Crystal structure of ammonium/potassium trans-bis­(N-methyl­iminodi­acetato-κ3O,N,O′)chromate(III) from synchrotron data

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

doi:10.1107/S2056989016011804

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 8| August 2016| Pages 1190-1193

https://doi.org/10.1107/S2056989016011804

Open

access

Crystal structure of ammonium/potassium trans-bis(N-methyliminodiacetato-κ³O,N,O′)chromate(III) from synchrotron 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 22 June 2016; accepted 19 July 2016; online 22 July 2016)

The structure of the title compound, [(NH₄)_0.8K_0.2][Cr(C₅H₇NO₄)₂] (C₅H₇NO₄ is methyliminodiacetate; mida), has been determined from synchrotron data. The Cr^III atom is located on a centre of symmetry and is coordinated by two N atoms and four O atoms of two facially arranged tridentate mida ligands, displaying a slightly distorted octahedral coordination environment. The Cr—N and mean Cr—O bond lengths are 2.0792 (14) and 1.958 (14) Å, respectively. The cation site is located on a twofold rotation axis and shows occupational disorder, being occupied by ammonium and potassium cations in a 0.8:0.2 ratio. In the crystal, intermolecular hydrogen bonds involving the N—H groups of the ammonium cation as donor and the two non-coordinating O atoms of the carboxylate group as acceptor groups consolidate the three-dimensional packing.

Keywords: crystal structure; synchrotron radiation; ammonium/potassium salt; bis(methyliminodiacetato)chromate(III) ion; mida; trans-facial configuration; hydrogen bonding.

CCDC reference: 1494843

1. Chemical context

Methyliminodiacetate (abbreviated here as mida; C₅H₇NO₄) can coordinate to a central metal ion as a tridentate ligand through one N atom and two O atoms. The mida ligand differs from iminodiacetate (ida) in the substitution of the imino hydrogen with a methyl group. This change has significant consequences with respect to the configuration of the bis-chromate(III) complexes with these ligands. Two facial configurations in cis or trans mode relative to the two N atoms have been observed: for example K[Cr(ida)₂]·3H₂O (Mootz & Wunderlich, 1980 ) and Na[Cr(ida)₂]·1.5H₂O (Li et al., 2003 ) are cis-fac structures whereas Na[Cr(mida)₂] is a trans-fac structure (Suh et al., 1997 ). However, the trans meridional isomer of octahedrally coordinated chromium(III) with ida or mida ligands has not yet been identified. In order to confirm the bonding mode of the methyliminodiacetato ligand and its structural arrangement, we report herein on the crystal structure of the title salt, [(NH₄)_0.8K_0.2][Cr(C₅H₇NO₄)₂], (I).

2. Structural commentary

Counter-ionic species play important roles in crystal packings and hydrogen-bonding patterns. The structure reported here is another example of a [Cr(mida)₂]⁻ salt but with a different cation (Suh et al., 1996 , 1997). The structural analysis shows that the two tridentate mida dianions octahedrally coordinate to the Cr^III metal atom through one N atom and two carboxylate O atoms in a facial configuration. The coordinating N atoms are mutually trans due to point group $[\overline{1}]$ for the entire anionic complex. The asymmetric unit of (I) comprises one half of the Cr^III complex anion and one occupationally disordered ammonium/potassium cation (situated on a twofold rotation axis), respectively. An ellipsoid plot of title compound together with the atomic numbering is illustrated in Fig. 1.

Figure 1
The structures of the molecular entities of (I)

, showing the atom-numbering scheme. Non-H atoms are shown as displacement ellipsoids at the 50% probability level. The primed atoms are related by symmetry code (−x + 1, −y + 1, −z + 1). Dashed lines represent hydrogen-bonding interactions.

The facial configuration of the complex anion in (I) can be compared with that of NH₄[Cr(pydc)₂] (pydc = pyridine-2,6-dicarboxylate; Moon & Choi, 2015 ) where it displays a trans meridional configuration. The Cr—N and mean Cr—O bond lengths involving the mida ligands are 2.0792 (14) and 1.958 (14) Å, respectively, in good agreement with the values observed for Na[Cr(mida)₂] (Suh et al., 1997). Bond angles about the central chromium atom are 90.23 (6) for O1—Cr1—O3, 84.66 (6) for O1—Cr1—N1 and 82.62 (5)° for N1—Cr1—O3 indicating a distorted octahedral coordination environment. The C–O bond lengths within the carboxylate group of the mida ligand range from 1.219 (2) to 1.296 (2) Å and can be compared with values of 1.225 (15) and 1.294 (15) Å for NH₄[Cr(pydc)₂] (Moon & Choi, 2015). The slightly longer C—O bond length (C1—O2 and C3—O4) and smaller O—C—O bond angles of the carboxylate groups in the mida ligand of (I) compared to the ligand in Na[Cr(mida)₂] (Suh et al., 1997) may be attributed to the involvement of the two non-coordinating O atoms in hydrogen bonds with the N—H groups of the ammonium cation. The N—C and C—C distances in the mida moieties are close to those found in the free H₂mida molecule (Shkol'nikova et al., 1986 ) and are equal to 1.479 (2)–1.494 (2) and 1.508 (3)–1.512 (2) Å, respectively.

3. Supramolecular features

The pattern of hydrogen bonding around the cation is different from the crystal packing network in the related sodium salt (Suh et al., 1996, 1997). The cation is linked to four non-coordinating O atoms of carboxylate groups from four neighboring mida ligands through classical N—H⋯O hydrogen bonds (Table 1). An array of these interactions generate a three-dimensional network of molecules whereby individual molecules are stacked along the b-axis direction (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1S—H1NS⋯O3ⁱ	0.92 (1)	2.07 (1)	2.9658 (16)	166 (3)
N1S—H2NS⋯O2	0.90 (1)	1.95 (1)	2.8485 (17)	175 (3)
Symmetry code: (i) $[x, -y, z+{\script{1\over 2}}]$ .

Figure 2
A packing diagram of (I)

, viewed perpendicular to the ac plane. Dashed lines represent hydrogen-bonding interactions N—H⋯O (cyan).

4. Database survey

A search of the Cambridge Structural Database (Version 5.37, Feb. 2016 with two updates; Groom et al., 2016 ) gave just two hits for a complex anion [Cr(C₅H₇NO₄)₂]⁻ unit. The crystal structures of Na[Cr(mida)₂] with three different space groups have been reported and compared previously (Suh et al., 1996, 1997).

5. Synthesis and crystallization

All chemicals were reagent-grade materials and were used without further purification. The starting material, K[Cr(mida)₂] was prepared by a method similar to that outlined previously (Wernicke et al., 1977 ; Uehara et al., 1970 ). The potassium salt (0.25 g) was dissolved in 15 mL of water at 343 K and added to 5 mL of water containing 0.50 g of NH₄Cl. The resulting solution was filtered to remove any impurities and allowed to stand at room temperature for several days to give pale pink plate-like crystals of the mixed-occupancy ammonium/potassium salt, (I), suitable for X-ray diffraction analysis.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms of the complex were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.97–0.98 Å and with U_iso(H) values of 1.5 (methyl) and 1.2 times U_eq (all others) of the parent atoms. The H atoms of the cation were located from difference Fourier maps and refined with DFIX and DANG restraints and fixed N—H distances of 0.855 (9) and 0.869 (9) Å, with U_iso(H) values of 1.2U_eq(N). The occupancy of mixed-occupied (NH₄/K) first was refined and then fixed at a ratio of 0.8:0.2. The corresponding (NH₄/K) sites was refined using EXYZ/EADP commands for the two atom types.

Table 2
Experimental details

Crystal data
Chemical formula	[(NH₄)_0.8K_0.2][Cr(C₅H₇NO₄)₂]
M_r	364.48
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	243
a, b, c (Å)	16.786 (3), 6.5240 (13), 13.925 (3)
β (°)	113.19 (3)
V (Å³)	1401.8 (6)
Z	4
Radiation type	Synchrotron, λ = 0.610 Å
μ (mm⁻¹)	0.61
Crystal size (mm)	0.02 × 0.02 × 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	0.989, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	6984, 1833, 1519
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.693

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.100, 1.05
No. of reflections	1833
No. of parameters	110
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.69
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: 1494843

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016011804/wm5304sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016011804/wm5304Isup2.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).

Ammonium/potassium trans-bis(N-methyliminodiacetato-κ³O,N,O')chromate(III) top

Crystal data top

[(NH₄)_0.8K_0.2][Cr(C₅H₇NO₄)₂]	F(000) = 754
M_r = 364.48	D_x = 1.727 Mg m⁻³
Monoclinic, C2/c	Synchrotron radiation, λ = 0.610 Å
a = 16.786 (3) Å	Cell parameters from 23758 reflections
b = 6.5240 (13) Å	θ = 0.4–33.7°
c = 13.925 (3) Å	µ = 0.61 mm⁻¹
β = 113.19 (3)°	T = 243 K
V = 1401.8 (6) Å³	Plate, pale pink
Z = 4	0.02 × 0.02 × 0.01 mm

Data collection top

ADSC Q210 CCD area-detector diffractometer	1519 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.028
ω scan	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	h = −23→23
T_min = 0.989, T_max = 0.995	k = −9→9
6984 measured reflections	l = −17→17
1833 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.035	w = 1/[σ²(F_o²) + (0.0702P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.100	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.40 e Å⁻³
1833 reflections	Δρ_min = −0.69 e Å⁻³
110 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.0118 (19)

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	Occ. (<1)
Cr1	0.5000	0.5000	0.5000	0.01108 (14)
O1	0.53582 (8)	0.3160 (2)	0.61977 (10)	0.0228 (3)
O2	0.64463 (9)	0.2272 (2)	0.76630 (10)	0.0267 (3)
O3	0.54917 (8)	0.3115 (2)	0.42746 (10)	0.0228 (3)
O4	0.65906 (10)	0.2681 (2)	0.37913 (13)	0.0361 (4)
N1	0.62700 (8)	0.6057 (2)	0.56638 (10)	0.0129 (3)
C1	0.61393 (11)	0.3333 (3)	0.68756 (13)	0.0175 (3)
C2	0.67027 (13)	0.4929 (3)	0.66707 (15)	0.0326 (5)
H2A	0.6886	0.5922	0.7245	0.039*
H2B	0.7225	0.4260	0.6668	0.039*
C3	0.62435 (11)	0.3600 (3)	0.42841 (13)	0.0196 (4)
C4	0.66622 (12)	0.5484 (3)	0.49128 (15)	0.0232 (4)
H4A	0.7283	0.5226	0.5297	0.028*
H4B	0.6601	0.6633	0.4435	0.028*
C5	0.63441 (13)	0.8296 (3)	0.58441 (19)	0.0333 (5)
H5A	0.6948	0.8699	0.6086	0.050*
H5B	0.6121	0.8653	0.6368	0.050*
H5C	0.6012	0.9003	0.5197	0.050*
K1S	0.5000	−0.0201 (2)	0.7500	0.0275 (3)	0.2
N1S	0.5000	−0.0201 (2)	0.7500	0.0275 (3)	0.8
H1NS	0.5139 (17)	−0.091 (4)	0.8115 (14)	0.033*	0.8
H2NS	0.5476 (13)	0.052 (4)	0.757 (2)	0.033*	0.8

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr1	0.00847 (19)	0.01210 (19)	0.0120 (2)	−0.00089 (12)	0.00332 (13)	−0.00138 (12)
O1	0.0173 (6)	0.0248 (6)	0.0209 (6)	−0.0064 (5)	0.0018 (5)	0.0078 (5)
O2	0.0231 (7)	0.0300 (7)	0.0217 (7)	0.0003 (5)	0.0030 (5)	0.0107 (5)
O3	0.0201 (6)	0.0223 (6)	0.0290 (7)	−0.0052 (5)	0.0130 (5)	−0.0119 (5)
O4	0.0328 (8)	0.0430 (9)	0.0416 (9)	−0.0005 (7)	0.0243 (7)	−0.0173 (7)
N1	0.0110 (6)	0.0145 (6)	0.0134 (6)	−0.0023 (5)	0.0050 (5)	−0.0013 (5)
C1	0.0174 (8)	0.0198 (8)	0.0152 (8)	−0.0010 (6)	0.0063 (6)	0.0000 (6)
C2	0.0205 (9)	0.0530 (14)	0.0160 (9)	−0.0150 (8)	−0.0018 (7)	0.0125 (8)
C3	0.0201 (8)	0.0219 (8)	0.0185 (9)	0.0005 (6)	0.0094 (6)	−0.0027 (6)
C4	0.0203 (8)	0.0327 (9)	0.0226 (10)	−0.0081 (7)	0.0148 (7)	−0.0083 (7)
C5	0.0221 (9)	0.0186 (9)	0.0574 (14)	−0.0070 (7)	0.0137 (9)	−0.0129 (8)
K1S	0.0277 (7)	0.0278 (8)	0.0270 (8)	0.000	0.0107 (6)	0.000
N1S	0.0277 (7)	0.0278 (8)	0.0270 (8)	0.000	0.0107 (6)	0.000

Geometric parameters (Å, º) top

Cr1—O1	1.9479 (13)	C2—H2B	0.9800
Cr1—O1ⁱ	1.9479 (13)	C3—C4	1.512 (2)
Cr1—O3	1.9673 (12)	C3—K1Sⁱⁱ	3.371 (2)
Cr1—O3ⁱ	1.9673 (12)	C4—H4A	0.9800
Cr1—N1	2.0792 (14)	C4—H4B	0.9800
Cr1—N1ⁱ	2.0792 (14)	C5—H5A	0.9700
O1—C1	1.284 (2)	C5—H5B	0.9700
O1—K1S	3.0524 (17)	C5—H5C	0.9700
O2—C1	1.226 (2)	K1S—O2ⁱⁱⁱ	2.8484 (16)
O2—K1S	2.8485 (17)	K1S—O3^iv	2.9658 (16)
O3—C3	1.296 (2)	K1S—O3ⁱⁱ	2.9658 (16)
O3—K1Sⁱⁱ	2.9658 (16)	K1S—O4^iv	3.033 (2)
O4—C3	1.219 (2)	K1S—O4ⁱⁱ	3.033 (2)
O4—K1Sⁱⁱ	3.033 (2)	K1S—O1ⁱⁱⁱ	3.0524 (17)
N1—C5	1.479 (2)	K1S—C1ⁱⁱⁱ	3.322 (2)
N1—C4	1.486 (2)	K1S—C3ⁱⁱ	3.371 (2)
N1—C2	1.494 (2)	K1S—C3^iv	3.371 (2)
C1—C2	1.508 (3)	N1S—H1NS	0.920 (10)
C1—K1S	3.322 (2)	N1S—H2NS	0.899 (10)
C2—H2A	0.9800

O1—Cr1—O1ⁱ	180.00 (5)	O2—K1S—O3ⁱⁱ	112.23 (4)
O1—Cr1—O3	90.23 (6)	O3^iv—K1S—O3ⁱⁱ	100.26 (7)
O1ⁱ—Cr1—O3	89.77 (6)	O2ⁱⁱⁱ—K1S—O4^iv	150.81 (4)
O1—Cr1—O3ⁱ	89.77 (6)	O2—K1S—O4^iv	74.40 (4)
O1ⁱ—Cr1—O3ⁱ	90.23 (6)	O3^iv—K1S—O4^iv	43.35 (4)
O3—Cr1—O3ⁱ	180.0	O3ⁱⁱ—K1S—O4^iv	92.48 (6)
O1—Cr1—N1	84.66 (6)	O2ⁱⁱⁱ—K1S—O4ⁱⁱ	74.40 (4)
O1ⁱ—Cr1—N1	95.34 (6)	O2—K1S—O4ⁱⁱ	150.82 (4)
O3—Cr1—N1	82.62 (5)	O3^iv—K1S—O4ⁱⁱ	92.48 (6)
O3ⁱ—Cr1—N1	97.38 (5)	O3ⁱⁱ—K1S—O4ⁱⁱ	43.36 (4)
O1—Cr1—N1ⁱ	95.34 (6)	O4^iv—K1S—O4ⁱⁱ	115.53 (8)
O1ⁱ—Cr1—N1ⁱ	84.66 (6)	O2ⁱⁱⁱ—K1S—O1ⁱⁱⁱ	43.90 (4)
O3—Cr1—N1ⁱ	97.38 (5)	O2—K1S—O1ⁱⁱⁱ	84.65 (6)
O3ⁱ—Cr1—N1ⁱ	82.62 (5)	O3^iv—K1S—O1ⁱⁱⁱ	91.19 (4)
N1—Cr1—N1ⁱ	180.00 (7)	O3ⁱⁱ—K1S—O1ⁱⁱⁱ	154.19 (4)
C1—O1—Cr1	117.20 (11)	O4^iv—K1S—O1ⁱⁱⁱ	111.36 (5)
C1—O1—K1S	90.53 (10)	O4ⁱⁱ—K1S—O1ⁱⁱⁱ	113.71 (4)
Cr1—O1—K1S	152.23 (6)	O2ⁱⁱⁱ—K1S—O1	84.65 (6)
C1—O2—K1S	101.75 (11)	O2—K1S—O1	43.90 (4)
C3—O3—Cr1	116.48 (11)	O3^iv—K1S—O1	154.19 (4)
C3—O3—K1Sⁱⁱ	96.63 (10)	O3ⁱⁱ—K1S—O1	91.19 (4)
Cr1—O3—K1Sⁱⁱ	142.48 (6)	O4^iv—K1S—O1	113.71 (4)
C3—O4—K1Sⁱⁱ	95.27 (12)	O4ⁱⁱ—K1S—O1	111.36 (5)
C5—N1—C4	109.69 (15)	O1ⁱⁱⁱ—K1S—O1	88.15 (7)
C5—N1—C2	110.46 (15)	O2ⁱⁱⁱ—K1S—C1ⁱⁱⁱ	21.17 (4)
C4—N1—C2	110.50 (15)	O2—K1S—C1ⁱⁱⁱ	98.43 (6)
C5—N1—Cr1	113.95 (11)	O3^iv—K1S—C1ⁱⁱⁱ	103.11 (4)
C4—N1—Cr1	105.34 (10)	O3ⁱⁱ—K1S—C1ⁱⁱⁱ	131.52 (4)
C2—N1—Cr1	106.75 (10)	O4^iv—K1S—C1ⁱⁱⁱ	132.69 (5)
O2—C1—O1	123.79 (16)	O4ⁱⁱ—K1S—C1ⁱⁱⁱ	93.56 (4)
O2—C1—C2	119.04 (16)	O1ⁱⁱⁱ—K1S—C1ⁱⁱⁱ	22.73 (4)
O1—C1—C2	117.17 (15)	O1—K1S—C1ⁱⁱⁱ	85.72 (6)
O2—C1—K1S	57.08 (10)	O2ⁱⁱⁱ—K1S—C1	98.43 (6)
O1—C1—K1S	66.74 (9)	O2—K1S—C1	21.17 (4)
C2—C1—K1S	175.95 (12)	O3^iv—K1S—C1	131.52 (4)
N1—C2—C1	114.11 (15)	O3ⁱⁱ—K1S—C1	103.11 (4)
N1—C2—H2A	108.7	O4^iv—K1S—C1	93.56 (4)
C1—C2—H2A	108.7	O4ⁱⁱ—K1S—C1	132.69 (5)
N1—C2—H2B	108.7	O1ⁱⁱⁱ—K1S—C1	85.72 (6)
C1—C2—H2B	108.7	O1—K1S—C1	22.73 (4)
H2A—C2—H2B	107.6	C1ⁱⁱⁱ—K1S—C1	92.12 (7)
O4—C3—O3	123.62 (17)	O2ⁱⁱⁱ—K1S—C3ⁱⁱ	93.03 (5)
O4—C3—C4	120.65 (16)	O2—K1S—C3ⁱⁱ	133.81 (4)
O3—C3—C4	115.66 (15)	O3^iv—K1S—C3ⁱⁱ	94.64 (6)
O4—C3—K1Sⁱⁱ	63.63 (11)	O3ⁱⁱ—K1S—C3ⁱⁱ	22.45 (4)
O3—C3—K1Sⁱⁱ	60.92 (9)	O4^iv—K1S—C3ⁱⁱ	103.37 (7)
C4—C3—K1Sⁱⁱ	166.70 (13)	O4ⁱⁱ—K1S—C3ⁱⁱ	21.10 (4)
N1—C4—C3	112.21 (14)	O1ⁱⁱⁱ—K1S—C3ⁱⁱ	134.49 (4)
N1—C4—H4A	109.2	O1—K1S—C3ⁱⁱ	104.15 (4)
C3—C4—H4A	109.2	C1ⁱⁱⁱ—K1S—C3ⁱⁱ	113.34 (5)
N1—C4—H4B	109.2	C1—K1S—C3ⁱⁱ	121.12 (4)
C3—C4—H4B	109.2	O2ⁱⁱⁱ—K1S—C3^iv	133.81 (4)
H4A—C4—H4B	107.9	O2—K1S—C3^iv	93.03 (5)
N1—C5—H5A	109.5	O3^iv—K1S—C3^iv	22.45 (4)
N1—C5—H5B	109.5	O3ⁱⁱ—K1S—C3^iv	94.64 (6)
H5A—C5—H5B	109.5	O4^iv—K1S—C3^iv	21.10 (4)
N1—C5—H5C	109.5	O4ⁱⁱ—K1S—C3^iv	103.37 (7)
H5A—C5—H5C	109.5	O1ⁱⁱⁱ—K1S—C3^iv	104.15 (4)
H5B—C5—H5C	109.5	O1—K1S—C3^iv	134.49 (4)
O2ⁱⁱⁱ—K1S—O2	111.01 (8)	C1ⁱⁱⁱ—K1S—C3^iv	121.12 (4)
O2ⁱⁱⁱ—K1S—O3^iv	112.23 (4)	C1—K1S—C3^iv	113.34 (5)
O2—K1S—O3^iv	110.35 (4)	C3ⁱⁱ—K1S—C3^iv	97.73 (8)
O2ⁱⁱⁱ—K1S—O3ⁱⁱ	110.35 (4)	H1NS—N1S—H2NS	105.9 (19)

K1S—O2—C1—O1	−1.9 (2)	K1Sⁱⁱ—O4—C3—C4	−165.65 (16)
K1S—O2—C1—C2	178.67 (16)	Cr1—O3—C3—O4	−173.25 (15)
Cr1—O1—C1—O2	−179.97 (14)	K1Sⁱⁱ—O3—C3—O4	−11.5 (2)
K1S—O1—C1—O2	1.73 (19)	Cr1—O3—C3—C4	3.7 (2)
Cr1—O1—C1—C2	−0.5 (2)	K1Sⁱⁱ—O3—C3—C4	165.51 (14)
K1S—O1—C1—C2	−178.83 (16)	Cr1—O3—C3—K1Sⁱⁱ	−161.79 (12)
Cr1—O1—C1—K1S	178.30 (12)	C5—N1—C4—C3	−151.02 (16)
C5—N1—C2—C1	127.82 (19)	C2—N1—C4—C3	86.96 (18)
C4—N1—C2—C1	−110.61 (19)	Cr1—N1—C4—C3	−27.99 (18)
Cr1—N1—C2—C1	3.4 (2)	O4—C3—C4—N1	−165.12 (17)
O2—C1—C2—N1	177.29 (16)	O3—C3—C4—N1	17.8 (2)
O1—C1—C2—N1	−2.2 (3)	K1Sⁱⁱ—C3—C4—N1	89.7 (5)
K1Sⁱⁱ—O4—C3—O3	11.2 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1S—H1NS···O3^iv	0.92 (1)	2.07 (1)	2.9658 (16)	166 (3)
N1S—H2NS···O2	0.90 (1)	1.95 (1)	2.8485 (17)	175 (3)

Symmetry code: (iv) x, −y, z+1/2.

Acknowledgements

This work was supported by a grant from 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.

References

Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, H., Xu, D.-J. & Yin, K.-L. (2003). Acta Cryst. E59, m671–m673. Web of Science CSD CrossRef IUCr Journals Google Scholar
Moon, D. & Choi, J.-H. (2015). Acta Cryst. E71, 210–212. CSD CrossRef IUCr Journals Google Scholar
Mootz, D. & Wunderlich, H. (1980). Acta Cryst. B36, 445–447. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Putz, H. & Brandenburg, K. (2014). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shin, J. W., Eom, K. & Moon, D. (2016). J. Synchrotron Rad. 23, 369–373. Web of Science CrossRef IUCr Journals Google Scholar
Shkol'nikova, L. M., Donchenko, N. V., Poznyak, A. L., Dyatlova, N. M. & Zavodnik, E. V. (1986). Zh. Strukt. Khim. 27, 89–94. CAS Google Scholar
Suh, I.-H., Lee, J.-H., Song, J.-H., Oh, M.-R., Suh, J.-S., Park, S.-J. & Lee, K.-W. (1996). J. Korean Phys. Soc. 29, 739–744. CAS Google Scholar
Suh, J.-S., Park, S.-J., Lee, K.-W., Suh, I.-H., Lee, J.-H., Song, J.-H. & Oh, M.-R. (1997). Acta Cryst. C53, 432–434. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Uehara, A., Kyuno, E. & Tsuchiya, R. (1970). Bull. Chem. Soc. Jpn, 43, 1394–1397. CrossRef CAS Google Scholar
Wernicke, R., Schmidtke, H.-H. & Hoggard, P. E. (1977). Inorg. Chim. Acta, 24, 145–148. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.