4-Methyl-2-phenyl-1-tosyl­piperazine

Meng, Y.; Hu, W.; Wu, K.

doi:10.1107/S160053680701906X

4-Methyl-2-phenyl-1-tosylpiperazine

The title compound, C₁₈H₂₂N₂O₂S, was obtained unintentionally in our work on the preparation of piperazine derivatives. The piperazine ring has a regular chair conformation, with the N atoms deviating by −0.586 (2) and 0.668 (2) Å from the mean plane formed by the four C atoms. This mean plane and phenyl ring make a dihedral angle of 83.03 (5)°. In the crystal structure, weak intermolecular C—H

O hydrogen bonds link the molecules into helical chains running along the a axis. The structure is an inversion twin.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680701906X/cv2229sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680701906X/cv2229Isup2.hkl Contains datablock I

CCDC reference: 647620

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.032
wR factor = 0.083
Data-to-parameter ratio = 18.1

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.500
           From the CIF: _refine_ls_abs_structure_Flack_su    0.070
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.50

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           27.50
           From the CIF: _reflns_number_total               3811
           Count of symmetry unique reflns         2221
           Completeness (_total/calc)            171.59%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1590
           Fraction of Friedel pairs measured     0.716
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2     = .          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 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
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Piperazine and its derivates are often are used as antielminitics, perfumes and starting materials in pharmaceutial and agrochemical industries (Kambala V. et al., 2002). In our work on the preparation of piperazine derivates we have obtained the title compound, (I).

In (I) (Fig.1), the piperazaine ring has a regular chair conformation; C2,C3,C5,C6 atoms are nearly at the same plane, atoms N1 and N4 deviate by -0.586 (2) Å and 0.668 (2) Å, respectively, from this plane. The benzene ring C7—C12 is twisted out of the plane C2/C3/C5/C6 by 83.03 (5)°. The atoms C20,S1 and the other benzene ring C14—C19 also situated in a plane which make a dihedral angle of 36.04 (6) ° with the plane C2/C3/C5/C6.

The weak intermolecular C—H···O hydrogen bonds (Table1) link the molecules into helical chains running along the a axis (Fig. 2).

Related literature top

For related literature, see: Subba Rao & Subrahmanyam (2002).

Experimental top

A suspension of sodium hydroxide (4.4 g, 0.11 mol) in DMF (70 ml) was prepared. p-Toluenesulfonamide(8.6 g, 0.05 mol) was dissolved in DMF (40 ml) and the solution was added to the sodium hydroxide suspension.After mixing at room temperature the mixture was heated to 65–70°C for 1 h. After that, the soulution of beta-chloro-N-methyl-N-chloroethyl phenylethylamine(11.6 g,0.05 mol) in DMF(40 ml) was added gradually from a separatory funnel. The reaction mixture was stirred for 2 h and poured into water(200 ml). After 2 h, the precipitate was filtered and dried to afford 13.3 g of product (yield 80.6%). The solid product was dissolved in acetone,the solution was evaporated gradually at room temperature to afford single crystals of (I). M.p. 383.9–385.3 K.

Structure description top

The weak intermolecular C—H···O hydrogen bonds (Table1) link the molecules into helical chains running along the a axis (Fig. 2).

For related literature, see: Subba Rao & Subrahmanyam (2002).

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram of (I), viewed along the a axis, showing the hydrogen-bond as dashed lines.

4-Methyl-2-phenyl-1-tosylpiperazine top

Crystal data top

C₁₈H₂₂N₂O₂S	F(000) = 704
M_r = 330.44	D_x = 1.296 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4930 reflections
a = 10.2066 (11) Å	θ = 2.3–28.3°
b = 10.6427 (11) Å	µ = 0.20 mm⁻¹
c = 15.5870 (17) Å	T = 296 K
V = 1693.1 (3) Å³	Prismatic, colourless
Z = 4	0.25 × 0.20 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3811 independent reflections
Radiation source: fine-focus sealed tube	3449 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.951, T_max = 0.960	k = −11→13
10807 measured reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0449P)² + 0.1655P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3811 reflections	Δρ_max = 0.15 e Å⁻³
210 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1590 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.50 (7)

Crystal data top

C₁₈H₂₂N₂O₂S	V = 1693.1 (3) Å³
M_r = 330.44	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 10.2066 (11) Å	µ = 0.20 mm⁻¹
b = 10.6427 (11) Å	T = 296 K
c = 15.5870 (17) Å	0.25 × 0.20 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3811 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3449 reflections with I > 2σ(I)
T_min = 0.951, T_max = 0.960	R_int = 0.022
10807 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.083	Δρ_max = 0.15 e Å⁻³
S = 1.04	Δρ_min = −0.25 e Å⁻³
3811 reflections	Absolute structure: Flack (1983), 1590 Friedel pairs
210 parameters	Absolute structure parameter: 0.50 (7)
0 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.02151 (4)	0.24266 (4)	0.79485 (2)	0.04437 (11)
O1	0.06934 (14)	0.11953 (12)	0.81423 (9)	0.0622 (3)
O2	0.07796 (13)	0.31207 (13)	0.72578 (8)	0.0604 (4)
N1	0.04159 (13)	0.32677 (12)	0.88091 (8)	0.0388 (3)
C2	0.03934 (15)	0.46591 (14)	0.87809 (9)	0.0371 (3)
H2	0.0470	0.4909	0.8178	0.045*
C3	−0.09104 (15)	0.51519 (16)	0.91085 (10)	0.0419 (3)
H3A	−0.0876	0.6062	0.9136	0.050*
H3B	−0.1596	0.4922	0.8707	0.050*
N4	−0.12352 (13)	0.46558 (13)	0.99565 (9)	0.0432 (3)
C5	−0.12911 (19)	0.32900 (16)	0.99267 (11)	0.0495 (4)
H5A	−0.1974	0.3030	0.9532	0.059*
H5B	−0.1509	0.2967	1.0491	0.059*
C6	0.00021 (17)	0.27504 (14)	0.96419 (9)	0.0449 (4)
H6A	0.0664	0.2936	1.0070	0.054*
H6B	−0.0074	0.1844	0.9596	0.054*
C7	0.15998 (16)	0.51458 (15)	0.92445 (10)	0.0403 (3)
C8	0.15569 (18)	0.59222 (16)	0.99594 (12)	0.0499 (4)
H8	0.0752	0.6175	1.0179	0.060*
C9	0.2703 (2)	0.63240 (19)	1.03499 (13)	0.0581 (5)
H9	0.2660	0.6837	1.0832	0.070*
C10	0.38992 (19)	0.5972 (2)	1.00302 (14)	0.0613 (5)
H10	0.4666	0.6244	1.0293	0.074*
C11	0.39541 (18)	0.5215 (2)	0.93211 (14)	0.0610 (5)
H11	0.4763	0.4980	0.9099	0.073*
C12	0.28189 (17)	0.47966 (18)	0.89330 (12)	0.0505 (4)
H12	0.2873	0.4274	0.8456	0.061*
C13	−0.2484 (2)	0.5164 (2)	1.02383 (15)	0.0668 (6)
H13A	−0.2701	0.4823	1.0790	0.100*
H13B	−0.3153	0.4943	0.9833	0.100*
H13C	−0.2422	0.6062	1.0278	0.100*
C14	−0.14845 (17)	0.22811 (15)	0.77585 (9)	0.0435 (4)
C15	−0.2118 (2)	0.31740 (18)	0.72704 (12)	0.0555 (4)
H15	−0.1650	0.3822	0.7013	0.067*
C16	−0.3463 (2)	0.3089 (2)	0.71697 (14)	0.0637 (5)
H16	−0.3893	0.3685	0.6836	0.076*
C17	−0.4182 (2)	0.2146 (2)	0.75493 (12)	0.0606 (5)
C18	−0.3523 (2)	0.1267 (2)	0.80406 (13)	0.0608 (5)
H18	−0.3992	0.0628	0.8308	0.073*
C19	−0.2177 (2)	0.13219 (17)	0.81409 (11)	0.0528 (4)
H19	−0.1744	0.0716	0.8464	0.063*
C20	−0.5649 (2)	0.2056 (3)	0.74181 (18)	0.0864 (8)
H20A	−0.6046	0.1697	0.7920	0.130*
H20B	−0.5829	0.1532	0.6931	0.130*
H20C	−0.6001	0.2880	0.7321	0.130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0496 (2)	0.0435 (2)	0.04002 (18)	0.00504 (18)	−0.00067 (16)	−0.00628 (16)
O1	0.0689 (8)	0.0465 (7)	0.0711 (8)	0.0178 (6)	−0.0130 (7)	−0.0160 (6)
O2	0.0642 (8)	0.0750 (9)	0.0421 (6)	−0.0034 (7)	0.0122 (6)	−0.0055 (6)
N1	0.0462 (8)	0.0340 (6)	0.0363 (6)	0.0001 (5)	−0.0013 (6)	0.0013 (5)
C2	0.0425 (8)	0.0339 (7)	0.0350 (7)	0.0010 (6)	0.0012 (6)	0.0039 (5)
C3	0.0409 (8)	0.0400 (8)	0.0449 (8)	0.0027 (7)	−0.0053 (7)	0.0014 (7)
N4	0.0391 (7)	0.0461 (8)	0.0444 (7)	−0.0045 (6)	0.0061 (6)	−0.0061 (6)
C5	0.0569 (10)	0.0508 (10)	0.0410 (8)	−0.0148 (8)	0.0070 (8)	0.0014 (7)
C6	0.0597 (10)	0.0376 (8)	0.0374 (7)	−0.0018 (7)	−0.0010 (7)	0.0059 (6)
C7	0.0421 (8)	0.0348 (8)	0.0441 (8)	−0.0024 (6)	0.0012 (7)	0.0090 (6)
C8	0.0470 (9)	0.0471 (9)	0.0556 (9)	−0.0071 (8)	0.0020 (8)	−0.0030 (8)
C9	0.0644 (11)	0.0503 (10)	0.0597 (11)	−0.0144 (9)	−0.0103 (9)	−0.0014 (9)
C10	0.0521 (10)	0.0598 (12)	0.0721 (12)	−0.0154 (9)	−0.0152 (9)	0.0136 (10)
C11	0.0394 (9)	0.0677 (12)	0.0758 (13)	−0.0008 (9)	0.0002 (9)	0.0149 (11)
C12	0.0447 (9)	0.0533 (10)	0.0535 (10)	0.0011 (8)	0.0031 (8)	0.0046 (8)
C13	0.0485 (10)	0.0792 (15)	0.0727 (13)	−0.0023 (10)	0.0163 (9)	−0.0186 (12)
C14	0.0540 (9)	0.0394 (8)	0.0370 (7)	0.0012 (7)	−0.0053 (6)	−0.0040 (6)
C15	0.0643 (11)	0.0507 (10)	0.0516 (10)	0.0004 (9)	−0.0101 (9)	0.0100 (8)
C16	0.0637 (12)	0.0635 (12)	0.0639 (12)	0.0108 (10)	−0.0150 (10)	0.0040 (9)
C17	0.0566 (10)	0.0706 (13)	0.0545 (10)	0.0031 (10)	−0.0052 (9)	−0.0144 (9)
C18	0.0672 (11)	0.0588 (11)	0.0564 (10)	−0.0165 (9)	−0.0040 (9)	−0.0037 (9)
C19	0.0673 (11)	0.0419 (9)	0.0492 (9)	−0.0050 (8)	−0.0097 (8)	0.0037 (7)
C20	0.0575 (12)	0.110 (2)	0.0918 (16)	0.0023 (13)	−0.0035 (12)	−0.0224 (15)

Geometric parameters (Å, º) top

S1—O2	1.4271 (13)	C9—H9	0.9300
S1—O1	1.4306 (13)	C10—C11	1.369 (3)
S1—N1	1.6257 (12)	C10—H10	0.9300
S1—C14	1.7666 (18)	C11—C12	1.381 (3)
N1—C6	1.4720 (18)	C11—H11	0.9300
N1—C2	1.4816 (19)	C12—H12	0.9300
C2—C7	1.519 (2)	C13—H13A	0.9599
C2—C3	1.519 (2)	C13—H13B	0.9599
C2—H2	0.9800	C13—H13C	0.9599
C3—N4	1.462 (2)	C14—C19	1.378 (2)
C3—H3A	0.9700	C14—C15	1.378 (2)
C3—H3B	0.9700	C15—C16	1.385 (3)
N4—C13	1.452 (2)	C15—H15	0.9300
N4—C5	1.456 (2)	C16—C17	1.376 (3)
C5—C6	1.506 (3)	C16—H16	0.9300
C5—H5A	0.9700	C17—C18	1.384 (3)
C5—H5B	0.9700	C17—C20	1.514 (3)
C6—H6A	0.9700	C18—C19	1.383 (3)
C6—H6B	0.9700	C18—H18	0.9300
C7—C12	1.386 (2)	C19—H19	0.9300
C7—C8	1.388 (2)	C20—H20A	0.9599
C8—C9	1.386 (3)	C20—H20B	0.9599
C8—H8	0.9300	C20—H20C	0.9599
C9—C10	1.371 (3)

O2—S1—O1	119.71 (9)	C10—C9—C8	120.49 (19)
O2—S1—N1	106.65 (7)	C10—C9—H9	119.8
O1—S1—N1	106.68 (7)	C8—C9—H9	119.8
O2—S1—C14	108.39 (8)	C11—C10—C9	119.41 (18)
O1—S1—C14	106.87 (8)	C11—C10—H10	120.3
N1—S1—C14	108.08 (7)	C9—C10—H10	120.3
C6—N1—C2	113.30 (12)	C10—C11—C12	120.60 (19)
C6—N1—S1	119.05 (10)	C10—C11—H11	119.7
C2—N1—S1	121.60 (10)	C12—C11—H11	119.7
N1—C2—C7	108.32 (12)	C11—C12—C7	120.89 (18)
N1—C2—C3	110.41 (13)	C11—C12—H12	119.6
C7—C2—C3	115.63 (12)	C7—C12—H12	119.6
N1—C2—H2	107.4	N4—C13—H13A	109.5
C7—C2—H2	107.4	N4—C13—H13B	109.5
C3—C2—H2	107.4	H13A—C13—H13B	109.5
N4—C3—C2	112.21 (13)	N4—C13—H13C	109.5
N4—C3—H3A	109.2	H13A—C13—H13C	109.5
C2—C3—H3A	109.2	H13B—C13—H13C	109.5
N4—C3—H3B	109.2	C19—C14—C15	120.60 (17)
C2—C3—H3B	109.2	C19—C14—S1	119.77 (13)
H3A—C3—H3B	107.9	C15—C14—S1	119.51 (14)
C13—N4—C5	110.32 (15)	C14—C15—C16	118.85 (19)
C13—N4—C3	109.75 (15)	C14—C15—H15	120.6
C5—N4—C3	109.92 (13)	C16—C15—H15	120.6
N4—C5—C6	110.84 (14)	C17—C16—C15	121.81 (19)
N4—C5—H5A	109.5	C17—C16—H16	119.1
C6—C5—H5A	109.5	C15—C16—H16	119.1
N4—C5—H5B	109.5	C16—C17—C18	118.17 (18)
C6—C5—H5B	109.5	C16—C17—C20	121.0 (2)
H5A—C5—H5B	108.1	C18—C17—C20	120.8 (2)
N1—C6—C5	111.63 (13)	C19—C18—C17	121.09 (19)
N1—C6—H6A	109.3	C19—C18—H18	119.5
C5—C6—H6A	109.3	C17—C18—H18	119.5
N1—C6—H6B	109.3	C14—C19—C18	119.48 (17)
C5—C6—H6B	109.3	C14—C19—H19	120.3
H6A—C6—H6B	108.0	C18—C19—H19	120.3
C12—C7—C8	117.97 (16)	C17—C20—H20A	109.5
C12—C7—C2	118.01 (15)	C17—C20—H20B	109.5
C8—C7—C2	124.02 (15)	H20A—C20—H20B	109.5
C9—C8—C7	120.63 (17)	C17—C20—H20C	109.5
C9—C8—H8	119.7	H20A—C20—H20C	109.5
C7—C8—H8	119.7	H20B—C20—H20C	109.5

O2—S1—N1—C6	−176.10 (12)	C2—C7—C8—C9	179.74 (16)
O1—S1—N1—C6	−47.07 (14)	C7—C8—C9—C10	0.7 (3)
C14—S1—N1—C6	67.55 (13)	C8—C9—C10—C11	−0.2 (3)
O2—S1—N1—C2	33.11 (15)	C9—C10—C11—C12	−0.6 (3)
O1—S1—N1—C2	162.13 (13)	C10—C11—C12—C7	0.9 (3)
C14—S1—N1—C2	−83.25 (14)	C8—C7—C12—C11	−0.3 (3)
C6—N1—C2—C7	77.84 (16)	C2—C7—C12—C11	179.51 (16)
S1—N1—C2—C7	−129.84 (12)	O2—S1—C14—C19	157.44 (13)
C6—N1—C2—C3	−49.71 (17)	O1—S1—C14—C19	27.15 (16)
S1—N1—C2—C3	102.62 (14)	N1—S1—C14—C19	−87.34 (15)
N1—C2—C3—N4	53.49 (16)	O2—S1—C14—C15	−26.46 (17)
C7—C2—C3—N4	−69.91 (16)	O1—S1—C14—C15	−156.75 (14)
C2—C3—N4—C13	179.64 (15)	N1—S1—C14—C15	88.76 (15)
C2—C3—N4—C5	−58.86 (17)	C19—C14—C15—C16	−0.1 (3)
C13—N4—C5—C6	−179.55 (15)	S1—C14—C15—C16	−176.18 (15)
C3—N4—C5—C6	59.28 (18)	C14—C15—C16—C17	0.6 (3)
C2—N1—C6—C5	51.48 (18)	C15—C16—C17—C18	−0.2 (3)
S1—N1—C6—C5	−101.61 (14)	C15—C16—C17—C20	−178.9 (2)
N4—C5—C6—N1	−55.84 (18)	C16—C17—C18—C19	−0.7 (3)
N1—C2—C7—C12	60.00 (18)	C20—C17—C18—C19	177.96 (19)
C3—C2—C7—C12	−175.50 (15)	C15—C14—C19—C18	−0.8 (3)
N1—C2—C7—C8	−120.20 (16)	S1—C14—C19—C18	175.28 (14)
C3—C2—C7—C8	4.3 (2)	C17—C18—C19—C14	1.2 (3)
C12—C7—C8—C9	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O1ⁱ	0.96	2.57	3.453 (3)	152

Symmetry code: (i) x−1/2, −y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₂N₂O₂S
M_r	330.44
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	10.2066 (11), 10.6427 (11), 15.5870 (17)
V (Å³)	1693.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.951, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	10807, 3811, 3449
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.083, 1.04
No. of reflections	3811
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.25
Absolute structure	Flack (1983), 1590 Friedel pairs
Absolute structure parameter	0.50 (7)

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2005), SHELXTL.