N-(2-Iodo­phenyl­meth­yl)hexa­methyl­enetetra­minium bromide dihydrate

The title compound, C₁₃H₁₈IN₄⁺·Br⁻·2H₂O, is a quaternary ammonium salt derived from 2-iodo­benzyl bromide and hexa­methyl­enetetra­mine. Two water mol­ecules per asymmetric unit act as hydrogen-bond donors to the bromide anion. Direct cation–anion contacts are established via C—H donors, mainly from methyl­ene groups in the α position to the ammonium centre.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](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

---

S1. Comment

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.

Related literature

For synthesis of the title compound, see Angyal et al. (1949). For the crystal structure of a related compound, see Shao et al. (1982).

S2. Experimental

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.

S3. Refinement

The H atoms on C atoms were located in a difference map and refined as riding on their parent atoms with a common U_iso 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 U_iso 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.

Computing details

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).

Figures

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level. Hydrogen atoms are presented as a spheres of arbitrary radius. Hydrogen bonds are indicated as dashed lines.
	Fig. 2. The packing of title compound, viewed along [0 1 0]. Some of the hydrogen bonds with water donors are drawn as dashed lines.

N-(2-Iodophenylmethyl)hexamethylenetetraminium bromide dihydrate

Crystal data

C13H18IN4^+·Br^−·2H2O	V = 819.8 (8) Å^3
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

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0335P)^2] where P = (Fo^2 + 2Fc^2)/3
3820 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.50 e Å^−3
6 restraints	Δρmin = −1.07 e Å^−3

Special details

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°.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···N3^i	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···Br^ii	0.79 (3)	2.65 (3)	3.433 (4)	174 (3)
C3—H3···I^iii	0.95	3.31	4.237 (4)	166
C5—H5···Br^iv	0.95	3.05	3.924 (4)	153
C6—H6···N4^v	0.95	2.73	3.558 (5)	146
C7—H72···Br	0.99	2.99	3.872 (4)	149
C8—H82···O1^v	0.99	2.78	3.640 (5)	145
C9—H91···O2^vi	0.99	2.40	3.326 (5)	156
C10—H101···Br	0.99	2.97	3.875 (4)	153
C10—H102···O2^vii	0.99	2.47	3.459 (5)	174
C12—H121···O1^v	0.99	2.78	3.643 (5)	146
C12—H122···Br	0.99	3.07	3.952 (4)	149
C13—H131···O1^v	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.