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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520614021325/gw5032sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614021325/gw5032Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520614021325/gw5032sup3.pdf
Extra tables and figures

CCDC reference: 1026079

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Computing details top

Program(s) used to refine structure: MoPro (J. Appl. Cryst. 2005, 38, 38-54).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
(I) top
Crystal data top
C10.98H7Br0.02ClN3.98O2F(000) = 537.8
Mr = 263.93Dx = 1.550 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ynCell parameters from 29906 reflections
a = 9.3618 (2) Åθ = 3.1–53.2°
b = 9.6497 (2) ŵ = 0.41 mm1
c = 12.9909 (2) ÅT = 100 K
β = 105.428 (2)°Plate, colourless
V = 1131.29 (4) Å30.78 × 0.60 × 0.15 mm
Z = 4
Data collection top
Xcalibur, Eos
diffractometer
10032 independent reflections
Radiation source: Enhance (Mo) X-ray Source10015 reflections with > 2.0σ(I)
Graphite monochromatorθmax = 53.3°, θmin = 3.1°
Detector resolution: 16.1544 pixels mm-1h = 2120
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 = 021
Tmin = 0.816, Tmax = 0.952l = 029
104943 measured reflections
Refinement top
Refinement on F27 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.021Secondary atom site location: difference Fourier map
wR(F2) = 0.022Hydrogen site location: inferred from neighbouring sites
S = 1.12H-atom parameters constrained
10032 reflectionsWeighting scheme based on measured s.u.'s
477 parameters(Δ/σ)max = 0.003
Crystal data top
C10.98H7Br0.02ClN3.98O2V = 1131.29 (4) Å3
Mr = 263.93Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.3618 (2) ŵ = 0.41 mm1
b = 9.6497 (2) ÅT = 100 K
c = 12.9909 (2) Å0.78 × 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 = 0.95210015 reflections with > 2.0σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.021477 parameters
wR(F2) = 0.02227 restraints
S = 1.12H-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
xyzUiso*/UeqOcc. (<1)
C10.71915 (3)0.44793 (3)0.75344 (2)0.01131 (2)
C20.84128 (3)0.38278 (3)0.73277 (2)0.01392 (2)
C30.86833 (3)0.39882 (3)0.63296 (2)0.01489 (2)
C40.77406 (3)0.48337 (3)0.55774 (2)0.01306 (2)
C50.65630 (3)0.55373 (3)0.58015 (2)0.01384 (2)
C60.62685 (3)0.53391 (3)0.67857 (2)0.01331 (2)
C70.57637 (3)0.33046 (3)0.86576 (2)0.01258 (2)
C710.48373 (4)0.24652 (3)0.77730 (2)0.01737 (2)
C80.66896 (3)0.42395 (3)1.01645 (2)0.01295 (2)
C90.74268 (3)0.48420 (3)0.94911 (2)0.01244 (1)
N10.68249 (3)0.42148 (3)0.85209 (2)0.01167 (1)
N20.56687 (3)0.33063 (3)0.96562 (2)0.01357 (2)
N80.69211 (3)0.45406 (3)1.12789 (2)0.01603 (2)
O810.61294 (4)0.39555 (4)1.17567 (2)0.02293 (3)
O820.78994 (5)0.53705 (5)1.16821 (3)0.02337 (3)
CL10.79800 (2)0.49908 (2)0.43095 (1)0.019172 (1)
H720.413620.313220.721220.03798
H710.417570.180400.810660.04218
H730.551600.187720.740170.03877
H60.531430.581390.696500.02815
H20.913140.321260.795230.03019
H30.955450.342800.610230.03351
H50.587010.621600.521140.03150
BR1a0.8794 (2)0.6396 (2)0.9677 (1)0.02149 (4)0.02
C91b0.85026 (3)0.58946 (3)0.96423 (2)0.01565 (2)0.98
N91b0.93843 (3)0.67627 (3)0.97429 (2)0.02309 (2)0.98
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.01156 (8)0.01168 (8)0.01126 (7)0.00042 (6)0.00400 (6)0.00102 (6)
C20.01277 (8)0.01528 (8)0.01457 (8)0.00309 (7)0.00514 (7)0.00355 (7)
C30.01396 (8)0.01666 (9)0.01579 (9)0.00325 (7)0.00696 (7)0.00237 (7)
C40.01360 (8)0.01476 (9)0.01170 (7)0.000052 (7)0.00486 (7)0.00033 (6)
C50.01437 (8)0.01541 (9)0.01191 (7)0.00279 (7)0.00379 (7)0.00237 (7)
C60.01344 (8)0.01440 (9)0.01285 (8)0.00327 (7)0.00481 (7)0.00182 (7)
C70.01406 (8)0.01263 (8)0.01146 (7)0.00184 (7)0.00412 (6)0.000049 (6)
C710.0205 (1)0.01665 (9)0.01492 (8)0.00605 (8)0.00463 (8)0.00204 (7)
C80.01324 (8)0.01553 (9)0.01023 (7)0.00103 (7)0.00342 (6)0.00029 (7)
C90.01196 (7)0.01375 (8)0.01130 (7)0.00075 (6)0.00254 (6)0.00045 (6)
N10.01267 (8)0.01243 (8)0.01040 (7)0.00153 (6)0.00392 (6)0.00013 (6)
N20.01464 (8)0.01527 (9)0.01168 (7)0.00079 (7)0.00503 (7)0.00110 (7)
N80.01629 (9)0.0212 (1)0.01029 (7)0.00325 (8)0.00300 (6)0.00014 (7)
O810.0254 (1)0.0324 (2)0.01330 (9)0.0009 (1)0.00908 (9)0.00113 (9)
O820.0237 (1)0.0305 (2)0.0138 (1)0.0027 (1)0.0014 (1)0.0048 (1)
CL10.02162 (3)0.02538 (3)0.01242 (2)0.00053 (2)0.00788 (2)0.00033 (2)
H720.03830.03800.03090.00170.00270.0019
H710.04850.04610.03600.02590.01850.0024
H730.03980.03920.04070.00280.01660.0152
H60.02480.03440.02750.01150.01080.0037
H20.02850.03600.02600.01350.00710.0093
H30.03070.04200.03280.01400.01710.0030
H50.03280.03750.02320.01180.00580.0104
BR1a0.0215 (2)0.0201 (2)0.0210 (2)0.0037 (2)0.0022 (2)0.0009 (2)
C91b0.01391 (8)0.01470 (9)0.01682 (8)0.00277 (7)0.00145 (6)0.00098 (7)
N91b0.01940 (10)0.01823 (9)0.0289 (1)0.00787 (8)0.00174 (8)0.00171 (8)
Geometric parameters (Å, º) top
C1—N11.4351 (3)C7—C711.4827 (3)
C1—C61.3907 (3)C71—H721.059
C1—C21.3921 (4)C71—H731.059
C2—C31.3944 (4)C71—H711.059
C2—H21.083C8—N81.4355 (3)
C3—C41.3930 (4)C8—N21.3508 (4)
C3—H31.083C8—C91.3786 (4)
C4—CL11.7270 (3)C9—BR1a1.944 (2)
C4—C51.3900 (4)C9—N11.3764 (3)
C5—C61.3910 (4)C9—C91b1.4069 (4)
C5—H51.083N8—O811.2240 (4)
C6—H61.083N8—O821.2244 (5)
C7—N11.3725 (3)C91b—N91b1.1588 (4)
C7—N21.3238 (3)
C1—N1—C9127.06 (2)C7—C71—H72109.2
C1—N1—C7125.64 (3)C7—C71—H73110.3
C1—C6—C5119.12 (3)C7—C71—H71107.3
C1—C6—H6119.8C71—C7—N1122.93 (2)
C1—C2—C3119.40 (3)C71—C7—N2125.61 (2)
C1—C2—H2118.8C8—N8—O81117.95 (3)
C2—C1—N1119.72 (3)C8—N8—O82117.32 (3)
C2—C1—C6121.59 (3)C8—C9—BR1a132.09 (6)
C2—C3—C4118.65 (3)C8—C9—N1104.09 (2)
C2—C3—H3122.3C8—C9—C91b132.57 (3)
C3—C4—CL1120.11 (3)C9—C8—N8126.00 (3)
C3—C4—C5121.94 (3)C9—C8—N2112.31 (3)
C3—C2—H2121.8C9—C91b—N91b178.50 (3)
C4—C5—C6119.18 (3)N1—C9—BR1a123.28 (5)
C4—C5—H5120.4N1—C9—C91b123.28 (2)
C4—C3—H3118.9N1—C7—N2111.45 (2)
C5—C4—CL1117.92 (2)N2—C8—N8121.68 (3)
C5—C6—H6121.1O81—N8—O82124.73 (4)
C6—C1—N1118.62 (2)H72—C71—H73110.4
C6—C5—H5120.4H72—C71—H71109.0
C7—N1—C9107.28 (2)H71—C71—H73110.5
C7—N2—C8104.86 (2)
C1—N1—C9—BR1a6.75 (6)C7—N2—C8—N8179.84 (2)
C1—N1—C9—C8179.21 (2)C7—N2—C8—C90.53 (2)
C1—N1—C9—C91b1.65 (2)C71—C7—N1—C9178.03 (2)
C1—N1—C7—N2178.99 (2)C71—C7—N2—C8178.56 (2)
C1—N1—C7—C710.28 (2)C8—N2—C7—N10.11 (2)
C1—C6—C5—C42.22 (2)C8—C9—C91b—N91b168.85 (3)
C1—C6—C5—H5179.0C9—N1—C7—N20.69 (2)
C1—C2—C3—C41.85 (2)C9—C8—N8—O81176.97 (3)
C1—C2—C3—H3174.1C9—C8—N8—O822.89 (3)
C2—C1—N1—C983.31 (2)N1—C9—C8—N8179.80 (2)
C2—C1—N1—C798.72 (2)N1—C9—C8—N20.93 (2)
C2—C1—C6—C50.86 (2)N1—C9—C91b—N91b7.94 (3)
C2—C1—C6—H6178.8N1—C7—C71—H7266.2
C2—C3—C4—CL1176.72 (2)N1—C7—C71—H7355.3
C2—C3—C4—C51.25 (2)N1—C7—C71—H71175.8
C3—C4—C5—C63.31 (2)N1—C1—C6—H61.7
C3—C4—C5—H5177.9N1—C1—C2—H26.2
C3—C2—C1—N1174.11 (2)N2—C7—C71—H72112.3
C3—C2—C1—C62.93 (2)N2—C7—C71—H73126.1
C4—C5—C6—H6175.6N2—C7—C71—H715.7
C4—C3—C2—H2177.8N2—C8—N8—O812.24 (3)
C5—C4—C3—H3177.3N2—C8—N8—O82177.90 (4)
C5—C6—C1—N1176.21 (2)N2—C8—C9—BR1a170.57 (6)
C6—C1—N1—C999.56 (2)N2—C8—C9—C91b176.31 (2)
C6—C1—N1—C778.42 (2)N8—C8—C9—BR1a8.70 (6)
C6—C1—C2—H2176.7N8—C8—C9—C91b2.97 (3)
C6—C5—C4—CL1174.70 (2)CL1—C4—C5—H54.1
C7—N1—C9—BR1a171.52 (7)CL1—C4—C3—H30.6
C7—N1—C9—C80.94 (2)H6—C6—C5—H53.2
C7—N1—C9—C91b176.63 (2)H2—C2—C3—H36.2
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···N91bi1.082.383.3687 (4)151
C6—H6···O81ii1.082.413.3690 (4)146
Symmetry codes: (i) x1/2, y+3/2, z1/2; (ii) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC10.98H7Br0.02ClN3.98O2
Mr263.93
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)9.3618 (2), 9.6497 (2), 12.9909 (2)
β (°) 105.428 (2)
V3)1131.29 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.41
Crystal size (mm)0.78 × 0.60 × 0.15
Data collection
DiffractometerXcalibur, Eos
diffractometer
Absorption correctionAnalytical
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, Tmax0.816, 0.952
No. of measured, independent and
observed [ > 2.0σ(I)] reflections
104943, 10032, 10015
Rint?
(sin θ/λ)max1)1.128
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.022, 1.12
No. of reflections10032
No. of parameters477
No. of restraints27
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)?, ?

Computer programs: MoPro (J. Appl. Cryst. 2005, 38, 38-54).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···N91bi1.0832.3793.3687 (4)151.2
C6—H6···O81ii1.0832.4143.3690 (4)146.3
Symmetry codes: (i) x1/2, y+3/2, z1/2; (ii) x+1, y+1, z+2.
 

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