Crystal structure of tris­[4-(di­methyl­amino)­pyridinium] tris­(oxalato-κ²O,O′)chromate(III) tetra­hydrate

In the crystal structure of the title compound, the mol­ecular components, viz. 4-(di­methyl­amino)­pyridinium cations, tris­[oxalatochromate(III)] anions and lattice water mol­ecules, are linked through O—H...O and N—H...O hydrogen bonds into a three-dimensional network. Additional π–π inter­actions between pyridinium rings stabilize this arrangement.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.120
• Data-to-parameter ratio = 21.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -1.529 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          6 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          4 Report
PLAT173_ALERT_4_G The CIF-Embedded .res File Contains DANG Records          2 Report
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          4 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          6 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          4 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         11 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SAINT (Bruker, 2014); cell refinement: APEX2 (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Tris[4-(dimethylamino)pyridinium] tris(oxalato-κ²O,O')chromate(III) tetrahydrate

Crystal data

(C7H11N2)3[Cr(C3O4)3]·4H2O	F(000) = 1588
Mr = 757.66	Dx = 1.445 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.1141 (5) Å	Cell parameters from 9987 reflections
b = 16.7537 (4) Å	θ = 2.4–27.8°
c = 11.0053 (2) Å	µ = 0.41 mm^−1
β = 98.803 (1)°	T = 296 K
V = 3482.73 (14) Å^3	Prism, violet
Z = 4	0.58 × 0.21 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer	3757 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	Rint = 0.038
φ and ω scans	θmax = 30.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −27→27
Tmin = 0.708, Tmax = 0.746	k = −23→23
56955 measured reflections	l = −15→15
5322 independent 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)] = 0.038	Hydrogen site location: mixed
wR(F^2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.056P)^2 + 1.554P] where P = (Fo^2 + 2Fc^2)/3
5322 reflections	(Δ/σ)max = 0.001
249 parameters	Δρmax = 0.23 e Å^−3
6 restraints	Δρmin = −0.42 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cr1	0.5000	0.25122 (2)	0.2500	0.04246 (11)
O2	0.44865 (6)	0.33279 (7)	0.32829 (9)	0.0502 (3)
O1	0.41659 (6)	0.25871 (7)	0.12056 (10)	0.0521 (3)
O5	0.45866 (6)	0.16208 (7)	0.33354 (10)	0.0522 (3)
O7W	0.82663 (8)	0.36686 (8)	0.49953 (15)	0.0698 (4)
O6	0.45686 (8)	0.02935 (8)	0.34038 (13)	0.0695 (4)
O3	0.35256 (8)	0.40942 (8)	0.29279 (12)	0.0714 (4)
N2	0.28924 (8)	0.40160 (8)	0.65828 (12)	0.0507 (3)
O8W	0.87475 (9)	0.52183 (8)	0.53015 (16)	0.0762 (4)
N1	0.33363 (7)	0.16521 (9)	0.60672 (13)	0.0499 (3)
O4	0.31735 (7)	0.32756 (9)	0.06984 (14)	0.0767 (4)
N3	0.5000	0.87873 (15)	0.2500	0.0615 (5)
C6	0.30440 (7)	0.32468 (9)	0.64377 (12)	0.0405 (3)
N4	0.5000	0.63400 (15)	0.2500	0.0730 (7)
C1	0.39125 (9)	0.35760 (9)	0.26335 (14)	0.0475 (3)
C7	0.34073 (8)	0.29953 (10)	0.54716 (12)	0.0442 (3)
H7	0.3556	0.3370	0.4943	0.053*
C2	0.37147 (9)	0.31285 (10)	0.13931 (15)	0.0496 (4)
C5	0.28590 (9)	0.26379 (10)	0.72219 (14)	0.0483 (4)
H5	0.2636	0.2770	0.7888	0.058*
C3	0.47543 (8)	0.09271 (10)	0.30033 (14)	0.0486 (4)
C4	0.30043 (9)	0.18699 (11)	0.70089 (14)	0.0521 (4)
H4	0.2872	0.1478	0.7527	0.063*
C12	0.5000	0.71391 (15)	0.2500	0.0505 (5)
C8	0.35377 (8)	0.22127 (10)	0.53192 (14)	0.0476 (3)
H8	0.3773	0.2057	0.4679	0.057*
C10	0.30788 (12)	0.46256 (11)	0.57456 (17)	0.0626 (5)
H10A	0.3583	0.4633	0.5769	0.094*
H10B	0.2924	0.5138	0.5991	0.094*
H10C	0.2853	0.4508	0.4925	0.094*
C13	0.47586 (10)	0.75888 (12)	0.34435 (16)	0.0563 (4)
H13	0.4593	0.7330	0.4091	0.068*
C14	0.47685 (9)	0.83913 (12)	0.34033 (17)	0.0608 (4)
H14	0.4608	0.8678	0.4030	0.073*
C9	0.25007 (13)	0.42746 (13)	0.75514 (19)	0.0741 (6)
H9A	0.2037	0.4041	0.7419	0.111*
H9B	0.2460	0.4846	0.7537	0.111*
H9C	0.2748	0.4108	0.8336	0.111*
C11	0.47408 (17)	0.58935 (16)	0.3474 (3)	0.1074 (10)
H11A	0.5028	0.6012	0.4247	0.161*
H11B	0.4764	0.5332	0.3310	0.161*
H11C	0.4259	0.6041	0.3509	0.161*
H3	0.5000	0.934 (2)	0.2500	0.091 (11)*
H7WA	0.7843 (7)	0.3544 (19)	0.481 (3)	0.136*
H8WA	0.8595 (16)	0.4767 (9)	0.528 (3)	0.136*
H8WB	0.8988 (14)	0.5268 (17)	0.475 (2)	0.136*
H7WB	0.8432 (14)	0.3280 (13)	0.540 (3)	0.136*
H1	0.3406 (11)	0.1122 (13)	0.5955 (18)	0.068 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr1	0.04232 (19)	0.0513 (2)	0.03681 (16)	0.000	0.01578 (13)	0.000
O2	0.0557 (6)	0.0565 (7)	0.0411 (5)	0.0033 (5)	0.0164 (5)	−0.0054 (4)
O1	0.0505 (6)	0.0617 (7)	0.0445 (6)	−0.0005 (5)	0.0087 (5)	−0.0094 (5)
O5	0.0572 (7)	0.0538 (6)	0.0530 (6)	−0.0008 (5)	0.0318 (5)	−0.0011 (5)
O7W	0.0775 (9)	0.0497 (7)	0.0849 (10)	−0.0032 (7)	0.0211 (8)	−0.0005 (7)
O6	0.0851 (9)	0.0556 (7)	0.0795 (9)	−0.0022 (7)	0.0499 (8)	0.0054 (6)
O3	0.0916 (10)	0.0639 (8)	0.0653 (8)	0.0297 (7)	0.0330 (7)	0.0100 (6)
N2	0.0646 (8)	0.0478 (7)	0.0431 (6)	−0.0014 (6)	0.0191 (6)	−0.0055 (5)
O8W	0.0914 (11)	0.0531 (8)	0.0954 (11)	−0.0067 (7)	0.0501 (9)	−0.0132 (7)
N1	0.0509 (7)	0.0481 (8)	0.0498 (7)	0.0025 (6)	0.0041 (6)	−0.0044 (6)
O4	0.0598 (8)	0.0853 (10)	0.0794 (9)	0.0068 (7)	−0.0076 (7)	0.0037 (8)
N3	0.0568 (12)	0.0558 (13)	0.0701 (14)	0.000	0.0036 (10)	0.000
C6	0.0399 (7)	0.0492 (8)	0.0323 (6)	−0.0036 (6)	0.0057 (5)	−0.0039 (5)
N4	0.0845 (17)	0.0570 (13)	0.0703 (14)	0.000	−0.0111 (12)	0.000
C1	0.0565 (9)	0.0447 (8)	0.0467 (8)	0.0018 (7)	0.0250 (7)	0.0078 (6)
C7	0.0462 (8)	0.0530 (8)	0.0351 (6)	−0.0040 (6)	0.0123 (6)	−0.0008 (6)
C2	0.0469 (8)	0.0526 (9)	0.0512 (8)	−0.0051 (7)	0.0132 (7)	0.0065 (7)
C5	0.0542 (9)	0.0568 (9)	0.0363 (7)	−0.0040 (7)	0.0150 (6)	−0.0003 (6)
C3	0.0462 (8)	0.0569 (9)	0.0469 (8)	−0.0014 (7)	0.0205 (6)	0.0010 (7)
C4	0.0598 (10)	0.0540 (9)	0.0431 (8)	−0.0056 (7)	0.0098 (7)	0.0052 (7)
C12	0.0461 (12)	0.0573 (14)	0.0448 (11)	0.000	−0.0033 (9)	0.000
C8	0.0435 (8)	0.0603 (9)	0.0401 (7)	0.0017 (7)	0.0097 (6)	−0.0075 (6)
C10	0.0877 (14)	0.0462 (9)	0.0567 (10)	−0.0061 (9)	0.0197 (9)	−0.0016 (7)
C13	0.0509 (9)	0.0763 (13)	0.0430 (8)	−0.0002 (8)	0.0113 (7)	0.0062 (7)
C14	0.0546 (10)	0.0712 (12)	0.0572 (10)	0.0095 (9)	0.0107 (8)	−0.0094 (8)
C9	0.1006 (16)	0.0638 (12)	0.0665 (11)	0.0046 (11)	0.0406 (11)	−0.0154 (9)
C11	0.127 (2)	0.0759 (16)	0.108 (2)	−0.0233 (15)	−0.0179 (17)	0.0327 (14)

Geometric parameters (Å, º)

Cr1—O2^i	1.9577 (11)	C6—C5	1.416 (2)
Cr1—O2	1.9577 (11)	N4—C12	1.339 (3)
Cr1—O1^i	1.9728 (12)	N4—C11	1.455 (3)
Cr1—O1	1.9728 (12)	N4—C11^i	1.455 (3)
Cr1—O5^i	1.9804 (11)	C1—C2	1.553 (2)
Cr1—O5	1.9804 (11)	C7—H7	0.9300
O2—C1	1.2834 (19)	C7—C8	1.350 (2)
O1—C2	1.290 (2)	C5—H5	0.9300
O5—C3	1.274 (2)	C5—C4	1.344 (2)
O7W—H7WA	0.830 (10)	C3—C3^i	1.558 (3)
O7W—H7WB	0.822 (10)	C4—H4	0.9300
O6—C3	1.223 (2)	C12—C13^i	1.416 (2)
O3—C1	1.2162 (19)	C12—C13	1.416 (2)
N2—C6	1.336 (2)	C8—H8	0.9300
N2—C10	1.456 (2)	C10—H10A	0.9600
N2—C9	1.459 (2)	C10—H10B	0.9600
O8W—H8WA	0.810 (10)	C10—H10C	0.9600
O8W—H8WB	0.818 (10)	C13—H13	0.9300
N1—C4	1.346 (2)	C13—C14	1.345 (3)
N1—C8	1.343 (2)	C14—H14	0.9300
N1—H1	0.91 (2)	C9—H9A	0.9600
O4—C2	1.214 (2)	C9—H9B	0.9600
N3—C14^i	1.326 (2)	C9—H9C	0.9600
N3—C14	1.326 (2)	C11—H11A	0.9600
N3—H3	0.92 (4)	C11—H11B	0.9600
C6—C7	1.4200 (19)	C11—H11C	0.9600
O2^i—Cr1—O2	91.45 (7)	O4—C2—O1	124.63 (17)
O2—Cr1—O1	82.48 (5)	O4—C2—C1	121.68 (16)
O2—Cr1—O1^i	92.41 (5)	C6—C5—H5	119.8
O2^i—Cr1—O1	92.41 (5)	C4—C5—C6	120.39 (15)
O2^i—Cr1—O1^i	82.47 (5)	C4—C5—H5	119.8
O2—Cr1—O5^i	173.35 (5)	O5—C3—C3^i	114.17 (8)
O2—Cr1—O5	93.41 (5)	O6—C3—O5	126.08 (14)
O2^i—Cr1—O5	173.35 (5)	O6—C3—C3^i	119.75 (9)
O2^i—Cr1—O5^i	93.41 (5)	N1—C4—H4	119.1
O1—Cr1—O1^i	172.70 (7)	C5—C4—N1	121.88 (15)
O1—Cr1—O5^i	92.78 (5)	C5—C4—H4	119.1
O1^i—Cr1—O5	92.79 (5)	N4—C12—C13	122.15 (11)
O1—Cr1—O5	92.72 (5)	N4—C12—C13^i	122.15 (11)
O1^i—Cr1—O5^i	92.72 (5)	C13—C12—C13^i	115.7 (2)
O5^i—Cr1—O5	82.11 (6)	N1—C8—C7	121.82 (14)
C1—O2—Cr1	115.12 (10)	N1—C8—H8	119.1
C2—O1—Cr1	114.55 (10)	C7—C8—H8	119.1
C3—O5—Cr1	114.77 (9)	N2—C10—H10A	109.5
H7WA—O7W—H7WB	102 (2)	N2—C10—H10B	109.5
C6—N2—C10	121.50 (13)	N2—C10—H10C	109.5
C6—N2—C9	121.25 (15)	H10A—C10—H10B	109.5
C10—N2—C9	117.18 (15)	H10A—C10—H10C	109.5
H8WA—O8W—H8WB	108 (2)	H10B—C10—H10C	109.5
C4—N1—H1	117.7 (13)	C12—C13—H13	120.0
C8—N1—C4	119.70 (15)	C14—C13—C12	119.98 (17)
C8—N1—H1	122.5 (13)	C14—C13—H13	120.0
C14—N3—C14^i	120.0 (3)	N3—C14—C13	122.18 (19)
C14^i—N3—H3	120.02 (13)	N3—C14—H14	118.9
C14—N3—H3	120.01 (13)	C13—C14—H14	118.9
N2—C6—C7	121.05 (14)	N2—C9—H9A	109.5
N2—C6—C5	122.92 (13)	N2—C9—H9B	109.5
C5—C6—C7	116.04 (14)	N2—C9—H9C	109.5
C12—N4—C11^i	120.94 (15)	H9A—C9—H9B	109.5
C12—N4—C11	120.93 (15)	H9A—C9—H9C	109.5
C11^i—N4—C11	118.1 (3)	H9B—C9—H9C	109.5
O2—C1—C2	113.93 (13)	N4—C11—H11A	109.5
O3—C1—O2	125.85 (16)	N4—C11—H11B	109.5
O3—C1—C2	120.19 (15)	N4—C11—H11C	109.5
C6—C7—H7	119.9	H11A—C11—H11B	109.5
C8—C7—C6	120.14 (14)	H11A—C11—H11C	109.5
C8—C7—H7	119.9	H11B—C11—H11C	109.5
O1—C2—C1	113.67 (13)
Cr1—O2—C1—O3	−177.75 (14)	C7—C6—C5—C4	−2.3 (2)
Cr1—O2—C1—C2	4.37 (16)	C5—C6—C7—C8	2.0 (2)
Cr1—O1—C2—O4	178.94 (14)	C4—N1—C8—C7	−1.0 (2)
Cr1—O1—C2—C1	−2.76 (16)	C12—C13—C14—N3	−0.1 (3)
Cr1—O5—C3—O6	179.09 (15)	C8—N1—C4—C5	0.7 (2)
Cr1—O5—C3—C3^i	−0.6 (2)	C10—N2—C6—C7	1.3 (2)
O2—C1—C2—O1	−1.05 (19)	C10—N2—C6—C5	−178.85 (16)
O2—C1—C2—O4	177.30 (15)	C13^i—C12—C13—C14	0.02 (12)
O3—C1—C2—O1	−179.06 (15)	C14^i—N3—C14—C13	0.03 (13)
O3—C1—C2—O4	−0.7 (2)	C9—N2—C6—C7	178.16 (16)
N2—C6—C7—C8	−178.10 (14)	C9—N2—C6—C5	−2.0 (3)
N2—C6—C5—C4	177.81 (15)	C11^i—N4—C12—C13	−179.27 (16)
C6—C7—C8—N1	−0.4 (2)	C11^i—N4—C12—C13^i	0.74 (16)
C6—C5—C4—N1	1.0 (3)	C11—N4—C12—C13^i	−179.26 (16)
N4—C12—C13—C14	−179.98 (12)	C11—N4—C12—C13	0.74 (16)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O8W^ii	0.91 (2)	1.84 (2)	2.702 (2)	157.8 (19)
N3—H3···O6^iii	0.92 (4)	2.12 (3)	2.879 (3)	139 (1)
N3—H3···O6^iv	0.92 (4)	2.12 (3)	2.879 (3)	139 (1)
O7W—H7WA···O4^i	0.83 (1)	1.99 (1)	2.819 (2)	178 (3)
O7W—H7WB···O1^v	0.82 (1)	2.12 (1)	2.9079 (19)	161 (3)
O8W—H8WA···O7W	0.81 (1)	1.95 (1)	2.7578 (19)	172 (3)
O8W—H8WB···O6^vi	0.82 (1)	1.99 (1)	2.8007 (19)	175 (3)

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