A complementary experimental and computational study of loxapine succinate and its monohydrate

The crystal structures of loxapine succinate [systematic name: 4-(2-chloro­dibenzo[b,f][1,4]oxazepin-11-yl)-1-methyl­pi­per­a­zin-1-ium 3-carboxypropano­ate], C₁₈H₁₉ClN₃O⁺·C₄H₅O₄^-, and loxapine succinate monohydrate {systematic name: bis­[4-(2-chloro­dibenzo[b,f][1,4]oxazepin-11-yl)-1-methyl­piper­azin-1-ium] succinate succinic acid dihydrate}, 2C₁₈H₁₉ClN₃O⁺·C₄H₄O₄^2-·C₄H₆O₄·2H₂O, have been determined using X-ray powder diffraction and single-crystal X-ray diffraction, respectively. Fixed cell geometry optimization calculations using density functional theory confirmed that the global optimum powder diffraction derived structure also matches an energy minimum structure. The energy calculations proved to be an effective tool in locating the positions of the H atoms reliably and verifying the salt configuration of the structure determined from powder data. Crystal packing analysis of these structures revealed that the loxapine succinate structure is based on chains of protonated loxapine mol­ecules while the monohydrate contains dispersion stabilized centrosymmetric dimers. Incorporation of water mol­ecules within the crystal lattice significantly alters the mol­ecular packing and proton­ation state of the succinic acid.

Computing details

Data collection: DIFFRAC plus XRD Commander (Kienle & Jacob, 2003) for loxapinesuccinate; APEX2 (Bruker, 2007) for Loxapine_succinate_monohydrate. Cell refinement: TOPAS Academic (Coelho, 2007) for loxapinesuccinate; SAINT (Bruker, 2007) for Loxapine_succinate_monohydrate. Data reduction: DASH (David et al., 2006) for loxapinesuccinate; SAINT (Bruker, 2007) for Loxapine_succinate_monohydrate. Program(s) used to solve structure: DASH (David et al., 2006) for loxapinesuccinate; SHELXS97 (Sheldrick, 2008) within WinGX suite (Farrugia, 2012) for Loxapine_succinate_monohydrate. Program(s) used to refine structure: TOPAS Academic (Coelho, 2007) for loxapinesuccinate; SHELXL97 (Sheldrick, 2008) within WinGX suite (Farrugia, 2012) for Loxapine_succinate_monohydrate. Molecular graphics: Mercury (Macrae et al., 2006) and ORTEP-3 for Windows (Farrugia, 2012) for loxapinesuccinate; Mercury (Macrae et al.,2006) and ORTEP-3 for Windows (Farrugia, 2012) for Loxapine_succinate_monohydrate. Software used to prepare material for publication: enCIFer (Allen et al., 2004), publCIF (Westrip, 2010) and PLATON (Spek, 2009) for loxapinesuccinate; enCIFer (Allen et al., 2004) for Loxapine_succinate_monohydrate.

(loxapinesuccinate) 4-(2-Chlorodibenzo[b,f][1,4]oxazepin-11-yl)-1-methylpiperazin-1-ium 3-carcoxypropanoate

Crystal data

C18H19ClN3O^+·C4H5O4^−	Z = 8
Mr = 445.89	F(000) = 1872
Monoclinic, C2/c	Dx = 1.346 Mg m^−3
Hall symbol: -C 2yc	Cu Kα1 radiation, λ = 1.54056 Å
a = 36.1824 (5) Å	µ = 1.87 mm^−1
b = 7.08622 (14) Å	T = 298 K
c = 18.7690 (2) Å	white
β = 113.8402 (10)°	cylinder, 12 × 0.7 mm
V = 4401.70 (12) Å^3	Specimen preparation: Prepared at 298 K

Data collection

Bruker AXS D8 Advance diffractometer	Data collection mode: transmission
Radiation source: sealed X-ray tube, Bruker AXS D8	Scan method: step
Primary focussing, Ge 111 monochromator	2θmin = 3.5°, 2θmax = 70.0°, 2θstep = 0.014°
Specimen mounting: 0.7 mm borosilicate capillary

Refinement

Refinement on Inet	Profile function: Fundamental parameters with axial divergence correction
Least-squares matrix: selected elements only	50 parameters
Rp = 0.030	Weighting scheme based on measured s.u.'s 1/σ(Yobs)^2
Rwp = 0.033	(Δ/σ)max = 0.04
Rexp = 0.015	Background function: Chebyshev polynomial
RBragg = 0.025	Preferred orientation correction: A spherical harmonics-based preferred orientation correction (Järvinen, 1993) was applied with Topas during the Rietveld refinement.
988 data points

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl	0.67070 (9)	1.0137 (4)	0.43307 (14)	0.0402*
O1	0.65088 (7)	0.3928 (3)	0.6214 (2)	0.0402*
N1	0.64916 (7)	0.6873 (4)	0.72580 (16)	0.0402*
N2	0.60736 (6)	0.9109 (3)	0.64543 (17)	0.0402*
N3	0.55103 (8)	1.2105 (4)	0.6244 (2)	0.0402*
C1	0.66461 (7)	0.8294 (4)	0.48862 (12)	0.0402*
C2	0.67172 (8)	0.6461 (4)	0.47246 (14)	0.0402*
C3	0.66763 (8)	0.5018 (3)	0.51811 (16)	0.0402*
C4	0.65565 (6)	0.5414 (3)	0.57802 (16)	0.0402*
C5	0.64774 (5)	0.7259 (3)	0.59370 (13)	0.0402*
C6	0.65302 (5)	0.8715 (3)	0.54858 (12)	0.0402*
C7	0.67988 (7)	0.3986 (3)	0.69886 (19)	0.0402*
C8	0.70725 (8)	0.2518 (4)	0.7252 (2)	0.0402*
C9	0.73435 (10)	0.2475 (5)	0.8025 (2)	0.0402*
C10	0.73387 (10)	0.3905 (5)	0.85225 (18)	0.0402*
C11	0.70628 (10)	0.5372 (5)	0.82546 (16)	0.0402*
C12	0.67863 (8)	0.5449 (4)	0.74754 (16)	0.0402*
C13	0.63462 (6)	0.7646 (3)	0.65795 (15)	0.0402*
C14	0.60010 (9)	0.9819 (4)	0.71209 (19)	0.0402*
C15	0.58766 (10)	1.1872 (4)	0.6986 (2)	0.0402*
C16	0.55858 (6)	1.1318 (4)	0.5576 (2)	0.0402*
C17	0.57064 (5)	0.9269 (3)	0.57338 (19)	0.0402*
C18	0.53849 (10)	1.4113 (4)	0.6106 (3)	0.0402*
O2	0.50351 (10)	0.7755 (6)	0.6585 (3)	0.0402*
O3	0.48246 (16)	1.0683 (6)	0.6194 (3)	0.0402*
O4	0.44803 (13)	0.3307 (6)	0.6578 (3)	0.0402*
O5	0.43568 (18)	0.5062 (7)	0.5513 (2)	0.0402*
C19	0.47619 (12)	0.9025 (5)	0.6357 (2)	0.0402*
C20	0.43427 (13)	0.8483 (6)	0.6293 (4)	0.0402*
C21	0.43250 (14)	0.6555 (6)	0.6630 (3)	0.0402*
C22	0.43898 (10)	0.4898 (5)	0.6187 (2)	0.0402*
H1N	0.53102 (9)	1.1459 (5)	0.6302 (3)	0.0483*
H1	0.64867 (5)	0.9988 (3)	0.55902 (13)	0.0483*
H2	0.67929 (10)	0.6199 (4)	0.43054 (15)	0.0483*
H3	0.67303 (9)	0.3753 (3)	0.50852 (19)	0.0483*
H4	0.70748 (9)	0.1547 (3)	0.6905 (2)	0.0483*
H5	0.75316 (10)	0.1468 (5)	0.8213 (2)	0.0483*
H6	0.75259 (12)	0.3883 (6)	0.90519 (18)	0.0483*
H7	0.70614 (11)	0.6338 (5)	0.86045 (15)	0.0483*
H8	0.62398 (10)	0.9698 (4)	0.75842 (17)	0.0483*
H9	0.57937 (9)	0.9101 (5)	0.7181 (2)	0.0483*
H10	0.60925 (10)	1.2597 (4)	0.69634 (19)	0.0483*
H11	0.58210 (12)	1.2324 (5)	0.7409 (2)	0.0483*
H13	0.57544 (5)	0.8759 (3)	0.53108 (18)	0.0483*
H14	0.54937 (5)	0.8571 (4)	0.5783 (2)	0.0483*
H15	0.57951 (7)	1.2010 (3)	0.55121 (19)	0.0483*
H16	0.53483 (6)	1.1424 (4)	0.5110 (2)	0.0483*
H17	0.55975 (10)	1.4841 (4)	0.6071 (3)	0.0483*
H18	0.51513 (10)	1.4218 (4)	0.5632 (3)	0.0483*
H19	0.53255 (12)	1.4564 (5)	0.6524 (3)	0.0483*
H20	0.4285 (2)	0.9475 (6)	0.6573 (5)	0.0483*
H21	0.41790 (11)	0.8522 (6)	0.5750 (4)	0.0483*
H22	0.40804 (19)	0.6349 (7)	0.6693 (5)	0.0483*
H23	0.4493 (2)	0.6352 (8)	0.7165 (3)	0.0483*
H24	0.45152 (16)	0.2305 (5)	0.6317 (5)	0.0483*

Geometric parameters (Å, º)

Cl—C1	1.740 (4)	C11—C12	1.400 (4)
O1—C4	1.384 (4)	C14—C15	1.514 (4)
O1—C7	1.408 (5)	C16—C17	1.511 (4)
O2—C19	1.276 (6)	C2—H2	0.950 (4)
O3—C19	1.258 (6)	C3—H3	0.950 (3)
O4—C22	1.313 (6)	C6—H1	0.950 (3)
O5—C22	1.227 (5)	C8—H4	0.950 (4)
O4—H24	0.900 (7)	C9—H5	0.950 (5)
N1—C13	1.287 (4)	C10—H6	0.950 (5)
N1—C12	1.404 (4)	C11—H7	0.950 (5)
N2—C13	1.384 (3)	C14—H9	0.950 (5)
N2—C17	1.468 (4)	C14—H8	0.950 (5)
N2—C14	1.467 (4)	C15—H10	0.950 (5)
N3—C16	1.495 (5)	C15—H11	0.950 (5)
N3—C18	1.484 (4)	C16—H16	0.950 (5)
N3—C15	1.494 (5)	C16—H15	0.950 (4)
N3—H1N	0.900 (5)	C17—H13	0.950 (4)
C1—C2	1.382 (4)	C17—H14	0.950 (3)
C1—C6	1.383 (3)	C18—H19	0.949 (7)
C2—C3	1.380 (4)	C18—H17	0.950 (6)
C3—C4	1.388 (4)	C18—H18	0.951 (7)
C4—C5	1.395 (3)	C19—C20	1.522 (7)
C5—C6	1.396 (3)	C20—C21	1.518 (7)
C5—C13	1.489 (3)	C21—C22	1.511 (6)
C7—C12	1.395 (4)	C20—H20	0.950 (8)
C7—C8	1.383 (4)	C20—H21	0.950 (10)
C8—C9	1.385 (5)	C21—H22	0.950 (10)
C9—C10	1.383 (5)	C21—H23	0.951 (7)
C10—C11	1.387 (5)
Cl···C20^i	3.627 (7)	C16···H21^i	2.940 (7)
Cl···H3^ii	2.912 (4)	C17···H1	2.986 (3)
Cl···H8^iii	3.023 (4)	C19···H24^ii	2.480 (6)
O1···N1	2.881 (4)	C19···H16^i	2.637 (5)
O2···C21^iv	3.322 (7)	C19···H1N	2.662 (6)
O2···O5	3.118 (7)	C20···H24^ii	2.776 (6)
O2···C18^v	3.161 (6)	C21···H9^iv	3.032 (6)
O2···C22	2.949 (6)	H1N···C19	2.662 (6)
O3···C22^ii	3.373 (6)	H1N···H9	2.498 (6)
O3···C17^i	3.341 (6)	H1N···O3	1.773 (7)
O3···C18	3.212 (6)	H1N···H14	2.470 (5)
O3···N3	2.644 (7)	H1···C17	2.986 (3)
O3···O4^ii	2.501 (7)	H1···N2	2.686 (3)
O3···C16^i	3.356 (6)	H2···C11^x	2.764 (5)
O4···O3^v	2.501 (7)	H2···C10^x	2.900 (5)
O4···C19^v	3.280 (6)	H3···Cl^v	2.912 (4)
O5···C16^i	3.338 (6)	H6···C1^xi	2.880 (5)
O5···C4^vi	3.231 (6)	H8···N1	2.380 (4)
O5···C19	3.266 (6)	H8···Cl^xii	3.023 (4)
O5···O2	3.118 (7)	H9···O2	2.686 (6)
O1···H15^v	2.739 (4)	H9···N1	2.932 (5)
O1···H10^v	2.617 (5)	H9···H14	2.429 (5)
O2···H9	2.686 (6)	H9···C21^iv	3.032 (6)
O2···H19^v	2.515 (6)	H9···H20^iv	2.482 (9)
O2···H14	2.715 (5)	H9···H1N	2.498 (6)
O2···H23	2.783 (8)	H10···C7^ii	2.721 (5)
O2···H23^iv	2.484 (7)	H10···C12^ii	3.059 (5)
O3···H13^i	2.782 (6)	H10···O1^ii	2.617 (5)
O3···H1N	1.773 (7)	H10···H17	2.473 (5)
O3···H24^ii	1.684 (8)	H10···H15	2.526 (5)
O3···H16^i	2.715 (6)	H11···H19	2.467 (6)
O4···H20^v	2.805 (6)	H11···O4^xiii	2.639 (7)
O4···H11^vii	2.639 (7)	H13···O3^i	2.782 (6)
O5···H21	2.618 (7)	H13···C6	2.691 (3)
O5···H18^v	2.855 (8)	H13···C5	2.621 (3)
O5···H15^i	2.730 (5)	H14···H1N	2.470 (5)
N1···O1	2.881 (4)	H14···H9	2.429 (5)
N2···N3	2.858 (4)	H14···O2	2.715 (5)
N3···N2	2.858 (4)	H15···O5^i	2.730 (5)
N3···O3	2.644 (7)	H15···H21^i	2.438 (7)
N1···H8	2.380 (4)	H15···H10	2.526 (5)
N1···H9	2.932 (5)	H15···H17	2.499 (4)
N2···H1	2.686 (3)	H15···O1^ii	2.739 (4)
C4···O5^vi	3.231 (6)	H16···H18	2.440 (5)
C6···C17	3.221 (3)	H16···O3^i	2.715 (6)
C16···C19^i	3.334 (5)	H16···C19^i	2.637 (5)
C16···O5^i	3.338 (6)	H17···H15	2.499 (4)
C16···O3^i	3.356 (6)	H17···H10	2.473 (5)
C17···C6	3.221 (3)	H18···H16	2.440 (5)
C17···O3^i	3.341 (6)	H18···H18^xiv	2.440 (7)
C18···O2^ii	3.161 (6)	H18···O5^ii	2.855 (8)
C18···O3	3.212 (6)	H19···O2^ii	2.516 (6)
C19···O4^ii	3.280 (6)	H19···H11	2.467 (6)
C19···O5	3.266 (6)	H20···O4^ii	2.805 (6)
C19···C16^i	3.334 (5)	H20···H24^ii	2.296 (7)
C20···Cl^i	3.627 (7)	H20···C14^iv	3.032 (9)
C21···O2^iv	3.322 (7)	H20···H9^iv	2.482 (9)
C22···O3^v	3.373 (6)	H21···O5	2.618 (7)
C22···O2	2.949 (6)	H21···C16^i	2.940 (7)
C1···H6^viii	2.880 (5)	H21···H15^i	2.438 (7)
C5···H13	2.621 (3)	H23···O2	2.783 (8)
C6···H13	2.691 (3)	H23···O2^iv	2.484 (7)
C7···H10^v	2.721 (5)	H24···O3^v	1.684 (8)
C10···H2^ix	2.900 (5)	H24···C19^v	2.480 (6)
C11···H2^ix	2.764 (5)	H24···C20^v	2.776 (6)
C12···H10^v	3.059 (5)	H24···H20^v	2.296 (7)
C14···H20^iv	3.032 (9)
C4—O1—C7	111.5 (2)	C10—C9—H5	120.2 (4)
C22—O4—H24	115.6 (7)	C11—C10—H6	119.7 (4)
C12—N1—C13	123.5 (3)	C9—C10—H6	119.7 (4)
C13—N2—C14	118.2 (3)	C10—C11—H7	119.6 (3)
C14—N2—C17	110.6 (2)	C12—C11—H7	119.5 (4)
C13—N2—C17	122.1 (2)	N2—C14—H9	109.9 (3)
C15—N3—C16	110.3 (3)	C15—C14—H8	109.8 (3)
C15—N3—C18	111.2 (3)	N2—C14—H8	109.8 (4)
C16—N3—C18	111.0 (3)	H8—C14—H9	108.2 (4)
C18—N3—H1N	107.7 (4)	C15—C14—H9	109.8 (4)
C16—N3—H1N	109.9 (4)	N3—C15—H11	109.5 (4)
C15—N3—H1N	106.6 (4)	C14—C15—H10	109.5 (4)
C2—C1—C6	121.7 (2)	C14—C15—H11	109.5 (4)
Cl—C1—C6	118.6 (2)	H10—C15—H11	108.1 (4)
Cl—C1—C2	119.6 (2)	N3—C15—H10	109.5 (4)
C1—C2—C3	119.0 (2)	N3—C16—H15	109.8 (3)
C2—C3—C4	120.0 (2)	N3—C16—H16	109.8 (3)
O1—C4—C3	118.5 (2)	C17—C16—H16	109.8 (3)
O1—C4—C5	120.3 (2)	H15—C16—H16	108.3 (4)
C3—C4—C5	121.2 (2)	C17—C16—H15	109.8 (3)
C4—C5—C6	118.3 (2)	N2—C17—H13	109.7 (3)
C4—C5—C13	120.2 (2)	C16—C17—H13	109.7 (3)
C6—C5—C13	121.45 (19)	C16—C17—H14	109.8 (3)
C1—C6—C5	119.7 (2)	N2—C17—H14	109.7 (3)
O1—C7—C8	118.3 (3)	H13—C17—H14	108.2 (3)
O1—C7—C12	119.4 (2)	N3—C18—H18	109.4 (4)
C8—C7—C12	122.2 (3)	N3—C18—H19	109.5 (4)
C7—C8—C9	119.5 (3)	H17—C18—H18	109.3 (6)
C8—C9—C10	119.6 (3)	H17—C18—H19	109.6 (5)
C9—C10—C11	120.5 (3)	H18—C18—H19	109.6 (6)
C10—C11—C12	120.9 (3)	N3—C18—H17	109.5 (4)
N1—C12—C11	118.0 (3)	O2—C19—O3	123.3 (5)
C7—C12—C11	117.2 (3)	O3—C19—C20	119.3 (4)
N1—C12—C7	124.5 (3)	O2—C19—C20	117.4 (4)
N2—C13—C5	116.0 (2)	C19—C20—C21	113.8 (4)
N1—C13—N2	117.7 (3)	C20—C21—C22	115.4 (4)
N1—C13—C5	125.9 (2)	O4—C22—C21	114.8 (4)
N2—C14—C15	109.3 (3)	O5—C22—C21	121.4 (4)
N3—C15—C14	110.7 (3)	O4—C22—O5	123.8 (4)
N3—C16—C17	109.3 (3)	C19—C20—H20	101.8 (6)
N2—C17—C16	109.7 (2)	C19—C20—H21	104.3 (6)
C1—C2—H2	120.5 (3)	C21—C20—H20	112.3 (7)
C3—C2—H2	120.6 (3)	C21—C20—H21	111.1 (5)
C4—C3—H3	120.0 (3)	H20—C20—H21	113.0 (8)
C2—C3—H3	120.0 (3)	C20—C21—H22	112.9 (6)
C5—C6—H1	120.1 (2)	C20—C21—H23	117.4 (6)
C1—C6—H1	120.2 (3)	C22—C21—H22	108.0 (5)
C7—C8—H4	120.2 (4)	C22—C21—H23	106.8 (5)
C9—C8—H4	120.3 (4)	H22—C21—H23	94.3 (8)
C8—C9—H5	120.2 (4)
C7—O1—C4—C3	113.1 (3)	O1—C4—C5—C13	0.8 (4)
C7—O1—C4—C5	−68.1 (3)	C3—C4—C5—C13	179.5 (2)
C4—O1—C7—C8	−116.6 (3)	C3—C4—C5—C6	−1.4 (4)
C4—O1—C7—C12	67.1 (4)	C6—C5—C13—N1	−137.2 (3)
C12—N1—C13—C5	−3.6 (4)	C4—C5—C6—C1	2.0 (3)
C12—N1—C13—N2	−176.4 (3)	C13—C5—C6—C1	−179.0 (2)
C13—N1—C12—C7	−38.8 (5)	C4—C5—C13—N1	41.8 (4)
C13—N1—C12—C11	148.0 (3)	C6—C5—C13—N2	35.7 (3)
C17—N2—C13—N1	−137.5 (3)	C4—C5—C13—N2	−145.3 (2)
C13—N2—C14—C15	152.2 (3)	C12—C7—C8—C9	0.4 (5)
C14—N2—C13—C5	−167.1 (2)	O1—C7—C12—N1	2.4 (4)
C17—N2—C13—C5	49.0 (3)	O1—C7—C8—C9	−175.7 (3)
C14—N2—C13—N1	6.5 (4)	C8—C7—C12—N1	−173.8 (3)
C14—N2—C17—C16	61.7 (3)	C8—C7—C12—C11	−0.5 (5)
C17—N2—C14—C15	−60.0 (3)	O1—C7—C12—C11	175.6 (3)
C13—N2—C17—C16	−151.9 (2)	C7—C8—C9—C10	−0.4 (5)
C18—N3—C15—C14	179.9 (3)	C8—C9—C10—C11	0.5 (6)
C15—N3—C16—C17	57.1 (3)	C9—C10—C11—C12	−0.6 (6)
C18—N3—C16—C17	−179.2 (3)	C10—C11—C12—C7	0.6 (5)
C16—N3—C15—C14	−56.5 (4)	C10—C11—C12—N1	174.3 (3)
C2—C1—C6—C5	−0.9 (4)	N2—C14—C15—N3	57.3 (4)
C6—C1—C2—C3	−0.9 (4)	N3—C16—C17—N2	−59.5 (3)
Cl—C1—C6—C5	179.7 (2)	O2—C19—C20—C21	8.7 (7)
Cl—C1—C2—C3	178.6 (2)	O3—C19—C20—C21	−170.5 (5)
C1—C2—C3—C4	1.5 (4)	C19—C20—C21—C22	−68.4 (6)
C2—C3—C4—C5	−0.3 (4)	C20—C21—C22—O4	162.8 (5)
C2—C3—C4—O1	178.4 (3)	C20—C21—C22—O5	−17.5 (7)
O1—C4—C5—C6	179.9 (2)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y+1, z; (iii) x, −y+2, z−1/2; (iv) −x+1, y, −z+3/2; (v) x, y−1, z; (vi) −x+1, −y+1, −z+1; (vii) −x+1, y−1, −z+3/2; (viii) −x+3/2, y+1/2, −z+3/2; (ix) x, −y+1, z+1/2; (x) x, −y+1, z−1/2; (xi) −x+3/2, y−1/2, −z+3/2; (xii) x, −y+2, z+1/2; (xiii) −x+1, y+1, −z+3/2; (xiv) −x+1, −y+3, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N···O3	0.900 (5)	1.773 (7)	2.644 (7)	162.4 (5)
O4—H24···O3^v	0.900 (7)	1.684 (8)	2.501 (7)	149.3 (8)
C18—H19···O2^ii	0.949 (7)	2.516 (6)	3.161 (6)	125.4 (4)
C21—H23···O2^iv	0.951 (7)	2.484 (7)	3.322 (7)	147.0 (5)

Symmetry codes: (ii) x, y+1, z; (iv) −x+1, y, −z+3/2; (v) x, y−1, z.

(Loxapine_succinate_monohydrate) Bis[4-(2-chlorodibenzo[b,f][1,4]oxazepin-11-yl)-1-methylpiperazin-1-ium] succinate succinic acid monosolvate monohydrate

Crystal data

2C18H19ClN3O^+·C4H4O4^2^−·C4H6O4·2H2O	Z = 1
Mr = 927.82	F(000) = 488
Triclinic, P1	Dx = 1.386 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4171 (6) Å	Cell parameters from 6072 reflections
b = 9.7604 (7) Å	θ = 2.4–26.3°
c = 13.7949 (9) Å	µ = 0.22 mm^−1
α = 74.708 (2)°	T = 123 K
β = 86.102 (2)°	Plate, colourless
γ = 65.518 (2)°	0.33 × 0.18 × 0.06 mm
V = 1111.86 (13) Å^3

Data collection

Bruker D8 diffractometer with APEX CCD detector	4287 independent reflections
Radiation source: fine-focus sealed tube	3385 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 66 pixels mm^-1	θmax = 26.0°, θmin = 2.4°
φ & ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2007)	k = −11→12
Tmin = 0.653, Tmax = 0.745	l = −17→16
15591 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0484P)^2 + 0.4552P] where P = (Fo^2 + 2Fc^2)/3
4287 reflections	(Δ/σ)max < 0.001
306 parameters	Δρmax = 0.25 e Å^−3
3 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
O2	0.59307 (17)	0.34796 (18)	0.96876 (13)	0.0428 (4)
O4	0.25552 (15)	0.45910 (15)	1.06687 (9)	0.0315 (3)
O3	0.31724 (17)	0.40868 (17)	0.91680 (10)	0.0357 (3)
C19	0.2175 (2)	0.4497 (2)	0.98668 (13)	0.0270 (4)
Cl	0.40819 (6)	0.50818 (5)	0.35678 (4)	0.03687 (15)
C20	0.0541 (2)	0.4878 (2)	0.95707 (13)	0.0283 (4)
H20	0.0521	0.4019	0.9326	0.034*
H21	0.0159	0.5836	0.9010	0.034*
C22	0.9907 (2)	0.9324 (2)	0.98823 (14)	0.0277 (4)
H22	0.9967	0.8546	1.0523	0.033*
H23	1.0798	0.8821	0.9487	0.033*
H1N	0.633 (3)	−0.059 (2)	0.8569 (16)	0.042 (6)*
H24	0.629 (3)	0.424 (3)	0.9462 (19)	0.064 (8)*
H25	0.662 (3)	0.269 (3)	0.943 (2)	0.080 (9)*
H3S	0.4111 (18)	0.398 (4)	0.930 (2)	0.085 (10)*
O1	0.98303 (13)	−0.06323 (13)	0.40074 (9)	0.0229 (3)
N3	0.53880 (17)	−0.01438 (16)	0.81396 (10)	0.0208 (3)
N2	0.67511 (17)	−0.05050 (15)	0.62574 (10)	0.0199 (3)
N1	0.80274 (17)	−0.21282 (16)	0.52527 (10)	0.0212 (3)
C16	0.5376 (2)	0.12201 (19)	0.73264 (12)	0.0206 (4)
H16	0.5398	0.2027	0.7627	0.025*
H15	0.4410	0.1681	0.6894	0.025*
C7	0.95809 (19)	−0.18240 (19)	0.37534 (12)	0.0211 (4)
C13	0.74361 (19)	−0.07312 (19)	0.53600 (12)	0.0186 (3)
C5	0.72601 (19)	0.07047 (19)	0.45642 (12)	0.0186 (3)
C6	0.5898 (2)	0.20738 (19)	0.44392 (12)	0.0210 (4)
H1	0.5049	0.2101	0.4859	0.025*
C10	0.9295 (2)	−0.4280 (2)	0.32989 (14)	0.0271 (4)
H6	0.9190	−0.5125	0.3141	0.032*
C15	0.5423 (2)	−0.1397 (2)	0.76954 (12)	0.0215 (4)
H10	0.4449	−0.1016	0.7283	0.026*
H11	0.5481	−0.2312	0.8242	0.026*
C4	0.8460 (2)	0.07001 (19)	0.39120 (12)	0.0212 (4)
C11	0.8558 (2)	−0.3759 (2)	0.41191 (13)	0.0245 (4)
H7	0.7963	−0.4259	0.4521	0.029*
C17	0.6787 (2)	0.06907 (19)	0.67029 (12)	0.0203 (4)
H13	0.6787	0.1590	0.6163	0.024*
H14	0.7753	0.0259	0.7132	0.024*
C3	0.8327 (2)	0.2027 (2)	0.31697 (13)	0.0266 (4)
H3	0.9155	0.1999	0.2730	0.032*
C1	0.5790 (2)	0.3390 (2)	0.37015 (13)	0.0254 (4)
C14	0.6814 (2)	−0.18759 (19)	0.70463 (12)	0.0216 (4)
H9	0.7794	−0.2329	0.7465	0.026*
H8	0.6799	−0.2677	0.6737	0.026*
C18	0.4030 (2)	0.0334 (2)	0.87795 (14)	0.0304 (4)
H18	0.4040	0.1152	0.9062	0.046*
H19	0.4092	−0.0567	0.9327	0.046*
H17	0.3061	0.0734	0.8372	0.046*
C12	0.8680 (2)	−0.25061 (19)	0.43627 (12)	0.0209 (4)
C2	0.6993 (2)	0.3387 (2)	0.30689 (14)	0.0295 (4)
H2	0.6903	0.4307	0.2573	0.035*
C9	1.0180 (2)	−0.3579 (2)	0.27091 (13)	0.0272 (4)
H5	1.0689	−0.3946	0.2152	0.033*
C8	1.0320 (2)	−0.2338 (2)	0.29355 (13)	0.0244 (4)
H4	1.0919	−0.1844	0.2532	0.029*
O6	0.75413 (15)	1.11491 (14)	0.89341 (9)	0.0303 (3)
O5	0.80886 (16)	0.86549 (14)	0.92070 (10)	0.0319 (3)
C21	0.8397 (2)	0.9754 (2)	0.93035 (12)	0.0212 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0322 (8)	0.0364 (8)	0.0645 (10)	−0.0143 (7)	0.0120 (7)	−0.0229 (8)
O4	0.0319 (8)	0.0344 (7)	0.0282 (7)	−0.0134 (6)	−0.0028 (6)	−0.0077 (6)
O3	0.0335 (8)	0.0426 (8)	0.0331 (8)	−0.0166 (7)	0.0056 (6)	−0.0127 (6)
C19	0.0335 (11)	0.0197 (9)	0.0256 (10)	−0.0109 (8)	0.0028 (8)	−0.0029 (7)
Cl	0.0305 (3)	0.0195 (2)	0.0504 (3)	−0.0057 (2)	−0.0043 (2)	0.0011 (2)
C20	0.0319 (10)	0.0267 (9)	0.0227 (9)	−0.0094 (8)	−0.0038 (8)	−0.0035 (7)
C22	0.0268 (10)	0.0265 (10)	0.0295 (10)	−0.0100 (8)	−0.0082 (8)	−0.0060 (8)
O1	0.0185 (6)	0.0262 (6)	0.0262 (6)	−0.0100 (5)	0.0026 (5)	−0.0094 (5)
N3	0.0204 (8)	0.0245 (7)	0.0169 (7)	−0.0095 (6)	0.0006 (6)	−0.0041 (6)
N2	0.0247 (8)	0.0188 (7)	0.0171 (7)	−0.0104 (6)	0.0025 (6)	−0.0038 (6)
N1	0.0215 (8)	0.0201 (7)	0.0203 (7)	−0.0072 (6)	0.0013 (6)	−0.0048 (6)
C16	0.0229 (9)	0.0186 (8)	0.0184 (8)	−0.0072 (7)	−0.0018 (7)	−0.0032 (7)
C7	0.0177 (9)	0.0216 (8)	0.0223 (9)	−0.0058 (7)	−0.0026 (7)	−0.0061 (7)
C13	0.0160 (8)	0.0222 (8)	0.0180 (8)	−0.0086 (7)	0.0001 (7)	−0.0045 (7)
C5	0.0196 (9)	0.0206 (8)	0.0175 (8)	−0.0100 (7)	−0.0018 (7)	−0.0045 (7)
C6	0.0217 (9)	0.0225 (9)	0.0209 (8)	−0.0107 (7)	0.0001 (7)	−0.0060 (7)
C10	0.0257 (10)	0.0252 (9)	0.0306 (10)	−0.0074 (8)	−0.0024 (8)	−0.0118 (8)
C15	0.0251 (9)	0.0235 (9)	0.0178 (8)	−0.0131 (7)	−0.0003 (7)	−0.0028 (7)
C4	0.0212 (9)	0.0236 (9)	0.0214 (8)	−0.0110 (7)	−0.0012 (7)	−0.0066 (7)
C11	0.0217 (9)	0.0210 (9)	0.0278 (9)	−0.0067 (7)	−0.0010 (7)	−0.0044 (7)
C17	0.0231 (9)	0.0190 (8)	0.0198 (8)	−0.0102 (7)	0.0011 (7)	−0.0044 (7)
C3	0.0280 (10)	0.0310 (10)	0.0246 (9)	−0.0177 (8)	0.0042 (8)	−0.0045 (8)
C1	0.0258 (10)	0.0200 (9)	0.0287 (9)	−0.0090 (8)	−0.0062 (8)	−0.0025 (7)
C14	0.0253 (9)	0.0199 (8)	0.0196 (8)	−0.0105 (7)	0.0005 (7)	−0.0030 (7)
C18	0.0292 (10)	0.0374 (11)	0.0255 (9)	−0.0142 (9)	0.0104 (8)	−0.0113 (8)
C12	0.0184 (9)	0.0202 (8)	0.0192 (8)	−0.0037 (7)	−0.0021 (7)	−0.0036 (7)
C2	0.0357 (11)	0.0252 (9)	0.0283 (10)	−0.0181 (9)	−0.0027 (8)	0.0024 (8)
C9	0.0243 (10)	0.0321 (10)	0.0226 (9)	−0.0056 (8)	−0.0012 (7)	−0.0123 (8)
C8	0.0202 (9)	0.0295 (9)	0.0209 (9)	−0.0083 (8)	0.0005 (7)	−0.0054 (7)
O6	0.0296 (7)	0.0242 (7)	0.0344 (7)	−0.0073 (6)	−0.0099 (6)	−0.0068 (6)
O5	0.0364 (8)	0.0255 (7)	0.0341 (7)	−0.0139 (6)	−0.0138 (6)	−0.0023 (6)
C21	0.0243 (9)	0.0246 (9)	0.0144 (8)	−0.0103 (8)	0.0014 (7)	−0.0041 (7)

Geometric parameters (Å, º)

O2—H24	0.908 (17)	C13—C5	1.489 (2)
O2—H25	0.912 (17)	C5—C4	1.395 (2)
O4—C19	1.222 (2)	C5—C6	1.396 (2)
O3—C19	1.319 (2)	C6—C1	1.383 (2)
O3—H3S	0.871 (10)	C6—H1	0.9500
C19—C20	1.485 (3)	C10—C9	1.383 (3)
Cl—C1	1.7394 (18)	C10—C11	1.387 (2)
C20—C20^i	1.511 (4)	C10—H6	0.9500
C20—H20	0.9900	C15—C14	1.513 (2)
C20—H21	0.9900	C15—H10	0.9900
C22—C22^ii	1.517 (3)	C15—H11	0.9900
C22—C21	1.523 (2)	C4—C3	1.387 (2)
C22—H22	0.9900	C11—C12	1.400 (2)
C22—H23	0.9900	C11—H7	0.9500
O1—C4	1.384 (2)	C17—H13	0.9900
O1—C7	1.408 (2)	C17—H14	0.9900
N3—C18	1.484 (2)	C3—C2	1.380 (3)
N3—C15	1.494 (2)	C3—H3	0.9500
N3—C16	1.494 (2)	C1—C2	1.382 (3)
N3—H1N	0.97 (2)	C14—H9	0.9900
N2—C13	1.384 (2)	C14—H8	0.9900
N2—C14	1.467 (2)	C18—H18	0.9800
N2—C17	1.468 (2)	C18—H19	0.9800
N1—C13	1.287 (2)	C18—H17	0.9800
N1—C12	1.404 (2)	C2—H2	0.9500
C16—C17	1.510 (2)	C9—C8	1.385 (2)
C16—H16	0.9900	C9—H5	0.9500
C16—H15	0.9900	C8—H4	0.9500
C7—C8	1.383 (2)	O6—C21	1.242 (2)
C7—C12	1.395 (2)	O5—C21	1.262 (2)
H24—O2—H25	102 (2)	N3—C15—H10	109.5
C19—O3—H3S	114 (2)	C14—C15—H10	109.5
O4—C19—O3	123.22 (18)	N3—C15—H11	109.5
O4—C19—C20	123.40 (17)	C14—C15—H11	109.5
O3—C19—C20	113.36 (16)	H10—C15—H11	108.1
C19—C20—C20^i	112.51 (19)	O1—C4—C3	118.49 (15)
C19—C20—H20	109.1	O1—C4—C5	120.28 (15)
C20^i—C20—H20	109.1	C3—C4—C5	121.22 (16)
C19—C20—H21	109.1	C10—C11—C12	120.92 (16)
C20^i—C20—H21	109.1	C10—C11—H7	119.5
H20—C20—H21	107.8	C12—C11—H7	119.5
C22^ii—C22—C21	115.22 (18)	N2—C17—C16	109.68 (13)
C22^ii—C22—H22	108.5	N2—C17—H13	109.7
C21—C22—H22	108.5	C16—C17—H13	109.7
C22^ii—C22—H23	108.5	N2—C17—H14	109.7
C21—C22—H23	108.5	C16—C17—H14	109.7
H22—C22—H23	107.5	H13—C17—H14	108.2
C4—O1—C7	111.53 (12)	C2—C3—C4	120.05 (17)
C18—N3—C15	111.28 (13)	C2—C3—H3	120.0
C18—N3—C16	110.98 (14)	C4—C3—H3	120.0
C15—N3—C16	110.26 (12)	C2—C1—C6	121.73 (17)
C18—N3—H1N	107.6 (13)	C2—C1—Cl	119.60 (14)
C15—N3—H1N	106.7 (13)	C6—C1—Cl	118.67 (14)
C16—N3—H1N	109.9 (13)	N2—C14—C15	109.30 (14)
C13—N2—C14	118.23 (13)	N2—C14—H9	109.8
C13—N2—C17	122.14 (13)	C15—C14—H9	109.8
C14—N2—C17	110.60 (12)	N2—C14—H8	109.8
C13—N1—C12	123.52 (14)	C15—C14—H8	109.8
N3—C16—C17	109.35 (13)	H9—C14—H8	108.3
N3—C16—H16	109.8	N3—C18—H18	109.5
C17—C16—H16	109.8	N3—C18—H19	109.5
N3—C16—H15	109.8	H18—C18—H19	109.5
C17—C16—H15	109.8	N3—C18—H17	109.5
H16—C16—H15	108.3	H18—C18—H17	109.5
C8—C7—C12	122.23 (16)	H19—C18—H17	109.5
C8—C7—O1	118.29 (15)	C7—C12—C11	117.17 (15)
C12—C7—O1	119.37 (14)	C7—C12—N1	124.48 (15)
N1—C13—N2	117.72 (14)	C11—C12—N1	118.02 (15)
N1—C13—C5	125.88 (14)	C3—C2—C1	118.94 (16)
N2—C13—C5	116.04 (14)	C3—C2—H2	120.5
C4—C5—C6	118.33 (15)	C1—C2—H2	120.5
C4—C5—C13	120.21 (15)	C10—C9—C8	119.64 (16)
C6—C5—C13	121.46 (15)	C10—C9—H5	120.2
C1—C6—C5	119.70 (16)	C8—C9—H5	120.2
C1—C6—H1	120.1	C7—C8—C9	119.51 (16)
C5—C6—H1	120.1	C7—C8—H4	120.2
C9—C10—C11	120.53 (16)	C9—C8—H4	120.2
C9—C10—H6	119.7	O6—C21—O5	122.85 (16)
C11—C10—H6	119.7	O6—C21—C22	119.51 (15)
N3—C15—C14	110.77 (13)	O5—C21—C22	117.63 (15)
O4—C19—C20—C20^i	−9.8 (3)	C13—N2—C17—C16	151.96 (15)
O3—C19—C20—C20^i	171.90 (19)	C14—N2—C17—C16	−61.64 (17)
C18—N3—C16—C17	179.14 (14)	N3—C16—C17—N2	59.48 (17)
C15—N3—C16—C17	−57.09 (17)	O1—C4—C3—C2	−178.42 (15)
C4—O1—C7—C8	116.62 (16)	C5—C4—C3—C2	0.4 (3)
C4—O1—C7—C12	−67.09 (19)	C5—C6—C1—C2	0.8 (3)
C12—N1—C13—N2	176.45 (14)	C5—C6—C1—Cl	−179.67 (13)
C12—N1—C13—C5	3.7 (3)	C13—N2—C14—C15	−152.16 (14)
C14—N2—C13—N1	3.1 (2)	C17—N2—C14—C15	59.97 (17)
C17—N2—C13—N1	147.11 (16)	N3—C15—C14—N2	−57.29 (18)
C14—N2—C13—C5	176.62 (14)	C8—C7—C12—C11	0.5 (2)
C17—N2—C13—C5	−39.4 (2)	O1—C7—C12—C11	−175.60 (14)
N1—C13—C5—C4	−41.8 (2)	C8—C7—C12—N1	173.79 (16)
N2—C13—C5—C4	145.26 (15)	O1—C7—C12—N1	−2.3 (2)
N1—C13—C5—C6	137.24 (18)	C10—C11—C12—C7	−0.6 (2)
N2—C13—C5—C6	−35.7 (2)	C10—C11—C12—N1	−174.32 (16)
C4—C5—C6—C1	−1.9 (2)	C13—N1—C12—C7	38.8 (3)
C13—C5—C6—C1	178.98 (15)	C13—N1—C12—C11	−148.04 (17)
C18—N3—C15—C14	−179.90 (14)	C4—C3—C2—C1	−1.5 (3)
C16—N3—C15—C14	56.50 (18)	C6—C1—C2—C3	0.9 (3)
C7—O1—C4—C3	−113.13 (17)	Cl—C1—C2—C3	−178.60 (14)
C7—O1—C4—C5	68.08 (19)	C11—C10—C9—C8	−0.6 (3)
C6—C5—C4—O1	−179.89 (14)	C12—C7—C8—C9	−0.5 (3)
C13—C5—C4—O1	−0.8 (2)	O1—C7—C8—C9	175.70 (15)
C6—C5—C4—C3	1.3 (2)	C10—C9—C8—C7	0.5 (3)
C13—C5—C4—C3	−179.54 (15)	C22^ii—C22—C21—O6	10.6 (3)
C9—C10—C11—C12	0.6 (3)	C22^ii—C22—C21—O5	−170.67 (19)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N···O5^iii	0.96 (3)	1.71 (3)	2.672 (2)	173 (2)
N3—H1N···O6^iii	0.96 (3)	2.57 (3)	3.172 (2)	120 (1)
O2—H24···O4^iv	0.91 (3)	1.85 (3)	2.732 (2)	163 (3)
O2—H25···O6^iii	0.92 (3)	1.69 (3)	2.594 (2)	167 (3)

Symmetry codes: (iii) x, y−1, z; (iv) −x+1, −y+1, −z+2.