)
C3	0.1875 (3)	0.5075 (2)	0.3660 (2)	0.0348 (7)
C4	0.1894 (3)	0.6125 (2)	0.4165 (2)	0.0386 (7)
C5	0.2566 (3)	0.5668 (3)	0.5445 (2)	0.0395 (7)
C6	0.3217 (3)	0.4184 (3)	0.6220 (2)	0.0386 (7)
C7	0.3916 (4)	0.1535 (3)	0.6614 (2)	0.0444 (8)
N11	0.2764 (3)	0.1749 (2)	0.16804 (19)	0.0441 (7)
C21	0.0851 (5)	0.1457 (4)	0.1904 (4)	0.0720 (11)
C22	0.3290 (4)	0.2633 (3)	0.0272 (3)	0.0530 (9)
C31	0.0758 (6)	0.0362 (4)	0.1367 (4)	0.0808 (14)
C32	0.5211 (5)	0.2871 (5)	0.0194 (4)	0.0827 (16)
H72	0.335 (6)	0.120 (4)	0.516 (4)	0.097 (12)*
H4	0.145000	0.715300	0.363800	0.0460*
H6	0.368800	0.389400	0.709400	0.0460*
H11A	0.281 (6)	0.223 (4)	0.224 (4)	0.055 (13)*
H11B	0.369 (6)	0.085 (5)	0.195 (4)	0.060 (12)*
H21A	0.052000	0.110600	0.289500	0.0870*
H21B	−0.012700	0.240100	0.146900	0.0870*
H22A	0.231200	0.360700	−0.003800	0.0640*
H22B	0.330400	0.210900	−0.034400	0.0640*
H31A	0.094300	0.074800	0.037200	0.1210*
H31B	−0.050200	0.016300	0.161700	0.1210*
H31C	0.177100	−0.056000	0.175200	0.1210*
H32A	0.519900	0.339100	0.080200	0.1240*
H32B	0.551500	0.347000	−0.074500	0.1240*
H32C	0.618700	0.190900	0.047200	0.1240*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0685 (12)	0.0354 (9)	0.0370 (9)	−0.0103 (8)	−0.0058 (8)	−0.0133 (7)
O31	0.144 (2)	0.0497 (12)	0.0535 (12)	0.0115 (13)	−0.0425 (14)	−0.0233 (10)
O32	0.1033 (17)	0.0376 (11)	0.0499 (12)	−0.0121 (10)	−0.0196 (11)	0.0007 (9)
O51	0.0839 (15)	0.0454 (12)	0.0846 (16)	−0.0196 (11)	0.0078 (12)	−0.0345 (11)
O52	0.0729 (14)	0.0814 (15)	0.0752 (15)	−0.0146 (11)	−0.0077 (12)	−0.0525 (13)
O71	0.0755 (14)	0.0520 (11)	0.0379 (10)	0.0101 (10)	−0.0146 (9)	−0.0186 (8)
O72	0.0977 (16)	0.0359 (10)	0.0420 (10)	−0.0046 (10)	−0.0145 (10)	−0.0112 (8)
N3	0.0443 (11)	0.0369 (11)	0.0349 (10)	−0.0058 (9)	0.0023 (8)	−0.0089 (9)
N5	0.0424 (12)	0.0600 (16)	0.0708 (16)	−0.0157 (10)	0.0107 (11)	−0.0420 (13)
C1	0.0332 (11)	0.0406 (13)	0.0315 (12)	−0.0034 (10)	0.0018 (9)	−0.0145 (10)
C2	0.0355 (11)	0.0371 (12)	0.0342 (12)	−0.0087 (9)	0.0040 (9)	−0.0156 (10)
C3	0.0304 (11)	0.0364 (12)	0.0319 (11)	−0.0069 (9)	0.0029 (8)	−0.0099 (9)
C4	0.0332 (11)	0.0328 (12)	0.0450 (13)	−0.0086 (9)	0.0072 (10)	−0.0128 (10)
C5	0.0306 (11)	0.0447 (13)	0.0491 (14)	−0.0096 (10)	0.0068 (10)	−0.0271 (11)
C6	0.0309 (11)	0.0489 (14)	0.0365 (12)	−0.0072 (10)	0.0024 (9)	−0.0203 (11)
C7	0.0494 (14)	0.0438 (14)	0.0318 (12)	−0.0003 (11)	−0.0004 (10)	−0.0155 (10)
N11	0.0550 (12)	0.0370 (11)	0.0381 (11)	−0.0018 (9)	−0.0074 (9)	−0.0177 (9)
C21	0.0630 (19)	0.063 (2)	0.089 (2)	−0.0134 (15)	0.0108 (17)	−0.0349 (18)
C22	0.0675 (17)	0.0510 (15)	0.0371 (13)	−0.0085 (13)	−0.0031 (12)	−0.0182 (11)
C31	0.096 (3)	0.060 (2)	0.083 (2)	−0.0269 (19)	−0.013 (2)	−0.0145 (17)
C32	0.086 (3)	0.097 (3)	0.070 (2)	−0.041 (2)	0.0097 (19)	−0.028 (2)

Geometric parameters (Å, º)

O2—C2	1.270 (3)	C3—C4	1.374 (3)
O31—N3	1.210 (3)	C4—C5	1.379 (3)
O32—N3	1.210 (3)	C5—C6	1.376 (4)
O51—N5	1.221 (4)	C4—H4	0.9504
O52—N5	1.220 (4)	C6—H6	0.9492
O71—C7	1.217 (3)	C21—C31	1.459 (6)
O72—C7	1.308 (4)	C22—C32	1.486 (5)
O72—H72	1.05 (4)	C21—H21A	0.9901
N3—C3	1.455 (3)	C21—H21B	0.9899
N5—C5	1.458 (4)	C22—H22A	0.9902
N11—C22	1.480 (4)	C22—H22B	0.9907
N11—C21	1.486 (5)	C31—H31A	0.9801
N11—H11A	0.92 (4)	C31—H31B	0.9799
N11—H11B	0.92 (5)	C31—H31C	0.9804
C1—C7	1.484 (4)	C32—H32A	0.9805
C1—C6	1.376 (4)	C32—H32B	0.9805
C1—C2	1.442 (3)	C32—H32C	0.9800
C2—C3	1.434 (3)
C7—O72—H72	102 (2)	O71—C7—O72	120.6 (3)
O31—N3—O32	121.1 (2)	C3—C4—H4	120.37
O32—N3—C3	118.9 (2)	C5—C4—H4	120.46
O31—N3—C3	119.9 (2)	C1—C6—H6	119.79
O51—N5—O52	123.9 (3)	C5—C6—H6	119.78
O51—N5—C5	118.6 (3)	N11—C21—C31	113.9 (3)
O52—N5—C5	117.5 (3)	N11—C22—C32	111.1 (3)
C21—N11—C22	116.6 (2)	N11—C21—H21A	108.75
C21—N11—H11B	108 (3)	N11—C21—H21B	108.79
C21—N11—H11A	108 (3)	C31—C21—H21A	108.79
H11A—N11—H11B	107 (4)	C31—C21—H21B	108.81
C22—N11—H11A	108 (3)	H21A—C21—H21B	107.67
C22—N11—H11B	108 (3)	N11—C22—H22A	109.45
C2—C1—C7	120.3 (2)	N11—C22—H22B	109.40
C2—C1—C6	121.6 (2)	C32—C22—H22A	109.35
C6—C1—C7	118.1 (2)	C32—C22—H22B	109.41
C1—C2—C3	114.5 (2)	H22A—C22—H22B	108.02
O2—C2—C3	125.09 (19)	C21—C31—H31A	109.45
O2—C2—C1	120.4 (2)	C21—C31—H31B	109.42
N3—C3—C4	115.75 (18)	C21—C31—H31C	109.45
N3—C3—C2	121.12 (19)	H31A—C31—H31B	109.52
C2—C3—C4	123.09 (19)	H31A—C31—H31C	109.49
C3—C4—C5	119.2 (2)	H31B—C31—H31C	109.50
N5—C5—C6	120.0 (2)	C22—C32—H32A	109.52
N5—C5—C4	118.8 (2)	C22—C32—H32B	109.44
C4—C5—C6	121.2 (2)	C22—C32—H32C	109.46
C1—C6—C5	120.4 (2)	H32A—C32—H32B	109.49
O72—C7—C1	117.1 (2)	H32A—C32—H32C	109.50
O71—C7—C1	122.3 (3)	H32B—C32—H32C	109.41
O31—N3—C3—C4	175.6 (2)	C7—C1—C2—O2	1.7 (4)
O32—N3—C3—C2	172.3 (2)	C2—C1—C7—O71	176.6 (3)
O31—N3—C3—C2	−6.6 (4)	C7—C1—C2—C3	−178.9 (2)
O32—N3—C3—C4	−5.5 (3)	C2—C1—C7—O72	−2.3 (4)
O52—N5—C5—C6	−2.8 (4)	C6—C1—C7—O71	−2.7 (4)
O52—N5—C5—C4	179.0 (2)	O2—C2—C3—C4	178.3 (2)
O51—N5—C5—C6	176.1 (2)	O2—C2—C3—N3	0.7 (4)
O51—N5—C5—C4	−2.1 (4)	C1—C2—C3—C4	−1.0 (3)
C21—N11—C22—C32	178.8 (3)	C1—C2—C3—N3	−178.6 (2)
C22—N11—C21—C31	73.6 (4)	C2—C3—C4—C5	0.8 (3)
C2—C1—C6—C5	0.5 (4)	N3—C3—C4—C5	178.6 (2)
C6—C1—C7—O72	178.4 (2)	C3—C4—C5—N5	178.3 (2)
C6—C1—C2—O2	−179.1 (2)	C3—C4—C5—C6	0.1 (4)
C7—C1—C6—C5	179.8 (2)	C4—C5—C6—C1	−0.7 (4)
C6—C1—C2—C3	0.3 (3)	N5—C5—C6—C1	−178.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O72—H72···O2	1.05 (4)	1.47 (4)	2.489 (3)	161 (4)
N11—H11A···O2	0.92 (4)	1.96 (4)	2.813 (3)	154 (4)
N11—H11A···O31	0.92 (4)	2.40 (4)	2.986 (3)	122 (3)
N11—H11B···O71^i	0.92 (5)	1.96 (5)	2.871 (3)	169 (4)
N11—H11B···O72^i	0.92 (5)	2.60 (4)	3.320 (3)	136 (4)
C22—H22A···O31	0.99	2.55	3.099 (4)	115
C22—H22B···O71^ii	0.99	2.54	3.469 (4)	156

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