Crystal structure of trans-cyclo­hexane-1,2-di­ammonium chromate(VI) from synchrotron X-ray diffraction data

Moon, D.; Choi, J.-H.

doi:10.1107/S2056989016019009

research communications

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ISSN: 2056-9890

Volume 72| Part 12| December 2016| Pages 1872-1874

https://doi.org/10.1107/S2056989016019009

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Crystal structure of trans-cyclohexane-1,2-diammonium chromate(VI) from synchrotron X-ray diffraction data

Dohyun Moon ^a and Jong-Ha Choi ^b ^*

^aPohang Accelerator Laboratory, POSTECH, Pohang 37673, Republic of Korea, and ^bDepartment of Chemistry, Andong National University, Andong 36729, Republic of Korea
^*Correspondence e-mail: jhchoi@anu.ac.kr

Edited by M. Weil, Vienna University of Technology, Austria (Received 19 November 2016; accepted 28 November 2016; online 30 November 2016)

The structure of the title hybrid compound, (C₆H₁₆N₂)[CrO₄], has been determined from synchrotron data. The organic cation adopts a chair conformation. The inorganic CrO₄²⁻ anion is slightly distorted owing to its involvement in N—H⋯O hydrogen-bonding interactions with neighbouring trans-cyclohexane-1,2-diammonium cations, whereby the two Cr—O bonds to the O atoms acting as acceptor atoms for two hydrogen bonds are slightly longer than the other two Cr—O bonds for which only one acceptor interaction per O atom is observed. In the crystal, cations and anions are packed into layers parallel to (001), held together through the aforementioned N—H⋯O hydrogen bonds.

Keywords: crystal structure; trans-cyclohexane-1,2-diammonium; chromate(VI); hydrogen bonding; synchrotron radiation; hybrid compound.

CCDC reference: 1519508

1. Chemical context

Organic–inorganic hybrid compounds are of interest because of the possibility of their forming extended networks through versatile hydrogen bonds (Mkaouar et al., 2016 ). The amine trans-1,2-cyclohexanediamine (chxn), C₆H₁₄N₂, is strongly basic and readily captures two protons to form a dication, (C₆H₁₆N₂)²⁺. Crystal structures of this amine or the dication have been determined for trans-1,2-cyclohexanediamine hydrobromide (Morse & Chesick, 1976 ), trans-cyclohexane-1,2-diammonium dichloride (Farrugia et al., 2001 ) and trans-cyclohexane-1,2-diammonium bis(3′-nitro-trans-cinnamate) (Hosomi et al., 2000 ). With respect to complex inorganic anions of the types ZnCl₄²⁻, CrO₄²⁻ or Cr₂O₇²⁻, the crystal structures of hybrid compounds with organic ammonium cations have been determined for propane-1,3-diammonium tetrachloridozincate (Kallel et al., 1980 ), propane-1,3-diammonium dichromate(VI) (Trabelsi et al., 2012 ) and propane-1,2-diammonium chromate(VI) (Trabelsi et al., 2014 ). However, a combination of trans-cyclohexane-1,2-diammonium and CrO₄²⁻ has not been reported. In this communication, we present details on the preparation of the new organic chromate(VI), (C₆H₁₆N₂)[CrO₄], (I) and its structural characterization by synchrotron single-crystal X-ray diffraction.

2. Structural commentary

Fig. 1 shows an ellipsoid plot of the molecular components of (I). The organic diammonium cation adopts a stable chair conformation with respect to the cyclohexane ring. The C—C and N—C distances range from 1.506 (5) to 1.525 (4) Å and from 1.492 (3) to 1.493 (3) Å, respectively; the range of N—C—C and C—C—C angles is 108.3 (2) to 113.7 (2)° and 109.2 (2) to 112.0 (3)°, respectively.

Figure 1
The molecular structures of the organic cation and the inorganic anion in (I)

, drawn with displacement ellipsoids at the 30% probability level. The dashed line represents a hydrogen-bonding interaction.

The bond lengths and angles are very similar than in the structure of the bis(3′-nitro-trans-cinnamate) compound with the same cation (Hosomi et al., 2000). The cyclohexane ring C—C bond lengths and angles and the torsion angles involving the C and N atoms are in essential agreement with the values obtained for [Cr(chxn)₃](ZnCl₄)Cl·3H₂O (Moon & Choi, 2016 ). The Cr^VI atom in the CrO₄²⁻ anion has the characteristic tetrahedral coordination environment of four O atoms, with Cr—O bond lengths ranging from 1.628 (2) to 1.6654 (19) Å and O—Cr—O angles ranging from 108.30 (10)–111.43 (11)° (Table 1). The distortion from ideal values is due to the influence of hydrogen bonding. For O atoms that are acceptor atoms of two hydrogen bonds (O1 and O4), the Cr—O bond lengths are slightly longer than those of the other two O atoms (O2 and O3) which are each involved in only one hydrogen-bonding interaction.

Table 1
Selected geometric parameters (Å, °)

Cr1—O3	1.628 (2)	Cr1—O1	1.6584 (19)
Cr1—O2	1.6394 (19)	Cr1—O4	1.6654 (19)

O3—Cr1—O2	108.60 (11)	O3—Cr1—O4	109.76 (10)
O3—Cr1—O1	111.43 (11)	O2—Cr1—O4	108.30 (10)
O2—Cr1—O1	109.72 (10)	O1—Cr1—O4	108.97 (10)

3. Supramolecular features

In the crystal structure, the cations and anions are arranged in layers parallel to (001). The ammonium group is directed towards the anion, hence causing polar and non-polar sections in the crystal structure, alternating along [001]. As mentioned above, each of the O atoms is involved in N—H⋯O hydrogen bonds that hold the polar (001) sheets together (Fig. 2, Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2ⁱ	0.91	1.99	2.896 (3)	172
N1—H3N1⋯O1ⁱⁱ	0.91	2.00	2.884 (3)	164
N1—H2N1⋯O4	0.91	1.81	2.713 (3)	175
N2—H1N2⋯O4ⁱ	0.91	1.87	2.771 (3)	169
N2—H3N2⋯O2ⁱⁱⁱ	0.91	2.56	3.104 (3)	119
N2—H3N2⋯O3ⁱⁱⁱ	0.91	2.04	2.927 (3)	166
N2—H2N2⋯O1^iv	0.91	1.86	2.748 (3)	165
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iv) x, y-1, z.

Figure 2
The crystal packing in (I)

, viewed along [010]. Hydrogen-bonding interactions are indicated by dashed lines.

4. Database survey

A search of the Cambridge Structural Database (Version 5.37, Feb 2016 with three updates; Groom et al., 2016 ) indicates a total of 31 hits for compounds containing the cyclohexanediammonium cation (C₆H₁₆N₂)²⁺.

5. Synthesis and crystallization

Compound (I) was prepared by dissolving 5 mmol of chromium trioxide (0.50 g, Sigma–Aldrich) and 0.5 mmol of trans-1,2-cyclohexanediamine (0.6 mL, Sigma-Aldrich) in 40 mL of distilled water with a molar ratio of 1:1. The mixture was stirred for 30 minutes and the resulting solution was allowed to stand at room temperature for one day to give plate-like yellow crystals suitable for X-ray structural analysis.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.99-1.00 Å and N—H = 0.91 Å, and with U_iso(H) values of 1.2 or 1.5U_eq of the parent atoms.

Table 3
Experimental details

Crystal data
Chemical formula	(C₆H₁₆N₂)[CrO₄]
M_r	232.21
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	9.910 (2), 8.3730 (17), 22.999 (5)
V (Å³)	1908.4 (7)
Z	8
Radiation type	Synchrotron, λ = 0.650 Å
μ (mm⁻¹)	0.92
Crystal size (mm)	0.10 × 0.09 × 0.01

Data collection
Diffractometer	ADSC Q210 CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.794, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16426, 2383, 1749
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.160, 0.99
No. of reflections	2383
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.95, −1.53
Computer programs: PAL BL2D-SMDC (Shin et al., 2016 ), HKL3000sm (Otwinowski & Minor, 1997), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Putz & Brandenburg, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1519508

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016019009/wm5343sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016019009/wm5343Isup2.hkl

checkCIF report

Computing details top

Data collection: PAL BL2D-SMDC (Shin et al., 2016); cell refinement: HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

trans-Cyclohexane-1,2-diammonium chromate(VI) top

Crystal data top

(C₆H₁₆N₂)[CrO₄]	D_x = 1.616 Mg m⁻³
M_r = 232.21	Synchrotron radiation, λ = 0.650 Å
Orthorhombic, Pbca	Cell parameters from 49521 reflections
a = 9.910 (2) Å	θ = 0.4–33.4°
b = 8.3730 (17) Å	µ = 0.92 mm⁻¹
c = 22.999 (5) Å	T = 173 K
V = 1908.4 (7) Å³	Plate, yellow
Z = 8	0.10 × 0.09 × 0.01 mm
F(000) = 976

Data collection top

ADSC Q210 CCD area detector diffractometer	1749 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.069
ω scan	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: empirical (using intensity measurements) (HKL3000sm Scalepack; Otwinowski & Minor, 1997)	h = −12→12
T_min = 0.794, T_max = 1.000	k = −11→11
16426 measured reflections	l = −31→31
2383 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.055	w = 1/[σ²(F_o²) + (0.116P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.160	(Δ/σ)_max < 0.001
S = 0.99	Δρ_max = 0.95 e Å⁻³
2383 reflections	Δρ_min = −1.53 e Å⁻³
121 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.017 (3)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.6842 (2)	0.3903 (3)	0.43614 (9)	0.0245 (5)
H1N1	0.6673	0.3156	0.4639	0.037*
H2N1	0.6444	0.4842	0.4463	0.037*
H3N1	0.7749	0.4049	0.4328	0.037*
N2	0.4159 (3)	0.2284 (3)	0.42353 (10)	0.0279 (5)
H1N2	0.4273	0.2758	0.4588	0.042*
H2N2	0.4575	0.1315	0.4235	0.042*
H3N2	0.3262	0.2151	0.4165	0.042*
C1	0.6285 (3)	0.3349 (3)	0.37930 (11)	0.0249 (6)
H1	0.6622	0.2241	0.3721	0.030*
C2	0.4758 (3)	0.3313 (3)	0.37730 (12)	0.0247 (5)
H2	0.4413	0.4427	0.3823	0.030*
C3	0.4292 (3)	0.2686 (4)	0.31840 (13)	0.0342 (7)
H3A	0.4600	0.1569	0.3137	0.041*
H3B	0.3293	0.2688	0.3171	0.041*
C4	0.4833 (3)	0.3687 (4)	0.26844 (14)	0.0410 (8)
H4A	0.4570	0.3192	0.2310	0.049*
H4B	0.4430	0.4768	0.2701	0.049*
C5	0.6347 (3)	0.3820 (4)	0.27138 (13)	0.0357 (7)
H5A	0.6665	0.4563	0.2408	0.043*
H5B	0.6754	0.2760	0.2638	0.043*
C6	0.6808 (3)	0.4421 (4)	0.33063 (12)	0.0318 (6)
H6A	0.6475	0.5523	0.3366	0.038*
H6B	0.7807	0.4447	0.3318	0.038*
Cr1	0.44912 (4)	0.79269 (5)	0.43056 (2)	0.0227 (2)
O1	0.53896 (18)	0.9403 (2)	0.40203 (9)	0.0308 (5)
O2	0.34508 (19)	0.8641 (2)	0.47950 (9)	0.0330 (5)
O3	0.3616 (2)	0.6998 (2)	0.38110 (10)	0.0362 (5)
O4	0.55315 (18)	0.6648 (2)	0.46324 (9)	0.0311 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0243 (12)	0.0215 (11)	0.0278 (11)	0.0015 (9)	−0.0012 (8)	0.0002 (8)
N2	0.0267 (13)	0.0252 (12)	0.0316 (13)	0.0024 (10)	0.0025 (9)	0.0012 (9)
C1	0.0249 (14)	0.0217 (12)	0.0279 (13)	0.0026 (10)	0.0002 (10)	−0.0011 (10)
C2	0.0257 (14)	0.0195 (12)	0.0289 (13)	0.0000 (10)	−0.0010 (10)	0.0009 (10)
C3	0.0314 (18)	0.0406 (16)	0.0307 (15)	−0.0072 (12)	−0.0047 (11)	−0.0009 (13)
C4	0.0376 (18)	0.055 (2)	0.0309 (15)	−0.0053 (16)	−0.0050 (12)	0.0073 (14)
C5	0.0317 (16)	0.0437 (17)	0.0315 (15)	−0.0018 (13)	0.0024 (11)	0.0029 (12)
C6	0.0298 (16)	0.0322 (14)	0.0334 (15)	−0.0062 (12)	0.0000 (11)	0.0044 (11)
Cr1	0.0223 (3)	0.0167 (3)	0.0290 (3)	0.00140 (14)	−0.00086 (15)	0.00134 (14)
O1	0.0285 (11)	0.0233 (10)	0.0405 (12)	−0.0002 (8)	0.0062 (8)	0.0049 (8)
O2	0.0305 (11)	0.0285 (10)	0.0402 (11)	0.0053 (8)	0.0078 (9)	0.0010 (8)
O3	0.0349 (12)	0.0293 (11)	0.0444 (13)	0.0026 (8)	−0.0129 (10)	−0.0053 (8)
O4	0.0356 (12)	0.0224 (9)	0.0354 (11)	0.0087 (8)	−0.0053 (8)	0.0010 (8)

Geometric parameters (Å, º) top

N1—C1	1.493 (3)	C3—H3A	0.9900
N1—H1N1	0.9100	C3—H3B	0.9900
N1—H2N1	0.9100	C4—C5	1.506 (5)
N1—H3N1	0.9100	C4—H4A	0.9900
N2—C2	1.492 (3)	C4—H4B	0.9900
N2—H1N2	0.9100	C5—C6	1.523 (4)
N2—H2N2	0.9100	C5—H5A	0.9900
N2—H3N2	0.9100	C5—H5B	0.9900
C1—C2	1.514 (4)	C6—H6A	0.9900
C1—C6	1.525 (4)	C6—H6B	0.9900
C1—H1	1.0000	Cr1—O3	1.628 (2)
C2—C3	1.525 (4)	Cr1—O2	1.6394 (19)
C2—H2	1.0000	Cr1—O1	1.6584 (19)
C3—C4	1.520 (4)	Cr1—O4	1.6654 (19)

C1—N1—H1N1	109.5	C4—C3—H3B	109.2
C1—N1—H2N1	109.5	C2—C3—H3B	109.2
H1N1—N1—H2N1	109.5	H3A—C3—H3B	107.9
C1—N1—H3N1	109.5	C5—C4—C3	111.0 (3)
H1N1—N1—H3N1	109.5	C5—C4—H4A	109.4
H2N1—N1—H3N1	109.5	C3—C4—H4A	109.4
C2—N2—H1N2	109.5	C5—C4—H4B	109.4
C2—N2—H2N2	109.5	C3—C4—H4B	109.4
H1N2—N2—H2N2	109.5	H4A—C4—H4B	108.0
C2—N2—H3N2	109.5	C4—C5—C6	111.3 (2)
H1N2—N2—H3N2	109.5	C4—C5—H5A	109.4
H2N2—N2—H3N2	109.5	C6—C5—H5A	109.4
N1—C1—C2	113.7 (2)	C4—C5—H5B	109.4
N1—C1—C6	109.5 (2)	C6—C5—H5B	109.4
C2—C1—C6	109.2 (2)	H5A—C5—H5B	108.0
N1—C1—H1	108.1	C5—C6—C1	111.1 (2)
C2—C1—H1	108.1	C5—C6—H6A	109.4
C6—C1—H1	108.1	C1—C6—H6A	109.4
N2—C2—C1	112.8 (2)	C5—C6—H6B	109.4
N2—C2—C3	108.3 (2)	C1—C6—H6B	109.4
C1—C2—C3	109.7 (2)	H6A—C6—H6B	108.0
N2—C2—H2	108.7	O3—Cr1—O2	108.60 (11)
C1—C2—H2	108.7	O3—Cr1—O1	111.43 (11)
C3—C2—H2	108.7	O2—Cr1—O1	109.72 (10)
C4—C3—C2	112.0 (3)	O3—Cr1—O4	109.76 (10)
C4—C3—H3A	109.2	O2—Cr1—O4	108.30 (10)
C2—C3—H3A	109.2	O1—Cr1—O4	108.97 (10)

N1—C1—C2—N2	−57.5 (3)	C2—C3—C4—C5	54.6 (4)
C6—C1—C2—N2	179.8 (2)	C3—C4—C5—C6	−53.4 (4)
N1—C1—C2—C3	−178.3 (2)	C4—C5—C6—C1	56.5 (3)
C6—C1—C2—C3	59.0 (3)	N1—C1—C6—C5	175.7 (2)
N2—C2—C3—C4	178.8 (3)	C2—C1—C6—C5	−59.1 (3)
C1—C2—C3—C4	−57.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2ⁱ	0.91	1.99	2.896 (3)	172
N1—H3N1···O1ⁱⁱ	0.91	2.00	2.884 (3)	164
N1—H2N1···O4	0.91	1.81	2.713 (3)	175
N2—H1N2···O4ⁱ	0.91	1.87	2.771 (3)	169
N2—H3N2···O2ⁱⁱⁱ	0.91	2.56	3.104 (3)	119
N2—H3N2···O3ⁱⁱⁱ	0.91	2.04	2.927 (3)	166
N2—H2N2···O1^iv	0.91	1.86	2.748 (3)	165

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y−1/2, z; (iii) −x+1/2, y−1/2, z; (iv) x, y−1, z.

Acknowledgements

This work was supported by a grant from the 2016 Research Funds of Andong National University. The X-ray crystallography experiment at PLS-II BL2D-SMC beamline was supported in part by MSIP and POSTECH.

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