A versatile environmental control cell for in situ guest exchange single-crystal diffraction

In situ single-crystal diffraction experiments provide researchers with the opportunity to study the response of crystalline systems, including metal-organic frameworks and other nanoporous materials, to changing local microenvironments. This paper reports a new environmental control cell that is remarkably easy to use, completely reusable, and capable of delivering static or dynamic vacuum, liquids or gases to a single-crystal sample. Furthermore the device is nearly identical in size to standard single-crystal mounts so a full unrestricted range of motion is expected for most commercial goniometers. In situ single-crystal X-ray diffraction experiments performed under dynamic gas-flow conditions revealed the cell was capable of stabilizing a novel metastable intermediate in the dehydration reaction of a previously reported metal-organic framework.

Computing details

Cell refinement: SAINT v7.68A (Bruker, 2009); data reduction: SAINT v7.68A (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: XL (Sheldrick, 2008); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(I)

Crystal data

C13H11CoN2O5·2(H2O)	F(000) = 760
Mr = 370.20	Dx = 1.662 Mg m^−3
Monoclinic, P21/c	Cell parameters from 9893 reflections
a = 12.6105 (6) Å	θ = 2.6–17.2°
b = 7.6858 (3) Å	µ = 0.26 mm^−1
c = 15.9256 (7) Å	T = 296 K
β = 106.541 (1)°	Plate, violet
V = 1479.66 (11) Å^3	0.15 × 0.12 × 0.04 mm
Z = 4

Data collection

Bruker SMART APEX2 area detector diffractometer	4261 independent reflections
Radiation source: synchrotron, Bending magnet, ID-15B, APS, ANL	3722 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.078
Detector resolution: 7.9 pixels mm^-1	θmax = 17.2°, θmin = 1.6°
ω and φ scans	h = −18→17
Absorption correction: multi-scan SADABS2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1579 before and 0.1047 after correction. The Ratio of minimum to maximum transmission is 0.8645. The λ/2 correction factor is 0.0015.	k = −10→8
Tmin = 0.617, Tmax = 0.714	l = −22→22
28364 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)] = 0.087	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.234	H-atom parameters constrained
S = 1.22	w = 1/[σ^2(Fo^2) + (0.1592P)^2 + 0.5543P] where P = (Fo^2 + 2Fc^2)/3
4261 reflections	(Δ/σ)max < 0.001
215 parameters	Δρmax = 1.61 e Å^−3
0 restraints	Δρmin = −1.73 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
Co1	0.30400 (3)	0.00854 (4)	0.17802 (2)	0.01507 (19)
O2	0.37286 (19)	−0.3360 (3)	0.33008 (12)	0.0283 (4)
C8	0.40714 (19)	−0.0856 (3)	0.62713 (14)	0.0161 (4)
H8	0.4195	−0.0635	0.6866	0.019*
C6	0.36927 (19)	0.0469 (3)	0.56608 (14)	0.0152 (4)
N1	0.45305 (17)	−0.1113 (3)	0.16169 (12)	0.0159 (4)
H1A	0.4934	−0.0305	0.1437	0.019*
H1B	0.4941	−0.1533	0.2135	0.019*
C4	0.35877 (18)	−0.1843 (3)	0.35387 (14)	0.0162 (4)
O1	0.32983 (18)	−0.0558 (3)	0.30328 (12)	0.0267 (4)
C3	0.37520 (18)	−0.1489 (3)	0.44963 (13)	0.0143 (4)
O4	0.37073 (17)	0.2547 (2)	0.18120 (11)	0.0234 (4)
C2	0.41121 (18)	−0.2824 (3)	0.51048 (14)	0.0151 (4)
H2	0.4251	−0.3925	0.4918	0.018*
O5	0.16518 (19)	0.1595 (3)	0.20415 (15)	0.0355 (5)
H5A	0.1886	0.2222	0.2518	0.053*
H5B	0.1136	0.0893	0.2111	0.053*
C1	0.42634 (18)	−0.2505 (3)	0.59908 (13)	0.0138 (4)
C7	0.3440 (2)	0.2802 (3)	0.09901 (15)	0.0176 (4)
N2	0.18485 (18)	−0.1706 (3)	0.11048 (14)	0.0219 (4)
O3	0.29523 (18)	0.1626 (3)	0.04740 (13)	0.0283 (4)
C11	0.0380 (2)	−0.4306 (4)	0.02352 (18)	0.0286 (6)
C5	0.3528 (2)	0.0156 (3)	0.47706 (17)	0.0165 (5)
H5	0.3272	0.1038	0.4364	0.020*
C13	0.1739 (3)	−0.3202 (5)	0.1481 (2)	0.0457 (10)
H13	0.2163	−0.3378	0.2057	0.055*
C9	0.1278 (4)	−0.1544 (6)	0.0278 (2)	0.0646 (15)
H9	0.1378	−0.0543	−0.0019	0.078*
C12	0.1029 (4)	−0.4530 (5)	0.1070 (2)	0.0488 (11)
H12	0.0999	−0.5565	0.1365	0.059*
C10	0.0538 (5)	−0.2777 (7)	−0.0174 (3)	0.087 (3)
H10	0.0145	−0.2582	−0.0756	0.104*
O7	0.2325 (2)	−0.6013 (4)	0.36079 (17)	0.0430 (6)
H7A	0.2776	−0.5247	0.3534	0.065*
H7B	0.2439	−0.6199	0.4153	0.065*
O6	−0.0098 (6)	−0.0409 (15)	0.2157 (6)	0.171 (4)
H6A	−0.0786	−0.0349	0.1893	0.256*
H6B	−0.0008	−0.0640	0.2694	0.256*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0235 (3)	0.0096 (3)	0.0107 (3)	−0.00518 (9)	0.00259 (17)	0.00018 (8)
O2	0.0460 (12)	0.0224 (10)	0.0164 (8)	0.0079 (8)	0.0087 (8)	−0.0042 (7)
C8	0.0262 (10)	0.0102 (9)	0.0112 (9)	0.0006 (7)	0.0043 (7)	−0.0009 (7)
C6	0.0259 (10)	0.0059 (9)	0.0140 (9)	0.0018 (7)	0.0059 (8)	0.0001 (7)
N1	0.0269 (9)	0.0091 (9)	0.0100 (8)	−0.0026 (7)	0.0025 (7)	−0.0014 (6)
C4	0.0205 (9)	0.0188 (11)	0.0094 (9)	0.0008 (8)	0.0044 (7)	0.0005 (7)
O1	0.0448 (11)	0.0235 (10)	0.0120 (8)	0.0041 (8)	0.0083 (7)	0.0054 (7)
C3	0.0216 (9)	0.0120 (10)	0.0092 (8)	0.0011 (7)	0.0041 (7)	0.0014 (7)
O4	0.0409 (10)	0.0122 (8)	0.0175 (8)	−0.0038 (7)	0.0090 (7)	0.0028 (6)
C2	0.0232 (10)	0.0102 (9)	0.0114 (9)	0.0036 (7)	0.0041 (7)	−0.0006 (7)
O5	0.0362 (11)	0.0325 (13)	0.0347 (12)	0.0045 (9)	0.0052 (9)	−0.0002 (9)
C1	0.0220 (9)	0.0080 (9)	0.0100 (8)	0.0007 (7)	0.0025 (7)	0.0011 (7)
C7	0.0246 (10)	0.0110 (10)	0.0173 (10)	−0.0009 (7)	0.0061 (8)	0.0013 (7)
N2	0.0239 (9)	0.0176 (10)	0.0205 (10)	−0.0072 (7)	0.0003 (7)	−0.0019 (7)
O3	0.0424 (11)	0.0134 (9)	0.0243 (9)	−0.0108 (7)	0.0017 (8)	−0.0010 (7)
C11	0.0307 (13)	0.0234 (14)	0.0237 (12)	−0.0128 (10)	−0.0052 (10)	0.0010 (10)
C5	0.0251 (12)	0.0109 (10)	0.0136 (11)	0.0020 (7)	0.0054 (9)	0.0024 (7)
C13	0.059 (2)	0.0353 (18)	0.0261 (14)	−0.0285 (15)	−0.0150 (13)	0.0104 (12)
C9	0.094 (3)	0.040 (2)	0.0323 (17)	−0.047 (2)	−0.0253 (18)	0.0159 (14)
C12	0.062 (2)	0.0315 (17)	0.0330 (17)	−0.0312 (17)	−0.0187 (15)	0.0142 (14)
C10	0.123 (5)	0.061 (3)	0.0368 (19)	−0.068 (3)	−0.041 (2)	0.026 (2)
O7	0.0518 (14)	0.0359 (14)	0.0359 (13)	−0.0041 (11)	0.0036 (11)	0.0040 (10)
O6	0.081 (4)	0.323 (11)	0.117 (6)	−0.101 (6)	0.042 (4)	0.000 (6)

Geometric parameters (Å, º)

Co1—N1	2.174 (2)	O5—H5A	0.8762
Co1—O1	1.9900 (18)	O5—H5B	0.8756
Co1—O4	2.0653 (19)	C1—N1^iii	1.430 (3)
Co1—O5	2.236 (2)	C7—C6^iv	1.496 (3)
Co1—N2	2.095 (2)	C7—O3	1.258 (3)
Co1—O3	2.369 (2)	N2—C13	1.322 (4)
O2—C4	1.254 (3)	N2—C9	1.314 (4)
C8—H8	0.9300	C11—C11^v	1.486 (5)
C8—C6	1.395 (3)	C11—C12	1.360 (4)
C8—C1	1.388 (3)	C11—C10	1.386 (5)
C6—C7^i	1.496 (3)	C5—H5	0.9300
C6—C5	1.394 (3)	C13—H13	0.9300
N1—H1A	0.9000	C13—C12	1.392 (4)
N1—H1B	0.9000	C9—H9	0.9300
N1—C1^ii	1.430 (3)	C9—C10	1.380 (5)
C4—O1	1.261 (3)	C12—H12	0.9300
C4—C3	1.504 (3)	C10—H10	0.9300
C3—C2	1.395 (3)	O7—H7A	0.8500
C3—C5	1.393 (3)	O7—H7B	0.8502
O4—C7	1.271 (3)	O6—H6A	0.8506
C2—H2	0.9300	O6—H6B	0.8500
C2—C1	1.391 (3)
N1—Co1—O5	172.50 (8)	C1—C2—C3	119.9 (2)
N1—Co1—O3	86.13 (8)	C1—C2—H2	120.0
O1—Co1—N1	96.57 (8)	Co1—O5—H5A	111.0
O1—Co1—O4	104.69 (8)	Co1—O5—H5B	110.7
O1—Co1—O5	81.70 (9)	H5A—O5—H5B	107.9
O1—Co1—N2	103.90 (9)	C8—C1—N1^iii	118.82 (18)
O1—Co1—O3	163.32 (8)	C8—C1—C2	120.08 (19)
O4—Co1—N1	91.77 (8)	C2—C1—N1^iii	120.92 (19)
O4—Co1—O5	81.67 (9)	O4—C7—C6^iv	118.5 (2)
O4—Co1—N2	147.37 (8)	O3—C7—C6^iv	121.5 (2)
O4—Co1—O3	58.70 (7)	O3—C7—O4	119.9 (2)
O5—Co1—O3	93.48 (8)	C13—N2—Co1	119.38 (18)
N2—Co1—N1	100.28 (8)	C9—N2—Co1	124.1 (2)
N2—Co1—O5	87.22 (9)	C9—N2—C13	116.0 (2)
N2—Co1—O3	91.73 (8)	C7—O3—Co1	83.89 (14)
C6—C8—H8	120.0	C12—C11—C11^v	121.6 (3)
C1—C8—H8	120.0	C12—C11—C10	116.1 (3)
C1—C8—C6	119.92 (19)	C10—C11—C11^v	122.0 (3)
C8—C6—C7^i	117.98 (19)	C6—C5—H5	120.3
C5—C6—C8	120.3 (2)	C3—C5—C6	119.4 (2)
C5—C6—C7^i	121.7 (2)	C3—C5—H5	120.3
Co1—N1—H1A	109.4	N2—C13—H13	118.0
Co1—N1—H1B	109.4	N2—C13—C12	124.1 (3)
H1A—N1—H1B	108.0	C12—C13—H13	118.0
C1^ii—N1—Co1	110.98 (14)	N2—C9—H9	118.2
C1^ii—N1—H1A	109.4	N2—C9—C10	123.6 (3)
C1^ii—N1—H1B	109.4	C10—C9—H9	118.2
O2—C4—O1	125.1 (2)	C11—C12—C13	119.6 (3)
O2—C4—C3	119.0 (2)	C11—C12—H12	120.2
O1—C4—C3	115.9 (2)	C13—C12—H12	120.2
C4—O1—Co1	140.34 (18)	C11—C10—H10	119.9
C2—C3—C4	119.7 (2)	C9—C10—C11	120.2 (3)
C5—C3—C4	120.0 (2)	C9—C10—H10	119.9
C5—C3—C2	120.30 (19)	H7A—O7—H7B	109.5
C7—O4—Co1	97.44 (15)	H6A—O6—H6B	109.4
C3—C2—H2	120.0
Co1—O4—C7—C6^iv	176.31 (18)	O4—Co1—N2—C9	15.3 (4)
Co1—O4—C7—O3	−2.1 (3)	O4—Co1—O3—C7	−1.14 (15)
Co1—N2—C13—C12	−175.4 (4)	O4—C7—O3—Co1	1.8 (2)
Co1—N2—C9—C10	176.3 (6)	C2—C3—C5—C6	1.5 (4)
O2—C4—O1—Co1	−7.0 (5)	O5—Co1—N1—C1^ii	−167.4 (5)
O2—C4—C3—C2	3.3 (3)	O5—Co1—O1—C4	142.1 (3)
O2—C4—C3—C5	−175.7 (2)	O5—Co1—O4—C7	−98.13 (16)
C8—C6—C5—C3	−0.4 (4)	O5—Co1—N2—C13	−103.5 (3)
C6—C8—C1—N1^iii	−173.0 (2)	O5—Co1—N2—C9	85.2 (4)
C6—C8—C1—C2	2.0 (3)	O5—Co1—O3—C7	76.93 (16)
C6^iv—C7—O3—Co1	−176.5 (2)	C1—C8—C6—C7^i	176.8 (2)
N1—Co1—O1—C4	−45.3 (3)	C1—C8—C6—C5	−1.4 (4)
N1—Co1—O4—C7	85.52 (16)	C7^i—C6—C5—C3	−178.5 (2)
N1—Co1—N2—C13	76.8 (3)	N2—Co1—N1—C1^ii	10.93 (15)
N1—Co1—N2—C9	−94.6 (4)	N2—Co1—O1—C4	57.1 (3)
N1—Co1—O3—C7	−95.57 (16)	N2—Co1—O4—C7	−26.8 (2)
C4—C3—C2—C1	−179.9 (2)	N2—Co1—O3—C7	164.24 (16)
C4—C3—C5—C6	−179.5 (2)	N2—C13—C12—C11	−1.3 (8)
O1—Co1—N1—C1^ii	116.39 (15)	N2—C9—C10—C11	−1.4 (11)
O1—Co1—O4—C7	−177.22 (15)	O3—Co1—N1—C1^ii	−80.13 (14)
O1—Co1—N2—C13	−22.7 (3)	O3—Co1—O1—C4	−143.8 (3)
O1—Co1—N2—C9	165.9 (4)	O3—Co1—O4—C7	1.13 (14)
O1—Co1—O3—C7	4.4 (4)	O3—Co1—N2—C13	163.1 (3)
O1—C4—C3—C2	−177.6 (2)	O3—Co1—N2—C9	−8.2 (4)
O1—C4—C3—C5	3.4 (3)	C11^v—C11—C12—C13	179.2 (5)
C3—C4—O1—Co1	174.0 (2)	C11^v—C11—C10—C9	−178.0 (6)
C3—C2—C1—C8	−0.9 (3)	C5—C3—C2—C1	−0.9 (3)
C3—C2—C1—N1^iii	174.0 (2)	C13—N2—C9—C10	4.7 (9)
O4—Co1—N1—C1^ii	−138.60 (14)	C9—N2—C13—C12	−3.3 (7)
O4—Co1—O1—C4	−138.8 (3)	C12—C11—C10—C9	−3.3 (9)
O4—Co1—N2—C13	−173.3 (3)	C10—C11—C12—C13	4.6 (8)

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