Redetermination of the salt hexa­methyl­ene­tetra­minium fumarate

Abstract

The crystal structure of the title compound [systematic name: 3,5,7-triaza-1-azoniatricyclo­[3.3.1.1^3,7]decane (E)-3-carb­oxy­prop-2-enoate], C₆H₁₃N₄ ⁺·C₄H₃O₄ ⁻, had been determined previously by Bowes et al. [Acta Cryst. (2003), B59, 100–117]. Their structure contained an approximately 3:1 ratio of fumarate and succinate monoanions disordered over the same position. The succinate anion component forms a similar structural role to the fumarate anion and came about due to an impurity in the starting material, fumaric acid. In this work, the crystal structure of the pure salt is presented, which is identical, apart from the lack of disorder of the anions, to the previous structure. In the crystal, the ions assemble in the solid state, forming chains via N⁺—H⋯O⁻ and O—H⋯O⁻ hydrogen bonds, which are linked into a three-dimensional network by C—H⋯O inter­actions.

Related literature

For the previous synthesis and structure determination, see: Bowes et al. (2003 ▶). For graph-set nomenclature of hydrogen bonds, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

• C₆H₁₃N₄ ⁺·C₄H₃O₄ ⁻

• M _r = 256.27

• Monoclinic,

• a = 6.3020 (3) Å

• b = 16.0828 (8) Å

• c = 11.2205 (6) Å

• β = 95.930 (2)°

• V = 1131.15 (10) ų

• Z = 4

• Mo Kα radiation

• μ = 0.12 mm⁻¹

• T = 173 K

• 0.4 × 0.26 × 0.1 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: integration (XPREP; Bruker, 2004 ▶) T _min = 0.936, T _max = 0.989

• 12032 measured reflections

• 2733 independent reflections

• 2263 reflections with I > 2σ(I)

• R _int = 0.114

Refinement

• R[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 0.128

• S = 1.04

• 2733 reflections

• 169 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.36 e Å⁻³

• Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.845 (19)	2.094 (19)	2.8704 (14)	153 (2)
O3—H3⋯O1i	1.034 (18)	1.458 (18)	2.4877 (13)	174 (2)
C1—H1A⋯O3ii	0.99	2.46	3.2708 (16)	138
C3—H3B⋯O4iii	0.99	2.55	3.4629 (18)	154
C4—H4B⋯O4iv	0.99	2.48	3.3668 (17)	149
C6—H6A⋯O4iv	0.99	2.43	3.3352 (18)	152

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

The fumarate anions forms a C(7) chain (Graph Set notation; Bernstein et al., 1995) along the a axis by unit cell translations only. The chain is formed by O—H···O^- hydrogen bonds. The hexamethylenetramanium cation is pendant to the chains, and linked to them by N⁺—H···O^- hydrogen bonds (Fig. 2). Fig. 3 shows the relative packing of the chains down the a axis.

Experimental

Crystals where grown by slow evaporation at ambient conditions of a methanol solution containing a stoichiometric quantity of hexamethylenetetramine and fumaric acid.

Refinement

The C-bound H atoms were geometrically placed (C—H bond lengths of 0.95 (ethylene CH) and 0.99 (CH₂) Å) and refined as riding with U_iso(H) = 1.2U_eq(C). The O-bound H atom and N-bound H were located in the difference map and their coordinates refined freely, with U_iso(H) = 1.5U_eq(O) or 1.5U_eq(N).

Figures

Fig. 1.

View of (I) (50% probability displacement ellipsoids)

Fig. 2.

Hydrogen bonding chain of (I) using N+—H···O- and O—H···O- hydrogen bonds (red dashed lines), generated by translation along the a axis.

Fig. 3.

Packing diagram of the four C(7) chains in the unit cell.

Crystal data

C6H13N4+·C4H3O4−	F(000) = 544
Mr = 256.27	Dx = 1.505 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4463 reflections
a = 6.3020 (3) Å	θ = 2.2–28.3°
b = 16.0828 (8) Å	µ = 0.12 mm−1
c = 11.2205 (6) Å	T = 173 K
β = 95.930 (2)°	Block, colourless
V = 1131.15 (10) Å3	0.4 × 0.26 × 0.1 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	2263 reflections with I > 2σ(I)
ω scans	Rint = 0.114
Absorption correction: integration (XPREP; Bruker, 2004)	θmax = 28.0°, θmin = 2.2°
Tmin = 0.936, Tmax = 0.989	h = −8→8
12032 measured reflections	k = −21→21
2733 independent reflections	l = −11→14

Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.045	w = 1/[σ2(Fo2) + (0.0679P)2 + 0.1146P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.128	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.36 e Å−3
2733 reflections	Δρmin = −0.26 e Å−3
169 parameters

Special details

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004)

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.

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

	x	y	z	Uiso*/Ueq
C1	0.5255 (2)	0.82554 (8)	0.61723 (12)	0.0247 (3)
H1A	0.5118	0.8385	0.7024	0.03*
H1B	0.6756	0.81	0.6098	0.03*
C2	0.2451 (2)	0.91915 (8)	0.55450 (13)	0.0272 (3)
H2A	0.207	0.9693	0.5057	0.033*
H2B	0.2281	0.9326	0.6391	0.033*
C3	0.1515 (2)	0.77886 (9)	0.58785 (13)	0.0262 (3)
H3A	0.0546	0.7325	0.5615	0.031*
H3B	0.1334	0.7915	0.6726	0.031*
C4	0.4040 (2)	0.73544 (8)	0.44620 (12)	0.0232 (3)
H4A	0.5531	0.7191	0.4376	0.028*
H4B	0.3097	0.6886	0.4182	0.028*
C5	0.4895 (2)	0.87723 (9)	0.41791 (12)	0.0271 (3)
H5A	0.4544	0.927	0.3678	0.033*
H5B	0.6394	0.8619	0.4096	0.033*
C6	0.1277 (2)	0.83150 (9)	0.38914 (12)	0.0266 (3)
H6A	0.0318	0.7851	0.3616	0.032*
H6B	0.087	0.8805	0.3384	0.032*
N1	0.37969 (18)	0.75391 (7)	0.57675 (10)	0.0208 (3)
H1	0.409 (3)	0.7097 (12)	0.6156 (16)	0.031*
N2	0.46828 (19)	0.89757 (7)	0.54400 (10)	0.0243 (3)
N3	0.09872 (18)	0.85121 (7)	0.51461 (10)	0.0244 (3)
N4	0.34884 (19)	0.80830 (7)	0.37423 (10)	0.0239 (3)
C7	0.6729 (2)	0.58907 (8)	0.63638 (11)	0.0176 (3)
C8	0.7983 (2)	0.50985 (8)	0.64094 (11)	0.0182 (3)
H8	0.7237	0.4585	0.6406	0.022*
C9	1.00774 (19)	0.50863 (8)	0.64536 (11)	0.0173 (3)
H9	1.0825	0.5599	0.6451	0.021*
C10	1.1315 (2)	0.42962 (8)	0.65074 (11)	0.0180 (3)
O1	0.46931 (14)	0.58179 (6)	0.62743 (8)	0.0214 (2)
O2	0.76697 (15)	0.65634 (6)	0.64178 (10)	0.0281 (3)
O3	1.33649 (14)	0.43696 (6)	0.64341 (9)	0.0220 (2)
H3	1.382 (3)	0.4983 (12)	0.6347 (15)	0.033*
O4	1.04798 (15)	0.36217 (6)	0.66187 (10)	0.0305 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0283 (7)	0.0205 (7)	0.0229 (6)	−0.0018 (5)	−0.0083 (5)	−0.0022 (5)
C2	0.0381 (8)	0.0157 (6)	0.0269 (7)	0.0061 (5)	−0.0004 (6)	−0.0016 (5)
C3	0.0258 (7)	0.0238 (7)	0.0294 (7)	0.0016 (5)	0.0045 (6)	0.0065 (5)
C4	0.0275 (7)	0.0174 (6)	0.0238 (7)	0.0009 (5)	−0.0016 (5)	−0.0051 (5)
C5	0.0326 (7)	0.0241 (7)	0.0246 (7)	−0.0079 (6)	0.0028 (6)	0.0021 (5)
C6	0.0297 (7)	0.0230 (7)	0.0245 (7)	0.0008 (5)	−0.0093 (6)	0.0024 (5)
N1	0.0259 (6)	0.0135 (5)	0.0216 (5)	0.0013 (4)	−0.0040 (4)	0.0035 (4)
N2	0.0315 (6)	0.0164 (5)	0.0236 (6)	−0.0032 (4)	−0.0034 (5)	−0.0009 (4)
N3	0.0254 (6)	0.0204 (6)	0.0267 (6)	0.0041 (4)	−0.0007 (5)	0.0032 (4)
N4	0.0308 (6)	0.0209 (6)	0.0191 (5)	−0.0019 (5)	−0.0022 (4)	−0.0016 (4)
C7	0.0189 (6)	0.0172 (6)	0.0160 (6)	0.0009 (5)	−0.0015 (4)	0.0007 (4)
C8	0.0200 (6)	0.0152 (6)	0.0185 (6)	−0.0005 (5)	−0.0028 (5)	0.0013 (4)
C9	0.0195 (6)	0.0144 (6)	0.0173 (5)	−0.0013 (4)	−0.0021 (4)	0.0004 (4)
C10	0.0188 (6)	0.0165 (6)	0.0175 (6)	−0.0002 (5)	−0.0037 (4)	0.0005 (4)
O1	0.0167 (4)	0.0185 (5)	0.0284 (5)	0.0017 (3)	0.0000 (4)	0.0021 (4)
O2	0.0241 (5)	0.0155 (5)	0.0428 (6)	−0.0015 (4)	−0.0049 (4)	0.0005 (4)
O3	0.0168 (4)	0.0175 (5)	0.0307 (5)	0.0012 (3)	−0.0020 (4)	0.0028 (4)
O4	0.0253 (5)	0.0167 (5)	0.0484 (7)	−0.0031 (4)	−0.0018 (4)	0.0038 (4)

Geometric parameters (Å, °)

C1—N2	1.4442 (17)	C5—H5A	0.99
C1—N1	1.5139 (17)	C5—H5B	0.99
C1—H1A	0.99	C6—N4	1.4691 (19)
C1—H1B	0.99	C6—N3	1.4727 (18)
C2—N2	1.4654 (19)	C6—H6A	0.99
C2—N3	1.4695 (18)	C6—H6B	0.99
C2—H2A	0.99	N1—H1	0.845 (19)
C2—H2B	0.99	C7—O2	1.2320 (15)
C3—N3	1.4435 (17)	C7—O1	1.2821 (15)
C3—N1	1.5105 (17)	C7—C8	1.4971 (17)
C3—H3A	0.99	C8—C9	1.3161 (17)
C3—H3B	0.99	C8—H8	0.95
C4—N4	1.4451 (17)	C9—C10	1.4889 (17)
C4—N1	1.5179 (17)	C9—H9	0.95
C4—H4A	0.99	C10—O4	1.2179 (16)
C4—H4B	0.99	C10—O3	1.3081 (15)
C5—N4	1.4715 (18)	O3—H3	1.034 (18)
C5—N2	1.4717 (18)
N2—C1—N1	109.36 (10)	N3—C6—H6A	109.2
N2—C1—H1A	109.8	N4—C6—H6B	109.2
N1—C1—H1A	109.8	N3—C6—H6B	109.2
N2—C1—H1B	109.8	H6A—C6—H6B	107.9
N1—C1—H1B	109.8	C3—N1—C1	109.07 (11)
H1A—C1—H1B	108.3	C3—N1—C4	108.88 (10)
N2—C2—N3	112.14 (11)	C1—N1—C4	108.65 (10)
N2—C2—H2A	109.2	C3—N1—H1	109.9 (12)
N3—C2—H2A	109.2	C1—N1—H1	113.1 (12)
N2—C2—H2B	109.2	C4—N1—H1	107.1 (12)
N3—C2—H2B	109.2	C1—N2—C2	109.24 (11)
H2A—C2—H2B	107.9	C1—N2—C5	109.06 (11)
N3—C3—N1	109.42 (11)	C2—N2—C5	108.26 (11)
N3—C3—H3A	109.8	C3—N3—C2	109.00 (11)
N1—C3—H3A	109.8	C3—N3—C6	109.07 (11)
N3—C3—H3B	109.8	C2—N3—C6	108.38 (11)
N1—C3—H3B	109.8	C4—N4—C6	108.59 (11)
H3A—C3—H3B	108.2	C4—N4—C5	108.84 (10)
N4—C4—N1	109.76 (10)	C6—N4—C5	108.47 (11)
N4—C4—H4A	109.7	O2—C7—O1	123.81 (12)
N1—C4—H4A	109.7	O2—C7—C8	119.76 (11)
N4—C4—H4B	109.7	O1—C7—C8	116.43 (11)
N1—C4—H4B	109.7	C9—C8—C7	122.51 (12)
H4A—C4—H4B	108.2	C9—C8—H8	118.7
N4—C5—N2	112.09 (11)	C7—C8—H8	118.7
N4—C5—H5A	109.2	C8—C9—C10	122.25 (12)
N2—C5—H5A	109.2	C8—C9—H9	118.9
N4—C5—H5B	109.2	C10—C9—H9	118.9
N2—C5—H5B	109.2	O4—C10—O3	121.80 (11)
H5A—C5—H5B	107.9	O4—C10—C9	122.28 (12)
N4—C6—N3	112.10 (11)	O3—C10—C9	115.92 (11)
N4—C6—H6A	109.2	C10—O3—H3	112.0 (9)
N3—C3—N1—C1	59.36 (14)	N2—C2—N3—C6	−58.33 (14)
N3—C3—N1—C4	−59.05 (14)	N4—C6—N3—C3	−60.71 (15)
N2—C1—N1—C3	−59.07 (14)	N4—C6—N3—C2	57.83 (14)
N2—C1—N1—C4	59.49 (14)	N1—C4—N4—C6	−59.03 (13)
N4—C4—N1—C3	59.28 (13)	N1—C4—N4—C5	58.87 (14)
N4—C4—N1—C1	−59.39 (13)	N3—C6—N4—C4	60.45 (14)
N1—C1—N2—C2	58.69 (14)	N3—C6—N4—C5	−57.68 (14)
N1—C1—N2—C5	−59.46 (14)	N2—C5—N4—C4	−60.05 (15)
N3—C2—N2—C1	−60.15 (14)	N2—C5—N4—C6	57.93 (14)
N3—C2—N2—C5	58.50 (14)	O2—C7—C8—C9	−3.04 (19)
N4—C5—N2—C1	60.51 (15)	O1—C7—C8—C9	177.28 (11)
N4—C5—N2—C2	−58.25 (15)	C7—C8—C9—C10	179.56 (11)
N1—C3—N3—C2	−59.05 (14)	C8—C9—C10—O4	−6.5 (2)
N1—C3—N3—C6	59.11 (14)	C8—C9—C10—O3	173.79 (11)
N2—C2—N3—C3	60.25 (14)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.845 (19)	2.094 (19)	2.8704 (14)	153 (2)
O3—H3···O1i	1.034 (18)	1.458 (18)	2.4877 (13)	174 (2)
C1—H1A···O3ii	0.99	2.46	3.2708 (16)	138
C3—H3B···O4iii	0.99	2.55	3.4629 (18)	154
C4—H4B···O4iv	0.99	2.48	3.3668 (17)	149
C6—H6A···O4iv	0.99	2.43	3.3352 (18)	152

Symmetry codes: (i) x+1, y, z; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+1, y+1/2, −z+3/2; (iv) −x+1, −y+1, −z+1.