Depicting the crystal structure of fibrous ferrierite from British Columbia using a combined synchrotron techniques approach

The ferrierite crystal structure has often been subject to discussion because of the possible lowering of symmetry from the space group Immm. It mainly occurs in nature with a fibrous crystal habit, and because of the existence of line/planar defects in the framework, texture and preferred orientation effects it has been difficult to obtain an exact crystallographic model based only on the results from powder diffraction data. Therefore, nano-single-crystal diffraction and tomography data have been combined in order to improve the refinement with a meaningful model. High-quality single-crystal data, providing reliable structural information, and tomography images have been used as input for a Rietveld refinement which took into account a phenomenological description of stacking disorder and the analytical description of the preferred orientation, by means of spherical harmonics for strong texture effects. This is one of the first examples of application of synchrotron nano-diffraction for the structure solution of fibrous minerals of micrometre to nanometre size. The high quality of the crystals allowed collection of single-crystal X-ray diffraction data of up to 0.6 Å resolution, leading to an unambiguous solution and precise anisotropic refinement. Nano-single-crystal diffraction and phase contrast tomography data were collected at ID11 and the high-resolution powder diffraction patterns at ID22 of the European Synchrotron Radiation Facility. This detailed crystallographic characterization provides a basis for understanding the potential of ferrierite for toxicity and carcinogenicity.

Computing details

Program(s) used to solve structure: SHELXT 2014/5 (Sheldrick, 2014); 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

Al6.24K1.03O77.8Si29.76·4(Mg0.5O2.8)	F(000) = 1252
Mr = 2514.66	Dx = 2.045 Mg m^−3
Orthorhombic, Immm	Synchrotron radiation, λ = 0.20645 Å
a = 7.5090 (1) Å	Cell parameters from 6211 reflections
b = 14.1395 (1) Å	θ = 1.3–6211°
c = 19.2362 (2) Å	µ = 0.07 mm^−1
V = 2042.37 (4) Å^3	T = 293 K
Z = 1	Fibre

Data collection

Nanoscope ID11 diffractometer	Rint = 0.072
rotation scans	θmax = 12.6°, θmin = 1.5°
38588 measured reflections	h = −14→14
3785 independent reflections	k = −28→27
3119 reflections with I > 2σ(I)	l = −30→30

Refinement

Refinement on F^2	117 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.071	w = 1/[σ^2(Fo^2) + (0.1123P)^2 + 0.8578P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.207	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.78 e Å^−3
3785 reflections	Δρmin = −0.46 e Å^−3

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	Occ. (<1)
K1	0.500000	1.000000	0.4254 (3)	0.0508 (13)	0.2572
Mg1	0.500000	0.500000	0.500000	0.0305 (7)
Si1	0.500000	1.000000	0.15498 (5)	0.0185 (7)	0.16
Al1	0.500000	1.000000	0.15498 (5)	0.0185 (7)	0.84
Si2	0.000000	0.70275 (4)	0.41582 (3)	0.0181 (6)	0.64
Al2	0.000000	0.70275 (4)	0.41582 (3)	0.0181 (6)	0.36
Si3	0.20782 (9)	1.000000	0.27223 (4)	0.0256 (7)
Si4	0.29377 (6)	0.79765 (3)	0.32302 (3)	0.0218 (6)
O1	0.000000	0.7163 (3)	0.500000	0.0407 (10)
O2	0.000000	1.000000	0.2494 (3)	0.0439 (10)
O3	0.000000	0.5892 (2)	0.3980 (2)	0.0664 (13)
O4	0.3205 (6)	1.000000	0.2016 (2)	0.0802 (16)
O5	0.250000	0.750000	0.250000	0.0577 (10)
O6	0.500000	0.7813 (2)	0.34276 (18)	0.0473 (9)
O7	0.1806 (3)	0.7511 (2)	0.38449 (12)	0.0584 (9)
O8	0.2527 (4)	0.90928 (14)	0.32131 (14)	0.0553 (9)
WAT1	0.2345 (4)	0.500000	0.500000	0.0411 (10)
WAT2	0.500000	0.4348 (9)	0.4034 (4)	0.073 (4)	0.50 (2)
WAT3	0.500000	0.3707 (8)	0.4503 (7)	0.072 (5)	0.398 (19)
WAT4	0.714 (6)	0.884 (2)	0.500000	0.142 (18)	0.37 (4)
WAT5	0.588 (6)	0.819 (7)	0.500000	0.28 (4)	0.35 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.067 (3)	0.042 (2)	0.043 (2)	0.000	0.000	0.000
Mg1	0.0213 (9)	0.0438 (12)	0.0264 (11)	0.000	0.000	0.000
Si1	0.0205 (7)	0.0167 (7)	0.0182 (8)	0.000	0.000	0.000
Al1	0.0205 (7)	0.0167 (7)	0.0182 (8)	0.000	0.000	0.000
Si2	0.0185 (7)	0.0176 (7)	0.0182 (7)	0.000	0.000	0.00023 (17)
Al2	0.0185 (7)	0.0176 (7)	0.0182 (7)	0.000	0.000	0.00023 (17)
Si3	0.0218 (7)	0.0248 (7)	0.0303 (7)	0.000	0.0038 (2)	0.000
Si4	0.0182 (6)	0.0221 (7)	0.0249 (7)	−0.00156 (12)	0.00055 (13)	0.00100 (14)
O1	0.057 (2)	0.0429 (17)	0.0216 (15)	0.000	0.000	0.000
O2	0.0247 (13)	0.0418 (17)	0.065 (3)	0.000	0.000	0.000
O3	0.121 (4)	0.0322 (13)	0.0458 (18)	0.000	0.000	−0.0126 (12)
O4	0.0503 (19)	0.141 (4)	0.050 (2)	0.000	0.0260 (16)	0.000
O5	0.075 (2)	0.0591 (19)	0.0388 (16)	−0.0087 (16)	−0.0075 (14)	−0.0168 (14)
O6	0.0210 (10)	0.0614 (18)	0.0594 (18)	0.000	0.000	0.0097 (14)
O7	0.0429 (11)	0.0909 (19)	0.0415 (12)	−0.0326 (11)	0.0078 (8)	0.0109 (11)
O8	0.0773 (17)	0.0278 (9)	0.0608 (16)	0.0129 (9)	−0.0125 (11)	−0.0002 (8)
WAT1	0.0224 (12)	0.067 (2)	0.0344 (17)	0.000	0.000	0.000
WAT2	0.048 (4)	0.135 (10)	0.037 (4)	0.000	0.000	−0.032 (5)
WAT3	0.047 (4)	0.073 (7)	0.095 (10)	0.000	0.000	−0.059 (7)
WAT4	0.24 (4)	0.12 (2)	0.063 (10)	0.09 (2)	0.000	0.000
WAT5	0.25 (6)	0.53 (10)	0.08 (2)	−0.12 (6)	0.000	0.000

Geometric parameters (Å, º)

K1—K1^i	2.870 (12)	Mg1—WAT3^vii	2.064 (8)
K1—O8^ii	3.017 (5)	Si1—O3^ix	1.622 (3)
K1—O8^iii	3.017 (5)	Si1—O3^x	1.622 (3)
K1—O8^iv	3.017 (5)	Si1—O4	1.619 (3)
K1—WAT4	2.705 (19)	Si1—O4^ii	1.619 (3)
K1—WAT4^iv	2.71 (2)	Si2—O1	1.6305 (8)
K1—WAT4^i	2.705 (19)	Si2—O3	1.642 (3)
K1—WAT4^v	2.705 (19)	Si2—O7^xi	1.6342 (18)
K1—WAT5^i	3.01 (8)	Si2—O7	1.6342 (18)
K1—WAT5^iv	3.01 (8)	Si3—O2	1.6211 (16)
K1—WAT5	3.01 (8)	Si3—O4	1.601 (4)
K1—WAT5^v	3.01 (8)	Si3—O8	1.628 (2)
Mg1—WAT1	1.994 (3)	Si3—O8^iv	1.628 (2)
Mg1—WAT1^vi	1.994 (3)	Si4—O5	1.5921 (5)
Mg1—WAT2^vii	2.075 (7)	Si4—O6	1.6112 (10)
Mg1—WAT2^vi	2.075 (7)	Si4—O7	1.5979 (19)
Mg1—WAT2	2.075 (7)	Si4—O8	1.6085 (19)
Mg1—WAT2^viii	2.075 (7)	WAT2—WAT3	1.280 (16)
Mg1—WAT3^vi	2.064 (8)	WAT4—WAT5	1.33 (6)
Mg1—WAT3	2.064 (8)	WAT5—WAT5^v	1.32 (10)
Mg1—WAT3^viii	2.064 (8)
K1^i—K1—O8^iii	131.57 (10)	WAT1^vi—Mg1—WAT3^viii	90.000 (1)
K1^i—K1—O8^ii	131.57 (10)	WAT2—Mg1—WAT2^vi	180.0
K1^i—K1—O8^iv	131.57 (10)	WAT2^vi—Mg1—WAT2^vii	127.2 (8)
K1^i—K1—WAT5	61.6 (8)	WAT2—Mg1—WAT2^vii	52.8 (8)
K1^i—K1—WAT5^i	61.6 (8)	WAT2^viii—Mg1—WAT2^vii	180.0
K1^i—K1—WAT5^iv	61.6 (8)	WAT2^vi—Mg1—WAT2^viii	52.8 (8)
K1^i—K1—WAT5^v	61.6 (8)	WAT2—Mg1—WAT2^viii	127.2 (8)
O8^iv—K1—O8^iii	96.9 (2)	WAT3^vi—Mg1—WAT2^vi	36.0 (5)
O8^iv—K1—O8^ii	75.98 (16)	WAT3^vi—Mg1—WAT2^vii	91.2 (7)
O8^iii—K1—O8^ii	50.32 (10)	WAT3^vii—Mg1—WAT2^vi	91.2 (7)
WAT4^v—K1—K1^i	58.0 (3)	WAT3^vi—Mg1—WAT2^viii	88.8 (7)
WAT4^i—K1—K1^i	58.0 (3)	WAT3^vii—Mg1—WAT2^vii	36.0 (5)
WAT4—K1—K1^i	58.0 (3)	WAT3^viii—Mg1—WAT2^viii	36.0 (5)
WAT4^iv—K1—K1^i	58.0 (3)	WAT3^viii—Mg1—WAT2	91.2 (7)
WAT4^v—K1—O8^iii	117.4 (8)	WAT3^vii—Mg1—WAT2^viii	144.0 (5)
WAT4—K1—O8^ii	104.1 (9)	WAT3^viii—Mg1—WAT2^vii	144.0 (5)
WAT4^v—K1—O8^ii	167.1 (6)	WAT3^vi—Mg1—WAT2	144.0 (5)
WAT4^i—K1—O8^iii	167.1 (6)	WAT3—Mg1—WAT2^vii	88.8 (7)
WAT4^iv—K1—O8^ii	74.3 (4)	WAT3^viii—Mg1—WAT2^vi	88.8 (7)
WAT4^i—K1—O8^ii	117.4 (8)	WAT3—Mg1—WAT2^vi	144.0 (5)
WAT4^i—K1—O8^iv	74.3 (4)	WAT3^vii—Mg1—WAT2	88.8 (7)
WAT4^v—K1—O8^iv	104.1 (9)	WAT3—Mg1—WAT2	36.0 (5)
WAT4^iv—K1—O8^iv	117.4 (8)	WAT3—Mg1—WAT2^viii	91.2 (7)
WAT4^iv—K1—O8^iii	104.1 (9)	WAT3^viii—Mg1—WAT3^vii	180.0
WAT4—K1—O8^iii	74.3 (4)	WAT3^vi—Mg1—WAT3^vii	55.2 (9)
WAT4—K1—O8^iv	167.1 (6)	WAT3^viii—Mg1—WAT3	55.2 (9)
WAT4—K1—WAT4^v	73 (2)	WAT3^vi—Mg1—WAT3^viii	124.8 (9)
WAT4^v—K1—WAT4^i	74.4 (17)	WAT3^vi—Mg1—WAT3	180.0
WAT4^iv—K1—WAT4^i	73 (2)	WAT3^vii—Mg1—WAT3	124.8 (9)
WAT4^iv—K1—WAT4^v	115.9 (5)	O3^ix—Si1—O3^x	102.1 (3)
WAT4—K1—WAT4^i	115.9 (5)	O4^ii—Si1—O3^ix	110.38 (12)
WAT4—K1—WAT4^iv	74.4 (17)	O4—Si1—O3^ix	110.38 (12)
WAT4^v—K1—WAT5^v	26.1 (9)	O4^ii—Si1—O3^x	110.38 (12)
WAT4^v—K1—WAT5^iv	113.1 (9)	O4—Si1—O3^x	110.38 (12)
WAT4^iv—K1—WAT5^i	50.4 (17)	O4—Si1—O4^ii	112.8 (4)
WAT4—K1—WAT5	26.1 (9)	O1—Si2—O3	108.8 (2)
WAT4—K1—WAT5^v	50.4 (17)	O1—Si2—O7^xi	108.49 (11)
WAT4^iv—K1—WAT5	97.6 (17)	O1—Si2—O7	108.49 (11)
WAT4^v—K1—WAT5^i	97.6 (17)	O7—Si2—O3	109.42 (12)
WAT4^v—K1—WAT5	50.4 (17)	O7^xi—Si2—O3	109.42 (13)
WAT4^i—K1—WAT5^iv	50.4 (17)	O7—Si2—O7^xi	112.2 (2)
WAT4^i—K1—WAT5^i	26.1 (9)	O2—Si3—K1	142.39 (19)
WAT4—K1—WAT5^i	113.1 (9)	O2—Si3—O8^iv	110.87 (15)
WAT4^i—K1—WAT5^v	97.6 (17)	O2—Si3—O8	110.87 (15)
WAT4^iv—K1—WAT5^v	113.1 (9)	O4—Si3—K1	111.43 (19)
WAT4—K1—WAT5^iv	97.6 (17)	O4—Si3—O2	106.2 (3)
WAT4^i—K1—WAT5	113.1 (9)	O4—Si3—O8	112.52 (15)
WAT4^iv—K1—WAT5^iv	26.1 (9)	O4—Si3—O8^iv	112.52 (15)
WAT5—K1—O8^iii	79.6 (7)	O8—Si3—K1	53.94 (10)
WAT5^iv—K1—O8^ii	79.6 (7)	O8^iv—Si3—K1	53.94 (10)
WAT5^i—K1—O8^iv	79.6 (7)	O8—Si3—O8^iv	104.00 (18)
WAT5^iv—K1—O8^iii	122.9 (8)	O5—Si4—K1	149.24 (8)
WAT5^v—K1—O8^ii	144.4 (12)	O5—Si4—O6	110.21 (13)
WAT5^i—K1—O8^iii	144.4 (12)	O5—Si4—O7	111.65 (9)
WAT5^v—K1—O8^iv	122.9 (8)	O5—Si4—O8	110.95 (10)
WAT5^v—K1—O8^iii	95.1 (11)	O6—Si4—K1	66.09 (13)
WAT5^i—K1—O8^ii	95.1 (11)	O7—Si4—K1	98.23 (12)
WAT5—K1—O8^iv	144.4 (12)	O7—Si4—O6	106.11 (15)
WAT5^iv—K1—O8^iv	95.1 (11)	O7—Si4—O8	108.49 (16)
WAT5—K1—O8^ii	122.9 (8)	O8—Si4—K1	49.50 (10)
WAT5^iv—K1—WAT5^i	25 (2)	O8—Si4—O6	109.28 (16)
WAT5^i—K1—WAT5^v	117 (2)	Si2^viii—O1—Si2	166.5 (3)
WAT5^iv—K1—WAT5^v	123.1 (17)	Si3^xii—O2—Si3	148.6 (4)
WAT5—K1—WAT5^v	25 (2)	Si1^ix—O3—Si2	153.1 (3)
WAT5—K1—WAT5^i	123.1 (17)	Si3—O4—Si1	155.5 (4)
WAT5—K1—WAT5^iv	117 (2)	Si4—O5—Si4^ix	180.0
WAT1—Mg1—WAT1^vi	180.0	Si4—O6—Si4^iii	148.0 (2)
WAT1^vi—Mg1—WAT2	90.000 (1)	Si4—O7—Si2	152.45 (16)
WAT1^vi—Mg1—WAT2^viii	90.000 (2)	Si3—O8—K1	100.20 (12)
WAT1^vi—Mg1—WAT2^vii	90.000 (2)	Si4—O8—K1	106.59 (12)
WAT1—Mg1—WAT2^vi	90.000 (1)	Si4—O8—Si3	145.56 (18)
WAT1—Mg1—WAT2^vii	90.000 (1)	WAT3—WAT2—Mg1	71.5 (4)
WAT1^vi—Mg1—WAT2^vi	90.000 (2)	WAT2—WAT3—Mg1	72.5 (6)
WAT1—Mg1—WAT2^viii	90.000 (2)	K1^i—WAT4—K1	64.1 (5)
WAT1—Mg1—WAT2	90.000 (2)	WAT5—WAT4—K1	90 (4)
WAT1—Mg1—WAT3	90.000 (2)	WAT5—WAT4—K1^i	90 (4)
WAT1—Mg1—WAT3^viii	90.000 (4)	K1^i—WAT5—K1	56.9 (17)
WAT1^vi—Mg1—WAT3^vii	90.000 (4)	WAT4—WAT5—K1	64 (4)
WAT1^vi—Mg1—WAT3	90.000 (1)	WAT4—WAT5—K1^i	64 (4)
WAT1—Mg1—WAT3^vii	90.000 (1)	WAT5^v—WAT5—K1	77.3 (10)
WAT1—Mg1—WAT3^vi	90.000 (1)	WAT5^v—WAT5—K1^i	77.3 (10)
WAT1^vi—Mg1—WAT3^vi	90.000 (2)	WAT5^v—WAT5—WAT4	136 (4)

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