Nicotinamide–2,2,2-trifluoro­ethanol (2/1)

Bardin, J.; Kennedy, A.R.; Wong, L.V.; Johnston, B.F.; Florence, A.J.

doi:10.1107/S1600536809007594

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages o727-o728

doi:10.1107/S1600536809007594

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Nicotinamide–2,2,2-trifluoroethanol (2/1)

Julie Bardin,^a Alan R. Kennedy,^b Li Ven Wong,^a Blair F. Johnston ^a and Alastair J. Florence ^a ^*

^aStrathclyde Institute of Pharmacy and Biomedical Sciences, The John Arbuthnott Building, University of Strathclyde, 27 Taylor Street, Glasgow G4 0NR, Scotland, and ^bWestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland
^*Correspondence e-mail: alastair.florence@strath.ac.uk

(Received 3 February 2009; accepted 2 March 2009; online 11 March 2009)

The nicotinamide (NA) molecules of the title compound, 2C₆H₆N₂O·C₂H₃F₃O, form centrosymmetric R²₂(8) hydrogen-bonded dimers via N—H⋯O contacts. The asymmetric unit contains two molecules of NA and one trifluoroethanol molecule disordered over two sites of equal occupancy. The packing consists of alternating layers of nicotinamide dimers and disordered 2,2,2-trifluoroethanol molecules stacking in the c-axis direction. Intramolecular C—H⋯O and intermolecular N—H⋯N, O—H⋯N, C—H⋯N, C—H⋯O and C—H⋯F interactions are present.

Related literature

For nicotinamide polymorphs, see: Wright & King (1954 ); Miwa et al. (1999 ); Hino et al. (2001 ). For nicotinamide co-crystals and salts, see: Fleischman et al. (2003 ); Koman et al. (2003 ); Athimoolam & Natarajan (2007a ,b ); Berry et al. (2008 ). For graph-set motifs, see: Etter (1990 ). For initial identification using multi-sample foil transmission X-ray powder diffraction analysis, see: Florence et al. (2003 ).

Experimental

Crystal data

2C₆H₆N₂O·C₂H₃F₃O
M_r = 344.30
Triclinic, $[P \overline 1]$
a = 5.0472 (3) Å
b = 11.2930 (7) Å
c = 15.0877 (10) Å
α = 107.002 (3)°
β = 96.636 (3)°
γ = 95.753 (3)°
V = 808.70 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 123 K
0.15 × 0.10 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.903, T_max = 0.998
15936 measured reflections
4008 independent reflections
3416 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.114
S = 1.04
4008 reflections
260 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯N3ⁱ	0.897 (16)	2.122 (16)	2.9994 (15)	165.7 (15)
N2—H2N⋯O1ⁱⁱ	0.898 (16)	2.013 (16)	2.9093 (13)	176.8 (14)
N4—H3N⋯O2ⁱⁱⁱ	0.877 (16)	2.047 (16)	2.9139 (13)	170.1 (16)
O3—H3O⋯N1^iv	0.84	1.91	2.7511 (15)	178
N4—H4N⋯O1^v	0.878 (17)	2.222 (17)	3.0867 (14)	168.4 (15)
C1—H1⋯N3ⁱ	0.95	2.51	3.4220 (16)	161
C3—H3⋯O2^vi	0.95	2.40	3.0103 (15)	122
C5—H5⋯F3A^vii	0.95	2.46	3.408 (7)	177
C7—H7⋯O1^v	0.95	2.36	3.2118 (14)	149
C11—H11⋯O3	0.95	2.50	3.2590 (16)	137
Symmetry codes: (i) x, y-1, z; (ii) -x+2, -y, -z+1; (iii) -x-1, -y+1, -z+1; (iv) x+1, y+1, z; (v) -x+1, -y+1, -z+1; (vi) x+1, y, z; (vii) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007594/fl2234sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007594/fl2234Isup2.hkl

checkCIF report

Comment top

The crystal structure of nicotinamide (NA) was first reported in 1954 (Wright & King, 1954; Miwa et al., 1999) and a number of polymorphic forms have also been identified (Hino et al., 2001). In recent years NA has also been investigated as a pharmaceutically acceptable co-crystal former to modify the crystal structure and physico-chemical properties of drug compounds including carbamazepine (Fleischman et al., 2003), salicylic acid and both racemic and S(+)-ibuprofen (Berry et al., 2008). Crystal structures of 3,5-dinitrosalicylate (Koman et al., 2003) as well as 2R,3R-tartrate and trifluoroacetate (Athimoolam & Natarajan, 2007a and Athimoolam & Natarajan, 2007b) salts of NA have also been reported.

In the 2,2,2-trifluoroethanol (TFE) hemisolvate reported here, the molecules crystallize in space group P1 with two molecules of NA and one molecule of TFE in the asymetric unit (Fig. 1). Both independent NA molecules form centro-symmetric R²₂(8) (Etter, 1990) dimer motifs via N—H..O hydrogen bonds (Table 1). The anti-oriented hydrogen atoms on both amide groups form further contacts between adjacent non-symmetry equivalent dimers, either to the aromatic nitrogen, N3 (N2—H1N···N3) or the carbonyl oxygen atom, O1 (N4—H4N···O1).This gives rise to a two-dimensional hydrogen bonded layer of nicotinamide dimers lying parallel to the a-b plane. The remaining aromatic acceptor nitrogen atom, N1, forms an N—H···O hydrogen bond to the solvent molecule producing a structure with alternating layers of NA dimers and TFE that stack in the direction of the c-axis (Fig. 2). The structure is further stabilized by six weak C—H···O and C—H···F interactions (Table 1). The CF₃atoms of the TFE molecule are disordered over two sites with equal occupancies.

Related literature top

For nicotinamide polymorphs, see: Wright & King (1954); Miwa et al. (1999); Hino et al. (2001). For nicotinamide co-crystals and salts, see: Fleischman et al. (2003); Koman et al. (2003); Athimoolam & Natarajan (2007a,b) ; Berry et al. (2008). For graph-set motifs, see: Etter (1990). For initial identification using multi-sample foil transmission X-ray powder diffraction analysis, see: Florence et al. (2003).

Experimental top

The novel structure reported here was discovered during a study of solvate formation in organic compounds with a range of fluorinated solvents. A crystalline sample was obtained by isothermal evaporation at 263 K from a saturated TFE solution held on a Reactarray RM2 crystalliser. Identification of the novel phase was initially made using multi-sample foil transmission X-ray powder diffraction analysis (Florence et al., 2003) and a suitable single-crystal for structure determination was selected from the sample.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. One of the disordered site for the CF₃ atoms has been omitted for clarity.
	Fig. 2. Crystal packing of the reported compound viewed down the a axis, showing the two-dimensional hydrogen-bonded network of alternating dimers, separated by layers of solvent molecules. Hydrogen bonds are shown as blue dashed lines.

nicotinamide–2,2,2-trifluoroethanol (2/1) top

Crystal data top

2(C₆H₆N₂O)·C₂H₃F₃O	Z = 2
M_r = 344.30	F(000) = 356
Triclinic, P1	D_x = 1.414 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.0472 (3) Å	Cell parameters from 8696 reflections
b = 11.2930 (7) Å	θ = 2.9–28.2°
c = 15.0877 (10) Å	µ = 0.12 mm⁻¹
α = 107.002 (3)°	T = 123 K
β = 96.636 (3)°	Slab, colourless
γ = 95.753 (3)°	0.15 × 0.10 × 0.02 mm
V = 808.70 (9) Å³

Data collection top

Bruker APEXII CCD diffractometer	4008 independent reflections
Radiation source: fine-focus sealed tube	3416 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −6→6
T_min = 0.903, T_max = 0.998	k = −15→14
15936 measured reflections	l = −20→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0611P)² + 0.2237P] where P = (F_o² + 2F_c²)/3
4008 reflections	(Δ/σ)_max < 0.001
260 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

2(C₆H₆N₂O)·C₂H₃F₃O	γ = 95.753 (3)°
M_r = 344.30	V = 808.70 (9) Å³
Triclinic, P1	Z = 2
a = 5.0472 (3) Å	Mo Kα radiation
b = 11.2930 (7) Å	µ = 0.12 mm⁻¹
c = 15.0877 (10) Å	T = 123 K
α = 107.002 (3)°	0.15 × 0.10 × 0.02 mm
β = 96.636 (3)°

Data collection top

Bruker APEXII CCD diffractometer	4008 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	3416 reflections with I > 2σ(I)
T_min = 0.903, T_max = 0.998	R_int = 0.025
15936 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.39 e Å⁻³
4008 reflections	Δρ_min = −0.29 e Å⁻³
260 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.87250 (15)	0.11455 (7)	0.45065 (6)	0.0226 (2)
N1	0.05569 (19)	−0.02252 (9)	0.23414 (7)	0.0240 (3)
N2	0.7054 (2)	−0.09004 (9)	0.40991 (7)	0.0225 (3)
C1	0.2538 (2)	−0.04184 (10)	0.29313 (8)	0.0212 (3)
C2	0.4782 (2)	0.04629 (9)	0.33748 (7)	0.0186 (3)
C3	0.4931 (2)	0.16131 (10)	0.32072 (8)	0.0236 (3)
C4	0.2882 (2)	0.18307 (11)	0.26047 (9)	0.0274 (3)
C5	0.0760 (2)	0.08876 (11)	0.21836 (8)	0.0261 (3)
C6	0.7000 (2)	0.02482 (9)	0.40354 (7)	0.0188 (3)
O2	−0.39941 (17)	0.44262 (7)	0.39075 (6)	0.0264 (3)
N3	0.33815 (19)	0.66946 (9)	0.31270 (7)	0.0236 (3)
N4	−0.2073 (2)	0.62420 (9)	0.49873 (7)	0.0236 (3)
C7	0.1753 (2)	0.65082 (10)	0.37294 (8)	0.0219 (3)
C8	−0.0429 (2)	0.55638 (9)	0.34852 (8)	0.0198 (3)
C9	−0.0899 (2)	0.47587 (11)	0.25734 (9)	0.0271 (3)
C10	0.0788 (3)	0.49317 (12)	0.19462 (9)	0.0303 (3)
C11	0.2891 (2)	0.59119 (11)	0.22515 (8)	0.0258 (3)
C12	−0.2296 (2)	0.53745 (10)	0.41530 (8)	0.0205 (3)
F1A	0.5655 (16)	0.6926 (4)	−0.0538 (5)	0.0869 (18)	0.500
F1B	0.5243 (12)	0.6494 (4)	−0.0430 (5)	0.0706 (13)	0.500
F2A	0.8008 (18)	0.8692 (5)	−0.0041 (6)	0.0644 (16)	0.500
F2B	0.7971 (17)	0.8192 (6)	−0.0144 (6)	0.0647 (19)	0.500
F3A	0.4000 (15)	0.8549 (5)	−0.0620 (5)	0.0653 (16)	0.500
F3B	0.3721 (15)	0.8033 (4)	−0.0738 (4)	0.0614 (12)	0.500
O3	0.6456 (2)	0.78427 (9)	0.14649 (7)	0.0424 (3)
C13	0.4745 (3)	0.82394 (14)	0.08562 (9)	0.0345 (4)
C14A	0.5622 (6)	0.8123 (3)	−0.0096 (2)	0.0320 (7)*	0.500
C14B	0.5411 (6)	0.7718 (4)	−0.0096 (2)	0.0322 (7)*	0.500
H1	0.24020	−0.12000	0.30530	0.0250*
H1N	0.592 (3)	−0.1567 (14)	0.3723 (11)	0.028 (4)*
H2N	0.839 (3)	−0.0991 (14)	0.4511 (11)	0.030 (4)*
H3	0.64230	0.22440	0.35030	0.0280*
H4	0.29370	0.26120	0.24840	0.0330*
H5	−0.06240	0.10330	0.17610	0.0310*
H3N	−0.324 (3)	0.6138 (15)	0.5355 (11)	0.036 (4)*
H4N	−0.094 (3)	0.6940 (15)	0.5172 (11)	0.032 (4)*
H7	0.21110	0.70510	0.43570	0.0260*
H9	−0.23630	0.40960	0.23810	0.0320*
H10	0.05080	0.43890	0.13200	0.0360*
H11	0.40360	0.60330	0.18190	0.0310*
H3O	0.77220	0.84210	0.17440	0.0640*
H13A	0.45750	0.91270	0.11620	0.0410*
H13B	0.29360	0.77480	0.07530	0.0410*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0234 (4)	0.0156 (4)	0.0256 (4)	−0.0015 (3)	−0.0023 (3)	0.0052 (3)
N1	0.0222 (5)	0.0233 (5)	0.0252 (5)	0.0009 (4)	0.0002 (4)	0.0075 (4)
N2	0.0224 (5)	0.0162 (4)	0.0274 (5)	−0.0010 (4)	−0.0029 (4)	0.0081 (4)
C1	0.0214 (5)	0.0181 (5)	0.0244 (5)	0.0015 (4)	0.0030 (4)	0.0075 (4)
C2	0.0195 (5)	0.0167 (5)	0.0191 (5)	0.0031 (4)	0.0035 (4)	0.0044 (4)
C3	0.0243 (5)	0.0177 (5)	0.0283 (6)	0.0007 (4)	0.0023 (4)	0.0075 (4)
C4	0.0306 (6)	0.0211 (5)	0.0330 (6)	0.0033 (4)	0.0018 (5)	0.0133 (5)
C5	0.0251 (5)	0.0278 (6)	0.0274 (6)	0.0054 (4)	0.0009 (4)	0.0124 (5)
C6	0.0191 (5)	0.0167 (5)	0.0200 (5)	0.0013 (4)	0.0036 (4)	0.0051 (4)
O2	0.0278 (4)	0.0172 (4)	0.0324 (5)	−0.0040 (3)	0.0079 (3)	0.0059 (3)
N3	0.0232 (5)	0.0181 (4)	0.0300 (5)	0.0001 (4)	0.0056 (4)	0.0084 (4)
N4	0.0251 (5)	0.0189 (4)	0.0258 (5)	−0.0022 (4)	0.0061 (4)	0.0062 (4)
C7	0.0231 (5)	0.0164 (5)	0.0254 (5)	0.0003 (4)	0.0038 (4)	0.0060 (4)
C8	0.0204 (5)	0.0150 (5)	0.0252 (5)	0.0027 (4)	0.0035 (4)	0.0079 (4)
C9	0.0253 (6)	0.0224 (5)	0.0290 (6)	−0.0047 (4)	0.0035 (4)	0.0039 (4)
C10	0.0329 (6)	0.0281 (6)	0.0244 (6)	−0.0029 (5)	0.0060 (5)	0.0014 (5)
C11	0.0261 (6)	0.0246 (5)	0.0287 (6)	0.0022 (4)	0.0079 (4)	0.0103 (5)
C12	0.0202 (5)	0.0157 (5)	0.0268 (5)	0.0016 (4)	0.0029 (4)	0.0089 (4)
F1A	0.112 (4)	0.063 (3)	0.058 (2)	0.019 (3)	0.003 (2)	−0.022 (3)
F1B	0.0614 (18)	0.055 (3)	0.064 (2)	0.0127 (19)	−0.0039 (15)	−0.026 (2)
F2A	0.0451 (16)	0.110 (4)	0.048 (2)	0.003 (3)	0.0128 (15)	0.040 (3)
F2B	0.0340 (15)	0.116 (5)	0.052 (2)	0.012 (3)	0.0162 (13)	0.034 (3)
F3A	0.054 (2)	0.107 (4)	0.042 (2)	0.018 (3)	−0.0097 (16)	0.038 (3)
F3B	0.0508 (17)	0.097 (3)	0.0316 (14)	0.008 (3)	−0.0059 (11)	0.018 (2)
O3	0.0431 (6)	0.0369 (5)	0.0434 (6)	−0.0155 (4)	−0.0138 (4)	0.0212 (4)
C13	0.0278 (6)	0.0432 (7)	0.0291 (6)	0.0010 (5)	0.0013 (5)	0.0083 (5)

Geometric parameters (Å, º) top

F1A—C14A	1.324 (7)	C2—C3	1.3906 (16)
F1B—C14B	1.316 (7)	C2—C6	1.4978 (14)
F2A—C14A	1.289 (9)	C3—C4	1.3858 (16)
F2B—C14B	1.366 (9)	C4—C5	1.3796 (17)
F3A—C14A	1.296 (8)	C1—H1	0.9500
F3B—C14B	1.365 (7)	C3—H3	0.9500
O1—C6	1.2446 (13)	C4—H4	0.9500
O2—C12	1.2366 (14)	C5—H5	0.9500
O3—C13	1.3874 (18)	C7—C8	1.3882 (15)
O3—H3O	0.8400	C8—C12	1.5013 (15)
N1—C5	1.3421 (17)	C8—C9	1.3876 (17)
N1—C1	1.3383 (15)	C9—C10	1.3855 (18)
N2—C6	1.3311 (15)	C10—C11	1.3847 (19)
N2—H2N	0.898 (16)	C7—H7	0.9500
N2—H1N	0.897 (16)	C9—H9	0.9500
N3—C7	1.3401 (15)	C10—H10	0.9500
N3—C11	1.3361 (15)	C11—H11	0.9500
N4—C12	1.3345 (15)	C13—C14B	1.477 (3)
N4—H3N	0.877 (16)	C13—C14A	1.525 (3)
N4—H4N	0.878 (17)	C13—H13A	0.9900
C1—C2	1.3894 (15)	C13—H13B	0.9900

F1A···O3	2.859 (7)	C4···O2ⁱⁱ	3.1510 (15)
F1A···C10ⁱ	3.342 (7)	C5···C3^vi	3.5363 (15)
F1A···F2A	2.096 (9)	C6···N1ⁱⁱ	3.2396 (14)
F1A···F3A	2.119 (9)	C6···C1ⁱⁱ	3.4524 (15)
F1B···F3B	2.118 (8)	C7···O2ⁱⁱ	3.3847 (14)
F1B···O3	2.780 (7)	C7···C12ⁱⁱ	3.4460 (15)
F2A···F3A	2.080 (12)	C7···O1^v	3.2118 (14)
F2A···O3	2.869 (8)	C9···C11^vi	3.5486 (15)
F2B···O3	2.750 (8)	C10···F1Aⁱ	3.342 (7)
F2B···F3B	2.196 (11)	C11···C9ⁱⁱ	3.5486 (15)
F3A···F1A	2.119 (9)	C11···O3	3.2590 (16)
F3A···F2A	2.080 (12)	C12···C7^vi	3.4460 (15)
F3B···F2B	2.196 (11)	C12···C12^xii	3.5927 (16)
F3B···F1B	2.118 (8)	C12···N3^vi	3.2557 (15)
F1A···H10ⁱ	2.7300	C12···N4^xii	3.3776 (15)
F1B···H10ⁱ	2.7800	C13···C1^xi	3.4220 (18)
F2A···H3O	2.8200	C13···N1^viii	3.4382 (18)
F2B···H13Bⁱⁱ	2.8700	C1···H13A^x	2.9000
F2B···H3O	2.8000	C1···H1N	2.627 (16)
F3A···H5ⁱⁱⁱ	2.4600	C1···H3O^ix	2.8000
F3B···H5ⁱⁱⁱ	2.5800	C3···H3N^xii	3.086 (16)
F3B···H9ⁱⁱⁱ	2.8600	C5···H3O^ix	2.8900
O1···N2^iv	2.9093 (13)	C6···H2N^iv	2.878 (16)
O1···N4^v	3.0867 (14)	C7···H4N	2.649 (16)
O1···C7^v	3.2118 (14)	C7···H1^xi	3.0500
O2···C7^vi	3.3847 (14)	C7···H1N^xi	2.872 (16)
O2···C3^vi	3.0103 (15)	C12···H3N^vii	2.984 (16)
O2···N4^vii	2.9139 (13)	H1···N3^x	2.5100
O2···C4^vi	3.1510 (15)	H1···C7^x	3.0500
O3···N1^viii	2.7511 (15)	H1···N2	2.6100
O3···F1A	2.859 (7)	H1···H1N	2.0800
O3···F2A	2.869 (8)	H1N···N3^x	2.122 (16)
O3···C11	3.2590 (16)	H1N···C1	2.627 (16)
O3···F2B	2.750 (8)	H1N···H1	2.0800
O3···F1B	2.780 (7)	H1N···C7^x	2.872 (16)
O1···H7^v	2.3600	H2N···H2N^iv	2.57 (2)
O1···H2N^iv	2.013 (16)	H2N···O1^iv	2.013 (16)
O1···H4N^v	2.222 (17)	H2N···C6^iv	2.878 (16)
O1···H3	2.4800	H3···O1	2.4800
O2···H3N^vii	2.047 (16)	H3···O2ⁱⁱ	2.4000
O2···H4^vi	2.6900	H3N···C12^vii	2.984 (16)
O2···H3^vi	2.4000	H3N···C3^xii	3.086 (16)
O2···H9	2.4700	H3N···O2^vii	2.047 (16)
O3···H11	2.5000	H3O···C1^viii	2.8000
N1···C6^vi	3.2396 (14)	H3O···C5^viii	2.8900
N1···C13^ix	3.4382 (18)	H3O···N1^viii	1.9100
N1···O3^ix	2.7510 (15)	H3O···F2A	2.8200
N2···O1^iv	2.9093 (13)	H3O···F2B	2.8000
N2···N3^x	2.9994 (15)	H4···O2ⁱⁱ	2.6900
N3···C1^xi	3.4220 (16)	H4N···O1^v	2.222 (17)
N3···C12ⁱⁱ	3.2557 (15)	H4N···C7	2.649 (16)
N3···N2^xi	2.9994 (15)	H4N···H7	2.0900
N4···C12^xii	3.3776 (15)	H5···F3Bⁱⁱⁱ	2.5800
N4···O1^v	3.0867 (14)	H5···F3Aⁱⁱⁱ	2.4600
N4···O2^vii	2.9139 (13)	H7···N4	2.6000
N1···H13A^x	2.8600	H7···H4N	2.0900
N1···H3O^ix	1.9100	H7···O1^v	2.3600
N2···H1	2.6100	H9···O2	2.4700
N3···H1N^xi	2.122 (16)	H9···F3Bⁱⁱⁱ	2.8600
N3···H1^xi	2.5100	H10···F1Aⁱ	2.7300
N4···H7	2.6000	H10···F1Bⁱ	2.7800
C1···N3^x	3.4220 (16)	H11···O3	2.5000
C1···C13^x	3.4220 (18)	H13A···N1^xi	2.8600
C1···C6^vi	3.4524 (15)	H13A···C1^xi	2.9000
C3···O2ⁱⁱ	3.0103 (15)	H13B···F2B^vi	2.8700
C3···C5ⁱⁱ	3.5363 (15)

C13—O3—H3O	109.00	C9—C10—C11	118.64 (12)
C1—N1—C5	117.62 (10)	N3—C11—C10	122.95 (11)
C6—N2—H2N	116.2 (11)	N4—C12—C8	118.69 (10)
C6—N2—H1N	122.9 (10)	O2—C12—N4	122.47 (10)
H1N—N2—H2N	120.7 (15)	O2—C12—C8	118.84 (10)
C7—N3—C11	117.80 (10)	C8—C7—H7	118.00
H3N—N4—H4N	117.7 (15)	N3—C7—H7	118.00
C12—N4—H4N	124.6 (10)	C8—C9—H9	120.00
C12—N4—H3N	117.4 (11)	C10—C9—H9	120.00
N1—C1—C2	123.48 (11)	C9—C10—H10	121.00
C1—C2—C6	123.54 (10)	C11—C10—H10	121.00
C3—C2—C6	118.67 (9)	C10—C11—H11	119.00
C1—C2—C3	117.78 (10)	N3—C11—H11	119.00
C2—C3—C4	119.37 (10)	O3—C13—C14B	107.67 (18)
C3—C4—C5	118.54 (12)	O3—C13—C14A	115.28 (16)
N1—C5—C4	123.19 (11)	F1A—C14A—F3A	108.0 (5)
O1—C6—C2	119.14 (9)	F1A—C14A—F2A	106.7 (5)
N2—C6—C2	118.66 (9)	F1A—C14A—C13	108.7 (4)
O1—C6—N2	122.20 (10)	F2A—C14A—F3A	107.2 (5)
C2—C1—H1	118.00	F2A—C14A—C13	113.6 (4)
N1—C1—H1	118.00	F3A—C14A—C13	112.5 (4)
C2—C3—H3	120.00	F1B—C14B—F2B	106.3 (5)
C4—C3—H3	120.00	F1B—C14B—F3B	104.3 (4)
C3—C4—H4	121.00	F1B—C14B—C13	117.2 (4)
C5—C4—H4	121.00	F2B—C14B—F3B	107.0 (5)
N1—C5—H5	118.00	F2B—C14B—C13	110.6 (4)
C4—C5—H5	118.00	F3B—C14B—C13	110.7 (4)
N3—C7—C8	123.44 (11)	O3—C13—H13A	108.00
C9—C8—C12	118.67 (10)	O3—C13—H13B	108.00
C7—C8—C9	117.85 (10)	C14A—C13—H13A	108.00
C7—C8—C12	123.48 (10)	C14B—C13—H13B	98.00
C8—C9—C10	119.30 (11)

C5—N1—C1—C2	−0.71 (16)	N3—C7—C8—C9	1.42 (17)
C1—N1—C5—C4	−0.62 (17)	C9—C8—C12—N4	−171.07 (11)
C11—N3—C7—C8	−1.22 (17)	C7—C8—C12—N4	8.74 (16)
C7—N3—C11—C10	0.22 (18)	C9—C8—C12—O2	8.43 (16)
N1—C1—C2—C6	180.00 (13)	C7—C8—C12—O2	−171.77 (11)
N1—C1—C2—C3	1.37 (16)	C7—C8—C9—C10	−0.60 (17)
C1—C2—C6—O1	−169.45 (10)	C12—C8—C9—C10	179.21 (11)
C3—C2—C6—N2	−170.96 (10)	C8—C9—C10—C11	−0.30 (19)
C3—C2—C6—O1	9.14 (15)	C9—C10—C11—N3	0.5 (2)
C1—C2—C6—N2	10.45 (15)	O3—C13—C14B—F1B	58.1 (4)
C6—C2—C3—C4	−179.39 (10)	O3—C13—C14B—F2B	−64.0 (5)
C1—C2—C3—C4	−0.72 (16)	O3—C13—C14B—F3B	177.6 (3)
C2—C3—C4—C5	−0.49 (17)	O3—C13—C14A—F1A	62.9 (4)
C3—C4—C5—N1	1.21 (18)	O3—C13—C14A—F2A	−55.7 (4)
N3—C7—C8—C12	−178.39 (11)	O3—C13—C14A—F3A	−177.7 (4)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1, y, z; (iii) −x, −y+1, −z; (iv) −x+2, −y, −z+1; (v) −x+1, −y+1, −z+1; (vi) x−1, y, z; (vii) −x−1, −y+1, −z+1; (viii) x+1, y+1, z; (ix) x−1, y−1, z; (x) x, y−1, z; (xi) x, y+1, z; (xii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···N3^x	0.897 (16)	2.122 (16)	2.9994 (15)	165.7 (15)
N2—H2N···O1^iv	0.898 (16)	2.013 (16)	2.9093 (13)	176.8 (14)
N4—H3N···O2^vii	0.877 (16)	2.047 (16)	2.9139 (13)	170.1 (16)
O3—H3O···N1^viii	0.84	1.91	2.7511 (15)	178
N4—H4N···O1^v	0.878 (17)	2.222 (17)	3.0867 (14)	168.4 (15)
C1—H1···N3^x	0.95	2.51	3.4220 (16)	161
C3—H3···O2ⁱⁱ	0.95	2.40	3.0103 (15)	122
C5—H5···F3Aⁱⁱⁱ	0.95	2.46	3.408 (7)	177
C7—H7···O1^v	0.95	2.36	3.2118 (14)	149
C11—H11···O3	0.95	2.50	3.2590 (16)	137

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

Experimental details

Crystal data
Chemical formula	2(C₆H₆N₂O)·C₂H₃F₃O
M_r	344.30
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	5.0472 (3), 11.2930 (7), 15.0877 (10)
α, β, γ (°)	107.002 (3), 96.636 (3), 95.753 (3)
V (Å³)	808.70 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.15 × 0.10 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.903, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	15936, 4008, 3416
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.114, 1.04
No. of reflections	4008
No. of parameters	260
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···N3ⁱ	0.897 (16)	2.122 (16)	2.9994 (15)	165.7 (15)
N2—H2N···O1ⁱⁱ	0.898 (16)	2.013 (16)	2.9093 (13)	176.8 (14)
N4—H3N···O2ⁱⁱⁱ	0.877 (16)	2.047 (16)	2.9139 (13)	170.1 (16)
O3—H3O···N1^iv	0.8400	1.9100	2.7511 (15)	178.00
N4—H4N···O1^v	0.878 (17)	2.222 (17)	3.0867 (14)	168.4 (15)
C1—H1···N3ⁱ	0.9500	2.5100	3.4220 (16)	161.00
C3—H3···O2^vi	0.9500	2.4000	3.0103 (15)	122.00
C5—H5···F3A^vii	0.9500	2.4600	3.408 (7)	177.00
C7—H7···O1^v	0.9500	2.3600	3.2118 (14)	149.00
C11—H11···O3	0.9500	2.5000	3.2590 (16)	137.00

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

Acknowledgements

The authors thank the University of Strathclyde for funding JB, the Basic Technology programme of the UK Research Councils for project funding under the Control and Prediction of the Organic Solid State (www.cposs.org.uk), and the Glasgow Centre for Physical Organic Chemistry for access to single-crystal diffraction facilities.

References

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