4-[(4-Chloro-phen-yl)(phen-yl)-meth-yl]-piperazin-1-ium picrate monohydrate.

The asymmetric unit of the title compound, C(17)H(20)ClN(2) (+)·C(6)H(2)N(3)O(7) (-)·H(2)O, contains a piperazin-1-ium cation, a picrate anion and one solvent water mol-ecule. The piperazene ring is protonated at one N atom and adopts a highly distorted chair conformation with the chloro-pheny(phen-yl)methyl substituent on the second N atom in an equatorial position. The crystal structure is stabilized by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For the biological activity of 1-benzyl­piperazine, see: Campbell et al. (1973 ▶). For related structures, see: Jasinski et al. (2011 ▶); Song et al. (2012 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C17H20ClN2 +·C6H2N3O7 −·H2O

M = 533.92

Monoclinic,

a = 21.144 (2) Å

b = 8.2997 (8) Å

c = 28.528 (3) Å

β = 93.029 (1)°

V = 4999.3 (8) Å3

Z = 8

Mo Kα radiation

μ = 0.21 mm−1

T = 296 K

0.25 × 0.22 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.949, T max = 0.985

12567 measured reflections

4417 independent reflections

2996 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.175

S = 1.04

4417 reflections

334 parameters

H-atom parameters constrained

Δρmax = 0.63 e Å−3

Δρmin = −0.46 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812031984/sj5246sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812031984/sj5246Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812031984/sj5246Isup3.cml

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

C17H20ClN2+·C6H2N3O7−·H2O	F(000) = 2224
Mr = 533.92	Dx = 1.419 Mg m−3
Monoclinic, C2/c	Melting point = 441–445 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 21.144 (2) Å	Cell parameters from 2514 reflections
b = 8.2997 (8) Å	θ = 2.3–21.0°
c = 28.528 (3) Å	µ = 0.21 mm−1
β = 93.029 (1)°	T = 296 K
V = 4999.3 (8) Å3	Block, yellow
Z = 8	0.25 × 0.22 × 0.07 mm

Bruker APEXII CCD diffractometer	4417 independent reflections
Radiation source: fine-focus sealed tube	2996 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 25.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −25→20
Tmin = 0.949, Tmax = 0.985	k = −9→8
12567 measured reflections	l = −31→33

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.175	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0837P)2 + 4.3115P] where P = (Fo2 + 2Fc2)/3
4417 reflections	(Δ/σ)max < 0.001
334 parameters	Δρmax = 0.63 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.4904 (2)	0.8333 (6)	0.18443 (11)	0.0783 (11)
C2	0.5527 (2)	0.8799 (4)	0.19014 (11)	0.0737 (10)
H2	0.5633	0.9873	0.1955	0.088*
C3	0.59944 (16)	0.7637 (4)	0.18770 (10)	0.0606 (8)
H3	0.6418	0.7938	0.1915	0.073*
C4	0.58414 (13)	0.6039 (4)	0.17965 (9)	0.0490 (7)
C5	0.52105 (16)	0.5623 (5)	0.17391 (12)	0.0700 (9)
H5	0.5100	0.4553	0.1682	0.084*
C6	0.47386 (18)	0.6774 (7)	0.17651 (14)	0.0917 (13)
H6	0.4314	0.6481	0.1729	0.110*
C7	0.63529 (13)	0.4768 (3)	0.17948 (9)	0.0471 (7)
H7	0.6158	0.3740	0.1699	0.057*
C8	0.66452 (14)	0.4592 (3)	0.22959 (9)	0.0472 (7)
C9	0.63449 (16)	0.3611 (4)	0.26056 (10)	0.0609 (8)
H9	0.5991	0.3016	0.2503	0.073*
C10	0.65702 (19)	0.3512 (4)	0.30690 (11)	0.0749 (10)
H10	0.6356	0.2884	0.3279	0.090*
C11	0.7106 (2)	0.4329 (4)	0.32234 (11)	0.0766 (11)
H11	0.7259	0.4240	0.3534	0.092*
C12	0.74098 (18)	0.5272 (4)	0.29149 (11)	0.0683 (9)
H12	0.7776	0.5820	0.3015	0.082*
C13	0.71784 (15)	0.5421 (3)	0.24554 (10)	0.0572 (8)
H13	0.7385	0.6089	0.2251	0.069*
C14	0.65583 (14)	0.5363 (4)	0.09816 (9)	0.0526 (7)
H14A	0.6220	0.6154	0.0980	0.063*
H14B	0.6379	0.4345	0.0874	0.063*
C15	0.70566 (15)	0.5901 (4)	0.06551 (10)	0.0569 (8)
H15A	0.6869	0.5989	0.0338	0.068*
H15B	0.7213	0.6956	0.0750	0.068*
C16	0.78429 (15)	0.4460 (4)	0.11470 (10)	0.0624 (8)
H16A	0.8031	0.5443	0.1274	0.075*
H16B	0.8170	0.3640	0.1148	0.075*
C17	0.73229 (14)	0.3923 (4)	0.14476 (10)	0.0535 (7)
H17A	0.7135	0.2937	0.1321	0.064*
H17B	0.7495	0.3703	0.1763	0.064*
C18	0.89491 (14)	0.6145 (3)	0.98892 (9)	0.0476 (7)
C19	0.92823 (13)	0.7277 (3)	1.01969 (9)	0.0458 (6)
C20	0.98723 (13)	0.7849 (3)	1.01257 (9)	0.0478 (7)
H20	1.0065	0.8563	1.0340	0.057*
C21	1.01856 (13)	0.7372 (3)	0.97362 (9)	0.0463 (6)
C22	0.98998 (13)	0.6302 (3)	0.94120 (9)	0.0473 (7)
H22	1.0111	0.5966	0.9151	0.057*
C23	0.93097 (14)	0.5763 (3)	0.94855 (8)	0.0456 (6)
Cl1	0.43227 (7)	0.9810 (2)	0.18712 (4)	0.1402 (6)
N1	0.68382 (10)	0.5177 (2)	0.14618 (7)	0.0434 (5)
N2	0.75908 (12)	0.4746 (3)	0.06606 (8)	0.0579 (7)
H2A	0.7458	0.3808	0.0531	0.069*
H2B	0.7900	0.5140	0.0488	0.069*
N3	0.89901 (14)	0.7854 (3)	1.06134 (9)	0.0658 (7)
N4	1.08105 (12)	0.7960 (3)	0.96648 (9)	0.0631 (7)
N5	0.90198 (15)	0.4691 (3)	0.91305 (9)	0.0638 (7)
O1	0.84301 (10)	0.5503 (3)	0.99573 (7)	0.0664 (6)
O2	0.84210 (16)	0.7700 (4)	1.06424 (12)	0.1309 (14)
O3	0.92957 (14)	0.8649 (4)	1.08951 (9)	0.1129 (11)
O4	1.10570 (11)	0.8886 (3)	0.99550 (9)	0.0830 (7)
O5	1.10730 (11)	0.7526 (4)	0.93145 (9)	0.0903 (8)
O6	0.93478 (15)	0.3624 (3)	0.89779 (9)	0.0927 (9)
O7	0.84749 (14)	0.4966 (4)	0.89915 (9)	0.0922 (9)
O1W	0.74452 (12)	0.3604 (3)	0.95584 (11)	0.0996 (9)
H1WA	0.7756	0.4210	0.9638	0.100*
H1WB	0.7219	0.4009	0.9333	0.100*

	U11	U22	U33	U12	U13	U23
C1	0.076 (3)	0.113 (3)	0.0465 (18)	0.037 (2)	0.0071 (17)	0.008 (2)
C2	0.104 (3)	0.069 (2)	0.0476 (18)	0.020 (2)	0.0063 (18)	−0.0020 (16)
C3	0.063 (2)	0.066 (2)	0.0534 (17)	0.0055 (16)	0.0062 (14)	−0.0042 (15)
C4	0.0517 (17)	0.0633 (19)	0.0323 (13)	−0.0009 (14)	0.0060 (11)	0.0012 (12)
C5	0.057 (2)	0.086 (2)	0.066 (2)	−0.0055 (18)	−0.0042 (16)	0.0045 (18)
C6	0.053 (2)	0.139 (4)	0.083 (3)	0.013 (2)	−0.0016 (19)	0.021 (3)
C7	0.0550 (17)	0.0479 (16)	0.0390 (14)	−0.0083 (13)	0.0066 (12)	−0.0017 (12)
C8	0.0609 (18)	0.0451 (15)	0.0362 (14)	0.0050 (13)	0.0099 (12)	0.0016 (12)
C9	0.070 (2)	0.0621 (19)	0.0514 (17)	−0.0011 (16)	0.0138 (15)	0.0072 (15)
C10	0.102 (3)	0.078 (2)	0.0464 (18)	0.010 (2)	0.0210 (18)	0.0172 (17)
C11	0.114 (3)	0.074 (2)	0.0407 (17)	0.022 (2)	−0.0060 (18)	−0.0037 (17)
C12	0.092 (3)	0.059 (2)	0.0517 (19)	0.0035 (18)	−0.0103 (17)	−0.0110 (16)
C13	0.076 (2)	0.0493 (17)	0.0459 (16)	−0.0060 (15)	0.0015 (14)	0.0000 (13)
C14	0.0597 (18)	0.0622 (18)	0.0360 (14)	−0.0025 (14)	0.0050 (12)	0.0029 (13)
C15	0.068 (2)	0.0625 (19)	0.0413 (15)	−0.0056 (15)	0.0105 (13)	0.0058 (13)
C16	0.0562 (19)	0.077 (2)	0.0551 (18)	0.0061 (16)	0.0105 (14)	−0.0074 (16)
C17	0.0615 (18)	0.0558 (17)	0.0437 (15)	0.0042 (14)	0.0074 (13)	−0.0004 (13)
C18	0.0596 (18)	0.0456 (15)	0.0377 (14)	−0.0050 (13)	0.0036 (12)	0.0050 (12)
C19	0.0569 (18)	0.0463 (15)	0.0349 (13)	−0.0004 (13)	0.0105 (12)	−0.0017 (11)
C20	0.0556 (18)	0.0469 (15)	0.0407 (14)	0.0011 (13)	0.0000 (12)	−0.0056 (12)
C21	0.0450 (16)	0.0524 (16)	0.0416 (14)	0.0024 (12)	0.0037 (12)	−0.0032 (12)
C22	0.0587 (18)	0.0481 (16)	0.0357 (14)	0.0051 (13)	0.0066 (12)	0.0004 (12)
C23	0.0615 (18)	0.0420 (15)	0.0332 (13)	−0.0034 (13)	0.0002 (12)	−0.0011 (11)
Cl1	0.1339 (11)	0.1911 (15)	0.0945 (9)	0.1027 (11)	−0.0038 (7)	0.0031 (8)
N1	0.0497 (13)	0.0483 (13)	0.0329 (11)	0.0007 (10)	0.0079 (9)	0.0009 (9)
N2	0.0628 (16)	0.0653 (16)	0.0474 (14)	−0.0124 (13)	0.0204 (11)	−0.0090 (12)
N3	0.073 (2)	0.0739 (18)	0.0525 (15)	−0.0172 (15)	0.0207 (14)	−0.0167 (13)
N4	0.0517 (16)	0.0783 (18)	0.0599 (16)	−0.0023 (13)	0.0082 (13)	−0.0124 (14)
N5	0.083 (2)	0.0657 (18)	0.0430 (14)	−0.0191 (16)	0.0051 (14)	−0.0043 (13)
O1	0.0707 (15)	0.0780 (15)	0.0518 (12)	−0.0294 (12)	0.0165 (10)	−0.0060 (10)
O2	0.110 (2)	0.157 (3)	0.134 (3)	−0.068 (2)	0.080 (2)	−0.084 (2)
O3	0.096 (2)	0.176 (3)	0.0682 (16)	−0.019 (2)	0.0176 (14)	−0.0608 (19)
O4	0.0640 (15)	0.1024 (19)	0.0827 (16)	−0.0237 (14)	0.0053 (12)	−0.0275 (15)
O5	0.0620 (15)	0.131 (2)	0.0809 (17)	−0.0089 (15)	0.0277 (13)	−0.0341 (16)
O6	0.142 (3)	0.0651 (15)	0.0704 (16)	−0.0023 (16)	0.0001 (16)	−0.0268 (13)
O7	0.0768 (18)	0.135 (2)	0.0642 (16)	−0.0288 (17)	−0.0021 (13)	−0.0199 (15)
O1W	0.0735 (17)	0.0920 (19)	0.133 (2)	−0.0152 (14)	0.0024 (16)	−0.0241 (17)

C1—C6	1.356 (6)	C15—H15B	0.9700
C1—C2	1.376 (5)	C16—N2	1.479 (4)
C1—Cl1	1.740 (4)	C16—C17	1.497 (4)
C2—C3	1.384 (5)	C16—H16A	0.9700
C2—H2	0.9300	C16—H16B	0.9700
C3—C4	1.382 (4)	C17—N1	1.463 (3)
C3—H3	0.9300	C17—H17A	0.9700
C4—C5	1.379 (4)	C17—H17B	0.9700
C4—C7	1.511 (4)	C18—O1	1.244 (3)
C5—C6	1.386 (5)	C18—C19	1.444 (4)
C5—H5	0.9300	C18—C23	1.449 (4)
C6—H6	0.9300	C19—C20	1.360 (4)
C7—N1	1.474 (3)	C19—N3	1.449 (4)
C7—C8	1.534 (4)	C20—C21	1.381 (4)
C7—H7	0.9800	C20—H20	0.9300
C8—C13	1.378 (4)	C21—C22	1.397 (4)
C8—C9	1.381 (4)	C21—N4	1.433 (4)
C9—C10	1.384 (4)	C22—C23	1.352 (4)
C9—H9	0.9300	C22—H22	0.9300
C10—C11	1.372 (5)	C23—N5	1.459 (4)
C10—H10	0.9300	N2—H2A	0.9000
C11—C12	1.364 (5)	N2—H2B	0.9000
C11—H11	0.9300	N3—O3	1.202 (3)
C12—C13	1.380 (4)	N3—O2	1.217 (4)
C12—H12	0.9300	N4—O5	1.223 (3)
C13—H13	0.9300	N4—O4	1.226 (3)
C14—N1	1.471 (3)	N5—O6	1.219 (4)
C14—C15	1.510 (4)	N5—O7	1.220 (4)
C14—H14A	0.9700	O1W—H1WA	0.8501
C14—H14B	0.9700	O1W—H1WA	0.8501
C15—N2	1.481 (4)	O1W—H1WB	0.8502
C15—H15A	0.9700
C6—C1—C2	121.6 (3)	H15A—C15—H15B	108.0
C6—C1—Cl1	120.2 (4)	N2—C16—C17	110.2 (2)
C2—C1—Cl1	118.2 (4)	N2—C16—H16A	109.6
C1—C2—C3	118.7 (4)	C17—C16—H16A	109.6
C1—C2—H2	120.6	N2—C16—H16B	109.6
C3—C2—H2	120.6	C17—C16—H16B	109.6
C4—C3—C2	121.0 (3)	H16A—C16—H16B	108.1
C4—C3—H3	119.5	N1—C17—C16	109.9 (2)
C2—C3—H3	119.5	N1—C17—H17A	109.7
C5—C4—C3	118.5 (3)	C16—C17—H17A	109.7
C5—C4—C7	120.9 (3)	N1—C17—H17B	109.7
C3—C4—C7	120.6 (3)	C16—C17—H17B	109.7
C4—C5—C6	121.0 (4)	H17A—C17—H17B	108.2
C4—C5—H5	119.5	O1—C18—C19	126.1 (3)
C6—C5—H5	119.5	O1—C18—C23	122.4 (2)
C1—C6—C5	119.2 (4)	C19—C18—C23	111.4 (2)
C1—C6—H6	120.4	C20—C19—C18	123.9 (2)
C5—C6—H6	120.4	C20—C19—N3	116.2 (2)
N1—C7—C4	111.4 (2)	C18—C19—N3	119.9 (3)
N1—C7—C8	111.3 (2)	C19—C20—C21	120.2 (2)
C4—C7—C8	108.5 (2)	C19—C20—H20	119.9
N1—C7—H7	108.6	C21—C20—H20	119.9
C4—C7—H7	108.6	C20—C21—C22	120.4 (3)
C8—C7—H7	108.6	C20—C21—N4	120.1 (2)
C13—C8—C9	118.6 (3)	C22—C21—N4	119.5 (2)
C13—C8—C7	122.8 (2)	C23—C22—C21	118.6 (2)
C9—C8—C7	118.5 (3)	C23—C22—H22	120.7
C8—C9—C10	120.0 (3)	C21—C22—H22	120.7
C8—C9—H9	120.0	C22—C23—C18	125.4 (2)
C10—C9—H9	120.0	C22—C23—N5	116.8 (2)
C11—C10—C9	120.9 (3)	C18—C23—N5	117.7 (3)
C11—C10—H10	119.5	C17—N1—C14	107.3 (2)
C9—C10—H10	119.5	C17—N1—C7	111.5 (2)
C12—C11—C10	119.1 (3)	C14—N1—C7	111.4 (2)
C12—C11—H11	120.5	C16—N2—C15	110.5 (2)
C10—C11—H11	120.5	C16—N2—H2A	109.5
C11—C12—C13	120.6 (3)	C15—N2—H2A	109.5
C11—C12—H12	119.7	C16—N2—H2B	109.5
C13—C12—H12	119.7	C15—N2—H2B	109.5
C8—C13—C12	120.8 (3)	H2A—N2—H2B	108.1
C8—C13—H13	119.6	O3—N3—O2	120.7 (3)
C12—C13—H13	119.6	O3—N3—C19	119.5 (3)
N1—C14—C15	110.2 (2)	O2—N3—C19	119.1 (3)
N1—C14—H14A	109.6	O5—N4—O4	122.8 (3)
C15—C14—H14A	109.6	O5—N4—C21	118.5 (3)
N1—C14—H14B	109.6	O4—N4—C21	118.7 (2)
C15—C14—H14B	109.6	O6—N5—O7	124.4 (3)
H14A—C14—H14B	108.1	O6—N5—C23	117.7 (3)
N2—C15—C14	111.0 (2)	O7—N5—C23	117.8 (3)
N2—C15—H15A	109.4	H1WA—O1W—H1WA	0.0
C14—C15—H15A	109.4	H1WA—O1W—H1WB	111.4
N2—C15—H15B	109.4	H1WA—O1W—H1WB	111.4
C14—C15—H15B	109.4

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1Wi	0.90	2.03	2.850 (4)	151
N2—H2B···O1ii	0.90	1.96	2.819 (3)	160
N2—H2B···O2ii	0.90	2.42	3.017 (4)	124
O1W—H1WA···O1	0.85	1.97	2.805 (3)	168
C16—H16B···O5iii	0.97	2.34	3.166 (4)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1W i	0.90	2.03	2.850 (4)	151
N2—H2B⋯O1ii	0.90	1.96	2.819 (3)	160
N2—H2B⋯O2ii	0.90	2.42	3.017 (4)	124
O1W—H1WA⋯O1	0.85	1.97	2.805 (3)	168
C16—H16B⋯O5iii	0.97	2.34	3.166 (4)	143

Symmetry codes: (i) ; (ii) ; (iii) .