Crystal structure of 1,4,8,11-tetra­methyl-1,4,8,11-tetra­azonia­cyclo­tetra­decane bis­[chlorido­chromate(VI)] dichloride from synchrotron X-ray data

The asymmetric unit of the title compound, (C₁₄H₃₆N₄)[CrO₃Cl]₂Cl₂, contains one half-cation (completed by crystallographic inversion symmetry), one chloro­chromate anion and one chloride anion. In the crystal, N—H...Cl, C—H...Cl and C—H...O hydrogen bonds connect the organic cations, chloro­chromate and chloride anions, forming a three-dimensional network.

Key indicators

• Single-crystal synchrotron study
• T = 220 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.050
• wR factor = 0.150
• Data-to-parameter ratio = 25.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT244_ALERT_4_C Low    Solvent Ueq as Compared to Neighbors of        Cr1 Check
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A      ..CL2      .       2.85 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5AB     ..CL1      .       2.86 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4B      ..CL1      .       2.88 Ang.
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         14 Report
PLAT918_ALERT_3_C Reflection(s) with I(obs) much Smaller I(calc) .          1 Check
PLAT975_ALERT_2_C Check Calcd Resid. Dens.  0.84A   From O3              0.53 eA-3

Alert level G
ABSMU01_ALERT_1_G  Calculation of _exptl_absorpt_correction_mu
                not performed for this radiation type.
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT013_ALERT_1_G N.O.K.   _shelx_hkl_checksum Found in CIF ......     Please Check
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT  Unusually Large       0.10 Report
PLAT092_ALERT_4_G Check: Wavelength Given is not Cu,Ga,Mo,Ag,In Ka    0.61000 Ang.
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)       0.03 Degree
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          3 Note
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          5 Note
PLAT793_ALERT_4_G Model has Chirality at N1          (Centro SPGR)          S Verify
PLAT793_ALERT_4_G Model has Chirality at N2          (Centro SPGR)          R Verify
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

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

   4 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
   3 ALERT type 3 Indicator that the structure quality may be low
   9 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

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: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND4 (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

1,4,8,11-Tetramethyl-1,4,8,11-tetraazoniacyclotetradecane bis[chloridochromate(VI)] dichloride

Crystal data

(C14H36N4)[CrO3Cl]2Cl2	Z = 1
Mr = 602.27	F(000) = 312
Triclinic, P1	Dx = 1.579 Mg m^−3
a = 7.0610 (14) Å	Synchrotron radiation, λ = 0.610 Å
b = 8.6740 (17) Å	Cell parameters from 41622 reflections
c = 10.775 (2) Å	θ = 0.4–33.7°
α = 77.61 (3)°	µ = 0.85 mm^−1
β = 88.20 (3)°	T = 220 K
γ = 79.39 (3)°	Block, red
V = 633.5 (2) Å^3	0.21 × 0.15 × 0.11 mm

Data collection

Rayonix MX225HS CCD area detector diffractometer	3357 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.022
ω scan	θmax = 25.0°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements) (HKL3000sm Scalepack; Otwinowski & Minor, 1997)	h = −9→9
Tmin = 0.552, Tmax = 1.000	k = −12→12
6933 measured reflections	l = −14→14
3503 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.150	w = 1/[σ^2(Fo^2) + (0.1021P)^2 + 0.4428P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3503 reflections	Δρmax = 0.81 e Å^−3
138 parameters	Δρmin = −1.08 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
N1	0.5951 (2)	0.43908 (19)	0.24944 (14)	0.0197 (3)
H1	0.655924	0.528759	0.203398	0.024*
N2	0.3111 (2)	0.75634 (17)	0.10259 (15)	0.0178 (3)
H2	0.448197	0.736710	0.077822	0.021*
C1	0.8079 (3)	0.1708 (2)	0.01696 (18)	0.0203 (3)
H1A	0.942223	0.140900	−0.007767	0.024*
H1AB	0.763915	0.071671	0.058488	0.024*
C2	0.8030 (2)	0.2755 (2)	0.11389 (17)	0.0202 (3)
H2A	0.850838	0.373545	0.074404	0.024*
H2AB	0.889395	0.217967	0.184918	0.024*
C3	0.6013 (3)	0.3211 (2)	0.16488 (18)	0.0216 (3)
H3A	0.511705	0.368064	0.093415	0.026*
H3AB	0.559012	0.224125	0.212911	0.026*
C4	0.7083 (4)	0.3635 (3)	0.3696 (2)	0.0350 (5)
H4A	0.710246	0.443738	0.419628	0.052*
H4B	0.839127	0.320257	0.348638	0.052*
H4C	0.648561	0.277582	0.418098	0.052*
C5	0.3917 (3)	0.5084 (2)	0.28166 (17)	0.0214 (3)
H5A	0.398383	0.581772	0.338417	0.026*
H5AB	0.331618	0.420559	0.329015	0.026*
C6	0.2612 (2)	0.5985 (2)	0.16973 (17)	0.0191 (3)
H6A	0.265642	0.529620	0.108100	0.023*
H6AB	0.128516	0.617792	0.200171	0.023*
C7	0.2870 (3)	0.8760 (2)	0.1871 (2)	0.0287 (4)
H7A	0.309296	0.978749	0.138299	0.043*
H7B	0.378911	0.838265	0.256843	0.043*
H7C	0.157143	0.888100	0.220467	0.043*
Cr1	0.20005 (5)	0.19152 (4)	0.58525 (3)	0.02581 (14)
Cl1	0.21038 (11)	0.11680 (9)	0.40216 (7)	0.04726 (19)
O1	0.2178 (4)	0.0382 (3)	0.6983 (2)	0.0578 (6)
O2	0.0005 (3)	0.3102 (3)	0.59266 (19)	0.0461 (5)
O3	0.3790 (3)	0.2812 (3)	0.5855 (2)	0.0459 (5)
Cl2	0.74460 (6)	0.71108 (6)	0.05475 (5)	0.02599 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0203 (7)	0.0201 (7)	0.0179 (6)	−0.0016 (5)	−0.0003 (5)	−0.0042 (5)
N2	0.0161 (6)	0.0139 (6)	0.0231 (7)	−0.0019 (5)	0.0036 (5)	−0.0049 (5)
C1	0.0175 (7)	0.0155 (7)	0.0252 (8)	0.0018 (6)	0.0016 (6)	−0.0024 (6)
C2	0.0168 (7)	0.0194 (8)	0.0226 (8)	−0.0002 (6)	0.0009 (6)	−0.0030 (6)
C3	0.0189 (8)	0.0223 (8)	0.0244 (8)	−0.0023 (6)	0.0029 (6)	−0.0085 (6)
C4	0.0384 (12)	0.0407 (12)	0.0216 (9)	0.0067 (9)	−0.0102 (8)	−0.0078 (8)
C5	0.0220 (8)	0.0216 (8)	0.0192 (7)	−0.0018 (6)	0.0050 (6)	−0.0038 (6)
C6	0.0174 (7)	0.0155 (7)	0.0239 (8)	−0.0034 (5)	0.0041 (6)	−0.0030 (6)
C7	0.0381 (11)	0.0196 (8)	0.0312 (9)	−0.0048 (7)	0.0047 (8)	−0.0124 (7)
Cr1	0.0292 (2)	0.0227 (2)	0.0242 (2)	−0.00618 (13)	0.00070 (13)	−0.00076 (13)
Cl1	0.0520 (4)	0.0530 (4)	0.0450 (4)	−0.0119 (3)	0.0076 (3)	−0.0274 (3)
O1	0.0855 (18)	0.0349 (10)	0.0450 (11)	−0.0130 (10)	−0.0045 (11)	0.0111 (8)
O2	0.0433 (10)	0.0534 (11)	0.0367 (9)	0.0066 (9)	0.0027 (7)	−0.0126 (8)
O3	0.0468 (11)	0.0535 (12)	0.0454 (10)	−0.0246 (9)	−0.0010 (8)	−0.0141 (9)
Cl2	0.0172 (2)	0.0255 (2)	0.0356 (3)	−0.00824 (16)	0.00510 (17)	−0.00431 (19)

Geometric parameters (Å, º)

N1—C4	1.501 (2)	C4—H4A	0.9700
N1—C3	1.503 (2)	C4—H4B	0.9700
N1—C5	1.511 (2)	C4—H4C	0.9700
N1—H1	0.9900	C5—C6	1.521 (3)
N2—C6	1.503 (2)	C5—H5A	0.9800
N2—C7	1.505 (2)	C5—H5AB	0.9800
N2—C1^i	1.513 (2)	C6—H6A	0.9800
N2—H2	0.9900	C6—H6AB	0.9800
C1—C2	1.520 (3)	C7—H7A	0.9700
C1—H1A	0.9800	C7—H7B	0.9700
C1—H1AB	0.9800	C7—H7C	0.9700
C2—C3	1.524 (2)	Cr1—O1	1.588 (2)
C2—H2A	0.9800	Cr1—O2	1.596 (2)
C2—H2AB	0.9800	Cr1—O3	1.602 (2)
C3—H3A	0.9800	Cr1—Cl1	2.2000 (9)
C3—H3AB	0.9800
C4—N1—C3	110.93 (15)	N1—C4—H4A	109.5
C4—N1—C5	109.63 (15)	N1—C4—H4B	109.5
C3—N1—C5	112.58 (14)	H4A—C4—H4B	109.5
C4—N1—H1	107.8	N1—C4—H4C	109.5
C3—N1—H1	107.8	H4A—C4—H4C	109.5
C5—N1—H1	107.8	H4B—C4—H4C	109.5
C6—N2—C7	112.00 (15)	N1—C5—C6	116.12 (14)
C6—N2—C1^i	112.21 (14)	N1—C5—H5A	108.3
C7—N2—C1^i	108.81 (14)	C6—C5—H5A	108.3
C6—N2—H2	107.9	N1—C5—H5AB	108.3
C7—N2—H2	107.9	C6—C5—H5AB	108.3
C1^i—N2—H2	107.9	H5A—C5—H5AB	107.4
N2^i—C1—C2	116.39 (14)	N2—C6—C5	115.04 (15)
N2^i—C1—H1A	108.2	N2—C6—H6A	108.5
C2—C1—H1A	108.2	C5—C6—H6A	108.5
N2^i—C1—H1AB	108.2	N2—C6—H6AB	108.5
C2—C1—H1AB	108.2	C5—C6—H6AB	108.5
H1A—C1—H1AB	107.3	H6A—C6—H6AB	107.5
C1—C2—C3	112.61 (15)	N2—C7—H7A	109.5
C1—C2—H2A	109.1	N2—C7—H7B	109.5
C3—C2—H2A	109.1	H7A—C7—H7B	109.5
C1—C2—H2AB	109.1	N2—C7—H7C	109.5
C3—C2—H2AB	109.1	H7A—C7—H7C	109.5
H2A—C2—H2AB	107.8	H7B—C7—H7C	109.5
N1—C3—C2	111.86 (15)	O1—Cr1—O2	110.49 (14)
N1—C3—H3A	109.2	O1—Cr1—O3	111.05 (14)
C2—C3—H3A	109.2	O2—Cr1—O3	111.22 (13)
N1—C3—H3AB	109.2	O1—Cr1—Cl1	109.69 (10)
C2—C3—H3AB	109.2	O2—Cr1—Cl1	108.34 (8)
H3A—C3—H3AB	107.9	O3—Cr1—Cl1	105.90 (9)
N2^i—C1—C2—C3	61.3 (2)	C3—N1—C5—C6	−59.5 (2)
C4—N1—C3—C2	−67.1 (2)	C7—N2—C6—C5	−64.42 (19)
C5—N1—C3—C2	169.64 (15)	C1^i—N2—C6—C5	172.85 (14)
C1—C2—C3—N1	−173.71 (14)	N1—C5—C6—N2	−69.9 (2)
C4—N1—C5—C6	176.52 (17)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.99	2.16	3.120 (2)	163
N2—H2···Cl2	0.99	2.08	3.0553 (17)	170
C2—H2A···Cl2	0.98	2.85	3.642 (2)	139
C4—H4C···O3	0.97	2.58	3.299 (4)	131
C5—H5AB···Cl1	0.98	2.86	3.804 (2)	161
C3—H3A···Cl2^i	0.98	2.72	3.541 (2)	142
C1—H1A···Cl2^ii	0.98	2.74	3.511 (2)	136
C1—H1AB···O1^iii	0.98	2.59	3.230 (3)	123
C2—H2AB···O1^iii	0.98	2.54	3.047 (3)	112
C3—H3AB···O1^iii	0.98	2.53	3.193 (3)	125
C4—H4A···O3^iv	0.97	2.34	3.168 (3)	143
C5—H5A···O3^iv	0.98	2.40	3.218 (3)	141
C7—H7B···O3^iv	0.97	2.38	3.343 (3)	173
C4—H4B···Cl1^v	0.97	2.88	3.773 (3)	154
C6—H6AB···O2^vi	0.98	2.54	3.260 (3)	130

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