The 143 and 300 K polymorphs of hexa­methyl­enetetraminium 2,4-di­nitro­phenolate monohydrate

The title compound, 3,5,7-tri­aza-1-azoniatri­cyclo­[3.3.1.1^3,7]­decane 2,4-di­nitro­phenolate monohydrate, C₆H₁₃N₄⁺·C₆H₃N₂O₅^-·H₂O, the 1:1 hydrate adduct of hexa­methyl­enetetr­amine (HMT) and 2,4-di­nitro­phenol, undergoes a temperature phase transition. In the room-temperature phase, the adduct crystallizes in the monoclinic P2₁/m space group, whereas in the low-temperature phase, the adduct crystallizes in the triclinic P space group. This phase transition is reversible, with the transition temperature at 273 K, and the phase transition is governed by hydrogen bonds and weak interactions. In both these temperature-dependent polymorphs, the crystal structure is alternately layered with sheets of hexa­methyl­enetetr­amine and sheets of di­nitro­phenol stacked along the c axis. The hexa­methyl­enetetr­amine and di­nitro­phenol moieties are linked by intermolecular hydrogen bonds. The water mol­ecule in the adduct plays an important role, forming O-H...O hydrogen bonds which, together with C-H...O hydrogen bonds, bridge the adducts into molecular ribbons. Extra hydrogen bonds and weak interactions exist for the low-temperature polymorph and these interconnect the molecular ribbons into a three-dimensional packing structure. Also in these two temperature-dependent polymorphs, di­nitro­phenol acts as a hydrogen-bond acceptor and HMT acts as a hydrogen-bond donor.

S1. Comment

The N—H···O-type of hydrogen bond is a versatile synthon in crystal engineering (Fan et al., 1994; Desiraju, 1995). Phenols, in general, are strong acids and tend to form N—H···O hydrogen bonds with aromatic or tertiary amines. Therefore, a number of studies have been conducted into phenol–hexamethylenetetramine adducts (with various ratios) to design and construct a variety of hydrogen-bonding systems. In general, in the adducts of hexamethylenetetramine (HMT) with simple phenols, HMT acts as either a mono-, bis- or tris-acceptor of hydrogen bonds (Jordan & Mak, 1970; Mak et al., 1977, 1978; Mahmoud & Wallwork, 1979; Coupar, Glidewell & Ferguson, 1997; Coupar, Ferguson et al., 1997).

We have now isolated the crystalline form of the hydrate, (I), of the 1:1 stoichiometric adduct of 2,4-dinitrophenol with HMT, and one water molecule is incorporated in the adduct during the crystallization.

The adduct undergoes a phase transition when the temperature is lowered. The room-temperature monoclinic P21/m phase transforms into a low-temperature triclinic P1 phase upon lowering the temperature below 273 K. The phase transition is reversible. We report here the crystal structures of these two temperature-dependent polymorphs, the monoclinic polymorph at 300 K and the triclinic polymorph at 143 K.

In these two temperature-dependent polymorphs, HMT, in an unusual manner, acts as a hydrogen-bond donor of the N—H···O hydrogen bonds observed in these structures.

At 300 K, the asymmetric unit contains one half of HMT, and the monoclinic unit-cell volume contains two adducts. One half of the HMT is related to the other by a centre of inversion passing through atoms N5, N3 and C10. At 143 K, the asymmetric unit contains the complete adduc and the triclinic unit-cell volume also contains two adducts. In both these two space groups, the geometry of dinitrophenol and HMT are as expected. The dinitrophenol transfers an H atom from the hydroxy group to the HMT and becomes negatively charged, with the transfered H atom being localized at the N3 atom of HMT, making it postively charged. A similar effect was also observed in the adduct of HMT with azelaic acid (Hostettler et al., 1999).

In the present adduct, the transfer of the H atom from the hydroxy group was followed by an increase in the delocalization of the π-electron resulting in slight distortions in the N—O, N—C and O—C bond distances of the functional groups within the dinitrophenol moiety, whereas due to the localization of the positive charge at the N3 atom, the C—N3 bond distances are as expected for C—N single bond in an ammonium ion (Allen et al., 1987). All the other bond lengths and angles in the adduct (I) show normal values and are listed in Table 1 for the monoclinic and Table 3 for the triclinic polymorphs.

In both these polymorphs, the dinitrophenol is essentially planar, with the O3 atom deviating by a maximum of 0.0 Å at 300 K and 0.080 (3) Å at 143 K. All the six-membered C—N—C—N—C—N rings of HMT adopt a chair conformation with almost the same puckering parameters (Cremer & Pople, 1975); see _geom_special_details of the archived CIF. These facts rule out that the temperature phase transformation is due to conformational changes since there are not much differences in the structures of these two temperature-dependent polymorphs. However, there are changes in the hydrogen-bond motifs of these two polymorphs.

In both these polymorphs, there are conventional hydrogen bonds (Table 2 and Table 4) and C9—H9B···O4 and N3—H13N···O4 weak interactions [C9···O4ⁱ and C9—H9B···O4ⁱ = 3.136 (2) Å and 117 (1)° at 300 K, and 3.114 (3) Å and 117 (2)° at 143 K; N3···O4ⁱⁱ and N3—H13N···O4ⁱⁱ = 2.873 (2) Å and 122 (3)° at 300 K, and 2.843 (3) Å and 125 (3)° at 143 K; symmetry codes: (i) 1 - x, 1/2 + y, 1 - z; (ii) 1 - x, 1/2 + y, 1 - z]. Figs. 2 and 3 show the packing diagrams with hydrogen bonds and weak interactions. The crystal structure of the adduct in both the polymorphs is built from molecular sheets of HMT and molecular sheets dinitrophenol alternatingly stacked along the c axis. HMT unusually takes a role as a donor of these intermolecular N—H···O hydrogen bonds, i.e. the N3 atom acts as donor to the O4 and O5 atoms in the dinitrophenol. The N···O distances within the N—H···O hydrogen bonds in these two polymorphs of adduct (I) are comparable with those observed for the O—H···N hydrogen bonds in other HMT—phenol adducts (Mak et al., 1978; Mahmoud & Wallock, 1979; Coupar, Glidewell & Ferguson, 1997; Coupar, Ferguson et al., 1997).

The water molecule in the adduct plays an important role forming O—H···O hydrogen bonds, which together with an intermolecular C—H···O hydrogen bond, i.e. C5—H5A···O3, bridge the dinitrophenols and links the adducts into molecular ribbons parallel to the b axis. These molecular ribbons pack on top of one another.

At low temperature, two extra intramolecular weak interactions [C9A—H9AB···O4 123 (2)° and C6—H6A···O1 101 (2)°] and two extra intermolecular C—H···O hydrogen bonds (Table 4) were observed; the extra weak interactions and hydrogen bonds link the four C atoms of the HMT and the two O atoms of the dinitrophenol, i.e. they link the C9 and C9A atoms and the O4 atom, and they link the C7 and C9 atoms and the O1 atom. These extra intermolecular C—H···O hydrogen bonds interconnects the molecular ribbons into a three-dimentional molecular packing, and stabilize the triclinic polymorphic structure.

Since the only difference in these two polymorphs are the packing structures which are governed by the different hydrogen-bonding and weak interaction patterns, we can attribute this reversible temperature phase transition, which we named as Fun-Anwar-Suchada-Transition (FAST), as due to the presence or absence of these extra hydrogen bonding and weak interactions.

In conclusion, the FAST observed in the 1:1 HMT–2,4-dinitrophenol hydrate adduct is a new type of reversible temperature phase transistion governed by hydrogen bonding and weak interactions. We have also observed similar FAST phenomena in other complexes which are presently under investigation in our research laboratory.

Related literature

For related literature, see: Allen et al. (1987); Coupar, Ferguson, Glidewell & Meehan (1997); Coupar, Glidewell & Ferguson (1997); Cremer & Pople (1975); Desiraju (1995); Fan et al. (1994); Hostettler et al. (1999); Jordan & Mak (1970); Mahmoud & Wallwork (1979); Mak et al. (1977, 1978).

S2. Experimental

HMT (1.4 g, 10 mmol) and 2,4-dinitrophenol (1.8 g, 10 mmol) were mixed and dissolved in acetone (30 ml) together with a few drops of water. The resulting mixture was heated until a clear solution was obtained. The solution was then filtered and the filtrate was left to evaporate slowly in air. Yellow single crystals suitable for X-ray diffraction studies were obtained after a few days.

S3. Refinement

For the two polymorphs, all the H atoms were located from the difference map and refined isotropically [C—H = 0.87 (3)–1.03 (2) Å].

Computing details

For both compounds, 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).

Figures

	Fig. 1. The structure of the title adduct showing 50% probability displacement ellipsoids with the atom-numbering scheme (a) for the monoclinic polymorph and (b) for the triclinic polymorph.
	Fig. 2. Packing diagram of the monoclinic polymorph.
	Fig. 3. Packing diagram of the triclinic polymorph.

(Iat300K) 3,5,7-triaza-1-azoniatricyclo[3.3.1.1^3,7]decane 2,4-dinitrophenolate monohydrate

Crystal data

C6H13N4^+·C6H3N2O5^−·H2O	F(000) = 360
Mr = 342.32	Dx = 1.524 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
a = 7.8610 (5) Å	Cell parameters from 3560 reflections
b = 6.5980 (4) Å	θ = 1.4–29.6°
c = 14.4339 (9) Å	µ = 0.12 mm^−1
β = 94.915 (1)°	T = 300 K
V = 745.89 (8) Å^3	Block, yellow
Z = 2	0.42 × 0.24 × 0.20 mm

Data collection

Siemens SMART CCD area-detector diffractometer	1900 independent reflections
Radiation source: fine-focus sealed tube	1288 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
Detector resolution: 8.33 pixels mm^-1	θmax = 28.0°, θmin = 2.6°
ω scans	h = −10→9
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −8→7
Tmin = 0.950, Tmax = 0.976	l = −19→18
5088 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)] = 0.059	All H-atom parameters refined
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.0622P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max < 0.001
1900 reflections	Δρmax = 0.33 e Å^−3
178 parameters	Δρmin = −0.31 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.145 (17)

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 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 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.

# loop_ # _publ_manuscript_incl_extra_item # # '_geom_extra_tableA_col_1' # '_geom_extra_tableA_col_2' # '_geom_extra_table_head_A' # '_geom_table_footnote_A' # # _geom_extra_table_head_A #; # Average C—N bond distances (Å) along with the puckering parameters (Å, °) # of the six-membered C—N—C—N—C—N rings of the HMT #; # # loop_ # _geom_extra_tableA_col_1 # _geom_extra_tableA_col_2 # 'Scheme 2 here' ? # ? ? # 'T = 300K' 'T = 143K' # ? ? # 'Average C—N = 1.474' 'Average C—N = 1.480 (3)' # 'Q₂ = 0.014 (2)' 'Q₂ = 0.009 (3)' # 'Q₃ = 0.592 (2)' 'Q₃ = 0.596 (3)' # 'Q_T = 0.593 (2)' 'Q_T = 0.596 (3)' # 'θ = 0.4 (2)' 'θ = 0.0 (3)' # ? ? # 'Average C—N = 1.474 (3)' 'Average C—N = 1.480 (3)' # 'Q₂ = 0.014 (2)' 'Q₂ = 0.017 (3)' # 'Q₃ = 0.592 (2)' 'Q₃ = 0.600 (3)' # 'Q_T = 0.593 (2)' 'Q_T = 0.600 (3)' # 'θ = 0.4 (2)' 'θ = 1.8 (3)' # ? ? # 'Average C—N = 1.471 (3)' 'Average C—N = 1.479 (3)' # 'Q₂ = 0.008 (2)' 'Q₂ = 0.007 (2)' # 'Q₃ = 0.598 (2)' 'Q₃ = 0.597 (2)' # 'Q_T = 0.598 (2)' 'Q_T = 0.597 (3)' # 'θ = 1.6 (2)' 'θ = 2.1 (3)' # ? ? # 'Average C—N = 1.469 (3)' 'Average C—N = 1.473 (3)' # 'Q₂ = 0.004 (2)' 'Q₂ = 0.009 (3)' # 'Q₃ = 0.584 (2)' 'Q₃ = 0.578 (3)' # 'Q_T = 0.585 (2)' 'Q_T = 0.578 (3)' # 'θ = 1.1 (2)' 'θ = 0.0 (3)' # ? ? # # _geom_table_footnote_A #; # Note: All the rings adopt a chair conformation. #; #

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
N1	0.3354 (3)	0.2500	0.24704 (13)	0.0402 (5)
N2	0.0558 (2)	0.2500	0.53083 (13)	0.0432 (6)
N3	0.7478 (2)	0.7500	0.20852 (12)	0.0325 (5)
H1N3	0.727 (4)	0.7500	0.265 (2)	0.047*
N4	0.88545 (17)	0.5660 (2)	0.09159 (9)	0.0337 (4)
N5	0.6216 (2)	0.7500	0.04920 (13)	0.0351 (5)
O1	0.4692 (3)	0.2500	0.20695 (11)	0.0526 (6)
O2	0.1928 (3)	0.2500	0.20416 (12)	0.0621 (6)
O3	−0.0775 (2)	0.2500	0.48100 (14)	0.0754 (8)
O4	0.0538 (2)	0.2500	0.61478 (13)	0.0811 (9)
O5	0.3979 (2)	0.2500	0.63206 (10)	0.0465 (5)
O1W	0.2668 (3)	0.7500	0.28182 (14)	0.0585 (6)
H1W1	0.379 (4)	0.7500	0.313 (2)	0.060 (9)*
H2W1	0.208 (6)	0.7500	0.318 (3)	0.109 (18)*
C1	0.3505 (3)	0.2500	0.34722 (14)	0.0315 (5)
C2	0.2036 (3)	0.2500	0.39233 (15)	0.0341 (6)
H2A	0.100 (3)	0.2500	0.3631 (18)	0.040 (7)*
C3	0.2154 (3)	0.2500	0.48886 (14)	0.0312 (5)
C4	0.3758 (3)	0.2500	0.54426 (14)	0.0317 (5)
C5	0.5219 (3)	0.2500	0.49069 (16)	0.0401 (6)
H5A	0.623 (4)	0.2500	0.522 (2)	0.049 (8)*
C6	0.5104 (3)	0.2500	0.39662 (15)	0.0356 (6)
H6A	0.607 (3)	0.2500	0.3653 (18)	0.045 (7)*
C7	0.5830 (3)	0.7500	0.14533 (17)	0.0393 (6)
H7A	0.516 (2)	0.628 (3)	0.1585 (13)	0.045 (5)*
C8	0.7247 (2)	0.5697 (3)	0.03182 (12)	0.0390 (4)
H8A	0.655 (2)	0.442 (3)	0.0453 (13)	0.047 (5)*
C9	0.8499 (2)	0.5642 (3)	0.18767 (11)	0.0353 (4)
H9B	0.957 (2)	0.563 (3)	0.2306 (13)	0.045*
C10	0.9820 (3)	0.7500	0.07362 (16)	0.0368 (6)
H11A	1.009 (3)	0.7500	0.0117 (19)	0.044*
H8B	0.754 (2)	0.579 (3)	−0.0316 (15)	0.048 (5)*
H9A	0.784 (3)	0.453 (3)	0.2013 (14)	0.053 (6)*
H11B	1.088 (4)	0.7500	0.1155 (19)	0.045 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0491 (13)	0.0472 (13)	0.0248 (10)	0.000	0.0058 (9)	0.000
N2	0.0238 (10)	0.0765 (16)	0.0296 (10)	0.000	0.0044 (8)	0.000
N3	0.0361 (11)	0.0453 (12)	0.0165 (9)	0.000	0.0049 (8)	0.000
N4	0.0412 (8)	0.0327 (8)	0.0269 (7)	0.0056 (6)	0.0007 (6)	−0.0029 (5)
N5	0.0344 (11)	0.0420 (12)	0.0276 (10)	0.000	−0.0053 (8)	0.000
O1	0.0588 (12)	0.0720 (14)	0.0295 (9)	0.000	0.0190 (8)	0.000
O2	0.0564 (13)	0.1013 (18)	0.0269 (9)	0.000	−0.0061 (9)	0.000
O3	0.0228 (9)	0.156 (2)	0.0465 (12)	0.000	−0.0018 (8)	0.000
O4	0.0330 (11)	0.182 (3)	0.0295 (10)	0.000	0.0110 (8)	0.000
O5	0.0292 (9)	0.0894 (15)	0.0210 (8)	0.000	0.0022 (6)	0.000
O1W	0.0396 (12)	0.0976 (18)	0.0368 (11)	0.000	−0.0054 (9)	0.000
C1	0.0385 (13)	0.0358 (13)	0.0209 (10)	0.000	0.0059 (9)	0.000
C2	0.0276 (12)	0.0477 (15)	0.0266 (11)	0.000	−0.0009 (9)	0.000
C3	0.0248 (11)	0.0451 (14)	0.0244 (11)	0.000	0.0063 (8)	0.000
C4	0.0277 (11)	0.0450 (14)	0.0228 (10)	0.000	0.0043 (8)	0.000
C5	0.0236 (11)	0.0676 (18)	0.0292 (12)	0.000	0.0023 (9)	0.000
C6	0.0301 (12)	0.0501 (15)	0.0281 (11)	0.000	0.0110 (9)	0.000
C7	0.0291 (12)	0.0535 (17)	0.0357 (13)	0.000	0.0045 (10)	0.000
C8	0.0489 (11)	0.0368 (10)	0.0301 (9)	−0.0013 (8)	−0.0043 (7)	−0.0063 (7)
C9	0.0438 (10)	0.0329 (9)	0.0289 (9)	0.0001 (7)	0.0010 (7)	0.0064 (7)
C10	0.0341 (13)	0.0516 (16)	0.0252 (11)	0.000	0.0064 (10)	0.000

Geometric parameters (Å, º)

N1—O2	1.234 (3)	O1W—H2W1	0.73 (5)
N1—O1	1.243 (3)	C1—C2	1.374 (3)
N1—C1	1.441 (3)	C1—C6	1.391 (3)
N2—O4	1.213 (3)	C2—C3	1.388 (3)
N2—O3	1.219 (3)	C2—H2A	0.88 (3)
N2—C3	1.440 (3)	C3—C4	1.434 (3)
N3—C9^i	1.510 (2)	C4—C5	1.438 (3)
N3—C9	1.510 (2)	C5—C6	1.353 (3)
N3—C7	1.519 (3)	C5—H5A	0.87 (3)
N3—H1N3	0.85 (3)	C6—H6A	0.91 (3)
N4—C9	1.438 (2)	C7—H7A	0.989 (19)
N4—C10	1.4666 (19)	C8—H8A	1.029 (19)
N4—C8	1.468 (2)	C8—H8B	0.97 (2)
N5—C7	1.446 (3)	C9—H9B	1.00 (2)
N5—C8^i	1.473 (2)	C9—H9A	0.93 (2)
N5—C8	1.473 (2)	C10—N4^i	1.4666 (19)
O5—C4	1.264 (3)	C10—H11A	0.94 (3)
O1W—H1W1	0.96 (3)	C10—H11B	0.99 (3)
O2—N1—O1	122.4 (2)	O5—C4—C5	119.4 (2)
O2—N1—C1	119.8 (2)	C3—C4—C5	113.87 (19)
O1—N1—C1	117.9 (2)	C6—C5—C4	123.5 (2)
O4—N2—O3	120.4 (2)	C6—C5—H5A	119.5 (18)
O4—N2—C3	120.4 (2)	C4—C5—H5A	117.1 (18)
O3—N2—C3	119.20 (19)	C5—C6—C1	119.6 (2)
C9^i—N3—C9	108.61 (18)	C5—C6—H6A	120.6 (17)
C9^i—N3—C7	108.71 (11)	C1—C6—H6A	119.8 (17)
C9—N3—C7	108.71 (11)	N5—C7—N3	109.74 (18)
C9^i—N3—H1N3	110.0 (10)	N5—C7—H7A	110.1 (11)
C9—N3—H1N3	110.0 (10)	N3—C7—H7A	109.0 (11)
C7—N3—H1N3	111 (2)	N4—C8—N5	111.82 (13)
C9—N4—C10	108.88 (14)	N4—C8—H8A	108.6 (11)
C9—N4—C8	109.75 (14)	N5—C8—H8A	108.6 (10)
C10—N4—C8	108.35 (15)	N4—C8—H8B	106.9 (12)
C7—N5—C8^i	109.10 (12)	N5—C8—H8B	106.9 (11)
C7—N5—C8	109.10 (12)	H8A—C8—H8B	114.0 (15)
C8^i—N5—C8	107.76 (19)	N4—C9—N3	109.65 (13)
H1W1—O1W—H2W1	106 (4)	N4—C9—H9B	112.0 (10)
C2—C1—C6	121.11 (19)	N3—C9—H9B	108.3 (11)
C2—C1—N1	118.4 (2)	N4—C9—H9A	111.7 (12)
C6—C1—N1	120.51 (19)	N3—C9—H9A	106.4 (12)
C1—C2—C3	119.3 (2)	H9B—C9—H9A	108.7 (16)
C1—C2—H2A	123.4 (16)	N4—C10—N4^i	111.77 (18)
C3—C2—H2A	117.4 (16)	N4—C10—H11A	109.4 (8)
C2—C3—C4	122.66 (19)	N4^i—C10—H11A	109.4 (8)
C2—C3—N2	115.9 (2)	N4—C10—H11B	108.3 (7)
C4—C3—N2	121.47 (18)	N4^i—C10—H11B	108.3 (7)
O5—C4—C3	126.68 (19)	H11A—C10—H11B	110 (2)
O2—N1—C1—C2	0.0	C4—C5—C6—C1	0.0
O1—N1—C1—C2	180.0	C2—C1—C6—C5	0.0
O2—N1—C1—C6	180.0	N1—C1—C6—C5	180.0
O1—N1—C1—C6	0.0	C8^i—N5—C7—N3	−58.75 (12)
C6—C1—C2—C3	0.0	C8—N5—C7—N3	58.75 (12)
N1—C1—C2—C3	180.0	C9^i—N3—C7—N5	59.03 (10)
C1—C2—C3—C4	0.0	C9—N3—C7—N5	−59.03 (10)
C1—C2—C3—N2	180.0	C9—N4—C8—N5	59.88 (18)
O4—N2—C3—C2	180.0	C10—N4—C8—N5	−58.89 (18)
O3—N2—C3—C2	0.0	C7—N5—C8—N4	−59.55 (19)
O4—N2—C3—C4	0.0	C8^i—N5—C8—N4	58.8 (2)
O3—N2—C3—C4	180.0	C10—N4—C9—N3	59.37 (19)
C2—C3—C4—O5	180.0	C8—N4—C9—N3	−59.07 (18)
N2—C3—C4—O5	0.0	C9^i—N3—C9—N4	−59.2 (2)
C2—C3—C4—C5	0.0	C7—N3—C9—N4	58.92 (18)
N2—C3—C4—C5	180.0	C9—N4—C10—N4^i	−60.7 (2)
O5—C4—C5—C6	180.0	C8—N4—C10—N4^i	58.6 (2)
C3—C4—C5—C6	0.0

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H13N···O5^ii	0.85 (3)	1.85 (3)	2.657 (2)	159 (3)
O1W—H11W···O5^ii	0.96 (3)	1.86 (3)	2.816 (3)	177 (3)
O1W—H21W···O4^iii	0.73 (5)	2.35 (5)	3.037 (3)	159 (5)
C5—H5A···O3^iv	0.88 (3)	2.48 (3)	3.164 (3)	135 (2)

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

(Iat143K) Hexamethylenetetramine-2,4-dinitrophenol Hydrate

Crystal data

C6H13N4^+·C6H3N2O5^−·H2O	Z = 2
Mr = 342.32	F(000) = 360
Triclinic, P1	Dx = 1.574 Mg m^−3
a = 6.3877 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9017 (5) Å	Cell parameters from 3560 reflections
c = 14.4042 (9) Å	θ = 1.4–29.6°
α = 84.412 (1)°	µ = 0.13 mm^−1
β = 86.367 (1)°	T = 143 K
γ = 89.304 (1)°	Block, yellow
V = 722.11 (8) Å^3	0.42 × 0.24 × 0.20 mm

Data collection

Siemens SMART CCD area-detector diffractometer	3227 independent reflections
Radiation source: fine-focus sealed tube	2201 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
Detector resolution: 8.33 pixels mm^-1	θmax = 28.0°, θmin = 2.6°
ω scans	h = −8→6
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −10→10
Tmin = 0.948, Tmax = 0.975	l = −18→18
4841 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)] = 0.087	All H-atom parameters refined
wR(F^2) = 0.206	w = 1/[σ^2(Fo^2) + (0.077P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max < 0.001
3227 reflections	Δρmax = 0.54 e Å^−3
281 parameters	Δρmin = −0.54 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.099 (15)

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 4 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.

# loop_ # _publ_manuscript_incl_extra_item # # '_geom_extra_tableA_col_1' # '_geom_extra_tableA_col_2' # '_geom_extra_table_head_A' # '_geom_table_footnote_A' # # _geom_extra_table_head_A #; # Average C—N bond distances (Å) along with the puckering parameters (Å, °) # of the six-membered C—N—C—N—C—N rings of the HMT #; # # loop_ # _geom_extra_tableA_col_1 # _geom_extra_tableA_col_2 # 'Scheme 2 here' ? # ? ? # 'T = 300K' 'T = 143K' # ? ? # 'Average C—N = 1.474' 'Average C—N = 1.480 (3)' # 'Q₂ = 0.014 (2)' 'Q₂ = 0.009 (3)' # 'Q₃ = 0.592 (2)' 'Q₃ = 0.596 (3)' # 'Q_T = 0.593 (2)' 'Q_T = 0.596 (3)' # 'θ = 0.4 (2)' 'θ = 0.0 (3)' # ? ? # 'Average C—N = 1.474 (3)' 'Average C—N = 1.480 (3)' # 'Q₂ = 0.014 (2)' 'Q₂ = 0.017 (3)' # 'Q₃ = 0.592 (2)' 'Q₃ = 0.600 (3)' # 'Q_T = 0.593 (2)' 'Q_T = 0.600 (3)' # 'θ = 0.4 (2)' 'θ = 1.8 (3)' # ? ? # 'Average C—N = 1.471 (3)' 'Average C—N = 1.479 (3)' # 'Q₂ = 0.008 (2)' 'Q₂ = 0.007 (2)' # 'Q₃ = 0.598 (2)' 'Q₃ = 0.597 (2)' # 'Q_T = 0.598 (2)' 'Q_T = 0.597 (3)' # 'θ = 1.6 (2)' 'θ = 2.1 (3)' # ? ? # 'Average C—N = 1.469 (3)' 'Average C—N = 1.473 (3)' # 'Q₂ = 0.004 (2)' 'Q₂ = 0.009 (3)' # 'Q₃ = 0.584 (2)' 'Q₃ = 0.578 (3)' # 'Q_T = 0.585 (2)' 'Q_T = 0.578 (3)' # 'θ = 1.1 (2)' 'θ = 0.0 (3)' # ? ? # # _geom_table_footnote_A #; # Note: All the rings adopt a chair conformation. #; #

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
N1	0.2752 (3)	0.6767 (3)	−0.25439 (15)	0.0154 (5)
N2	0.2440 (3)	0.9482 (3)	0.03112 (14)	0.0147 (5)
N3	0.2238 (3)	0.7463 (3)	0.29237 (15)	0.0133 (5)
H1N3	0.219 (5)	0.733 (4)	0.239 (2)	0.025*
N4	0.4515 (3)	0.8628 (3)	0.39867 (15)	0.0140 (5)
N4A	0.0720 (3)	0.9031 (3)	0.41653 (15)	0.0145 (5)
N5	0.2253 (3)	0.6220 (3)	0.45392 (15)	0.0145 (5)
O1	0.2775 (3)	0.5438 (2)	−0.29495 (13)	0.0222 (5)
O2	0.2812 (3)	0.8190 (3)	−0.29746 (13)	0.0233 (5)
O3	0.2575 (4)	1.0828 (2)	−0.01981 (14)	0.0272 (5)
O4	0.2269 (4)	0.9473 (3)	0.11750 (14)	0.0288 (6)
O5	0.2311 (3)	0.6037 (2)	0.13357 (12)	0.0178 (5)
O1W	−0.2302 (3)	0.7318 (3)	−0.22082 (14)	0.0242 (5)
H1W1	−0.234 (5)	0.622 (5)	−0.189 (2)	0.028*
H2W1	−0.240 (5)	0.796 (5)	−0.175 (2)	0.029*
C1	0.2629 (4)	0.6592 (3)	−0.15335 (16)	0.0127 (5)
C2	0.2576 (4)	0.8054 (3)	−0.10769 (18)	0.0140 (6)
H2	0.256 (5)	0.919 (5)	−0.140 (2)	0.035 (10)*
C3	0.2473 (4)	0.7898 (3)	−0.01062 (16)	0.0115 (5)
C4	0.2418 (4)	0.6288 (3)	0.04504 (17)	0.0123 (5)
C5	0.2503 (4)	0.4839 (3)	−0.00912 (18)	0.0156 (6)
H5A	0.247 (5)	0.373 (4)	0.020 (2)	0.022 (8)*
C6	0.2602 (4)	0.4979 (3)	−0.10400 (18)	0.0136 (5)
H6A	0.263 (4)	0.404 (4)	−0.139 (2)	0.021 (8)*
C7	0.2059 (4)	0.5831 (3)	0.35838 (18)	0.0156 (6)
H7B	0.069 (5)	0.532 (4)	0.348 (2)	0.020 (8)*
H7A	0.322 (5)	0.505 (4)	0.334 (2)	0.024*
C8	0.4297 (4)	0.7033 (3)	0.45981 (19)	0.0162 (6)
H8B	0.554 (5)	0.625 (4)	0.451 (2)	0.022*
H8A	0.438 (5)	0.727 (4)	0.519 (2)	0.028 (9)*
C8A	0.0584 (4)	0.7438 (3)	0.47820 (18)	0.0152 (6)
H8AB	−0.084 (5)	0.689 (4)	0.469 (2)	0.022*
H8AA	0.072 (5)	0.767 (4)	0.547 (2)	0.027 (8)*
C9	0.4339 (4)	0.8273 (3)	0.30282 (18)	0.0148 (6)
H9B	0.448 (5)	0.931 (4)	0.259 (2)	0.021 (8)*
H9A	0.545 (5)	0.749 (4)	0.283 (2)	0.028*
C9A	0.0505 (4)	0.8664 (3)	0.32122 (18)	0.0150 (5)
H9AB	0.069 (5)	0.961 (4)	0.278 (2)	0.024*
H9AA	−0.084 (5)	0.801 (4)	0.314 (2)	0.019 (8)*
C10	0.2787 (4)	0.9795 (3)	0.42406 (18)	0.0149 (6)
H10B	0.290 (5)	1.087 (4)	0.385 (2)	0.029*
H10A	0.279 (4)	1.002 (4)	0.486 (2)	0.019 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0139 (11)	0.0187 (11)	0.0140 (11)	0.0035 (9)	−0.0013 (8)	−0.0036 (9)
N2	0.0242 (12)	0.0093 (10)	0.0112 (10)	0.0044 (9)	−0.0043 (8)	−0.0023 (8)
N3	0.0184 (12)	0.0132 (11)	0.0091 (10)	0.0033 (8)	−0.0036 (8)	−0.0040 (9)
N4	0.0137 (11)	0.0131 (11)	0.0158 (11)	0.0003 (8)	−0.0034 (8)	−0.0029 (9)
N4A	0.0141 (11)	0.0139 (11)	0.0162 (11)	0.0024 (8)	−0.0015 (8)	−0.0045 (9)
N5	0.0174 (12)	0.0117 (10)	0.0145 (11)	0.0015 (8)	−0.0016 (8)	−0.0020 (9)
O1	0.0297 (12)	0.0217 (11)	0.0172 (10)	0.0072 (8)	−0.0035 (8)	−0.0115 (8)
O2	0.0368 (13)	0.0184 (10)	0.0144 (10)	0.0032 (8)	−0.0017 (8)	0.0000 (8)
O3	0.0528 (14)	0.0087 (9)	0.0203 (11)	0.0015 (9)	−0.0044 (9)	−0.0005 (8)
O4	0.0617 (16)	0.0135 (10)	0.0122 (9)	0.0042 (9)	−0.0043 (9)	−0.0053 (8)
O5	0.0334 (12)	0.0110 (9)	0.0092 (9)	0.0013 (8)	−0.0029 (7)	−0.0020 (7)
O1W	0.0399 (13)	0.0158 (10)	0.0165 (10)	0.0018 (9)	−0.0022 (8)	−0.0001 (9)
C1	0.0142 (13)	0.0163 (13)	0.0083 (11)	0.0035 (10)	−0.0020 (9)	−0.0043 (10)
C2	0.0152 (13)	0.0122 (12)	0.0148 (12)	0.0024 (10)	−0.0013 (9)	−0.0021 (10)
C3	0.0158 (13)	0.0074 (11)	0.0121 (12)	0.0024 (9)	−0.0043 (9)	−0.0033 (10)
C4	0.0137 (12)	0.0099 (12)	0.0144 (12)	0.0022 (9)	−0.0030 (9)	−0.0050 (10)
C5	0.0235 (14)	0.0083 (12)	0.0155 (13)	0.0022 (10)	−0.0022 (9)	−0.0026 (10)
C6	0.0156 (13)	0.0120 (12)	0.0142 (12)	0.0026 (9)	−0.0017 (9)	−0.0055 (10)
C7	0.0207 (14)	0.0090 (12)	0.0184 (13)	0.0021 (10)	−0.0052 (10)	−0.0050 (10)
C8	0.0170 (14)	0.0162 (13)	0.0155 (12)	0.0003 (10)	−0.0051 (10)	0.0007 (11)
C8A	0.0165 (13)	0.0146 (13)	0.0145 (12)	0.0020 (10)	−0.0005 (9)	−0.0025 (10)
C9	0.0135 (13)	0.0156 (13)	0.0150 (12)	0.0008 (10)	0.0010 (9)	−0.0018 (11)
C9A	0.0128 (13)	0.0166 (13)	0.0165 (12)	0.0045 (10)	−0.0035 (9)	−0.0059 (11)
C10	0.0180 (14)	0.0136 (13)	0.0141 (12)	0.0017 (10)	−0.0029 (9)	−0.0057 (11)

Geometric parameters (Å, º)

N1—O2	1.230 (3)	C1—C2	1.383 (3)
N1—O1	1.250 (3)	C1—C6	1.398 (4)
N1—C1	1.446 (3)	C2—C3	1.389 (3)
N2—O3	1.232 (3)	C2—H2	0.97 (4)
N2—O4	1.241 (3)	C3—C4	1.436 (3)
N2—C3	1.440 (3)	C4—C5	1.446 (3)
N3—C9A	1.514 (3)	C5—C6	1.358 (3)
N3—C9	1.516 (3)	C5—H5A	0.93 (3)
N3—C7	1.526 (3)	C6—H6A	0.94 (3)
N3—H1N3	0.79 (3)	C7—H7B	1.00 (3)
N4—C9	1.447 (3)	C7—H7A	1.03 (3)
N4—C8	1.469 (3)	C8—H8B	1.01 (3)
N4—C10	1.480 (3)	C8—H8A	0.90 (3)
N4A—C9A	1.446 (3)	C8A—H8AB	1.03 (3)
N4A—C8A	1.468 (3)	C8A—H8AA	1.03 (3)
N4A—C10	1.473 (3)	C9—H9B	0.99 (3)
N5—C7	1.452 (3)	C9—H9A	0.98 (3)
N5—C8	1.473 (3)	C9A—H9AB	0.93 (3)
N5—C8A	1.476 (3)	C9A—H9AA	1.03 (3)
O5—C4	1.269 (3)	C10—H10B	0.97 (3)
O1W—H1W1	0.94 (3)	C10—H10A	0.92 (3)
O1W—H2W1	0.87 (4)
O2—N1—O1	122.3 (2)	C5—C6—H6A	123.3 (19)
O2—N1—C1	120.0 (2)	C1—C6—H6A	117.3 (19)
O1—N1—C1	117.8 (2)	N5—C7—N3	109.75 (19)
O3—N2—O4	121.1 (2)	N5—C7—H7B	113.7 (17)
O3—N2—C3	119.2 (2)	N3—C7—H7B	106.0 (18)
O4—N2—C3	119.7 (2)	N5—C7—H7A	114.4 (18)
C9A—N3—C9	108.9 (2)	N3—C7—H7A	104.7 (17)
C9A—N3—C7	108.2 (2)	H7B—C7—H7A	108 (3)
C9—N3—C7	108.6 (2)	N4—C8—N5	112.3 (2)
C9A—N3—H1N3	110 (3)	N4—C8—H8B	111.7 (17)
C9—N3—H1N3	107 (2)	N5—C8—H8B	114.1 (18)
C7—N3—H1N3	115 (2)	N4—C8—H8A	108 (2)
C9—N4—C8	109.0 (2)	N5—C8—H8A	107 (2)
C9—N4—C10	108.4 (2)	H8B—C8—H8A	102 (3)
C8—N4—C10	108.8 (2)	N4A—C8A—N5	112.07 (19)
C9A—N4A—C8A	109.2 (2)	N4A—C8A—H8AB	107.4 (18)
C9A—N4A—C10	109.48 (19)	N5—C8A—H8AB	107.8 (17)
C8A—N4A—C10	108.5 (2)	N4A—C8A—H8AA	110.5 (18)
C7—N5—C8	108.7 (2)	N5—C8A—H8AA	107.6 (19)
C7—N5—C8A	108.8 (2)	H8AB—C8A—H8AA	112 (2)
C8—N5—C8A	108.3 (2)	N4—C9—N3	110.08 (19)
H1W1—O1W—H2W1	102 (3)	N4—C9—H9B	112.0 (18)
C2—C1—C6	121.4 (2)	N3—C9—H9B	108.9 (18)
C2—C1—N1	118.3 (2)	N4—C9—H9A	111 (2)
C6—C1—N1	120.3 (2)	N3—C9—H9A	108 (2)
C1—C2—C3	118.7 (2)	H9B—C9—H9A	107 (2)
C1—C2—H2	123 (2)	N4A—C9A—N3	109.7 (2)
C3—C2—H2	118 (2)	N4A—C9A—H9AB	113 (2)
C2—C3—C4	123.2 (2)	N3—C9A—H9AB	103.5 (19)
C2—C3—N2	115.0 (2)	N4A—C9A—H9AA	112.2 (16)
C4—C3—N2	121.8 (2)	N3—C9A—H9AA	103.7 (17)
O5—C4—C3	127.1 (2)	H9AB—C9A—H9AA	114 (3)
O5—C4—C5	119.0 (2)	N4A—C10—N4	111.5 (2)
C3—C4—C5	113.9 (2)	N4A—C10—H10B	110 (2)
C6—C5—C4	123.3 (2)	N4—C10—H10B	110.8 (19)
C6—C5—H5A	115 (2)	N4A—C10—H10A	104.1 (18)
C4—C5—H5A	122 (2)	N4—C10—H10A	111.9 (19)
C5—C6—C1	119.4 (2)	H10B—C10—H10A	108 (3)
O2—N1—C1—C2	0.2 (3)	C9A—N3—C7—N5	−59.4 (3)
O1—N1—C1—C2	−179.2 (2)	C9—N3—C7—N5	58.7 (3)
O2—N1—C1—C6	−178.7 (2)	C9—N4—C8—N5	−60.5 (3)
O1—N1—C1—C6	1.9 (3)	C10—N4—C8—N5	57.6 (3)
C6—C1—C2—C3	−0.6 (4)	C7—N5—C8—N4	60.6 (3)
N1—C1—C2—C3	−179.5 (2)	C8A—N5—C8—N4	−57.5 (3)
C1—C2—C3—C4	−0.1 (4)	C9A—N4A—C8A—N5	60.4 (3)
C1—C2—C3—N2	179.5 (2)	C10—N4A—C8A—N5	−58.9 (3)
O3—N2—C3—C2	−2.5 (4)	C7—N5—C8A—N4A	−59.9 (3)
O4—N2—C3—C2	177.3 (2)	C8—N5—C8A—N4A	58.1 (3)
O3—N2—C3—C4	177.1 (2)	C8—N4—C9—N3	58.9 (3)
O4—N2—C3—C4	−3.1 (4)	C10—N4—C9—N3	−59.5 (3)
C2—C3—C4—O5	−179.5 (2)	C9A—N3—C9—N4	59.0 (3)
N2—C3—C4—O5	0.9 (4)	C7—N3—C9—N4	−58.5 (3)
C2—C3—C4—C5	0.7 (4)	C8A—N4A—C9A—N3	−59.8 (3)
N2—C3—C4—C5	−178.9 (2)	C10—N4A—C9A—N3	58.8 (3)
O5—C4—C5—C6	179.4 (2)	C9—N3—C9A—N4A	−58.2 (3)
C3—C4—C5—C6	−0.7 (4)	C7—N3—C9A—N4A	59.6 (3)
C4—C5—C6—C1	0.1 (4)	C9A—N4A—C10—N4	−60.7 (3)
C2—C1—C6—C5	0.6 (4)	C8A—N4A—C10—N4	58.4 (3)
N1—C1—C6—C5	179.5 (2)	C9—N4—C10—N4A	60.7 (3)
C8—N5—C7—N3	−59.0 (3)	C8—N4—C10—N4A	−57.8 (3)
C8A—N5—C7—N3	58.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H13N···O5	0.79 (3)	1.91 (3)	2.644 (3)	155 (3)
O1W—H11W···O5^i	0.94 (4)	1.88 (4)	2.821 (3)	176 (3)
O1W—H21W···O4^ii	0.87 (3)	2.27 (4)	3.064 (3)	152 (3)
C5—H5A···O3^iii	0.93 (3)	2.42 (3)	3.188 (3)	140 (2)
C7—H7B···O1^i	0.99 (3)	2.49 (3)	3.462 (3)	168 (2)
C9—H9A···O1^iv	0.98 (3)	2.56 (3)	3.452 (3)	151 (2)

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