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Crystallographic, thermal and stability analyses are presented of three different anhydrated forms of bendamustine hydro­chloride [(I), (III) and (IV)] and a fourth, monohydrated one (II). Since form (I) presents the higher melting point and the higher heat of fusion, according to the `heat of fusion' rule it should be the most stable in thermodynamic terms [Burger & Ramberger (1979). Mikrochim. Acta, 72, 259–271], though it is unstable in high-humidity conditions. The monohydrate structure (II), in turn, dehydrates by heating and topotactically transform into anhydrate (III). This latter form appears as less stable than anhydrate (I), to which it is linked via a monotropic relationship. For these three different forms, the crystal structure has been determined by single crystal X-ray diffraction. The crystal structures and molecular conformations of forms (II) and (III) are quite similar, as expected from the topotactic transformation linking them; furthermore, under high-humidity conditions, form (III) shows changes compatible with a transformation into form (II) within 24 h. The crystal structure of form (I) is different from the other two. The remaining polymorphic form (IV) could only be obtained as a powder, from which its crystalline structure could not be determined. The relative thermodynamic stability of the different crystalline forms was determined by differential scanning calorimetry and thermogravimetrical studies, and their stability under different humidity conditions analysed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520619010837/bm5115sup1.cif
Contains datablocks I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520619010837/bm5115Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520619010837/bm5115IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520619010837/bm5115IIIsup4.hkl
Contains datablock III

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520619010837/bm5115sup5.pdf
File contains Figs. S1 and S2

CCDC references: 1945029; 1945030; 1945031

Computing details top

For all structures, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS Version 2013/1 (Sheldrick, 2013); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2018); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2018/1 (Sheldrick, 2018).

y-[l-methyl-5-bis-([3-chloroethyl)-aminobenzimidazolo-(2)]-butyryl chloride (I) top
Crystal data top
C16H22Cl2N3O2·ClF(000) = 1648
Mr = 394.71Dx = 1.445 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 23.0502 (6) ÅCell parameters from 684 reflections
b = 6.7836 (2) Åθ = 3.9–20.2°
c = 25.4596 (7) ŵ = 0.52 mm1
β = 114.262 (1)°T = 150 K
V = 3629.33 (18) Å3Plate, colourless
Z = 80.42 × 0.38 × 0.12 mm
Data collection top
CCD Oxford Diffraction Xcalibur, Eos, Gemini
diffractometer
6634 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray SourceRint = 0.056
thick slices scansθmax = 36.4°, θmin = 3.1°
Absorption correction: multi-scan
CrysAlisPro (Oxford Diffraction, 2009)
h = 3837
Tmin = 0.84, Tmax = 0.96k = 1111
64102 measured reflectionsl = 4242
8857 independent reflections
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.112 w = 1/[σ2(Fo2) + (0.0488P)2 + 3.3772P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.002
8857 reflectionsΔρmax = 0.79 e Å3
224 parametersΔρmin = 0.78 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.24309 (2)1.51415 (4)0.40707 (2)0.02180 (6)
Cl20.59057 (3)0.38243 (9)0.78128 (2)0.06521 (18)
Cl30.71751 (2)0.22949 (5)0.77895 (2)0.03581 (9)
O10.37026 (5)1.41128 (15)0.41972 (5)0.0320 (2)
H1O0.3334 (8)1.426 (3)0.4177 (9)0.038*
O20.45162 (4)1.20862 (15)0.45452 (5)0.0307 (2)
N10.37307 (4)0.48988 (13)0.57752 (4)0.01502 (15)
N20.45725 (4)0.59515 (13)0.56726 (4)0.01614 (15)
H2N0.4816 (7)0.664 (2)0.5573 (7)0.019*
N30.59399 (4)0.04575 (14)0.67377 (4)0.01808 (16)
C10.39716 (5)1.24790 (17)0.44682 (5)0.01975 (19)
C20.35860 (5)1.11280 (15)0.46699 (5)0.01588 (17)
H2A0.3217421.0621010.4331760.019*
H2B0.3420621.1880950.4912190.019*
C30.39820 (5)0.93992 (16)0.50149 (5)0.01611 (17)
H3A0.4352940.9905110.5351200.019*
H3B0.4143710.8636750.4771540.019*
C40.35907 (5)0.80478 (15)0.52230 (5)0.01605 (17)
H4A0.3433100.8814290.5468650.019*
H4B0.3216240.7565600.4885750.019*
C50.39599 (4)0.63353 (15)0.55540 (4)0.01443 (16)
C60.30768 (5)0.47940 (17)0.57290 (5)0.02031 (19)
H6A0.2780890.4725970.5321910.030*
H6B0.2984300.5970490.5904500.030*
H6C0.3027580.3615420.5929520.030*
C70.42142 (4)0.35331 (15)0.60517 (4)0.01484 (16)
C80.42436 (5)0.17921 (16)0.63504 (5)0.01779 (18)
H80.3883180.1300360.6399570.021*
C90.48208 (5)0.08060 (16)0.65731 (5)0.01825 (18)
H90.4851440.0382700.6780190.022*
C100.53716 (5)0.14934 (15)0.65059 (4)0.01574 (17)
C110.59641 (6)0.15099 (16)0.69710 (5)0.02032 (19)
H11A0.6318190.2253820.6939880.024*
H11B0.5562810.2211480.6740740.024*
C120.60586 (6)0.1451 (2)0.75981 (5)0.0277 (2)
H12A0.5766060.0471470.7646540.033*
H12B0.6500530.1048070.7843940.033*
C130.64952 (5)0.11955 (18)0.66676 (5)0.0216 (2)
H13A0.6365310.1567480.6258830.026*
H13B0.6808360.0111080.6753590.026*
C140.68217 (6)0.2951 (2)0.70404 (6)0.0290 (3)
H14A0.6507090.4016670.6979020.035*
H14B0.7155440.3454660.6925150.035*
C150.53301 (5)0.32413 (16)0.62009 (5)0.01645 (17)
H150.5685440.3744350.6145300.020*
C160.47484 (5)0.42099 (15)0.59830 (4)0.01486 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.01733 (10)0.02133 (12)0.02558 (13)0.00173 (9)0.00765 (9)0.00146 (9)
Cl20.0773 (4)0.0628 (3)0.0422 (2)0.0276 (3)0.0110 (2)0.0264 (2)
Cl30.03073 (15)0.03170 (16)0.02932 (16)0.00741 (12)0.00351 (12)0.00414 (12)
O10.0213 (4)0.0284 (5)0.0517 (6)0.0081 (3)0.0204 (4)0.0229 (4)
O20.0168 (4)0.0320 (5)0.0485 (6)0.0063 (3)0.0188 (4)0.0175 (4)
N10.0116 (3)0.0146 (3)0.0184 (4)0.0007 (3)0.0057 (3)0.0026 (3)
N20.0119 (3)0.0154 (4)0.0210 (4)0.0013 (3)0.0066 (3)0.0052 (3)
N30.0153 (3)0.0153 (4)0.0212 (4)0.0032 (3)0.0051 (3)0.0048 (3)
C10.0153 (4)0.0208 (5)0.0248 (5)0.0025 (3)0.0100 (4)0.0068 (4)
C20.0127 (4)0.0160 (4)0.0203 (4)0.0020 (3)0.0082 (3)0.0046 (3)
C30.0126 (4)0.0171 (4)0.0189 (4)0.0031 (3)0.0067 (3)0.0044 (3)
C40.0123 (4)0.0147 (4)0.0204 (4)0.0022 (3)0.0060 (3)0.0042 (3)
C50.0117 (3)0.0148 (4)0.0164 (4)0.0005 (3)0.0053 (3)0.0016 (3)
C60.0122 (4)0.0203 (5)0.0296 (5)0.0006 (3)0.0096 (4)0.0041 (4)
C70.0115 (3)0.0152 (4)0.0167 (4)0.0009 (3)0.0046 (3)0.0023 (3)
C80.0145 (4)0.0176 (4)0.0206 (4)0.0008 (3)0.0065 (3)0.0047 (3)
C90.0158 (4)0.0168 (4)0.0199 (4)0.0001 (3)0.0051 (3)0.0051 (3)
C100.0133 (4)0.0157 (4)0.0157 (4)0.0012 (3)0.0034 (3)0.0017 (3)
C110.0230 (5)0.0157 (4)0.0210 (5)0.0049 (4)0.0078 (4)0.0039 (4)
C120.0254 (5)0.0339 (6)0.0207 (5)0.0013 (5)0.0064 (4)0.0074 (5)
C130.0167 (4)0.0233 (5)0.0243 (5)0.0057 (4)0.0079 (4)0.0051 (4)
C140.0214 (5)0.0266 (6)0.0304 (6)0.0039 (4)0.0021 (4)0.0088 (5)
C150.0124 (4)0.0168 (4)0.0193 (4)0.0019 (3)0.0056 (3)0.0046 (3)
C160.0125 (4)0.0147 (4)0.0168 (4)0.0006 (3)0.0053 (3)0.0030 (3)
Geometric parameters (Å, º) top
Cl2—C121.7814 (15)C4—H4B0.9900
Cl3—C141.7951 (14)C6—H6A0.9800
O1—C11.3181 (14)C6—H6B0.9800
O1—H1O0.837 (15)C6—H6C0.9800
O2—C11.2177 (13)C7—C161.3910 (14)
N1—C51.3380 (13)C7—C81.3912 (14)
N1—C71.3969 (13)C8—C91.3853 (15)
N1—C61.4645 (13)C8—H80.9500
N2—C51.3426 (13)C9—C101.4273 (15)
N2—C161.3861 (13)C9—H90.9500
N2—H2N0.847 (13)C10—C151.3989 (15)
N3—C101.3868 (13)C11—C121.5206 (17)
N3—C131.4522 (15)C11—H11A0.9900
N3—C111.4525 (14)C11—H11B0.9900
C1—C21.5061 (15)C12—H12A0.9900
C2—C31.5236 (14)C12—H12B0.9900
C2—H2A0.9900C13—C141.5159 (19)
C2—H2B0.9900C13—H13A0.9900
C3—C41.5256 (14)C13—H13B0.9900
C3—H3A0.9900C14—H14A0.9900
C3—H3B0.9900C14—H14B0.9900
C4—C51.4815 (14)C15—C161.3879 (14)
C4—H4A0.9900C15—H150.9500
C1—O1—H1O112.4 (15)C16—C7—N1106.37 (9)
C5—N1—C7108.89 (8)C8—C7—N1133.48 (9)
C5—N1—C6124.95 (9)C9—C8—C7117.16 (9)
C7—N1—C6126.15 (9)C9—C8—H8121.4
C5—N2—C16109.13 (8)C7—C8—H8121.4
C5—N2—H2N126.2 (11)C8—C9—C10123.03 (10)
C16—N2—H2N124.7 (11)C8—C9—H9118.5
C10—N3—C13119.95 (9)C10—C9—H9118.5
C10—N3—C11120.70 (9)N3—C10—C15120.19 (9)
C13—N3—C11118.64 (9)N3—C10—C9120.97 (9)
O2—C1—O1120.02 (10)C15—C10—C9118.84 (9)
O2—C1—C2121.71 (10)N3—C11—C12111.72 (10)
O1—C1—C2118.26 (9)N3—C11—H11A109.3
C1—C2—C3111.55 (8)C12—C11—H11A109.3
C1—C2—H2A109.3N3—C11—H11B109.3
C3—C2—H2A109.3C12—C11—H11B109.3
C1—C2—H2B109.3H11A—C11—H11B107.9
C3—C2—H2B109.3C11—C12—Cl2109.72 (10)
H2A—C2—H2B108.0C11—C12—H12A109.7
C2—C3—C4111.29 (8)Cl2—C12—H12A109.7
C2—C3—H3A109.4C11—C12—H12B109.7
C4—C3—H3A109.4Cl2—C12—H12B109.7
C2—C3—H3B109.4H12A—C12—H12B108.2
C4—C3—H3B109.4N3—C13—C14115.44 (11)
H3A—C3—H3B108.0N3—C13—H13A108.4
C5—C4—C3112.66 (8)C14—C13—H13A108.4
C5—C4—H4A109.1N3—C13—H13B108.4
C3—C4—H4A109.1C14—C13—H13B108.4
C5—C4—H4B109.1H13A—C13—H13B107.5
C3—C4—H4B109.1C13—C14—Cl3111.25 (9)
H4A—C4—H4B107.8C13—C14—H14A109.4
N1—C5—N2108.96 (9)Cl3—C14—H14A109.4
N1—C5—C4125.21 (9)C13—C14—H14B109.4
N2—C5—C4125.82 (9)Cl3—C14—H14B109.4
N1—C6—H6A109.5H14A—C14—H14B108.0
N1—C6—H6B109.5C16—C15—C10117.23 (9)
H6A—C6—H6B109.5C16—C15—H15121.4
N1—C6—H6C109.5C10—C15—H15121.4
H6A—C6—H6C109.5N2—C16—C15129.77 (9)
H6B—C6—H6C109.5N2—C16—C7106.64 (8)
C16—C7—C8120.15 (9)C15—C16—C7123.59 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O2i0.85 (1)1.89 (1)2.7293 (13)169 (2)
C15—H15···O1i0.952.423.3283 (14)159
O1—H1O···Cl10.84 (2)2.07 (2)2.8994 (10)170 (2)
C4—H4B···Cl1ii0.992.683.6325 (11)161
C4—H4A···Cl1iii0.992.793.7105 (11)156
C6—H6A···Cl1ii0.982.963.8640 (13)154
C6—H6B···Cl1iii0.982.823.7314 (12)156
C6—H6C···Cl1iv0.982.763.6510 (12)152
C8—H8···Cl1iv0.952.933.7904 (11)151
C13—H13B···Cl3v0.992.873.8502 (12)169
C14—H14B···Cl3vi0.992.963.6600 (13)128
C12—H12B···Cl30.992.793.5053 (14)130
Symmetry codes: (i) x+1, y+2, z+1; (ii) x, y1, z; (iii) x+1/2, y+5/2, z+1; (iv) x+1/2, y+3/2, z+1; (v) x+3/2, y1/2, z+3/2; (vi) x+3/2, y+1/2, z+3/2.
y-[l-methyl-5-bis-([3-chloroethyl)-aminobenzimidazolo-(2)]-butyryl chloride, hydrate (II) top
Crystal data top
C16H22Cl2N3O2·Cl·H2OF(000) = 864
Mr = 412.73Dx = 1.411 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 4.6490 (6) ÅCell parameters from 453 reflections
b = 47.213 (5) Åθ = 1.3–28.3°
c = 8.9051 (10) ŵ = 0.49 mm1
β = 96.222 (7)°T = 100 K
V = 1943.1 (4) Å3Needle, colourless
Z = 40.24 × 0.06 × 0.04 mm
Data collection top
CCD Oxford Diffraction Xcalibur, Eos, Gemini
diffractometer
2180 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray SourceRint = 0.188
thick slices scansθmax = 25.3°, θmin = 2.3°
Absorption correction: multi-scan
CrysAlisPro (Oxford Diffraction, 2009)
h = 55
Tmin = 0.92, Tmax = 0.96k = 5656
19169 measured reflectionsl = 108
3545 independent reflections
Refinement top
Refinement on F25 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.081H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.157 w = 1/[σ2(Fo2) + (0.0253P)2 + 8.2062P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
3545 reflectionsΔρmax = 0.40 e Å3
239 parametersΔρmin = 0.51 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.5030 (3)0.10517 (3)0.06192 (16)0.0179 (4)
Cl21.9159 (3)0.24305 (3)0.55536 (19)0.0262 (4)
Cl31.3510 (4)0.19906 (3)0.18388 (17)0.0277 (4)
O10.7927 (10)0.01123 (8)0.1394 (5)0.0242 (10)
H1O0.854 (13)0.0271 (7)0.113 (7)0.029*
O20.5765 (10)0.03454 (9)0.3136 (5)0.0326 (12)
N10.9362 (10)0.09702 (9)0.4886 (5)0.0115 (11)
N20.8392 (10)0.10743 (10)0.2498 (5)0.0129 (10)
H2N0.743 (11)0.1059 (12)0.164 (3)0.015*
N31.5490 (10)0.18500 (9)0.2608 (5)0.0129 (11)
C10.6199 (13)0.01289 (12)0.2501 (7)0.0177 (14)
C20.4849 (12)0.01485 (11)0.2816 (7)0.0160 (14)
H2A0.3775540.0128080.3711750.019*
H2B0.3437760.0200020.1946160.019*
C30.7064 (12)0.03883 (11)0.3104 (7)0.0150 (13)
H3A0.8156270.0408820.2215810.018*
H3B0.8457720.0339900.3987290.018*
C40.5581 (12)0.06693 (11)0.3399 (6)0.0118 (13)
H4A0.4120790.0712880.2536770.014*
H4B0.4564370.0651190.4315310.014*
C50.7700 (12)0.09051 (11)0.3608 (6)0.0113 (12)
C60.9282 (13)0.08437 (12)0.6379 (6)0.0170 (13)
H6A0.7883220.0687730.6311750.026*
H6B0.8704680.0987420.7081580.026*
H6C1.1206170.0771080.6745030.026*
C71.1186 (12)0.11960 (11)0.4585 (6)0.0125 (13)
C81.3258 (12)0.13446 (11)0.5476 (6)0.0139 (13)
H81.3697200.1302450.6518730.017*
C91.4674 (12)0.15575 (11)0.4793 (6)0.0139 (13)
H91.6132590.1661630.5386320.017*
C101.4046 (12)0.16279 (11)0.3243 (6)0.0117 (13)
C111.7706 (12)0.20164 (12)0.3520 (6)0.0125 (13)
H11A1.8982900.2108700.2845490.015*
H11B1.8910340.1888210.4207360.015*
C121.6363 (13)0.22410 (12)0.4444 (7)0.0163 (13)
H12A1.5062700.2150600.5112430.020*
H12B1.5201460.2373560.3762650.020*
C131.4267 (12)0.19760 (12)0.1183 (6)0.0136 (13)
H13A1.4671660.2181950.1205010.016*
H13B1.2140930.1950590.1072000.016*
C141.5489 (13)0.18457 (13)0.0170 (6)0.0185 (14)
H14A1.5271920.1637160.0155860.022*
H14B1.7571870.1891370.0148190.022*
C151.1949 (12)0.14708 (11)0.2346 (6)0.0129 (13)
H151.1509220.1509120.1299330.015*
C161.0558 (12)0.12594 (11)0.3043 (6)0.0110 (12)
O1W0.9736 (9)0.05941 (8)0.0273 (5)0.0204 (10)
H1WA0.809 (9)0.0764 (12)0.030 (7)0.031*
H1WB1.128 (7)0.0675 (11)0.065 (7)0.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0179 (8)0.0213 (8)0.0141 (8)0.0004 (7)0.0000 (6)0.0022 (7)
Cl20.0189 (8)0.0228 (8)0.0360 (10)0.0013 (7)0.0007 (7)0.0152 (8)
Cl30.0409 (10)0.0299 (9)0.0122 (8)0.0010 (8)0.0027 (7)0.0029 (7)
O10.031 (3)0.014 (2)0.031 (3)0.004 (2)0.016 (2)0.003 (2)
O20.046 (3)0.014 (2)0.043 (3)0.003 (2)0.027 (2)0.008 (2)
N10.015 (3)0.010 (2)0.010 (2)0.006 (2)0.004 (2)0.004 (2)
N20.011 (3)0.015 (3)0.012 (3)0.000 (2)0.001 (2)0.002 (2)
N30.013 (3)0.011 (2)0.015 (3)0.003 (2)0.003 (2)0.001 (2)
C10.014 (3)0.017 (3)0.022 (3)0.001 (3)0.002 (3)0.000 (3)
C20.013 (3)0.011 (3)0.024 (4)0.001 (3)0.003 (3)0.002 (3)
C30.016 (3)0.011 (3)0.020 (3)0.000 (3)0.008 (3)0.001 (3)
C40.014 (3)0.007 (3)0.015 (3)0.001 (2)0.005 (3)0.000 (2)
C50.011 (3)0.014 (3)0.010 (3)0.002 (2)0.003 (2)0.002 (3)
C60.020 (3)0.020 (3)0.012 (3)0.004 (3)0.006 (3)0.006 (3)
C70.013 (3)0.007 (3)0.018 (3)0.000 (2)0.005 (3)0.004 (3)
C80.015 (3)0.014 (3)0.013 (3)0.004 (3)0.002 (3)0.001 (3)
C90.014 (3)0.011 (3)0.017 (3)0.004 (3)0.004 (3)0.004 (3)
C100.010 (3)0.008 (3)0.018 (3)0.004 (2)0.008 (3)0.001 (3)
C110.008 (3)0.016 (3)0.012 (3)0.004 (3)0.003 (2)0.003 (3)
C120.016 (3)0.013 (3)0.019 (3)0.002 (3)0.001 (3)0.003 (3)
C130.016 (3)0.010 (3)0.014 (3)0.001 (3)0.002 (2)0.004 (3)
C140.022 (3)0.022 (3)0.011 (3)0.002 (3)0.002 (3)0.002 (3)
C150.017 (3)0.011 (3)0.012 (3)0.002 (3)0.005 (3)0.002 (3)
C160.018 (3)0.004 (3)0.011 (3)0.002 (2)0.001 (3)0.003 (2)
O1W0.025 (3)0.017 (2)0.020 (2)0.004 (2)0.009 (2)0.0032 (19)
Geometric parameters (Å, º) top
Cl2—C121.786 (6)C6—H6A0.9800
Cl3—C141.796 (6)C6—H6B0.9800
O1—C11.340 (7)C6—H6C0.9800
O1—H1O0.84 (2)C7—C81.372 (8)
O2—C11.196 (7)C7—C161.405 (8)
N1—C51.340 (7)C8—C91.379 (8)
N1—C71.406 (7)C8—H80.9500
N1—C61.462 (7)C9—C101.420 (8)
N2—C51.337 (7)C9—H90.9500
N2—C161.381 (7)C10—C151.403 (8)
N2—H2N0.85 (2)C11—C121.518 (8)
N3—C101.397 (7)C11—H11A0.9900
N3—C131.460 (7)C11—H11B0.9900
N3—C111.469 (7)C12—H12A0.9900
C1—C21.492 (8)C12—H12B0.9900
C2—C31.533 (7)C13—C141.517 (8)
C2—H2A0.9900C13—H13A0.9900
C2—H2B0.9900C13—H13B0.9900
C3—C41.531 (7)C14—H14A0.9900
C3—H3A0.9900C14—H14B0.9900
C3—H3B0.9900C15—C161.373 (7)
C4—C51.485 (7)C15—H150.9500
C4—H4A0.9900O1W—H1WA1.11 (5)
C4—H4B0.9900O1W—H1WB0.851 (14)
C1—O1—H1O113 (4)C16—C7—N1106.4 (5)
C5—N1—C7108.4 (4)C7—C8—C9117.2 (5)
C5—N1—C6127.6 (5)C7—C8—H8121.4
C7—N1—C6123.9 (5)C9—C8—H8121.4
C5—N2—C16110.1 (5)C8—C9—C10122.8 (5)
C5—N2—H2N118 (4)C8—C9—H9118.6
C16—N2—H2N132 (4)C10—C9—H9118.6
C10—N3—C13119.9 (5)N3—C10—C15120.1 (5)
C10—N3—C11121.1 (5)N3—C10—C9120.8 (5)
C13—N3—C11116.5 (4)C15—C10—C9119.1 (5)
O2—C1—O1122.9 (5)N3—C11—C12111.6 (4)
O2—C1—C2124.4 (5)N3—C11—H11A109.3
O1—C1—C2112.7 (5)C12—C11—H11A109.3
C1—C2—C3113.0 (5)N3—C11—H11B109.3
C1—C2—H2A109.0C12—C11—H11B109.3
C3—C2—H2A109.0H11A—C11—H11B108.0
C1—C2—H2B109.0C11—C12—Cl2109.4 (4)
C3—C2—H2B109.0C11—C12—H12A109.8
H2A—C2—H2B107.8Cl2—C12—H12A109.8
C2—C3—C4111.2 (4)C11—C12—H12B109.8
C2—C3—H3A109.4Cl2—C12—H12B109.8
C4—C3—H3A109.4H12A—C12—H12B108.2
C2—C3—H3B109.4N3—C13—C14112.4 (4)
C4—C3—H3B109.4N3—C13—H13A109.1
H3A—C3—H3B108.0C14—C13—H13A109.1
C5—C4—C3111.5 (4)N3—C13—H13B109.1
C5—C4—H4A109.3C14—C13—H13B109.1
C3—C4—H4A109.3H13A—C13—H13B107.9
C5—C4—H4B109.3C13—C14—Cl3107.5 (4)
C3—C4—H4B109.3C13—C14—H14A110.2
H4A—C4—H4B108.0Cl3—C14—H14A110.2
N2—C5—N1109.2 (5)C13—C14—H14B110.2
N2—C5—C4124.4 (5)Cl3—C14—H14B110.2
N1—C5—C4126.3 (5)H14A—C14—H14B108.5
N1—C6—H6A109.5C16—C15—C10117.3 (5)
N1—C6—H6B109.5C16—C15—H15121.3
H6A—C6—H6B109.5C10—C15—H15121.3
N1—C6—H6C109.5C15—C16—N2131.5 (5)
H6A—C6—H6C109.5C15—C16—C7122.6 (5)
H6B—C6—H6C109.5N2—C16—C7105.9 (5)
C8—C7—C16120.9 (5)H1WA—O1W—H1WB103 (4)
C8—C7—N1132.7 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O1W0.84 (2)1.82 (2)2.657 (6)171 (6)
N2—H2N···Cl1i0.85 (2)2.20 (2)3.048 (5)176 (6)
C6—H6A···O2ii0.982.433.383 (7)164
C6—H6C···O2iii0.982.453.287 (7)143
C8—H8···Cl1iii0.952.813.747 (6)167
C12—H12A···Cl3iv0.992.983.882 (6)152
C13—H13A···Cl2v0.992.883.690 (6)139
C14—H14A···Cl1vi0.992.803.775 (6)170
O1W—H1WA···Cl11.11 (5)2.01 (5)3.114 (4)172 (5)
O1W—H1WB···Cl1vii0.85 (1)2.49 (3)3.264 (4)151 (5)
C6—H6B···Cl1ii0.982.843.646 (6)140
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z+1; (iii) x+2, y, z+1; (iv) x, y, z+1; (v) x, y+1/2, z1/2; (vi) x+2, y, z; (vii) x+1, y, z.
y-[l-methyl-5-bis-([3-chloroethyl)-aminobenzimidazolo-(2)]-butyryl chloride (III) top
Crystal data top
C16H22Cl2N3O2·ClF(000) = 824
Mr = 394.71Dx = 1.394 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 4.722 (4) ÅCell parameters from 1149 reflections
b = 45.671 (19) Åθ = 0.4–29.6°
c = 8.798 (7) ŵ = 0.50 mm1
β = 97.66 (6)°T = 150 K
V = 1880 (2) Å3Needle, colourless
Z = 40.48 × 0.18 × 0.14 mm
Data collection top
CCD Oxford Diffraction Xcalibur, Eos, Gemini
diffractometer
2612 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray SourceRint = 0.131
thick slices scansθmax = 25.3°, θmin = 2.3°
Absorption correction: multi-scan
CrysAlisPro (Oxford Diffraction, 2009)
h = 55
Tmin = 0.84, Tmax = 0.94k = 5452
34373 measured reflectionsl = 1010
3384 independent reflections
Refinement top
Refinement on F223 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.171H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.379 w = 1/[σ2(Fo2) + 62.7847P]
where P = (Fo2 + 2Fc2)/3
S = 1.24(Δ/σ)max < 0.001
3384 reflectionsΔρmax = 0.71 e Å3
225 parametersΔρmin = 0.81 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.6398 (8)0.09912 (7)0.0915 (4)0.0308 (8)
Cl21.8395 (8)0.24367 (8)0.5208 (5)0.0423 (10)
Cl31.2721 (10)0.19744 (9)0.2208 (4)0.0444 (11)
O10.443 (2)0.0363 (2)0.1203 (12)0.040 (3)
H1O0.56 (3)0.051 (2)0.137 (19)0.048*
O20.704 (2)0.0298 (2)0.3491 (13)0.042 (3)
N10.828 (2)0.0941 (2)0.4566 (11)0.019 (2)
N20.753 (2)0.1031 (2)0.2087 (13)0.025 (2)
H2N0.64 (2)0.104 (3)0.126 (9)0.030*
N31.466 (2)0.1824 (2)0.2279 (11)0.024 (2)
C10.526 (3)0.0213 (3)0.2469 (16)0.033 (3)
C20.389 (3)0.0089 (3)0.2477 (18)0.033 (3)
H2A0.2804250.0127660.1454200.039*
H2B0.2519650.0090720.3236680.039*
C30.607 (3)0.0327 (3)0.2862 (18)0.030 (3)
H3A0.7317850.0339420.2045760.036*
H3B0.7277240.0279430.3836860.036*
C40.460 (2)0.0627 (3)0.3017 (15)0.020 (2)
H4A0.3239270.0665250.2082210.023*
H4B0.3507790.0620930.3901720.023*
C50.673 (3)0.0868 (3)0.3240 (15)0.026 (3)
C60.803 (3)0.0822 (3)0.6097 (17)0.034 (3)
H6A0.6335000.0696370.6039330.052*
H6B0.7836640.0984270.6807840.052*
H6C0.9735800.0707950.6463410.052*
C71.010 (3)0.1167 (3)0.4292 (14)0.024 (3)
C81.224 (2)0.1322 (3)0.5223 (13)0.015 (2)
H81.2678680.1282580.6288120.018*
C91.365 (3)0.1531 (3)0.4525 (13)0.023 (3)
H91.5055770.1642630.5150370.027*
C101.319 (2)0.1598 (3)0.2924 (13)0.017 (3)
C111.685 (3)0.1998 (3)0.3224 (13)0.022 (3)
H11A1.8117420.2089650.2550230.026*
H11B1.8030680.1866330.3944540.026*
C121.556 (3)0.2237 (3)0.4138 (18)0.031 (3)
H12A1.4336470.2148070.4840760.037*
H12B1.4373660.2370490.3430790.037*
C131.344 (3)0.1951 (3)0.0873 (14)0.025 (3)
H13A1.3842190.2163620.0902010.031*
H13B1.1338190.1925260.0758140.031*
C141.455 (3)0.1820 (3)0.0486 (13)0.026 (3)
H14A1.4268050.1605040.0490730.031*
H14B1.6628390.1858870.0426610.031*
C151.114 (3)0.1434 (3)0.1979 (13)0.020 (3)
H151.0785670.1464690.0902710.025*
C160.963 (3)0.1224 (3)0.2713 (13)0.018 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0373 (19)0.0329 (18)0.0206 (16)0.0008 (15)0.0019 (14)0.0079 (14)
Cl20.034 (2)0.035 (2)0.055 (3)0.0003 (16)0.0045 (18)0.0187 (18)
Cl30.067 (3)0.043 (2)0.0217 (18)0.001 (2)0.0004 (18)0.0010 (16)
O10.057 (7)0.028 (6)0.032 (6)0.008 (5)0.004 (5)0.008 (4)
O20.057 (7)0.023 (5)0.044 (7)0.003 (5)0.006 (6)0.011 (5)
N10.023 (6)0.021 (5)0.012 (5)0.002 (4)0.007 (4)0.004 (4)
N20.016 (6)0.025 (6)0.035 (7)0.010 (5)0.007 (5)0.004 (5)
N30.038 (7)0.028 (6)0.010 (5)0.006 (5)0.011 (5)0.001 (4)
C10.050 (8)0.034 (5)0.015 (7)0.003 (5)0.004 (6)0.002 (5)
C20.026 (5)0.030 (4)0.040 (8)0.006 (4)0.001 (5)0.006 (5)
C30.015 (5)0.024 (4)0.049 (9)0.003 (4)0.003 (5)0.008 (4)
C40.013 (5)0.023 (4)0.023 (7)0.001 (4)0.004 (4)0.005 (4)
C50.025 (6)0.029 (5)0.024 (7)0.007 (5)0.002 (5)0.007 (5)
C60.035 (8)0.034 (8)0.037 (9)0.004 (6)0.014 (7)0.007 (6)
C70.036 (8)0.027 (7)0.010 (6)0.004 (6)0.001 (6)0.010 (5)
C80.011 (6)0.025 (6)0.009 (6)0.002 (5)0.002 (5)0.002 (5)
C90.031 (7)0.028 (7)0.008 (6)0.003 (6)0.005 (5)0.005 (5)
C100.014 (6)0.025 (7)0.011 (6)0.003 (5)0.004 (5)0.001 (5)
C110.025 (7)0.034 (7)0.007 (6)0.008 (6)0.005 (5)0.002 (5)
C120.021 (7)0.023 (7)0.049 (9)0.004 (6)0.012 (6)0.003 (6)
C130.034 (8)0.027 (7)0.017 (6)0.001 (6)0.010 (6)0.002 (5)
C140.034 (8)0.038 (8)0.009 (6)0.006 (6)0.012 (6)0.000 (5)
C150.022 (7)0.029 (7)0.008 (6)0.003 (5)0.006 (5)0.004 (5)
C160.024 (7)0.024 (7)0.007 (6)0.001 (5)0.003 (5)0.004 (5)
Geometric parameters (Å, º) top
Cl2—C121.780 (15)C4—H4B0.9900
Cl3—C141.787 (13)C6—H6A0.9800
O1—C11.324 (17)C6—H6B0.9800
O1—H1O0.85 (2)C6—H6C0.9800
O2—C11.210 (18)C7—C161.402 (17)
N1—C51.334 (16)C7—C81.406 (17)
N1—C71.384 (16)C8—C91.359 (17)
N1—C61.470 (17)C8—H80.9500
N2—C51.352 (17)C9—C101.428 (17)
N2—C161.385 (16)C9—H90.9500
N2—H2N0.85 (2)C10—C151.405 (17)
N3—C101.403 (16)C11—C121.529 (17)
N3—C131.418 (17)C11—H11A0.9900
N3—C111.472 (17)C11—H11B0.9900
C1—C21.52 (2)C12—H12A0.9900
C2—C31.507 (18)C12—H12B0.9900
C2—H2A0.9900C13—C141.495 (16)
C2—H2B0.9900C13—H13A0.9900
C3—C41.547 (17)C13—H13B0.9900
C3—H3A0.9900C14—H14A0.9900
C3—H3B0.9900C14—H14B0.9900
C4—C51.486 (17)C15—C161.403 (17)
C4—H4A0.9900C15—H150.9500
C1—O1—H1O99 (10)N1—C7—C8133.7 (11)
C5—N1—C7108.3 (10)C16—C7—C8119.2 (12)
C5—N1—C6127.5 (11)C9—C8—C7116.8 (11)
C7—N1—C6124.1 (11)C9—C8—H8121.6
C5—N2—C16108.0 (11)C7—C8—H8121.6
C5—N2—H2N117 (10)C8—C9—C10125.1 (12)
C16—N2—H2N131 (10)C8—C9—H9117.4
C10—N3—C13119.3 (11)C10—C9—H9117.4
C10—N3—C11121.1 (10)C15—C10—N3119.4 (11)
C13—N3—C11116.4 (10)C15—C10—C9118.2 (11)
O2—C1—O1123.9 (13)N3—C10—C9122.4 (11)
O2—C1—C2122.8 (13)N3—C11—C12112.6 (11)
O1—C1—C2113.2 (13)N3—C11—H11A109.1
C3—C2—C1112.2 (12)C12—C11—H11A109.1
C3—C2—H2A109.2N3—C11—H11B109.1
C1—C2—H2A109.2C12—C11—H11B109.1
C3—C2—H2B109.2H11A—C11—H11B107.8
C1—C2—H2B109.2C11—C12—Cl2108.7 (9)
H2A—C2—H2B107.9C11—C12—H12A109.9
C2—C3—C4111.1 (11)Cl2—C12—H12A109.9
C2—C3—H3A109.4C11—C12—H12B109.9
C4—C3—H3A109.4Cl2—C12—H12B109.9
C2—C3—H3B109.4H12A—C12—H12B108.3
C4—C3—H3B109.4N3—C13—C14112.8 (11)
H3A—C3—H3B108.0N3—C13—H13A109.0
C5—C4—C3111.4 (10)C14—C13—H13A109.0
C5—C4—H4A109.4N3—C13—H13B109.0
C3—C4—H4A109.4C14—C13—H13B109.0
C5—C4—H4B109.4H13A—C13—H13B107.8
C3—C4—H4B109.4C13—C14—Cl3109.7 (9)
H4A—C4—H4B108.0C13—C14—H14A109.7
N1—C5—N2110.1 (11)Cl3—C14—H14A109.7
N1—C5—C4125.6 (12)C13—C14—H14B109.7
N2—C5—C4124.2 (11)Cl3—C14—H14B109.7
N1—C6—H6A109.5H14A—C14—H14B108.2
N1—C6—H6B109.5C10—C15—C16116.4 (11)
H6A—C6—H6B109.5C10—C15—H15121.8
N1—C6—H6C109.5C16—C15—H15121.8
H6A—C6—H6C109.5N2—C16—C15129.2 (11)
H6B—C6—H6C109.5N2—C16—C7106.5 (11)
N1—C7—C16107.0 (10)C15—C16—C7124.2 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···Cl10.85 (2)2.29 (9)3.036 (10)147 (15)
N2—H2N···Cl1i0.85 (2)2.18 (3)3.024 (12)171 (14)
C6—H6A···O2ii0.982.493.438 (18)163
C6—H6C···O2iii0.982.413.329 (18)156
C8—H8···Cl1iii0.952.783.696 (12)162
C12—H12A···Cl3iv0.992.913.838 (16)156
C13—H13A···Cl2v0.992.953.743 (14)138
C14—H14A···Cl1vi0.992.843.824 (15)172
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z+1; (iii) x+2, y, z+1; (iv) x, y, z+1; (v) x, y+1/2, z1/2; (vi) x+2, y, z.
 

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