Literature DB >> 21582462

Nicotinamide-2,2,2-trifluoro-ethanol (2/1).

Julie Bardin, Alan R Kennedy, Li Ven Wong, Blair F Johnston, Alastair J Florence.   

Abstract

The nicotinamide (NA) mol-ecules of the title compound, 2C(6)H(6)N(2)O·C(2)H(3)F(3)O, form centrosymmetric R(2) (2)(8) hydrogen-bonded dimers via N-H⋯O contacts. The asymmetric unit contains two mol-ecules 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-trifluoro-ethanol mol-ecules stacking in the c-axis direction. Intra-molecular C-H⋯O and inter-molecular N-H⋯N, O-H⋯N, C-H⋯N, C-H⋯O and C-H⋯F inter-actions are present.

Entities:  

Year:  2009        PMID： 21582462      PMCID： PMC2968831          DOI： 10.1107/S1600536809007594

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


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 = 344.30 Triclinic, 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[F 2 > 2σ(F 2)] = 0.039 wR(F 2) = 0.114 S = 1.04 4008 reflections 260 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.39 e Å−3 Δρmin = −0.29 e Å−3 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. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007594/fl2234sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007594/fl2234Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
2(C6H6N2O)·C2H3F3OZ = 2
Mr = 344.30F(000) = 356
Triclinic, P1Dx = 1.414 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.0472 (3) ÅCell parameters from 8696 reflections
b = 11.2930 (7) Åθ = 2.9–28.2°
c = 15.0877 (10) ŵ = 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
Bruker APEXII CCD diffractometer4008 independent reflections
Radiation source: fine-focus sealed tube3416 reflections with I > 2σ(I)
graphiteRint = 0.025
φ and ω scansθmax = 28.3°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)h = −6→6
Tmin = 0.903, Tmax = 0.998k = −15→14
15936 measured reflectionsl = −20→19
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.0611P)2 + 0.2237P] where P = (Fo2 + 2Fc2)/3
4008 reflections(Δ/σ)max < 0.001
260 parametersΔρmax = 0.39 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
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.
xyzUiso*/UeqOcc. (<1)
O10.87250 (15)0.11455 (7)0.45065 (6)0.0226 (2)
N10.05569 (19)−0.02252 (9)0.23414 (7)0.0240 (3)
N20.7054 (2)−0.09004 (9)0.40991 (7)0.0225 (3)
C10.2538 (2)−0.04184 (10)0.29313 (8)0.0212 (3)
C20.4782 (2)0.04629 (9)0.33748 (7)0.0186 (3)
C30.4931 (2)0.16131 (10)0.32072 (8)0.0236 (3)
C40.2882 (2)0.18307 (11)0.26047 (9)0.0274 (3)
C50.0760 (2)0.08876 (11)0.21836 (8)0.0261 (3)
C60.7000 (2)0.02482 (9)0.40354 (7)0.0188 (3)
O2−0.39941 (17)0.44262 (7)0.39075 (6)0.0264 (3)
N30.33815 (19)0.66946 (9)0.31270 (7)0.0236 (3)
N4−0.2073 (2)0.62420 (9)0.49873 (7)0.0236 (3)
C70.1753 (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)
C100.0788 (3)0.49317 (12)0.19462 (9)0.0303 (3)
C110.2891 (2)0.59119 (11)0.22515 (8)0.0258 (3)
C12−0.2296 (2)0.53745 (10)0.41530 (8)0.0205 (3)
F1A0.5655 (16)0.6926 (4)−0.0538 (5)0.0869 (18)0.500
F1B0.5243 (12)0.6494 (4)−0.0430 (5)0.0706 (13)0.500
F2A0.8008 (18)0.8692 (5)−0.0041 (6)0.0644 (16)0.500
F2B0.7971 (17)0.8192 (6)−0.0144 (6)0.0647 (19)0.500
F3A0.4000 (15)0.8549 (5)−0.0620 (5)0.0653 (16)0.500
F3B0.3721 (15)0.8033 (4)−0.0738 (4)0.0614 (12)0.500
O30.6456 (2)0.78427 (9)0.14649 (7)0.0424 (3)
C130.4745 (3)0.82394 (14)0.08562 (9)0.0345 (4)
C14A0.5622 (6)0.8123 (3)−0.0096 (2)0.0320 (7)*0.500
C14B0.5411 (6)0.7718 (4)−0.0096 (2)0.0322 (7)*0.500
H10.24020−0.120000.305300.0250*
H1N0.592 (3)−0.1567 (14)0.3723 (11)0.028 (4)*
H2N0.839 (3)−0.0991 (14)0.4511 (11)0.030 (4)*
H30.642300.224400.350300.0280*
H40.293700.261200.248400.0330*
H5−0.062400.103300.176100.0310*
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)*
H70.211100.705100.435700.0260*
H9−0.236300.409600.238100.0320*
H100.050800.438900.132000.0360*
H110.403600.603300.181900.0310*
H3O0.772200.842100.174400.0640*
H13A0.457500.912700.116200.0410*
H13B0.293600.774800.075300.0410*
U11U22U33U12U13U23
O10.0234 (4)0.0156 (4)0.0256 (4)−0.0015 (3)−0.0023 (3)0.0052 (3)
N10.0222 (5)0.0233 (5)0.0252 (5)0.0009 (4)0.0002 (4)0.0075 (4)
N20.0224 (5)0.0162 (4)0.0274 (5)−0.0010 (4)−0.0029 (4)0.0081 (4)
C10.0214 (5)0.0181 (5)0.0244 (5)0.0015 (4)0.0030 (4)0.0075 (4)
C20.0195 (5)0.0167 (5)0.0191 (5)0.0031 (4)0.0035 (4)0.0044 (4)
C30.0243 (5)0.0177 (5)0.0283 (6)0.0007 (4)0.0023 (4)0.0075 (4)
C40.0306 (6)0.0211 (5)0.0330 (6)0.0033 (4)0.0018 (5)0.0133 (5)
C50.0251 (5)0.0278 (6)0.0274 (6)0.0054 (4)0.0009 (4)0.0124 (5)
C60.0191 (5)0.0167 (5)0.0200 (5)0.0013 (4)0.0036 (4)0.0051 (4)
O20.0278 (4)0.0172 (4)0.0324 (5)−0.0040 (3)0.0079 (3)0.0059 (3)
N30.0232 (5)0.0181 (4)0.0300 (5)0.0001 (4)0.0056 (4)0.0084 (4)
N40.0251 (5)0.0189 (4)0.0258 (5)−0.0022 (4)0.0061 (4)0.0062 (4)
C70.0231 (5)0.0164 (5)0.0254 (5)0.0003 (4)0.0038 (4)0.0060 (4)
C80.0204 (5)0.0150 (5)0.0252 (5)0.0027 (4)0.0035 (4)0.0079 (4)
C90.0253 (6)0.0224 (5)0.0290 (6)−0.0047 (4)0.0035 (4)0.0039 (4)
C100.0329 (6)0.0281 (6)0.0244 (6)−0.0029 (5)0.0060 (5)0.0014 (5)
C110.0261 (6)0.0246 (5)0.0287 (6)0.0022 (4)0.0079 (4)0.0103 (5)
C120.0202 (5)0.0157 (5)0.0268 (5)0.0016 (4)0.0029 (4)0.0089 (4)
F1A0.112 (4)0.063 (3)0.058 (2)0.019 (3)0.003 (2)−0.022 (3)
F1B0.0614 (18)0.055 (3)0.064 (2)0.0127 (19)−0.0039 (15)−0.026 (2)
F2A0.0451 (16)0.110 (4)0.048 (2)0.003 (3)0.0128 (15)0.040 (3)
F2B0.0340 (15)0.116 (5)0.052 (2)0.012 (3)0.0162 (13)0.034 (3)
F3A0.054 (2)0.107 (4)0.042 (2)0.018 (3)−0.0097 (16)0.038 (3)
F3B0.0508 (17)0.097 (3)0.0316 (14)0.008 (3)−0.0059 (11)0.018 (2)
O30.0431 (6)0.0369 (5)0.0434 (6)−0.0155 (4)−0.0138 (4)0.0212 (4)
C130.0278 (6)0.0432 (7)0.0291 (6)0.0010 (5)0.0013 (5)0.0083 (5)
F1A—C14A1.324 (7)C2—C31.3906 (16)
F1B—C14B1.316 (7)C2—C61.4978 (14)
F2A—C14A1.289 (9)C3—C41.3858 (16)
F2B—C14B1.366 (9)C4—C51.3796 (17)
F3A—C14A1.296 (8)C1—H10.9500
F3B—C14B1.365 (7)C3—H30.9500
O1—C61.2446 (13)C4—H40.9500
O2—C121.2366 (14)C5—H50.9500
O3—C131.3874 (18)C7—C81.3882 (15)
O3—H3O0.8400C8—C121.5013 (15)
N1—C51.3421 (17)C8—C91.3876 (17)
N1—C11.3383 (15)C9—C101.3855 (18)
N2—C61.3311 (15)C10—C111.3847 (19)
N2—H2N0.898 (16)C7—H70.9500
N2—H1N0.897 (16)C9—H90.9500
N3—C71.3401 (15)C10—H100.9500
N3—C111.3361 (15)C11—H110.9500
N4—C121.3345 (15)C13—C14B1.477 (3)
N4—H3N0.877 (16)C13—C14A1.525 (3)
N4—H4N0.878 (17)C13—H13A0.9900
C1—C21.3894 (15)C13—H13B0.9900
F1A···O32.859 (7)C4···O2ii3.1510 (15)
F1A···C10i3.342 (7)C5···C3vi3.5363 (15)
F1A···F2A2.096 (9)C6···N1ii3.2396 (14)
F1A···F3A2.119 (9)C6···C1ii3.4524 (15)
F1B···F3B2.118 (8)C7···O2ii3.3847 (14)
F1B···O32.780 (7)C7···C12ii3.4460 (15)
F2A···F3A2.080 (12)C7···O1v3.2118 (14)
F2A···O32.869 (8)C9···C11vi3.5486 (15)
F2B···O32.750 (8)C10···F1Ai3.342 (7)
F2B···F3B2.196 (11)C11···C9ii3.5486 (15)
F3A···F1A2.119 (9)C11···O33.2590 (16)
F3A···F2A2.080 (12)C12···C7vi3.4460 (15)
F3B···F2B2.196 (11)C12···C12xii3.5927 (16)
F3B···F1B2.118 (8)C12···N3vi3.2557 (15)
F1A···H10i2.7300C12···N4xii3.3776 (15)
F1B···H10i2.7800C13···C1xi3.4220 (18)
F2A···H3O2.8200C13···N1viii3.4382 (18)
F2B···H13Bii2.8700C1···H13Ax2.9000
F2B···H3O2.8000C1···H1N2.627 (16)
F3A···H5iii2.4600C1···H3Oix2.8000
F3B···H5iii2.5800C3···H3Nxii3.086 (16)
F3B···H9iii2.8600C5···H3Oix2.8900
O1···N2iv2.9093 (13)C6···H2Niv2.878 (16)
O1···N4v3.0867 (14)C7···H4N2.649 (16)
O1···C7v3.2118 (14)C7···H1xi3.0500
O2···C7vi3.3847 (14)C7···H1Nxi2.872 (16)
O2···C3vi3.0103 (15)C12···H3Nvii2.984 (16)
O2···N4vii2.9139 (13)H1···N3x2.5100
O2···C4vi3.1510 (15)H1···C7x3.0500
O3···N1viii2.7511 (15)H1···N22.6100
O3···F1A2.859 (7)H1···H1N2.0800
O3···F2A2.869 (8)H1N···N3x2.122 (16)
O3···C113.2590 (16)H1N···C12.627 (16)
O3···F2B2.750 (8)H1N···H12.0800
O3···F1B2.780 (7)H1N···C7x2.872 (16)
O1···H7v2.3600H2N···H2Niv2.57 (2)
O1···H2Niv2.013 (16)H2N···O1iv2.013 (16)
O1···H4Nv2.222 (17)H2N···C6iv2.878 (16)
O1···H32.4800H3···O12.4800
O2···H3Nvii2.047 (16)H3···O2ii2.4000
O2···H4vi2.6900H3N···C12vii2.984 (16)
O2···H3vi2.4000H3N···C3xii3.086 (16)
O2···H92.4700H3N···O2vii2.047 (16)
O3···H112.5000H3O···C1viii2.8000
N1···C6vi3.2396 (14)H3O···C5viii2.8900
N1···C13ix3.4382 (18)H3O···N1viii1.9100
N1···O3ix2.7510 (15)H3O···F2A2.8200
N2···O1iv2.9093 (13)H3O···F2B2.8000
N2···N3x2.9994 (15)H4···O2ii2.6900
N3···C1xi3.4220 (16)H4N···O1v2.222 (17)
N3···C12ii3.2557 (15)H4N···C72.649 (16)
N3···N2xi2.9994 (15)H4N···H72.0900
N4···C12xii3.3776 (15)H5···F3Biii2.5800
N4···O1v3.0867 (14)H5···F3Aiii2.4600
N4···O2vii2.9139 (13)H7···N42.6000
N1···H13Ax2.8600H7···H4N2.0900
N1···H3Oix1.9100H7···O1v2.3600
N2···H12.6100H9···O22.4700
N3···H1Nxi2.122 (16)H9···F3Biii2.8600
N3···H1xi2.5100H10···F1Ai2.7300
N4···H72.6000H10···F1Bi2.7800
C1···N3x3.4220 (16)H11···O32.5000
C1···C13x3.4220 (18)H13A···N1xi2.8600
C1···C6vi3.4524 (15)H13A···C1xi2.9000
C3···O2ii3.0103 (15)H13B···F2Bvi2.8700
C3···C5ii3.5363 (15)
C13—O3—H3O109.00C9—C10—C11118.64 (12)
C1—N1—C5117.62 (10)N3—C11—C10122.95 (11)
C6—N2—H2N116.2 (11)N4—C12—C8118.69 (10)
C6—N2—H1N122.9 (10)O2—C12—N4122.47 (10)
H1N—N2—H2N120.7 (15)O2—C12—C8118.84 (10)
C7—N3—C11117.80 (10)C8—C7—H7118.00
H3N—N4—H4N117.7 (15)N3—C7—H7118.00
C12—N4—H4N124.6 (10)C8—C9—H9120.00
C12—N4—H3N117.4 (11)C10—C9—H9120.00
N1—C1—C2123.48 (11)C9—C10—H10121.00
C1—C2—C6123.54 (10)C11—C10—H10121.00
C3—C2—C6118.67 (9)C10—C11—H11119.00
C1—C2—C3117.78 (10)N3—C11—H11119.00
C2—C3—C4119.37 (10)O3—C13—C14B107.67 (18)
C3—C4—C5118.54 (12)O3—C13—C14A115.28 (16)
N1—C5—C4123.19 (11)F1A—C14A—F3A108.0 (5)
O1—C6—C2119.14 (9)F1A—C14A—F2A106.7 (5)
N2—C6—C2118.66 (9)F1A—C14A—C13108.7 (4)
O1—C6—N2122.20 (10)F2A—C14A—F3A107.2 (5)
C2—C1—H1118.00F2A—C14A—C13113.6 (4)
N1—C1—H1118.00F3A—C14A—C13112.5 (4)
C2—C3—H3120.00F1B—C14B—F2B106.3 (5)
C4—C3—H3120.00F1B—C14B—F3B104.3 (4)
C3—C4—H4121.00F1B—C14B—C13117.2 (4)
C5—C4—H4121.00F2B—C14B—F3B107.0 (5)
N1—C5—H5118.00F2B—C14B—C13110.6 (4)
C4—C5—H5118.00F3B—C14B—C13110.7 (4)
N3—C7—C8123.44 (11)O3—C13—H13A108.00
C9—C8—C12118.67 (10)O3—C13—H13B108.00
C7—C8—C9117.85 (10)C14A—C13—H13A108.00
C7—C8—C12123.48 (10)C14B—C13—H13B98.00
C8—C9—C10119.30 (11)
C5—N1—C1—C2−0.71 (16)N3—C7—C8—C91.42 (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—N48.74 (16)
C7—N3—C11—C100.22 (18)C9—C8—C12—O28.43 (16)
N1—C1—C2—C6180.00 (13)C7—C8—C12—O2−171.77 (11)
N1—C1—C2—C31.37 (16)C7—C8—C9—C10−0.60 (17)
C1—C2—C6—O1−169.45 (10)C12—C8—C9—C10179.21 (11)
C3—C2—C6—N2−170.96 (10)C8—C9—C10—C11−0.30 (19)
C3—C2—C6—O19.14 (15)C9—C10—C11—N30.5 (2)
C1—C2—C6—N210.45 (15)O3—C13—C14B—F1B58.1 (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—F3B177.6 (3)
C2—C3—C4—C5−0.49 (17)O3—C13—C14A—F1A62.9 (4)
C3—C4—C5—N11.21 (18)O3—C13—C14A—F2A−55.7 (4)
N3—C7—C8—C12−178.39 (11)O3—C13—C14A—F3A−177.7 (4)
D—H···AD—HH···AD···AD—H···A
N2—H1N···N3x0.897 (16)2.122 (16)2.9994 (15)165.7 (15)
N2—H2N···O1iv0.898 (16)2.013 (16)2.9093 (13)176.8 (14)
N4—H3N···O2vii0.877 (16)2.047 (16)2.9139 (13)170.1 (16)
O3—H3O···N1viii0.841.912.7511 (15)178
N4—H4N···O1v0.878 (17)2.222 (17)3.0867 (14)168.4 (15)
C1—H1···N3x0.952.513.4220 (16)161
C3—H3···O2ii0.952.403.0103 (15)122
C5—H5···F3Aiii0.952.463.408 (7)177
C7—H7···O1v0.952.363.2118 (14)149
C11—H11···O30.952.503.2590 (16)137
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N2—H1N⋯N3i0.897 (16)2.122 (16)2.9994 (15)165.7 (15)
N2—H2N⋯O1ii0.898 (16)2.013 (16)2.9093 (13)176.8 (14)
N4—H3N⋯O2iii0.877 (16)2.047 (16)2.9139 (13)170.1 (16)
O3—H3O⋯N1iv0.841.912.7511 (15)178
N4—H4N⋯O1v0.878 (17)2.222 (17)3.0867 (14)168.4 (15)
C1—H1⋯N3i0.952.513.4220 (16)161
C3—H3⋯O2vi0.952.403.0103 (15)122
C5—H5⋯F3Avii0.952.463.408 (7)177
C7—H7⋯O1v0.952.363.2118 (14)149
C11—H11⋯O30.952.503.2590 (16)137

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

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1.  Indexing powder patterns in physical form screening: instrumentation and data quality.

Authors:  Alastair J Florence; Bruno Baumgartner; Chris Weston; Norman Shankland; Alan R Kennedy; Kenneth Shankland; William I F David
Journal:  J Pharm Sci       Date:  2003-09       Impact factor: 3.534

2.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

3.  Experimental charge density and electrostatic potential in nicotinamide.

Authors: 
Journal:  Acta Crystallogr B       Date:  1999-02-01

4.  Structure validation in chemical crystallography.

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Journal:  Acta Crystallogr D Biol Crystallogr       Date:  2009-01-20
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1.  3-Amino-carbonyl-pyridinium difluoro-acetate at 123 K.

Authors:  Julie Bardin; Alastair J Florence; Jean-Baptiste Arlin; Alan R Kennedy; Li Ven Wong
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2009-10-28
  1 in total

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