e,e-trans-Cyclo­hexane-1,4-carb­oxy­lic acid–hexa­methyl­ene­tetra­mine (1/2)

Abstract

The asymmetric unit of the title compound, 2C₆H₁₂N₄·C₈H₁₂O₄, contains one half-mol­ecule of e,e-trans-cyclo­hexane-1,4-dicarb­oxy­lic acid (the complete molecule being generated by inversion symmetry) and one mol­ecule of hexa­methyl­ene­tetra­mine (HMTA), which are connected by O—H⋯N hydrogen bonds. This forms isolated trimers that pack in a herringbone fashion.

Related literature

For related co-crystals featuring one hydrogen bond to HMTA, see: Feng et al. (2006 ▶); Li et al. (2001 ▶); Mak et al. (1986 ▶). For related co-crystals featuring two hydrogen bonds to HMTA, see: Coupar et al. (1997a ▶); Gardon et al. (2003 ▶); Ghosh et al. (2005 ▶). For related co-crystals featuring three hydrogen bonds to HMTA, see: Coupar et al. (1997b ▶); De Bruyn et al. (1996 ▶); Jordan & Mak (1970 ▶). For related co-crystals featuring four hydrogen bonds to HMTA, see: Daka & Wheeler (2006 ▶); MacLean et al. (1999 ▶); Zakaria et al. (2003 ▶).

Experimental

Crystal data

• 2C₆H₁₂N₄·C₈H₁₂O₄

• M _r = 452.57

• Monoclinic,

• a = 5.9182 (1) Å

• b = 31.5242 (6) Å

• c = 6.1193 (1) Å

• β = 109.144 (1)°

• V = 1078.52 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.1 mm⁻¹

• T = 173 K

• 0.4 × 0.35 × 0.04 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: integration (XPREP; Bruker, 2004 ▶) T _min = 0.960, T _max = 0.996

• 13851 measured reflections

• 2594 independent reflections

• 2218 reflections with I > 2σ(I)

• R _int = 0.045

Refinement

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.113

• S = 0.89

• 2594 reflections

• 146 parameters

• H-atom parameters constrained

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.19 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
O1—H1⋯N1	0.84	1.84	2.6710 (12)	170

supplementary crystallographic information

Comment

The molecule hexamethylenetetramine (HMTA) acts as a good hydrogen bond acceptor for carboxylic acid or phenol hydrogen bond donors to make binary co-crystals. HMTA can accept any number from one to four hydrogen bonds due to its tetravalent hydrogen bond acceptors, the lone pairs on each of the four N atoms. Most common are two hydrogen bonds per HMTA molecule (Coupar et al., 1997a; Gardon et al., 2003; Ghosh et al., 2005.), with a smaller frequency of one, three or four hydrogen bonds (Coupar et al., 1997b; Daka & Wheeler, 2006; De Bruyn et al., 1996; Feng et al., 2006; Jordan & Mak, 1970; Li et al., 2001; MacLean et al., 1999; Mak et al., 1986; Zakaria et al., 2003.). The title compound is an example of HMTA only accepting one hydrogen bond. As the cis-cyclohexane-1,4-dicarboxylic acid (CHDA) molecule has two carboxylic acid groups, the observed hydrogen bonded assembly is dumb-bell shaped, where one central CHDA molecule (the bar) hydrogen bonds to two pendant HMTA molecules (the bells) (Fig. 2). The dumb-bell trimers are situated on a centre of inversion, located at the centre of the CHDA molecule. The dumbells pack in a herring-bone fashion (Fig. 3).

Experimental

Crystals where grown by slow evaporation at ambient conditions of a methanol solution containing a 2:1 stoichiometric quantity of hexamethylenetetramine and cis-1,4-cyclohexanecarboxylic acid.

Refinement

The C-bound H atoms were geometrically placed with C—H bond lengths of 1.00Å for methine CH and 0.99Å for ethylene CH₂ and refined as riding with U_iso(H) = 1.2U_eq(C). The O-bound H atom was geometrically placed (O—H bond length 0.84 Å) and refined as riding with U_iso(H) = 1.5U_eq(O).

Figures

Fig. 1.

View of (I) (50% probability displacement ellipsoids). Symmetry code: (i):2 - x, 1 - y, 2 - z.

Fig. 2.

Hydrogen bonded centrosymmetric trimers formed by simple hydrogen bonds (red dashed lines) between one CHDA and two HMTA molecules.

Fig. 3.

Packing diagram of the trimers viewed down the c axis.

Crystal data

2C6H12N4·C8H12O4	F(000) = 488
Mr = 452.57	Dx = 1.394 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5661 reflections
a = 5.9182 (1) Å	θ = 3.7–28.3°
b = 31.5242 (6) Å	µ = 0.1 mm−1
c = 6.1193 (1) Å	T = 173 K
β = 109.144 (1)°	Plate, colourless
V = 1078.52 (3) Å3	0.4 × 0.35 × 0.04 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	2218 reflections with I > 2σ(I)
ω scans	Rint = 0.045
Absorption correction: integration (XPREP; Bruker, 2004)	θmax = 28.0°, θmin = 1.3°
Tmin = 0.960, Tmax = 0.996	h = −7→7
13851 measured reflections	k = −41→41
2594 independent reflections	l = −8→8

Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040	w = 1/[σ2(Fo2) + (0.0739P)2 + 0.3667P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.113	(Δ/σ)max = 0.001
S = 0.89	Δρmax = 0.39 e Å−3
2594 reflections	Δρmin = −0.19 e Å−3
146 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	−0.0247 (2)	0.63264 (4)	0.4650 (2)	0.0246 (3)
H1A	−0.1214	0.6094	0.3707	0.029*
H1B	−0.0231	0.6289	0.6261	0.029*
C2	−0.1335 (2)	0.67841 (4)	0.1382 (2)	0.0282 (3)
H2A	−0.2086	0.7058	0.0755	0.034*
H2B	−0.2303	0.6555	0.041	0.034*
C3	0.2502 (2)	0.71082 (4)	0.2722 (2)	0.0290 (3)
H3A	0.1799	0.7386	0.2111	0.035*
H3B	0.4155	0.7101	0.2667	0.035*
C4	0.2168 (2)	0.63619 (4)	0.2177 (2)	0.0282 (3)
H4A	0.3818	0.6348	0.2117	0.034*
H4B	0.1235	0.613	0.1201	0.034*
C5	0.3614 (2)	0.66535 (4)	0.6002 (2)	0.0256 (3)
H5A	0.3658	0.662	0.7623	0.031*
H5B	0.5281	0.6642	0.5986	0.031*
C6	0.0111 (2)	0.70746 (4)	0.5164 (2)	0.0267 (3)
H6A	0.0126	0.7045	0.678	0.032*
H6B	−0.0621	0.7352	0.4574	0.032*
N1	0.22317 (16)	0.62980 (3)	0.45945 (16)	0.0202 (2)
N2	−0.13588 (17)	0.67350 (3)	0.37597 (19)	0.0250 (2)
N3	0.1098 (2)	0.67701 (3)	0.12396 (18)	0.0273 (2)
N4	0.25799 (18)	0.70679 (3)	0.51366 (18)	0.0257 (2)
C7	0.76647 (19)	0.52006 (3)	0.88313 (19)	0.0188 (2)
H7	0.6734	0.4942	0.8128	0.023*
C8	0.9750 (2)	0.52451 (4)	0.78814 (19)	0.0219 (2)
H8A	0.9119	0.5271	0.6175	0.026*
H8B	1.0667	0.5506	0.851	0.026*
C9	1.1394 (2)	0.48596 (4)	0.85539 (19)	0.0213 (2)
H9A	1.0504	0.4603	0.7819	0.026*
H9B	1.2758	0.4897	0.7973	0.026*
C10	0.6008 (2)	0.55801 (3)	0.8143 (2)	0.0212 (2)
O1	0.47562 (17)	0.55861 (3)	0.59260 (15)	0.0319 (2)
H1	0.3883	0.5803	0.5629	0.048*
O2	0.58343 (19)	0.58498 (3)	0.94835 (17)	0.0397 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0217 (5)	0.0197 (6)	0.0322 (6)	0.0004 (4)	0.0087 (5)	0.0055 (4)
C2	0.0237 (6)	0.0261 (6)	0.0265 (6)	0.0051 (5)	−0.0031 (5)	0.0042 (5)
C3	0.0264 (6)	0.0249 (6)	0.0384 (7)	0.0007 (5)	0.0145 (5)	0.0100 (5)
C4	0.0356 (7)	0.0266 (6)	0.0238 (6)	0.0119 (5)	0.0115 (5)	0.0007 (5)
C5	0.0203 (5)	0.0246 (6)	0.0253 (6)	0.0009 (4)	−0.0015 (4)	0.0010 (4)
C6	0.0330 (6)	0.0203 (6)	0.0297 (6)	0.0059 (5)	0.0143 (5)	−0.0018 (4)
N1	0.0193 (5)	0.0187 (5)	0.0205 (5)	0.0044 (3)	0.0038 (4)	0.0017 (3)
N2	0.0178 (5)	0.0221 (5)	0.0353 (6)	0.0038 (4)	0.0091 (4)	0.0049 (4)
N3	0.0350 (6)	0.0273 (6)	0.0206 (5)	0.0083 (4)	0.0104 (4)	0.0052 (4)
N4	0.0247 (5)	0.0190 (5)	0.0296 (5)	−0.0022 (4)	0.0037 (4)	−0.0008 (4)
C7	0.0179 (5)	0.0154 (5)	0.0212 (5)	0.0034 (4)	0.0039 (4)	0.0004 (4)
C8	0.0242 (6)	0.0216 (5)	0.0206 (5)	0.0059 (4)	0.0084 (4)	0.0050 (4)
C9	0.0216 (5)	0.0220 (6)	0.0218 (5)	0.0056 (4)	0.0090 (4)	0.0026 (4)
C10	0.0183 (5)	0.0181 (5)	0.0246 (6)	0.0025 (4)	0.0037 (4)	0.0006 (4)
O1	0.0369 (5)	0.0259 (5)	0.0249 (5)	0.0161 (4)	−0.0007 (4)	−0.0002 (3)
O2	0.0487 (6)	0.0305 (5)	0.0306 (5)	0.0201 (4)	0.0002 (4)	−0.0064 (4)

Geometric parameters (Å, °)

C1—N2	1.4676 (14)	C5—H5B	0.99
C1—N1	1.4808 (15)	C6—N2	1.4663 (16)
C1—H1A	0.99	C6—N4	1.4671 (16)
C1—H1B	0.99	C6—H6A	0.99
C2—N2	1.4678 (17)	C6—H6B	0.99
C2—N3	1.4713 (17)	C7—C10	1.5160 (15)
C2—H2A	0.99	C7—C9i	1.5238 (15)
C2—H2B	0.99	C7—C8	1.5331 (15)
C3—N3	1.4679 (17)	C7—H7	1
C3—N4	1.4686 (16)	C8—C9	1.5268 (15)
C3—H3A	0.99	C8—H8A	0.99
C3—H3B	0.99	C8—H8B	0.99
C4—N3	1.4657 (15)	C9—C7i	1.5238 (15)
C4—N1	1.4812 (15)	C9—H9A	0.99
C4—H4A	0.99	C9—H9B	0.99
C4—H4B	0.99	C10—O2	1.2091 (15)
C5—N4	1.4662 (15)	C10—O1	1.3154 (14)
C5—N1	1.4848 (15)	O1—H1	0.84
C5—H5A	0.99
N2—C1—N1	111.82 (9)	H6A—C6—H6B	107.8
N2—C1—H1A	109.3	C1—N1—C4	108.27 (9)
N1—C1—H1A	109.3	C1—N1—C5	107.61 (9)
N2—C1—H1B	109.3	C4—N1—C5	107.78 (9)
N1—C1—H1B	109.3	C6—N2—C1	108.39 (9)
H1A—C1—H1B	107.9	C6—N2—C2	107.89 (9)
N2—C2—N3	112.54 (9)	C1—N2—C2	108.14 (9)
N2—C2—H2A	109.1	C4—N3—C3	108.13 (10)
N3—C2—H2A	109.1	C4—N3—C2	107.97 (10)
N2—C2—H2B	109.1	C3—N3—C2	107.96 (9)
N3—C2—H2B	109.1	C5—N4—C6	107.94 (9)
H2A—C2—H2B	107.8	C5—N4—C3	108.17 (10)
N3—C3—N4	112.56 (9)	C6—N4—C3	107.91 (9)
N3—C3—H3A	109.1	C10—C7—C9i	111.75 (9)
N4—C3—H3A	109.1	C10—C7—C8	110.48 (9)
N3—C3—H3B	109.1	C9i—C7—C8	110.30 (9)
N4—C3—H3B	109.1	C10—C7—H7	108.1
H3A—C3—H3B	107.8	C9i—C7—H7	108.1
N3—C4—N1	112.12 (9)	C8—C7—H7	108.1
N3—C4—H4A	109.2	C9—C8—C7	110.25 (9)
N1—C4—H4A	109.2	C9—C8—H8A	109.6
N3—C4—H4B	109.2	C7—C8—H8A	109.6
N1—C4—H4B	109.2	C9—C8—H8B	109.6
H4A—C4—H4B	107.9	C7—C8—H8B	109.6
N4—C5—N1	112.20 (9)	H8A—C8—H8B	108.1
N4—C5—H5A	109.2	C7i—C9—C8	111.31 (9)
N1—C5—H5A	109.2	C7i—C9—H9A	109.4
N4—C5—H5B	109.2	C8—C9—H9A	109.4
N1—C5—H5B	109.2	C7i—C9—H9B	109.4
H5A—C5—H5B	107.9	C8—C9—H9B	109.4
N2—C6—N4	112.61 (9)	H9A—C9—H9B	108
N2—C6—H6A	109.1	O2—C10—O1	123.03 (11)
N4—C6—H6A	109.1	O2—C10—C7	123.88 (10)
N2—C6—H6B	109.1	O1—C10—C7	113.09 (10)
N4—C6—H6B	109.1	C10—O1—H1	109.5
N2—C1—N1—C4	−57.93 (12)	N2—C2—N3—C4	58.78 (12)
N2—C1—N1—C5	58.31 (12)	N2—C2—N3—C3	−57.91 (12)
N3—C4—N1—C1	57.99 (13)	N1—C5—N4—C6	58.47 (13)
N3—C4—N1—C5	−58.15 (13)	N1—C5—N4—C3	−58.05 (13)
N4—C5—N1—C1	−58.63 (12)	N2—C6—N4—C5	−58.39 (12)
N4—C5—N1—C4	57.94 (12)	N2—C6—N4—C3	58.29 (12)
N4—C6—N2—C1	58.57 (13)	N3—C3—N4—C5	58.48 (12)
N4—C6—N2—C2	−58.32 (12)	N3—C3—N4—C6	−58.06 (12)
N1—C1—N2—C6	−58.43 (13)	C10—C7—C8—C9	−179.28 (9)
N1—C1—N2—C2	58.29 (12)	C9i—C7—C8—C9	56.67 (13)
N3—C2—N2—C6	58.06 (12)	C7—C8—C9—C7i	−57.25 (13)
N3—C2—N2—C1	−58.99 (12)	C9i—C7—C10—O2	13.98 (17)
N1—C4—N3—C3	58.54 (13)	C8—C7—C10—O2	−109.24 (14)
N1—C4—N3—C2	−58.04 (13)	C9i—C7—C10—O1	−165.62 (10)
N4—C3—N3—C4	−58.70 (13)	C8—C7—C10—O1	71.17 (12)
N4—C3—N3—C2	57.88 (12)

Symmetry codes: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	1.84	2.6710 (12)	170