Hexamethyl­enetetra­minium 2,4-dinitro­benzoate monohydrate

In the crystal structure of the proton-transfer compound, C₆H₁₃N₄⁺·C₇H₃N₂O₆⁻·H₂O, the hexa­methylenetetraminium and 2,4-dinitro­benzoate ions are linked by bifurcated N—H...O hydrogen bonds. The crystal structure is stabilized by O—H...N hydrogen bonds and weak C—H...O inter­actions to form a three-dimensional network. The benzene rings of the 2,4-dinitro­benzoate ion make a π–π inter­action with a centroid–centroid distance of 3.689 (1) Å.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.001 Å
• Disorder in solvent or counterion
• R factor = 0.055
• wR factor = 0.175
• Data-to-parameter ratio = 31.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N5
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C7
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........        O2W
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          4
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C7 H3 N2 O6

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   3 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Hexamethylenetetraminium 2,4-dinitrobenzoate monohydrate

Crystal data

C6H13N4^+·C7H3N2O6^−·H2O	Z = 2
Mr = 370.33	F(000) = 388
Triclinic, P1	Dx = 1.545 Mg m^−3
Hall symbol: -P 1	Melting point = 447–449 K
a = 6.4118 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1042 (2) Å	Cell parameters from 7304 reflections
c = 14.1521 (2) Å	θ = 1.5–32.5°
α = 77.986 (1)°	µ = 0.13 mm^−1
β = 80.464 (1)°	T = 297 K
γ = 85.585 (1)°	Block, colourless
V = 796.09 (2) Å^3	0.55 × 0.43 × 0.33 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer	7817 independent reflections
Radiation source: fine-focus sealed tube	5034 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 8.33 pixels mm^-1	θmax = 37.2°, θmin = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −15→15
Tmin = 0.855, Tmax = 0.959	l = −24→23
23506 measured reflections

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.175	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0818P)^2 + 0.0892P] where P = (Fo^2 + 2Fc^2)/3
7817 reflections	(Δ/σ)max < 0.001
248 parameters	Δρmax = 0.30 e Å^−3
6 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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	Occ. (<1)
O1	0.43154 (18)	−0.38653 (11)	−0.08514 (6)	0.0558 (2)
O2	0.15356 (19)	−0.38930 (13)	0.02469 (8)	0.0647 (3)
O3	0.2353 (2)	−0.17461 (16)	0.32250 (8)	0.0815 (4)
O4	0.3126 (2)	0.05258 (13)	0.25324 (9)	0.0736 (3)
O5	0.7460 (2)	−0.04214 (14)	0.27708 (8)	0.0774 (4)
O6	0.87437 (19)	0.09736 (13)	0.13601 (9)	0.0713 (3)
N1	0.97302 (18)	0.50746 (13)	0.26680 (7)	0.0483 (2)
N2	0.63081 (15)	0.42901 (11)	0.35801 (7)	0.0422 (2)
N3	0.88444 (17)	0.24770 (12)	0.29802 (8)	0.0473 (2)
H13	0.8970	0.1654	0.2742	0.063*
N4	0.94966 (15)	0.35576 (11)	0.43087 (6)	0.03939 (19)
N5	0.31967 (16)	−0.08237 (12)	0.25573 (7)	0.0445 (2)
N6	0.33219 (17)	−0.35200 (11)	−0.01005 (7)	0.0427 (2)
C1	0.43929 (16)	−0.26179 (10)	0.04078 (6)	0.03279 (18)
C2	0.33086 (16)	−0.22149 (11)	0.12540 (7)	0.03311 (18)
H14	0.1941	−0.2513	0.1511	0.040*
C3	0.43754 (15)	−0.13443 (10)	0.16951 (6)	0.02987 (16)
C4	0.64301 (15)	−0.09009 (9)	0.13470 (7)	0.03028 (17)
C5	0.74401 (17)	−0.13498 (12)	0.04996 (8)	0.0383 (2)
H16	0.8818	−0.1070	0.0247	0.046*
C6	0.64289 (18)	−0.22075 (12)	0.00242 (7)	0.0396 (2)
H15	0.7115	−0.2500	−0.0544	0.048*
C7	0.76525 (18)	−0.00361 (12)	0.18672 (9)	0.0422 (2)
C8	0.7469 (2)	0.54779 (14)	0.28691 (11)	0.0548 (3)
H1	0.6881	0.5661	0.2264	0.066*
H2	0.7287	0.6400	0.3121	0.066*
C9	0.9993 (2)	0.37293 (18)	0.22652 (9)	0.0552 (3)
H5	1.1486	0.3445	0.2134	0.066*
H6	0.9431	0.3914	0.1654	0.066*
C10	1.05861 (18)	0.47735 (14)	0.35931 (8)	0.0428 (2)
H3	1.0433	0.5680	0.3861	0.051*
H4	1.2084	0.4499	0.3470	0.051*
C11	0.65298 (18)	0.29509 (14)	0.31808 (9)	0.0431 (2)
H9	0.5930	0.3137	0.2579	0.052*
H10	0.5768	0.2153	0.3639	0.052*
C12	0.72427 (18)	0.39986 (16)	0.44840 (8)	0.0449 (2)
H7	0.7069	0.4897	0.4761	0.054*
H8	0.6499	0.3204	0.4954	0.054*
C13	0.9729 (2)	0.22039 (14)	0.39256 (11)	0.0525 (3)
H11	0.8983	0.1408	0.4394	0.063*
H12	1.1214	0.1889	0.3814	0.063*
O1W	0.7083 (4)	−0.1730 (3)	0.46307 (15)	0.0747 (9)	0.574 (5)
H1W1	0.7142 (4)	−0.1332 (5)	0.4040 (7)	0.112*	0.574 (5)
H2W1	0.8204 (13)	−0.2200 (6)	0.4759 (2)	0.112*	0.574 (5)
O2W	0.5973 (7)	−0.0726 (5)	0.4858 (2)	0.0929 (15)	0.426 (5)
H1W2	0.6332 (8)	−0.0772 (5)	0.4244 (7)	0.139*	0.426 (5)
H2W2	0.4724 (16)	−0.0315 (6)	0.4876 (2)	0.139*	0.426 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0820 (7)	0.0545 (5)	0.0415 (4)	0.0017 (4)	−0.0243 (4)	−0.0235 (4)
O2	0.0699 (7)	0.0725 (7)	0.0610 (6)	−0.0336 (5)	−0.0188 (5)	−0.0164 (5)
O3	0.0982 (9)	0.0937 (9)	0.0493 (5)	−0.0385 (7)	0.0284 (6)	−0.0255 (6)
O4	0.0886 (8)	0.0576 (6)	0.0790 (7)	0.0109 (5)	0.0046 (6)	−0.0421 (5)
O5	0.1199 (10)	0.0687 (7)	0.0593 (6)	−0.0141 (7)	−0.0462 (6)	−0.0192 (5)
O6	0.0656 (6)	0.0677 (6)	0.0903 (8)	−0.0354 (5)	0.0069 (5)	−0.0407 (6)
N1	0.0552 (6)	0.0552 (6)	0.0361 (4)	−0.0219 (5)	−0.0065 (4)	−0.0063 (4)
N2	0.0327 (4)	0.0477 (5)	0.0483 (5)	0.0067 (3)	−0.0104 (3)	−0.0137 (4)
N3	0.0460 (5)	0.0471 (5)	0.0588 (6)	−0.0020 (4)	−0.0075 (4)	−0.0333 (4)
N4	0.0364 (4)	0.0507 (5)	0.0344 (4)	0.0017 (4)	−0.0107 (3)	−0.0132 (3)
N5	0.0424 (5)	0.0545 (5)	0.0405 (4)	−0.0035 (4)	0.0012 (3)	−0.0237 (4)
N6	0.0598 (6)	0.0377 (4)	0.0370 (4)	−0.0077 (4)	−0.0201 (4)	−0.0095 (3)
C1	0.0435 (5)	0.0292 (4)	0.0291 (4)	−0.0042 (3)	−0.0108 (3)	−0.0084 (3)
C2	0.0337 (4)	0.0342 (4)	0.0332 (4)	−0.0066 (3)	−0.0053 (3)	−0.0085 (3)
C3	0.0337 (4)	0.0287 (4)	0.0284 (3)	−0.0011 (3)	−0.0036 (3)	−0.0093 (3)
C4	0.0342 (4)	0.0246 (3)	0.0340 (4)	−0.0025 (3)	−0.0061 (3)	−0.0090 (3)
C5	0.0364 (5)	0.0390 (5)	0.0408 (5)	−0.0087 (4)	0.0023 (4)	−0.0149 (4)
C6	0.0474 (6)	0.0406 (5)	0.0328 (4)	−0.0061 (4)	0.0006 (4)	−0.0154 (4)
C7	0.0392 (5)	0.0374 (5)	0.0587 (6)	0.0011 (4)	−0.0149 (4)	−0.0246 (4)
C8	0.0660 (8)	0.0395 (6)	0.0608 (7)	0.0023 (5)	−0.0277 (6)	−0.0018 (5)
C9	0.0503 (7)	0.0863 (10)	0.0362 (5)	−0.0194 (6)	0.0040 (4)	−0.0310 (6)
C10	0.0394 (5)	0.0542 (6)	0.0420 (5)	−0.0108 (4)	−0.0070 (4)	−0.0219 (4)
C11	0.0371 (5)	0.0513 (6)	0.0453 (5)	−0.0106 (4)	−0.0111 (4)	−0.0123 (4)
C12	0.0376 (5)	0.0636 (7)	0.0355 (5)	0.0017 (5)	0.0001 (4)	−0.0202 (5)
C13	0.0484 (7)	0.0423 (6)	0.0694 (8)	0.0105 (5)	−0.0197 (6)	−0.0131 (5)
O1W	0.0642 (13)	0.0999 (19)	0.0502 (10)	0.0065 (12)	−0.0096 (8)	0.0042 (10)
O2W	0.111 (3)	0.089 (3)	0.0626 (18)	−0.009 (2)	−0.0009 (17)	0.0137 (16)

Geometric parameters (Å, º)

O1—N6	1.2319 (14)	C2—H14	0.9300
O2—N6	1.2135 (15)	C3—C4	1.3876 (13)
O3—N5	1.2086 (15)	C4—C5	1.3895 (13)
O4—N5	1.2193 (14)	C4—C7	1.5177 (13)
O5—C7	1.2414 (17)	C5—C6	1.3871 (14)
O6—C7	1.2279 (16)	C5—H16	0.9300
N1—C9	1.4424 (18)	C6—H15	0.9300
N1—C8	1.4639 (19)	C8—H1	0.9700
N1—C10	1.4683 (15)	C8—H2	0.9700
N2—C11	1.4351 (16)	C9—H5	0.9700
N2—C12	1.4677 (15)	C9—H6	0.9700
N2—C8	1.4692 (17)	C10—H3	0.9700
N3—C13	1.5048 (18)	C10—H4	0.9700
N3—C9	1.5060 (18)	C11—H9	0.9700
N3—C11	1.5107 (16)	C11—H10	0.9700
N3—H13	0.88	C12—H7	0.9700
N4—C13	1.4346 (16)	C12—H8	0.9700
N4—C12	1.4645 (15)	C13—H11	0.9700
N4—C10	1.4686 (15)	C13—H12	0.9700
N5—C3	1.4713 (12)	O1W—H1W1	0.835 (10)
N6—C1	1.4697 (12)	O1W—H2W1	0.834 (8)
C1—C6	1.3763 (15)	O2W—H1W2	0.870 (10)
C1—C2	1.3856 (13)	O2W—H2W2	0.856 (11)
C2—C3	1.3845 (13)
C9—N1—C8	108.96 (10)	O6—C7—C4	117.38 (11)
C9—N1—C10	109.01 (11)	O5—C7—C4	116.70 (10)
C8—N1—C10	108.51 (10)	N1—C8—N2	111.96 (9)
C11—N2—C12	109.20 (9)	N1—C8—H1	109.2
C11—N2—C8	108.45 (10)	N2—C8—H1	109.2
C12—N2—C8	108.72 (10)	N1—C8—H2	109.2
C13—N3—C9	109.22 (9)	N2—C8—H2	109.2
C13—N3—C11	108.43 (9)	H1—C8—H2	107.9
C9—N3—C11	108.83 (10)	N1—C9—N3	109.50 (9)
C13—N3—H13	110.4	N1—C9—H5	109.8
C9—N3—H13	110.7	N3—C9—H5	109.8
C11—N3—H13	109.3	N1—C9—H6	109.8
C13—N4—C12	108.76 (9)	N3—C9—H6	109.8
C13—N4—C10	109.91 (9)	H5—C9—H6	108.2
C12—N4—C10	108.27 (10)	N1—C10—N4	111.64 (8)
O3—N5—O4	124.99 (11)	N1—C10—H3	109.3
O3—N5—C3	118.38 (10)	N4—C10—H3	109.3
O4—N5—C3	116.62 (10)	N1—C10—H4	109.3
O2—N6—O1	124.09 (10)	N4—C10—H4	109.3
O2—N6—C1	118.44 (10)	H3—C10—H4	108.0
O1—N6—C1	117.47 (10)	N2—C11—N3	109.69 (8)
C6—C1—C2	122.71 (8)	N2—C11—H9	109.7
C6—C1—N6	118.72 (9)	N3—C11—H9	109.7
C2—C1—N6	118.57 (9)	N2—C11—H10	109.7
C3—C2—C1	116.26 (8)	N3—C11—H10	109.7
C3—C2—H14	121.9	H9—C11—H10	108.2
C1—C2—H14	121.9	N4—C12—N2	111.72 (8)
C2—C3—C4	123.74 (8)	N4—C12—H7	109.3
C2—C3—N5	116.92 (8)	N2—C12—H7	109.3
C4—C3—N5	119.29 (8)	N4—C12—H8	109.3
C3—C4—C5	117.29 (8)	N2—C12—H8	109.3
C3—C4—C7	123.74 (8)	H7—C12—H8	107.9
C5—C4—C7	118.88 (9)	N4—C13—N3	109.60 (9)
C6—C5—C4	121.13 (9)	N4—C13—H11	109.8
C6—C5—H16	119.4	N3—C13—H11	109.8
C4—C5—H16	119.4	N4—C13—H12	109.8
C1—C6—C5	118.85 (9)	N3—C13—H12	109.8
C1—C6—H15	120.6	H11—C13—H12	108.2
C5—C6—H15	120.6	H1W1—O1W—H2W1	112.9 (4)
O6—C7—O5	125.92 (11)	H1W2—O2W—H2W2	102.8 (6)
O2—N6—C1—C6	179.19 (11)	C9—N1—C8—N2	60.71 (13)
O1—N6—C1—C6	0.03 (14)	C10—N1—C8—N2	−57.86 (13)
O2—N6—C1—C2	−0.85 (15)	C11—N2—C8—N1	−61.00 (13)
O1—N6—C1—C2	179.99 (9)	C12—N2—C8—N1	57.63 (13)
C6—C1—C2—C3	1.01 (14)	C8—N1—C9—N3	−58.91 (13)
N6—C1—C2—C3	−178.95 (8)	C10—N1—C9—N3	59.34 (13)
C1—C2—C3—C4	−1.33 (14)	C13—N3—C9—N1	−59.33 (14)
C1—C2—C3—N5	176.10 (9)	C11—N3—C9—N1	58.87 (13)
O3—N5—C3—C2	53.26 (15)	C9—N1—C10—N4	−59.88 (12)
O4—N5—C3—C2	−125.72 (12)	C8—N1—C10—N4	58.66 (13)
O3—N5—C3—C4	−129.19 (13)	C13—N4—C10—N1	59.59 (13)
O4—N5—C3—C4	51.83 (15)	C12—N4—C10—N1	−59.09 (12)
C2—C3—C4—C5	0.88 (14)	C12—N2—C11—N3	−58.73 (12)
N5—C3—C4—C5	−176.50 (9)	C8—N2—C11—N3	59.59 (12)
C2—C3—C4—C7	−175.72 (9)	C13—N3—C11—N2	59.12 (12)
N5—C3—C4—C7	6.91 (14)	C9—N3—C11—N2	−59.58 (11)
C3—C4—C5—C6	−0.06 (15)	C13—N4—C12—N2	−60.63 (13)
C7—C4—C5—C6	176.71 (10)	C10—N4—C12—N2	58.77 (12)
C2—C1—C6—C5	−0.27 (16)	C11—N2—C12—N4	60.07 (13)
N6—C1—C6—C5	179.68 (9)	C8—N2—C12—N4	−58.09 (13)
C4—C5—C6—C1	−0.23 (17)	C12—N4—C13—N3	60.17 (13)
C3—C4—C7—O6	−139.59 (12)	C10—N4—C13—N3	−58.20 (13)
C5—C4—C7—O6	43.87 (15)	C9—N3—C13—N4	58.56 (13)
C3—C4—C7—O5	40.66 (16)	C11—N3—C13—N4	−59.89 (13)
C5—C4—C7—O5	−135.89 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O5	0.84 (1)	1.80 (1)	2.633 (2)	176 (1)
O2W—H1W2···O5	0.87 (1)	2.06 (1)	2.912 (3)	167 (1)
N3—H13···O5	0.88	2.18	2.935 (2)	144
N3—H13···O6	0.88	2.20	2.916 (2)	138
O1W—H2W1···N4^i	0.83 (1)	2.26 (1)	3.053 (3)	158 (1)
C11—H9···O1^ii	0.97	2.42	3.352 (2)	159
C13—H12···O4^iii	0.97	2.51	3.207 (2)	128
C13—H12···O1W^i	0.97	2.59	3.069 (3)	110
C5—H16···O6^iv	0.93	2.53	3.264 (2)	136

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