A second polymorphic form of pentazocine hydro­chloride at 105 K

The crystal structure of pentazocine hydro­chloride [systematic name: 2-hydroxy-5,9-di­methyl-2-(3-methyl­buten-2-yl)-6,7-ben­zomorphanium chloride], C₁₉H₂₈NO⁺·Cl^-, has been determined at 105 K and found to be a second polymorphic form with space group C2/c. The space group and the unit-cell parameters are different from a reported crystal structure at 293 K [Majeste, Poindexter, Jones & Klein (1994). Acta Cryst. C50, 1633-1636]. There are only small differences in the molecular conformation, but the association between the protonated pentazocine mol­ecules and the chloride ion is different.

Key indicators

• Single-crystal X-ray study
• T = 105 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.102
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT222_ALERT_3_A Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       6.23 Ratio

Author Response: 'see _publ_section_exptl-refinement'

Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.80 Ratio
PLAT733_ALERT_1_B Torsion Calc  -87.93(13), Rep   -87.9(10) ......       7.69 su-Rat
              C13 -C5  -C6  -C7     1.555   1.555   1.555   1.555
PLAT733_ALERT_1_B Torsion Calc   64.31(13), Rep    64.3(10) ......       7.69 su-Rat
              C6  -C5  -C10 -C11    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_B Torsion Calc  177.82(17), Rep   177.8(10) ......       5.88 su-Rat
              C15 -C16 -C17 -C19    1.555   1.555   1.555   1.555

Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C17

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

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

2-Hydroxy-5,9-dimethyl-2-(3-methylbuten-2-yl)-6,7-benzomorphanium chloride

Crystal data

C19H28NO^+·Cl^−	F(000) = 1392
Mr = 321.87	Dx = 1.160 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.541 (5) Å	Cell parameters from 23580 reflections
b = 11.537 (2) Å	θ = 2.3–28.4°
c = 14.897 (3) Å	µ = 0.21 mm^−1
β = 119.05 (3)°	T = 105 K
V = 3687 (1) Å^3	Needle, colorless
Z = 8	0.5 × 0.2 × 0.2 mm

Data collection

Bruker SMART diffractometer	4582 independent reflections
Radiation source: fine-focus sealed tube	4113 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 8 pixels mm^-1	θmax = 28.3°, θmin = 2.3°
ω scans	h = −32→32
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	k = −15→15
Tmin = 0.896, Tmax = 0.957	l = −19→19
28837 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: difference Fourier map
wR(F^2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0594P)^2 + 2.1933P] where P = (Fo^2 + 2Fc^2)/3
4582 reflections	(Δ/σ)max = 0.001
311 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.25 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.

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 > 2σ(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	0.099357 (13)	0.94822 (2)	0.46915 (2)	0.02873 (9)
O1	0.26950 (5)	0.49359 (9)	1.00396 (7)	0.0378 (2)
H20	0.3034 (10)	0.4755 (19)	1.0028 (16)	0.062 (6)*
N1	0.09920 (4)	0.03564 (7)	0.66765 (7)	0.02093 (18)
H1N	0.1018 (7)	0.0096 (13)	0.6127 (12)	0.030 (4)*
C1	0.22452 (5)	0.36806 (9)	0.85493 (8)	0.0241 (2)
H1	0.2615 (7)	0.3774 (13)	0.8469 (11)	0.029 (3)*
C2	0.22244 (5)	0.42351 (10)	0.93631 (8)	0.0277 (2)
C3	0.17022 (6)	0.41082 (11)	0.94911 (9)	0.0319 (3)
H3	0.1698 (8)	0.4493 (14)	1.0057 (13)	0.037 (4)*
C4	0.12101 (6)	0.34253 (10)	0.88100 (9)	0.0286 (2)
H4	0.0842 (7)	0.3329 (13)	0.8898 (12)	0.032 (4)*
C5	0.17658 (5)	0.24072 (9)	0.69511 (8)	0.0227 (2)
C6	0.17411 (5)	0.30117 (9)	0.78432 (8)	0.0210 (2)
C7	0.12187 (5)	0.28734 (9)	0.79801 (8)	0.0222 (2)
C8	0.06565 (5)	0.21538 (9)	0.72593 (8)	0.0231 (2)
H8B	0.0275 (6)	0.2694 (13)	0.6916 (11)	0.027 (3)*
H8A	0.0573 (7)	0.1594 (13)	0.7657 (12)	0.032 (4)*
C9	0.07065 (5)	0.15551 (9)	0.63857 (8)	0.0211 (2)
H9	0.0283 (6)	0.1437 (12)	0.5807 (11)	0.022 (3)*
C10	0.10965 (5)	0.22675 (9)	0.60363 (8)	0.0227 (2)
H10	0.1118 (6)	0.1838 (12)	0.5489 (11)	0.026 (3)*
C11	0.07663 (6)	0.34145 (10)	0.55662 (9)	0.0299 (2)
H11A	0.0997 (7)	0.3866 (14)	0.5273 (12)	0.035 (4)*
H11B	0.0730 (7)	0.3888 (14)	0.6054 (12)	0.035 (4)*
H11C	0.0337 (8)	0.3278 (15)	0.5023 (14)	0.045 (4)*
C12	0.21778 (6)	0.30478 (12)	0.65991 (10)	0.0324 (3)
H12A	0.2048 (7)	0.3879 (15)	0.6444 (12)	0.038 (4)*
H12B	0.2631 (8)	0.2972 (14)	0.7133 (12)	0.036 (4)*
H12C	0.2121 (8)	0.2707 (15)	0.5952 (14)	0.046 (5)*
C13	0.20434 (5)	0.11782 (10)	0.72961 (9)	0.0267 (2)
H13B	0.2092 (7)	0.0847 (13)	0.6752 (12)	0.032 (4)*
H13A	0.2458 (7)	0.1220 (13)	0.7906 (12)	0.032 (4)*
C14	0.16422 (5)	0.04027 (9)	0.75593 (9)	0.0244 (2)
H14B	0.1623 (6)	0.0668 (12)	0.8145 (11)	0.022 (3)*
H14A	0.1791 (7)	−0.0400 (14)	0.7685 (13)	0.034 (4)*
C15	0.05989 (5)	−0.05115 (9)	0.68776 (9)	0.0259 (2)
H15A	0.0679 (7)	−0.0342 (12)	0.7569 (12)	0.026 (3)*
H15B	0.0169 (7)	−0.0315 (13)	0.6411 (12)	0.032 (4)*
C16	0.07649 (6)	−0.17209 (10)	0.67229 (9)	0.0274 (2)
H16	0.0701 (7)	−0.1878 (14)	0.6048 (13)	0.039 (4)*
C17	0.09693 (7)	−0.25768 (10)	0.74021 (10)	0.0345 (3)
C18	0.10961 (15)	−0.24819 (15)	0.84893 (14)	0.0798 (8)
H18A	0.1089	−0.1681	0.8658	0.085 (7)*
H18B	0.1498	−0.2806	0.8942	0.137 (13)*
H18C	0.0782	−0.2898	0.8565	0.122 (11)*
C19	0.10942 (10)	−0.37613 (12)	0.71111 (13)	0.0476 (4)
H19A	0.1011 (8)	−0.3794 (15)	0.6372 (14)	0.045 (4)*
H19C	0.0801 (11)	−0.4301 (19)	0.7177 (17)	0.070 (6)*
H19B	0.1539 (11)	−0.402 (2)	0.7588 (18)	0.074 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.03206 (15)	0.02966 (15)	0.02503 (15)	0.00280 (10)	0.01432 (12)	−0.00276 (9)
O1	0.0338 (5)	0.0455 (5)	0.0279 (4)	−0.0098 (4)	0.0101 (4)	−0.0150 (4)
N1	0.0214 (4)	0.0189 (4)	0.0223 (4)	−0.0009 (3)	0.0104 (3)	−0.0006 (3)
C1	0.0238 (5)	0.0250 (5)	0.0218 (5)	−0.0029 (4)	0.0096 (4)	−0.0014 (4)
C2	0.0295 (5)	0.0277 (5)	0.0207 (5)	−0.0030 (4)	0.0082 (4)	−0.0036 (4)
C3	0.0375 (6)	0.0347 (6)	0.0255 (5)	−0.0013 (5)	0.0169 (5)	−0.0073 (5)
C4	0.0302 (5)	0.0310 (6)	0.0288 (5)	−0.0008 (4)	0.0177 (5)	−0.0039 (4)
C5	0.0236 (5)	0.0236 (5)	0.0229 (5)	−0.0053 (4)	0.0128 (4)	−0.0041 (4)
C6	0.0230 (5)	0.0197 (4)	0.0197 (4)	−0.0005 (4)	0.0099 (4)	−0.0001 (4)
C7	0.0237 (5)	0.0205 (5)	0.0225 (5)	0.0006 (4)	0.0112 (4)	−0.0001 (4)
C8	0.0217 (5)	0.0225 (5)	0.0265 (5)	−0.0002 (4)	0.0127 (4)	−0.0011 (4)
C9	0.0203 (4)	0.0187 (4)	0.0215 (5)	0.0002 (4)	0.0080 (4)	0.0004 (3)
C10	0.0263 (5)	0.0210 (5)	0.0202 (5)	−0.0034 (4)	0.0109 (4)	−0.0018 (4)
C11	0.0371 (6)	0.0226 (5)	0.0252 (5)	−0.0026 (4)	0.0113 (5)	0.0020 (4)
C12	0.0354 (6)	0.0374 (6)	0.0314 (6)	−0.0132 (5)	0.0219 (5)	−0.0083 (5)
C13	0.0211 (5)	0.0271 (5)	0.0322 (6)	−0.0009 (4)	0.0131 (4)	−0.0061 (4)
C14	0.0203 (5)	0.0219 (5)	0.0257 (5)	0.0025 (4)	0.0070 (4)	0.0006 (4)
C15	0.0266 (5)	0.0212 (5)	0.0307 (6)	−0.0022 (4)	0.0145 (4)	0.0018 (4)
C16	0.0337 (6)	0.0218 (5)	0.0253 (5)	−0.0033 (4)	0.0132 (4)	−0.0023 (4)
C17	0.0509 (7)	0.0234 (5)	0.0319 (6)	0.0012 (5)	0.0221 (6)	0.0009 (4)
C18	0.172 (2)	0.0362 (8)	0.0444 (9)	0.0232 (12)	0.0630 (13)	0.0116 (7)
C19	0.0774 (11)	0.0231 (6)	0.0483 (8)	0.0050 (6)	0.0354 (8)	0.0018 (5)

Geometric parameters (Å, º)

O1—C2	1.369 (1)	C10—H10	0.98 (2)
O1—H20	0.87 (2)	C11—H11A	1.01 (2)
N1—C14	1.497 (2)	C11—H11B	0.95 (2)
N1—C9	1.515 (1)	C11—H11C	0.98 (2)
N1—C15	1.518 (1)	C12—H12A	1.00 (2)
N1—H1N	0.90 (2)	C12—H12B	1.01 (2)
C1—C2	1.393 (2)	C12—H12C	0.99 (2)
C1—C6	1.403 (2)	C13—C14	1.516 (2)
C1—H1	0.97 (2)	C13—H13B	0.95 (2)
C2—C3	1.392 (2)	C13—H13A	0.98 (2)
C3—C4	1.385 (2)	C14—H14B	0.95 (2)
C3—H3	0.96 (2)	C14—H14A	0.98 (2)
C4—C7	1.400 (2)	C15—C16	1.502 (2)
C4—H4	0.98 (2)	C15—H15A	0.97 (2)
C5—C6	1.528 (1)	C15—H15B	0.97 (2)
C5—C12	1.536 (2)	C16—C17	1.326 (2)
C5—C13	1.549 (2)	C16—H16	0.96 (2)
C5—C10	1.552 (2)	C17—C18	1.498 (2)
C6—C7	1.402 (2)	C17—C19	1.509 (2)
C7—C8	1.519 (2)	C18—H18A	0.9600
C8—C9	1.530 (2)	C18—H18B	0.9600
C8—H8B	1.03 (1)	C18—H18C	0.9600
C8—H8A	0.96 (2)	C19—H19A	1.02 (2)
C9—C10	1.532 (1)	C19—H19C	0.99 (2)
C9—H9	0.99 (1)	C19—H19B	1.02 (2)
C10—C11	1.532 (2)
C2—O1—H20	108 (1)	C10—C11—H11A	111 (1)
C14—N1—C9	111.4 (1)	C10—C11—H11B	111 (1)
C14—N1—C15	111.0 (1)	H11A—C11—H11B	108 (1)
C9—N1—C15	114.1 (1)	C10—C11—H11C	110 (1)
C14—N1—H1N	107 (1)	H11A—C11—H11C	109 (1)
C9—N1—H1N	105 (1)	H11B—C11—H11C	105 (1)
C15—N1—H1N	107 (1)	C5—C12—H12A	110 (1)
C2—C1—C6	120.9 (1)	C5—C12—H12B	110 (1)
C2—C1—H1	119 (1)	H12A—C12—H12B	111 (1)
C6—C1—H1	120 (1)	C5—C12—H12C	109 (1)
O1—C2—C3	117.7 (1)	H12A—C12—H12C	106 (1)
O1—C2—C1	122.5 (1)	H12B—C12—H12C	108 (1)
C3—C2—C1	119.7 (1)	C14—C13—C5	112.9 (1)
C4—C3—C2	119.5 (1)	C14—C13—H13B	110 (1)
C4—C3—H3	122 (1)	C5—C13—H13B	107 (1)
C2—C3—H3	118 (1)	C14—C13—H13A	107 (1)
C3—C4—C7	121.6 (1)	C5—C13—H13A	110 (1)
C3—C4—H4	119 (1)	H13B—C13—H13A	107 (1)
C7—C4—H4	118 (1)	N1—C14—C13	110.1 (1)
C6—C5—C12	112.8 (1)	N1—C14—H14B	108 (1)
C6—C5—C13	109.0 (1)	C13—C14—H14B	112 (1)
C12—C5—C13	107.3 (1)	N1—C14—H14A	106 (1)
C6—C5—C10	109.8 (1)	C13—C14—H14A	112 (1)
C12—C5—C10	110.0 (1)	H14B—C14—H14A	108 (1)
C13—C5—C10	107.7 (1)	C16—C15—N1	109.7 (1)
C7—C6—C1	119.3 (1)	C16—C15—H15A	115 (1)
C7—C6—C5	120.0 (1)	N1—C15—H15A	105 (1)
C1—C6—C5	120.7 (1)	C16—C15—H15B	113 (1)
C4—C7—C6	118.9 (1)	N1—C15—H15B	106 (1)
C4—C7—C8	118.4 (1)	H15A—C15—H15B	108 (1)
C6—C7—C8	122.7 (1)	C17—C16—C15	127.2 (1)
C7—C8—C9	115.3 (1)	C17—C16—H16	118 (1)
C7—C8—H8B	108 (1)	C15—C16—H16	115 (1)
C9—C8—H8B	106 (1)	C16—C17—C18	125.0 (1)
C7—C8—H8A	108 (1)	C16—C17—C19	120.6 (1)
C9—C8—H8A	110 (1)	C18—C17—C19	114.4 (1)
H8B—C8—H8A	107 (1)	C17—C18—H18A	109
N1—C9—C8	112.7 (1)	C17—C18—H18B	109
N1—C9—C10	108.0 (1)	H18A—C18—H18B	109
C8—C9—C10	111.6 (1)	C17—C18—H18C	109
N1—C9—H9	105 (1)	H18A—C18—H18C	109
C8—C9—H9	108 (1)	H18B—C18—H18C	109
C10—C9—H9	110 (1)	C17—C19—H19A	113 (1)
C11—C10—C9	109.9 (1)	C17—C19—H19C	106 (1)
C11—C10—C5	114.2 (1)	H19A—C19—H19C	108 (2)
C9—C10—C5	109.0 (1)	C17—C19—H19B	111 (1)
C11—C10—H10	106 (1)	H19A—C19—H19B	109 (2)
C9—C10—H10	107 (1)	H19C—C19—H19B	109 (2)
C5—C10—H10	108 (1)
C6—C1—C2—O1	−177.0 (1)	C15—N1—C9—C10	−170.7 (1)
C6—C1—C2—C3	1.2 (2)	C7—C8—C9—N1	89.8 (1)
O1—C2—C3—C4	178.7 (1)	C7—C8—C9—C10	−31.9 (1)
C1—C2—C3—C4	0.4 (2)	N1—C9—C10—C11	170.6 (1)
C2—C3—C4—C7	−1.2 (2)	C8—C9—C10—C11	−65.0 (1)
C2—C1—C6—C7	−2.0 (2)	N1—C9—C10—C5	−63.4 (1)
C2—C1—C6—C5	179.9 (1)	C8—C9—C10—C5	61.0 (1)
C12—C5—C6—C7	153.0 (1)	C6—C5—C10—C11	64.3 (10)
C13—C5—C6—C7	−87.9 (10)	C12—C5—C10—C11	−60.4 (1)
C10—C5—C6—C7	29.9 (1)	C13—C5—C10—C11	−177.1 (1)
C12—C5—C6—C1	−28.9 (1)	C6—C5—C10—C9	−59.1 (1)
C13—C5—C6—C1	90.2 (1)	C12—C5—C10—C9	176.2 (1)
C10—C5—C6—C1	−152.0 (1)	C13—C5—C10—C9	59.5 (1)
C3—C4—C7—C6	0.5 (2)	C6—C5—C13—C14	63.6 (1)
C3—C4—C7—C8	−179.1 (1)	C12—C5—C13—C14	−173.9 (1)
C1—C6—C7—C4	1.1 (2)	C10—C5—C13—C14	−55.6 (1)
C5—C6—C7—C4	179.3 (1)	C9—N1—C14—C13	−57.5 (1)
C1—C6—C7—C8	−179.3 (1)	C15—N1—C14—C13	174.1 (1)
C5—C6—C7—C8	−1.2 (2)	C5—C13—C14—N1	54.5 (1)
C4—C7—C8—C9	−178.7 (1)	C14—N1—C15—C16	−76.5 (1)
C6—C7—C8—C9	1.8 (2)	C9—N1—C15—C16	156.5 (1)
C14—N1—C9—C8	−61.2 (1)	N1—C15—C16—C17	122.0 (1)
C15—N1—C9—C8	65.5 (1)	C15—C16—C17—C18	−2.2 (3)
C14—N1—C9—C10	62.5 (1)	C15—C16—C17—C19	177.8 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15B···Cl1^i	0.97 (2)	2.69 (2)	3.644 (2)	171 (1)
N1—H1N···Cl1^ii	0.90 (2)	2.23 (2)	3.126 (1)	175 (1)
O1—H20···Cl1^iii	0.87 (2)	2.24 (2)	3.089 (1)	168 (2)
C14—H14B···O1^iv	0.95 (2)	2.49 (1)	3.153 (2)	127 (1)

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