Pargyl­ine hydro­chloride: a monoclinic form

In the crystal structure of the title compound, N-benzyl-N-methyl­prop-2-yn-1-aminium chloride, C₁₁H₁₄N⁺·Cl⁻, the asymmetric unit contains two independent enantiomeric cations related by a pseudo-center of symmetry. In both cations, the protonation occurs at the N atom, and the side chains are roughly perpendicular to the benzene rings. In addition to the conventional N—H...Cl hydrogen bonds, there are several weak hydrogen bonds of the type C—H...Cl. The cations are arranged head-to-head and tail-to-tail, producing hydro­philic and hydro­phobic areas

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.016 Å
• R factor = 0.072
• wR factor = 0.206
• Data-to-parameter ratio = 8.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............      64.99 Deg.

Author Response: ...'see _exptl_special_details'

PLAT035_ALERT_1_A No _chemical_absolute_configuration info given .          ?

Author Response: ...inapplicable

Alert level B
PLAT340_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ...         16

Alert level C
REFNR01_ALERT_3_C  Ratio of reflections to parameters is < 8 for a
            non-centrosymmetric structure, where ZMAX < 18
            sine(theta)/lambda                0.5878
            Proportion of unique data used    1.0000
            Ratio reflections to parameters   7.9585
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.410
           From the CIF: _refine_ls_abs_structure_Flack_su    0.100
THETM01_ALERT_3_C  The value of sine(theta_max)/wavelength is less than 0.590
            Calculated sin(theta_max)/wavelength =    0.5878
PLAT023_ALERT_3_C Resolution (too) Low [sin(th)/Lambda < 0.6].....      64.99 Deg.
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.41
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.96
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         10
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C11 H14 N
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              Cl
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              Cl

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           64.99
           From the CIF: _reflns_number_total               1918
           Count of symmetry unique reflns         1918
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present          yes

   2 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  10 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
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: Picker Operating Manual (Picker, 1967); cell refinement: Picker; data reduction: DATRDN (Stewart, 1976); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

N-benzyl-N-methylprop-2-yn-1-aminium chloride

Crystal data

C11H14N^+·Cl^−	F(000) = 416
Mr = 195.68	Dx = 1.170 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
a = 5.739 (2) Å	Cell parameters from 32 reflections
b = 33.684 (5) Å	θ = 19–43°
c = 6.003 (2) Å	µ = 2.67 mm^−1
β = 106.79 (4)°	T = 294 K
V = 1111.0 (6) Å^3	Needle, colorless
Z = 4	0.28 × 0.09 × 0.05 mm

Data collection

Picker FACS-1 four-circle diffractometer	1651 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Ni filtered radiation monochromator	θmax = 65.0°, θmin = 2.6°
ω/2θ scans	h = −6→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→39
Tmin = 0.747, Tmax = 0.870	l = 0→7
2105 measured reflections	3 standard reflections every 100 reflections
1918 independent reflections	intensity decay: 2.7%

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)] = 0.072	H-atom parameters constrained
wR(F^2) = 0.206	w = 1/[σ^2(Fo^2) + (0.1459P)^2 + 0.5682P] where P = (Fo^2 + 2Fc^2)/3
S = 1.52	(Δ/σ)max < 0.001
1918 reflections	Δρmax = 0.73 e Å^−3
241 parameters	Δρmin = −0.49 e Å^−3
1 restraint	Absolute structure: Flack (1983), 0 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.41 (10)

Special details

Experimental. PICKER FACS-1 mechanical limit does not allow for data collection above θ = 65°

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
C1A	1.2239 (13)	0.3584 (3)	0.4477 (14)	0.0552 (18)
C2A	1.3257 (19)	0.3715 (3)	0.6749 (17)	0.072 (2)
H2A	1.4783	0.3624	0.7611	0.089 (7)*
C3A	1.199 (2)	0.3980 (3)	0.7717 (19)	0.086 (3)
H3A	1.2685	0.4071	0.9226	0.089 (7)*
C4A	0.974 (3)	0.4110 (3)	0.650 (3)	0.093 (3)
H4A	0.8879	0.4282	0.7190	0.089 (7)*
C5A	0.874 (2)	0.3987 (4)	0.425 (2)	0.086 (3)
H5A	0.7213	0.4080	0.3414	0.089 (7)*
C6A	0.9983 (17)	0.3724 (3)	0.320 (2)	0.071 (2)
H6A	0.9303	0.3644	0.1666	0.089 (7)*
C7A	1.3670 (15)	0.3290 (3)	0.3478 (16)	0.0584 (19)
H7A1	1.3818	0.3393	0.2018	0.089 (7)*
H7A2	1.5297	0.3267	0.4540	0.089 (7)*
N8A	1.2565 (10)	0.2890 (2)	0.3066 (10)	0.0489 (14)
H8A	1.1140	0.2914	0.1912	0.089 (7)*
C9A	1.4155 (17)	0.2621 (3)	0.2196 (17)	0.068 (2)
H9A1	1.4553	0.2744	0.0910	0.079 (11)*
H9A2	1.3319	0.2376	0.1696	0.079 (11)*
H9A3	1.5623	0.2570	0.3420	0.079 (11)*
C10A	1.1967 (16)	0.2717 (3)	0.5139 (14)	0.0534 (19)
H10A	1.3452	0.2692	0.6411	0.089 (7)*
H10B	1.0892	0.2897	0.5630	0.089 (7)*
C11A	1.0840 (15)	0.2340 (3)	0.4678 (15)	0.0569 (19)
C12A	0.9898 (17)	0.2021 (3)	0.4347 (17)	0.066 (2)
H12A	0.9164	0.1773	0.4091	0.089 (7)*
C1B	0.4260 (15)	0.0364 (3)	0.8367 (15)	0.0583 (19)
C2B	0.3384 (18)	0.0230 (3)	0.6085 (16)	0.071 (2)
H2B	0.1882	0.0320	0.5168	0.089 (7)*
C3B	0.466 (3)	−0.0031 (4)	0.516 (2)	0.092 (3)
H3B	0.4056	−0.0111	0.3612	0.089 (7)*
C4B	0.684 (3)	−0.0174 (4)	0.651 (3)	0.098 (4)
H4B	0.7674	−0.0360	0.5892	0.089 (7)*
C5B	0.781 (2)	−0.0048 (4)	0.877 (3)	0.097 (4)
H5B	0.9321	−0.0139	0.9663	0.089 (7)*
C6B	0.6490 (18)	0.0219 (3)	0.967 (2)	0.078 (3)
H6B	0.7120	0.0302	1.1206	0.089 (7)*
C7B	0.2834 (15)	0.0661 (3)	0.9339 (15)	0.059 (2)
H7B1	0.1213	0.0685	0.8266	0.089 (7)*
H7B2	0.2668	0.0560	1.0797	0.089 (7)*
N8B	0.3952 (10)	0.1063 (2)	0.9752 (10)	0.0498 (14)
H8B	0.5370	0.1040	1.0916	0.089 (7)*
C9B	0.2331 (18)	0.1339 (3)	1.0587 (18)	0.070 (3)
H9B1	0.0867	0.1387	0.9351	0.079 (11)*
H9B2	0.3162	0.1586	1.1061	0.079 (11)*
H9B3	0.1926	0.1222	1.1884	0.079 (11)*
C10B	0.4570 (15)	0.1217 (3)	0.7645 (14)	0.057 (2)
H10C	0.5687	0.1036	0.7227	0.089 (7)*
H10D	0.3102	0.1232	0.6345	0.089 (7)*
C11B	0.5694 (14)	0.1615 (3)	0.8106 (13)	0.0537 (18)
C12B	0.6659 (19)	0.1933 (4)	0.8440 (17)	0.064 (2)
H12B	0.7409	0.2180	0.8700	0.089 (7)*
Cl1A	0.8221 (3)	0.29581 (8)	−0.1251 (3)	0.0584 (6)
Cl2B	0.8292 (3)	0.10017 (8)	1.4032 (3)	0.0587 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.050 (4)	0.052 (4)	0.067 (5)	−0.005 (3)	0.022 (4)	0.004 (4)
C2A	0.085 (6)	0.070 (6)	0.064 (5)	−0.002 (5)	0.029 (5)	0.001 (4)
C3A	0.113 (9)	0.078 (7)	0.071 (6)	0.012 (6)	0.035 (6)	0.000 (5)
C4A	0.113 (9)	0.055 (6)	0.129 (10)	−0.005 (6)	0.063 (8)	−0.015 (6)
C5A	0.067 (5)	0.087 (8)	0.106 (8)	0.001 (6)	0.025 (6)	−0.016 (6)
C6A	0.060 (5)	0.059 (5)	0.089 (6)	0.001 (4)	0.016 (5)	−0.008 (5)
C7A	0.052 (4)	0.061 (5)	0.069 (5)	−0.004 (4)	0.028 (4)	0.006 (4)
N8A	0.044 (3)	0.062 (4)	0.048 (3)	0.002 (3)	0.025 (2)	0.001 (3)
C9A	0.056 (5)	0.087 (7)	0.069 (5)	0.006 (5)	0.032 (4)	−0.008 (5)
C10A	0.062 (5)	0.057 (5)	0.049 (4)	0.006 (4)	0.029 (4)	0.006 (3)
C11A	0.053 (4)	0.057 (5)	0.068 (5)	0.002 (4)	0.028 (4)	0.006 (4)
C12A	0.065 (5)	0.058 (5)	0.085 (6)	0.001 (4)	0.034 (5)	0.004 (4)
C1B	0.062 (5)	0.061 (5)	0.056 (4)	−0.001 (4)	0.024 (4)	0.006 (4)
C2B	0.081 (6)	0.072 (6)	0.061 (5)	−0.008 (5)	0.019 (4)	0.001 (4)
C3B	0.119 (10)	0.068 (7)	0.091 (8)	−0.002 (7)	0.036 (7)	−0.014 (6)
C4B	0.119 (10)	0.059 (6)	0.133 (11)	−0.002 (6)	0.062 (9)	−0.019 (7)
C5B	0.071 (6)	0.059 (7)	0.154 (13)	0.019 (5)	0.023 (7)	0.004 (7)
C6B	0.068 (6)	0.081 (7)	0.078 (6)	−0.002 (5)	0.012 (5)	0.010 (5)
C7B	0.057 (4)	0.071 (6)	0.055 (4)	−0.007 (4)	0.025 (4)	0.005 (4)
N8B	0.042 (3)	0.067 (4)	0.046 (3)	0.003 (3)	0.020 (2)	0.004 (3)
C9B	0.071 (6)	0.078 (7)	0.078 (6)	0.009 (5)	0.049 (5)	0.000 (5)
C10B	0.046 (4)	0.081 (6)	0.052 (4)	−0.018 (4)	0.024 (3)	−0.014 (4)
C11B	0.049 (4)	0.069 (5)	0.047 (4)	0.003 (4)	0.020 (3)	0.005 (4)
C12B	0.066 (5)	0.066 (6)	0.065 (5)	0.005 (4)	0.025 (4)	0.006 (4)
Cl1A	0.0487 (11)	0.0739 (14)	0.0516 (9)	−0.0019 (9)	0.0130 (7)	0.0007 (9)
Cl2B	0.0509 (11)	0.0754 (14)	0.0496 (9)	−0.0023 (9)	0.0141 (7)	0.0012 (9)

Geometric parameters (Å, º)

C1A—C2A	1.391 (12)	C1B—C6B	1.383 (13)
C1A—C6A	1.384 (12)	C1B—C2B	1.392 (12)
C1A—C7A	1.516 (12)	C1B—C7B	1.511 (13)
C2A—C3A	1.383 (14)	C2B—C3B	1.362 (16)
C2A—H2A	0.9300	C2B—H2B	0.9300
C3A—C4A	1.360 (17)	C3B—C4B	1.365 (19)
C3A—H3A	0.9300	C3B—H3B	0.9300
C4A—C5A	1.368 (17)	C4B—C5B	1.377 (19)
C4A—H4A	0.9300	C4B—H4B	0.9300
C5A—C6A	1.398 (15)	C5B—C6B	1.383 (17)
C5A—H5A	0.9300	C5B—H5B	0.9300
C6A—H6A	0.9300	C6B—H6B	0.9300
C7A—N8A	1.478 (11)	C7B—N8B	1.487 (11)
C7A—H7A1	0.9700	C7B—H7B1	0.9700
C7A—H7A2	0.9700	C7B—H7B2	0.9700
N8A—C9A	1.484 (10)	N8B—C10B	1.502 (9)
N8A—C10A	1.502 (9)	N8B—C9B	1.502 (10)
N8A—H8A	0.9100	N8B—H8B	0.9100
C9A—H9A1	0.9600	C9B—H9B1	0.9600
C9A—H9A2	0.9600	C9B—H9B2	0.9600
C9A—H9A3	0.9600	C9B—H9B3	0.9600
C10A—C11A	1.414 (12)	C10B—C11B	1.478 (13)
C10A—H10A	0.9700	C10B—H10C	0.9700
C10A—H10B	0.9700	C10B—H10D	0.9700
C11A—C12A	1.194 (13)	C11B—C12B	1.196 (14)
C12A—H12A	0.9300	C12B—H12B	0.9300
C2A—C1A—C6A	119.7 (9)	C6B—C1B—C2B	117.0 (10)
C2A—C1A—C7A	118.2 (8)	C6B—C1B—C7B	122.1 (8)
C6A—C1A—C7A	122.1 (8)	C2B—C1B—C7B	120.9 (8)
C1A—C2A—C3A	119.6 (10)	C3B—C2B—C1B	122.0 (10)
C1A—C2A—H2A	120.2	C3B—C2B—H2B	119.0
C3A—C2A—H2A	120.2	C1B—C2B—H2B	119.0
C4A—C3A—C2A	121.1 (11)	C2B—C3B—C4B	119.4 (12)
C4A—C3A—H3A	119.5	C2B—C3B—H3B	120.3
C2A—C3A—H3A	119.5	C4B—C3B—H3B	120.3
C3A—C4A—C5A	119.6 (11)	C3B—C4B—C5B	121.3 (12)
C3A—C4A—H4A	120.2	C3B—C4B—H4B	119.4
C5A—C4A—H4A	120.2	C5B—C4B—H4B	119.4
C6A—C5A—C4A	121.1 (12)	C6B—C5B—C4B	118.3 (12)
C6A—C5A—H5A	119.5	C6B—C5B—H5B	120.8
C4A—C5A—H5A	119.5	C4B—C5B—H5B	120.8
C5A—C6A—C1A	118.9 (10)	C5B—C6B—C1B	122.0 (11)
C5A—C6A—H6A	120.5	C5B—C6B—H6B	119.0
C1A—C6A—H6A	120.5	C1B—C6B—H6B	119.0
N8A—C7A—C1A	113.9 (6)	N8B—C7B—C1B	114.3 (6)
N8A—C7A—H7A1	108.8	N8B—C7B—H7B1	108.7
C1A—C7A—H7A1	108.8	C1B—C7B—H7B1	108.7
N8A—C7A—H7A2	108.8	N8B—C7B—H7B2	108.7
C1A—C7A—H7A2	108.8	C1B—C7B—H7B2	108.7
H7A1—C7A—H7A2	107.7	H7B1—C7B—H7B2	107.6
C7A—N8A—C9A	109.7 (6)	C7B—N8B—C10B	111.7 (6)
C7A—N8A—C10A	113.9 (7)	C7B—N8B—C9B	110.0 (6)
C9A—N8A—C10A	111.4 (7)	C10B—N8B—C9B	112.7 (7)
C7A—N8A—H8A	107.2	C7B—N8B—H8B	107.4
C9A—N8A—H8A	107.2	C10B—N8B—H8B	107.4
C10A—N8A—H8A	107.2	C9B—N8B—H8B	107.4
N8A—C9A—H9A1	109.5	N8B—C9B—H9B1	109.5
N8A—C9A—H9A2	109.5	N8B—C9B—H9B2	109.5
H9A1—C9A—H9A2	109.5	H9B1—C9B—H9B2	109.5
N8A—C9A—H9A3	109.5	N8B—C9B—H9B3	109.5
H9A1—C9A—H9A3	109.5	H9B1—C9B—H9B3	109.5
H9A2—C9A—H9A3	109.5	H9B2—C9B—H9B3	109.5
C11A—C10A—N8A	112.8 (7)	C11B—C10B—N8B	110.7 (7)
C11A—C10A—H10A	109.0	C11B—C10B—H10C	109.5
N8A—C10A—H10A	109.0	N8B—C10B—H10C	109.5
C11A—C10A—H10B	109.0	C11B—C10B—H10D	109.5
N8A—C10A—H10B	109.0	N8B—C10B—H10D	109.5
H10A—C10A—H10B	107.8	H10C—C10B—H10D	108.1
C12A—C11A—C10A	178.3 (10)	C12B—C11B—C10B	177.8 (9)
C11A—C12A—H12A	180.0	C11B—C12B—H12B	180.0
C6A—C1A—C2A—C3A	0.8 (14)	C6B—C1B—C2B—C3B	−0.6 (14)
C7A—C1A—C2A—C3A	−179.4 (8)	C7B—C1B—C2B—C3B	178.5 (9)
C1A—C2A—C3A—C4A	1.2 (15)	C1B—C2B—C3B—C4B	1.8 (17)
C2A—C3A—C4A—C5A	−2.2 (17)	C2B—C3B—C4B—C5B	−3 (2)
C3A—C4A—C5A—C6A	1.1 (18)	C3B—C4B—C5B—C6B	2 (2)
C4A—C5A—C6A—C1A	0.9 (17)	C4B—C5B—C6B—C1B	−1.1 (18)
C2A—C1A—C6A—C5A	−1.8 (14)	C2B—C1B—C6B—C5B	0.3 (15)
C7A—C1A—C6A—C5A	178.4 (9)	C7B—C1B—C6B—C5B	−178.8 (10)
C2A—C1A—C7A—N8A	111.8 (9)	C6B—C1B—C7B—N8B	69.2 (11)
C6A—C1A—C7A—N8A	−68.4 (11)	C2B—C1B—C7B—N8B	−109.8 (9)
C1A—C7A—N8A—C9A	−177.4 (7)	C1B—C7B—N8B—C10B	50.9 (9)
C1A—C7A—N8A—C10A	−51.7 (9)	C1B—C7B—N8B—C9B	176.9 (7)
C7A—N8A—C10A—C11A	178.1 (7)	C7B—N8B—C10B—C11B	−179.5 (6)
C9A—N8A—C10A—C11A	−57.2 (9)	C9B—N8B—C10B—C11B	56.0 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N8A—H8A···Cl1A	0.91	2.14	3.042 (7)	169
N8B—H8B···Cl2B	0.91	2.13	3.025 (6)	170
C10A—H10B···Cl1A^i	0.97	2.75	3.559 (8)	142
C10B—H10C···Cl2B^ii	0.97	2.75	3.531 (8)	138
C10B—H10D···Cl2B^iii	0.97	2.82	3.701 (8)	152
C12A—H12A···Cl2B^ii	0.93	2.64	3.546 (11)	164
C12B—H12B···Cl1A^i	0.93	2.66	3.559 (13)	163
C7A—H7A2···Cl1A^iv	0.97	2.80	3.648 (9)	147
C7B—H7B1···Cl2B^iii	0.97	2.82	3.669 (10)	147

Symmetry codes: (i) x, y, z+1; (ii) x, y, z−1; (iii) x−1, y, z−1; (iv) x+1, y, z+1.