Carvedilol dihydrogen phosphate hemihydrate: a powder study.

IN THE CATION OF THE TITLE COMPOUND [SYSTEMATIC NAME: 3-(9H-carbazol-4-yl-oxy)-2-hydr-oxy-N-[2-(2-methoxy-phen-oxy)eth-yl]propan-1-aminium dihydrogen phosphate hemihydrate], C(24)H(27)N(2)O(4) (+)·H(2)PO(4) (-)·0.5H(2)O, the mean planes of the tricyclic ring system and the benzene ring form a dihedral angle of 87.2 (2)°. In the crystal structure, the solvent water mol-ecule is situated on a twofold rotation axis linking two cations via O-H⋯O and N-H⋯O hydrogen bonds. The anions contribute to the formation O-H⋯O and N-H⋯O hydrogen bonds between the anions and cations, which consolidate the crystal packing.

Related literature

For the synthesis of the title compound, claimed as Form I, see: Brook et al. (2005 ▶). For the crystal structures of two polymorphs of the carvedilol free base, see: Chen et al. (1998 ▶); Yathirajan et al. (2007 ▶). For details of the indexing algorithm, see: Visser (1969 ▶). The methodology of bond-restrained Rietveld refinement used in this study was the same as described by Chernyshev et al. (2003 ▶).

Experimental

Crystal data

C24H27N2O4 +·H2PO4 −·0.5H2O

M = 513.47

Monoclinic,

a = 26.600 (2) Å

b = 12.3767 (12) Å

c = 16.5101 (15) Å

β = 106.662 (11)°

V = 5207.2 (8) Å3

Z = 8

Cu Kα1 radiation

μ = 1.38 mm−1

T = 295 K

Specimen shape: flat sheet

15 × 1 × 1 mm

Specimen prepared at 101 kPa

Specimen prepared at 295 K

Particle morphology: no specific habit, light grey

Data collection

Guinier G670 image plate camera

Specimen mounting: thin layer in the specimen holder of the camera

Specimen mounted in transmission mode

Scan method: continuous

2θmin = 5.0, 2θmax = 75.0°

Increment in 2θ = 0.01°

Refinement

R p = 0.026

R wp = 0.035

R exp = 0.014

R B = 0.064

S = 2.43

Wavelength of incident radiation: 1.54059 Å

Excluded region(s): none

Profile function: split-type pseudo-Voigt (Toraya, 1986 ▶)

1346 reflections

157 parameters

125 restraints

H-atom parameters not refined

Preferred orientation correction: March-Dollase (Dollase, 1986 ▶); direction of preferred orientation 100, texture parameter r = 1.038 (5)

Data collection: G670 Imaging Plate Guinier Camera Software (Huber, 2002 ▶); cell refinement: MRIA (Zlokazov & Chernyshev, 1992 ▶); data reduction: G670 Imaging Plate Guinier Camera Software; method used to solve structure: simulated annealing (Zhukov et al., 2001 ▶); program(s) used to refine structure: MRIA; molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: MRIA and SHELXL97 (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809029353/lh2866sup1.cif

Rietveld powder data: contains datablocks I. DOI: 10.1107/S1600536809029353/lh2866Isup2.rtv

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

C24H27N2O4+·H2PO4−·0.5H2O	F(000) = 2168
Mr = 513.47	Dx = 1.310 Mg m−3
Monoclinic, C2/c	Cu Kα1 radiation, λ = 1.54059 Å
Hall symbol: -C 2yc	µ = 1.38 mm−1
a = 26.600 (2) Å	T = 295 K
b = 12.3767 (12) Å	Particle morphology: no specific habit
c = 16.5101 (15) Å	light grey
β = 106.662 (11)°	flat_sheet, 15 × 1 mm
V = 5207.2 (8) Å3	Specimen preparation: Prepared at 295 K and 101 kPa
Z = 8

Guinier G670 diffractometer	Data collection mode: transmission
Radiation source: line-focus sealed tube	Scan method: continuous
Curved Germanium (111)	2θmin = 5.00°, 2θmax = 75.00°, 2θstep = 0.01°
Specimen mounting: thin layer in the specimen holder of the camera

Refinement on Inet	Profile function: split-type pseudo-Voigt (Toraya, 1986)
Least-squares matrix: full with fixed elements per cycle	157 parameters
Rp = 0.026	125 restraints
Rwp = 0.035	27 constraints
Rexp = 0.014	H-atom parameters not refined
RBragg = 0.064	Weighting scheme based on measured s.u.'s
χ2 = 5.928	(Δ/σ)max = 0.004
7001 data points	Background function: Chebyshev polynomial up to the 5th order
Excluded region(s): none	Preferred orientation correction: March-Dollase (Dollase, 1986); direction of preferred orientation 100, texture parameter r = 1.038(5)

	x	y	z	Uiso*/Ueq
C1	0.1090 (10)	0.7439 (16)	0.8662 (14)	0.096 (9)*
H1A	0.1218	0.6723	0.8585	0.115*
H1B	0.1339	0.7771	0.9146	0.115*
C2	0.1044 (9)	0.8122 (14)	0.7871 (12)	0.096 (9)*
H2	0.1110	0.8888	0.8012	0.115*
C3	0.1405 (11)	0.7694 (13)	0.7371 (13)	0.096 (9)*
H3A	0.1289	0.6980	0.7153	0.115*
H3B	0.1386	0.8167	0.6895	0.115*
C4	0.2317 (10)	0.7415 (15)	0.7495 (11)	0.078 (7)*
C5	0.2335 (8)	0.7825 (16)	0.6713 (14)	0.078 (7)*
H5	0.2069	0.8273	0.6402	0.094*
C6	0.2761 (11)	0.7553 (13)	0.6398 (12)	0.078 (7)*
H6	0.2745	0.7766	0.5851	0.094*
C7	0.3201 (9)	0.6987 (17)	0.6859 (15)	0.078 (7)*
H7	0.3502	0.6922	0.6684	0.094*
C8	0.3156 (9)	0.6522 (16)	0.7609 (13)	0.078 (7)*
N9	0.3515 (8)	0.5885 (13)	0.8183 (10)	0.078 (7)*
H9	0.3797	0.5622	0.8107	0.094*
C10	0.3351 (9)	0.5734 (15)	0.8899 (14)	0.078 (7)*
C11	0.3572 (11)	0.5123 (16)	0.9629 (15)	0.078 (7)*
H11	0.3890	0.4766	0.9703	0.094*
C12	0.3304 (12)	0.5062 (17)	1.0244 (15)	0.078 (7)*
H12	0.3454	0.4682	1.0741	0.094*
C13	0.2814 (10)	0.5561 (14)	1.0128 (12)	0.078 (7)*
H13	0.2646	0.5522	1.0550	0.094*
C14	0.2580 (9)	0.6116 (13)	0.9379 (14)	0.078 (7)*
H14	0.2243	0.6393	0.9280	0.094*
C15	0.2854 (11)	0.6256 (15)	0.8773 (13)	0.078 (7)*
C16	0.2737 (10)	0.6768 (16)	0.7952 (12)	0.078 (7)*
O17	0.1930 (7)	0.7639 (11)	0.7893 (9)	0.078 (7)*
O18	0.0509 (8)	0.7940 (12)	0.7362 (9)	0.096 (9)*
H18	0.0479	0.8342	0.6957	0.144*
N19	0.0560 (8)	0.7353 (13)	0.8820 (11)	0.096 (9)*
H19A	0.0435	0.8022	0.8851	0.115*
H19B	0.0337	0.7015	0.8379	0.115*
C20	0.0576 (10)	0.6750 (16)	0.9617 (14)	0.096 (9)*
H20A	0.0807	0.7124	1.0098	0.115*
H20B	0.0718	0.6032	0.9592	0.115*
C21	0.0031 (11)	0.6657 (15)	0.9737 (12)	0.096 (9)*
H21A	0.0051	0.6343	1.0283	0.115*
H21B	−0.0133	0.7362	0.9701	0.115*
O22	−0.0260 (7)	0.5974 (11)	0.9071 (8)	0.096 (9)*
C23	−0.0747 (10)	0.5587 (16)	0.9079 (13)	0.096 (9)*
C24	−0.0925 (12)	0.4644 (14)	0.8587 (14)	0.096 (9)*
C25	−0.1401 (9)	0.4201 (15)	0.8616 (15)	0.096 (9)*
H25	−0.1524	0.3577	0.8309	0.115*
C26	−0.1699 (10)	0.4678 (16)	0.9099 (12)	0.096 (9)*
H26	−0.2032	0.4412	0.9062	0.115*
C27	−0.1502 (9)	0.5542 (17)	0.9631 (14)	0.096 (9)*
H27	−0.1677	0.5796	1.0006	0.115*
C28	−0.1033 (11)	0.6023 (14)	0.9590 (12)	0.096 (9)*
H28	−0.0911	0.6640	0.9907	0.115*
O29	−0.0584 (8)	0.4261 (12)	0.8162 (9)	0.096 (9)*
C30	−0.0784 (11)	0.3728 (16)	0.7357 (14)	0.096 (9)*
H30A	−0.0497	0.3514	0.7150	0.144*
H30B	−0.1008	0.4215	0.6961	0.144*
H30C	−0.0981	0.3101	0.7424	0.144*
P31	−0.0045 (5)	1.0448 (8)	0.8733 (7)	0.063 (6)*
O32	0.0094 (8)	0.9380 (12)	0.9182 (10)	0.124 (11)*
O33	0.0409 (8)	1.0822 (11)	0.8416 (11)	0.124 (11)*
H33	0.0373	1.0524	0.7960	0.186*
O34	−0.0127 (8)	1.1325 (13)	0.9331 (10)	0.124 (11)*
H34	−0.0244	1.1016	0.9678	0.186*
O35	−0.0536 (9)	1.0330 (11)	0.7999 (9)	0.124 (11)*
O36	0.0000	0.5716 (11)	0.7500	0.076 (7)*
H36	−0.0103	0.5310	0.7836	0.114*

P31—O35	1.51 (2)	C12—C13	1.40 (4)
P31—O34	1.52 (2)	C13—C14	1.40 (3)
P31—O33	1.52 (2)	C14—C15	1.41 (3)
P31—O32	1.509 (18)	C15—C16	1.45 (3)
O17—C4	1.40 (3)	C20—C21	1.52 (4)
O17—C3	1.42 (3)	C23—C28	1.40 (3)
O18—C2	1.45 (3)	C23—C24	1.42 (3)
O22—C23	1.38 (3)	C24—C25	1.39 (4)
O22—C21	1.43 (2)	C25—C26	1.41 (3)
O29—C24	1.38 (3)	C26—C27	1.39 (3)
O29—C30	1.44 (3)	C27—C28	1.40 (4)
O18—H18	0.82	C1—H1A	0.97
O33—H33	0.82	C1—H1B	0.97
O34—H34	0.82	C2—H2	0.98
O36—H36	0.85	C3—H3A	0.97
O36—H36i	0.85	C3—H3B	0.97
N9—C10	1.39 (3)	C5—H5	0.93
N9—C8	1.38 (3)	C6—H6	0.93
N19—C1	1.51 (3)	C7—H7	0.93
N19—C20	1.50 (3)	C11—H11	0.93
N9—H9	0.86	C12—H12	0.93
N19—H19A	0.90	C13—H13	0.93
N19—H19B	0.90	C14—H14	0.93
C1—C2	1.53 (3)	C20—H20B	0.97
C2—C3	1.53 (3)	C20—H20A	0.97
C4—C16	1.41 (3)	C21—H21B	0.97
C4—C5	1.40 (3)	C21—H21A	0.97
C5—C6	1.42 (4)	C25—H25	0.93
C6—C7	1.39 (3)	C26—H26	0.93
C7—C8	1.40 (3)	C27—H27	0.93
C8—C16	1.42 (4)	C28—H28	0.93
C10—C15	1.43 (4)	C30—H30A	0.96
C10—C11	1.40 (3)	C30—H30B	0.96
C11—C12	1.40 (4)	C30—H30C	0.96
O34—P31—O35	109.7 (13)	O29—C24—C25	128.2 (18)
O32—P31—O35	110.0 (11)	C24—C25—C26	121.3 (19)
O32—P31—O33	109.2 (13)	C25—C26—C27	121 (2)
O32—P31—O34	111.5 (11)	C26—C27—C28	118 (2)
O33—P31—O34	106.4 (12)	C23—C28—C27	120.8 (19)
O33—P31—O35	110.0 (12)	N19—C1—H1B	109.77
C3—O17—C4	117.0 (16)	N19—C1—H1A	109.78
C21—O22—C23	120.0 (18)	H1A—C1—H1B	108.18
C24—O29—C30	120 (2)	C2—C1—H1A	109.73
C2—O18—H18	103.23	C2—C1—H1B	109.71
P31—O33—H33	106.53	C1—C2—H2	111.50
P31—O34—H34	105.88	C3—C2—H2	111.46
H36—O36—H36i	107.52	O18—C2—H2	111.57
C8—N9—C10	110 (2)	O17—C3—H3A	109.57
C1—N19—C20	113.1 (18)	C2—C3—H3A	109.48
C10—N9—H9	125.12	C2—C3—H3B	109.48
C8—N9—H9	125.17	O17—C3—H3B	109.59
C1—N19—H19B	108.95	H3A—C3—H3B	108.18
H19A—N19—H19B	107.79	C4—C5—H5	120.24
C20—N19—H19B	108.92	C6—C5—H5	120.11
C1—N19—H19A	108.90	C7—C6—H6	118.16
C20—N19—H19A	109.00	C5—C6—H6	118.07
N19—C1—C2	109.6 (19)	C6—C7—H7	122.62
C1—C2—C3	111.1 (17)	C8—C7—H7	122.59
O18—C2—C1	103.5 (18)	C10—C11—H11	120.69
O18—C2—C3	107.3 (16)	C12—C11—H11	120.78
O17—C3—C2	110.5 (16)	C11—C12—H12	119.21
O17—C4—C16	116.1 (17)	C13—C12—H12	119.26
C5—C4—C16	118 (2)	C12—C13—H13	120.07
O17—C4—C5	125.8 (19)	C14—C13—H13	120.07
C4—C5—C6	120 (2)	C13—C14—H14	120.01
C5—C6—C7	123.8 (19)	C15—C14—H14	119.97
C6—C7—C8	115 (2)	C21—C20—H20A	109.42
N9—C8—C16	108.4 (18)	C21—C20—H20B	109.44
C7—C8—C16	123 (2)	H20A—C20—H20B	107.96
N9—C8—C7	128 (2)	N19—C20—H20A	109.38
N9—C10—C11	131 (2)	N19—C20—H20B	109.33
N9—C10—C15	108.6 (18)	O22—C21—H21A	110.63
C11—C10—C15	121 (2)	C20—C21—H21B	110.63
C10—C11—C12	119 (2)	O22—C21—H21B	110.54
C11—C12—C13	122 (2)	C20—C21—H21A	110.55
C12—C13—C14	120 (2)	H21A—C21—H21B	108.76
C13—C14—C15	120 (2)	C26—C25—H25	119.37
C10—C15—C16	106 (2)	C24—C25—H25	119.29
C14—C15—C16	135 (2)	C25—C26—H26	119.69
C10—C15—C14	119.1 (19)	C27—C26—H26	119.59
C4—C16—C8	120.1 (18)	C26—C27—H27	120.79
C4—C16—C15	133 (2)	C28—C27—H27	120.75
C8—C16—C15	107 (2)	C27—C28—H28	119.57
N19—C20—C21	111.3 (19)	C23—C28—H28	119.65
O22—C21—C20	105.7 (18)	O29—C30—H30B	109.47
O22—C23—C28	123.0 (19)	O29—C30—H30C	109.44
C24—C23—C28	121 (2)	H30A—C30—H30C	109.53
O22—C23—C24	116 (2)	H30B—C30—H30C	109.45
C23—C24—C25	117 (2)	H30A—C30—H30B	109.43
O29—C24—C23	114 (2)	O29—C30—H30A	109.50

D—H···A	D—H	H···A	D···A	D—H···A
N19—H19A···O32	0.90	2.06	2.93 (2)	165
N19—H19B···O36	0.90	2.18	3.04 (2)	159
N9—H9···O35ii	0.86	1.87	2.72 (3)	168
O18—H18···O32i	0.82	2.42	3.15 (2)	148
O18—H18···O35i	0.82	2.46	3.02 (2)	126
O33—H33···O35i	0.82	1.77	2.53 (2)	153
O34—H34···O32iii	0.82	1.87	2.58 (2)	144
O36—H36···O22	0.85	2.34	2.887 (15)	122
O36—H36···O29	0.85	2.00	2.80 (2)	155
C21—H21B···O34iii	0.97	2.24	2.91 (2)	125

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N19—H19A⋯O32	0.90	2.06	2.93 (2)	165
N19—H19B⋯O36	0.90	2.18	3.04 (2)	159
N9—H9⋯O35i	0.86	1.87	2.72 (3)	168
O18—H18⋯O32ii	0.82	2.42	3.15 (2)	148
O18—H18⋯O35ii	0.82	2.46	3.02 (2)	126
O33—H33⋯O35ii	0.82	1.77	2.53 (2)	153
O34—H34⋯O32iii	0.82	1.87	2.58 (2)	144
O36—H36⋯O22	0.85	2.34	2.887 (15)	122
O36—H36⋯O29	0.85	2.00	2.80 (2)	155
C21—H21B⋯O34iii	0.97	2.24	2.91 (2)	125

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