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High-resolution crystal structure determination and spherical and multipolar refinement enabled an organic solid solution of 1-(4′-chlorophenyl)-2-methyl-4-nitro-1H-imidazole-5-carbonitrile and 5-bromo-1-(4′-chlorophenyl)-2-methyl-4-nitro-1H-imidazole to be found, which would not normally be revealed using only standard resolution data (ca 0.8 Å), as the disordered part is only visible at high resolution. Therefore, this new structure would have been reported as just another polymorphic form, even more reasonably as isostructural with other derivatives. To the best of our knowledge this is the first example of organic solid solution modelled via charge density Hansen–Coppens formalism and analysed by means of quantum theory of atoms in molecules (QTAIM) theory.
Supporting information
CCDC reference: 1026079
Crystal data, data collection and structure refinement details are summarized
in Table 1.
S2. Results and discussion
top
Program(s) used to refine structure: MoPro (J. Appl. Cryst. 2005, 38, 38-54).
Crystal data top
C10.98H7Br0.02ClN3.98O2 | F(000) = 537.8 |
Mr = 263.93 | Dx = 1.550 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yn | Cell parameters from 29906 reflections |
a = 9.3618 (2) Å | θ = 3.1–53.2° |
b = 9.6497 (2) Å | µ = 0.41 mm−1 |
c = 12.9909 (2) Å | T = 100 K |
β = 105.428 (2)° | Plate, colourless |
V = 1131.29 (4) Å3 | 0.78 × 0.60 × 0.15 mm |
Z = 4 | |
Data collection top
Xcalibur, Eos diffractometer | 10032 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 10015 reflections with > 2.0σ(I) |
Graphite monochromator | θmax = 53.3°, θmin = 3.1° |
Detector resolution: 16.1544 pixels mm-1 | h = −21→20 |
Absorption correction: analytical CrysAlis PRO, Agilent Technologies,
Version 1.171.35.4 (release 09-12-2010 CrysAlis171 .NET)
(compiled Dec 9 2010,10:47:41)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) | k = 0→21 |
Tmin = 0.816, Tmax = 0.952 | l = 0→29 |
104943 measured reflections | |
Refinement top
Refinement on F | 27 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.021 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.022 | Hydrogen site location: inferred from neighbouring sites |
S = 1.12 | H-atom parameters constrained |
10032 reflections | Weighting scheme based on measured s.u.'s |
477 parameters | (Δ/σ)max = 0.003 |
Crystal data top
C10.98H7Br0.02ClN3.98O2 | V = 1131.29 (4) Å3 |
Mr = 263.93 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.3618 (2) Å | µ = 0.41 mm−1 |
b = 9.6497 (2) Å | T = 100 K |
c = 12.9909 (2) Å | 0.78 × 0.60 × 0.15 mm |
β = 105.428 (2)° | |
Data collection top
Xcalibur, Eos diffractometer | 104943 measured reflections |
Absorption correction: analytical CrysAlis PRO, Agilent Technologies,
Version 1.171.35.4 (release 09-12-2010 CrysAlis171 .NET)
(compiled Dec 9 2010,10:47:41)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) | 10032 independent reflections |
Tmin = 0.816, Tmax = 0.952 | 10015 reflections with > 2.0σ(I) |
Refinement top
R[F2 > 2σ(F2)] = 0.021 | 477 parameters |
wR(F2) = 0.022 | 27 restraints |
S = 1.12 | H-atom parameters constrained |
10032 reflections | |
Special details top
Refinement. Refinement of F1 against reflections. The threshold expression of
F2 > σ(F2) is used for calculating R-factors(gt) 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 | Uiso*/Ueq | Occ. (<1) |
C1 | 0.71915 (3) | 0.44793 (3) | 0.75344 (2) | 0.01131 (2) | |
C2 | 0.84128 (3) | 0.38278 (3) | 0.73277 (2) | 0.01392 (2) | |
C3 | 0.86833 (3) | 0.39882 (3) | 0.63296 (2) | 0.01489 (2) | |
C4 | 0.77406 (3) | 0.48337 (3) | 0.55774 (2) | 0.01306 (2) | |
C5 | 0.65630 (3) | 0.55373 (3) | 0.58015 (2) | 0.01384 (2) | |
C6 | 0.62685 (3) | 0.53391 (3) | 0.67857 (2) | 0.01331 (2) | |
C7 | 0.57637 (3) | 0.33046 (3) | 0.86576 (2) | 0.01258 (2) | |
C71 | 0.48373 (4) | 0.24652 (3) | 0.77730 (2) | 0.01737 (2) | |
C8 | 0.66896 (3) | 0.42395 (3) | 1.01645 (2) | 0.01295 (2) | |
C9 | 0.74268 (3) | 0.48420 (3) | 0.94911 (2) | 0.01244 (1) | |
N1 | 0.68249 (3) | 0.42148 (3) | 0.85209 (2) | 0.01167 (1) | |
N2 | 0.56687 (3) | 0.33063 (3) | 0.96562 (2) | 0.01357 (2) | |
N8 | 0.69211 (3) | 0.45406 (3) | 1.12789 (2) | 0.01603 (2) | |
O81 | 0.61294 (4) | 0.39555 (4) | 1.17567 (2) | 0.02293 (3) | |
O82 | 0.78994 (5) | 0.53705 (5) | 1.16821 (3) | 0.02337 (3) | |
CL1 | 0.79800 (2) | 0.49908 (2) | 0.43095 (1) | 0.019172 (1) | |
H72 | 0.41362 | 0.31322 | 0.72122 | 0.03798 | |
H71 | 0.41757 | 0.18040 | 0.81066 | 0.04218 | |
H73 | 0.55160 | 0.18772 | 0.74017 | 0.03877 | |
H6 | 0.53143 | 0.58139 | 0.69650 | 0.02815 | |
H2 | 0.91314 | 0.32126 | 0.79523 | 0.03019 | |
H3 | 0.95545 | 0.34280 | 0.61023 | 0.03351 | |
H5 | 0.58701 | 0.62160 | 0.52114 | 0.03150 | |
BR1a | 0.8794 (2) | 0.6396 (2) | 0.9677 (1) | 0.02149 (4) | 0.02 |
C91b | 0.85026 (3) | 0.58946 (3) | 0.96423 (2) | 0.01565 (2) | 0.98 |
N91b | 0.93843 (3) | 0.67627 (3) | 0.97429 (2) | 0.02309 (2) | 0.98 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.01156 (8) | 0.01168 (8) | 0.01126 (7) | 0.00042 (6) | 0.00400 (6) | 0.00102 (6) |
C2 | 0.01277 (8) | 0.01528 (8) | 0.01457 (8) | 0.00309 (7) | 0.00514 (7) | 0.00355 (7) |
C3 | 0.01396 (8) | 0.01666 (9) | 0.01579 (9) | 0.00325 (7) | 0.00696 (7) | 0.00237 (7) |
C4 | 0.01360 (8) | 0.01476 (9) | 0.01170 (7) | −0.000052 (7) | 0.00486 (7) | 0.00033 (6) |
C5 | 0.01437 (8) | 0.01541 (9) | 0.01191 (7) | 0.00279 (7) | 0.00379 (7) | 0.00237 (7) |
C6 | 0.01344 (8) | 0.01440 (9) | 0.01285 (8) | 0.00327 (7) | 0.00481 (7) | 0.00182 (7) |
C7 | 0.01406 (8) | 0.01263 (8) | 0.01146 (7) | −0.00184 (7) | 0.00412 (6) | 0.000049 (6) |
C71 | 0.0205 (1) | 0.01665 (9) | 0.01492 (8) | −0.00605 (8) | 0.00463 (8) | −0.00204 (7) |
C8 | 0.01324 (8) | 0.01553 (9) | 0.01023 (7) | 0.00103 (7) | 0.00342 (6) | 0.00029 (7) |
C9 | 0.01196 (7) | 0.01375 (8) | 0.01130 (7) | −0.00075 (6) | 0.00254 (6) | −0.00045 (6) |
N1 | 0.01267 (8) | 0.01243 (8) | 0.01040 (7) | −0.00153 (6) | 0.00392 (6) | 0.00013 (6) |
N2 | 0.01464 (8) | 0.01527 (9) | 0.01168 (7) | −0.00079 (7) | 0.00503 (7) | 0.00110 (7) |
N8 | 0.01629 (9) | 0.0212 (1) | 0.01029 (7) | 0.00325 (8) | 0.00300 (6) | −0.00014 (7) |
O81 | 0.0254 (1) | 0.0324 (2) | 0.01330 (9) | 0.0009 (1) | 0.00908 (9) | 0.00113 (9) |
O82 | 0.0237 (1) | 0.0305 (2) | 0.0138 (1) | −0.0027 (1) | 0.0014 (1) | −0.0048 (1) |
CL1 | 0.02162 (3) | 0.02538 (3) | 0.01242 (2) | 0.00053 (2) | 0.00788 (2) | 0.00033 (2) |
H72 | 0.0383 | 0.0380 | 0.0309 | −0.0017 | −0.0027 | 0.0019 |
H71 | 0.0485 | 0.0461 | 0.0360 | −0.0259 | 0.0185 | −0.0024 |
H73 | 0.0398 | 0.0392 | 0.0407 | −0.0028 | 0.0166 | −0.0152 |
H6 | 0.0248 | 0.0344 | 0.0275 | 0.0115 | 0.0108 | 0.0037 |
H2 | 0.0285 | 0.0360 | 0.0260 | 0.0135 | 0.0071 | 0.0093 |
H3 | 0.0307 | 0.0420 | 0.0328 | 0.0140 | 0.0171 | 0.0030 |
H5 | 0.0328 | 0.0375 | 0.0232 | 0.0118 | 0.0058 | 0.0104 |
BR1a | 0.0215 (2) | 0.0201 (2) | 0.0210 (2) | −0.0037 (2) | 0.0022 (2) | 0.0009 (2) |
C91b | 0.01391 (8) | 0.01470 (9) | 0.01682 (8) | −0.00277 (7) | 0.00145 (6) | −0.00098 (7) |
N91b | 0.01940 (10) | 0.01823 (9) | 0.0289 (1) | −0.00787 (8) | 0.00174 (8) | −0.00171 (8) |
Geometric parameters (Å, º) top
C1—N1 | 1.4351 (3) | C7—C71 | 1.4827 (3) |
C1—C6 | 1.3907 (3) | C71—H72 | 1.059 |
C1—C2 | 1.3921 (4) | C71—H73 | 1.059 |
C2—C3 | 1.3944 (4) | C71—H71 | 1.059 |
C2—H2 | 1.083 | C8—N8 | 1.4355 (3) |
C3—C4 | 1.3930 (4) | C8—N2 | 1.3508 (4) |
C3—H3 | 1.083 | C8—C9 | 1.3786 (4) |
C4—CL1 | 1.7270 (3) | C9—BR1a | 1.944 (2) |
C4—C5 | 1.3900 (4) | C9—N1 | 1.3764 (3) |
C5—C6 | 1.3910 (4) | C9—C91b | 1.4069 (4) |
C5—H5 | 1.083 | N8—O81 | 1.2240 (4) |
C6—H6 | 1.083 | N8—O82 | 1.2244 (5) |
C7—N1 | 1.3725 (3) | C91b—N91b | 1.1588 (4) |
C7—N2 | 1.3238 (3) | | |
| | | |
C1—N1—C9 | 127.06 (2) | C7—C71—H72 | 109.2 |
C1—N1—C7 | 125.64 (3) | C7—C71—H73 | 110.3 |
C1—C6—C5 | 119.12 (3) | C7—C71—H71 | 107.3 |
C1—C6—H6 | 119.8 | C71—C7—N1 | 122.93 (2) |
C1—C2—C3 | 119.40 (3) | C71—C7—N2 | 125.61 (2) |
C1—C2—H2 | 118.8 | C8—N8—O81 | 117.95 (3) |
C2—C1—N1 | 119.72 (3) | C8—N8—O82 | 117.32 (3) |
C2—C1—C6 | 121.59 (3) | C8—C9—BR1a | 132.09 (6) |
C2—C3—C4 | 118.65 (3) | C8—C9—N1 | 104.09 (2) |
C2—C3—H3 | 122.3 | C8—C9—C91b | 132.57 (3) |
C3—C4—CL1 | 120.11 (3) | C9—C8—N8 | 126.00 (3) |
C3—C4—C5 | 121.94 (3) | C9—C8—N2 | 112.31 (3) |
C3—C2—H2 | 121.8 | C9—C91b—N91b | 178.50 (3) |
C4—C5—C6 | 119.18 (3) | N1—C9—BR1a | 123.28 (5) |
C4—C5—H5 | 120.4 | N1—C9—C91b | 123.28 (2) |
C4—C3—H3 | 118.9 | N1—C7—N2 | 111.45 (2) |
C5—C4—CL1 | 117.92 (2) | N2—C8—N8 | 121.68 (3) |
C5—C6—H6 | 121.1 | O81—N8—O82 | 124.73 (4) |
C6—C1—N1 | 118.62 (2) | H72—C71—H73 | 110.4 |
C6—C5—H5 | 120.4 | H72—C71—H71 | 109.0 |
C7—N1—C9 | 107.28 (2) | H71—C71—H73 | 110.5 |
C7—N2—C8 | 104.86 (2) | | |
| | | |
C1—N1—C9—BR1a | 6.75 (6) | C7—N2—C8—N8 | 179.84 (2) |
C1—N1—C9—C8 | 179.21 (2) | C7—N2—C8—C9 | 0.53 (2) |
C1—N1—C9—C91b | 1.65 (2) | C71—C7—N1—C9 | 178.03 (2) |
C1—N1—C7—N2 | −178.99 (2) | C71—C7—N2—C8 | −178.56 (2) |
C1—N1—C7—C71 | −0.28 (2) | C8—N2—C7—N1 | 0.11 (2) |
C1—C6—C5—C4 | 2.22 (2) | C8—C9—C91b—N91b | −168.85 (3) |
C1—C6—C5—H5 | −179.0 | C9—N1—C7—N2 | −0.69 (2) |
C1—C2—C3—C4 | 1.85 (2) | C9—C8—N8—O81 | 176.97 (3) |
C1—C2—C3—H3 | −174.1 | C9—C8—N8—O82 | −2.89 (3) |
C2—C1—N1—C9 | 83.31 (2) | N1—C9—C8—N8 | 179.80 (2) |
C2—C1—N1—C7 | −98.72 (2) | N1—C9—C8—N2 | −0.93 (2) |
C2—C1—C6—C5 | 0.86 (2) | N1—C9—C91b—N91b | 7.94 (3) |
C2—C1—C6—H6 | 178.8 | N1—C7—C71—H72 | −66.2 |
C2—C3—C4—CL1 | −176.72 (2) | N1—C7—C71—H73 | 55.3 |
C2—C3—C4—C5 | 1.25 (2) | N1—C7—C71—H71 | 175.8 |
C3—C4—C5—C6 | −3.31 (2) | N1—C1—C6—H6 | 1.7 |
C3—C4—C5—H5 | 177.9 | N1—C1—C2—H2 | −6.2 |
C3—C2—C1—N1 | 174.11 (2) | N2—C7—C71—H72 | 112.3 |
C3—C2—C1—C6 | −2.93 (2) | N2—C7—C71—H73 | −126.1 |
C4—C5—C6—H6 | −175.6 | N2—C7—C71—H71 | −5.7 |
C4—C3—C2—H2 | −177.8 | N2—C8—N8—O81 | −2.24 (3) |
C5—C4—C3—H3 | 177.3 | N2—C8—N8—O82 | 177.90 (4) |
C5—C6—C1—N1 | −176.21 (2) | N2—C8—C9—BR1a | 170.57 (6) |
C6—C1—N1—C9 | −99.56 (2) | N2—C8—C9—C91b | 176.31 (2) |
C6—C1—N1—C7 | 78.42 (2) | N8—C8—C9—BR1a | −8.70 (6) |
C6—C1—C2—H2 | 176.7 | N8—C8—C9—C91b | −2.97 (3) |
C6—C5—C4—CL1 | 174.70 (2) | CL1—C4—C5—H5 | −4.1 |
C7—N1—C9—BR1a | −171.52 (7) | CL1—C4—C3—H3 | −0.6 |
C7—N1—C9—C8 | 0.94 (2) | H6—C6—C5—H5 | 3.2 |
C7—N1—C9—C91b | −176.63 (2) | H2—C2—C3—H3 | 6.2 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···N91bi | 1.08 | 2.38 | 3.3687 (4) | 151 |
C6—H6···O81ii | 1.08 | 2.41 | 3.3690 (4) | 146 |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+2. |
Experimental details
Crystal data |
Chemical formula | C10.98H7Br0.02ClN3.98O2 |
Mr | 263.93 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 9.3618 (2), 9.6497 (2), 12.9909 (2) |
β (°) | 105.428 (2) |
V (Å3) | 1131.29 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.41 |
Crystal size (mm) | 0.78 × 0.60 × 0.15 |
|
Data collection |
Diffractometer | Xcalibur, Eos diffractometer |
Absorption correction | Analytical CrysAlis PRO, Agilent Technologies,
Version 1.171.35.4 (release 09-12-2010 CrysAlis171 .NET)
(compiled Dec 9 2010,10:47:41)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
Tmin, Tmax | 0.816, 0.952 |
No. of measured, independent and observed [ > 2.0σ(I)] reflections | 104943, 10032, 10015 |
Rint | ? |
(sin θ/λ)max (Å−1) | 1.128 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.022, 1.12 |
No. of reflections | 10032 |
No. of parameters | 477 |
No. of restraints | 27 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | ?, ? |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···N91bi | 1.083 | 2.379 | 3.3687 (4) | 151.2 |
C6—H6···O81ii | 1.083 | 2.414 | 3.3690 (4) | 146.3 |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+2. |
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