The crystal structure, morphology and mechanical properties of diaqua­bis(omeprazolate)magnesium dihydrate

The crystal structure of diaqua­bis(omeprazolate)magnesium dihydrate (DABOMD) in the solid state has been determined using single-crystal X-ray diffraction. Single crystals of DABOMD were obtained by slow crystallization in ethanol with water used as an antisolvent. The crystal structure shows a dihydrated salt comprising a magnesium cation coordinating two omeprazolate anions and two water molecules (W1) that are strongly bound to magnesium. In addition, two further water molecules (W2) are more weakly hydrogen-bonded to the pyridine nitro­gen atom of each omeprazolate anion. The crystal structure was utilized to estimate key material properties for DABOMD, including crystal habit and mechanical properties, which are required for improved understanding and prediction of the behaviour of particles during pharmaceutical processing such as milling. The results from the material properties calculations indicate that DABOMD exhibits a hexagonal morphology and consists of a flat slip plane through the (100) face. It can be classed as a soft material based on elastic constant calculation and exhibits a two-dimensional hydrogen-bonding framework. Based on the crystal structure, habit and mechanical properties, it is anticipated that DABOMD will experience large disorder accompanied by plastic deformation during milling.

Computing details

Data collection: CrysAlis PRO 1.171.39.43c (Rigaku OD, 2018); cell refinement: CrysAlis PRO 1.171.39.43c (Rigaku OD, 2018); data reduction: CrysAlis PRO 1.171.39.43c (Rigaku OD, 2018); program(s) used to solve structure: ShelXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(I)

Crystal data

C34H40MgN6O8S2·2H2O	F(000) = 828
Mr = 785.18	Dx = 1.389 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 17.475 (9) Å	Cell parameters from 455 reflections
b = 8.051 (2) Å	θ = 6.2–68.5°
c = 14.190 (5) Å	µ = 1.99 mm^−1
β = 109.91 (5)°	T = 120 K
V = 1877.1 (14) Å^3	Plate, colourless
Z = 2	0.11 × 0.03 × 0.01 mm

Data collection

SuperNova, Dual, Cu at home/near, Atlas diffractometer	3546 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	1689 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.166
Detector resolution: 5.3095 pixels mm^-1	θmax = 73.6°, θmin = 5.4°
ω scans	h = −15→21
Absorption correction: gaussian CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→9
Tmin = 0.812, Tmax = 1.000	l = −15→17
8269 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.150	H-atom parameters constrained
wR(F^2) = 0.416	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
3546 reflections	Δρmax = 1.71 e Å^−3
249 parameters	Δρmin = −0.66 e Å^−3
216 restraints

Special details

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

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

	x	y	z	Uiso*/Ueq
S1	0.58530 (16)	0.6073 (3)	0.72447 (16)	0.0288 (6)
Mg1	0.5000	0.5000	0.5000	0.0305 (11)
O1	0.5987 (5)	0.5499 (9)	0.6294 (5)	0.0350 (16)
O2	0.1453 (6)	0.8220 (14)	0.6272 (7)	0.062 (2)
O3	0.8991 (6)	0.8318 (12)	0.9725 (8)	0.064 (2)
O4	0.5015 (5)	0.7391 (8)	0.4444 (5)	0.0348 (16)
H4A	0.4719	0.7436	0.3810	0.052*
H4B	0.5500	0.7651	0.4445	0.052*
N1	0.4341 (5)	0.6023 (10)	0.5913 (5)	0.0285 (15)
N2	0.4408 (5)	0.7129 (10)	0.7408 (6)	0.0314 (16)
N3	0.7275 (6)	0.9068 (11)	0.6906 (6)	0.0390 (19)
C1	0.3565 (7)	0.6506 (13)	0.5844 (8)	0.035 (2)
C2	0.2826 (7)	0.6417 (13)	0.5067 (8)	0.040 (2)
H2	0.2793	0.5968	0.4450	0.048*
C3	0.2135 (7)	0.7016 (15)	0.5230 (9)	0.044 (2)
H3	0.1633	0.6969	0.4717	0.053*
C4	0.2190 (7)	0.7703 (14)	0.6182 (9)	0.041 (2)
C5	0.2908 (7)	0.7750 (14)	0.6939 (8)	0.040 (2)
H5	0.2931	0.8171	0.7559	0.048*
C6	0.3617 (7)	0.7175 (12)	0.6806 (7)	0.0332 (19)
C7	0.1475 (10)	0.893 (2)	0.7219 (11)	0.067 (4)
H7A	0.0945	0.9351	0.7157	0.100*
H7B	0.1861	0.9828	0.7396	0.100*
H7C	0.1632	0.8097	0.7731	0.100*
C8	0.4778 (6)	0.6396 (11)	0.6839 (6)	0.0272 (17)
C9	0.6156 (6)	0.8249 (12)	0.7413 (7)	0.0304 (19)
H9A	0.5871	0.8857	0.6804	0.036*
H9B	0.5999	0.8718	0.7951	0.036*
C10	0.7054 (7)	0.8450 (12)	0.7656 (8)	0.0337 (19)
C11	0.7619 (7)	0.8097 (13)	0.8603 (8)	0.041 (2)
C12	0.8433 (8)	0.8488 (15)	0.8786 (10)	0.049 (2)
C13	0.8676 (8)	0.9129 (18)	0.8006 (10)	0.055 (3)
C14	0.8074 (7)	0.9366 (15)	0.7102 (9)	0.045 (2)
H14	0.8229	0.9766	0.6578	0.054*
C15	0.7374 (9)	0.7365 (16)	0.9439 (9)	0.050 (3)
H15A	0.6870	0.7853	0.9429	0.075*
H15B	0.7789	0.7593	1.0071	0.075*
H15C	0.7307	0.6186	0.9348	0.075*
C16	0.9366 (11)	0.673 (2)	0.9940 (16)	0.093 (6)
H16A	0.9532	0.6382	0.9392	0.140*
H16B	0.8985	0.5942	1.0032	0.140*
H16C	0.9833	0.6793	1.0540	0.140*
C17	0.9564 (9)	0.956 (3)	0.8180 (13)	0.080 (5)
H17A	0.9882	0.8564	0.8291	0.120*
H17B	0.9767	1.0272	0.8756	0.120*
H17C	0.9603	1.0129	0.7602	0.120*
O5	0.6036 (6)	0.9976 (10)	0.5097 (6)	0.0449 (19)
H5A	0.5792	1.0495	0.5434	0.067*
H5B	0.6528	0.9918	0.5485	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0526 (13)	0.0191 (11)	0.0168 (10)	−0.0003 (9)	0.0145 (9)	−0.0002 (8)
Mg1	0.061 (3)	0.018 (2)	0.0162 (19)	−0.0011 (18)	0.018 (2)	−0.0021 (15)
O1	0.057 (4)	0.028 (4)	0.022 (3)	0.002 (3)	0.017 (3)	−0.006 (2)
O2	0.075 (5)	0.058 (6)	0.057 (5)	0.003 (4)	0.029 (4)	−0.005 (4)
O3	0.075 (5)	0.040 (5)	0.062 (5)	−0.001 (4)	0.005 (4)	−0.001 (4)
O4	0.066 (5)	0.016 (3)	0.028 (3)	−0.005 (3)	0.023 (3)	0.002 (2)
N1	0.055 (4)	0.015 (3)	0.016 (3)	0.000 (3)	0.014 (3)	0.004 (2)
N2	0.057 (4)	0.018 (4)	0.022 (3)	−0.004 (3)	0.018 (3)	−0.001 (3)
N3	0.064 (4)	0.024 (4)	0.032 (4)	−0.006 (3)	0.020 (3)	−0.006 (3)
C1	0.052 (4)	0.022 (5)	0.030 (4)	0.000 (3)	0.014 (3)	0.000 (3)
C2	0.058 (4)	0.021 (5)	0.038 (4)	−0.003 (3)	0.012 (4)	0.007 (4)
C3	0.053 (5)	0.034 (6)	0.040 (5)	−0.003 (4)	0.007 (4)	0.001 (4)
C4	0.053 (4)	0.025 (5)	0.041 (4)	−0.002 (3)	0.013 (4)	0.003 (4)
C5	0.057 (4)	0.028 (5)	0.037 (4)	−0.005 (3)	0.019 (3)	0.000 (4)
C6	0.056 (4)	0.020 (4)	0.026 (4)	−0.004 (3)	0.017 (3)	0.000 (3)
C7	0.081 (9)	0.063 (9)	0.063 (7)	0.006 (7)	0.034 (7)	−0.010 (6)
C8	0.055 (4)	0.014 (4)	0.016 (3)	−0.001 (3)	0.016 (3)	0.003 (3)
C9	0.056 (4)	0.013 (4)	0.020 (4)	−0.003 (3)	0.010 (4)	−0.006 (3)
C10	0.055 (4)	0.017 (4)	0.031 (4)	−0.002 (3)	0.016 (3)	−0.004 (3)
C11	0.063 (4)	0.022 (5)	0.034 (4)	0.000 (3)	0.012 (3)	−0.002 (3)
C12	0.062 (5)	0.029 (5)	0.053 (5)	0.000 (4)	0.014 (4)	−0.003 (4)
C13	0.059 (5)	0.048 (7)	0.055 (5)	−0.009 (4)	0.016 (4)	−0.006 (4)
C14	0.062 (5)	0.032 (6)	0.045 (5)	−0.010 (4)	0.022 (4)	−0.011 (4)
C15	0.080 (8)	0.036 (6)	0.032 (5)	−0.008 (5)	0.016 (5)	0.000 (4)
C16	0.098 (11)	0.047 (7)	0.102 (13)	0.010 (7)	−0.006 (10)	0.007 (7)
C17	0.065 (6)	0.100 (14)	0.074 (9)	−0.019 (6)	0.023 (6)	−0.015 (9)
O5	0.073 (5)	0.028 (4)	0.037 (4)	−0.002 (4)	0.024 (4)	−0.004 (3)

Geometric parameters (Å, º)

S1—O1	1.518 (7)	C4—C5	1.347 (16)
S1—C8	1.786 (11)	C5—H5	0.9300
S1—C9	1.822 (10)	C5—C6	1.396 (16)
Mg1—O1^i	2.086 (7)	C7—H7A	0.9600
Mg1—O1	2.086 (7)	C7—H7B	0.9600
Mg1—O4^i	2.084 (7)	C7—H7C	0.9600
Mg1—O4	2.084 (7)	C9—H9A	0.9700
Mg1—N1^i	2.168 (8)	C9—H9B	0.9700
Mg1—N1	2.168 (8)	C9—C10	1.497 (15)
O2—C4	1.400 (15)	C10—C11	1.398 (15)
O2—C7	1.450 (16)	C11—C12	1.394 (17)
O3—C12	1.364 (16)	C11—C15	1.511 (16)
O3—C16	1.421 (19)	C12—C13	1.410 (19)
O4—H4A	0.8729	C13—C14	1.367 (19)
O4—H4B	0.8732	C13—C17	1.528 (19)
N1—C1	1.381 (14)	C14—H14	0.9300
N1—C8	1.310 (12)	C15—H15A	0.9600
N2—C6	1.355 (14)	C15—H15B	0.9600
N2—C8	1.333 (12)	C15—H15C	0.9600
N3—C10	1.345 (14)	C16—H16A	0.9600
N3—C14	1.350 (15)	C16—H16B	0.9600
C1—C2	1.385 (16)	C16—H16C	0.9600
C1—C6	1.442 (13)	C17—H17A	0.9600
C2—H2	0.9300	C17—H17B	0.9600
C2—C3	1.392 (17)	C17—H17C	0.9600
C3—H3	0.9300	O5—H5A	0.8500
C3—C4	1.433 (16)	O5—H5B	0.8498
O1—S1—C8	102.8 (4)	O2—C7—H7B	109.5
O1—S1—C9	106.4 (4)	O2—C7—H7C	109.5
C8—S1—C9	97.4 (5)	H7A—C7—H7B	109.5
O1—Mg1—O1^i	180.0	H7A—C7—H7C	109.5
O1^i—Mg1—N1^i	81.3 (3)	H7B—C7—H7C	109.5
O1^i—Mg1—N1	98.7 (3)	N1—C8—S1	118.7 (7)
O1—Mg1—N1	81.3 (3)	N1—C8—N2	118.2 (9)
O1—Mg1—N1^i	98.7 (3)	N2—C8—S1	122.9 (7)
O4^i—Mg1—O1	87.6 (3)	S1—C9—H9A	109.3
O4^i—Mg1—O1^i	92.4 (3)	S1—C9—H9B	109.3
O4—Mg1—O1^i	87.6 (3)	H9A—C9—H9B	108.0
O4—Mg1—O1	92.4 (3)	C10—C9—S1	111.7 (7)
O4^i—Mg1—O4	180.0 (5)	C10—C9—H9A	109.3
O4^i—Mg1—N1^i	87.3 (3)	C10—C9—H9B	109.3
O4—Mg1—N1^i	92.7 (3)	N3—C10—C9	114.7 (9)
O4—Mg1—N1	87.3 (3)	N3—C10—C11	122.5 (10)
O4^i—Mg1—N1	92.7 (3)	C11—C10—C9	122.7 (9)
N1^i—Mg1—N1	180.0	C10—C11—C15	122.5 (11)
S1—O1—Mg1	120.6 (4)	C12—C11—C10	118.3 (11)
C4—O2—C7	117.9 (11)	C12—C11—C15	119.1 (11)
C12—O3—C16	115.1 (12)	O3—C12—C11	120.3 (12)
Mg1—O4—H4A	110.4	O3—C12—C13	119.9 (12)
Mg1—O4—H4B	111.0	C11—C12—C13	119.8 (12)
H4A—O4—H4B	103.0	C12—C13—C17	121.2 (13)
C1—N1—Mg1	140.6 (6)	C14—C13—C12	116.6 (12)
C8—N1—Mg1	116.1 (7)	C14—C13—C17	122.3 (13)
C8—N1—C1	103.3 (8)	N3—C14—C13	125.4 (12)
C8—N2—C6	103.3 (8)	N3—C14—H14	117.3
C10—N3—C14	117.3 (10)	C13—C14—H14	117.3
N1—C1—C2	131.9 (10)	C11—C15—H15A	109.5
N1—C1—C6	107.1 (9)	C11—C15—H15B	109.5
C2—C1—C6	121.0 (10)	C11—C15—H15C	109.5
C1—C2—H2	120.8	H15A—C15—H15B	109.5
C1—C2—C3	118.4 (11)	H15A—C15—H15C	109.5
C3—C2—H2	120.8	H15B—C15—H15C	109.5
C2—C3—H3	119.7	O3—C16—H16A	109.5
C2—C3—C4	120.5 (11)	O3—C16—H16B	109.5
C4—C3—H3	119.7	O3—C16—H16C	109.5
O2—C4—C3	115.6 (10)	H16A—C16—H16B	109.5
C5—C4—O2	123.7 (11)	H16A—C16—H16C	109.5
C5—C4—C3	120.5 (11)	H16B—C16—H16C	109.5
C4—C5—H5	119.6	C13—C17—H17A	109.5
C4—C5—C6	120.8 (11)	C13—C17—H17B	109.5
C6—C5—H5	119.6	C13—C17—H17C	109.5
N2—C6—C1	108.0 (9)	H17A—C17—H17B	109.5
N2—C6—C5	133.3 (9)	H17A—C17—H17C	109.5
C5—C6—C1	118.7 (10)	H17B—C17—H17C	109.5
O2—C7—H7A	109.5	H5A—O5—H5B	104.5

Symmetry code: (i) −x+1, −y+1, −z+1.