Morpholinium styphnate

In the title mol­ecular salt (systematic name: morpholinium 3-hy­droxy-2,4,6-trinitro­phenolate), C₄H₁₀NO⁺·C₆H₂N₃O₈⁻, two of the nitro groups of the anion are close to parallel with the plane of the benzene ring [dihedral angles = 3.46 (9) and 11.60 (10)°] and one is almost perpendicular [dihedral angle = 82.23 (8)°]. An intra­molecular O—H...O hydrogen bond occurs in the anion. The morpholinium cation has a slightly distorted chair conformation. In the crystal, the components are linked by simple N—H...O and trifurcated N—H...(O,O,O) hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.050
• wR factor = 0.157
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT919_ALERT_3_B Reflection(s) # Likely Affected by the Beamstop           1

Alert level C
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      0.769
            Test value =      0.600
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.03
PLAT097_ALERT_2_C Large Reported Max.  (Positive) Residual Density       0.77 eA-3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C4 H10 N O
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         10

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C10 H12 N4 O9
            Atom count from _chemical_formula_moiety:C10 H12 N1 O9
PLAT153_ALERT_1_G The su's on the Cell Axes   are Equal (x 100000)        500 Ang.
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        500 Deg.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

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

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Picric acid (1-hydroxy – 2,4,6- trinitrobenzene) forms 1:1 donor –acceptor adducts with amines and in these adducts, the main stabilizing factor is the proton transfer from OH of nitro compound to the nitrogen atom of amine (Radha et al.,1987). Unlike picric acid, styphnic acid (2,4,6-trinitro -1,3-benzene diol) contains two phenolic OH groups and hence the type of adduct formation with amines and the mode of interaction are to be envisaged. This necessitates the synthesis of the title molecule from styphnic acid and morpholine (tetrahydro – 1,4-oxazine). Single crystal X-ray analysis data clearly indicate that 1:1 adduct (Scheme 1)is formed from styphnic acid and morpholine and the main contributing factor for the formation of the adduct is the proton transfer from phenolic OH of styphnic acid to the nitrogen atom of morpholine. Hydrogen bond (N—H···O) is noticed between cation and anion moieties. Intramolecular hydrogen bond [O—H···O; R₁¹(6) motif] is also observed. Puckering parameters[(q2 = 0.0243(0.0017), q3=0.5764 (0.0019), φ2=-175.98(5.69), QT=0.5770(0.0019);θ2=2.41(0.17)] of the cation moiety (morpholinium ion) indicate that it has slightly distorted chair conformation.

Related literature

For related molecular salts, see: Radha et al. (1987).

S2. Experimental

Styphnic acid (2.45 g, 0.01 mol) was dissolved in the minimum quantity of ethanol. Morpholine(0.90 g, 0.01 mol) dissolved in the minimum amount of ethanol was added to styphnic acid solution. The mixture was stirred well for 3 h and kept as such for another 6 h. The mixture was then poured into ice cold water with stirring. The adduct formed was filtered and washed first with water and then with alcohol and dried. The dried adduct was washed several times with ether and recrystallized from ethanol (yield 70–75% mp.481–483 K). Yellow prisms of (I) were obtained by slow evaporation of ethanol at room temperature. The same product was obtained when styphnic acid (0.01 mol) was mixed with excess morpholine (0.03 mol).

S3. Refinement

The highset difference peak is 0.90Å from O4.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I) showing 50% displecement ellipsoids.
	Fig. 2. The hydrogen bonding pattern
	Fig. 3. The packing view of the adduct

morpholinium 3-hydroxy-2,4,6-trinitrophenolate

Crystal data

C4H10NO^+·C6H2N3O8^−	Z = 2
Mr = 332.24	F(000) = 344
Triclinic, P1	Dx = 1.637 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.680 (5) Å	Cell parameters from 5851 reflections
b = 7.973 (5) Å	θ = 1.8–29.8°
c = 11.852 (5) Å	µ = 0.15 mm^−1
α = 94.785 (5)°	T = 293 K
β = 99.016 (5)°	Prism, yellow
γ = 108.188 (5)°	0.30 × 0.16 × 0.16 mm
V = 674.1 (7) Å^3

Data collection

Bruker Kappa APEXII CCD diffractometer	3841 independent reflections
Radiation source: fine-focus sealed tube	2944 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω and φ scan	θmax = 29.8°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→10
Tmin = 0.957, Tmax = 0.977	k = −11→11
16214 measured reflections	l = −16→16

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.157	w = 1/[σ^2(Fo^2) + (0.0867P)^2 + 0.1583P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
3841 reflections	Δρmax = 0.77 e Å^−3
225 parameters	Δρmin = −0.38 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.049 (7)

Special details

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
C1	0.48003 (18)	0.27015 (18)	−0.13460 (12)	0.0293 (3)
C2	0.31234 (18)	0.11938 (18)	−0.14972 (11)	0.0287 (3)
C3	0.24207 (17)	0.02930 (17)	−0.06486 (12)	0.0270 (3)
C4	0.33875 (18)	0.09746 (17)	0.05024 (11)	0.0274 (3)
C5	0.49948 (18)	0.24441 (18)	0.07302 (12)	0.0288 (3)
C6	0.57105 (17)	0.32628 (17)	−0.01487 (12)	0.0278 (3)
C7	0.7665 (3)	0.2429 (2)	−0.41273 (15)	0.0457 (4)
H7A	0.7022	0.1253	−0.3954	0.055*
H7B	0.8644	0.2344	−0.4533	0.055*
C8	0.6313 (3)	0.3086 (3)	−0.48707 (15)	0.0497 (4)
H8A	0.5789	0.2278	−0.5589	0.060*
H8B	0.5298	0.3097	−0.4479	0.060*
C9	0.7903 (3)	0.6028 (3)	−0.40700 (17)	0.0536 (5)
H9A	0.6880	0.6021	−0.3681	0.064*
H9B	0.8454	0.7225	−0.4244	0.064*
C10	0.9345 (2)	0.5533 (2)	−0.32858 (15)	0.0453 (4)
H10A	1.0405	0.5600	−0.3652	0.054*
H10B	0.9784	0.6355	−0.2571	0.054*
N1	0.74511 (16)	0.47391 (16)	0.01785 (11)	0.0332 (3)
N2	0.21517 (18)	0.0548 (2)	−0.26913 (11)	0.0398 (3)
N3	0.27441 (17)	0.01490 (17)	0.14458 (11)	0.0352 (3)
N4	0.84911 (19)	0.36922 (19)	−0.30416 (11)	0.0373 (3)
O1	0.81876 (17)	0.54823 (17)	−0.05681 (12)	0.0544 (4)
O2	0.81128 (17)	0.52044 (18)	0.12078 (11)	0.0533 (3)
O3	0.1114 (3)	0.1265 (3)	−0.31268 (14)	0.0847 (6)
O4	0.2437 (3)	−0.0695 (3)	−0.31820 (14)	0.0838 (6)
O5	0.14855 (16)	−0.13353 (15)	0.12339 (10)	0.0440 (3)
O6	0.3436 (2)	0.0883 (2)	0.24304 (10)	0.0587 (4)
O7	0.53339 (16)	0.33703 (18)	−0.21939 (10)	0.0463 (3)
O8	0.08817 (14)	−0.11441 (14)	−0.09399 (10)	0.0371 (3)
O9	0.7206 (2)	0.4823 (2)	−0.51108 (10)	0.0534 (3)
H4A	0.762 (3)	0.371 (3)	−0.2657 (19)	0.053 (6)*
H4B	0.931 (3)	0.333 (3)	−0.2646 (18)	0.047 (5)*
H5	0.562 (3)	0.285 (3)	0.1470 (19)	0.048 (5)*
H8	0.079 (4)	−0.160 (3)	−0.026 (2)	0.069 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0251 (6)	0.0320 (6)	0.0319 (7)	0.0093 (5)	0.0077 (5)	0.0079 (5)
C2	0.0269 (6)	0.0312 (6)	0.0266 (6)	0.0088 (5)	0.0033 (5)	0.0025 (5)
C3	0.0242 (6)	0.0244 (6)	0.0323 (7)	0.0082 (5)	0.0050 (5)	0.0033 (5)
C4	0.0273 (6)	0.0269 (6)	0.0288 (6)	0.0088 (5)	0.0066 (5)	0.0067 (5)
C5	0.0273 (6)	0.0283 (6)	0.0297 (7)	0.0090 (5)	0.0030 (5)	0.0033 (5)
C6	0.0221 (5)	0.0250 (6)	0.0352 (7)	0.0065 (5)	0.0045 (5)	0.0049 (5)
C7	0.0533 (9)	0.0447 (9)	0.0365 (8)	0.0164 (7)	0.0019 (7)	0.0028 (7)
C8	0.0473 (9)	0.0627 (11)	0.0332 (8)	0.0175 (8)	−0.0039 (7)	0.0003 (7)
C9	0.0680 (12)	0.0471 (10)	0.0506 (10)	0.0233 (9)	0.0134 (9)	0.0136 (8)
C10	0.0451 (9)	0.0448 (9)	0.0385 (8)	0.0042 (7)	0.0080 (7)	0.0061 (7)
N1	0.0245 (5)	0.0284 (6)	0.0452 (7)	0.0076 (4)	0.0049 (5)	0.0047 (5)
N2	0.0351 (6)	0.0491 (8)	0.0297 (6)	0.0079 (5)	0.0050 (5)	0.0014 (5)
N3	0.0343 (6)	0.0384 (6)	0.0337 (6)	0.0106 (5)	0.0084 (5)	0.0124 (5)
N4	0.0343 (6)	0.0486 (8)	0.0272 (6)	0.0108 (6)	0.0046 (5)	0.0101 (5)
O1	0.0419 (6)	0.0498 (7)	0.0578 (8)	−0.0079 (5)	0.0139 (6)	0.0147 (6)
O2	0.0385 (6)	0.0535 (7)	0.0484 (7)	−0.0044 (5)	−0.0036 (5)	−0.0010 (6)
O3	0.0871 (12)	0.1311 (16)	0.0459 (8)	0.0682 (12)	−0.0171 (8)	−0.0025 (9)
O4	0.1088 (14)	0.0908 (13)	0.0509 (9)	0.0491 (11)	−0.0020 (9)	−0.0255 (8)
O5	0.0432 (6)	0.0382 (6)	0.0473 (7)	0.0038 (5)	0.0130 (5)	0.0167 (5)
O6	0.0635 (8)	0.0691 (9)	0.0290 (6)	0.0013 (7)	0.0071 (5)	0.0107 (6)
O7	0.0364 (6)	0.0621 (8)	0.0379 (6)	0.0070 (5)	0.0117 (5)	0.0204 (5)
O8	0.0320 (5)	0.0316 (5)	0.0389 (6)	−0.0003 (4)	0.0047 (4)	0.0040 (4)
O9	0.0640 (8)	0.0711 (9)	0.0337 (6)	0.0321 (7)	0.0077 (5)	0.0185 (6)

Geometric parameters (Å, º)

C1—O7	1.2426 (17)	C8—H8B	0.9700
C1—C2	1.4356 (19)	C9—O9	1.416 (2)
C1—C6	1.446 (2)	C9—C10	1.503 (3)
C2—C3	1.3665 (19)	C9—H9A	0.9700
C2—N2	1.4603 (19)	C9—H9B	0.9700
C3—O8	1.3378 (17)	C10—N4	1.482 (2)
C3—C4	1.4194 (19)	C10—H10A	0.9700
C4—C5	1.3817 (19)	C10—H10B	0.9700
C4—N3	1.4214 (17)	N1—O1	1.2203 (17)
C5—C6	1.3719 (19)	N1—O2	1.2233 (18)
C5—H5	0.91 (2)	N2—O3	1.197 (2)
C6—N1	1.4498 (18)	N2—O4	1.203 (2)
C7—N4	1.484 (2)	N3—O6	1.2184 (18)
C7—C8	1.502 (3)	N3—O5	1.2482 (18)
C7—H7A	0.9700	N4—H4A	0.87 (2)
C7—H7B	0.9700	N4—H4B	0.86 (2)
C8—O9	1.416 (3)	O8—H8	0.91 (3)
C8—H8A	0.9700
O7—C1—C2	120.48 (13)	O9—C9—C10	111.16 (15)
O7—C1—C6	126.99 (13)	O9—C9—H9A	109.4
C2—C1—C6	112.53 (11)	C10—C9—H9A	109.4
C3—C2—C1	126.43 (12)	O9—C9—H9B	109.4
C3—C2—N2	118.38 (12)	C10—C9—H9B	109.4
C1—C2—N2	115.13 (12)	H9A—C9—H9B	108.0
O8—C3—C2	119.07 (12)	N4—C10—C9	108.79 (14)
O8—C3—C4	124.16 (12)	N4—C10—H10A	109.9
C2—C3—C4	116.77 (12)	C9—C10—H10A	109.9
C5—C4—C3	120.65 (12)	N4—C10—H10B	109.9
C5—C4—N3	118.42 (12)	C9—C10—H10B	109.9
C3—C4—N3	120.92 (12)	H10A—C10—H10B	108.3
C6—C5—C4	120.95 (13)	O1—N1—O2	122.51 (13)
C6—C5—H5	119.1 (13)	O1—N1—C6	119.61 (13)
C4—C5—H5	119.9 (13)	O2—N1—C6	117.88 (12)
C5—C6—C1	122.56 (12)	O3—N2—O4	123.56 (16)
C5—C6—N1	116.61 (13)	O3—N2—C2	118.88 (15)
C1—C6—N1	120.83 (12)	O4—N2—C2	117.55 (15)
N4—C7—C8	109.05 (15)	O6—N3—O5	121.80 (13)
N4—C7—H7A	109.9	O6—N3—C4	119.89 (13)
C8—C7—H7A	109.9	O5—N3—C4	118.30 (13)
N4—C7—H7B	109.9	C10—N4—C7	110.99 (13)
C8—C7—H7B	109.9	C10—N4—H4A	107.0 (14)
H7A—C7—H7B	108.3	C7—N4—H4A	109.7 (14)
O9—C8—C7	111.04 (15)	C10—N4—H4B	110.8 (14)
O9—C8—H8A	109.4	C7—N4—H4B	107.9 (14)
C7—C8—H8A	109.4	H4A—N4—H4B	110.4 (19)
O9—C8—H8B	109.4	C3—O8—H8	103.0 (16)
C7—C8—H8B	109.4	C8—O9—C9	109.86 (13)
H8A—C8—H8B	108.0
O7—C1—C2—C3	177.37 (14)	C2—C1—C6—N1	178.50 (11)
C6—C1—C2—C3	−2.0 (2)	N4—C7—C8—O9	57.88 (19)
O7—C1—C2—N2	0.1 (2)	O9—C9—C10—N4	−58.2 (2)
C6—C1—C2—N2	−179.23 (12)	C5—C6—N1—O1	177.61 (13)
C1—C2—C3—O8	−176.85 (13)	C1—C6—N1—O1	−2.3 (2)
N2—C2—C3—O8	0.29 (19)	C5—C6—N1—O2	−3.30 (19)
C1—C2—C3—C4	3.7 (2)	C1—C6—N1—O2	176.81 (13)
N2—C2—C3—C4	−179.14 (12)	C3—C2—N2—O3	99.3 (2)
O8—C3—C4—C5	178.49 (12)	C1—C2—N2—O3	−83.3 (2)
C2—C3—C4—C5	−2.12 (19)	C3—C2—N2—O4	−80.3 (2)
O8—C3—C4—N3	−0.6 (2)	C1—C2—N2—O4	97.2 (2)
C2—C3—C4—N3	178.84 (12)	C5—C4—N3—O6	10.8 (2)
C3—C4—C5—C6	−1.0 (2)	C3—C4—N3—O6	−170.13 (14)
N3—C4—C5—C6	178.09 (12)	C5—C4—N3—O5	−168.37 (13)
C4—C5—C6—C1	2.8 (2)	C3—C4—N3—O5	10.7 (2)
C4—C5—C6—N1	−177.07 (12)	C9—C10—N4—C7	54.78 (19)
O7—C1—C6—C5	179.29 (14)	C8—C7—N4—C10	−54.73 (19)
C2—C1—C6—C5	−1.38 (19)	C7—C8—O9—C9	−61.7 (2)
O7—C1—C6—N1	−0.8 (2)	C10—C9—O9—C8	62.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O5	0.91 (3)	1.75 (3)	2.571 (2)	149 (2)
N4—H4A···O7	0.87 (2)	1.87 (2)	2.715 (2)	164 (2)
N4—H4B···O2^i	0.86 (2)	2.31 (2)	2.962 (2)	132.4 (17)
N4—H4B···O5^ii	0.86 (2)	2.42 (2)	2.967 (2)	121.5 (17)
N4—H4B···O3^iii	0.86 (2)	2.54 (2)	3.206 (3)	134.3 (17)

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