A monoclinic polymorph of 4,4'-dichloro-2,2'-(piperazine-1,4-diyl-dimethyl-ene)diphenol.

The titile compound, C(18)H(20)Cl(2)N(2)O(2), crystallizes as a monoclinic form in the space group P2(1)/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 mol-ecule lies on a crystallographic inversion centre at the piperazine ring centroid. An intra-molecular O-H⋯N hydrogen bond forms an S(6) ring motif. Inter-molecular C-H⋯O hydrogen bonding generates a C(5) chain motif propagating along the b axis, forming sheets parallel to (02) with a first-level graph set S(6)C(5)R(6) (6)(34).

Related literature

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

Crystal data

C18H20Cl2N2O2

M = 367.26

Monoclinic,

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 F 2 > 2σ(F 2)

R int = 0.020

3 standard reflections every 150 reflections intensity decay: 0.3%

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 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

Data collection: WinAFC (Rigaku/MSC, 2006 ▶); cell refinement: WinAFC; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038750/si2131sup1.cif

Structure factors: contains datablocks II. DOI: 10.1107/S1600536808038750/si2131IIsup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C18H20Cl2N2O2	F000 = 384.00
Mr = 367.26	Dx = 1.407 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 15.755 (4) Å	θ = 15.2–17.3º
b = 9.2667 (17) Å	µ = 0.39 mm−1
c = 5.9771 (19) Å	T = 298.1 K
β = 96.45 (2)º	Column, colorless
V = 867.1 (4) Å3	0.35 × 0.15 × 0.15 mm
Z = 2

Rigaku AFC-7R diffractometer	θmax = 27.5º
ω–2θ scans	h = −20→20
Absorption correction: none	k = 0→12
2462 measured reflections	l = −7→4
1994 independent reflections	3 standard reflections
1316 reflections with F2 > 2σ(F2)	every 150 reflections
Rint = 0.020	intensity decay: 0.4%

Refinement on F2	All 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 = 1.01	Δρmax = 0.54 e Å−3
1994 reflections	Δρmin = −0.52 e Å−3
119 parameters	Extinction correction: none

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).

	x	y	z	Uiso*/Ueq
Cl1	0.70334 (4)	0.71539 (6)	0.65673 (12)	0.0627 (2)
O1	0.59890 (10)	0.28682 (15)	1.2938 (2)	0.0497 (4)
N1	0.50843 (9)	0.15177 (16)	0.9674 (2)	0.0354 (3)
C1	0.62416 (12)	0.3779 (2)	1.1357 (3)	0.0378 (4)
C2	0.69309 (12)	0.4691 (2)	1.1990 (3)	0.0461 (5)
C3	0.71835 (13)	0.5701 (2)	1.0514 (4)	0.0473 (5)
C4	0.67524 (12)	0.5798 (2)	0.8384 (3)	0.0436 (5)
C5	0.60947 (12)	0.4866 (2)	0.7692 (3)	0.0385 (5)
C6	0.58325 (11)	0.38356 (19)	0.9157 (3)	0.0337 (4)
C7	0.50735 (12)	0.28755 (19)	0.8387 (3)	0.0390 (5)
C8	0.57289 (12)	0.0497 (2)	0.9043 (4)	0.0417 (5)
C9	0.57559 (11)	−0.0814 (2)	1.0552 (4)	0.0422 (5)
H1	0.5656	0.2261	1.2298	0.059*
H2	0.7224	0.4609	1.3462	0.054*
H3	0.7650	0.6328	1.0950	0.056*
H4	0.5819	0.4926	0.6198	0.047*
H5	0.5090	0.2653	0.6841	0.046*
H6	0.4562	0.3383	0.8565	0.046*
H7	0.5580	0.0195	0.7531	0.051*
H8	0.6272	0.0954	0.9174	0.051*
H9	0.6173	−0.1479	1.0157	0.051*
H10	0.5898	−0.0510	1.2065	0.051*

	U11	U22	U33	U12	U13	U23
Cl1	0.0679 (4)	0.0428 (3)	0.0828 (5)	−0.0173 (2)	0.0324 (3)	−0.0034 (2)
O1	0.0618 (9)	0.0389 (8)	0.0467 (9)	−0.0050 (6)	−0.0016 (7)	−0.0006 (6)
N1	0.0266 (6)	0.0258 (6)	0.0545 (10)	−0.0007 (5)	0.0077 (6)	−0.0043 (6)
C1	0.0365 (9)	0.0272 (8)	0.0493 (11)	0.0049 (7)	0.0029 (8)	−0.0052 (8)
C2	0.0383 (10)	0.0387 (10)	0.0582 (13)	0.0016 (8)	−0.0081 (9)	−0.0107 (9)
C3	0.0323 (9)	0.0367 (9)	0.0727 (15)	−0.0036 (8)	0.0044 (9)	−0.0146 (10)
C4	0.0363 (9)	0.0299 (9)	0.0670 (14)	−0.0038 (7)	0.0158 (9)	−0.0074 (8)
C5	0.0372 (9)	0.0304 (9)	0.0481 (11)	−0.0024 (7)	0.0057 (8)	−0.0045 (8)
C6	0.0295 (8)	0.0255 (7)	0.0463 (10)	0.0007 (7)	0.0043 (7)	−0.0059 (7)
C7	0.0349 (9)	0.0302 (9)	0.0510 (12)	−0.0037 (7)	0.0002 (8)	−0.0011 (8)
C8	0.0314 (8)	0.0295 (9)	0.0665 (13)	−0.0012 (7)	0.0153 (8)	−0.0067 (8)
C9	0.0286 (8)	0.0293 (8)	0.0689 (13)	−0.0005 (7)	0.0062 (8)	−0.0048 (9)

Cl1—C4	1.750 (2)	C8—C9	1.510 (2)
O1—C1	1.360 (2)	O1—H1	0.832
N1—C7	1.474 (2)	C2—H2	0.950
N1—C8	1.468 (2)	C3—H3	0.950
N1—C9i	1.468 (2)	C5—H4	0.950
C1—C2	1.395 (2)	C7—H5	0.950
C1—C6	1.399 (2)	C7—H6	0.950
C2—C3	1.375 (3)	C8—H7	0.950
C3—C4	1.377 (3)	C8—H8	0.950
C4—C5	1.376 (2)	C9—H9	0.950
C5—C6	1.389 (2)	C9—H10	0.950
C6—C7	1.520 (2)
C7—N1—C8	112.58 (15)	C3—C2—H2	120.2
C7—N1—C9i	111.96 (14)	C2—C3—H3	120.7
C8—N1—C9i	109.43 (14)	C4—C3—H3	120.0
O1—C1—C2	117.87 (17)	C4—C5—H4	119.7
O1—C1—C6	122.46 (16)	C6—C5—H4	119.7
C2—C1—C6	119.67 (18)	N1—C7—H5	108.8
C1—C2—C3	120.75 (19)	N1—C7—H6	108.9
C2—C3—C4	119.27 (18)	C6—C7—H5	108.3
Cl1—C4—C3	119.17 (14)	C6—C7—H6	109.0
Cl1—C4—C5	119.92 (16)	H5—C7—H6	109.5
C3—C4—C5	120.90 (19)	N1—C8—H7	109.3
C4—C5—C6	120.60 (18)	N1—C8—H8	109.5
C1—C6—C5	118.68 (16)	C9—C8—H7	108.6
C1—C6—C7	121.77 (17)	C9—C8—H8	110.1
C5—C6—C7	119.41 (16)	H7—C8—H8	109.5
N1—C7—C6	112.28 (15)	N1i—C9—H9	109.3
N1—C8—C9	109.81 (17)	N1i—C9—H10	109.5
N1i—C9—C8	109.75 (15)	C8—C9—H9	110.4
C1—O1—H1	108.6	C8—C9—H10	108.5
C1—C2—H2	119.0	H9—C9—H10	109.5
C7—N1—C8—C9	175.34 (15)	C6—C1—C2—C3	3.6 (3)
C8—N1—C7—C6	−74.1 (2)	C1—C2—C3—C4	−0.6 (3)
C7—N1—C9i—C8i	−175.02 (17)	C2—C3—C4—Cl1	176.21 (16)
C9i—N1—C7—C6	162.11 (16)	C2—C3—C4—C5	−2.3 (3)
C8—N1—C9i—C8i	59.4 (2)	Cl1—C4—C5—C6	−176.38 (15)
C9i—N1—C8—C9	−59.5 (2)	C3—C4—C5—C6	2.1 (3)
O1—C1—C2—C3	−175.83 (18)	C4—C5—C6—C1	0.9 (2)
O1—C1—C6—C5	175.67 (17)	C4—C5—C6—C7	176.70 (17)
O1—C1—C6—C7	0.0 (2)	C1—C6—C7—N1	−27.3 (2)
C2—C1—C6—C5	−3.8 (2)	C5—C6—C7—N1	157.10 (17)
C2—C1—C6—C7	−179.42 (17)	N1—C8—C9—N1i	59.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.83	1.85	2.604 (2)	150
C3—H3···O1ii	0.95	2.60	3.547 (2)	175

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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) .