Crystal structure of 2-(morpholino)ethyl­ammonium picrate monohydrate

The title compound was synthesized via slow evaporation of an aqueous solution of picric acid with the substituted morpholine base and crystallized with one cation (C₆H₁₅N₂O)⁺, one anion (C₆H₂N₃O₇)⁻ and a water mol­ecule in the asymmetric unit. The morpholine ring in the cation adopts a chair conformation. The structure is stabilized by C–H...O, O—H...O, O—H...N and N—H...O hydrogen-bonding inter­actions and π–π stacking. The inter­molecular inter­actions of the synthesized compound were qu­anti­fied by Hirshfeld surface analysis.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.041
• wR factor = 0.117
• Data-to-parameter ratio = 13.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT048_ALERT_1_C MoietyFormula Not Given (or Incomplete) ........     Please Check
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N3       --C2       .        5.6 s.u.
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         33 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....         23 Note

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          7 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT398_ALERT_2_G Deviating  C-O-C   Angle From 120 for O8       .      108.8 Degree
PLAT480_ALERT_4_G Long H...A H-Bond Reported H10B     ..O6       .       2.63 Ang.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          5 Note
PLAT883_ALERT_1_G No Info/Value for _atom_sites_solution_primary .     Please Do !
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         40 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          8 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   2 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
   4 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: APEX3/SAINT (Bruker, 2016); data reduction: SAINT/XPREP (Bruker, 2016); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018/2 (Sheldrick, 2015b).

2-(Morpholin-4-yl)ethan-1-aminium 2,4,6-trinitrobenzen-1-olate monohydrate

Crystal data

C6H15N2O^+·C6H2N3O7·H2O	Z = 2
Mr = 377.32	F(000) = 396
Triclinic, P1	Dx = 1.489 Mg m^−3
a = 6.938 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.583 (5) Å	Cell parameters from 7824 reflections
c = 12.077 (5) Å	θ = 3.2–26.2°
α = 114.362 (13)°	µ = 0.13 mm^−1
β = 94.261 (14)°	T = 297 K
γ = 103.841 (15)°	Block, yellow
V = 841.8 (6) Å^3	0.40 × 0.38 × 0.19 mm

Data collection

Bruker D8 Venture Diffractometer	2781 reflections with I > 2σ(I)
Radiation source: fine focus sealed tube	Rint = 0.039
φ and ω scans	θmax = 26.4°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker 2016)	h = −8→8
Tmin = 0.504, Tmax = 0.562	k = −14→14
19297 measured reflections	l = −15→15
3378 independent reflections

Refinement

Refinement on F^2	5 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0542P)^2 + 0.2721P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3378 reflections	Δρmax = 0.25 e Å^−3
250 parameters	Δρmin = −0.21 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6187 (2)	0.30558 (14)	0.82290 (13)	0.0335 (3)
C2	0.6867 (2)	0.43310 (15)	0.82356 (13)	0.0349 (3)
C3	0.7623 (2)	0.55224 (14)	0.92800 (13)	0.0355 (3)
H3	0.802400	0.631735	0.922088	0.043*
C4	0.7771 (2)	0.55051 (14)	1.04247 (13)	0.0336 (3)
C5	0.7107 (2)	0.43331 (15)	1.05278 (13)	0.0360 (3)
H5	0.716562	0.434004	1.130246	0.043*
C6	0.6359 (2)	0.31567 (14)	0.94612 (14)	0.0359 (3)
C7	0.0106 (3)	0.30407 (19)	0.38759 (18)	0.0542 (5)
H7A	0.121632	0.382644	0.406388	0.065*
H7B	−0.037972	0.314606	0.463429	0.065*
C8	−0.1579 (4)	0.2906 (3)	0.2924 (2)	0.0739 (6)
H8A	−0.272185	0.215447	0.277962	0.089*
H8B	−0.201836	0.369717	0.324210	0.089*
C9	−0.0362 (3)	0.1539 (2)	0.13116 (18)	0.0581 (5)
H9A	0.003134	0.139093	0.052136	0.070*
H9B	−0.150414	0.078921	0.117385	0.070*
C10	0.1378 (3)	0.16274 (16)	0.21970 (14)	0.0432 (4)
H10A	0.174467	0.080947	0.185378	0.052*
H10B	0.254271	0.234838	0.230153	0.052*
C11	0.2592 (3)	0.20986 (16)	0.43386 (14)	0.0425 (4)
H11A	0.214563	0.221718	0.511030	0.051*
H11B	0.358912	0.292112	0.449159	0.051*
C12	0.3601 (2)	0.10098 (17)	0.39727 (15)	0.0438 (4)
H12A	0.408246	0.090738	0.321368	0.053*
H12B	0.477074	0.128043	0.461345	0.053*
N1	0.5579 (2)	0.19374 (14)	0.95933 (14)	0.0490 (4)
N2	0.8605 (2)	0.67574 (14)	1.15356 (12)	0.0428 (3)
N3	0.6630 (2)	0.43738 (14)	0.70341 (12)	0.0476 (4)
N4	0.08400 (19)	0.18564 (12)	0.34122 (11)	0.0370 (3)
N5	0.2271 (2)	−0.02941 (14)	0.37799 (13)	0.0420 (3)
H5C	0.206 (3)	−0.0270 (19)	0.4503 (15)	0.050*
H5A	0.291 (3)	−0.0899 (17)	0.3458 (17)	0.050*
H5B	0.117 (2)	−0.0515 (19)	0.3291 (16)	0.050*
O1	0.54301 (17)	0.19894 (10)	0.72393 (10)	0.0447 (3)
O2	0.5959 (3)	0.09346 (14)	0.88953 (15)	0.0832 (5)
O3	0.4599 (2)	0.19858 (15)	1.03953 (15)	0.0684 (4)
O4	0.8730 (3)	0.67488 (14)	1.25430 (11)	0.0688 (4)
O5	0.9152 (2)	0.77882 (12)	1.14134 (12)	0.0644 (4)
O6	0.5699 (3)	0.50981 (15)	0.69044 (13)	0.0705 (4)
O7	0.7341 (3)	0.36689 (18)	0.62204 (13)	0.0786 (5)
O8	−0.0951 (2)	0.27241 (15)	0.17867 (14)	0.0665 (4)
O9	0.19445 (19)	−0.00465 (13)	0.61101 (11)	0.0519 (3)
H9D	0.137 (3)	−0.055 (2)	0.640 (2)	0.078*
H9C	0.293 (3)	0.055 (2)	0.661 (2)	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0244 (7)	0.0322 (7)	0.0346 (7)	0.0087 (5)	0.0061 (5)	0.0060 (6)
C2	0.0309 (7)	0.0369 (8)	0.0294 (7)	0.0056 (6)	0.0067 (5)	0.0100 (6)
C3	0.0317 (7)	0.0308 (7)	0.0358 (7)	0.0044 (6)	0.0063 (6)	0.0098 (6)
C4	0.0277 (7)	0.0330 (7)	0.0290 (7)	0.0096 (6)	0.0031 (5)	0.0036 (6)
C5	0.0344 (7)	0.0420 (8)	0.0321 (7)	0.0170 (6)	0.0075 (6)	0.0136 (6)
C6	0.0332 (7)	0.0331 (7)	0.0411 (8)	0.0128 (6)	0.0086 (6)	0.0144 (6)
C7	0.0680 (12)	0.0527 (10)	0.0598 (11)	0.0313 (9)	0.0337 (9)	0.0311 (9)
C8	0.0679 (13)	0.0920 (17)	0.1018 (18)	0.0464 (13)	0.0368 (13)	0.0651 (15)
C9	0.0679 (12)	0.0549 (11)	0.0506 (10)	0.0109 (9)	0.0020 (9)	0.0282 (9)
C10	0.0536 (10)	0.0408 (8)	0.0351 (8)	0.0137 (7)	0.0126 (7)	0.0163 (7)
C11	0.0480 (9)	0.0355 (8)	0.0338 (7)	0.0058 (7)	0.0037 (6)	0.0102 (6)
C12	0.0360 (8)	0.0482 (9)	0.0415 (8)	0.0089 (7)	0.0031 (6)	0.0174 (7)
N1	0.0560 (9)	0.0392 (8)	0.0507 (8)	0.0138 (6)	0.0090 (7)	0.0195 (6)
N2	0.0392 (7)	0.0411 (8)	0.0327 (7)	0.0122 (6)	0.0005 (5)	0.0028 (6)
N3	0.0478 (8)	0.0444 (8)	0.0316 (7)	−0.0044 (6)	0.0051 (6)	0.0092 (6)
N4	0.0404 (7)	0.0353 (7)	0.0366 (6)	0.0106 (5)	0.0110 (5)	0.0170 (5)
N5	0.0398 (7)	0.0380 (7)	0.0397 (7)	0.0140 (6)	0.0005 (6)	0.0091 (6)
O1	0.0401 (6)	0.0337 (6)	0.0401 (6)	0.0054 (5)	0.0035 (5)	0.0012 (5)
O2	0.1348 (15)	0.0412 (8)	0.0806 (11)	0.0375 (9)	0.0376 (10)	0.0248 (7)
O3	0.0757 (10)	0.0671 (9)	0.0775 (10)	0.0192 (7)	0.0320 (8)	0.0447 (8)
O4	0.0949 (11)	0.0606 (9)	0.0300 (6)	0.0171 (8)	−0.0013 (6)	0.0059 (6)
O5	0.0817 (10)	0.0347 (7)	0.0472 (7)	−0.0018 (6)	−0.0032 (6)	0.0034 (5)
O6	0.0939 (11)	0.0636 (9)	0.0541 (8)	0.0165 (8)	−0.0004 (7)	0.0324 (7)
O7	0.0844 (11)	0.0975 (12)	0.0404 (7)	0.0240 (9)	0.0276 (7)	0.0171 (7)
O8	0.0720 (9)	0.0768 (10)	0.0768 (9)	0.0316 (8)	0.0178 (7)	0.0532 (8)
O9	0.0455 (7)	0.0502 (7)	0.0456 (7)	−0.0059 (5)	0.0019 (5)	0.0199 (6)

Geometric parameters (Å, º)

C1—O1	1.2683 (18)	C9—H9B	0.9700
C1—C2	1.435 (2)	C10—N4	1.4736 (19)
C1—C6	1.437 (2)	C10—H10A	0.9700
C2—C3	1.375 (2)	C10—H10B	0.9700
C2—N3	1.471 (2)	C11—N4	1.477 (2)
C3—C4	1.387 (2)	C11—C12	1.511 (2)
C3—H3	0.9300	C11—H11A	0.9700
C4—C5	1.385 (2)	C11—H11B	0.9700
C4—N2	1.4547 (19)	C12—N5	1.482 (2)
C5—C6	1.378 (2)	C12—H12A	0.9700
C5—H5	0.9300	C12—H12B	0.9700
C6—N1	1.465 (2)	N1—O3	1.214 (2)
C7—N4	1.482 (2)	N1—O2	1.225 (2)
C7—C8	1.509 (3)	N2—O4	1.2175 (19)
C7—H7A	0.9700	N2—O5	1.236 (2)
C7—H7B	0.9700	N3—O7	1.216 (2)
C8—O8	1.420 (3)	N3—O6	1.224 (2)
C8—H8A	0.9700	N5—H5C	0.887 (15)
C8—H8B	0.9700	N5—H5A	0.889 (15)
C9—O8	1.426 (3)	N5—H5B	0.845 (15)
C9—C10	1.507 (3)	O9—H9D	0.836 (16)
C9—H9A	0.9700	O9—H9C	0.821 (17)
O1—C1—C2	122.65 (14)	N4—C10—H10A	109.4
O1—C1—C6	125.22 (14)	C9—C10—H10A	109.4
C2—C1—C6	112.03 (12)	N4—C10—H10B	109.4
C3—C2—C1	125.19 (14)	C9—C10—H10B	109.4
C3—C2—N3	117.32 (14)	H10A—C10—H10B	108.0
C1—C2—N3	117.40 (13)	N4—C11—C12	114.81 (13)
C2—C3—C4	118.10 (14)	N4—C11—H11A	108.6
C2—C3—H3	120.9	C12—C11—H11A	108.6
C4—C3—H3	120.9	N4—C11—H11B	108.6
C5—C4—C3	121.52 (13)	C12—C11—H11B	108.6
C5—C4—N2	119.86 (14)	H11A—C11—H11B	107.5
C3—C4—N2	118.61 (14)	N5—C12—C11	114.31 (14)
C6—C5—C4	118.77 (14)	N5—C12—H12A	108.7
C6—C5—H5	120.6	C11—C12—H12A	108.7
C4—C5—H5	120.6	N5—C12—H12B	108.7
C5—C6—C1	124.34 (14)	C11—C12—H12B	108.7
C5—C6—N1	117.80 (14)	H12A—C12—H12B	107.6
C1—C6—N1	117.76 (13)	O3—N1—O2	123.96 (16)
N4—C7—C8	110.78 (17)	O3—N1—C6	117.76 (14)
N4—C7—H7A	109.5	O2—N1—C6	118.28 (15)
C8—C7—H7A	109.5	O4—N2—O5	122.81 (14)
N4—C7—H7B	109.5	O4—N2—C4	118.89 (15)
C8—C7—H7B	109.5	O5—N2—C4	118.30 (14)
H7A—C7—H7B	108.1	O7—N3—O6	123.84 (16)
O8—C8—C7	111.62 (16)	O7—N3—C2	117.99 (17)
O8—C8—H8A	109.3	O6—N3—C2	118.16 (14)
C7—C8—H8A	109.3	C10—N4—C11	112.03 (13)
O8—C8—H8B	109.3	C10—N4—C7	108.96 (12)
C7—C8—H8B	109.3	C11—N4—C7	108.03 (13)
H8A—C8—H8B	108.0	C12—N5—H5C	109.9 (13)
O8—C9—C10	111.11 (16)	C12—N5—H5A	108.4 (13)
O8—C9—H9A	109.4	H5C—N5—H5A	106.8 (17)
C10—C9—H9A	109.4	C12—N5—H5B	111.1 (13)
O8—C9—H9B	109.4	H5C—N5—H5B	111.2 (18)
C10—C9—H9B	109.4	H5A—N5—H5B	109.2 (18)
H9A—C9—H9B	108.0	C8—O8—C9	108.77 (14)
N4—C10—C9	111.04 (14)	H9D—O9—H9C	112 (2)
O1—C1—C2—C3	177.25 (14)	C1—C6—N1—O3	−136.51 (16)
C6—C1—C2—C3	0.8 (2)	C5—C6—N1—O2	−139.62 (17)
O1—C1—C2—N3	0.9 (2)	C1—C6—N1—O2	43.8 (2)
C6—C1—C2—N3	−175.60 (12)	C5—C4—N2—O4	1.0 (2)
C1—C2—C3—C4	0.8 (2)	C3—C4—N2—O4	179.69 (15)
N3—C2—C3—C4	177.14 (13)	C5—C4—N2—O5	−178.77 (14)
C2—C3—C4—C5	−2.5 (2)	C3—C4—N2—O5	−0.1 (2)
C2—C3—C4—N2	178.84 (12)	C3—C2—N3—O7	129.37 (17)
C3—C4—C5—C6	2.6 (2)	C1—C2—N3—O7	−54.0 (2)
N2—C4—C5—C6	−178.78 (13)	C3—C2—N3—O6	−51.9 (2)
C4—C5—C6—C1	−0.9 (2)	C1—C2—N3—O6	124.75 (16)
C4—C5—C6—N1	−177.21 (13)	C9—C10—N4—C11	−173.52 (13)
O1—C1—C6—C5	−177.07 (14)	C9—C10—N4—C7	−54.04 (18)
C2—C1—C6—C5	−0.7 (2)	C12—C11—N4—C10	−56.71 (17)
O1—C1—C6—N1	−0.8 (2)	C12—C11—N4—C7	−176.74 (13)
C2—C1—C6—N1	175.61 (13)	C8—C7—N4—C10	53.41 (19)
N4—C7—C8—O8	−58.1 (2)	C8—C7—N4—C11	175.35 (14)
O8—C9—C10—N4	58.90 (19)	C7—C8—O8—C9	60.6 (2)
N4—C11—C12—N5	−61.64 (18)	C10—C9—O8—C8	−60.8 (2)
C5—C6—N1—O3	40.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O7^i	0.97	2.55	3.465 (2)	158
C10—H10B···O6^ii	0.97	2.63	3.503 (3)	150
C12—H12A···O2^iii	0.97	2.55	3.349 (3)	139
N5—H5C···O9	0.89 (2)	1.86 (2)	2.741 (2)	172 (2)
N5—H5A···O1^iii	0.89 (2)	1.89 (2)	2.777 (2)	172 (2)
N5—H5B···O5^iv	0.85 (2)	2.35 (2)	3.054 (2)	142 (2)
N5—H5B···O9^v	0.85 (2)	2.48 (2)	3.048 (2)	126 (2)
O9—H9D···N4^v	0.84 (2)	1.98 (2)	2.7722 (19)	158 (2)
O9—H9C···O1	0.82 (2)	1.94 (2)	2.7196 (19)	160 (2)

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