N,N,N′,N′-Tetra­methyl­strept­amine 2,4,6-orthoformate hydro­chloride

In the title compound, rac-(1s,3s,5R,6r,7S,8R,9S)-8,9-bis­(di­methyl­amino)-2,4,10-trioxatri­cyclo­[3.3.1.1^3,7]­decan-6-ol hydro­chloride, C₁₁H₂₁N₂O₄⁺·Cl⁻, there is an intramolecular asymmetric hydrogen-bond system N—H...N and a further classical hydrogen bond O—H...Cl⁻. The structure is pseudo-A-centred.

Key indicators

• Single-crystal X-ray study
• T = 143 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.050
• wR factor = 0.135
• Data-to-parameter ratio = 17.0

checkCIF results

No syntax errors found


 Alert Level A:



PLAT_113  Alert A ADDSYM Suggests Possible Pseudo/New Spacegroup       C2/m

Author response: The C-centring is only approximate, as can be seen from an inspection of the reflection intensities, and in Fig. 2.

 Alert Level B:



PLAT_110  Alert B ADDSYM Detects Potential Lattice Centering or Halving   ?

Author response: see above

 Alert Level C:



ABSTM_02  Alert C The ratio of Tmax/Tmin expected RT(exp) is > 1.10
          Absorption corrections should be applied.
          Tmin and Tmax expected:      0.868     0.956
          RT(exp) =      1.101


 1 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

We have studied the reactions of a number of derivatives of the synaxial diaminoalcohol (1) (Beckmann, 1998; Dean, 2000). The system is of interest in the context of enzyme mechanism and efficiency because of the close and fixed geometrical relationship between the two amino groups and the axial oxygen centre, and we have reported the crystal and molecular structure of (1) in the previous paper (Beckmann et al., 2003). We report here the structure of the chloride of the conjugate acid, (1H⁺·Cl⁻), and the different hydrogen-bonding arrangement in the ammonium cation.

In contrast to the diaminoalcohol (1), which has an internal hydrogen bond between the alcohol OH group and one of the dimethylamino groups, the intramolecular hydrogen bond in the conjugate acid (1H⁺) is unsymmetrically shared (Table 2 and Fig. 1) between the two amino groups. The angle N—H···N is 146° and the H atom is also relatively close to the neighbouring axial hydroxy-group O atom [H···O = 2.44 (3) Å]. Despite the narrow N—H···O angle, this could be regarded as the minor component of a highly asymmetric three-centre hydrogen bond. The hydroxy group is itself involved in a hydrogen bond to the chloride anion. An extensive system of non-classical hydrogen bonds (Table 2) links the residues to form a three-dimensional network (Fig. 2).

The bond lengths at the protonated nitrogen N1 are as expected longer than those at N2 (Table 1).

S2. Experimental

Crystals of compound (1H⁺·Cl⁻) (Brown & Kirby, 1997) were grown from a saturated solution in ethanol.

S3. Refinement

H atoms bonded to N and O atoms were identified in a difference synthesis and refined freely. Methyl H atoms were similarly identified, the methyl groups then idealized (C—H = 0.98 Å, all angles 109.5°) and refined as rigid groups allowed to rotate but not tip. Other H atoms were included using a riding model with fixed C—H bond lengths of 1.00 Å; U_iso(H) values were fixed at 1.2U_eq of the parent atom. The structure is pseudo-A-centred; the higher symmetry cell, corresponding after reorientation to space group C2/m, would however require the cation to display mirror symmetry, which is only approximate in the true structure (cf. Fig. 2). Furthermore, a large number of highly significant reflections are observed that do not correspond to a centred lattice.

Computing details

Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The cation of the title compound in the crystal. Ellipsoids are shown at the 50% probability level. H-atom radii are arbitrary.
	Fig. 2. Packing diagram of the title compound showing hydrogen bonds as thin dashed lines. The view direction is perpendicular to the bc plane.

(I)

Crystal data

C11H21N2O4^+·Cl^−	F(000) = 600
Mr = 280.75	Dx = 1.432 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.804 (2) Å	Cell parameters from 52 reflections
b = 9.730 (2) Å	θ = 10–11.5°
c = 13.896 (3) Å	µ = 0.30 mm^−1
β = 100.82 (2)°	T = 143 K
V = 1302.1 (5) Å^3	Tablet, colourless
Z = 4	0.50 × 0.40 × 0.15 mm

Data collection

Stoe STADI-4 diffractometer	Rint = 0.021
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 3.2°
Graphite monochromator	h = −12→1
ω/θ scans	k = 0→12
3416 measured reflections	l = −17→18
2977 independent reflections	3 standard reflections every 60 min
2090 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0544P)^2 + 0.641P] where P = (Fo^2 + 2Fc^2)/3
2977 reflections	(Δ/σ)max < 0.001
175 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

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.

Non-bonded distances:

2.8633 (0.0025) O1 - N1 2.9794 (0.0026) O1 - N2 2.5615 (0.0032) C8 - C9 2.5547 (0.0030) C6 - C9 2.5840 (0.0032) C6 - C8

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.

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

	x	y	z	Uiso*/Ueq
C1	0.6876 (2)	0.3646 (3)	0.29236 (15)	0.0243 (5)
H1	0.6376	0.2747	0.2808	0.029*
C3	0.8165 (2)	0.5056 (2)	0.41368 (15)	0.0257 (5)
H3	0.8524	0.5111	0.4858	0.031*
C5	0.6682 (2)	0.6162 (3)	0.28395 (15)	0.0249 (5)
H5	0.6041	0.6962	0.2676	0.030*
C6	0.5866 (2)	0.4825 (3)	0.26452 (15)	0.0273 (5)
H6	0.5161	0.4795	0.3079	0.033*
C7	0.8862 (2)	0.5063 (2)	0.26162 (14)	0.0187 (4)
H7	0.9688	0.5106	0.2290	0.022*
C8	0.7914 (2)	0.6299 (2)	0.23015 (15)	0.0214 (5)
H8	0.8436	0.7158	0.2532	0.026*
C9	0.8109 (2)	0.3675 (2)	0.23805 (14)	0.0185 (4)
H9	0.8766	0.2921	0.2647	0.022*
C11	0.8924 (2)	0.3255 (3)	0.08160 (16)	0.0264 (5)
H11A	0.9642	0.3933	0.1068	0.032*
H11B	0.8647	0.3363	0.0105	0.032*
H11C	0.9291	0.2327	0.0966	0.032*
C12	0.6720 (2)	0.2289 (3)	0.10228 (17)	0.0319 (6)
H12A	0.7109	0.1470	0.1383	0.038*
H12B	0.6599	0.2115	0.0317	0.038*
H12C	0.5818	0.2505	0.1193	0.038*
C13	0.6369 (3)	0.7297 (3)	0.08771 (18)	0.0381 (7)
H13A	0.5518	0.6936	0.1058	0.046*
H13B	0.6234	0.7387	0.0163	0.046*
H13C	0.6583	0.8199	0.1181	0.046*
C14	0.8720 (2)	0.6830 (3)	0.08041 (17)	0.0294 (5)
H14A	0.8909	0.7796	0.0981	0.035*
H14B	0.8506	0.6741	0.0089	0.035*
H14C	0.9538	0.6274	0.1067	0.035*
N1	0.76874 (18)	0.3475 (2)	0.12896 (13)	0.0207 (4)
H02	0.732 (3)	0.438 (3)	0.103 (2)	0.054 (9)*
N2	0.75245 (18)	0.6348 (2)	0.12195 (12)	0.0220 (4)
O2	0.74755 (16)	0.37942 (17)	0.39475 (10)	0.0264 (4)
H01	0.431 (5)	0.481 (4)	0.163 (3)	0.087 (14)*
O4	0.72744 (17)	0.61697 (18)	0.38783 (11)	0.0293 (4)
O10	0.93126 (15)	0.51173 (16)	0.36659 (10)	0.0241 (4)
O1	0.51722 (17)	0.4677 (2)	0.16633 (12)	0.0357 (5)
Cl	0.22043 (5)	0.50808 (7)	0.18133 (5)	0.03420 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0248 (10)	0.0350 (13)	0.0139 (10)	−0.0068 (10)	0.0061 (8)	−0.0025 (9)
C3	0.0324 (11)	0.0289 (12)	0.0158 (9)	0.0006 (10)	0.0047 (8)	−0.0007 (9)
C5	0.0234 (10)	0.0349 (13)	0.0173 (10)	0.0102 (10)	0.0060 (8)	0.0010 (9)
C6	0.0192 (10)	0.0472 (15)	0.0177 (10)	0.0025 (10)	0.0092 (8)	0.0000 (10)
C7	0.0179 (9)	0.0243 (11)	0.0137 (9)	0.0005 (8)	0.0023 (7)	0.0013 (8)
C8	0.0216 (10)	0.0238 (12)	0.0192 (10)	0.0029 (8)	0.0049 (8)	0.0022 (9)
C9	0.0181 (9)	0.0251 (11)	0.0122 (9)	0.0005 (8)	0.0025 (7)	−0.0016 (8)
C11	0.0234 (11)	0.0344 (13)	0.0239 (11)	0.0012 (10)	0.0108 (9)	−0.0055 (10)
C12	0.0303 (12)	0.0428 (15)	0.0235 (11)	−0.0116 (11)	0.0070 (10)	−0.0109 (11)
C13	0.0337 (13)	0.0528 (18)	0.0285 (12)	0.0181 (12)	0.0075 (11)	0.0150 (12)
C14	0.0282 (12)	0.0342 (14)	0.0269 (12)	0.0010 (10)	0.0083 (10)	0.0106 (10)
N1	0.0175 (8)	0.0293 (11)	0.0159 (8)	−0.0008 (8)	0.0049 (7)	−0.0030 (8)
N2	0.0205 (8)	0.0304 (11)	0.0159 (8)	0.0065 (8)	0.0051 (7)	0.0067 (8)
O2	0.0363 (9)	0.0298 (9)	0.0142 (7)	−0.0038 (7)	0.0078 (6)	0.0016 (6)
O4	0.0382 (9)	0.0342 (10)	0.0168 (7)	0.0065 (8)	0.0086 (7)	−0.0031 (7)
O10	0.0250 (7)	0.0310 (9)	0.0147 (7)	−0.0002 (7)	−0.0005 (6)	−0.0005 (6)
O1	0.0157 (7)	0.0703 (14)	0.0211 (8)	0.0022 (8)	0.0038 (6)	−0.0019 (8)
Cl	0.0178 (3)	0.0400 (4)	0.0451 (4)	0.0018 (2)	0.0067 (2)	−0.0049 (3)

Geometric parameters (Å, º)

C1—O2	1.441 (2)	C9—N1	1.507 (2)
C1—C6	1.517 (3)	C9—H9	1.0000
C1—C9	1.541 (3)	C11—N1	1.499 (3)
C1—H1	1.0000	C11—H11A	0.9800
C3—O4	1.396 (3)	C11—H11B	0.9800
C3—O2	1.402 (3)	C11—H11C	0.9800
C3—O10	1.405 (3)	C12—N1	1.495 (3)
C3—H3	1.0000	C12—H12A	0.9800
C5—O4	1.451 (3)	C12—H12B	0.9800
C5—C6	1.524 (3)	C12—H12C	0.9800
C5—C8	1.541 (3)	C13—N2	1.470 (3)
C5—H5	1.0000	C13—H13A	0.9800
C6—O1	1.413 (3)	C13—H13B	0.9800
C6—H6	1.0000	C13—H13C	0.9800
C7—O10	1.444 (2)	C14—N2	1.477 (3)
C7—C8	1.533 (3)	C14—H14A	0.9800
C7—C9	1.544 (3)	C14—H14B	0.9800
C7—H7	1.0000	C14—H14C	0.9800
C8—N2	1.481 (3)	N1—H02	0.99 (3)
C8—H8	1.0000	O1—H01	0.85 (4)
O2—C1—C6	107.55 (18)	C1—C9—H9	108.3
O2—C1—C9	105.64 (16)	C7—C9—H9	108.3
C6—C1—C9	113.29 (18)	N1—C11—H11A	109.5
O2—C1—H1	110.1	N1—C11—H11B	109.5
C6—C1—H1	110.1	H11A—C11—H11B	109.5
C9—C1—H1	110.1	N1—C11—H11C	109.5
O4—C3—O2	112.06 (18)	H11A—C11—H11C	109.5
O4—C3—O10	111.32 (18)	H11B—C11—H11C	109.5
O2—C3—O10	110.48 (18)	N1—C12—H12A	109.5
O4—C3—H3	107.6	N1—C12—H12B	109.5
O2—C3—H3	107.6	H12A—C12—H12B	109.5
O10—C3—H3	107.6	N1—C12—H12C	109.5
O4—C5—C6	106.23 (18)	H12A—C12—H12C	109.5
O4—C5—C8	106.16 (17)	H12B—C12—H12C	109.5
C6—C5—C8	114.91 (18)	N2—C13—H13A	109.5
O4—C5—H5	109.8	N2—C13—H13B	109.5
C6—C5—H5	109.8	H13A—C13—H13B	109.5
C8—C5—H5	109.8	N2—C13—H13C	109.5
O1—C6—C1	110.02 (19)	H13A—C13—H13C	109.5
O1—C6—C5	113.54 (19)	H13B—C13—H13C	109.5
C1—C6—C5	107.73 (17)	N2—C14—H14A	109.5
O1—C6—H6	108.5	N2—C14—H14B	109.5
C1—C6—H6	108.5	H14A—C14—H14B	109.5
C5—C6—H6	108.5	N2—C14—H14C	109.5
O10—C7—C8	108.26 (16)	H14A—C14—H14C	109.5
O10—C7—C9	106.86 (16)	H14B—C14—H14C	109.5
C8—C7—C9	112.68 (17)	C12—N1—C11	107.97 (17)
O10—C7—H7	109.7	C12—N1—C9	112.99 (17)
C8—C7—H7	109.7	C11—N1—C9	111.58 (16)
C9—C7—H7	109.7	C12—N1—H02	114.9 (18)
N2—C8—C7	109.97 (17)	C11—N1—H02	104.0 (18)
N2—C8—C5	114.78 (17)	C9—N1—H02	105.1 (18)
C7—C8—C5	106.38 (17)	C13—N2—C14	107.11 (18)
N2—C8—H8	108.5	C13—N2—C8	112.64 (17)
C7—C8—H8	108.5	C14—N2—C8	109.56 (17)
C5—C8—H8	108.5	C3—O2—C1	111.47 (16)
N1—C9—C1	113.43 (16)	C3—O4—C5	111.46 (16)
N1—C9—C7	110.88 (17)	C3—O10—C7	110.44 (15)
C1—C9—C7	107.47 (17)	C6—O1—H01	109 (3)
N1—C9—H9	108.3
O2—C1—C6—O1	−175.87 (17)	O10—C7—C9—C1	59.6 (2)
C9—C1—C6—O1	67.8 (2)	C8—C7—C9—C1	−59.2 (2)
O2—C1—C6—C5	59.9 (2)	C1—C9—N1—C12	−47.8 (3)
C9—C1—C6—C5	−56.5 (2)	C7—C9—N1—C12	−168.80 (18)
O4—C5—C6—O1	177.72 (16)	C1—C9—N1—C11	−169.66 (19)
C8—C5—C6—O1	−65.2 (2)	C7—C9—N1—C11	69.3 (2)
O4—C5—C6—C1	−60.2 (2)	C7—C8—N2—C13	166.40 (19)
C8—C5—C6—C1	56.9 (2)	C5—C8—N2—C13	46.5 (3)
O10—C7—C8—N2	175.20 (16)	C7—C8—N2—C14	−74.5 (2)
C9—C7—C8—N2	−66.8 (2)	C5—C8—N2—C14	165.63 (19)
O10—C7—C8—C5	−59.9 (2)	O4—C3—O2—C1	59.9 (2)
C9—C7—C8—C5	58.0 (2)	O10—C3—O2—C1	−64.9 (2)
O4—C5—C8—N2	−178.51 (18)	C6—C1—O2—C3	−59.1 (2)
C6—C5—C8—N2	64.4 (2)	C9—C1—O2—C3	62.2 (2)
O4—C5—C8—C7	59.6 (2)	O2—C3—O4—C5	−61.0 (2)
C6—C5—C8—C7	−57.5 (2)	O10—C3—O4—C5	63.3 (2)
O2—C1—C9—N1	177.73 (17)	C6—C5—O4—C3	60.7 (2)
C6—C1—C9—N1	−64.8 (2)	C8—C5—O4—C3	−62.1 (2)
O2—C1—C9—C7	−59.4 (2)	O4—C3—O10—C7	−61.5 (2)
C6—C1—C9—C7	58.1 (2)	O2—C3—O10—C7	63.7 (2)
O10—C7—C9—N1	−175.92 (15)	C8—C7—O10—C3	60.5 (2)
C8—C7—C9—N1	65.3 (2)	C9—C7—O10—C3	−61.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H01···Cl	0.85 (4)	2.14 (5)	2.9821 (18)	170 (4)
N1—H02···N2	0.99 (3)	1.94 (3)	2.801 (3)	144 (3)
N1—H02···O1	0.99 (3)	2.44 (3)	2.863 (2)	105 (2)
C12—H12B···O2^i	0.98	2.40	3.283 (3)	150
C13—H13B···O4^ii	0.98	2.62	3.414 (3)	138
C3—H3···O10^iii	1.00	2.67	3.555 (3)	148
C11—H11C···O10^iv	0.98	2.55	3.516 (3)	169
C7—H7···Cl^v	1.00	2.67	3.654 (2)	167
C11—H11A···Cl^v	0.98	2.77	3.708 (2)	161
C14—H14C···Cl^v	0.98	2.87	3.839 (2)	170
C12—H12A···Cl^vi	0.98	2.82	3.685 (3)	148

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+2, −y+1, −z+1; (iv) −x+2, y−1/2, −z+1/2; (v) x+1, y, z; (vi) −x+1, y−1/2, −z+1/2.