Bis(hexa­methyl­enetetra­minium) chloranilate tetra­hydrate

The anion of the title compound, 2C₆H₁₃N₄⁺·C₆Cl₂O₄^2-·4H₂O, is centrosymmetric. The crystal structure is stabilized by a network of inter­molecular hydrogen bonds. The solvent water mol­ecules are disordered, each with approximate 2:1 occupancy of two positions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.049
• wR factor = 0.133
• Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor      >O3     -  >H3A    ...          ?

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT301_ALERT_3_C Main Residue  Disorder .........................       8.00 Perc.
PLAT333_ALERT_2_C Large Average Benzene C-C Dist.  C1     -C3_a          1.45 Ang.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C2     -   C3     ...       1.54 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4D    ..  CL1     ..       3.03 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4C    ..  O3      ..       2.62 Ang.

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

   3 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
   0 ALERT type 5 Informative message, check

---

S1. Comment

As part of our continuing studies on co-crystals involving chloranilic acid (Yang & Qu, 2006), we report herein the crystal structure of the title compound, (I).

In (I), the H atoms have been transferred from the hydroxyl group of the chloranilic acid molecule to the amine group N atom of hexamethylenetetramine molecule, forming a 1:2 organic salt. In addition, there are two solvent water molecules in the asymmetric unit (Fig.1). The protonated amine atom N3 acts as hydrogen bond donor, via H3, to two adjacent O atoms, forming the inter-ion three-centre hydrogen bond. In addition, the C–N bond distances involved the protonated atom N3 are slightly longer than for the unprotonated ones N atoms. On the contrary, the deprotonated C–O(hydroxyl) bond distances of 1.251 (5) and 1.237 (5)Å are shorter than the C–O(hydroxyl) value of 1.362 (15) Å in phenol, but longer than the standard bond distance of a C=O double bond (in benzoquinones), 1.222 (13) Å. (Allen et al., 1987).

A combination of N (or O)–H···O, C–H···O(or N) and C–H···Cl hydrogen bonds (Table 1) stabilizes the crystal structure (Fig. 2).

Related literature

For related literature, see: Allen et al. (1987); Yang & Qu (2006).

S2. Experimental

All the reagents and solvents were used as obtained without further purification. Equivalent molar amount of Chloranilic acid and hexamethylenetetramine were dissolved in methanol (20 ml). The mixture was stirred for half an hour at ambient temperature and then filtered. The resulting red solution was kept in air for one week. Crystals of (I) suitable for single-crystal X-ray diffraction analysis were grown by slow evaporation of the solution at the bottom of the vessel.

S3. Refinement

H atoms bonded to C atoms were included in calculated positions with C–H=0.97 Å and U_iso(H) = 1.2U_eq(C). Atom H3 was located in a difference map its positional parameters were refined and its U_iso value was set 1.2 times of the U_eq of N3 atom. The water H atoms were located from the difference maps and their U_iso values were set 1.5 times of their carrier atoms. The O(water)-H distances were refined by using the DFIX command in SHELXL (Sheldrick, 1997). Both water molecules containing atoms O3 and O4 atoms were disordered over two positions with a ratio of refined occupacies of 0.68 (6):0.32 (6) and 0.63 (3):0.36 (3), respectively, for the major and minor components. The disorder with respect to the solvent water molecules made it difficult to interpret all the hydrogen bond interactions in which they are involved. Table 1 lists only seclected hydrogen bond involving the water molecules.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures

	Fig. 1. Molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. hydrogen bonds are shown as dashed lines. Atoms marked with suffix 'a' are realted by the symmetry operator (1 - x, 1 - y, 1 - z).
	Fig. 2. Part of the crystal structure of (I), showing the formation of the three-dimensional network. Hydrogen bonding are shown as dashed lines. For the sake of clarity, H atoms not involved in the motif have been omitted.

Bis(hexamethylenetetraminium) chloranilate tetrahydrate

Crystal data

2C6H13N4^+·C6Cl2O4^2^−·4H2O	F(000) = 592
Mr = 561.44	Dx = 1.479 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1255 reflections
a = 6.1794 (4) Å	θ = 2.4–25.4°
b = 16.8362 (12) Å	µ = 0.32 mm^−1
c = 12.2627 (9) Å	T = 298 K
β = 98.791 (1)°	Block, red
V = 1260.79 (15) Å^3	0.20 × 0.16 × 0.15 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer	2737 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2185 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
0.3° wide ω exposures scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −7→7
Tmin = 0.939, Tmax = 0.981	k = −21→21
10757 measured reflections	l = −15→15

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0705P)^2 + 0.2943P] where P = (Fo^2 + 2Fc^2)/3
2737 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.31 e Å^−3
37 restraints	Δρmin = −0.23 e Å^−3

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	Occ. (<1)
Cl1	0.89623 (9)	0.50143 (3)	0.69782 (5)	0.0446 (2)
C1	0.6796 (3)	0.50143 (10)	0.58940 (16)	0.0314 (4)
C2	0.6864 (3)	0.44703 (10)	0.50282 (15)	0.0302 (4)
C3	0.4961 (3)	0.44760 (10)	0.40595 (15)	0.0307 (4)
C4	0.8090 (4)	0.29530 (14)	0.2118 (2)	0.0515 (6)
H4A	0.6521	0.3007	0.1900	0.062*
H4B	0.8790	0.3421	0.1871	0.062*
C5	0.7769 (5)	0.15608 (15)	0.1997 (2)	0.0588 (7)
H5A	0.8241	0.1088	0.1646	0.071*
H5B	0.6198	0.1611	0.1781	0.071*
C6	1.1214 (4)	0.21767 (15)	0.1967 (2)	0.0564 (7)
H6A	1.1737	0.1711	0.1622	0.068*
H6B	1.1950	0.2637	0.1721	0.068*
C7	0.7510 (4)	0.21626 (14)	0.3717 (2)	0.0513 (6)
H7A	0.7842	0.2110	0.4513	0.062*
H7B	0.5936	0.2213	0.3516	0.062*
C8	1.0649 (4)	0.14114 (14)	0.3518 (3)	0.0595 (7)
H8A	1.0990	0.1361	0.4314	0.071*
H8B	1.1173	0.0937	0.3193	0.071*
C9	1.1054 (4)	0.28014 (14)	0.3675 (2)	0.0476 (6)
H9A	1.1787	0.3266	0.3440	0.057*
H9B	1.1418	0.2758	0.4470	0.057*
N1	0.8852 (3)	0.22567 (12)	0.16102 (16)	0.0503 (5)
N2	0.8262 (3)	0.14696 (11)	0.31982 (18)	0.0524 (5)
N3	0.8615 (3)	0.28880 (10)	0.33541 (15)	0.0409 (4)
H3	0.816 (4)	0.3304 (14)	0.366 (2)	0.049*
N4	1.1781 (3)	0.21049 (12)	0.31625 (18)	0.0502 (5)
O1	0.8326 (2)	0.39727 (8)	0.49978 (12)	0.0423 (4)
O2	0.5122 (2)	0.40054 (9)	0.32866 (12)	0.0454 (4)
O3	0.339 (3)	0.3923 (6)	0.1059 (5)	0.105 (3)	0.68 (3)
H3A	0.251 (12)	0.425 (3)	0.075 (6)	0.157*	0.68 (3)
H3B	0.392 (13)	0.405 (4)	0.169 (3)	0.157*	0.68 (3)
O4	0.7867 (13)	0.4992 (3)	0.0620 (5)	0.137 (3)	0.642 (11)
H4C	0.676 (9)	0.471 (5)	0.055 (9)	0.206*	0.642 (11)
H4D	0.776 (9)	0.539 (4)	0.100 (7)	0.206*	0.642 (11)
O3'	0.453 (5)	0.4187 (15)	0.1031 (11)	0.104 (6)	0.32 (3)
H3C	0.334 (14)	0.439 (8)	0.079 (16)	0.156*	0.32 (3)
H3D	0.556 (17)	0.450 (7)	0.116 (15)	0.156*	0.32 (3)
O4'	0.943 (5)	0.5497 (18)	0.021 (2)	0.260 (10)	0.358 (11)
H4E	1.06 (3)	0.54 (2)	0.01 (4)	0.390*	0.358 (11)
H4F	0.90 (6)	0.595 (9)	0.00 (3)	0.390*	0.358 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0437 (3)	0.0419 (3)	0.0436 (3)	0.0050 (2)	−0.0080 (2)	−0.0038 (2)
C1	0.0325 (10)	0.0295 (9)	0.0309 (10)	0.0002 (7)	0.0007 (8)	0.0003 (7)
C2	0.0326 (10)	0.0266 (9)	0.0326 (10)	0.0005 (7)	0.0094 (8)	0.0034 (7)
C3	0.0348 (10)	0.0260 (9)	0.0320 (10)	−0.0008 (7)	0.0071 (8)	0.0000 (7)
C4	0.0582 (15)	0.0463 (13)	0.0477 (14)	0.0078 (11)	0.0008 (11)	−0.0004 (10)
C5	0.0600 (16)	0.0520 (14)	0.0635 (17)	−0.0149 (12)	0.0066 (12)	−0.0202 (12)
C6	0.0503 (14)	0.0611 (15)	0.0633 (17)	−0.0018 (11)	0.0259 (12)	−0.0168 (12)
C7	0.0402 (12)	0.0630 (15)	0.0539 (15)	−0.0022 (11)	0.0173 (11)	−0.0025 (11)
C8	0.0620 (17)	0.0454 (14)	0.0707 (18)	0.0168 (12)	0.0088 (13)	0.0034 (12)
C9	0.0384 (12)	0.0527 (13)	0.0505 (13)	−0.0056 (10)	0.0031 (10)	−0.0151 (10)
N1	0.0590 (13)	0.0508 (11)	0.0414 (11)	−0.0029 (9)	0.0082 (9)	−0.0117 (8)
N2	0.0557 (13)	0.0402 (10)	0.0628 (13)	−0.0086 (9)	0.0134 (10)	−0.0015 (9)
N3	0.0414 (10)	0.0374 (9)	0.0447 (11)	0.0088 (8)	0.0092 (8)	−0.0118 (8)
N4	0.0331 (10)	0.0567 (12)	0.0615 (13)	0.0057 (8)	0.0097 (9)	−0.0114 (10)
O1	0.0414 (8)	0.0420 (8)	0.0428 (9)	0.0139 (6)	0.0040 (6)	−0.0058 (6)
O2	0.0495 (9)	0.0470 (9)	0.0384 (8)	0.0105 (7)	0.0031 (7)	−0.0140 (7)
O3	0.139 (7)	0.121 (4)	0.049 (2)	0.008 (4)	−0.004 (3)	−0.024 (2)
O4	0.195 (7)	0.098 (4)	0.100 (4)	0.042 (3)	−0.041 (4)	−0.028 (3)
O3'	0.119 (10)	0.116 (9)	0.075 (6)	0.028 (7)	0.008 (6)	−0.002 (6)
O4'	0.256 (13)	0.278 (13)	0.245 (13)	0.004 (10)	0.036 (9)	−0.023 (10)

Geometric parameters (Å, º)

C1—C2	1.408 (3)	C5—H5A	0.9700
C1—C3^i	1.392 (3)	C5—H5B	0.9700
C2—O1	1.237 (2)	C6—H6A	0.9700
C2—C3	1.539 (3)	C6—H6B	0.9700
C3—O2	1.251 (2)	C7—H7A	0.9700
C4—N1	1.440 (3)	C7—H7B	0.9700
C5—N1	1.464 (3)	C8—H8A	0.9700
C6—N1	1.465 (3)	C8—H8B	0.9700
C5—N2	1.466 (3)	C9—H9A	0.9700
C7—N2	1.440 (3)	C9—H9B	0.9700
C8—N2	1.471 (3)	N3—H3	0.86 (2)
C4—N3	1.505 (3)	O3—H3A	0.825 (11)
C7—N3	1.499 (3)	O3—H3B	0.827 (11)
C9—N3	1.506 (3)	O3—H3C	0.85 (14)
C6—N4	1.459 (3)	O4—H4C	0.828 (11)
C8—N4	1.461 (3)	O4—H4D	0.828 (10)
C9—N4	1.434 (3)	O3'—H3B	0.98 (7)
Cl1—C1	1.737 (2)	O3'—H3C	0.824 (11)
C3—C1^i	1.392 (3)	O3'—H3D	0.824 (11)
C4—H4A	0.9700	O4'—H4E	0.825 (11)
C4—H4B	0.9700	O4'—H4F	0.826 (11)
C3^i—C1—C2	123.07 (18)	N4—C8—N2	111.90 (19)
C3^i—C1—Cl1	118.91 (15)	N4—C8—H8A	109.2
C2—C1—Cl1	117.97 (14)	N2—C8—H8A	109.2
O1—C2—C1	124.72 (19)	N4—C8—H8B	109.2
O1—C2—C3	117.17 (16)	N2—C8—H8B	109.2
C1—C2—C3	118.08 (16)	H8A—C8—H8B	107.9
O2—C3—C1^i	125.08 (19)	N4—C9—N3	109.44 (17)
O2—C3—C2	116.15 (16)	N4—C9—H9A	109.8
C1^i—C3—C2	118.76 (16)	N3—C9—H9A	109.8
N1—C4—N3	110.01 (18)	N4—C9—H9B	109.8
N1—C4—H4A	109.7	N3—C9—H9B	109.8
N3—C4—H4A	109.7	H9A—C9—H9B	108.2
N1—C4—H4B	109.7	C4—N1—C5	108.42 (19)
N3—C4—H4B	109.7	C4—N1—C6	108.79 (19)
H4A—C4—H4B	108.2	C5—N1—C6	108.3 (2)
N1—C5—N2	111.97 (19)	C7—N2—C5	109.1 (2)
N1—C5—H5A	109.2	C7—N2—C8	108.31 (19)
N2—C5—H5A	109.2	C5—N2—C8	108.8 (2)
N1—C5—H5B	109.2	C7—N3—C4	108.70 (18)
N2—C5—H5B	109.2	C7—N3—C9	109.06 (18)
H5A—C5—H5B	107.9	C4—N3—C9	108.83 (18)
N4—C6—N1	112.53 (18)	C7—N3—H3	109.8 (16)
N4—C6—H6A	109.1	C4—N3—H3	110.0 (16)
N1—C6—H6A	109.1	C9—N3—H3	110.4 (16)
N4—C6—H6B	109.1	C9—N4—C6	109.21 (19)
N1—C6—H6B	109.1	C9—N4—C8	109.05 (18)
H6A—C6—H6B	107.8	C6—N4—C8	108.3 (2)
N2—C7—N3	109.67 (17)	H3A—O3—H3B	113 (2)
N2—C7—H7A	109.7	H4C—O4—H4D	113 (2)
N3—C7—H7A	109.7	H3A—O3'—H3D	135 (10)
N2—C7—H7B	109.7	H3B—O3'—H3D	112 (10)
N3—C7—H7B	109.7	H3C—O3'—H3D	115 (2)
H7A—C7—H7B	108.2	H4E—O4'—H4F	115 (2)
C3^i—C1—C2—O1	−174.85 (18)	N1—C5—N2—C7	60.3 (3)
Cl1—C1—C2—O1	2.4 (3)	N1—C5—N2—C8	−57.6 (3)
C3^i—C1—C2—C3	3.5 (3)	N4—C8—N2—C7	−60.7 (3)
Cl1—C1—C2—C3	−179.25 (12)	N4—C8—N2—C5	57.8 (3)
O1—C2—C3—O2	−4.2 (2)	N2—C7—N3—C4	59.0 (2)
C1—C2—C3—O2	177.33 (17)	N2—C7—N3—C9	−59.6 (2)
O1—C2—C3—C1^i	175.12 (17)	N1—C4—N3—C7	−59.6 (2)
C1—C2—C3—C1^i	−3.4 (3)	N1—C4—N3—C9	59.1 (2)
N3—C4—N1—C5	59.4 (3)	N4—C9—N3—C7	59.1 (2)
N3—C4—N1—C6	−58.2 (2)	N4—C9—N3—C4	−59.3 (2)
N2—C5—N1—C4	−60.3 (3)	N3—C9—N4—C6	59.1 (2)
N2—C5—N1—C6	57.6 (2)	N3—C9—N4—C8	−59.0 (3)
N4—C6—N1—C4	59.3 (3)	N1—C6—N4—C9	−60.1 (2)
N4—C6—N1—C5	−58.3 (2)	N1—C6—N4—C8	58.5 (2)
N3—C7—N2—C5	−58.9 (3)	N2—C8—N4—C9	60.8 (3)
N3—C7—N2—C8	59.4 (3)	N2—C8—N4—C6	−57.9 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O2^ii	0.97	2.44	3.320 (3)	151
C7—H7B···N4^iii	0.97	2.54	3.503 (3)	170
C7—H7A···O3^iv	0.97	2.56	3.378 (6)	142
C6—H6B···O3^ii	0.97	2.52	3.485 (16)	173
O4—H4D···Cl1^v	0.83 (1)	3.03 (8)	3.278 (5)	100 (6)
C4—H4A···O3	0.97	2.57	3.413 (10)	146
O4—H4C···O3	0.83 (1)	2.62 (4)	3.41 (2)	160 (10)
O3—H3B···O2	0.83 (1)	1.98 (2)	2.781 (6)	162 (8)
N3—H3···O2	0.86 (2)	2.20 (2)	2.854 (2)	132 (2)
N3—H3···O1	0.86 (2)	1.98 (2)	2.746 (2)	147 (2)

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