organic compounds
N-Benzyl-N-[2-(N-benzyl-N′,N′,N′′,N′′-tetramethylguanidiniumyl)ethyl]-N′,N′,N′′,N′′-tetramethylguanidinium dibromide 1.5-hydrate
aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: willi.kantlehner@hs-aalen.de
The 26H42N62+·2Br−·1.5H2O, comprises one cation, two bromide anions and one and a half water molecules, as one water molecule is fully occupied and the other is only half occupied [0.500 (6)]. Both bromide ions are disordered over two sites with refined occupancies of 0.938 (3):0.062 (3) and 0.520 (9):0.480 (9). The C—N bond lengths in both central C3N units of the bisguanidinium ion range between 1.336 (3) and 1.349 (3) Å, indicating a degree of double-bond character. The central C atoms are bonded to the three N atoms in a nearly ideal trigonal–planar geometry and the positive charges are delocalized in both CN3 planes. The is stabilized by a three-dimensional network of O—H⋯O, O—H⋯Br and C—H⋯Br hydrogen bonds.
of the hydrated title compound, CKeywords: crystal structure; bisguanidinium salt; bromide; hydrate; hydrogen bonds.
CCDC reference: 1446278
Structure description
By reaction of two equivalents of N,N,N′,N′-tetramethylchloroformamidinium chloride (Tiritiris & Kantlehner, 2008a) with 1,2-diaminoethane, a bisguanidinium dichloride (Wittmann et al., 2000) has been obtained which, after treating with an aqueous sodium hydroxide solution, yields N,N,N′,N′-tetramethyl-N′′-[2-(N′,N′,N′′,N′′-tetramethylguanidino)ethyl]guanidine (Tiritiris & Kantlehner, 2012). By alkylation of the free nitrogen atoms, various bisguanidinium salts can be prepared. The hydrated title salt presented here is the first alkylated bisguanidinium derivative in our series to have been structurally characterized. The of the structure contains one cation, two bromide anions and one and a half water molecules (Fig. 1). Prominent bond parameters in the bisguanidinium cation are: C1—N1 = 1.336 (3), C1—N2 = 1.336 (3), C1—N3 = 1.349 (3) Å and C15—N4 = 1.349 (3), C15—N5 = 1.339 (3), C15—N6 = 1.339 (3) Å, indicating partial double-bond character for all. The N—C1—N and N—C15—N angles range from 119.4 (2)° to 120.4 (2)°, indicating that the carbon centres C1 and C15 adopt nearly ideal trigonal–planar environments. The positive charges of the dication are completely delocalized in both CN3 planes. The analysis reveals that the C—N and C—C bond lengths in the dication are in very good agreement with the values obtained for the diprotonated salt 1,2-bis-[2N′-(1,1,3,3-tetramethylguanidinium)]ethane dichloride tetrahydrate (Wittmann et al., 2000). The of the related N,N,N′,N′-tetramethyl-N′′-[2-(N′,N′,N′′,N′′- tetramethylguanidino)ethyl]guanidine, has also been reported (Tiritiris & Kantlehner, 2012).
The . O—H⋯O hydrogen bonds between the water molecules and O—H⋯Br hydrogen bonds between water molecules and bromide ions are observed, Fig. 2. In addition, C—H⋯Br hydrogen bonds form between the –N(CH3)2, –CH2 and aromatic –CH groups of the cation and the bromide ions, forming a three-dimensional network, Fig. 3.
is stabilized by a network of O—H⋯O, O—H⋯Br and C—H⋯Br hydrogen bonds, Table 1Synthesis and crystallization
The title compound was obtained by reaction of N,N,N′,N′-tetramethyl-N′′-[2-(N′,N′,N′′,N′′-tetramethylguanidino)ethyl]guanidine (Tiritiris & Kantlehner, 2012) with two equivalents of benzyl bromide in acetonitrile at room temperature in nearly quantitative yield. After evaporation of the solvent, the crude product was recrystallized from a saturated acetonitrile-water solution. After several days at 273 K, colorless single crystals suitable for X-ray analysis were obtained.
Refinement
Crystal data, data collection and structure . Atoms Br1 and Br2 are each disordered over two sites (Br1A and Br1B; Br2A and Br2B) with refined occupancy ratios of 0.938 (3):0.062 (3) and 0.520 (9):0.480 (9), respectively. The atoms Br1A and Br1B were restrained to have similar anisotropic displacement parameters. The position of O2 is only half occupied, the site occupancy factor was refined and converged to 0.500 (6). The occupancy factors of H29 and H30 were fixed to 0.5 and their Uiso(H) set at 0.050 Å2.
details are summarized in Table 2
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Structural data
CCDC reference: 1446278
10.1107/S241431461600047X/sj4008sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S241431461600047X/sj4008Isup2.hkl
The title compound was obtained by reaction of N,N,N',N'-tetramethyl- N''-[2-(N',N',N'',N''- tetramethylguanidino)ethyl]guanidine (Tiritiris & Kantlehner, 2012) with two equivalents of benzyl bromide in acetonitrile at room temperature in nearly quantitative yield. After evaporation of the solvent, the crude product was recrystallized from a saturated acetonitrile-water solution. After several days at 273 K, colorless single crystals suitable for X-ray analysis were obtained.
Crystal data, data collection and structure
details are summarized in Table 1 The O-bound H atoms of the water molecules were located in a difference Fourier map and their bond lengths were restrained to 0.90 (1) Å using the DFIX command. The atoms Br1 and Br2 are disordered over two sets of sites (Br1A and Br1B; Br2A and Br2B) with refined occupancies of 0.938 (3):0.062 (3) and 0.520 (9):0.480 (9) respectively. The atoms Br1A and Br1B were restrained to have similar anisotropic displacement parameters. The position of O2 is only half occupied, the site occupancy factor was refined and converged to 0.500 (6). The occupancy factors of H29 and H30 were fixed to 0.5 and their Uiso(H) set at to 0.050 Å2.The title compound was obtained by reaction of N,N,N',N'-tetramethyl- N''-[2-(N',N',N'',N''- tetramethylguanidino)ethyl]guanidine (Tiritiris & Kantlehner, 2012) with two equivalents of benzyl bromide in acetonitrile at room temperature in nearly quantitative yield. After evaporation of the solvent, the crude product was recrystallized from a saturated acetonitrile-water solution. After several days at 273 K, colorless single crystals suitable for X-ray analysis were obtained.
Crystal data, data collection and structure
details are summarized in Table 2. Atoms Br1 and Br2 are each disordered over two sites (Br1A and Br1B; Br2A and Br2B) with refined occupancy ratios of 0.938 (3):0.062 (3) and 0.520 (9):0.480 (9), respectively. The atoms Br1A and Br1B were restrained to have similar anisotropic displacement parameters. The position of O2 is only half occupied, the site occupancy factor was refined and converged to 0.500 (6). The occupancy factors of H29 and H30 were fixed to 0.5 and their Uiso(H) set at 0.050 Å2.By reaction of two equivalents of N,N,N',N'-tetramethylchloroformamidinium chloride (Tiritiris & Kantlehner, 2008a) with 1,2-diaminoethane, a bisguanidinium dichloride (Wittmann et al., 2000) has been obtained which, after treating with an aqueous sodium hydroxide solution, yields N,N,N',N'-tetramethyl- N''-[2-(N',N',N'',N''- tetramethylguanidino)ethyl]guanidine (Tiritiris & Kantlehner, 2012). By alkylation of the free nitrogen atoms, various bisguanidinium salts can be prepared. The hydrated title salt presented here is the first alkylated bisguanidinium derivative in our series to have been structurally characterized. The
of the structure contains one cation, two bromide anions and two water molecules (Fig. 1). Br1 and Br2 are each disordered over two sites with refined occupancies of 0.938 (3):0.062 (3) and 0.520 (9):0.480 (9) respectively·The position of one water molecule (O1) is fully occupied while that of the second water solvate (O2) has a refined occupancy of [0.500 (6)], yielding a 1.5-hydrate salt. Prominent bond parameters in the bisguanidinium cation are: C1—N1 = 1.336 (3), C1—N2 = 1.336 (3), C1—N3 = 1.349 (3) Å and C15—N4 = 1.349 (3), C15—N5 = 1.339 (3), C15—N6 = 1.339 (3) Å, indicating partial double-bond character for all. The N—C1—N and N—C15—N angles range from 119.4 (2)° to 120.4 (2)°, indicating that the carbon centres C1 and C15 adopt nearly ideal trigonal–planar environments. The positive charges of the dication are completely delocalized in both CN3 planes. The analysis reveals that the C—N and C—C bond lengths in the dication are in very good agreement with the values obtained for the diprotonated salt 1,2-bis-[2N'-(1,1,3,3-tetramethylguanidinium)]ethane dichloride tetrahydrate (Wittmann et al., 2000). The of the related N,N,N',N'-tetramethyl-N''- [2-(N',N',N'',N''- tetramethylguanidino)ethyl]guanidine, has also been reported (Tiritiris & Kantlehner, 2012).The
is stabilized by a network of O—H···O, O—H···Br and C—H···Br hydrogen bonds, Table 1. O—H···O hydrogen bonds between the water molecules and O—H···Br hydrogen bonds between water molecules and bromide ions are observed, Fig. 2. In addition, C—H···Br hydrogen bonds form between the –N(CH3)2, –CH2 and aromatic –CH groups of the cation and the bromide ions, forming a three-dimensional network, Fig. 3.Data collection: COLLECT (Hooft, 2004); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).Fig. 1. The structure of the title compound with displacement ellipsoids at the 50% probability level. All hydrogen atoms are omitted for the sake of clarity. Only the disordered bromine atoms with the major occupancy are shown. | |
Fig. 2. O—H···O and O—H···Br hydrogen bonds (black dashed lines) in the crystal structure of the title compound (view along ac). | |
Fig. 3. Molecular packing of the title compound. The O—H···O, O—H···Br and C—H···Br hydrogen bonds are depicted by black dashed lines (view along ac). |
C26H42N62+·2Br−·1.5H2O | F(000) = 1300 |
Mr = 625.50 | Dx = 1.417 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.1957 (9) Å | Cell parameters from 5843 reflections |
b = 7.9654 (5) Å | θ = 0.4–28.3° |
c = 30.4821 (18) Å | µ = 2.80 mm−1 |
β = 97.934 (4)° | T = 100 K |
V = 2932.8 (3) Å3 | Block, colorless |
Z = 4 | 0.35 × 0.26 × 0.10 mm |
Bruker–Nonius KappaCCD diffractometer | 7000 independent reflections |
Radiation source: fine-focus sealed tube | 5093 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
φ scans, and ω scans | θmax = 28.1°, θmin = 1.7° |
Absorption correction: multi-scan (Blessing, 1995) | h = −16→16 |
Tmin = 0.455, Tmax = 0.705 | k = −10→9 |
11867 measured reflections | l = −40→40 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: mixed |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0334P)2 + 1.9458P] where P = (Fo2 + 2Fc2)/3 |
7000 reflections | (Δ/σ)max < 0.001 |
362 parameters | Δρmax = 0.59 e Å−3 |
5 restraints | Δρmin = −0.51 e Å−3 |
C26H42N62+·2Br−·1.5H2O | V = 2932.8 (3) Å3 |
Mr = 625.50 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.1957 (9) Å | µ = 2.80 mm−1 |
b = 7.9654 (5) Å | T = 100 K |
c = 30.4821 (18) Å | 0.35 × 0.26 × 0.10 mm |
β = 97.934 (4)° |
Bruker–Nonius KappaCCD diffractometer | 7000 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 5093 reflections with I > 2σ(I) |
Tmin = 0.455, Tmax = 0.705 | Rint = 0.034 |
11867 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 5 restraints |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.59 e Å−3 |
7000 reflections | Δρmin = −0.51 e Å−3 |
362 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 | Occ. (<1) | |
Br1A | 0.61652 (3) | 0.32199 (15) | 0.09074 (2) | 0.02821 (18) | 0.938 (3) |
Br1B | 0.6107 (5) | 0.3919 (18) | 0.0962 (2) | 0.02821 (18) | 0.062 (3) |
Br2A | 0.08222 (13) | 0.1353 (4) | 0.08416 (14) | 0.0282 (5) | 0.520 (9) |
Br2B | 0.08977 (8) | 0.1763 (3) | 0.10105 (14) | 0.0240 (5) | 0.480 (9) |
C1 | 0.35370 (16) | 0.7762 (3) | 0.08670 (6) | 0.0131 (5) | |
N1 | 0.36249 (14) | 0.9429 (2) | 0.09049 (6) | 0.0146 (4) | |
N2 | 0.39307 (14) | 0.6969 (2) | 0.05355 (6) | 0.0152 (4) | |
N3 | 0.30713 (14) | 0.6861 (2) | 0.11675 (6) | 0.0131 (4) | |
C2 | 0.37669 (19) | 1.0285 (3) | 0.13337 (7) | 0.0187 (5) | |
H2A | 0.3928 | 0.9456 | 0.1571 | 0.028* | |
H2B | 0.3086 | 1.0890 | 0.1371 | 0.028* | |
H2C | 0.4382 | 1.1084 | 0.1346 | 0.028* | |
C3 | 0.3532 (2) | 1.0538 (3) | 0.05186 (7) | 0.0224 (5) | |
H3A | 0.3354 | 0.9871 | 0.0248 | 0.034* | |
H3B | 0.4236 | 1.1123 | 0.0512 | 0.034* | |
H3C | 0.2944 | 1.1363 | 0.0537 | 0.034* | |
C4 | 0.49080 (18) | 0.7544 (3) | 0.03505 (7) | 0.0234 (5) | |
H4A | 0.5215 | 0.8537 | 0.0513 | 0.035* | |
H4B | 0.4700 | 0.7830 | 0.0037 | 0.035* | |
H4C | 0.5465 | 0.6649 | 0.0377 | 0.035* | |
C5 | 0.34310 (18) | 0.5430 (3) | 0.03370 (7) | 0.0192 (5) | |
H5A | 0.3905 | 0.4470 | 0.0435 | 0.029* | |
H5B | 0.3354 | 0.5517 | 0.0013 | 0.029* | |
H5C | 0.2699 | 0.5271 | 0.0429 | 0.029* | |
C6 | 0.35329 (18) | 0.5204 (3) | 0.13192 (7) | 0.0156 (5) | |
H6A | 0.4244 | 0.5016 | 0.1205 | 0.019* | |
H6B | 0.3014 | 0.4302 | 0.1203 | 0.019* | |
C7 | 0.37139 (17) | 0.5150 (3) | 0.18194 (7) | 0.0139 (5) | |
C8 | 0.30142 (17) | 0.4218 (3) | 0.20481 (7) | 0.0148 (5) | |
H8 | 0.2453 | 0.3543 | 0.1888 | 0.018* | |
C9 | 0.31251 (18) | 0.4262 (3) | 0.25082 (7) | 0.0166 (5) | |
H9 | 0.2646 | 0.3613 | 0.2661 | 0.020* | |
C10 | 0.39372 (18) | 0.5255 (3) | 0.27427 (7) | 0.0178 (5) | |
H10 | 0.4000 | 0.5316 | 0.3056 | 0.021* | |
C11 | 0.46563 (19) | 0.6157 (3) | 0.25182 (8) | 0.0209 (5) | |
H11 | 0.5224 | 0.6818 | 0.2678 | 0.025* | |
C12 | 0.45473 (18) | 0.6095 (3) | 0.20599 (7) | 0.0186 (5) | |
H12 | 0.5049 | 0.6706 | 0.1908 | 0.022* | |
C13 | 0.20801 (17) | 0.7456 (3) | 0.13420 (7) | 0.0137 (4) | |
H13A | 0.1928 | 0.8635 | 0.1251 | 0.016* | |
H13B | 0.2204 | 0.7414 | 0.1670 | 0.016* | |
C14 | 0.10851 (17) | 0.6355 (3) | 0.11665 (7) | 0.0187 (5) | |
H14A | 0.0905 | 0.6512 | 0.0842 | 0.022* | |
H14B | 0.1278 | 0.5160 | 0.1223 | 0.022* | |
C15 | −0.08422 (18) | 0.7306 (3) | 0.11457 (7) | 0.0202 (5) | |
N4 | 0.01152 (14) | 0.6780 (2) | 0.13802 (5) | 0.0158 (4) | |
N5 | −0.11477 (16) | 0.6733 (3) | 0.07340 (6) | 0.0301 (5) | |
N6 | −0.15023 (15) | 0.8373 (3) | 0.13257 (6) | 0.0196 (4) | |
C16 | 0.02466 (18) | 0.6553 (3) | 0.18648 (7) | 0.0180 (5) | |
H16A | 0.0436 | 0.7656 | 0.2005 | 0.022* | |
H16B | 0.0886 | 0.5799 | 0.1950 | 0.022* | |
C17 | −0.07320 (17) | 0.5853 (3) | 0.20581 (7) | 0.0156 (5) | |
C18 | −0.08041 (18) | 0.6212 (3) | 0.24996 (7) | 0.0173 (5) | |
H18 | −0.0277 | 0.6943 | 0.2659 | 0.021* | |
C19 | −0.16346 (18) | 0.5518 (3) | 0.27109 (7) | 0.0195 (5) | |
H19 | −0.1663 | 0.5751 | 0.3015 | 0.023* | |
C20 | −0.24237 (19) | 0.4481 (3) | 0.24770 (7) | 0.0230 (5) | |
H20 | −0.3000 | 0.4016 | 0.2619 | 0.028* | |
C21 | −0.23666 (19) | 0.4129 (3) | 0.20374 (8) | 0.0253 (6) | |
H21 | −0.2910 | 0.3428 | 0.1876 | 0.030* | |
C22 | −0.15173 (19) | 0.4794 (3) | 0.18294 (7) | 0.0214 (5) | |
H22 | −0.1474 | 0.4523 | 0.1529 | 0.026* | |
C23 | −0.0885 (2) | 0.5048 (4) | 0.05929 (9) | 0.0488 (9) | |
H23A | −0.0523 | 0.4414 | 0.0848 | 0.073* | |
H23B | −0.0386 | 0.5123 | 0.0368 | 0.073* | |
H23C | −0.1568 | 0.4475 | 0.0468 | 0.073* | |
C24 | −0.1789 (2) | 0.7764 (5) | 0.03946 (8) | 0.0523 (10) | |
H24A | −0.2551 | 0.7347 | 0.0340 | 0.078* | |
H24B | −0.1456 | 0.7705 | 0.0120 | 0.078* | |
H24C | −0.1789 | 0.8931 | 0.0496 | 0.078* | |
C25 | −0.27108 (18) | 0.8224 (3) | 0.12385 (8) | 0.0260 (6) | |
H25A | −0.2910 | 0.7196 | 0.1069 | 0.039* | |
H25B | −0.3018 | 0.9199 | 0.1068 | 0.039* | |
H25C | −0.3012 | 0.8176 | 0.1520 | 0.039* | |
C26 | −0.10728 (19) | 0.9705 (3) | 0.16283 (8) | 0.0248 (6) | |
H26A | −0.1106 | 0.9350 | 0.1934 | 0.037* | |
H26B | −0.1520 | 1.0720 | 0.1564 | 0.037* | |
H26C | −0.0303 | 0.9943 | 0.1591 | 0.037* | |
O1 | 0.1101 (2) | 0.8214 (4) | 0.02327 (11) | 0.0675 (7) | |
H27 | 0.103 (4) | 0.843 (5) | −0.0055 (4) | 0.091 (17)* | |
H28 | 0.088 (3) | 0.916 (3) | 0.0345 (12) | 0.070 (14)* | |
O2 | 0.8250 (3) | 0.1418 (5) | 0.05550 (12) | 0.0313 (13) | 0.500 (6) |
H29 | 0.773 (3) | 0.198 (7) | 0.0678 (15) | 0.050* | 0.5 |
H30 | 0.885 (2) | 0.150 (7) | 0.0762 (13) | 0.050* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1A | 0.01796 (13) | 0.0464 (5) | 0.01941 (14) | −0.00219 (17) | −0.00051 (10) | −0.0025 (2) |
Br1B | 0.01796 (13) | 0.0464 (5) | 0.01941 (14) | −0.00219 (17) | −0.00051 (10) | −0.0025 (2) |
Br2A | 0.0256 (3) | 0.0281 (6) | 0.0315 (10) | 0.0112 (3) | 0.0065 (5) | 0.0102 (7) |
Br2B | 0.0177 (3) | 0.0254 (6) | 0.0284 (10) | 0.0038 (3) | 0.0014 (4) | 0.0068 (7) |
C1 | 0.0094 (10) | 0.0189 (12) | 0.0102 (10) | −0.0001 (9) | −0.0013 (8) | 0.0041 (9) |
N1 | 0.0157 (9) | 0.0169 (10) | 0.0111 (8) | −0.0017 (8) | 0.0012 (7) | 0.0026 (8) |
N2 | 0.0120 (9) | 0.0228 (11) | 0.0114 (8) | −0.0018 (8) | 0.0037 (7) | −0.0028 (8) |
N3 | 0.0115 (9) | 0.0156 (10) | 0.0129 (8) | 0.0041 (8) | 0.0047 (7) | 0.0026 (8) |
C2 | 0.0171 (11) | 0.0213 (13) | 0.0166 (11) | −0.0016 (10) | −0.0017 (9) | −0.0017 (10) |
C3 | 0.0254 (13) | 0.0223 (13) | 0.0188 (12) | −0.0016 (11) | 0.0006 (10) | 0.0084 (10) |
C4 | 0.0167 (11) | 0.0382 (15) | 0.0168 (11) | −0.0045 (11) | 0.0070 (9) | −0.0015 (11) |
C5 | 0.0169 (11) | 0.0246 (13) | 0.0159 (11) | −0.0004 (10) | 0.0018 (9) | −0.0065 (10) |
C6 | 0.0132 (10) | 0.0173 (12) | 0.0169 (11) | 0.0019 (9) | 0.0046 (9) | 0.0010 (9) |
C7 | 0.0112 (10) | 0.0140 (11) | 0.0160 (10) | 0.0054 (9) | 0.0004 (8) | 0.0008 (9) |
C8 | 0.0125 (10) | 0.0133 (12) | 0.0183 (11) | 0.0011 (9) | 0.0010 (9) | 0.0010 (9) |
C9 | 0.0137 (11) | 0.0186 (12) | 0.0182 (11) | −0.0014 (9) | 0.0049 (9) | 0.0040 (9) |
C10 | 0.0180 (11) | 0.0209 (13) | 0.0141 (10) | 0.0036 (10) | 0.0006 (9) | 0.0008 (10) |
C11 | 0.0171 (11) | 0.0221 (13) | 0.0215 (11) | −0.0050 (10) | −0.0044 (9) | 0.0034 (10) |
C12 | 0.0138 (11) | 0.0200 (12) | 0.0219 (12) | −0.0010 (10) | 0.0024 (9) | 0.0073 (10) |
C13 | 0.0133 (10) | 0.0160 (11) | 0.0126 (10) | 0.0034 (9) | 0.0043 (8) | 0.0026 (9) |
C14 | 0.0124 (10) | 0.0281 (14) | 0.0156 (11) | 0.0027 (10) | 0.0025 (9) | −0.0044 (10) |
C15 | 0.0143 (11) | 0.0340 (14) | 0.0123 (10) | 0.0045 (11) | 0.0019 (9) | 0.0025 (10) |
N4 | 0.0100 (8) | 0.0270 (11) | 0.0105 (8) | 0.0031 (8) | 0.0019 (7) | 0.0004 (8) |
N5 | 0.0158 (10) | 0.0607 (16) | 0.0127 (9) | 0.0124 (10) | −0.0019 (8) | −0.0083 (10) |
N6 | 0.0116 (9) | 0.0318 (12) | 0.0153 (9) | 0.0038 (9) | 0.0019 (7) | −0.0015 (9) |
C16 | 0.0119 (10) | 0.0287 (14) | 0.0125 (10) | −0.0006 (10) | −0.0013 (8) | 0.0011 (10) |
C17 | 0.0117 (10) | 0.0179 (12) | 0.0170 (11) | 0.0039 (9) | 0.0011 (8) | 0.0030 (9) |
C18 | 0.0158 (11) | 0.0178 (12) | 0.0175 (11) | 0.0019 (10) | −0.0004 (9) | 0.0015 (10) |
C19 | 0.0210 (12) | 0.0209 (13) | 0.0173 (11) | 0.0051 (10) | 0.0056 (9) | 0.0031 (10) |
C20 | 0.0173 (12) | 0.0276 (14) | 0.0246 (12) | 0.0005 (11) | 0.0044 (10) | 0.0110 (11) |
C21 | 0.0183 (12) | 0.0276 (14) | 0.0279 (13) | −0.0070 (11) | −0.0042 (10) | 0.0046 (11) |
C22 | 0.0203 (12) | 0.0285 (14) | 0.0144 (11) | −0.0029 (11) | −0.0012 (9) | 0.0001 (10) |
C23 | 0.0229 (14) | 0.087 (3) | 0.0344 (16) | 0.0087 (16) | −0.0034 (12) | −0.0379 (17) |
C24 | 0.0231 (14) | 0.118 (3) | 0.0150 (12) | 0.0198 (18) | −0.0010 (11) | 0.0095 (16) |
C25 | 0.0117 (11) | 0.0438 (17) | 0.0227 (12) | 0.0056 (11) | 0.0038 (9) | −0.0004 (12) |
C26 | 0.0212 (12) | 0.0340 (15) | 0.0202 (12) | 0.0023 (11) | 0.0064 (10) | 0.0007 (11) |
O1 | 0.0614 (17) | 0.0511 (18) | 0.090 (2) | −0.0120 (14) | 0.0107 (16) | 0.0147 (17) |
O2 | 0.027 (2) | 0.029 (2) | 0.036 (2) | 0.0050 (17) | −0.0023 (16) | −0.0022 (17) |
Br1A—Br1B | 0.588 (14) | C14—H14A | 0.9900 |
Br2A—Br2B | 0.6061 (8) | C14—H14B | 0.9900 |
C1—N1 | 1.336 (3) | C15—N4 | 1.349 (3) |
C1—N2 | 1.336 (3) | C15—N5 | 1.339 (3) |
C1—N3 | 1.349 (3) | C15—N6 | 1.339 (3) |
N1—C2 | 1.463 (3) | N4—C16 | 1.475 (3) |
N1—C3 | 1.464 (3) | N5—C23 | 1.459 (4) |
N2—C4 | 1.461 (3) | N5—C24 | 1.460 (3) |
N2—C5 | 1.463 (3) | N6—C26 | 1.455 (3) |
N3—C13 | 1.465 (3) | N6—C25 | 1.466 (3) |
N3—C6 | 1.484 (3) | C16—C17 | 1.509 (3) |
C2—H2A | 0.9800 | C16—H16A | 0.9900 |
C2—H2B | 0.9800 | C16—H16B | 0.9900 |
C2—H2C | 0.9800 | C17—C22 | 1.389 (3) |
C3—H3A | 0.9800 | C17—C18 | 1.390 (3) |
C3—H3B | 0.9800 | C18—C19 | 1.388 (3) |
C3—H3C | 0.9800 | C18—H18 | 0.9500 |
C4—H4A | 0.9800 | C19—C20 | 1.388 (3) |
C4—H4B | 0.9800 | C19—H19 | 0.9500 |
C4—H4C | 0.9800 | C20—C21 | 1.380 (3) |
C5—H5A | 0.9800 | C20—H20 | 0.9500 |
C5—H5B | 0.9800 | C21—C22 | 1.392 (3) |
C5—H5C | 0.9800 | C21—H21 | 0.9500 |
C6—C7 | 1.511 (3) | C22—H22 | 0.9500 |
C6—H6A | 0.9900 | C23—H23A | 0.9800 |
C6—H6B | 0.9900 | C23—H23B | 0.9800 |
C7—C8 | 1.389 (3) | C23—H23C | 0.9800 |
C7—C12 | 1.389 (3) | C24—H24A | 0.9800 |
C8—C9 | 1.391 (3) | C24—H24B | 0.9800 |
C8—H8 | 0.9500 | C24—H24C | 0.9800 |
C9—C10 | 1.386 (3) | C25—H25A | 0.9800 |
C9—H9 | 0.9500 | C25—H25B | 0.9800 |
C10—C11 | 1.385 (3) | C25—H25C | 0.9800 |
C10—H10 | 0.9500 | C26—H26A | 0.9800 |
C11—C12 | 1.386 (3) | C26—H26B | 0.9800 |
C11—H11 | 0.9500 | C26—H26C | 0.9800 |
C12—H12 | 0.9500 | O1—H27 | 0.89 (1) |
C13—C14 | 1.532 (3) | O1—H28 | 0.89 (1) |
C13—H13A | 0.9900 | O2—H29 | 0.89 (1) |
C13—H13B | 0.9900 | O2—H30 | 0.90 (1) |
C14—N4 | 1.467 (3) | ||
N2—C1—N1 | 120.15 (19) | N4—C14—H14A | 109.4 |
N2—C1—N3 | 119.4 (2) | C13—C14—H14A | 109.4 |
N1—C1—N3 | 120.40 (19) | N4—C14—H14B | 109.4 |
C1—N1—C2 | 122.59 (18) | C13—C14—H14B | 109.4 |
C1—N1—C3 | 122.27 (18) | H14A—C14—H14B | 108.0 |
C2—N1—C3 | 115.08 (18) | N5—C15—N6 | 119.7 (2) |
C1—N2—C4 | 122.81 (19) | N5—C15—N4 | 120.0 (2) |
C1—N2—C5 | 122.44 (18) | N6—C15—N4 | 120.4 (2) |
C4—N2—C5 | 114.73 (18) | C15—N4—C14 | 121.91 (18) |
C1—N3—C13 | 121.39 (18) | C15—N4—C16 | 122.37 (18) |
C1—N3—C6 | 120.50 (17) | C14—N4—C16 | 115.70 (16) |
C13—N3—C6 | 118.08 (17) | C15—N5—C23 | 123.1 (2) |
N1—C2—H2A | 109.5 | C15—N5—C24 | 121.7 (2) |
N1—C2—H2B | 109.5 | C23—N5—C24 | 115.2 (2) |
H2A—C2—H2B | 109.5 | C15—N6—C26 | 122.57 (19) |
N1—C2—H2C | 109.5 | C15—N6—C25 | 121.4 (2) |
H2A—C2—H2C | 109.5 | C26—N6—C25 | 116.04 (19) |
H2B—C2—H2C | 109.5 | N4—C16—C17 | 117.00 (17) |
N1—C3—H3A | 109.5 | N4—C16—H16A | 108.0 |
N1—C3—H3B | 109.5 | C17—C16—H16A | 108.0 |
H3A—C3—H3B | 109.5 | N4—C16—H16B | 108.0 |
N1—C3—H3C | 109.5 | C17—C16—H16B | 108.0 |
H3A—C3—H3C | 109.5 | H16A—C16—H16B | 107.3 |
H3B—C3—H3C | 109.5 | C22—C17—C18 | 118.6 (2) |
N2—C4—H4A | 109.5 | C22—C17—C16 | 123.8 (2) |
N2—C4—H4B | 109.5 | C18—C17—C16 | 117.45 (19) |
H4A—C4—H4B | 109.5 | C19—C18—C17 | 121.0 (2) |
N2—C4—H4C | 109.5 | C19—C18—H18 | 119.5 |
H4A—C4—H4C | 109.5 | C17—C18—H18 | 119.5 |
H4B—C4—H4C | 109.5 | C20—C19—C18 | 119.8 (2) |
N2—C5—H5A | 109.5 | C20—C19—H19 | 120.1 |
N2—C5—H5B | 109.5 | C18—C19—H19 | 120.1 |
H5A—C5—H5B | 109.5 | C21—C20—C19 | 119.7 (2) |
N2—C5—H5C | 109.5 | C21—C20—H20 | 120.2 |
H5A—C5—H5C | 109.5 | C19—C20—H20 | 120.2 |
H5B—C5—H5C | 109.5 | C20—C21—C22 | 120.3 (2) |
N3—C6—C7 | 109.64 (17) | C20—C21—H21 | 119.8 |
N3—C6—H6A | 109.7 | C22—C21—H21 | 119.8 |
C7—C6—H6A | 109.7 | C17—C22—C21 | 120.5 (2) |
N3—C6—H6B | 109.7 | C17—C22—H22 | 119.8 |
C7—C6—H6B | 109.7 | C21—C22—H22 | 119.8 |
H6A—C6—H6B | 108.2 | N5—C23—H23A | 109.5 |
C8—C7—C12 | 118.7 (2) | N5—C23—H23B | 109.5 |
C8—C7—C6 | 120.48 (19) | H23A—C23—H23B | 109.5 |
C12—C7—C6 | 120.8 (2) | N5—C23—H23C | 109.5 |
C7—C8—C9 | 120.8 (2) | H23A—C23—H23C | 109.5 |
C7—C8—H8 | 119.6 | H23B—C23—H23C | 109.5 |
C9—C8—H8 | 119.6 | N5—C24—H24A | 109.5 |
C10—C9—C8 | 119.8 (2) | N5—C24—H24B | 109.5 |
C10—C9—H9 | 120.1 | H24A—C24—H24B | 109.5 |
C8—C9—H9 | 120.1 | N5—C24—H24C | 109.5 |
C11—C10—C9 | 119.8 (2) | H24A—C24—H24C | 109.5 |
C11—C10—H10 | 120.1 | H24B—C24—H24C | 109.5 |
C9—C10—H10 | 120.1 | N6—C25—H25A | 109.5 |
C10—C11—C12 | 120.0 (2) | N6—C25—H25B | 109.5 |
C10—C11—H11 | 120.0 | H25A—C25—H25B | 109.5 |
C12—C11—H11 | 120.0 | N6—C25—H25C | 109.5 |
C11—C12—C7 | 120.8 (2) | H25A—C25—H25C | 109.5 |
C11—C12—H12 | 119.6 | H25B—C25—H25C | 109.5 |
C7—C12—H12 | 119.6 | N6—C26—H26A | 109.5 |
N3—C13—C14 | 109.99 (18) | N6—C26—H26B | 109.5 |
N3—C13—H13A | 109.7 | H26A—C26—H26B | 109.5 |
C14—C13—H13A | 109.7 | N6—C26—H26C | 109.5 |
N3—C13—H13B | 109.7 | H26A—C26—H26C | 109.5 |
C14—C13—H13B | 109.7 | H26B—C26—H26C | 109.5 |
H13A—C13—H13B | 108.2 | H27—O1—H28 | 103 (4) |
N4—C14—C13 | 111.17 (18) | H29—O2—H30 | 102.8 (15) |
N2—C1—N1—C2 | −147.57 (19) | N5—C15—N4—C14 | 32.3 (3) |
N3—C1—N1—C2 | 31.1 (3) | N6—C15—N4—C14 | −149.1 (2) |
N2—C1—N1—C3 | 35.5 (3) | N5—C15—N4—C16 | −146.1 (2) |
N3—C1—N1—C3 | −145.9 (2) | N6—C15—N4—C16 | 32.5 (3) |
N1—C1—N2—C4 | 32.9 (3) | C13—C14—N4—C15 | 120.6 (2) |
N3—C1—N2—C4 | −145.7 (2) | C13—C14—N4—C16 | −61.0 (3) |
N1—C1—N2—C5 | −148.7 (2) | N6—C15—N5—C23 | −146.0 (2) |
N3—C1—N2—C5 | 32.6 (3) | N4—C15—N5—C23 | 32.6 (4) |
N2—C1—N3—C13 | −140.3 (2) | N6—C15—N5—C24 | 33.1 (4) |
N1—C1—N3—C13 | 41.0 (3) | N4—C15—N5—C24 | −148.3 (2) |
N2—C1—N3—C6 | 37.6 (3) | N5—C15—N6—C26 | −145.8 (2) |
N1—C1—N3—C6 | −141.07 (19) | N4—C15—N6—C26 | 35.6 (3) |
C1—N3—C6—C7 | 129.2 (2) | N5—C15—N6—C25 | 36.3 (3) |
C13—N3—C6—C7 | −52.8 (2) | N4—C15—N6—C25 | −142.3 (2) |
N3—C6—C7—C8 | 106.4 (2) | C15—N4—C16—C17 | 37.8 (3) |
N3—C6—C7—C12 | −70.5 (2) | C14—N4—C16—C17 | −140.7 (2) |
C12—C7—C8—C9 | 1.7 (3) | N4—C16—C17—C22 | 28.2 (3) |
C6—C7—C8—C9 | −175.2 (2) | N4—C16—C17—C18 | −156.0 (2) |
C7—C8—C9—C10 | 0.5 (3) | C22—C17—C18—C19 | 0.7 (3) |
C8—C9—C10—C11 | −2.0 (3) | C16—C17—C18—C19 | −175.4 (2) |
C9—C10—C11—C12 | 1.4 (4) | C17—C18—C19—C20 | −1.6 (3) |
C10—C11—C12—C7 | 0.8 (4) | C18—C19—C20—C21 | 1.0 (3) |
C8—C7—C12—C11 | −2.3 (3) | C19—C20—C21—C22 | 0.6 (4) |
C6—C7—C12—C11 | 174.6 (2) | C18—C17—C22—C21 | 0.9 (3) |
C1—N3—C13—C14 | 110.1 (2) | C16—C17—C22—C21 | 176.7 (2) |
C6—N3—C13—C14 | −67.8 (2) | C20—C21—C22—C17 | −1.5 (4) |
N3—C13—C14—N4 | 172.62 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H27···O2i | 0.89 (1) | 1.87 (2) | 2.646 (2) | 146 (1) |
O1—H28···Br2Aii | 0.89 (1) | 2.31 (2) | 3.160 (2) | 159 (1) |
O1—H28···Br2Bii | 0.89 (1) | 2.90 (2) | 3.720 (2) | 155 (1) |
O2—H29···Br1A | 0.89 (1) | 2.34 (2) | 3.230 (2) | 170 (1) |
O2—H29···Br1B | 0.89 (1) | 2.75 (2) | 3.637 (2) | 173 (1) |
O2—H30···Br2Aiii | 0.90 (1) | 2.39 (2) | 3.139 (2) | 141 (1) |
O2—H30···Br2Biii | 0.90 (1) | 2.52 (2) | 3.346 (2) | 153 (1) |
C2—H2B···Br2Bii | 0.98 | 2.83 | 3.694 (2) | 148 |
C3—H3C···Br2Aii | 0.98 | 2.87 | 3.634 (2) | 136 |
C4—H4C···Br1B | 0.98 | 2.85 | 3.632 (2) | 137 |
C6—H6A···Br1B | 0.99 | 2.64 | 3.611 (2) | 169 |
C13—H13A···Br2Aii | 0.99 | 2.76 | 3.697 (2) | 159 |
C13—H13A···Br2Bii | 0.99 | 2.84 | 3.804 (2) | 165 |
C14—H14B···Br2B | 0.99 | 2.81 | 3.692 (2) | 149 |
C21—H21···Br1Biv | 0.95 | 2.90 | 3.544 (2) | 126 |
C23—H23A···Br2B | 0.98 | 2.73 | 3.525 (2) | 138 |
C25—H25A···Br1Biv | 0.98 | 2.87 | 3.770 (2) | 153 |
C26—H26C···Br2Bii | 0.98 | 2.84 | 3.641 (2) | 139 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H27···O2i | 0.89 (1) | 1.87 (2) | 2.646 (2) | 146 (1) |
O1—H28···Br2Aii | 0.89 (1) | 2.31 (2) | 3.160 (2) | 159 (1) |
O1—H28···Br2Bii | 0.89 (1) | 2.90 (2) | 3.720 (2) | 155 (1) |
O2—H29···Br1A | 0.89 (1) | 2.34 (2) | 3.230 (2) | 170 (1) |
O2—H29···Br1B | 0.89 (1) | 2.75 (2) | 3.637 (2) | 173 (1) |
O2—H30···Br2Aiii | 0.90 (1) | 2.39 (2) | 3.139 (2) | 141 (1) |
O2—H30···Br2Biii | 0.90 (1) | 2.52 (2) | 3.346 (2) | 153 (1) |
C2—H2B···Br2Bii | 0.98 | 2.83 | 3.694 (2) | 148 |
C3—H3C···Br2Aii | 0.98 | 2.87 | 3.634 (2) | 136 |
C4—H4C···Br1B | 0.98 | 2.85 | 3.632 (2) | 137 |
C6—H6A···Br1B | 0.99 | 2.64 | 3.611 (2) | 169 |
C13—H13A···Br2Aii | 0.99 | 2.76 | 3.697 (2) | 159 |
C13—H13A···Br2Bii | 0.99 | 2.84 | 3.804 (2) | 165 |
C14—H14B···Br2B | 0.99 | 2.81 | 3.692 (2) | 149 |
C21—H21···Br1Biv | 0.95 | 2.90 | 3.544 (2) | 126 |
C23—H23A···Br2B | 0.98 | 2.73 | 3.525 (2) | 138 |
C25—H25A···Br1Biv | 0.98 | 2.87 | 3.770 (2) | 153 |
C26—H26C···Br2Bii | 0.98 | 2.84 | 3.641 (2) | 139 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C26H42N62+·2Br−·1.5H2O |
Mr | 625.50 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 12.1957 (9), 7.9654 (5), 30.4821 (18) |
β (°) | 97.934 (4) |
V (Å3) | 2932.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.80 |
Crystal size (mm) | 0.35 × 0.26 × 0.10 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.455, 0.705 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11867, 7000, 5093 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.664 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.088, 1.02 |
No. of reflections | 7000 |
No. of parameters | 362 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.59, −0.51 |
Computer programs: COLLECT (Hooft, 2004), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg & Putz, 2005).
Acknowledgements
The authors thank Dr F. Lissner (Institut für Anorganische Chemie, Universität Stuttgart) for measuring of the diffraction data.
References
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