Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048623/rk2048sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048623/rk2048Isup2.hkl |
CCDC reference: 667325
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.004 Å
- R factor = 0.026
- wR factor = 0.061
- Data-to-parameter ratio = 18.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT420_ALERT_2_B D-H Without Acceptor O1 - H12 ... ?
Alert level C CRYSC01_ALERT_1_C The word below has not been recognised as a standard identifier. Colourless' CRYSC01_ALERT_1_C No recognised colour has been given for crystal colour. PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H12 .. N3 .. 2.72 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H3 .. I .. 3.31 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H5 .. BR .. 3.05 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H6 .. N4 .. 2.73 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H72 .. BR .. 2.99 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H82 .. O1 .. 2.78 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H101 .. BR .. 2.97 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H121 .. O1 .. 2.78 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H122 .. BR .. 3.07 Ang. PLAT481_ALERT_4_C Long D...A H-Bond Reported C3 .. I .. 4.24 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 13 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 10 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was obtained as an intermediate in the synthesis of ortho–iodomandelic acid according to a published procedure (Angyal et al., 1949) upon addition of ortho–iodobenzyl bromide to a solution of hexamethylenetetramine in chloroform. Crystals suitable for X–ray analysis were obtained upon the cooling of a saturated aqueous solution to 277 K.
The H atoms on C atoms were located in a difference map and refined as riding on their parent atoms with a common Uiso value. The H atoms on the water molecules were located in a difference map and refined with a common O—H distance and a constant 105° bond angle. A common Uiso value was refined for the O–bonded H atoms. Position of the residual peak - deepest hole, -1.07 e Å-3 at 0.3169 0.8397 0.5303 with the distance 0.82 Å from I.
In the quaternary ammonium salt, hexamethylenetetramine is N–alkylated by an ortho–iodobenzyl moiety. The positive charge of the ammonium centre atom is counterbalanced by a bromide ion (Fig. 1). Intramolecular bond lengths and angles are normal.
The bromide ions are embedded into an environment of 7 hydrogen–bond donors (CIF: the _geom_special_details item for the applied criteria). One hemisphere around the anion contains three O—H donors, the other hemisphere is established by four C—H···Br contacts. Of these, three bonds have methylene functions as donors which are in α–position to the quaternary ammonium centre (Fig. 1), the fourth stemming from a phenyl–CH. The O2 donors are part of OH2Br2H2O rhombs (Fig. 2). All the water molecules are close to the boundary planes of the chosen unit cell. There are no hydrogen–bonded contacts between water molecules. Instead, the acceptor functions of the O atoms are occupied by C—H donors. Again, there is a predominance of α–methylene donors. The acceptor capability of the amine–N atoms is less pronounced than that of the anion and the water–O atoms. There are relatively long bonds from water (N3) and phenyl–CH donors (N4), whereas N2 is not found as an acceptor within the applied criteria.
For synthesis of the title compound, see Angyal et al. (1949). For the crystal structure of a related compound, see Shao et al. (1982).
Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 1990).
C13H18IN4+·Br−·2H2O | V = 819.8 (8) Å3 |
Mr = 473.15 | Z = 2 |
Triclinic, P1 | F(000) = 464 |
Hall symbol: -P 1 | Dx = 1.917 Mg m−3 |
a = 9.084 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.500 (5) Å | θ = 3.8–27.5° |
c = 10.495 (7) Å | µ = 4.40 mm−1 |
α = 69.28 (5)° | T = 200 K |
β = 75.47 (5)° | Block, colourless' |
γ = 83.76 (4)° | 0.28 × 0.15 × 0.14 mm |
Nonius KappaCCD diffractometer | 3820 independent reflections |
Radiation source: Fine-focus sealed tube | 2865 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 27.6°, θmin = 3.8° |
Absorption correction: numerical [crystal faces optimized with X-SHAPE (Stoe & Cie, 1997) and absorption correction with X-RED (Stoe & Cie, 1997)] | h = −11→11 |
Tmin = 0.409, Tmax = 0.610 | k = −12→12 |
10405 measured reflections | l = −13→13 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0335P)2] where P = (Fo2 + 2Fc2)/3 |
3820 reflections | (Δ/σ)max < 0.001 |
205 parameters | Δρmax = 0.50 e Å−3 |
6 restraints | Δρmin = −1.07 e Å−3 |
C13H18IN4+·Br−·2H2O | γ = 83.76 (4)° |
Mr = 473.15 | V = 819.8 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.084 (4) Å | Mo Kα radiation |
b = 9.500 (5) Å | µ = 4.40 mm−1 |
c = 10.495 (7) Å | T = 200 K |
α = 69.28 (5)° | 0.28 × 0.15 × 0.14 mm |
β = 75.47 (5)° |
Nonius KappaCCD diffractometer | 3820 independent reflections |
Absorption correction: numerical [crystal faces optimized with X-SHAPE (Stoe & Cie, 1997) and absorption correction with X-RED (Stoe & Cie, 1997)] | 2865 reflections with I > 2σ(I) |
Tmin = 0.409, Tmax = 0.610 | Rint = 0.032 |
10405 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 6 restraints |
wR(F2) = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | Δρmax = 0.50 e Å−3 |
3820 reflections | Δρmin = −1.07 e Å−3 |
205 parameters |
Geometry. The hydrogen–bond list was generated with the PLATON command "hbond 1.. 4 140", i.e., D···A is less than the sum of the vdW radii + 1 Å, H···A is less than the sum of the vdW radii + 0.4 Å, the D—H···A angle is greater than 140°. |
x | y | z | Uiso*/Ueq | ||
I | 0.33565 (2) | 0.89354 (2) | 0.44815 (2) | 0.03398 (8) | |
Br | 0.09573 (4) | 0.28677 (3) | 0.33816 (3) | 0.03467 (9) | |
O1 | 0.2401 (3) | 0.2543 (4) | 0.0283 (3) | 0.0676 (9) | |
H11 | 0.199 (4) | 0.258 (5) | 0.101 (3) | 0.063 (7)* | |
H12 | 0.177 (3) | 0.274 (5) | −0.013 (4) | 0.063 (7)* | |
O2 | 0.0335 (3) | 0.0367 (3) | 0.6679 (3) | 0.0435 (6) | |
H21 | 0.037 (5) | 0.088 (4) | 0.590 (3) | 0.063 (7)* | |
H22 | −0.001 (4) | −0.038 (3) | 0.672 (4) | 0.063 (7)* | |
N1 | 0.2986 (2) | 0.7033 (2) | 0.1572 (2) | 0.0182 (5) | |
N2 | 0.3446 (3) | 0.9209 (3) | −0.0563 (3) | 0.0279 (5) | |
N3 | 0.1101 (3) | 0.7836 (3) | 0.0132 (3) | 0.0250 (5) | |
N4 | 0.3522 (3) | 0.6716 (3) | −0.0710 (2) | 0.0268 (5) | |
C1 | 0.4668 (3) | 0.6402 (3) | 0.3306 (3) | 0.0206 (6) | |
C2 | 0.5020 (3) | 0.7436 (3) | 0.3847 (3) | 0.0216 (6) | |
C3 | 0.6450 (3) | 0.7475 (3) | 0.4062 (3) | 0.0265 (6) | |
H3 | 0.6666 | 0.8194 | 0.4427 | 0.0245 (18)* | |
C4 | 0.7556 (3) | 0.6472 (4) | 0.3748 (3) | 0.0289 (7) | |
H4 | 0.8546 | 0.6511 | 0.3880 | 0.0245 (18)* | |
C5 | 0.7247 (3) | 0.5399 (3) | 0.3240 (3) | 0.0275 (6) | |
H5 | 0.8014 | 0.4696 | 0.3036 | 0.0245 (18)* | |
C6 | 0.5811 (3) | 0.5368 (3) | 0.3035 (3) | 0.0244 (6) | |
H6 | 0.5594 | 0.4623 | 0.2702 | 0.0245 (18)* | |
C7 | 0.3114 (3) | 0.6314 (3) | 0.3075 (3) | 0.0220 (6) | |
H71 | 0.2364 | 0.6808 | 0.3655 | 0.0245 (18)* | |
H72 | 0.2844 | 0.5241 | 0.3404 | 0.0245 (18)* | |
C8 | 0.3672 (3) | 0.8595 (3) | 0.0848 (3) | 0.0242 (6) | |
H81 | 0.3181 | 0.9267 | 0.1377 | 0.0245 (18)* | |
H82 | 0.4773 | 0.8525 | 0.0824 | 0.0245 (18)* | |
C9 | 0.1816 (3) | 0.9313 (3) | −0.0520 (3) | 0.0299 (7) | |
H91 | 0.1664 | 0.9774 | −0.1485 | 0.0245 (18)* | |
H92 | 0.1312 | 0.9979 | 0.0013 | 0.0245 (18)* | |
C10 | 0.1299 (3) | 0.7186 (3) | 0.1554 (3) | 0.0217 (6) | |
H101 | 0.0833 | 0.6181 | 0.2001 | 0.0245 (18)* | |
H102 | 0.0775 | 0.7833 | 0.2099 | 0.0245 (18)* | |
C11 | 0.1891 (3) | 0.6848 (3) | −0.0663 (3) | 0.0275 (6) | |
H111 | 0.1444 | 0.5836 | −0.0218 | 0.0245 (18)* | |
H112 | 0.1736 | 0.7264 | −0.1629 | 0.0245 (18)* | |
C12 | 0.3752 (3) | 0.6060 (3) | 0.0696 (3) | 0.0230 (6) | |
H121 | 0.4855 | 0.5965 | 0.0666 | 0.0245 (18)* | |
H122 | 0.3323 | 0.5039 | 0.1134 | 0.0245 (18)* | |
C13 | 0.4181 (3) | 0.8223 (3) | −0.1354 (3) | 0.0307 (7) | |
H131 | 0.5284 | 0.8137 | −0.1383 | 0.0245 (18)* | |
H132 | 0.4053 | 0.8669 | −0.2327 | 0.0245 (18)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I | 0.02658 (11) | 0.03900 (13) | 0.04832 (15) | 0.00253 (8) | −0.00951 (9) | −0.02950 (11) |
Br | 0.03848 (18) | 0.02750 (17) | 0.0393 (2) | −0.00699 (13) | −0.01011 (14) | −0.01016 (14) |
O1 | 0.0583 (19) | 0.099 (3) | 0.053 (2) | −0.0062 (18) | −0.0106 (14) | −0.0341 (19) |
O2 | 0.0603 (16) | 0.0328 (13) | 0.0465 (16) | −0.0065 (12) | −0.0284 (14) | −0.0117 (12) |
N1 | 0.0171 (11) | 0.0205 (11) | 0.0178 (12) | −0.0020 (9) | −0.0049 (9) | −0.0062 (9) |
N2 | 0.0337 (14) | 0.0234 (13) | 0.0271 (14) | −0.0051 (11) | −0.0131 (11) | −0.0036 (11) |
N3 | 0.0250 (12) | 0.0236 (12) | 0.0328 (14) | 0.0027 (10) | −0.0137 (11) | −0.0132 (11) |
N4 | 0.0303 (13) | 0.0309 (14) | 0.0244 (13) | 0.0048 (11) | −0.0106 (11) | −0.0141 (11) |
C1 | 0.0197 (13) | 0.0240 (14) | 0.0157 (14) | −0.0038 (11) | −0.0027 (11) | −0.0039 (11) |
C2 | 0.0194 (13) | 0.0235 (14) | 0.0219 (15) | −0.0032 (11) | −0.0028 (11) | −0.0083 (12) |
C3 | 0.0235 (14) | 0.0319 (16) | 0.0268 (16) | −0.0071 (12) | −0.0045 (12) | −0.0124 (13) |
C4 | 0.0192 (14) | 0.0404 (17) | 0.0244 (16) | −0.0029 (13) | −0.0054 (12) | −0.0066 (13) |
C5 | 0.0277 (15) | 0.0308 (16) | 0.0217 (16) | 0.0086 (13) | −0.0065 (12) | −0.0082 (13) |
C6 | 0.0313 (15) | 0.0227 (14) | 0.0217 (15) | 0.0006 (12) | −0.0073 (12) | −0.0100 (12) |
C7 | 0.0231 (14) | 0.0263 (14) | 0.0182 (14) | −0.0067 (11) | −0.0057 (11) | −0.0073 (12) |
C8 | 0.0302 (15) | 0.0172 (13) | 0.0273 (16) | −0.0069 (12) | −0.0096 (12) | −0.0063 (12) |
C9 | 0.0378 (17) | 0.0227 (15) | 0.0321 (18) | 0.0041 (13) | −0.0164 (14) | −0.0085 (13) |
C10 | 0.0172 (13) | 0.0216 (14) | 0.0301 (16) | 0.0003 (11) | −0.0070 (11) | −0.0124 (12) |
C11 | 0.0326 (16) | 0.0302 (16) | 0.0275 (16) | 0.0027 (13) | −0.0135 (13) | −0.0157 (13) |
C12 | 0.0264 (14) | 0.0239 (15) | 0.0227 (15) | 0.0062 (12) | −0.0066 (12) | −0.0141 (12) |
C13 | 0.0287 (15) | 0.0400 (18) | 0.0196 (16) | −0.0036 (13) | −0.0053 (12) | −0.0050 (13) |
I—C2 | 2.111 (3) | C3—C4 | 1.369 (4) |
O1—H11 | 0.78 (2) | C3—H3 | 0.9500 |
O1—H12 | 0.78 (2) | C4—C5 | 1.387 (4) |
O2—H21 | 0.78 (2) | C4—H4 | 0.9500 |
O2—H22 | 0.78 (2) | C5—C6 | 1.379 (4) |
N1—C7 | 1.510 (3) | C5—H5 | 0.9500 |
N1—C12 | 1.525 (3) | C6—H6 | 0.9500 |
N1—C8 | 1.527 (4) | C7—H71 | 0.9900 |
N1—C10 | 1.528 (3) | C7—H72 | 0.9900 |
N2—C8 | 1.446 (4) | C8—H81 | 0.9900 |
N2—C9 | 1.464 (4) | C8—H82 | 0.9900 |
N2—C13 | 1.466 (4) | C9—H91 | 0.9900 |
N3—C10 | 1.449 (4) | C9—H92 | 0.9900 |
N3—C9 | 1.468 (4) | C10—H101 | 0.9900 |
N3—C11 | 1.483 (3) | C10—H102 | 0.9900 |
N4—C12 | 1.444 (4) | C11—H111 | 0.9900 |
N4—C11 | 1.463 (4) | C11—H112 | 0.9900 |
N4—C13 | 1.470 (4) | C12—H121 | 0.9900 |
C1—C2 | 1.393 (4) | C12—H122 | 0.9900 |
C1—C6 | 1.397 (4) | C13—H131 | 0.9900 |
C1—C7 | 1.507 (4) | C13—H132 | 0.9900 |
C2—C3 | 1.380 (4) | ||
H11—O1—H12 | 105 (2) | N1—C7—H72 | 108.7 |
H21—O2—H22 | 103 (2) | H71—C7—H72 | 107.6 |
C7—N1—C12 | 111.5 (2) | N2—C8—N1 | 109.7 (2) |
C7—N1—C8 | 113.9 (2) | N2—C8—H81 | 109.7 |
C12—N1—C8 | 107.5 (2) | N1—C8—H81 | 109.7 |
C7—N1—C10 | 108.0 (2) | N2—C8—H82 | 109.7 |
C12—N1—C10 | 107.67 (19) | N1—C8—H82 | 109.7 |
C8—N1—C10 | 108.0 (2) | H81—C8—H82 | 108.2 |
C8—N2—C9 | 109.4 (2) | N2—C9—N3 | 112.2 (2) |
C8—N2—C13 | 109.9 (2) | N2—C9—H91 | 109.2 |
C9—N2—C13 | 108.7 (2) | N3—C9—H91 | 109.2 |
C10—N3—C9 | 108.8 (2) | N2—C9—H92 | 109.2 |
C10—N3—C11 | 108.6 (2) | N3—C9—H92 | 109.2 |
C9—N3—C11 | 108.3 (2) | H91—C9—H92 | 107.9 |
C12—N4—C11 | 109.4 (2) | N3—C10—N1 | 110.7 (2) |
C12—N4—C13 | 109.0 (2) | N3—C10—H101 | 109.5 |
C11—N4—C13 | 109.3 (2) | N1—C10—H101 | 109.5 |
C2—C1—C6 | 117.2 (2) | N3—C10—H102 | 109.5 |
C2—C1—C7 | 123.1 (2) | N1—C10—H102 | 109.5 |
C6—C1—C7 | 119.7 (2) | H101—C10—H102 | 108.1 |
C3—C2—C1 | 121.6 (2) | N4—C11—N3 | 111.5 (2) |
C3—C2—I | 116.74 (19) | N4—C11—H111 | 109.3 |
C1—C2—I | 121.55 (19) | N3—C11—H111 | 109.3 |
C4—C3—C2 | 119.7 (3) | N4—C11—H112 | 109.3 |
C4—C3—H3 | 120.2 | N3—C11—H112 | 109.3 |
C2—C3—H3 | 120.2 | H111—C11—H112 | 108.0 |
C3—C4—C5 | 120.7 (3) | N4—C12—N1 | 110.6 (2) |
C3—C4—H4 | 119.6 | N4—C12—H121 | 109.5 |
C5—C4—H4 | 119.6 | N1—C12—H121 | 109.5 |
C6—C5—C4 | 119.0 (3) | N4—C12—H122 | 109.5 |
C6—C5—H5 | 120.5 | N1—C12—H122 | 109.5 |
C4—C5—H5 | 120.5 | H121—C12—H122 | 108.1 |
C5—C6—C1 | 121.7 (2) | N2—C13—N4 | 111.0 (2) |
C5—C6—H6 | 119.1 | N2—C13—H131 | 109.4 |
C1—C6—H6 | 119.1 | N4—C13—H131 | 109.4 |
C1—C7—N1 | 114.4 (2) | N2—C13—H132 | 109.4 |
C1—C7—H71 | 108.7 | N4—C13—H132 | 109.4 |
N1—C7—H71 | 108.7 | H131—C13—H132 | 108.0 |
C1—C7—H72 | 108.7 | ||
C6—C1—C2—C3 | 2.2 (4) | C13—N2—C9—N3 | 58.9 (3) |
C7—C1—C2—C3 | 179.2 (2) | C10—N3—C9—N2 | 60.1 (3) |
C6—C1—C2—I | −174.31 (19) | C11—N3—C9—N2 | −57.7 (3) |
C7—C1—C2—I | 2.6 (4) | C9—N3—C10—N1 | −58.4 (3) |
C1—C2—C3—C4 | −0.4 (4) | C11—N3—C10—N1 | 59.3 (3) |
I—C2—C3—C4 | 176.3 (2) | C7—N1—C10—N3 | −178.5 (2) |
C2—C3—C4—C5 | −1.2 (4) | C12—N1—C10—N3 | −57.9 (3) |
C3—C4—C5—C6 | 0.9 (4) | C8—N1—C10—N3 | 57.9 (3) |
C4—C5—C6—C1 | 1.0 (4) | C12—N4—C11—N3 | 61.0 (3) |
C2—C1—C6—C5 | −2.5 (4) | C13—N4—C11—N3 | −58.2 (3) |
C7—C1—C6—C5 | −179.6 (3) | C10—N3—C11—N4 | −60.8 (3) |
C2—C1—C7—N1 | 101.8 (3) | C9—N3—C11—N4 | 57.2 (3) |
C6—C1—C7—N1 | −81.3 (3) | C11—N4—C12—N1 | −59.5 (3) |
C12—N1—C7—C1 | 75.0 (3) | C13—N4—C12—N1 | 59.9 (3) |
C8—N1—C7—C1 | −46.9 (3) | C7—N1—C12—N4 | 175.9 (2) |
C10—N1—C7—C1 | −166.8 (2) | C8—N1—C12—N4 | −58.6 (3) |
C9—N2—C8—N1 | 59.6 (3) | C10—N1—C12—N4 | 57.6 (3) |
C13—N2—C8—N1 | −59.8 (3) | C8—N2—C13—N4 | 61.1 (3) |
C7—N1—C8—N2 | −178.0 (2) | C9—N2—C13—N4 | −58.7 (3) |
C12—N1—C8—N2 | 57.9 (3) | C12—N4—C13—N2 | −60.6 (3) |
C10—N1—C8—N2 | −58.0 (3) | C11—N4—C13—N2 | 58.9 (3) |
C8—N2—C9—N3 | −61.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···Br | 0.77 (3) | 2.53 (3) | 3.297 (4) | 172 (3) |
O1—H12···N3i | 0.77 (3) | 2.72 (3) | 3.390 (5) | 146 (4) |
O2—H21···Br | 0.78 (3) | 2.61 (3) | 3.381 (4) | 168 (4) |
O2—H22···Brii | 0.79 (3) | 2.65 (3) | 3.433 (4) | 174 (3) |
C3—H3···Iiii | 0.95 | 3.31 | 4.237 (4) | 166 |
C5—H5···Briv | 0.95 | 3.05 | 3.924 (4) | 153 |
C6—H6···N4v | 0.95 | 2.73 | 3.558 (5) | 146 |
C7—H72···Br | 0.99 | 2.99 | 3.872 (4) | 149 |
C8—H82···O1v | 0.99 | 2.78 | 3.640 (5) | 145 |
C9—H91···O2vi | 0.99 | 2.40 | 3.326 (5) | 156 |
C10—H101···Br | 0.99 | 2.97 | 3.875 (4) | 153 |
C10—H102···O2vii | 0.99 | 2.47 | 3.459 (5) | 174 |
C12—H121···O1v | 0.99 | 2.78 | 3.643 (5) | 146 |
C12—H122···Br | 0.99 | 3.07 | 3.952 (4) | 149 |
C13—H131···O1v | 0.99 | 2.56 | 3.481 (5) | 154 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y, −z+1; (iii) −x+1, −y+2, −z+1; (iv) x+1, y, z; (v) −x+1, −y+1, −z; (vi) x, y+1, z−1; (vii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C13H18IN4+·Br−·2H2O |
Mr | 473.15 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 9.084 (4), 9.500 (5), 10.495 (7) |
α, β, γ (°) | 69.28 (5), 75.47 (5), 83.76 (4) |
V (Å3) | 819.8 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.40 |
Crystal size (mm) | 0.28 × 0.15 × 0.14 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Numerical [crystal faces optimized with X-SHAPE (Stoe & Cie, 1997) and absorption correction with X-RED (Stoe & Cie, 1997)] |
Tmin, Tmax | 0.409, 0.610 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10405, 3820, 2865 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.061, 0.95 |
No. of reflections | 3820 |
No. of parameters | 205 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.50, −1.07 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), SHELXS97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···Br | 0.77 (3) | 2.53 (3) | 3.297 (4) | 172 (3) |
O1—H12···N3i | 0.77 (3) | 2.72 (3) | 3.390 (5) | 146 (4) |
O2—H21···Br | 0.78 (3) | 2.61 (3) | 3.381 (4) | 168 (4) |
O2—H22···Brii | 0.79 (3) | 2.65 (3) | 3.433 (4) | 174 (3) |
C3—H3···Iiii | 0.95 | 3.31 | 4.237 (4) | 166 |
C5—H5···Briv | 0.95 | 3.05 | 3.924 (4) | 153 |
C6—H6···N4v | 0.95 | 2.73 | 3.558 (5) | 146 |
C7—H72···Br | 0.99 | 2.99 | 3.872 (4) | 149 |
C8—H82···O1v | 0.99 | 2.78 | 3.640 (5) | 145 |
C9—H91···O2vi | 0.99 | 2.40 | 3.326 (5) | 156 |
C10—H101···Br | 0.99 | 2.97 | 3.875 (4) | 153 |
C10—H102···O2vii | 0.99 | 2.47 | 3.459 (5) | 174 |
C12—H121···O1v | 0.99 | 2.78 | 3.643 (5) | 146 |
C12—H122···Br | 0.99 | 3.07 | 3.952 (4) | 149 |
C13—H131···O1v | 0.99 | 2.56 | 3.481 (5) | 154 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y, −z+1; (iii) −x+1, −y+2, −z+1; (iv) x+1, y, z; (v) −x+1, −y+1, −z; (vi) x, y+1, z−1; (vii) −x, −y+1, −z+1. |
In the quaternary ammonium salt, hexamethylenetetramine is N–alkylated by an ortho–iodobenzyl moiety. The positive charge of the ammonium centre atom is counterbalanced by a bromide ion (Fig. 1). Intramolecular bond lengths and angles are normal.
The bromide ions are embedded into an environment of 7 hydrogen–bond donors (CIF: the _geom_special_details item for the applied criteria). One hemisphere around the anion contains three O—H donors, the other hemisphere is established by four C—H···Br contacts. Of these, three bonds have methylene functions as donors which are in α–position to the quaternary ammonium centre (Fig. 1), the fourth stemming from a phenyl–CH. The O2 donors are part of OH2Br2H2O rhombs (Fig. 2). All the water molecules are close to the boundary planes of the chosen unit cell. There are no hydrogen–bonded contacts between water molecules. Instead, the acceptor functions of the O atoms are occupied by C—H donors. Again, there is a predominance of α–methylene donors. The acceptor capability of the amine–N atoms is less pronounced than that of the anion and the water–O atoms. There are relatively long bonds from water (N3) and phenyl–CH donors (N4), whereas N2 is not found as an acceptor within the applied criteria.