organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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A monoclinic polymorph of 4,4′-di­chloro-2,2′-(piperazine-1,4-diyl­di­methyl­ene)diphenol

aDivision of Natural Sciences, Osaka Kyoiku University, Kashiwara, Osaka 582-8582, Japan
*Correspondence e-mail: kubono@cc.osaka-kyoiku.ac.jp

(Received 7 November 2008; accepted 19 November 2008; online 26 November 2008)

The titile compound, C18H20Cl2N2O2, crystallizes as a monoclinic form in the space group P21/n, with Z′ = 1/2. It is polymorphic with the previously reported orthorhombic form [Kubono, Tsuno, Tani & Yokoi (2008). Acta Cryst. E64, o2309]. In the present polymorph, the mol­ecule lies on a crystallographic inversion centre at the piperazine ring centroid. An intra­molecular O—H⋯N hydrogen bond forms an S(6) ring motif. Inter­molecular C—H⋯O hydrogen bonding generates a C(5) chain motif propagating along the b axis, forming sheets parallel to ([\overline{2}]02) with a first-level graph set S(6)C(5)R66(34).

Related literature

For the Pbca polymorph, see: Kubono et al. (2008[Kubono, K., Tsuno, Y., Tani, K. & Yokoi, K. (2008). Acta Cryst. E64, o2309.]). For graph-set notation in hydrogen bonds, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). For the synthesis of a ligand with two piperazine arms, see: Bharathi et al. (2006[Bharathi, K. S., Rahiman, A. K., Rajesh, K., Sreedaran, S., Aravindan, P. G., Velmurugan, D. & Narayanan, V. (2006). Polyhedron, 25, 2859-2868.]). For the monoclinic and ortho­rhom­bic polymorphs of a tetra­chloro-2,2′-(piperazine-1,4-diyl­dimeth­yl­­ene)diphenol, see: Kubono & Yokoi (2007[Kubono, K. & Yokoi, K. (2007). Acta Cryst. C63, o535-o537.]). For the structure of 1,4-bis­(2-hydr­oxy-5-methyl­benz­yl)piperazine, see: Kuppayee et al. (1999[Kuppayee, M., Kumaran, D., Ponnuswamy, M. N., Kandaswamy, M., Violet, M. J., Chinnakali, K. & Fun, H.-K. (1999). Acta Cryst. C55, 2147-2149.]).

[Scheme 1]

Experimental

Crystal data
  • C18H20Cl2N2O2

  • Mr = 367.26

  • Monoclinic, P 21 /n

  • a = 15.755 (4) Å

  • b = 9.2667 (17) Å

  • c = 5.9771 (19) Å

  • β = 96.45 (2)°

  • V = 867.1 (4) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.39 mm−1

  • T = 298.1 K

  • 0.35 × 0.15 × 0.15 mm

Data collection
  • Rigaku AFC-7R diffractometer

  • Absorption correction: none

  • 2462 measured reflections

  • 1994 independent reflections

  • 1316 reflections with F2 > 2σ(F2)

  • Rint = 0.020

  • 3 standard reflections every 150 reflections intensity decay: 0.3%

Refinement
  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.149

  • S = 1.01

  • 1994 reflections

  • 119 parameters

  • All H-atom parameters refined

  • Δρmax = 0.54 e Å−3

  • Δρmin = −0.52 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯N1 0.83 1.85 2.604 (2) 150
C3—H3⋯O1i 0.95 2.60 3.547 (2) 175
Symmetry code: (i) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{5\over 2}}].

Data collection: WinAFC (Rigaku/MSC, 2006[Rigaku/MSC (2006). WinAFC and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); cell refinement: WinAFC; data reduction: CrystalStructure (Rigaku/MSC, 2006[Rigaku/MSC (2006). WinAFC and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); program(s) used to solve structure: SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: CrystalStructure.

Supporting information


Comment top

We have recently reported the crystal structure of 4,4'-dichloro-2,2'-(piperazine-1,4-diyldimethylene)diphenol, (I) (Kubono et al., 2008), which crystallizes as an orthorhombic form in space group Pbca with Z' = 1. (I) can act as complexing reagents (Bharathi et al., 2006), so trying to synthesize the zinc complex with this ligand. The crystalline metal complexes were not given, however, a small amount of a new polymorph of the title compound, (II), was obtained from the reaction solution. We report here the molecular and crystal structure of (II).

The molecule of (II) crystallizes in the centrosymmetric space group P21/n with Z' = 1/2 in the asymmetric unit. The molecular structure of (II) is shown in Fig. 1. The molecule lies on a crystallographic inversion centre at the piperazine ring centroid. It is interesting to note that in the orthorhombic form (I) (Kubono et al., 2008) the molecule has a pseudo-inversion centre. The piperazine ring adopts a chair conformation. The bond lengths and angles in (II) are normal and comparable with those in the orthorhombic form (I) (Kubono et al., 2008), in the monoclinic and orthorhombic polymorph of dichlorophenol derivative (Kubono & Yokoi, 2007) and in the p-cresol one (Kuppayee et al., 1999). The molecular structures of (I) and (II) are closely similar, so the only slight differences were observed. The maximum differences of bond distance and angle between the two polymorphs are less than 0.02 Å [C1—C2: (I) 1.377 (4) Å, (II) 1.395 (2) Å] and less than 2 ° [C7—N1—C8: (I) 110.6 (2) °, (II) 112.58 (15) °], respectively. The most obvious differences are the torsion angles C5—C6—C7—N1 [(I) 149.3 (2) °, (II) 157.10 (17) °]. The intramolecular O1—H1···N1 hydrogen bond distance is 2.604 (2) Å (Table 1), forming a S(6) ring motif (Bernstein et al., 1995).

In the crystal structure of (II), there is intermolecular C—H···O hydrogen bond, involving a aromatic H atom (Table 1). Atom C3 in the molecule at (x, y, z) acts as hydrogen bond donor to atom O1 in the molecule at (3/2 - x,1/2 + y,5/2 - z), so forming a C(5) chain running parallel to the [010] direction and generated by the n-glide plane at y = 1/4. The molecules are linked by the combination of the S(6) ring and the C(5) chain into a sheet parallel to (202) with a first level graph set S(6)C(5)R66(34) (Fig. 2). In the crystal structure of (I), intermolecular C—H···O hydrogen bonds involving methylene H atoms generate C(5) chain motifs to form a sheet with a first level graph set S(6)C(5)R66(26) (Kubono et al., 2008). Each polymorph is characterized by the hydrogen bonding network structure.

Related literature top

For the Pbca polymorph, see: Kubono et al. (2008). For graph-set notation in hydrogen bonds, see: Bernstein et al. (1995). For the synthesis of a ligand with two piperazine arms, see: Bharathi et al. (2006). For the monoclinic and orthorhombic polymorphs of a tetrachloro-2,2'-(piperazine-1,4-diyldimethylene)diphenol, see: Kubono & Yokoi (2007). For the structure of 1,4-bis(2-hydroxy-5-methylbenzyl)piperazine, see: Kuppayee et al. (1999).

Experimental top

The title compound was prepared by the reaction of 4-chlorophenol, piperazine and paraformaldehyde as described previously (Kubono et al. 2008). The orthorhombic form, (I) (36.7 mg, 0.10 mmol) was dissolved in 25 ml hot chloroform. Then 15 ml of a methanol solution of zinc acetate dihydrate (22.0 mg, 0.10 mmol) were added to this solution. The mixture was stirred for 20 min at 340 K. After a few days at room temperature, trace amount of column crystals of (II) were picked out manually in the reaction solution. Melting point: 512–514 K. ESI-Ms: m/z, 367 for [M]+.

Refinement top

The H atoms of the hydroxyl groups were found from a difference Fourier map. The other H atoms were placed at idealized positions with C—H = 0.95 Å. All the H atoms were refined as a riding model with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: WinAFC (Rigaku/MSC, 2006); cell refinement: WinAFC (Rigaku/MSC, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2006); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006).

Figures top
[Figure 1] Fig. 1. The molecular structure of (II) with the atom-labelling scheme and displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size. [Symmetry code: (i) 1 - x, -y, 2 - z.]
[Figure 2] Fig. 2. The molecular packing of (II), showing the formation of a sheet with a first level graph set S(6)C(5)R66(34). The hydrogen bonds are shown as dashed lines. The H atoms not involved in the hydrogen bonds have been omitted for clarity.
4,4'-dichloro-2,2'-(piperazine-1,4-diyldimethylene)diphenol top
Crystal data top
C18H20Cl2N2O2F(000) = 384.00
Mr = 367.26Dx = 1.407 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 15.755 (4) Åθ = 15.2–17.3°
b = 9.2667 (17) ŵ = 0.39 mm1
c = 5.9771 (19) ÅT = 298 K
β = 96.45 (2)°Column, colorless
V = 867.1 (4) Å30.35 × 0.15 × 0.15 mm
Z = 2
Data collection top
Rigaku AFC-7R
diffractometer
θmax = 27.5°
ω–2θ scansh = 2020
2462 measured reflectionsk = 012
1994 independent reflectionsl = 74
1316 reflections with F2 > 2σ(F2)3 standard reflections every 150 reflections
Rint = 0.020 intensity decay: 0.4%
Refinement top
Refinement on F2All H-atom parameters refined
R[F2 > 2σ(F2)] = 0.041 w = 1/[0.002Fo2 + σ(Fo2)]/(4Fo2)
wR(F2) = 0.149(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.54 e Å3
1994 reflectionsΔρmin = 0.52 e Å3
119 parameters
Crystal data top
C18H20Cl2N2O2V = 867.1 (4) Å3
Mr = 367.26Z = 2
Monoclinic, P21/nMo Kα radiation
a = 15.755 (4) ŵ = 0.39 mm1
b = 9.2667 (17) ÅT = 298 K
c = 5.9771 (19) Å0.35 × 0.15 × 0.15 mm
β = 96.45 (2)°
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.020
2462 measured reflections3 standard reflections every 150 reflections
1994 independent reflections intensity decay: 0.4%
1316 reflections with F2 > 2σ(F2)
Refinement top
R[F2 > 2σ(F2)] = 0.041119 parameters
wR(F2) = 0.149All H-atom parameters refined
S = 1.01Δρmax = 0.54 e Å3
1994 reflectionsΔρmin = 0.52 e Å3
Special details top

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.70334 (4)0.71539 (6)0.65673 (12)0.0627 (2)
O10.59890 (10)0.28682 (15)1.2938 (2)0.0497 (4)
N10.50843 (9)0.15177 (16)0.9674 (2)0.0354 (3)
C10.62416 (12)0.3779 (2)1.1357 (3)0.0378 (4)
C20.69309 (12)0.4691 (2)1.1990 (3)0.0461 (5)
C30.71835 (13)0.5701 (2)1.0514 (4)0.0473 (5)
C40.67524 (12)0.5798 (2)0.8384 (3)0.0436 (5)
C50.60947 (12)0.4866 (2)0.7692 (3)0.0385 (5)
C60.58325 (11)0.38356 (19)0.9157 (3)0.0337 (4)
C70.50735 (12)0.28755 (19)0.8387 (3)0.0390 (5)
C80.57289 (12)0.0497 (2)0.9043 (4)0.0417 (5)
C90.57559 (11)0.0814 (2)1.0552 (4)0.0422 (5)
H10.56560.22611.22980.059*
H20.72240.46091.34620.054*
H30.76500.63281.09500.056*
H40.58190.49260.61980.047*
H50.50900.26530.68410.046*
H60.45620.33830.85650.046*
H70.55800.01950.75310.051*
H80.62720.09540.91740.051*
H90.61730.14791.01570.051*
H100.58980.05101.20650.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0679 (4)0.0428 (3)0.0828 (5)0.0173 (2)0.0324 (3)0.0034 (2)
O10.0618 (9)0.0389 (8)0.0467 (9)0.0050 (6)0.0016 (7)0.0006 (6)
N10.0266 (6)0.0258 (6)0.0545 (10)0.0007 (5)0.0077 (6)0.0043 (6)
C10.0365 (9)0.0272 (8)0.0493 (11)0.0049 (7)0.0029 (8)0.0052 (8)
C20.0383 (10)0.0387 (10)0.0582 (13)0.0016 (8)0.0081 (9)0.0107 (9)
C30.0323 (9)0.0367 (9)0.0727 (15)0.0036 (8)0.0044 (9)0.0146 (10)
C40.0363 (9)0.0299 (9)0.0670 (14)0.0038 (7)0.0158 (9)0.0074 (8)
C50.0372 (9)0.0304 (9)0.0481 (11)0.0024 (7)0.0057 (8)0.0045 (8)
C60.0295 (8)0.0255 (7)0.0463 (10)0.0007 (7)0.0043 (7)0.0059 (7)
C70.0349 (9)0.0302 (9)0.0510 (12)0.0037 (7)0.0002 (8)0.0011 (8)
C80.0314 (8)0.0295 (9)0.0665 (13)0.0012 (7)0.0153 (8)0.0067 (8)
C90.0286 (8)0.0293 (8)0.0689 (13)0.0005 (7)0.0062 (8)0.0048 (9)
Geometric parameters (Å, º) top
Cl1—C41.750 (2)C8—C91.510 (2)
O1—C11.360 (2)O1—H10.832
N1—C71.474 (2)C2—H20.950
N1—C81.468 (2)C3—H30.950
N1—C9i1.468 (2)C5—H40.950
C1—C21.395 (2)C7—H50.950
C1—C61.399 (2)C7—H60.950
C2—C31.375 (3)C8—H70.950
C3—C41.377 (3)C8—H80.950
C4—C51.376 (2)C9—H90.950
C5—C61.389 (2)C9—H100.950
C6—C71.520 (2)
C7—N1—C8112.58 (15)C3—C2—H2120.2
C7—N1—C9i111.96 (14)C2—C3—H3120.7
C8—N1—C9i109.43 (14)C4—C3—H3120.0
O1—C1—C2117.87 (17)C4—C5—H4119.7
O1—C1—C6122.46 (16)C6—C5—H4119.7
C2—C1—C6119.67 (18)N1—C7—H5108.8
C1—C2—C3120.75 (19)N1—C7—H6108.9
C2—C3—C4119.27 (18)C6—C7—H5108.3
Cl1—C4—C3119.17 (14)C6—C7—H6109.0
Cl1—C4—C5119.92 (16)H5—C7—H6109.5
C3—C4—C5120.90 (19)N1—C8—H7109.3
C4—C5—C6120.60 (18)N1—C8—H8109.5
C1—C6—C5118.68 (16)C9—C8—H7108.6
C1—C6—C7121.77 (17)C9—C8—H8110.1
C5—C6—C7119.41 (16)H7—C8—H8109.5
N1—C7—C6112.28 (15)N1i—C9—H9109.3
N1—C8—C9109.81 (17)N1i—C9—H10109.5
N1i—C9—C8109.75 (15)C8—C9—H9110.4
C1—O1—H1108.6C8—C9—H10108.5
C1—C2—H2119.0H9—C9—H10109.5
C7—N1—C8—C9175.34 (15)C6—C1—C2—C33.6 (3)
C8—N1—C7—C674.1 (2)C1—C2—C3—C40.6 (3)
C7—N1—C9i—C8i175.02 (17)C2—C3—C4—Cl1176.21 (16)
C9i—N1—C7—C6162.11 (16)C2—C3—C4—C52.3 (3)
C8—N1—C9i—C8i59.4 (2)Cl1—C4—C5—C6176.38 (15)
C9i—N1—C8—C959.5 (2)C3—C4—C5—C62.1 (3)
O1—C1—C2—C3175.83 (18)C4—C5—C6—C10.9 (2)
O1—C1—C6—C5175.67 (17)C4—C5—C6—C7176.70 (17)
O1—C1—C6—C70.0 (2)C1—C6—C7—N127.3 (2)
C2—C1—C6—C53.8 (2)C5—C6—C7—N1157.10 (17)
C2—C1—C6—C7179.42 (17)N1—C8—C9—N1i59.7 (2)
Symmetry code: (i) x+1, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.831.852.604 (2)150
C3—H3···O1ii0.952.603.547 (2)175
Symmetry code: (ii) x+3/2, y+1/2, z+5/2.

Experimental details

Crystal data
Chemical formulaC18H20Cl2N2O2
Mr367.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)15.755 (4), 9.2667 (17), 5.9771 (19)
β (°) 96.45 (2)
V3)867.1 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.39
Crystal size (mm)0.35 × 0.15 × 0.15
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correction
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections
2462, 1994, 1316
Rint0.020
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.149, 1.01
No. of reflections1994
No. of parameters119
No. of restraints?
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.54, 0.52

Computer programs: WinAFC (Rigaku/MSC, 2006), CrystalStructure (Rigaku/MSC, 2006), SIR92 (Altomare et al., 1993), CRYSTALS (Betteridge et al., 2003), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.8321.8522.604 (2)149.6
C3—H3···O1i0.952.5993.547 (2)175.3
Symmetry code: (i) x+3/2, y+1/2, z+5/2.
 

Acknowledgements

This study was supported financially in part by Grants-in-Aid (Nos. 19550040 and 20550075) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.

References

First citationAltomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350.  CrossRef Web of Science IUCr Journals Google Scholar
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBetteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.  Web of Science CrossRef IUCr Journals Google Scholar
First citationBharathi, K. S., Rahiman, A. K., Rajesh, K., Sreedaran, S., Aravindan, P. G., Velmurugan, D. & Narayanan, V. (2006). Polyhedron, 25, 2859–2868.  Web of Science CSD CrossRef CAS Google Scholar
First citationKubono, K., Tsuno, Y., Tani, K. & Yokoi, K. (2008). Acta Cryst. E64, o2309.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationKubono, K. & Yokoi, K. (2007). Acta Cryst. C63, o535–o537.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationKuppayee, M., Kumaran, D., Ponnuswamy, M. N., Kandaswamy, M., Violet, M. J., Chinnakali, K. & Fun, H.-K. (1999). Acta Cryst. C55, 2147–2149.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationRigaku/MSC (2006). WinAFC and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.  Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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