Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105020913/hj1060sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105020913/hj1060Isup2.hkl |
CCDC reference: 282212
The method of synthesis of compound (I) has been described elsewhere (Salwińska et al., 1991; Walczak et al., 2001). Crystals for data collection were grown from an aqueous solution by slow evaporation.
The H atoms of CH groups were refined freely. Those of methyl groups were allowed to ride on the appropriate C atom and rotate as a rigid group around the C—C bond (C—H = 0.98 Å); one Uiso value was refined for each methyl group. The positions of H atoms of the water molecule were freely refined; a common Uiso value was also refined for these atoms.
Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: program (reference)?; software used to prepare material for publication: program (reference)?.
C8H8N6O4·H2O | F(000) = 280 |
Mr = 270.22 | Dx = 1.522 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2200 reflections |
a = 6.5951 (8) Å | θ = 3–20° |
b = 13.4920 (13) Å | µ = 0.13 mm−1 |
c = 7.2032 (9) Å | T = 100 K |
β = 113.084 (12)° | Prism, colourless |
V = 589.63 (13) Å3 | 0.15 × 0.1 × 0.1 mm |
Z = 2 |
Kuma KM-4 CCD four-circle diffractometer | 1595 independent reflections |
Radiation source: fine-focus sealed tube | 1060 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 29.8°, θmin = 3.9° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | h = −9→8 |
Tmin = 0.989, Tmax = 0.989 | k = −18→18 |
5482 measured reflections | l = −8→9 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.049 | w = 1/[σ2(Fo2) + (0.01P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.84 | (Δ/σ)max = 0.002 |
1598 reflections | Δρmax = 0.21 e Å−3 |
192 parameters | Δρmin = −0.22 e Å−3 |
1 restraint | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.026 (2) |
C8H8N6O4·H2O | V = 589.63 (13) Å3 |
Mr = 270.22 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.5951 (8) Å | µ = 0.13 mm−1 |
b = 13.4920 (13) Å | T = 100 K |
c = 7.2032 (9) Å | 0.15 × 0.1 × 0.1 mm |
β = 113.084 (12)° |
Kuma KM-4 CCD four-circle diffractometer | 1595 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 1060 reflections with I > 2σ(I) |
Tmin = 0.989, Tmax = 0.989 | Rint = 0.039 |
5482 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 1 restraint |
wR(F2) = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.84 | Δρmax = 0.21 e Å−3 |
1598 reflections | Δρmin = −0.22 e Å−3 |
192 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C2 | 0.6422 (4) | 0.42840 (18) | 0.3674 (4) | 0.0196 (6) | |
C2' | 0.3758 (4) | 0.68804 (19) | −0.0050 (4) | 0.0179 (6) | |
C21 | 0.4027 (4) | 0.40469 (19) | 0.2704 (4) | 0.0230 (7) | |
C21' | 0.1941 (5) | 0.7611 (2) | −0.0462 (4) | 0.0277 (7) | |
C4 | 0.9873 (4) | 0.42481 (19) | 0.5458 (4) | 0.0163 (6) | |
C4' | 0.6283 (4) | 0.57824 (18) | 0.1624 (4) | 0.0178 (6) | |
C5 | 0.9611 (4) | 0.5072 (2) | 0.4311 (4) | 0.0187 (6) | |
C5' | 0.6347 (4) | 0.59922 (19) | −0.0196 (4) | 0.0173 (6) | |
N1 | 0.7386 (3) | 0.50957 (16) | 0.3148 (3) | 0.0168 (5) | |
N1' | 0.4785 (3) | 0.66724 (16) | −0.1256 (3) | 0.0196 (5) | |
N3 | 0.7926 (3) | 0.37558 (14) | 0.5079 (3) | 0.0193 (5) | |
N3' | 0.4613 (4) | 0.63594 (16) | 0.1703 (3) | 0.0183 (5) | |
N4 | 1.1900 (4) | 0.38726 (18) | 0.6932 (3) | 0.0251 (6) | |
N5' | 0.7775 (4) | 0.55884 (16) | −0.1091 (4) | 0.0225 (5) | |
O1W | 0.2974 (3) | 0.67645 (14) | 0.4462 (3) | 0.0204 (4) | |
O41 | 1.1832 (3) | 0.30927 (14) | 0.7794 (3) | 0.0323 (5) | |
O42 | 1.3590 (3) | 0.43515 (13) | 0.7227 (3) | 0.0311 (5) | |
O51' | 0.7456 (3) | 0.58377 (14) | −0.2823 (3) | 0.0302 (5) | |
O52' | 0.9230 (3) | 0.50088 (13) | −0.0061 (3) | 0.0283 (5) | |
H1W | 0.235 (6) | 0.744 (3) | 0.426 (5) | 0.068 (9)* | |
H21A | 0.3760 | 0.3392 | 0.3153 | 0.051 (6)* | |
H21B | 0.3561 | 0.4045 | 0.1234 | 0.051 (6)* | |
H21C | 0.3186 | 0.4547 | 0.3087 | 0.051 (6)* | |
H21D | 0.0947 | 0.7385 | 0.0166 | 0.062 (6)* | |
H21E | 0.1119 | 0.7672 | −0.1923 | 0.062 (6)* | |
H21F | 0.2562 | 0.8257 | 0.0099 | 0.062 (6)* | |
H2W | 0.371 (6) | 0.676 (3) | 0.582 (5) | 0.068 (9)* | |
H3' | 0.418 (4) | 0.6461 (18) | 0.264 (4) | 0.019 (8)* | |
H5 | 1.058 (4) | 0.5590 (19) | 0.426 (4) | 0.025 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C2 | 0.0228 (14) | 0.0185 (15) | 0.0181 (14) | 0.0026 (12) | 0.0086 (12) | 0.0001 (12) |
C2' | 0.0185 (14) | 0.0175 (15) | 0.0175 (15) | 0.0018 (12) | 0.0070 (12) | −0.0003 (12) |
C21 | 0.0176 (14) | 0.0236 (17) | 0.0261 (16) | 0.0000 (12) | 0.0067 (12) | 0.0026 (13) |
C21' | 0.0259 (16) | 0.0288 (17) | 0.0286 (18) | 0.0073 (14) | 0.0107 (15) | 0.0062 (14) |
C4 | 0.0145 (13) | 0.0165 (14) | 0.0151 (14) | 0.0009 (12) | 0.0030 (11) | −0.0013 (12) |
C4' | 0.0159 (13) | 0.0175 (15) | 0.0177 (15) | 0.0017 (12) | 0.0042 (11) | −0.0017 (12) |
C5 | 0.0189 (14) | 0.0214 (15) | 0.0157 (14) | −0.0030 (13) | 0.0067 (12) | −0.0012 (13) |
C5' | 0.0182 (13) | 0.0173 (15) | 0.0178 (15) | 0.0016 (11) | 0.0086 (12) | −0.0010 (12) |
N1 | 0.0177 (11) | 0.0173 (12) | 0.0148 (12) | 0.0003 (11) | 0.0056 (9) | 0.0007 (10) |
N1' | 0.0221 (12) | 0.0184 (12) | 0.0182 (13) | 0.0010 (10) | 0.0079 (10) | −0.0004 (10) |
N3 | 0.0195 (11) | 0.0192 (13) | 0.0166 (12) | 0.0017 (10) | 0.0044 (10) | −0.0006 (10) |
N3' | 0.0209 (12) | 0.0203 (12) | 0.0158 (13) | 0.0021 (10) | 0.0093 (11) | 0.0009 (10) |
N4 | 0.0269 (15) | 0.0268 (14) | 0.0192 (13) | 0.0025 (12) | 0.0064 (11) | −0.0028 (12) |
N5' | 0.0210 (13) | 0.0254 (14) | 0.0207 (13) | 0.0002 (11) | 0.0077 (11) | −0.0021 (11) |
O1W | 0.0262 (10) | 0.0186 (11) | 0.0160 (11) | 0.0030 (10) | 0.0077 (9) | −0.0007 (9) |
O41 | 0.0306 (12) | 0.0281 (12) | 0.0324 (12) | 0.0038 (10) | 0.0061 (10) | 0.0118 (10) |
O42 | 0.0171 (10) | 0.0353 (12) | 0.0337 (12) | −0.0037 (9) | 0.0023 (9) | 0.0001 (10) |
O51' | 0.0384 (12) | 0.0361 (12) | 0.0199 (12) | 0.0089 (10) | 0.0156 (9) | 0.0056 (10) |
O52' | 0.0256 (11) | 0.0292 (13) | 0.0283 (12) | 0.0110 (10) | 0.0087 (9) | 0.0039 (10) |
N1—C5 | 1.376 (3) | N1'—C5' | 1.367 (3) |
N1—C2 | 1.391 (3) | C2'—N3' | 1.359 (3) |
N1—C4' | 1.402 (3) | C2'—C21' | 1.489 (4) |
C2—N3 | 1.315 (3) | C21'—H21D | 0.9800 |
C2—C21 | 1.490 (3) | C21'—H21E | 0.9800 |
C21—H21A | 0.9800 | C21'—H21F | 0.9800 |
C21—H21B | 0.9800 | N3'—C4' | 1.368 (3) |
C21—H21C | 0.9800 | N3'—H3' | 0.84 (2) |
N3—C4 | 1.375 (3) | C5'—C4' | 1.358 (3) |
C4—C5 | 1.354 (4) | C5'—N5' | 1.440 (3) |
C4—N4 | 1.434 (3) | N5'—O51' | 1.228 (2) |
N4—O41 | 1.231 (3) | N5'—O52' | 1.235 (3) |
N4—O42 | 1.233 (3) | O1W—H1W | 0.99 (4) |
C5—H5 | 0.96 (2) | O1W—H2W | 0.91 (4) |
N1'—C2' | 1.325 (3) | ||
C5—N1—C2 | 107.9 (2) | N1'—C2'—N3' | 111.5 (2) |
C5—N1—C4' | 126.5 (2) | N1'—C2'—C21' | 126.0 (2) |
C2—N1—C4' | 125.5 (2) | N3'—C2'—C21' | 122.4 (2) |
N3—C2—N1 | 110.4 (2) | C2'—C21'—H21D | 109.5 |
N3—C2—C21 | 125.9 (2) | C2'—C21'—H21E | 109.5 |
N1—C2—C21 | 123.7 (2) | H21D—C21'—H21E | 109.5 |
C2—C21—H21A | 109.5 | C2'—C21'—H21F | 109.5 |
C2—C21—H21B | 109.5 | H21D—C21'—H21F | 109.5 |
H21A—C21—H21B | 109.5 | H21E—C21'—H21F | 109.5 |
C2—C21—H21C | 109.5 | C2'—N3'—C4' | 107.7 (2) |
H21A—C21—H21C | 109.5 | C2'—N3'—H3' | 121.0 (17) |
H21B—C21—H21C | 109.5 | C4'—N3'—H3' | 131.1 (17) |
C2—N3—C4 | 104.8 (2) | C4'—C5'—N1' | 112.2 (2) |
C5—C4—N3 | 112.9 (2) | C4'—C5'—N5' | 128.8 (2) |
C5—C4—N4 | 126.9 (2) | N1'—C5'—N5' | 119.1 (2) |
N3—C4—N4 | 120.2 (2) | C5'—C4'—N3' | 104.6 (2) |
O41—N4—O42 | 124.7 (2) | C5'—C4'—N1 | 133.7 (2) |
O41—N4—C4 | 117.9 (2) | N3'—C4'—N1 | 121.5 (2) |
O42—N4—C4 | 117.4 (2) | O51'—N5'—O52' | 124.5 (2) |
C4—C5—N1 | 104.0 (2) | O51'—N5'—C5' | 118.0 (2) |
C4—C5—H5 | 134.0 (15) | O52'—N5'—C5' | 117.5 (2) |
N1—C5—H5 | 121.9 (15) | H1W—O1W—H2W | 100 (3) |
C2'—N1'—C5' | 104.1 (2) | ||
C5—N1—C2—N3 | −0.6 (3) | N1'—C2'—N3'—C4' | −0.1 (3) |
C4'—N1—C2—N3 | 176.3 (2) | C21'—C2'—N3'—C4' | −178.2 (2) |
C5—N1—C2—C21 | −178.7 (2) | C2'—N1'—C5'—C4' | 0.1 (3) |
C4'—N1—C2—C21 | −1.8 (3) | C2'—N1'—C5'—N5' | 179.3 (2) |
N1—C2—N3—C4 | 0.5 (3) | N1'—C5'—C4'—N3' | −0.2 (3) |
C21—C2—N3—C4 | 178.5 (2) | N5'—C5'—C4'—N3' | −179.2 (2) |
C2—N3—C4—C5 | −0.2 (3) | N1'—C5'—C4'—N1 | 173.9 (3) |
C2—N3—C4—N4 | −179.8 (2) | N5'—C5'—C4'—N1 | −5.1 (5) |
C5—C4—N4—O41 | −177.9 (2) | C2'—N3'—C4'—C5' | 0.1 (3) |
N3—C4—N4—O41 | 1.7 (3) | C2'—N3'—C4'—N1 | −174.9 (2) |
C5—C4—N4—O42 | 1.3 (3) | C5—N1—C4'—C5' | 64.9 (4) |
N3—C4—N4—O42 | −179.1 (2) | C2—N1—C4'—C5' | −111.5 (3) |
N3—C4—C5—N1 | −0.2 (3) | C5—N1—C4'—N3' | −121.8 (3) |
N4—C4—C5—N1 | 179.4 (2) | C2—N1—C4'—N3' | 61.8 (3) |
C2—N1—C5—C4 | 0.5 (3) | C4'—C5'—N5'—O51' | 175.4 (3) |
C4'—N1—C5—C4 | −176.4 (2) | N1'—C5'—N5'—O51' | −3.5 (3) |
C5'—N1'—C2'—N3' | 0.0 (3) | C4'—C5'—N5'—O52' | −4.1 (4) |
C5'—N1'—C2'—C21' | 178.0 (2) | N1'—C5'—N5'—O52' | 176.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21B···O41i | 0.98 | 2.62 | 3.499 (3) | 149 |
C5—H5···O1Wii | 0.96 (2) | 2.20 (3) | 3.155 (3) | 175 (2) |
N3′—H3′···O1W | 0.84 (2) | 1.83 (2) | 2.665 (3) | 173 (2) |
C21′—H21F···O52′iii | 0.98 | 2.64 | 3.381 (3) | 133 |
O1W—H1W···N3iv | 0.99 (4) | 1.86 (3) | 2.799 (3) | 157 (3) |
O1W—H2W···N1′v | 0.91 (4) | 1.94 (4) | 2.840 (3) | 170 (3) |
Symmetry codes: (i) x−1, y, z−1; (ii) x+1, y, z; (iii) −x+1, y+1/2, −z; (iv) −x+1, y+1/2, −z+1; (v) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C8H8N6O4·H2O |
Mr | 270.22 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 100 |
a, b, c (Å) | 6.5951 (8), 13.4920 (13), 7.2032 (9) |
β (°) | 113.084 (12) |
V (Å3) | 589.63 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.15 × 0.1 × 0.1 |
Data collection | |
Diffractometer | Kuma KM-4 CCD four-circle diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.989, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5482, 1595, 1060 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.699 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.049, 0.84 |
No. of reflections | 1598 |
No. of parameters | 192 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.22 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2002), CrysAlis CCD, CrysAlis RED (Oxford Diffraction, 2002), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), program (reference)?.
N1—C5 | 1.376 (3) | N1'—C2' | 1.325 (3) |
N1—C2 | 1.391 (3) | N1'—C5' | 1.367 (3) |
N1—C4' | 1.402 (3) | C2'—N3' | 1.359 (3) |
C2—N3 | 1.315 (3) | N3'—C4' | 1.368 (3) |
N3—C4 | 1.375 (3) | ||
C5—N1—C2 | 107.9 (2) | C2'—N1'—C5' | 104.1 (2) |
C5—N1—C4' | 126.5 (2) | C2'—N3'—C4' | 107.7 (2) |
C2—N1—C4' | 125.5 (2) | N3'—C4'—N1 | 121.5 (2) |
N3—C2—N1 | 110.4 (2) | O51'—N5'—O52' | 124.5 (2) |
O41—N4—O42 | 124.7 (2) | O51'—N5'—C5' | 118.0 (2) |
O41—N4—C4 | 117.9 (2) | O52'—N5'—C5' | 117.5 (2) |
O42—N4—C4 | 117.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21B···O41i | 0.98 | 2.62 | 3.499 (3) | 149 |
C5—H5···O1Wii | 0.96 (2) | 2.20 (3) | 3.155 (3) | 175 (2) |
N3'—H3'···O1W | 0.84 (2) | 1.83 (2) | 2.665 (3) | 173 (2) |
C21'—H21F···O52'iii | 0.98 | 2.64 | 3.381 (3) | 133 |
O1W—H1W···N3iv | 0.99 (4) | 1.86 (3) | 2.799 (3) | 157 (3) |
O1W—H2W···N1'v | 0.91 (4) | 1.94 (4) | 2.840 (3) | 170 (3) |
Symmetry codes: (i) x−1, y, z−1; (ii) x+1, y, z; (iii) −x+1, y+1/2, −z; (iv) −x+1, y+1/2, −z+1; (v) x, y, z+1. |
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There are 28 organic and 62 organometallic crystal structures containing 2,2'-biimidazole in the Cambridge Structural Database (Allen, 2002; November 2004 version, February 2005 updates). It therefore seems strange that for 1,5'-biimidazole there is only one known crystal structure (Kubicki et al., 2001). What is more, examples of other biimidazoles are also scarce; there are only a few examples of 4,4'- (four structures) and 5,5'-biimidazoles (three examples).
Since the 4-nitroimidazole derivatives proved to be convenient subjects for studying weak intermolecular interactions in crystals (e.g. Kubicki, 2004, and references therein), it should be of interest to determine the crystal structures of their biimidazole analogues as well. Here, the crystal structure of one of the simplest members of this family, 2,2'-dimethyl-4,5'-dinitro-3'H-[1,4']-biimidazole, is reported. This compound crystallizes as a hydrate, (I).
Fig. 1 shows a perspective view of the molecule. Both imidazole rings are almost perfectly planar; the maximum deviations from the least-squares planes are 0.0032 (14) and 0.0008 (15) Å for rings A and B (hereinafter A will denote the non-primed and B the primed imidazole rings). The nitro groups are only slightly twisted with respect to the imidazole planes [the twist angles are 1.9 (3)° for A and 3.9 (4)° for B]. The dihedral angle between the imidazole rings is 63.01 (10)°; this value is large compared with the typical values for 2,2'-biimidazoles, for which angles significantly larger than a few degrees are observed only in the case of large substituents [for example, 60.5° in cis-1,1'-diacetyl-2,2'-bi-imidazole (Secondo et al., 1996)] or for charged species, i.e. biimidazolium [for example, 89.0° in 2,2'-bi(1,3-diisopropyl-4,5-dimethylimidazolyl) bis(tetrafluoroborate) monohydrate (Kuhn et al., 2001)]. The bond lengths and angles are typical.
The architecture of the crystal structure of (I) is determined mainly by hydrogen bonds involving the water molecule, which acts as a di-donor and a di-acceptor. It takes part in two OW—H···N hydrogen bonds, in which two different N atoms (i.e. N3 and N1') from two different molecules are acceptors, and also accepts one N—H···OW and one exceptionally short C—H···OW hydrogen bonds. The hydrogen-bonding geometry is given in Table 2. These four directional bonds (the D—H···A angles are larger than 156°) form a regular tetrahedral coordination of the water O atom (the H···O—H angles are in the range 98–125°). The three-dimensional hydrogen-bond network may be described using graph-set notation (Etter et al., 1990; Bernstein et al., 1995). C12(7) and C22(8) chains of biimidazole and water molecules are interwoven to produce some relatively large rings; two examples, R66(21) and R66(23), are shown in Figs. 2(a) and 2(b). This tight network of hydrogen bonds may be responsible for relatively the high melting point of the title compound (542–543 K). Such a correlation between the hydrogen-bond network and melting points was noticed, for example, in the case of two isomeric 2-hydroxy-bornane 3-carboxylic acids (Kubicki et al., 2000).