4-(4-Carboxy-benz-yl)-1-methyl-piperazin-1-ium picrate.

The title compound, C(13)H(19)N(2)O(2) (+)·C(6)H(2)N(3)O(7) (-), is a salt obtained by cocrystallization of 4-[(4-methyl-piperazin-1-yl)meth-yl]benzoic acid and picric acid. The cations adopt an 'L-shaped' conformation and are linked into chains along [010] by O-H⋯N hydrogen bonds. The NH group of each piperazinium ring forms a hydrogen bond to the phenolate O atom of a picrate anion, and the picrate anions form face-to-face contacts with an inter-planar separation of 3.023 (1) Å.

Related literature

For general background, see: Druker et al. (2001 ▶). For related structures, see: Swamy et al. (2007 ▶); Bindya et al. (2007 ▶); Sarojini et al. (2007 ▶); Wang & Jia (2008 ▶).

Experimental

Crystal data

C13H19N2O2 +·C6H2N3O7 −

M = 463.41

Triclinic,

a = 7.3020 (12) Å

b = 9.5993 (16) Å

c = 15.131 (3) Å

α = 86.448 (2)°

β = 79.145 (2)°

γ = 79.950 (2)°

V = 1025.2 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 296 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.965, T max = 0.976

5373 measured reflections

3565 independent reflections

2745 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.104

S = 1.06

3565 reflections

305 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.17 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 datablocks global, I. DOI: 10.1107/S1600536809004474/bi2341sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809004474/bi2341Isup2.hkl

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

C13H19N2O2+·C6H2N3O7−	Z = 2
Mr = 463.41	F(000) = 484
Triclinic, P1	Dx = 1.501 Mg m−3
Hall symbol: -P 1	Melting point = 510–504 K
a = 7.3020 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5993 (16) Å	Cell parameters from 1962 reflections
c = 15.131 (3) Å	θ = 2.5–26.9°
α = 86.448 (2)°	µ = 0.12 mm−1
β = 79.145 (2)°	T = 296 K
γ = 79.950 (2)°	Block, colourless
V = 1025.2 (3) Å3	0.30 × 0.20 × 0.20 mm

Bruker SMART CCD diffractometer	3565 independent reflections
Radiation source: fine-focus sealed tube	2745 reflections with I > 2σ(I)
graphite	Rint = 0.016
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −8→6
Tmin = 0.965, Tmax = 0.976	k = −11→9
5373 measured reflections	l = −18→18

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104	w = 1/[σ2(Fo2) + (0.0447P)2 + 0.2218P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3565 reflections	Δρmax = 0.18 e Å−3
305 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.023 (2)

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	0.5333 (3)	1.0778 (2)	0.14228 (14)	0.0426 (5)
C2	0.6431 (3)	1.0691 (2)	0.05175 (13)	0.0438 (5)
C3	0.7751 (3)	0.9547 (2)	0.02127 (13)	0.0430 (5)
H3	0.8395	0.9546	−0.0379	0.052*
C4	0.8126 (3)	0.8398 (2)	0.07793 (12)	0.0379 (4)
C5	0.7175 (2)	0.83776 (19)	0.16598 (12)	0.0359 (4)
H5	0.7422	0.7595	0.2039	0.043*
C6	0.5870 (3)	0.9521 (2)	0.19627 (12)	0.0372 (4)
C7	0.1636 (3)	1.33630 (19)	0.60024 (12)	0.0366 (4)
C8	0.1280 (2)	1.18702 (18)	0.60753 (11)	0.0320 (4)
C9	0.2178 (3)	1.09572 (19)	0.53938 (12)	0.0380 (4)
H9	0.2943	1.1292	0.4892	0.046*
C10	0.1949 (3)	0.95535 (19)	0.54527 (12)	0.0391 (4)
H10	0.2557	0.8954	0.4989	0.047*
C11	0.0818 (2)	0.90303 (18)	0.61993 (12)	0.0349 (4)
C12	−0.0108 (2)	0.99528 (18)	0.68722 (12)	0.0361 (4)
H12	−0.0897	0.9622	0.7367	0.043*
C13	0.0123 (2)	1.13606 (18)	0.68187 (12)	0.0348 (4)
H13	−0.0494	1.1964	0.7279	0.042*
C14	0.0608 (3)	0.74891 (19)	0.62770 (13)	0.0413 (5)
H14A	−0.0640	0.7413	0.6616	0.050*
H14B	0.0677	0.7156	0.5677	0.050*
C15	0.3984 (3)	0.6541 (2)	0.62183 (12)	0.0399 (5)
H15A	0.4281	0.7488	0.6208	0.048*
H15B	0.4063	0.6282	0.5601	0.048*
C16	0.5410 (3)	0.5522 (2)	0.66450 (12)	0.0415 (5)
H16A	0.5196	0.4562	0.6598	0.050*
H16B	0.6674	0.5591	0.6324	0.050*
C17	0.3292 (3)	0.5816 (2)	0.80965 (12)	0.0402 (5)
H17A	0.3189	0.6046	0.8721	0.048*
H17B	0.2985	0.4875	0.8083	0.048*
C18	0.1914 (3)	0.68674 (19)	0.76667 (12)	0.0375 (4)
H18A	0.0639	0.6846	0.7991	0.045*
H18B	0.2190	0.7813	0.7701	0.045*
C19	0.6653 (3)	0.4834 (2)	0.80485 (15)	0.0598 (6)
H19A	0.6595	0.5121	0.8651	0.090*
H19B	0.7903	0.4841	0.7710	0.090*
H19C	0.6355	0.3896	0.8065	0.090*
N1	0.6141 (3)	1.1856 (2)	−0.01420 (15)	0.0587 (5)
N2	0.9524 (2)	0.71935 (19)	0.04516 (11)	0.0471 (4)
N3	0.4925 (2)	0.9427 (2)	0.28970 (11)	0.0469 (4)
N4	0.2038 (2)	0.65332 (14)	0.67160 (9)	0.0340 (4)
N5	0.5264 (2)	0.58329 (17)	0.76126 (10)	0.0375 (4)
O1	0.4059 (2)	1.17657 (15)	0.17135 (11)	0.0614 (4)
O2	0.5114 (3)	1.2956 (2)	0.00975 (14)	0.0921 (6)
O3	0.6952 (3)	1.16659 (19)	−0.09220 (12)	0.0799 (6)
O4	1.0379 (2)	0.72647 (18)	−0.03240 (10)	0.0680 (5)
O5	0.9804 (2)	0.61680 (16)	0.09632 (11)	0.0649 (5)
O6	0.4639 (2)	0.82634 (18)	0.32167 (10)	0.0633 (4)
O7	0.4470 (2)	1.05126 (19)	0.33248 (10)	0.0707 (5)
O8	0.1067 (2)	1.40458 (13)	0.67570 (8)	0.0445 (4)
H8	0.1397	1.4825	0.6691	0.067*
O9	0.2400 (2)	1.38891 (15)	0.53152 (9)	0.0605 (4)
H5A	0.551 (3)	0.669 (2)	0.7674 (13)	0.045 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0386 (11)	0.0359 (11)	0.0586 (13)	−0.0106 (8)	−0.0166 (9)	−0.0054 (9)
C2	0.0462 (12)	0.0407 (11)	0.0508 (12)	−0.0163 (9)	−0.0195 (10)	0.0092 (9)
C3	0.0449 (11)	0.0537 (13)	0.0350 (10)	−0.0208 (10)	−0.0079 (9)	0.0021 (9)
C4	0.0359 (10)	0.0421 (11)	0.0355 (10)	−0.0087 (8)	−0.0032 (8)	−0.0036 (8)
C5	0.0377 (10)	0.0382 (10)	0.0345 (10)	−0.0097 (8)	−0.0102 (8)	−0.0007 (8)
C6	0.0368 (10)	0.0426 (11)	0.0348 (10)	−0.0100 (8)	−0.0079 (8)	−0.0059 (8)
C7	0.0393 (10)	0.0345 (10)	0.0353 (10)	−0.0079 (8)	−0.0036 (8)	−0.0002 (8)
C8	0.0339 (9)	0.0298 (9)	0.0334 (9)	−0.0060 (7)	−0.0086 (8)	−0.0001 (7)
C9	0.0457 (11)	0.0366 (10)	0.0307 (9)	−0.0071 (8)	−0.0045 (8)	0.0000 (8)
C10	0.0491 (11)	0.0327 (10)	0.0349 (10)	−0.0028 (8)	−0.0081 (9)	−0.0067 (8)
C11	0.0360 (10)	0.0296 (10)	0.0423 (10)	−0.0070 (7)	−0.0141 (8)	0.0004 (8)
C12	0.0311 (10)	0.0339 (10)	0.0415 (10)	−0.0064 (7)	−0.0026 (8)	0.0042 (8)
C13	0.0327 (9)	0.0311 (10)	0.0378 (10)	−0.0029 (7)	−0.0008 (8)	−0.0027 (8)
C14	0.0461 (11)	0.0317 (10)	0.0503 (11)	−0.0104 (8)	−0.0157 (9)	−0.0015 (8)
C15	0.0448 (11)	0.0371 (10)	0.0347 (10)	−0.0087 (8)	0.0013 (8)	0.0020 (8)
C16	0.0423 (11)	0.0371 (11)	0.0385 (10)	−0.0016 (8)	0.0047 (8)	−0.0018 (8)
C17	0.0392 (10)	0.0418 (11)	0.0348 (10)	−0.0040 (8)	0.0030 (8)	−0.0016 (8)
C18	0.0349 (10)	0.0371 (10)	0.0380 (10)	−0.0026 (8)	−0.0013 (8)	−0.0070 (8)
C19	0.0513 (13)	0.0579 (14)	0.0596 (14)	0.0144 (11)	−0.0087 (11)	0.0092 (11)
N1	0.0678 (13)	0.0507 (12)	0.0688 (14)	−0.0265 (10)	−0.0316 (11)	0.0184 (10)
N2	0.0420 (10)	0.0529 (11)	0.0439 (10)	−0.0091 (8)	0.0012 (8)	−0.0076 (8)
N3	0.0368 (9)	0.0614 (12)	0.0420 (9)	−0.0061 (8)	−0.0046 (7)	−0.0111 (9)
N4	0.0385 (8)	0.0289 (8)	0.0338 (8)	−0.0064 (6)	−0.0031 (6)	−0.0028 (6)
N5	0.0363 (9)	0.0317 (9)	0.0407 (9)	−0.0006 (7)	−0.0023 (7)	−0.0001 (7)
O1	0.0513 (9)	0.0413 (9)	0.0904 (12)	−0.0006 (7)	−0.0138 (8)	−0.0095 (8)
O2	0.1085 (16)	0.0526 (11)	0.1104 (16)	0.0045 (11)	−0.0328 (12)	0.0230 (11)
O3	0.1177 (16)	0.0729 (12)	0.0587 (11)	−0.0338 (11)	−0.0321 (11)	0.0242 (9)
O4	0.0656 (10)	0.0825 (12)	0.0461 (9)	−0.0069 (9)	0.0138 (8)	−0.0138 (8)
O5	0.0638 (10)	0.0524 (10)	0.0677 (10)	0.0059 (8)	−0.0006 (8)	0.0038 (8)
O6	0.0623 (10)	0.0701 (11)	0.0503 (9)	−0.0117 (8)	0.0055 (7)	0.0075 (8)
O7	0.0693 (11)	0.0822 (12)	0.0591 (10)	−0.0126 (9)	0.0035 (8)	−0.0371 (9)
O8	0.0599 (9)	0.0308 (7)	0.0409 (7)	−0.0161 (6)	0.0051 (6)	−0.0049 (6)
O9	0.0948 (12)	0.0441 (9)	0.0388 (8)	−0.0271 (8)	0.0105 (8)	0.0014 (6)

C1—O1	1.244 (2)	C14—H14B	0.970
C1—C2	1.450 (3)	C15—N4	1.479 (2)
C1—C6	1.453 (3)	C15—C16	1.509 (3)
C2—C3	1.369 (3)	C15—H15A	0.970
C2—N1	1.466 (3)	C15—H15B	0.970
C3—C4	1.375 (3)	C16—N5	1.493 (2)
C3—H3	0.930	C16—H16A	0.970
C4—C5	1.382 (2)	C16—H16B	0.970
C4—N2	1.447 (2)	C17—N5	1.490 (2)
C5—C6	1.362 (2)	C17—C18	1.505 (2)
C5—H5	0.930	C17—H17A	0.970
C6—N3	1.456 (2)	C17—H17B	0.970
C7—O9	1.209 (2)	C18—N4	1.476 (2)
C7—O8	1.313 (2)	C18—H18A	0.970
C7—C8	1.494 (2)	C18—H18B	0.970
C8—C9	1.385 (2)	C19—N5	1.489 (2)
C8—C13	1.391 (2)	C19—H19A	0.960
C9—C10	1.382 (3)	C19—H19B	0.960
C9—H9	0.930	C19—H19C	0.960
C10—C11	1.390 (3)	N1—O2	1.215 (3)
C10—H10	0.930	N1—O3	1.226 (3)
C11—C12	1.386 (2)	N2—O4	1.225 (2)
C11—C14	1.509 (2)	N2—O5	1.227 (2)
C12—C13	1.386 (2)	N3—O7	1.223 (2)
C12—H12	0.930	N3—O6	1.226 (2)
C13—H13	0.930	N5—H5A	0.89 (2)
C14—N4	1.491 (2)	O8—H8	0.820
C14—H14A	0.970
O1—C1—C2	125.88 (19)	C16—C15—H15A	109.3
O1—C1—C6	122.99 (19)	N4—C15—H15B	109.3
C2—C1—C6	111.10 (16)	C16—C15—H15B	109.3
C3—C2—C1	123.83 (18)	H15A—C15—H15B	108.0
C3—C2—N1	115.70 (19)	N5—C16—C15	111.14 (14)
C1—C2—N1	120.46 (19)	N5—C16—H16A	109.4
C2—C3—C4	120.19 (18)	C15—C16—H16A	109.4
C2—C3—H3	119.9	N5—C16—H16B	109.4
C4—C3—H3	119.9	C15—C16—H16B	109.4
C3—C4—C5	120.72 (17)	H16A—C16—H16B	108.0
C3—C4—N2	119.81 (17)	N5—C17—C18	110.62 (15)
C5—C4—N2	119.47 (17)	N5—C17—H17A	109.5
C6—C5—C4	118.97 (17)	C18—C17—H17A	109.5
C6—C5—H5	120.5	N5—C17—H17B	109.5
C4—C5—H5	120.5	C18—C17—H17B	109.5
C5—C6—C1	125.15 (17)	H17A—C17—H17B	108.1
C5—C6—N3	115.99 (17)	N4—C18—C17	110.48 (14)
C1—C6—N3	118.84 (16)	N4—C18—H18A	109.6
O9—C7—O8	123.05 (17)	C17—C18—H18A	109.6
O9—C7—C8	123.12 (16)	N4—C18—H18B	109.6
O8—C7—C8	113.82 (15)	C17—C18—H18B	109.6
C9—C8—C13	119.15 (16)	H18A—C18—H18B	108.1
C9—C8—C7	118.80 (16)	N5—C19—H19A	109.5
C13—C8—C7	122.01 (15)	N5—C19—H19B	109.5
C10—C9—C8	120.65 (17)	H19A—C19—H19B	109.5
C10—C9—H9	119.7	N5—C19—H19C	109.5
C8—C9—H9	119.7	H19A—C19—H19C	109.5
C9—C10—C11	120.59 (16)	H19B—C19—H19C	109.5
C9—C10—H10	119.7	O2—N1—O3	122.7 (2)
C11—C10—H10	119.7	O2—N1—C2	119.6 (2)
C12—C11—C10	118.64 (16)	O3—N1—C2	117.7 (2)
C12—C11—C14	120.67 (16)	O4—N2—O5	123.64 (17)
C10—C11—C14	120.69 (16)	O4—N2—C4	117.71 (17)
C13—C12—C11	121.00 (17)	O5—N2—C4	118.64 (16)
C13—C12—H12	119.5	O7—N3—O6	123.34 (18)
C11—C12—H12	119.5	O7—N3—C6	118.32 (18)
C12—C13—C8	119.95 (16)	O6—N3—C6	118.34 (17)
C12—C13—H13	120.0	C18—N4—C15	110.02 (14)
C8—C13—H13	120.0	C18—N4—C14	112.50 (13)
N4—C14—C11	115.44 (15)	C15—N4—C14	111.92 (14)
N4—C14—H14A	108.4	C17—N5—C19	111.33 (15)
C11—C14—H14A	108.4	C17—N5—C16	109.59 (15)
N4—C14—H14B	108.4	C19—N5—C16	112.03 (15)
C11—C14—H14B	108.4	C17—N5—H5A	106.5 (13)
H14A—C14—H14B	107.5	C19—N5—H5A	105.9 (13)
N4—C15—C16	111.45 (14)	C16—N5—H5A	111.3 (13)
N4—C15—H15A	109.3	C7—O8—H8	109.5
O1—C1—C2—C3	−176.28 (19)	C9—C8—C13—C12	0.4 (3)
C6—C1—C2—C3	2.0 (3)	C7—C8—C13—C12	−177.54 (16)
O1—C1—C2—N1	2.5 (3)	C12—C11—C14—N4	−90.9 (2)
C6—C1—C2—N1	−179.22 (16)	C10—C11—C14—N4	88.9 (2)
C1—C2—C3—C4	−1.1 (3)	N4—C15—C16—N5	−55.9 (2)
N1—C2—C3—C4	−179.94 (17)	N5—C17—C18—N4	59.5 (2)
C2—C3—C4—C5	0.3 (3)	C3—C2—N1—O2	−173.7 (2)
C2—C3—C4—N2	−179.94 (17)	C1—C2—N1—O2	7.4 (3)
C3—C4—C5—C6	−0.7 (3)	C3—C2—N1—O3	6.7 (3)
N2—C4—C5—C6	179.59 (16)	C1—C2—N1—O3	−172.20 (18)
C4—C5—C6—C1	1.9 (3)	C3—C4—N2—O4	2.3 (3)
C4—C5—C6—N3	−179.92 (16)	C5—C4—N2—O4	−177.91 (17)
O1—C1—C6—C5	175.93 (18)	C3—C4—N2—O5	−178.37 (18)
C2—C1—C6—C5	−2.4 (3)	C5—C4—N2—O5	1.4 (3)
O1—C1—C6—N3	−2.2 (3)	C5—C6—N3—O7	146.71 (18)
C2—C1—C6—N3	179.41 (16)	C1—C6—N3—O7	−35.0 (2)
O9—C7—C8—C9	13.3 (3)	C5—C6—N3—O6	−32.8 (2)
O8—C7—C8—C9	−165.86 (16)	C1—C6—N3—O6	145.57 (18)
O9—C7—C8—C13	−168.83 (19)	C17—C18—N4—C15	−58.31 (19)
O8—C7—C8—C13	12.1 (2)	C17—C18—N4—C14	176.17 (15)
C13—C8—C9—C10	−0.7 (3)	C16—C15—N4—C18	56.68 (19)
C7—C8—C9—C10	177.30 (16)	C16—C15—N4—C14	−177.48 (15)
C8—C9—C10—C11	−0.3 (3)	C11—C14—N4—C18	64.0 (2)
C9—C10—C11—C12	1.5 (3)	C11—C14—N4—C15	−60.5 (2)
C9—C10—C11—C14	−178.33 (16)	C18—C17—N5—C19	178.02 (17)
C10—C11—C12—C13	−1.8 (3)	C18—C17—N5—C16	−57.47 (19)
C14—C11—C12—C13	178.01 (16)	C15—C16—N5—C17	55.6 (2)
C11—C12—C13—C8	0.9 (3)	C15—C16—N5—C19	179.69 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···N4i	0.82	1.79	2.6006 (19)	172
N5—H5A···O1ii	0.89 (2)	1.89 (2)	2.734 (2)	156.9 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8⋯N4i	0.82	1.79	2.6006 (19)	172
N5—H5A⋯O1ii	0.89 (2)	1.89 (2)	2.734 (2)	156.9 (18)

Symmetry codes: (i) ; (ii) .