Tetra­methyl­ammonium tetra­aqua­di­chloro­chromium(III) trichloride dihydrate

The title metal-organic octahedral chromium compound, (C₄H₁₂N)₂[CrCl₂(H₂O)₄]Cl₃·2H₂O, was synthesized according to the Palmer method. The chromium complex ion possesses mirror symmetry and has two axial Cl^- ions and four equatorial water mol­ecules. The octahedral complex cation and tetramethyl ammonium tetrahedra pack in a `parquet'-style pattern, with Cl<sup>-</sup> ions and water molecules in between the `bricks'. The structure is compared with aqua­penta­chloro­chromate(III) complexes in the literature.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](Cr-O) = 0.003 Å
• R factor = 0.053
• wR factor = 0.149
• Data-to-parameter ratio = 18.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         N1
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         N2
PLAT417_ALERT_2_C Short Inter D-H..H-D       H3A    ..  H4A     ..       2.12 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H3A    ..  H4A     ..       2.12 Ang.
PLAT731_ALERT_1_C Bond    Calc     0.83(4), Rep   0.833(19) ......       2.11 su-Rat
              O2   -H2A     1.555   1.555

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXTL.

Ditetramethylammonium tetraaquodichlorochromate(III) trichloride dihydrate

Crystal data

(C4H12N)2[CrCl2(H2O)4]Cl3·2H2O	F(000) = 1020
Mr = 485.64	Dx = 1.392 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 8192 reflections
a = 18.4374 (2) Å	θ = 2.2–27.3°
b = 6.8192 (1) Å	µ = 1.09 mm^−1
c = 18.4330 (2) Å	T = 173 K
V = 2317.55 (5) Å^3	Plate, green
Z = 4	0.20 × 0.08 × 0.04 mm

Data collection

Siemens SMART 1K CCD area-detector diffractometer	2822 independent reflections
Radiation source: fine-focus sealed tube	2139 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
ω scans	θmax = 27.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −23→23
Tmin = 0.811, Tmax = 0.958	k = −8→8
27823 measured reflections	l = −23→23

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.09P)^2 + 2.33P] where P = (Fo^2 + 2Fc^2)/3
2822 reflections	(Δ/σ)max = 0.001
156 parameters	Δρmax = 0.73 e Å^−3
14 restraints	Δρmin = −0.59 e Å^−3

Special details

Experimental. Data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with an LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal-to-detector distance of 3.97 cm, 15 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 5499 reflections with I>10σ(I) after integration of all the frames data using SAINT (Siemens, 1995).

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	Occ. (<1)
Cr1	0.71940 (4)	0.2500	0.14394 (4)	0.0169 (2)
Cl1	0.61233 (7)	0.2500	0.07851 (7)	0.0263 (3)
Cl2	0.82359 (7)	0.2500	0.21146 (7)	0.0270 (3)
Cl3	0.78375 (9)	0.2500	−0.06564 (7)	0.0377 (4)
Cl4	0.55765 (7)	0.7500	0.18657 (8)	0.0280 (3)
Cl5	0.88503 (7)	0.7500	0.07961 (7)	0.0273 (3)
O1	0.75817 (14)	0.0422 (4)	0.07719 (13)	0.0243 (6)
H1A	0.791 (2)	−0.037 (6)	0.090 (3)	0.067 (18)*
H1B	0.763 (2)	0.081 (7)	0.0341 (13)	0.049 (15)*
O2	0.68020 (14)	0.0414 (4)	0.20859 (14)	0.0239 (5)
H2A	0.706 (2)	−0.044 (5)	0.228 (2)	0.044 (14)*
H2B	0.6420 (15)	−0.018 (5)	0.198 (2)	0.024 (11)*
O3	0.4018 (2)	0.7500	0.2518 (2)	0.0466 (12)
H3A	0.398 (4)	0.7500	0.2981 (12)	0.07 (3)*
H3B	0.4439 (17)	0.7500	0.233 (3)	0.034 (17)*
O4	0.2583 (2)	0.7500	0.2291 (2)	0.0254 (8)
H4A	0.3041 (11)	0.7500	0.232 (4)	0.05 (2)*
H4B	0.246 (3)	0.7500	0.1849 (14)	0.04 (2)*
N1	0.0393 (2)	0.2500	0.1310 (2)	0.0285 (10)
N2	0.3874 (2)	0.2500	0.0763 (2)	0.0227 (9)
C11	0.0827 (3)	0.0695 (9)	0.1176 (3)	0.0684 (16)
H11A	0.1256	0.0699	0.1490	0.058 (5)*
H11B	0.0980	0.0660	0.0667	0.058 (5)*
H11C	0.0531	−0.0463	0.1283	0.058 (5)*
C12	−0.0235 (4)	0.2500	0.0797 (3)	0.0454 (16)
H12A	−0.0577	0.1463	0.0935	0.058 (5)*	0.50
H12B	−0.0061	0.2264	0.0303	0.058 (5)*	0.50
H12C	−0.0481	0.3774	0.0817	0.058 (5)*	0.50
C13	0.0134 (4)	0.2500	0.2076 (3)	0.0398 (14)
H13A	0.0549	0.2639	0.2404	0.058 (5)*	0.50
H13B	−0.0117	0.1263	0.2178	0.058 (5)*	0.50
H13C	−0.0201	0.3598	0.2150	0.058 (5)*	0.50
C21	0.4163 (2)	0.0711 (6)	0.1126 (2)	0.0386 (10)
H21A	0.3991	−0.0458	0.0869	0.058 (5)*
H21B	0.3993	0.0673	0.1630	0.058 (5)*
H21C	0.4694	0.0742	0.1118	0.058 (5)*
C22	0.4095 (4)	0.2500	−0.0016 (3)	0.0410 (15)
H22A	0.3984	0.3779	−0.0231	0.058 (5)*	0.50
H22B	0.3828	0.1474	−0.0275	0.058 (5)*	0.50
H22C	0.4617	0.2247	−0.0052	0.058 (5)*	0.50
C23	0.3066 (3)	0.2500	0.0819 (4)	0.0451 (16)
H23A	0.2869	0.1377	0.0551	0.058 (5)*	0.50
H23B	0.2874	0.3718	0.0613	0.058 (5)*	0.50
H23C	0.2924	0.2404	0.1330	0.058 (5)*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr1	0.0190 (4)	0.0129 (4)	0.0189 (4)	0.000	−0.0017 (3)	0.000
Cl1	0.0244 (6)	0.0215 (6)	0.0329 (7)	0.000	−0.0090 (5)	0.000
Cl2	0.0222 (6)	0.0317 (7)	0.0271 (6)	0.000	−0.0068 (5)	0.000
Cl3	0.0586 (10)	0.0327 (7)	0.0219 (7)	0.000	0.0041 (6)	0.000
Cl4	0.0224 (6)	0.0222 (6)	0.0396 (7)	0.000	0.0014 (5)	0.000
Cl5	0.0310 (7)	0.0228 (6)	0.0281 (7)	0.000	0.0029 (5)	0.000
O1	0.0340 (15)	0.0193 (13)	0.0195 (13)	0.0043 (11)	−0.0020 (11)	−0.0022 (11)
O2	0.0260 (14)	0.0181 (12)	0.0275 (13)	−0.0015 (11)	−0.0026 (11)	0.0048 (11)
O3	0.026 (2)	0.081 (3)	0.033 (2)	0.000	0.008 (2)	0.000
O4	0.026 (2)	0.0254 (19)	0.025 (2)	0.000	0.0017 (16)	0.000
N1	0.032 (2)	0.026 (2)	0.028 (2)	0.000	0.0054 (19)	0.000
N2	0.031 (2)	0.021 (2)	0.016 (2)	0.000	−0.0039 (17)	0.000
C11	0.071 (2)	0.070 (2)	0.064 (2)	0.0153 (17)	0.0028 (17)	0.0016 (17)
C12	0.043 (4)	0.053 (4)	0.040 (4)	0.000	−0.007 (3)	0.000
C13	0.048 (4)	0.045 (4)	0.026 (3)	0.000	0.012 (3)	0.000
C21	0.052 (3)	0.026 (2)	0.037 (2)	0.0101 (19)	0.001 (2)	0.0077 (18)
C22	0.068 (4)	0.031 (3)	0.024 (3)	0.000	0.004 (3)	0.000
C23	0.038 (3)	0.055 (4)	0.043 (4)	0.000	−0.015 (3)	0.000

Geometric parameters (Å, º)

Cr1—O2^i	1.992 (2)	N2—C21	1.490 (4)
Cr1—O2	1.992 (2)	N2—C21^i	1.490 (4)
Cr1—O1^i	2.008 (3)	C11—H11A	0.9800
Cr1—O1	2.008 (3)	C11—H11B	0.9800
Cr1—Cl2	2.2889 (14)	C11—H11C	0.9800
Cr1—Cl1	2.3133 (14)	C12—H12A	0.9800
O1—H1A	0.85 (2)	C12—H12B	0.9800
O1—H1B	0.842 (19)	C12—H12C	0.9800
O2—H2A	0.833 (19)	C13—H13A	0.9800
O2—H2B	0.838 (19)	C13—H13B	0.9800
O3—H3A	0.86 (2)	C13—H13C	0.9800
O3—H3B	0.85 (2)	C21—H21A	0.9800
O4—H4A	0.85 (2)	C21—H21B	0.9800
O4—H4B	0.85 (2)	C21—H21C	0.9800
N1—C13	1.490 (7)	C22—H22A	0.9800
N1—C11^i	1.489 (6)	C22—H22B	0.9800
N1—C11	1.489 (6)	C22—H22C	0.9800
N1—C12	1.496 (8)	C23—H23A	0.9800
N2—C22	1.492 (7)	C23—H23B	0.9800
N2—C23	1.494 (8)	C23—H23C	0.9800
O2^i—Cr1—O2	91.17 (15)	N1—C11—H11B	109.5
O2^i—Cr1—O1^i	89.52 (11)	H11A—C11—H11B	109.5
O2—Cr1—O1^i	178.97 (11)	N1—C11—H11C	109.5
O2^i—Cr1—O1	178.97 (11)	H11A—C11—H11C	109.5
O2—Cr1—O1	89.53 (11)	H11B—C11—H11C	109.5
O1^i—Cr1—O1	89.77 (15)	N1—C12—H12A	109.5
O2^i—Cr1—Cl2	88.81 (8)	N1—C12—H12B	109.5
O2—Cr1—Cl2	88.81 (8)	H12A—C12—H12B	109.5
O1^i—Cr1—Cl2	91.98 (8)	N1—C12—H12C	109.5
O1—Cr1—Cl2	91.97 (8)	H12A—C12—H12C	109.5
O2^i—Cr1—Cl1	90.13 (8)	H12B—C12—H12C	109.5
O2—Cr1—Cl1	90.13 (8)	N1—C13—H13A	109.5
O1^i—Cr1—Cl1	89.10 (8)	N1—C13—H13B	109.5
O1—Cr1—Cl1	89.10 (8)	H13A—C13—H13B	109.5
Cl2—Cr1—Cl1	178.48 (6)	N1—C13—H13C	109.5
Cr1—O1—H1A	123 (4)	H13A—C13—H13C	109.5
Cr1—O1—H1B	114 (3)	H13B—C13—H13C	109.5
H1A—O1—H1B	112 (5)	N2—C21—H21A	109.5
Cr1—O2—H2A	123 (3)	N2—C21—H21B	109.5
Cr1—O2—H2B	120 (3)	H21A—C21—H21B	109.5
H2A—O2—H2B	104 (4)	N2—C21—H21C	109.5
H3A—O3—H3B	119 (7)	H21A—C21—H21C	109.5
H4A—O4—H4B	109 (6)	H21B—C21—H21C	109.5
C13—N1—C11^i	109.2 (3)	N2—C22—H22A	109.5
C13—N1—C11	109.2 (3)	N2—C22—H22B	109.5
C11^i—N1—C11	111.5 (5)	H22A—C22—H22B	109.5
C13—N1—C12	110.5 (5)	N2—C22—H22C	109.5
C11^i—N1—C12	108.1 (3)	H22A—C22—H22C	109.5
C11—N1—C12	108.2 (3)	H22B—C22—H22C	109.5
C22—N2—C23	109.8 (5)	N2—C23—H23A	109.5
C22—N2—C21	109.5 (3)	N2—C23—H23B	109.5
C23—N2—C21	109.0 (3)	H23A—C23—H23B	109.5
C22—N2—C21^i	109.6 (3)	N2—C23—H23C	109.5
C23—N2—C21^i	109.0 (3)	H23A—C23—H23C	109.5
C21—N2—C21^i	109.9 (4)	H23B—C23—H23C	109.5
N1—C11—H11A	109.5

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl5^ii	0.85 (2)	2.27 (3)	3.073 (3)	159 (5)
O1—H1B···Cl3	0.84 (2)	2.20 (2)	3.027 (3)	166 (5)
O2—H2A···O4^iii	0.83 (2)	1.88 (2)	2.709 (3)	175 (5)
O2—H2B···Cl4^ii	0.84 (2)	2.23 (2)	3.036 (3)	163 (4)
O3—H3A···Cl5^iv	0.86 (2)	2.27 (2)	3.123 (5)	178 (7)
O3—H3B···Cl4	0.85 (2)	2.26 (2)	3.115 (4)	177 (6)
O4—H4A···O3	0.85 (2)	1.84 (2)	2.679 (6)	172 (7)
O4—H4B···Cl3^v	0.85 (2)	2.27 (2)	3.112 (4)	178 (6)
C12—H12C···Cl5^vi	0.98	2.82	3.803 (3)	177
C22—H22A···Cl1^v	0.98	2.74	3.715 (2)	172

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