Synthesis, structure and non-linear optical properties of new isostructural β-D-fructo­pyran­ose alkaline halide metal–organic frameworks: a theoretical and an experimental study

In this work four metal–organic framework isomorphs, based on fructose and alkali-earth halogenides, were investigated to better understand the effect of the size of the cation and the different polarizability of the anion on the calculated hyperpolarizability and optical susceptibility, which are correlated to non-linear optical properties. The compounds were characterized by X-ray diffraction and the first hyperpolarizability and the second-order susceptibility were obtained from theoretical calculations. Furthermore, a new method to measure the second-harmonic (SH) efficiency on a small quantity of powder at different wavelengths of excitation was optimized and an attempt was made to assess the reduction of the SH intensity for small quantities of nano-crystals, in order to ascertain the possibility of applications in biological systems. The results of this work show that both the intrinsic nature of the anion and the induced dissociation of cations and anions by fructose play a role in the second-harmonic generating properties of such compounds.

Computing details

Data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) for srfrubr1. Cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) for srfrubr1. Data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) for srfrubr1. Program(s) used to solve structure: ShelXT (Sheldrick, 2015) for CaFRUBr; olex2.solve (Bourhis et al., 2015) for srfrubr1. For both structures, 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).

(CaFRUBr)

Crystal data

C12H28CaO14·2Br·HO	F(000) = 622
Mr = 613.23	Dx = 1.790 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 16.1449 (7) Å	Cell parameters from 3289 reflections
b = 7.8881 (3) Å	θ = 3.6–30.5°
c = 11.4702 (5) Å	µ = 3.86 mm^−1
β = 128.842 (4)°	T = 293 K
V = 1137.75 (10) Å^3	Prism, colourless
Z = 2	0.43 × 0.28 × 0.09 mm

Data collection

Xcalibur, Ruby, Gemini ultra diffractometer	3298 independent reflections
Graphite monochromator	2917 reflections with I > 2σ(I)
Detector resolution: 10.2890 pixels mm^-1	Rint = 0.036
ω scans	θmax = 30.5°, θmin = 3.2°
Absorption correction: gaussian CrysAlisPro, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −22→22
Tmin = 0.397, Tmax = 0.727	k = −11→11
7940 measured reflections	l = −16→16

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0318P)^2 + 0.0153P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.076	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.35 e Å^−3
3298 reflections	Δρmin = −0.56 e Å^−3
156 parameters	Absolute structure: Flack x determined using 1126 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
9 restraints	Absolute structure parameter: 0.009 (7)

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)
Ca1	−1.0000	−0.69352 (14)	−1.0000	0.0210 (2)
O1	−0.74861 (19)	−0.1768 (5)	−0.6594 (3)	0.0276 (5)
O1W	−0.9740 (3)	−0.7962 (4)	−1.1766 (4)	0.0409 (8)
H1WA	−0.944 (5)	−0.754 (7)	−1.210 (7)	0.061*
H1WB	−0.989 (5)	−0.895 (4)	−1.213 (7)	0.061*
O2	−0.8936 (3)	−0.4869 (4)	−0.7913 (4)	0.0356 (7)
H2	−0.910 (2)	−0.411 (5)	−0.756 (5)	0.053*
O3	−0.8452 (2)	−0.5650 (4)	−0.9619 (3)	0.0302 (6)
H3	−0.817 (3)	−0.600 (5)	−1.000 (5)	0.045*
O4	−0.7914 (2)	−0.2353 (4)	−1.0083 (3)	0.0297 (6)
H4	−0.8495	−0.2271	−1.0915	0.045*
O5	−0.63282 (19)	−0.1592 (4)	−0.7166 (3)	0.0287 (6)
H5	−0.5948	−0.0933	−0.6466	0.043*
O6	−0.8755 (2)	0.0705 (4)	−0.8537 (4)	0.0330 (7)
H6	−0.8806	0.0156	−0.7976	0.09 (3)*
C1	−0.7210 (4)	−0.3445 (5)	−0.5997 (5)	0.0330 (9)
H1A	−0.7350	−0.3569	−0.5292	0.040*
H1B	−0.6455	−0.3620	−0.5455	0.040*
C2	−0.7826 (4)	−0.4785 (5)	−0.7201 (5)	0.0301 (8)
H2A	−0.7509	−0.5891	−0.6747	0.036*
C3	−0.7743 (3)	−0.4486 (5)	−0.8434 (5)	0.0238 (8)
H3A	−0.7013	−0.4697	−0.8050	0.029*
C4	−0.8059 (3)	−0.2674 (4)	−0.9004 (4)	0.0205 (7)
H4A	−0.8810	−0.2508	−0.9469	0.025*
C5	−0.7387 (3)	−0.1424 (4)	−0.7717 (4)	0.0217 (7)
C6	−0.7738 (3)	0.0414 (4)	−0.8152 (6)	0.0278 (9)
H6A	−0.7218	0.1144	−0.7322	0.033*
H6B	−0.7767	0.0707	−0.8998	0.033*
O2W	−0.5000	0.0667 (6)	−0.5000	0.0357 (9)
H2W	−0.5153	0.1170	−0.4511	0.054*	0.5
Br1	−1.02993 (3)	−0.17635 (5)	−1.31381 (5)	0.03926 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0212 (4)	0.0143 (5)	0.0301 (5)	0.000	0.0174 (4)	0.000
O1	0.0341 (13)	0.0224 (11)	0.0283 (12)	−0.0008 (16)	0.0206 (11)	−0.0022 (15)
O1W	0.056 (2)	0.0323 (16)	0.057 (2)	−0.0178 (15)	0.046 (2)	−0.0165 (15)
O2	0.0418 (19)	0.0308 (15)	0.0484 (19)	−0.0135 (13)	0.0352 (17)	−0.0129 (14)
O3	0.0301 (15)	0.0239 (13)	0.0460 (18)	−0.0089 (11)	0.0284 (15)	−0.0139 (13)
O4	0.0299 (15)	0.0350 (15)	0.0280 (15)	−0.0058 (11)	0.0200 (14)	−0.0015 (11)
O5	0.0181 (12)	0.0256 (15)	0.0379 (14)	−0.0038 (12)	0.0155 (12)	−0.0111 (14)
O6	0.0321 (16)	0.0277 (14)	0.0482 (19)	0.0131 (12)	0.0296 (16)	0.0125 (13)
C1	0.036 (2)	0.0260 (19)	0.027 (2)	−0.0019 (16)	0.015 (2)	0.0030 (16)
C2	0.037 (2)	0.0184 (17)	0.033 (2)	0.0002 (15)	0.021 (2)	0.0020 (16)
C3	0.0181 (19)	0.0187 (17)	0.032 (2)	−0.0043 (14)	0.0148 (17)	−0.0053 (15)
C4	0.0192 (17)	0.0192 (16)	0.0254 (18)	−0.0024 (13)	0.0151 (16)	−0.0015 (14)
C5	0.0188 (16)	0.0187 (18)	0.0276 (18)	−0.0008 (12)	0.0146 (15)	−0.0031 (13)
C6	0.024 (2)	0.0186 (18)	0.042 (2)	0.0010 (15)	0.021 (2)	0.0010 (18)
O2W	0.035 (3)	0.031 (2)	0.032 (2)	0.000	0.017 (2)	0.000
Br1	0.0433 (2)	0.0309 (2)	0.0423 (2)	−0.0006 (2)	0.0263 (2)	−0.0013 (2)

Geometric parameters (Å, º)

Ca1—O1W	2.450 (3)	O3—C3	1.431 (5)
Ca1—O1W^i	2.450 (3)	O4—C4	1.419 (4)
Ca1—O2	2.486 (3)	O5—C5	1.409 (4)
Ca1—O2^i	2.486 (3)	O6—Ca1^iv	2.468 (3)
Ca1—O3^i	2.470 (3)	O6—C6	1.427 (4)
Ca1—O3	2.470 (3)	C1—C2	1.513 (6)
Ca1—O6^ii	2.468 (3)	C2—C3	1.520 (6)
Ca1—O6^iii	2.468 (3)	C3—C4	1.521 (5)
O1—C1	1.427 (5)	C4—C5	1.523 (5)
O1—C5	1.420 (4)	C5—C6	1.522 (5)
O2—C2	1.432 (5)
O1W—Ca1—O1W^i	141.38 (17)	O6^ii—Ca1—O3	83.53 (10)
O1W^i—Ca1—O2	78.09 (11)	O6^iii—Ca1—O3^i	83.53 (10)
O1W—Ca1—O2^i	78.09 (11)	O6^iii—Ca1—O6^ii	82.06 (16)
O1W—Ca1—O2	129.79 (10)	C5—O1—C1	115.7 (3)
O1W^i—Ca1—O2^i	129.78 (10)	C2—O2—Ca1	116.2 (2)
O1W—Ca1—O3^i	131.98 (12)	C3—O3—Ca1	123.3 (2)
O1W—Ca1—O3	66.58 (9)	C6—O6—Ca1^iv	128.3 (2)
O1W^i—Ca1—O3^i	66.58 (9)	O1—C1—C2	112.4 (3)
O1W^i—Ca1—O3	131.99 (12)	O2—C2—C1	115.1 (3)
O1W^i—Ca1—O6^ii	71.14 (10)	O2—C2—C3	106.6 (4)
O1W^i—Ca1—O6^iii	79.88 (12)	C1—C2—C3	110.5 (3)
O1W—Ca1—O6^ii	79.88 (12)	O3—C3—C2	107.5 (3)
O1W—Ca1—O6^iii	71.14 (10)	O3—C3—C4	110.0 (3)
O2—Ca1—O2^i	98.07 (17)	C2—C3—C4	110.1 (3)
O3—Ca1—O2	63.21 (9)	O4—C4—C3	110.4 (3)
O3—Ca1—O2^i	84.98 (10)	O4—C4—C5	108.9 (3)
O3^i—Ca1—O2^i	63.21 (9)	C3—C4—C5	110.4 (3)
O3^i—Ca1—O2	84.98 (11)	O1—C5—C4	109.8 (3)
O3^i—Ca1—O3	131.53 (14)	O1—C5—C6	104.4 (3)
O6^iii—Ca1—O2	157.76 (9)	O5—C5—O1	111.7 (3)
O6^ii—Ca1—O2	93.64 (11)	O5—C5—C4	107.5 (3)
O6^iii—Ca1—O2^i	93.64 (11)	O5—C5—C6	109.5 (3)
O6^ii—Ca1—O2^i	157.76 (9)	C6—C5—C4	114.0 (3)
O6^iii—Ca1—O3	137.05 (9)	O6—C6—C5	112.0 (3)
O6^ii—Ca1—O3^i	137.05 (9)

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

(srfrubr1)

Crystal data

C12H28O14Sr·2Br·HO	F(000) = 658
Mr = 660.80	Dx = 1.890 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 16.4390 (12) Å	Cell parameters from 3111 reflections
b = 8.0240 (5) Å	θ = 3.7–29.3°
c = 11.1931 (8) Å	µ = 5.83 mm^−1
β = 128.142 (7)°	T = 293 K
V = 1161.20 (16) Å^3	Prism, colourless
Z = 2	0.21 × 0.19 × 0.17 mm

Data collection

Xcalibur, Ruby, Gemini ultra diffractometer	5390 independent reflections
Graphite monochromator	3933 reflections with I > 2σ(I)
Detector resolution: 10.2890 pixels mm^-1	Rint = 0.044
ω scans	θmax = 37.6°, θmin = 3.7°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −27→27
Tmin = 0.844, Tmax = 1.000	k = −13→13
11419 measured reflections	l = −18→18

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(Fo^2) + (0.0236P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.096	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.51 e Å^−3
5390 reflections	Δρmin = −0.89 e Å^−3
145 parameters	Absolute structure: Flack x determined using 1074 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
6 restraints	Absolute structure parameter: 0.014 (8)

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)
Sr1	0.0000	−0.05550 (7)	0.0000	0.02056 (11)
Br2	0.52921 (4)	0.95880 (6)	0.31064 (6)	0.03823 (15)
C1	0.2850 (5)	0.2908 (6)	0.4129 (6)	0.0347 (12)
H1A	0.2754	0.2757	0.4894	0.042*
H1B	0.3580	0.2761	0.4617	0.042*
O2	0.1169 (3)	0.1506 (5)	0.2270 (5)	0.0350 (9)
H2	0.103 (5)	0.222 (6)	0.268 (7)	0.053*
O3	0.1606 (3)	0.0769 (4)	0.0418 (4)	0.0285 (8)
H3	0.187 (4)	0.041 (7)	0.002 (6)	0.043*
O4	0.2077 (3)	0.4061 (4)	−0.0083 (4)	0.0284 (8)
H4	0.1729	0.3403	−0.0790	0.043*
O5	0.3639 (2)	0.4804 (4)	0.2864 (4)	0.0292 (7)
H5	0.3998	0.5521	0.3508	0.044*
O6	0.1264 (3)	0.6968 (5)	0.1560 (4)	0.0340 (9)
H6	0.1175	0.6292	0.2019	0.06 (2)*
O1	0.2547 (2)	0.4569 (6)	0.3531 (3)	0.0269 (6)
C2	0.2235 (4)	0.1596 (6)	0.2908 (6)	0.0304 (11)
H2A	0.2552	0.0509	0.3355	0.037*
C3	0.2291 (4)	0.1916 (6)	0.1619 (6)	0.0251 (10)
H3A	0.2999	0.1735	0.1980	0.030*
C4	0.1963 (4)	0.3699 (5)	0.1054 (5)	0.0211 (8)
H4A	0.1236	0.3841	0.0619	0.025*
C5	0.2620 (3)	0.4940 (5)	0.2357 (5)	0.0207 (8)
C6	0.2256 (4)	0.6723 (6)	0.1945 (6)	0.0269 (11)
H6A	0.2751	0.7437	0.2796	0.032*
H6B	0.2234	0.7052	0.1091	0.032*
O1W	−0.0317 (3)	−0.1611 (5)	0.1836 (5)	0.0420 (11)
H1WA	−0.0049	−0.2581	0.2160	0.063*
H1WB	−0.0657	−0.1496	0.2108	0.063*
O2W	0.0000	0.2010 (6)	0.5000	0.0349 (12)
H2W	0.0078	0.2692	0.4497	0.052*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sr1	0.0194 (2)	0.0156 (2)	0.0301 (3)	0.000	0.0170 (2)	0.000
Br2	0.0400 (3)	0.0310 (3)	0.0438 (3)	0.0001 (3)	0.0258 (2)	0.0023 (3)
C1	0.044 (3)	0.026 (2)	0.024 (3)	−0.001 (2)	0.016 (3)	0.0022 (19)
O2	0.043 (2)	0.0299 (18)	0.048 (2)	−0.0132 (17)	0.036 (2)	−0.0126 (16)
O3	0.0268 (18)	0.0258 (16)	0.040 (2)	−0.0098 (14)	0.0240 (17)	−0.0156 (15)
O4	0.0296 (17)	0.0326 (19)	0.0290 (18)	−0.0098 (14)	0.0212 (16)	−0.0065 (13)
O5	0.0172 (14)	0.0255 (17)	0.0397 (19)	−0.0040 (13)	0.0150 (14)	−0.0123 (14)
O6	0.034 (2)	0.0287 (17)	0.051 (2)	0.0146 (16)	0.032 (2)	0.0168 (17)
O1	0.0310 (16)	0.0230 (14)	0.0270 (15)	−0.0029 (19)	0.0181 (14)	−0.0023 (15)
C2	0.035 (3)	0.019 (2)	0.031 (3)	0.0016 (19)	0.018 (2)	0.0044 (18)
C3	0.025 (2)	0.019 (2)	0.035 (3)	−0.0018 (18)	0.021 (2)	−0.0063 (18)
C4	0.019 (2)	0.0213 (19)	0.026 (2)	0.0000 (16)	0.0152 (19)	0.0005 (16)
C5	0.0165 (18)	0.0180 (17)	0.028 (2)	−0.0023 (15)	0.0136 (18)	−0.0047 (15)
C6	0.027 (3)	0.0156 (19)	0.043 (3)	0.0047 (17)	0.024 (3)	0.0021 (18)
O1W	0.058 (3)	0.035 (2)	0.061 (3)	0.0187 (19)	0.050 (3)	0.0173 (19)
O2W	0.038 (3)	0.023 (2)	0.038 (3)	0.000	0.020 (3)	0.000

Geometric parameters (Å, º)

Sr1—O2^i	2.618 (4)	O3—C3	1.433 (6)
Sr1—O2	2.618 (4)	O4—C4	1.425 (5)
Sr1—O3	2.606 (3)	O5—C5	1.401 (5)
Sr1—O3^i	2.606 (3)	O6—Sr1^iv	2.614 (3)
Sr1—O6^ii	2.614 (3)	O6—C6	1.420 (6)
Sr1—O6^iii	2.614 (3)	O1—C5	1.424 (5)
Sr1—O1W	2.557 (4)	C2—C3	1.522 (7)
Sr1—O1W^i	2.557 (4)	C3—C4	1.522 (7)
C1—O1	1.435 (7)	C4—C5	1.529 (6)
C1—C2	1.514 (7)	C5—C6	1.509 (6)
O2—C2	1.429 (7)
O2—Sr1—O2^i	101.64 (19)	O1W—Sr1—O6^ii	71.57 (12)
O3^i—Sr1—O2^i	60.86 (10)	O1W^i—Sr1—O6^ii	79.19 (13)
O3—Sr1—O2	60.86 (10)	O1W^i—Sr1—O1W	141.30 (18)
O3—Sr1—O2^i	88.38 (12)	O1—C1—C2	112.2 (4)
O3^i—Sr1—O2	88.38 (12)	C2—O2—Sr1	117.1 (3)
O3—Sr1—O3^i	131.88 (15)	C3—O3—Sr1	123.5 (3)
O3^i—Sr1—O6^iii	83.73 (12)	C6—O6—Sr1^iv	126.7 (3)
O3—Sr1—O6^ii	83.74 (12)	C5—O1—C1	114.9 (4)
O3—Sr1—O6^iii	136.80 (10)	C1—C2—C3	109.9 (4)
O3^i—Sr1—O6^ii	136.80 (10)	O2—C2—C1	114.6 (4)
O6^ii—Sr1—O2^i	158.87 (11)	O2—C2—C3	107.9 (4)
O6^iii—Sr1—O2	158.87 (11)	O3—C3—C2	108.0 (4)
O6^ii—Sr1—O2	91.59 (13)	O3—C3—C4	110.0 (4)
O6^iii—Sr1—O2^i	91.59 (13)	C2—C3—C4	109.9 (4)
O6^iii—Sr1—O6^ii	81.04 (19)	O4—C4—C3	110.8 (4)
O1W—Sr1—O2	79.69 (12)	O4—C4—C5	108.3 (3)
O1W—Sr1—O2^i	126.69 (12)	C3—C4—C5	110.8 (4)
O1W^i—Sr1—O2	126.69 (12)	O5—C5—O1	111.8 (4)
O1W^i—Sr1—O2^i	79.69 (12)	O5—C5—C4	107.4 (3)
O1W—Sr1—O3^i	65.95 (11)	O5—C5—C6	110.3 (4)
O1W—Sr1—O3	132.66 (13)	O1—C5—C4	109.4 (4)
O1W^i—Sr1—O3^i	132.66 (13)	O1—C5—C6	103.7 (4)
O1W^i—Sr1—O3	65.95 (11)	C6—C5—C4	114.3 (4)
O1W^i—Sr1—O6^iii	71.57 (12)	O6—C6—C5	112.9 (4)
O1W—Sr1—O6^iii	79.19 (13)

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