(3aR,8bR)-(+)-1-Methyl-1,2,3,3a,4,8b-hexa­hydro­pyrrolo[2′,3′:3,4]cyclo­penta[1,2-b]pyridine-1,5-diium dichloride monohydrate

The title compound, C₁₁H₁₆N₂²⁺·2Cl⁻·H₂O, is a novel conformationally constrained tricyclic analogue of nicotine, in which the pyridine and pyrrolidine rings of the latter are bridged by a CH₂ group. As result of this bridge, these two rings are no longer approximately perpendicular as in various salts of nicotine.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.051
• wR factor = 0.092
• Data-to-parameter ratio = 22.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96

Author Response: Small amount of missing data due to detector angular setting and beam-stop cutoffs.

PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              H2 O

Author Response: Water molecule is hydrogen bonded to Cl1, which is inside unit cell.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           29.98
           From the CIF: _reflns_number_total               3554
           Count of symmetry unique reflns         2185
           Completeness (_total/calc)            162.65%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1369
           Fraction of Friedel pairs measured     0.627
           Are heavy atom types Z>Si present        yes

Author Response: checkCIF/PLATON estimated 1369 Friedel pairs, recalculation with SHELXL97 (MERG 3) showed that there were 1449 Friedel pairs.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   3 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT, SADABS and XPREP (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL.

(3aR,8bR)-(+)-1-Methyl-1,2,3,3a,4,8 b- hexahydropyrrolo[2',3':3,4]cyclopenta[1,2-b]pyridine-1,5-diium dichloride monohydrate

Crystal data

C11H16N2^2+·2Cl^−·H2O	F(000) = 560
Mr = 265.17	Dx = 1.358 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 988 reflections
a = 6.853 (3) Å	θ = 2.7–27.2°
b = 8.789 (4) Å	µ = 0.48 mm^−1
c = 21.537 (9) Å	T = 295 K
V = 1297.2 (10) Å^3	Prism, colourless
Z = 4	0.55 × 0.07 × 0.03 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3554 independent reflections
Radiation source: fine-focus sealed tube	2829 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ω scans	θmax = 30.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
Tmin = 0.92, Tmax = 0.99	k = −12→12
17008 measured reflections	l = −29→29

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0323P)^2 + 0.2916P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
3554 reflections	Δρmax = 0.23 e Å^−3
158 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 1449 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (7)

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.

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
Cl1	0.07129 (11)	0.92716 (8)	0.32361 (3)	0.0585 (2)
Cl2	0.87265 (8)	0.40559 (7)	0.45321 (3)	0.04544 (15)
N1	0.2661 (3)	0.6958 (2)	0.40512 (10)	0.0415 (5)
H1N	0.213 (4)	0.771 (3)	0.3811 (12)	0.050*
N2	0.5612 (3)	0.2368 (2)	0.37692 (9)	0.0365 (4)
H2N	0.654 (4)	0.284 (3)	0.4030 (11)	0.044*
C1	0.2824 (3)	0.5525 (2)	0.38371 (11)	0.0356 (5)
C2	0.3518 (3)	0.4403 (2)	0.42193 (9)	0.0298 (4)
C3	0.4022 (3)	0.4731 (3)	0.48276 (10)	0.0368 (5)
H3	0.4491	0.3976	0.5091	0.044*
C4	0.3808 (3)	0.6215 (3)	0.50338 (11)	0.0434 (6)
H4	0.4107	0.6466	0.5442	0.052*
C5	0.3155 (3)	0.7306 (3)	0.46339 (13)	0.0459 (6)
H5	0.3054	0.8308	0.4769	0.055*
C6	0.3534 (3)	0.2912 (2)	0.38838 (10)	0.0338 (5)
H6	0.2763	0.2144	0.4104	0.041*
C7	0.2667 (4)	0.3259 (3)	0.32312 (12)	0.0417 (6)
H7	0.1448	0.2695	0.3171	0.050*
C8	0.4210 (4)	0.2709 (3)	0.27764 (11)	0.0552 (7)
H8A	0.3998	0.1651	0.2666	0.066*
H8B	0.4204	0.3319	0.2401	0.066*
C9	0.6099 (4)	0.2901 (3)	0.31255 (11)	0.0496 (6)
H9A	0.7125	0.2284	0.2944	0.060*
H9B	0.6510	0.3957	0.3128	0.060*
C10	0.5792 (4)	0.0686 (3)	0.38457 (13)	0.0510 (6)
H10A	0.7071	0.0366	0.3718	0.077*
H10B	0.4828	0.0187	0.3594	0.077*
H10C	0.5594	0.0422	0.4274	0.077*
C11	0.2273 (4)	0.4999 (3)	0.32114 (12)	0.0506 (7)
H11A	0.3064	0.5488	0.2896	0.061*
H11B	0.0908	0.5207	0.3128	0.061*
O1	−0.2776 (4)	0.6796 (3)	0.36463 (12)	0.0777 (7)
H1OA	−0.175 (5)	0.742 (5)	0.3444 (15)	0.093*
H1OB	−0.211 (6)	0.612 (5)	0.3927 (17)	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0599 (4)	0.0469 (4)	0.0687 (4)	0.0044 (3)	−0.0048 (3)	0.0153 (3)
Cl2	0.0363 (3)	0.0445 (3)	0.0555 (3)	−0.0060 (3)	−0.0034 (3)	−0.0009 (3)
N1	0.0381 (11)	0.0300 (10)	0.0564 (14)	0.0017 (9)	0.0028 (10)	0.0018 (9)
N2	0.0342 (9)	0.0354 (10)	0.0399 (10)	−0.0012 (8)	−0.0003 (8)	−0.0085 (8)
C1	0.0278 (10)	0.0313 (11)	0.0478 (13)	−0.0009 (9)	0.0035 (10)	0.0016 (10)
C2	0.0259 (10)	0.0286 (11)	0.0350 (11)	−0.0021 (9)	0.0040 (8)	0.0022 (8)
C3	0.0314 (13)	0.0401 (12)	0.0389 (12)	−0.0003 (10)	0.0026 (9)	0.0016 (9)
C4	0.0352 (11)	0.0496 (15)	0.0456 (13)	−0.0045 (12)	0.0030 (11)	−0.0128 (11)
C5	0.0354 (12)	0.0344 (12)	0.0680 (18)	−0.0021 (10)	0.0088 (12)	−0.0126 (12)
C6	0.0333 (11)	0.0297 (10)	0.0384 (11)	−0.0025 (9)	0.0005 (10)	0.0017 (9)
C7	0.0410 (14)	0.0402 (13)	0.0438 (14)	−0.0033 (10)	−0.0101 (11)	−0.0032 (11)
C8	0.0689 (18)	0.0579 (16)	0.0387 (13)	−0.0024 (15)	−0.0035 (13)	−0.0080 (12)
C9	0.0509 (15)	0.0545 (15)	0.0435 (13)	−0.0048 (13)	0.0115 (12)	−0.0055 (11)
C10	0.0504 (15)	0.0363 (13)	0.0665 (16)	0.0099 (12)	−0.0021 (13)	−0.0055 (12)
C11	0.0617 (18)	0.0486 (14)	0.0416 (14)	0.0053 (13)	−0.0078 (13)	0.0066 (12)
O1	0.0680 (15)	0.0846 (17)	0.0805 (17)	−0.0093 (12)	−0.0130 (13)	0.0188 (13)

Geometric parameters (Å, º)

N1—C1	1.346 (3)	C3—H3	0.9300
N1—C5	1.336 (3)	C4—H4	0.9300
N2—C6	1.523 (3)	C5—H5	0.9300
N2—C9	1.501 (3)	C6—H6	0.9800
N2—C10	1.493 (3)	C7—H7	0.9800
C1—C2	1.370 (3)	C8—H8A	0.9700
C1—C11	1.474 (4)	C8—H8B	0.9700
C2—C3	1.385 (3)	C9—H9A	0.9700
C2—C6	1.497 (3)	C9—H9B	0.9700
C3—C4	1.385 (3)	C10—H10A	0.9600
C4—C5	1.364 (4)	C10—H10B	0.9600
C6—C7	1.556 (3)	C10—H10C	0.9600
C7—C8	1.520 (4)	C11—H11A	0.9700
C8—C9	1.507 (4)	C11—H11B	0.9700
C7—C11	1.553 (3)	O1—H1OA	0.99 (4)
N1—H1N	0.91 (3)	O1—H1OB	0.96 (4)
N2—H2N	0.95 (3)
C1—C2—C6	110.0 (2)	C8—C7—C11	114.6 (2)
C3—C2—C6	129.6 (2)	C8—C7—C6	104.7 (2)
C1—C11—C7	103.8 (2)	C11—C7—C6	106.5 (2)
C5—N1—C1	121.0 (2)	C8—C7—H7	110.3
C5—N1—H1N	117.8 (17)	C11—C7—H7	110.3
C1—N1—H1N	121.0 (17)	C6—C7—H7	110.3
C10—N2—C9	113.14 (18)	C9—C8—C7	103.92 (19)
C10—N2—C6	111.78 (18)	C9—C8—H8A	111.0
C9—N2—C6	105.04 (18)	C7—C8—H8A	111.0
C10—N2—H2N	108.3 (15)	C9—C8—H8B	111.0
C9—N2—H2N	105.1 (15)	C7—C8—H8B	111.0
C6—N2—H2N	113.4 (15)	H8A—C8—H8B	109.0
N1—C1—C2	119.8 (2)	N2—C9—C8	103.6 (2)
N1—C1—C11	125.8 (2)	N2—C9—H9A	111.0
C2—C1—C11	114.4 (2)	C8—C9—H9A	111.0
C1—C2—C3	120.4 (2)	N2—C9—H9B	111.0
C4—C3—C2	118.2 (2)	C8—C9—H9B	111.0
C4—C3—H3	120.9	H9A—C9—H9B	109.0
C2—C3—H3	120.9	N2—C10—H10A	109.5
C5—C4—C3	119.6 (2)	N2—C10—H10B	109.5
C5—C4—H4	120.2	H10A—C10—H10B	109.5
C3—C4—H4	120.2	N2—C10—H10C	109.5
N1—C5—C4	121.0 (2)	H10A—C10—H10C	109.5
N1—C5—H5	119.5	H10B—C10—H10C	109.5
C4—C5—H5	119.5	C1—C11—H11A	111.0
C2—C6—N2	111.14 (17)	C7—C11—H11A	111.0
C2—C6—C7	105.18 (17)	C1—C11—H11B	111.0
N2—C6—C7	105.80 (18)	C7—C11—H11B	111.0
C2—C6—H6	111.5	H11A—C11—H11B	109.0
N2—C6—H6	111.5	H1OA—O1—H1OB	106 (3)
C7—C6—H6	111.5
C1—C2—C6—C7	−1.9 (2)	C2—C1—C11—C7	1.4 (3)
C1—C2—C6—N2	112.2 (2)	C1—C11—C7—C8	−117.7 (2)
C2—C6—C7—C8	124.5 (2)	C1—C11—C7—C6	−2.5 (3)
C6—C7—C8—C9	−29.4 (3)	C3—C2—C6—N2	−70.2 (3)
C5—N1—C1—C2	−0.4 (3)	C3—C2—C6—C7	175.8 (2)
C5—N1—C1—C11	178.2 (2)	C10—N2—C6—C2	141.81 (19)
N1—C1—C2—C3	1.1 (3)	C9—N2—C6—C2	−95.1 (2)
C11—C1—C2—C3	−177.6 (2)	C10—N2—C6—C7	−104.5 (2)
N1—C1—C2—C6	179.0 (2)	C9—N2—C6—C7	18.5 (2)
C11—C1—C2—C6	0.3 (3)	C11—C7—C6—C2	2.7 (3)
C1—C2—C3—C4	−0.2 (3)	C8—C7—C6—N2	6.7 (2)
C6—C2—C3—C4	−177.7 (2)	C11—C7—C6—N2	−115.0 (2)
C2—C3—C4—C5	−1.4 (3)	C11—C7—C8—C9	86.9 (3)
C1—N1—C5—C4	−1.2 (4)	C10—N2—C9—C8	85.1 (3)
C3—C4—C5—N1	2.1 (4)	C6—N2—C9—C8	−37.1 (2)
N1—C1—C11—C7	−177.2 (2)	C7—C8—C9—N2	41.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1	0.91 (3)	2.09 (3)	3.000 (2)	174 (2)
N2—H2N···Cl2	0.95 (3)	2.13 (3)	3.075 (2)	174 (2)
O1—H1OA···Cl1	0.99 (4)	2.39 (4)	3.351 (3)	164 (3)
O1—H1OB···Cl2^i	0.96 (4)	2.31 (4)	3.240 (3)	163 (3)

Symmetry code: (i) x−1, y, z.