Oxonium trans-bis­(oxalato)rhodate and related sodium salts: a rare example of crystalline complex acid

New coordination compounds trans-bis­(oxalato)di­aqua­rhodiate sodium dihydrate Na[Rh(H₂O)₂Ox₂]·2H₂O (crystallizes in two polymorphic forms NaRh-1 and NaRh-2), trans-bis­(oxalato)hydroxo­aqua­rhodiate sodium tetrahydrate Na₂[Rh(H₂O)(OH)Ox₂]·4H₂O (Na2Rh) and trans-bis­(oxalato)di­aqua­rhodic acid tetrahydrate (H₃O)[Rh(H₂O)₂Ox₂]·4H₂O (HRh) are synthesized. The compounds are characterized by IR spectroscopy, elemental analysis and single crystal X-ray diffraction. NaRh-1, NaRh-2 and Na2Rh crystallize in space group P1. Trans-bis­(oxalato)di­aqua­rhodic acid exists not only in solution, but can also crystallize as a tetrahydrate (space group C2/c). The formation of various species in solution of rhodium hydroxide in oxalic acid and their redistribution were studied using ¹⁰³Rh NMR spectroscopy.

Computing details

Data collection: Bruker APEX3 for HRh; Bruker APEX2 for Na2Rh; CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015) for NaRh-2. Cell refinement: Bruker SAINT for HRh, Na2Rh; CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015) for NaRh-2. Data reduction: Bruker SAINT for HRh, Na2Rh; CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015) for NaRh-2. Program(s) used to solve structure: ShelXT (Sheldrick, 2015) for HRh, Na2Rh; SHELXS97 (Sheldrick, 2008) for NaRh-1; SHELXT-2018 (Sheldrick, 2015) for NaRh-2. Program(s) used to refine structure: SHELXL (Sheldrick, 2015) for HRh, Na2Rh, NaRh-1; SHELXL2018 (Sheldrick, 2015) for NaRh-2. Molecular graphics: Olex2 (Dolomanov et al., 2009) for HRh, Na2Rh, NaRh-1; ShelXle (Hübschle, 2011) for NaRh-2. Software used to prepare material for publication: Olex2 (Dolomanov et al., 2009) for HRh, Na2Rh, NaRh-1; CIFTAB (Sheldrick, 2015) for NaRh-2.

(HRh)

Crystal data

C4H4O10Rh·3(H2O)·(H5O2)	F(000) = 816
Mr = 406.07	Dx = 2.054 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.2131 (8) Å	Cell parameters from 8655 reflections
b = 13.0362 (6) Å	θ = 2.6–30.5°
c = 6.3015 (3) Å	µ = 1.38 mm^−1
β = 99.572 (2)°	T = 150 K
V = 1313.32 (11) Å^3	Block, light yellow
Z = 4	0.13 × 0.1 × 0.08 mm

Data collection

Bruker D8 Venture diffractometer	1996 independent reflections
Radiation source: Incoatec IuS3.0 microfocus X-ray tube	1774 reflections with I > 2σ(I)
Incoatec HELIOS multilayer mirrors monochromator	Rint = 0.025
Detector resolution: 7.41 pixels mm^-1	θmax = 30.5°, θmin = 2.0°
ω and φ scans	h = −23→23
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0746 before and 0.0555 after correction. The Ratio of minimum to maximum transmission is 0.8463. The λ/2 correction factor is Not present.	k = −17→18
Tmin = 0.631, Tmax = 0.746	l = −9→7
7956 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.062	w = 1/[σ^2(Fo^2) + (0.0165P)^2 + 4.4254P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1996 reflections	Δρmax = 0.70 e Å^−3
102 parameters	Δρmin = −0.73 e Å^−3
0 restraints

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)
Rh1	0.250000	−0.250000	0.500000	0.01806 (7)
O1	0.18127 (9)	−0.12063 (11)	0.4605 (3)	0.0200 (3)
O1A	0.20064 (9)	0.04681 (11)	0.4244 (2)	0.0197 (3)
O2	0.33893 (10)	−0.15918 (11)	0.4132 (3)	0.0222 (3)
O2A	0.35667 (10)	0.00480 (11)	0.3290 (2)	0.0199 (3)
C1	0.22535 (13)	−0.04303 (15)	0.4268 (3)	0.0157 (3)
C2	0.31488 (13)	−0.06547 (15)	0.3862 (3)	0.0159 (4)
O2W	0.45548 (11)	−0.22119 (14)	0.9158 (3)	0.0275 (4)
O1W	0.28772 (11)	−0.21350 (12)	0.8130 (3)	0.0254 (3)
H1WA	0.271065	−0.154420	0.838548	0.038*
H1WB	0.340066	−0.208557	0.840836	0.038*
H2WB	0.467876	−0.282329	0.947337	0.038*	0.5
H2W	0.480316	−0.202119	0.815927	0.038*	0.5
H2WA	0.470186	−0.184169	1.025327	0.038*
O3W	0.500000	−0.09158 (18)	1.250000	0.0232 (4)
H3WA	0.541289	−0.052780	1.248569	0.035*	0.5
H3WB	0.462999	−0.053234	1.285883	0.035*	0.5
O4W	0.04220 (14)	0.0884 (2)	0.4373 (5)	0.0621 (8)
H4WC	0.019018	0.045741	0.508160	0.14 (5)*	0.5
H4WA	0.087598	0.064101	0.412329	0.109 (19)*
H4WB	0.051548	0.142881	0.508500	0.08 (3)*	0.5
H4W	0.010648	0.100931	0.320449	0.13 (5)*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.02282 (12)	0.00693 (10)	0.02589 (12)	−0.00165 (8)	0.00834 (8)	−0.00095 (8)
O1	0.0231 (7)	0.0092 (6)	0.0286 (8)	−0.0011 (5)	0.0066 (6)	−0.0012 (5)
O1A	0.0203 (7)	0.0113 (6)	0.0268 (7)	0.0014 (5)	0.0018 (6)	0.0023 (5)
O2	0.0245 (7)	0.0095 (6)	0.0354 (9)	−0.0016 (6)	0.0131 (6)	−0.0014 (6)
O2A	0.0254 (7)	0.0146 (7)	0.0201 (7)	−0.0043 (6)	0.0051 (6)	0.0028 (5)
C1	0.0210 (9)	0.0115 (8)	0.0141 (8)	−0.0008 (7)	0.0016 (7)	0.0005 (7)
C2	0.0221 (9)	0.0121 (8)	0.0138 (8)	−0.0022 (7)	0.0037 (7)	−0.0015 (6)
O2W	0.0249 (8)	0.0313 (9)	0.0266 (8)	−0.0050 (7)	0.0052 (6)	−0.0056 (7)
O1W	0.0339 (9)	0.0112 (6)	0.0317 (8)	0.0005 (6)	0.0072 (7)	0.0024 (6)
O3W	0.0153 (9)	0.0263 (12)	0.0289 (11)	0.000	0.0060 (8)	0.000
O4W	0.0330 (11)	0.0491 (15)	0.113 (2)	0.0211 (10)	0.0374 (14)	0.0469 (16)

Geometric parameters (Å, º)

Rh1—O1^i	2.0140 (15)	O2W—H2W	0.8394
Rh1—O1	2.0139 (15)	O2W—H2WA	0.8432
Rh1—O2^i	2.0104 (15)	O1W—H1WA	0.8404
Rh1—O2	2.0105 (15)	O1W—H1WB	0.8401
Rh1—O1W^i	2.0225 (17)	O3W—H3WA	0.8403
Rh1—O1W	2.0225 (17)	O3W—H3WA^ii	0.84 (15)
O1—C1	1.277 (2)	O3W—H3WB^ii	0.84 (15)
O1A—C1	1.237 (2)	O3W—H3WB	0.8403
O2—C2	1.285 (2)	O4W—H4WC	0.8400
O2A—C2	1.228 (2)	O4W—H4WA	0.8401
C1—C2	1.543 (3)	O4W—H4WB	0.8400
O2W—H2WB	0.8377	O4W—H4W	0.8400
O1—Rh1—O1^i	180.0	O1A—C1—C2	119.28 (17)
O1^i—Rh1—O1W	90.29 (6)	O2—C2—C1	115.55 (17)
O1^i—Rh1—O1W^i	89.71 (6)	O2A—C2—O2	125.29 (19)
O1—Rh1—O1W	89.71 (6)	O2A—C2—C1	119.15 (18)
O1—Rh1—O1W^i	90.29 (6)	H2WB—O2W—H2WA	109.1
O2^i—Rh1—O1^i	83.13 (6)	H2W—O2W—H2WA	109.8
O2—Rh1—O1^i	96.87 (6)	Rh1—O1W—H1WA	110.3
O2—Rh1—O1	83.13 (6)	Rh1—O1W—H1WB	110.6
O2^i—Rh1—O1	96.87 (6)	H1WA—O1W—H1WB	103.6
O2^i—Rh1—O2	180.0	H3WA—O3W—H3WA^ii	106.0
O2^i—Rh1—O1W	89.28 (7)	H3WA^ii—O3W—H3WB^ii	104.5
O2^i—Rh1—O1W^i	90.72 (7)	H3WA—O3W—H3WB	104.5
O2—Rh1—O1W^i	89.28 (7)	H3WA—O3W—H3WB^ii	14.8
O2—Rh1—O1W	90.72 (7)	H3WB—O3W—H3WA^ii	14.8
O1W^i—Rh1—O1W	180.0	H3WB—O3W—H3WB^ii	107.0
C1—O1—Rh1	111.75 (13)	H4WC—O4W—H4WA	109.5
C2—O2—Rh1	112.35 (13)	H4WA—O4W—H4WB	109.5
O1—C1—C2	116.45 (17)	H4WA—O4W—H4W	109.5
O1A—C1—O1	124.27 (19)
Rh1—O1—C1—O1A	−170.50 (16)	O1—C1—C2—O2	−7.2 (3)
Rh1—O1—C1—C2	9.7 (2)	O1—C1—C2—O2A	171.87 (18)
Rh1—O2—C2—O2A	−178.50 (16)	O1A—C1—C2—O2	173.04 (18)
Rh1—O2—C2—C1	0.5 (2)	O1A—C1—C2—O2A	−7.9 (3)

Symmetry codes: (i) −x+1/2, −y−1/2, −z+1; (ii) −x+1, y, −z+5/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1A^iii	0.84	1.94	2.745 (2)	160
O1W—H1WB···O2W	0.84	1.86	2.691 (2)	170
O2W—H2WB···O4W^iv	0.84	1.85	2.647 (4)	158
O2W—H2W···O2W^v	0.84	1.95	2.730 (3)	155
O2W—H2WA···O3W	0.84	1.86	2.703 (2)	175
O3W—H3WA···O2A^v	0.84	1.95	2.7589 (19)	161
O3W—H3WB···O2A^vi	0.84	1.94	2.7589 (19)	164
O4W—H4WC···O4W^vii	0.84	2.07	2.858 (5)	157
O4W—H4WA···O1A	0.84	1.84	2.640 (3)	160
O4W—H4WB···O2W^viii	0.84	1.84	2.647 (4)	160
O4W—H4W···O4W^ix	0.84	1.71	2.524 (7)	162

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

(Na2Rh)

Crystal data

C4H11Na2O14Rh	Z = 1
Mr = 432.02	F(000) = 214
Triclinic, P1	Dx = 2.404 Mg m^−3
a = 5.5500 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.4400 (13) Å	Cell parameters from 3338 reflections
c = 8.5900 (17) Å	θ = 3.2–31.5°
α = 94.20 (3)°	µ = 1.59 mm^−1
β = 99.40 (3)°	T = 150 K
γ = 98.10 (3)°	Plate, light yellow
V = 298.42 (11) Å^3	0.2 × 0.12 × 0.06 mm

Data collection

Bruker APEX diffractometer	1984 independent reflections
Radiation source: sealed tube	1975 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 8.33 pixels mm^-1	θmax = 31.5°, θmin = 2.4°
φ and ω scans	h = −8→7
Absorption correction: multi-scan SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0409 before and 0.0312 after correction. The Ratio of minimum to maximum transmission is 0.8860. The λ/2 correction factor is 0.0015.	k = −6→9
Tmin = 0.661, Tmax = 0.746	l = −12→9
3654 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.017	Only H-atom coordinates refined
wR(F^2) = 0.043	w = 1/[σ^2(Fo^2) + 0.2058P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1984 reflections	Δρmax = 0.81 e Å^−3
115 parameters	Δρmin = −1.15 e Å^−3
6 restraints

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)
Rh1	1.000000	0.500000	1.000000	0.00490 (4)
Na1	0.34339 (11)	0.27579 (10)	0.39134 (7)	0.01407 (12)
O1	0.82155 (18)	0.43668 (15)	0.77298 (11)	0.00861 (17)
O2	0.84634 (17)	0.20136 (15)	1.01610 (11)	0.00840 (17)
O2A	0.64014 (18)	−0.08094 (15)	0.85859 (12)	0.01118 (18)
O1W	0.69920 (17)	0.61254 (16)	1.06057 (12)	0.00876 (17)
H1WA	0.688 (4)	0.715 (3)	1.015 (2)	0.013*
H1W	0.562 (5)	0.549 (6)	1.019 (5)	0.013*	0.5
O2W	0.2773 (2)	0.49025 (19)	0.61525 (14)	0.0160 (2)
H2WA	0.176 (4)	0.575 (3)	0.608 (3)	0.024*
H2WB	0.276 (5)	0.437 (4)	0.701 (2)	0.024*
O1A	0.6014 (3)	0.16343 (19)	0.61175 (14)	0.0244 (3)
O3W	−0.0789 (2)	0.1099 (2)	0.33619 (15)	0.0203 (2)
H3WA	−0.150 (5)	0.105 (4)	0.244 (2)	0.031*
H3WB	−0.193 (4)	0.060 (4)	0.377 (3)	0.031*
C1	0.7167 (3)	0.2435 (2)	0.74093 (16)	0.0103 (2)
C2	0.7346 (2)	0.1061 (2)	0.88150 (15)	0.0075 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.00469 (6)	0.00475 (6)	0.00449 (7)	−0.00056 (4)	0.00005 (4)	−0.00041 (4)
Na1	0.0128 (3)	0.0173 (3)	0.0106 (3)	0.0000 (2)	0.0012 (2)	−0.0016 (2)
O1	0.0103 (4)	0.0083 (4)	0.0058 (4)	−0.0005 (3)	−0.0007 (3)	0.0005 (3)
O2	0.0097 (4)	0.0065 (4)	0.0076 (4)	−0.0016 (3)	−0.0001 (3)	0.0005 (3)
O2A	0.0129 (4)	0.0063 (4)	0.0128 (4)	−0.0014 (3)	0.0011 (3)	−0.0010 (3)
O1W	0.0067 (4)	0.0093 (4)	0.0106 (4)	0.0011 (3)	0.0028 (3)	0.0005 (3)
O2W	0.0157 (5)	0.0193 (5)	0.0140 (5)	0.0026 (4)	0.0061 (4)	0.0010 (4)
O1A	0.0432 (7)	0.0116 (5)	0.0106 (5)	−0.0032 (5)	−0.0102 (5)	−0.0019 (4)
O3W	0.0170 (5)	0.0267 (6)	0.0168 (5)	−0.0013 (4)	0.0039 (4)	0.0055 (5)
C1	0.0133 (5)	0.0083 (5)	0.0079 (5)	0.0011 (4)	−0.0007 (4)	−0.0004 (4)
C2	0.0070 (5)	0.0070 (5)	0.0083 (5)	0.0011 (4)	0.0012 (4)	−0.0001 (4)

Geometric parameters (Å, º)

Rh1—O1^i	2.0221 (11)	Na1—O3W	2.3907 (16)
Rh1—O1	2.0221 (11)	O1—C1	1.2868 (17)
Rh1—O2^i	2.0150 (11)	O2—C2	1.2854 (16)
Rh1—O2	2.0151 (11)	O2A—C2	1.2324 (16)
Rh1—O1W^i	2.0377 (10)	O1W—H1WA	0.797 (15)
Rh1—O1W	2.0378 (10)	O1W—H1W	0.823 (19)
Na1—Na1^ii	3.4033 (18)	O2W—H2WA	0.837 (16)
Na1—O1^ii	2.5879 (13)	O2W—H2WB	0.836 (16)
Na1—O2A^iii	2.4277 (14)	O1A—C1	1.2239 (18)
Na1—O2W^ii	2.4211 (15)	O3W—H3WA	0.823 (17)
Na1—O2W	2.3928 (15)	O3W—H3WB	0.813 (17)
Na1—O1A^iii	2.8864 (15)	C1—C2	1.5467 (19)
Na1—O1A	2.4012 (15)
O1—Rh1—O1^i	180.0	O1A—Na1—O1A^iii	61.20 (5)
O1—Rh1—O1W	89.72 (5)	O3W—Na1—Na1^ii	134.80 (5)
O1^i—Rh1—O1W	90.28 (5)	O3W—Na1—O1^ii	83.95 (5)
O1^i—Rh1—O1W^i	89.72 (5)	O3W—Na1—O2A^iii	82.91 (5)
O1—Rh1—O1W^i	90.28 (5)	O3W—Na1—O2W^ii	162.24 (5)
O2^i—Rh1—O1	97.36 (5)	O3W—Na1—O2W	92.21 (6)
O2—Rh1—O1	82.64 (5)	O3W—Na1—O1A	116.31 (6)
O2^i—Rh1—O1^i	82.64 (5)	O3W—Na1—O1A^iii	78.79 (5)
O2—Rh1—O1^i	97.36 (5)	Rh1—O1—Na1^ii	122.51 (5)
O2^i—Rh1—O2	180.0	C1—O1—Rh1	112.54 (9)
O2—Rh1—O1W^i	88.78 (5)	C1—O1—Na1^ii	119.86 (8)
O2—Rh1—O1W	91.22 (5)	C2—O2—Rh1	112.78 (9)
O2^i—Rh1—O1W^i	91.22 (5)	C2—O2A—Na1^iii	118.35 (9)
O2^i—Rh1—O1W	88.78 (5)	Rh1—O1W—H1WA	105.2 (16)
O1W^i—Rh1—O1W	180.0	Rh1—O1W—H1W	117 (3)
O1^ii—Na1—Na1^ii	78.44 (4)	H1WA—O1W—H1W	95 (4)
O1^ii—Na1—O1A^iii	145.39 (4)	Na1—O2W—Na1^ii	89.98 (5)
O2A^iii—Na1—Na1^ii	136.52 (5)	Na1—O2W—H2WA	122.8 (17)
O2A^iii—Na1—O1^ii	87.27 (4)	Na1^ii—O2W—H2WA	100.8 (17)
O2A^iii—Na1—O1A^iii	61.11 (4)	Na1—O2W—H2WB	118.5 (17)
O2W—Na1—Na1^ii	45.35 (4)	Na1^ii—O2W—H2WB	113.4 (18)
O2W^ii—Na1—Na1^ii	44.67 (4)	H2WA—O2W—H2WB	108 (2)
O2W^ii—Na1—O1^ii	78.69 (5)	Na1—O1A—Na1^iii	118.80 (5)
O2W—Na1—O1^ii	85.03 (4)	C1—O1A—Na1^iii	104.44 (10)
O2W^ii—Na1—O2A^iii	92.47 (5)	C1—O1A—Na1	136.60 (10)
O2W—Na1—O2A^iii	171.28 (5)	Na1—O3W—H3WA	116.3 (19)
O2W—Na1—O2W^ii	90.02 (5)	Na1—O3W—H3WB	143.4 (19)
O2W—Na1—O1A^iii	125.11 (5)	H3WA—O3W—H3WB	100 (3)
O2W—Na1—O1A	76.15 (5)	O1—C1—C2	115.81 (11)
O2W^ii—Na1—O1A^iii	113.96 (5)	O1A—C1—O1	125.71 (13)
O1A^iii—Na1—Na1^ii	133.89 (4)	O1A—C1—C2	118.46 (13)
O1A—Na1—Na1^ii	74.00 (4)	O2—C2—C1	115.75 (11)
O1A—Na1—O1^ii	152.43 (5)	O2A—C2—O2	125.11 (13)
O1A—Na1—O2A^iii	112.48 (5)	O2A—C2—C1	119.13 (12)
O1A—Na1—O2W^ii	81.32 (5)

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

(NaRh-1)

Crystal data

C4H8NaO12Rh	Z = 1
Mr = 374.00	F(000) = 184
Triclinic, P1	Dx = 2.439 Mg m^−3
a = 5.2554 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.4584 (2) Å	Cell parameters from 5321 reflections
c = 8.2102 (2) Å	θ = 3.9–33.2°
α = 97.796 (1)°	µ = 1.79 mm^−1
β = 92.099 (1)°	T = 150 K
γ = 112.113 (1)°	Block, orange
V = 254.61 (1) Å^3	0.35 × 0.24 × 0.2 mm

Data collection

Bruker APEX-II CCD diffractometer	1909 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 33.2°, θmin = 3.9°
Absorption correction: multi-scan SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0452 before and 0.0317 after correction. The Ratio of minimum to maximum transmission is 0.8480. The λ/2 correction factor is 0.0015.	h = −7→8
Tmin = 0.633, Tmax = 0.747	k = −9→9
5308 measured reflections	l = −8→12
1912 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.016	H-atom parameters constrained
wR(F^2) = 0.042	w = 1/[σ^2(Fo^2) + (0.0172P)^2 + 0.1339P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
1912 reflections	Δρmax = 0.67 e Å^−3
85 parameters	Δρmin = −1.28 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
Rh1	0.000000	0.000000	1.000000	0.00756 (4)
Na1	0.500000	0.500000	0.500000	0.01231 (13)
O1	−0.11311 (17)	0.04743 (14)	0.77586 (11)	0.01107 (14)
O1A	0.06677 (18)	0.24543 (15)	0.57680 (11)	0.01345 (15)
O1W	0.04954 (18)	−0.28639 (14)	0.90209 (11)	0.01221 (15)
H1WA	0.150910	−0.263265	0.817245	0.018*
H1WB	−0.121770	−0.398025	0.849605	0.018*
O2	0.37559 (17)	0.20081 (14)	0.94881 (11)	0.01078 (14)
O2A	0.57540 (18)	0.39956 (14)	0.75369 (11)	0.01248 (15)
O3W	0.64269 (18)	0.21646 (15)	0.35643 (12)	0.01398 (16)
H3WA	0.483158	0.095091	0.328138	0.021*
H3WB	0.739648	0.187651	0.428218	0.021*
C1	0.0870 (2)	0.18476 (17)	0.70994 (14)	0.00915 (17)
C2	0.3726 (2)	0.27217 (17)	0.81136 (14)	0.00889 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.00489 (6)	0.00923 (5)	0.00694 (6)	−0.00005 (4)	0.00054 (3)	0.00411 (4)
Na1	0.0134 (3)	0.0131 (3)	0.0111 (3)	0.0043 (2)	0.0037 (2)	0.0059 (2)
O1	0.0071 (3)	0.0145 (3)	0.0092 (3)	0.0000 (3)	0.0004 (3)	0.0061 (3)
O1A	0.0118 (4)	0.0161 (3)	0.0105 (4)	0.0018 (3)	−0.0005 (3)	0.0066 (3)
O1W	0.0092 (3)	0.0116 (3)	0.0136 (4)	0.0013 (3)	0.0012 (3)	0.0025 (3)
O2	0.0067 (3)	0.0141 (3)	0.0097 (3)	0.0004 (3)	0.0010 (3)	0.0061 (3)
O2A	0.0084 (3)	0.0142 (3)	0.0120 (4)	−0.0001 (3)	0.0019 (3)	0.0058 (3)
O3W	0.0099 (3)	0.0155 (3)	0.0144 (4)	0.0028 (3)	−0.0005 (3)	0.0020 (3)
C1	0.0074 (4)	0.0093 (4)	0.0094 (4)	0.0013 (3)	0.0005 (3)	0.0025 (3)
C2	0.0075 (4)	0.0090 (4)	0.0090 (4)	0.0017 (3)	0.0006 (3)	0.0023 (3)

Geometric parameters (Å, º)

Rh1—O1	2.0109 (9)	Na1—C1^ii	3.1186 (11)
Rh1—O1^i	2.0109 (9)	Na1—C2^ii	3.0907 (11)
Rh1—O1W	2.0272 (9)	Na1—C2	3.0906 (11)
Rh1—O1W^i	2.0272 (9)	O1—C1	1.2866 (13)
Rh1—O2^i	2.0090 (8)	O1A—C1	1.2243 (14)
Rh1—O2	2.0090 (8)	O1W—H1WA	0.8870
Na1—O1A^ii	2.4192 (9)	O1W—H1WB	0.9564
Na1—O1A	2.4192 (9)	O2—C2	1.2773 (14)
Na1—O2A	2.3272 (9)	O2A—C2	1.2325 (13)
Na1—O2A^ii	2.3272 (9)	O3W—H3WA	0.9016
Na1—O3W	2.4121 (9)	O3W—H3WB	0.8490
Na1—O3W^ii	2.4121 (9)	C1—C2	1.5516 (16)
Na1—C1	3.1186 (11)
O1—Rh1—O1^i	180.00 (5)	O3W^ii—Na1—O1A	82.45 (3)
O1—Rh1—O1W	91.60 (4)	O3W^ii—Na1—O1A^ii	97.55 (3)
O1—Rh1—O1W^i	88.40 (4)	O3W—Na1—O1A^ii	82.45 (3)
O1^i—Rh1—O1W^i	91.61 (4)	O3W—Na1—O1A	97.55 (3)
O1^i—Rh1—O1W	88.40 (4)	O3W—Na1—O3W^ii	180.00 (5)
O1W^i—Rh1—O1W	180.0	O3W—Na1—C1^ii	83.20 (3)
O2—Rh1—O1	82.53 (3)	O3W^ii—Na1—C1^ii	96.80 (3)
O2^i—Rh1—O1^i	82.53 (3)	O3W—Na1—C1	96.80 (3)
O2—Rh1—O1^i	97.47 (3)	O3W^ii—Na1—C1	83.20 (3)
O2^i—Rh1—O1	97.47 (3)	O3W^ii—Na1—C2^ii	94.36 (3)
O2—Rh1—O1W^i	87.16 (4)	O3W^ii—Na1—C2	85.64 (3)
O2^i—Rh1—O1W^i	92.84 (4)	O3W—Na1—C2	94.36 (3)
O2^i—Rh1—O1W	87.16 (4)	O3W—Na1—C2^ii	85.64 (3)
O2—Rh1—O1W	92.84 (4)	C1—Na1—C1^ii	180.0
O2—Rh1—O2^i	180.0	C2—Na1—C1	28.94 (3)
O1A^ii—Na1—O1A	180.0	C2^ii—Na1—C1	151.06 (3)
O1A^ii—Na1—C1	158.92 (3)	C2^ii—Na1—C1^ii	28.94 (3)
O1A—Na1—C1	21.08 (3)	C2—Na1—C1^ii	151.06 (3)
O1A^ii—Na1—C1^ii	21.08 (3)	C2—Na1—C2^ii	180.0
O1A—Na1—C1^ii	158.92 (3)	C1—O1—Rh1	113.28 (7)
O1A^ii—Na1—C2	129.98 (3)	C1—O1A—Na1	113.62 (7)
O1A^ii—Na1—C2^ii	50.02 (3)	Rh1—O1W—H1WA	110.9
O1A—Na1—C2^ii	129.98 (3)	Rh1—O1W—H1WB	110.5
O1A—Na1—C2	50.02 (3)	H1WA—O1W—H1WB	101.3
O2A—Na1—O1A^ii	109.20 (3)	C2—O2—Rh1	113.24 (7)
O2A^ii—Na1—O1A	109.20 (3)	C2—O2A—Na1	117.14 (7)
O2A—Na1—O1A	70.80 (3)	Na1—O3W—H3WA	103.6
O2A^ii—Na1—O1A^ii	70.80 (3)	Na1—O3W—H3WB	105.7
O2A—Na1—O2A^ii	180.0	H3WA—O3W—H3WB	108.9
O2A—Na1—O3W^ii	88.57 (3)	O1—C1—Na1	170.44 (8)
O2A^ii—Na1—O3W	88.57 (3)	O1—C1—C2	114.98 (10)
O2A^ii—Na1—O3W^ii	91.43 (3)	O1A—C1—Na1	45.29 (6)
O2A—Na1—O3W	91.43 (3)	O1A—C1—O1	125.18 (10)
O2A^ii—Na1—C1^ii	49.72 (3)	O1A—C1—C2	119.83 (10)
O2A^ii—Na1—C1	130.28 (3)	C2—C1—Na1	74.53 (6)
O2A—Na1—C1^ii	130.28 (3)	O2—C2—Na1	167.65 (8)
O2A—Na1—C1	49.72 (3)	O2—C2—C1	115.82 (9)
O2A^ii—Na1—C2^ii	20.79 (3)	O2A—C2—Na1	42.07 (6)
O2A—Na1—C2	20.79 (3)	O2A—C2—O2	125.58 (10)
O2A—Na1—C2^ii	159.21 (3)	O2A—C2—C1	118.59 (10)
O2A^ii—Na1—C2	159.21 (3)	C1—C2—Na1	76.53 (6)
Rh1—O1—C1—O1A	−177.53 (9)	Na1—C1—C2—O2	−179.99 (9)
Rh1—O1—C1—C2	3.44 (12)	Na1—C1—C2—O2A	−0.99 (9)
Rh1—O2—C2—Na1	178.0 (3)	O1—C1—C2—Na1	179.04 (9)
Rh1—O2—C2—O2A	179.01 (9)	O1—C1—C2—O2	−0.95 (14)
Rh1—O2—C2—C1	−2.06 (12)	O1—C1—C2—O2A	178.05 (10)
Na1—O1A—C1—O1	−178.92 (9)	O1A—C1—C2—Na1	−0.05 (9)
Na1—O1A—C1—C2	0.07 (13)	O1A—C1—C2—O2	179.96 (10)
Na1—O2A—C2—O2	−179.67 (8)	O1A—C1—C2—O2A	−1.04 (16)
Na1—O2A—C2—C1	1.43 (13)

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

(NaRh-2)

Crystal data

C4H8NaO12Rh	Z = 2
Mr = 374.00	F(000) = 368
Triclinic, P1	Dx = 2.446 Mg m^−3
a = 6.2055 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8091 (3) Å	Cell parameters from 2269 reflections
c = 10.7762 (4) Å	θ = 2.6–28.4°
α = 95.557 (3)°	µ = 1.79 mm^−1
β = 98.352 (3)°	T = 295 K
γ = 98.065 (3)°	Plate, orange
V = 507.88 (4) Å^3	0.19 × 0.17 × 0.05 mm

Data collection

New Xcalibur, AtlasS2 diffractometer	2214 independent reflections
Radiation source: fine-focus sealed tube	2024 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 10.6 pixels mm^-1	θmax = 29.0°, θmin = 1.9°
ω scans	h = −7→7
Absorption correction: multi-scan CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→8
Tmin = 0.957, Tmax = 1.000	l = −13→12
3910 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: difference Fourier map
wR(F^2) = 0.059	Only H-atom coordinates refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0217P)^2 + 0.0121P] where P = (Fo^2 + 2Fc^2)/3
2214 reflections	(Δ/σ)max = 0.001
187 parameters	Δρmax = 0.52 e Å^−3
13 restraints	Δρmin = −0.74 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
Rh1	0.25557 (4)	0.69752 (3)	0.76733 (2)	0.01553 (9)
Na1	0.8339 (2)	0.79886 (18)	0.42497 (11)	0.0340 (3)
O1M	0.0411 (3)	0.4743 (3)	0.69957 (18)	0.0190 (4)
H11M	0.001 (5)	0.431 (4)	0.7628 (18)	0.023*
H12M	−0.063 (3)	0.512 (4)	0.656 (2)	0.023*
O2M	0.4769 (4)	0.9138 (3)	0.8244 (2)	0.0381 (6)
H21M	0.451 (6)	1.015 (2)	0.820 (3)	0.046*
H22M	0.564 (5)	0.908 (4)	0.890 (2)	0.046*
O3M	1.1219 (4)	0.9878 (3)	0.37673 (19)	0.0278 (5)
H31M	1.102 (5)	1.019 (4)	0.3037 (15)	0.033*
H32M	1.226 (4)	0.930 (4)	0.379 (3)	0.033*
O4M	0.6437 (4)	0.7806 (3)	0.19877 (19)	0.0282 (5)
H41M	0.538 (4)	0.697 (3)	0.192 (3)	0.034*
H42M	0.709 (4)	0.759 (3)	0.136 (2)	0.034*
O1	0.2794 (4)	0.6357 (3)	0.94445 (17)	0.0235 (5)
O2	0.0049 (3)	0.8111 (3)	0.81852 (17)	0.0206 (5)
O3	−0.1834 (4)	0.8354 (3)	0.97744 (18)	0.0262 (5)
O4	0.1342 (4)	0.6815 (3)	1.11812 (18)	0.0338 (6)
O5	0.5086 (3)	0.5867 (3)	0.71829 (17)	0.0199 (4)
O6	0.2343 (3)	0.7660 (3)	0.59134 (17)	0.0209 (5)
O7	0.4487 (4)	0.7911 (3)	0.44324 (17)	0.0232 (5)
O8	0.7266 (3)	0.6032 (2)	0.57151 (17)	0.0182 (4)
C1	0.1396 (5)	0.6932 (4)	1.0064 (3)	0.0206 (7)
C2	−0.0311 (5)	0.7882 (4)	0.9304 (3)	0.0189 (6)
C3	0.5640 (5)	0.6369 (4)	0.6165 (2)	0.0168 (6)
C4	0.4051 (5)	0.7423 (4)	0.5420 (3)	0.0179 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.01418 (14)	0.01987 (15)	0.01441 (13)	0.00590 (10)	0.00346 (9)	0.00492 (9)
Na1	0.0302 (8)	0.0414 (8)	0.0342 (7)	0.0038 (6)	0.0155 (6)	0.0104 (6)
O1M	0.0169 (11)	0.0229 (12)	0.0184 (11)	0.0038 (9)	0.0032 (8)	0.0076 (8)
O2M	0.0284 (15)	0.0218 (13)	0.0575 (16)	0.0041 (11)	−0.0142 (12)	0.0036 (11)
O3M	0.0282 (14)	0.0334 (14)	0.0265 (12)	0.0122 (11)	0.0059 (10)	0.0144 (10)
O4M	0.0301 (15)	0.0302 (13)	0.0273 (12)	0.0059 (10)	0.0112 (10)	0.0067 (9)
O1	0.0243 (13)	0.0321 (13)	0.0174 (10)	0.0121 (10)	0.0026 (9)	0.0084 (8)
O2	0.0210 (12)	0.0279 (12)	0.0163 (10)	0.0119 (9)	0.0057 (8)	0.0037 (8)
O3	0.0206 (12)	0.0392 (14)	0.0215 (11)	0.0100 (10)	0.0084 (9)	0.0024 (9)
O4	0.0369 (15)	0.0494 (15)	0.0178 (11)	0.0064 (12)	0.0079 (10)	0.0133 (10)
O5	0.0166 (12)	0.0266 (12)	0.0209 (10)	0.0100 (9)	0.0073 (8)	0.0080 (8)
O6	0.0177 (12)	0.0306 (12)	0.0200 (10)	0.0124 (9)	0.0073 (8)	0.0115 (8)
O7	0.0240 (13)	0.0304 (12)	0.0199 (11)	0.0099 (10)	0.0086 (9)	0.0109 (8)
O8	0.0149 (11)	0.0213 (11)	0.0201 (10)	0.0062 (9)	0.0046 (8)	0.0042 (8)
C1	0.0207 (17)	0.0229 (17)	0.0174 (15)	0.0012 (13)	0.0004 (12)	0.0061 (11)
C2	0.0197 (17)	0.0174 (15)	0.0186 (15)	0.0007 (13)	0.0034 (12)	−0.0003 (11)
C3	0.0168 (16)	0.0157 (15)	0.0170 (14)	0.0035 (12)	0.0006 (11)	−0.0012 (10)
C4	0.0184 (16)	0.0181 (15)	0.0181 (15)	0.0055 (12)	0.0030 (12)	0.0034 (11)

Geometric parameters (Å, º)

Rh1—O1M	2.040 (2)	O1M—H12M	0.843 (10)
Rh1—O2M	2.005 (2)	O2M—H21M	0.833 (9)
Rh1—O1	2.0037 (19)	O2M—H22M	0.836 (10)
Rh1—O2	2.013 (2)	O3M—H31M	0.844 (10)
Rh1—O5	2.007 (2)	O3M—H32M	0.838 (10)
Rh1—O6	2.0109 (18)	O4M—H41M	0.849 (10)
Na1—Na1^i	3.601 (3)	O4M—H42M	0.852 (10)
Na1—O1M^ii	2.677 (2)	O1—C1	1.273 (4)
Na1—O3M	2.307 (3)	O2—C2	1.283 (3)
Na1—O3M^i	2.536 (2)	O3—C2	1.219 (4)
Na1—H32M	2.64 (3)	O4—C1	1.221 (3)
Na1—O4M	2.531 (3)	O5—C3	1.277 (3)
Na1—O6^iii	2.903 (2)	O6—C4	1.281 (3)
Na1—O7	2.419 (3)	O7—C4	1.219 (3)
Na1—O8	2.400 (2)	O8—C3	1.230 (3)
Na1—C3	3.095 (3)	C1—C2	1.558 (4)
Na1—C4	3.101 (3)	C3—C4	1.556 (4)
O1M—H11M	0.843 (10)
O2M—Rh1—O1M	176.23 (9)	O8—Na1—O1M^ii	86.35 (7)
O2M—Rh1—O2	93.06 (10)	O8—Na1—O3M^i	79.91 (8)
O2M—Rh1—O5	86.17 (10)	O8—Na1—H32M	131.4 (5)
O2M—Rh1—O6	87.82 (10)	O8—Na1—O4M	124.22 (9)
O1—Rh1—O1M	91.82 (8)	O8—Na1—O6^iii	73.45 (7)
O1—Rh1—O2M	90.84 (10)	O8—Na1—O7	68.98 (8)
O1—Rh1—O2	82.14 (8)	O8—Na1—C3	21.45 (7)
O1—Rh1—O5	97.47 (8)	O8—Na1—C4	49.70 (7)
O1—Rh1—O6	178.53 (8)	C3—Na1—Na1^i	109.07 (7)
O2—Rh1—O1M	89.95 (9)	C3—Na1—H32M	146.9 (6)
O5—Rh1—O1M	90.84 (8)	C3—Na1—C4	29.08 (7)
O5—Rh1—O2	179.14 (8)	C4—Na1—Na1^i	108.80 (7)
O5—Rh1—O6	83.03 (8)	C4—Na1—H32M	162.4 (6)
O6—Rh1—O1M	89.54 (8)	Rh1—O1M—Na1^ii	122.09 (10)
O6—Rh1—O2	97.34 (8)	Rh1—O1M—H11M	107 (2)
Na1^i—Na1—H32M	53.7 (6)	Rh1—O1M—H12M	103 (2)
O1M^ii—Na1—Na1^i	128.76 (8)	Na1^ii—O1M—H11M	102 (2)
O1M^ii—Na1—H32M	77.3 (6)	Na1^ii—O1M—H12M	112 (2)
O1M^ii—Na1—O6^iii	79.17 (7)	H11M—O1M—H12M	112 (2)
O1M^ii—Na1—C3	104.19 (8)	Rh1—O2M—H21M	125 (2)
O1M^ii—Na1—C4	118.98 (8)	Rh1—O2M—H22M	114 (2)
O3M^i—Na1—Na1^i	39.58 (6)	H21M—O2M—H22M	111 (2)
O3M—Na1—Na1^i	44.46 (6)	Na1—O3M—Na1^i	95.96 (9)
O3M—Na1—O1M^ii	91.83 (8)	Na1—O3M—H31M	115 (2)
O3M^i—Na1—O1M^ii	149.32 (9)	Na1^i—O3M—H31M	122 (2)
O3M—Na1—O3M^i	84.04 (9)	Na1—O3M—H32M	104 (2)
O3M—Na1—H32M	17.9 (4)	Na1^i—O3M—H32M	111 (2)
O3M^i—Na1—H32M	91.4 (6)	H31M—O3M—H32M	106 (2)
O3M—Na1—O4M	88.89 (8)	Na1—O4M—H41M	104 (2)
O3M^i—Na1—O6^iii	70.68 (7)	Na1—O4M—H42M	122 (2)
O3M—Na1—O6^iii	71.42 (8)	H41M—O4M—H42M	106 (2)
O3M—Na1—O7	139.07 (10)	C1—O1—Rh1	113.96 (18)
O3M—Na1—O8	144.52 (9)	C2—O2—Rh1	113.72 (18)
O3M^i—Na1—C3	70.27 (8)	C3—O5—Rh1	111.54 (17)
O3M—Na1—C3	151.77 (9)	Rh1—O6—Na1^iv	126.56 (9)
O3M^i—Na1—C4	71.21 (8)	C4—O6—Rh1	111.93 (17)
O3M—Na1—C4	149.00 (9)	C4—O6—Na1^iv	118.36 (16)
O4M—Na1—Na1^i	119.52 (8)	C4—O7—Na1	112.74 (19)
O4M—Na1—O1M^ii	74.20 (7)	C3—O8—Na1	113.01 (18)
O4M—Na1—O3M^i	135.83 (9)	O1—C1—C2	115.4 (2)
O4M—Na1—H32M	94.9 (6)	O4—C1—O1	125.0 (3)
O4M—Na1—O6^iii	146.23 (9)	O4—C1—C2	119.6 (3)
O4M—Na1—C3	117.58 (9)	O2—C2—C1	114.5 (3)
O4M—Na1—C4	95.93 (9)	O3—C2—O2	124.8 (3)
O6^iii—Na1—Na1^i	64.08 (6)	O3—C2—C1	120.7 (2)
O6^iii—Na1—H32M	58.7 (5)	O5—C3—Na1	162.3 (2)
O6^iii—Na1—C3	88.69 (7)	O5—C3—C4	116.3 (2)
O6^iii—Na1—C4	115.20 (8)	O8—C3—Na1	45.53 (14)
O7—Na1—Na1^i	112.09 (8)	O8—C3—O5	125.3 (3)
O7—Na1—O1M^ii	119.14 (9)	O8—C3—C4	118.4 (2)
O7—Na1—O3M^i	81.18 (8)	C4—C3—Na1	75.69 (16)
O7—Na1—H32M	156.9 (4)	O6—C4—Na1	163.7 (2)
O7—Na1—O4M	76.13 (8)	O6—C4—C3	115.1 (2)
O7—Na1—O6^iii	136.19 (8)	O7—C4—Na1	46.01 (15)
O7—Na1—C3	49.66 (7)	O7—C4—O6	126.0 (3)
O7—Na1—C4	21.24 (7)	O7—C4—C3	118.9 (3)
O8—Na1—Na1^i	113.47 (7)	C3—C4—Na1	75.23 (16)

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