A second tetragonal polymorph of bis­(tetra-n-butyl­ammonium) tetrakis­[chloro(μ₃-sulfido)­copper(I)]­molybdate(VI)

The title compound, bis­(tetra-n-butyl­ammonium) tetra­chloro­tetra-μ₃-sulfidotetracopper(I)molybdenum(VI), (C₁₆H₃₆N)₂[MoS₄(CuCl)₄], has been obtained in a second polymorphic form. The anion, in which four of the six S...S edges of the central MoS₄ tetrahedron are bridged by CuCl neutral molecular units to give a planar pentanuclear MoCu₄ framework, is disordered on a crystallographic fourfold rotation axis, requiring equal occupancy of two sets of four positions for the S atoms. There is additional disorder as a result of 8.2 (2)% substitution of Cl by Br, arising from tetra-n-butyl­ammonium bromide used in the synthesis. Copper has distorted trigonal planar coordination, involving two μ₃-S atoms and a terminal halogen atom. The two independent cations lie on positions of symmetry .

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.024
• wR factor = 0.058
• Data-to-parameter ratio = 23.5

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSTM02_ALERT_3_B  The ratio of expected to reported Tmax/Tmin(RR) is > 1.50
            Tmin and Tmax reported:      0.701     0.876
            Tmin and Tmax expected:      0.363     0.876
            RR =      1.932
            Please check that your absorption correction is appropriate.
PLAT060_ALERT_3_B Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.94

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT301_ALERT_3_C Main Residue  Disorder .........................      10.00 Perc.

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   5 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
   0 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

(I)

Crystal data

(C16H36N)2[MoS4(CuCl)4]	Dx = 1.532 Mg m^−3
Mr = 1119.51	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/n	Cell parameters from 86 reflections
a = 13.3356 (6) Å	θ = 2.5–25.0°
c = 13.6495 (9) Å	µ = 2.64 mm^−1
V = 2427.4 (2) Å^3	T = 150 K
Z = 2	Plate, purple
F(000) = 1148	0.40 × 0.40 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer	2796 independent reflections
Radiation source: sealed tube	2191 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 27.5°, θmin = 4.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −17→17
Tmin = 0.701, Tmax = 0.876	k = −15→17
19584 measured reflections	l = −17→17

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.058	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0191P)^2 + 1.5691P] where P = (Fo^2 + 2Fc^2)/3
2796 reflections	(Δ/σ)max = 0.001
119 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mo	0.2500	0.2500	0.26798 (2)	0.02315 (9)
Cu	0.066050 (18)	0.319184 (19)	0.262395 (18)	0.02955 (8)
Cl	−0.08479 (3)	0.37625 (4)	0.25092 (3)	0.0390 (2)	0.918 (2)
Br	−0.08479 (3)	0.37625 (4)	0.25092 (3)	0.0390 (2)	0.082 (2)
S	0.19314 (8)	0.37513 (9)	0.17358 (8)	0.0326 (2)	0.50
S'	0.19175 (8)	0.37831 (8)	0.35937 (7)	0.0287 (2)	0.50
N1	0.7500	0.2500	0.0000	0.0221 (7)
C1	0.83183 (14)	0.28816 (14)	−0.06781 (13)	0.0254 (4)
H1A	0.8485	0.2339	−0.1145	0.030*
H1B	0.8040	0.3445	−0.1064	0.030*
C2	0.92831 (15)	0.32343 (15)	−0.02096 (15)	0.0294 (4)
H2A	0.9630	0.2664	0.0107	0.035*
H2B	0.9138	0.3745	0.0297	0.035*
C3	0.99475 (17)	0.36846 (18)	−0.10127 (17)	0.0394 (5)
H3A	1.0003	0.3200	−0.1559	0.047*
H3B	0.9625	0.4299	−0.1270	0.047*
C4	1.09892 (18)	0.39429 (19)	−0.0651 (2)	0.0546 (7)
H4A	1.0939	0.4405	−0.0095	0.082*
H4B	1.1370	0.4262	−0.1181	0.082*
H4C	1.1333	0.3329	−0.0444	0.082*
N2	0.7500	0.2500	0.5000	0.0243 (7)
C5	0.82834 (15)	0.29530 (15)	0.56782 (14)	0.0273 (4)
H5A	0.7941	0.3422	0.6130	0.033*
H5B	0.8573	0.2407	0.6080	0.033*
C6	0.91377 (16)	0.35107 (18)	0.51841 (16)	0.0383 (5)
H6A	0.8874	0.4116	0.4852	0.046*
H6B	0.9451	0.3075	0.4683	0.046*
C7	0.99263 (18)	0.38174 (17)	0.59482 (18)	0.0411 (6)
H7A	1.0366	0.4338	0.5660	0.049*
H7B	0.9580	0.4119	0.6518	0.049*
C8	1.05661 (19)	0.2959 (2)	0.62988 (19)	0.0497 (7)
H8A	1.0139	0.2449	0.6604	0.075*
H8B	1.1053	0.3206	0.6779	0.075*
H8C	1.0923	0.2664	0.5741	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo	0.02494 (12)	0.02494 (12)	0.01956 (16)	0.000	0.000	0.000
Cu	0.02496 (14)	0.03581 (15)	0.02788 (14)	0.00148 (11)	−0.00074 (10)	0.00147 (11)
Cl	0.0252 (3)	0.0633 (4)	0.0286 (3)	0.0060 (2)	−0.00074 (18)	0.0018 (2)
Br	0.0252 (3)	0.0633 (4)	0.0286 (3)	0.0060 (2)	−0.00074 (18)	0.0018 (2)
S	0.0252 (5)	0.0437 (6)	0.0290 (5)	−0.0016 (5)	−0.0023 (4)	0.0128 (5)
S'	0.0285 (5)	0.0318 (6)	0.0259 (5)	−0.0023 (4)	0.0028 (4)	−0.0072 (4)
N1	0.0235 (10)	0.0235 (10)	0.0192 (15)	0.000	0.000	0.000
C1	0.0296 (11)	0.0239 (10)	0.0225 (9)	0.0005 (8)	0.0054 (8)	0.0008 (8)
C2	0.0299 (11)	0.0280 (11)	0.0305 (10)	−0.0010 (9)	0.0065 (9)	−0.0008 (8)
C3	0.0387 (13)	0.0354 (13)	0.0442 (13)	−0.0028 (10)	0.0155 (10)	0.0022 (10)
C4	0.0377 (14)	0.0411 (14)	0.085 (2)	−0.0092 (11)	0.0174 (14)	0.0015 (14)
N2	0.0258 (11)	0.0258 (11)	0.0213 (16)	0.000	0.000	0.000
C5	0.0301 (11)	0.0278 (11)	0.0240 (9)	−0.0025 (8)	−0.0051 (8)	0.0001 (8)
C6	0.0377 (13)	0.0427 (13)	0.0345 (11)	−0.0124 (10)	−0.0078 (10)	0.0089 (10)
C7	0.0422 (14)	0.0384 (13)	0.0428 (13)	−0.0135 (11)	−0.0107 (11)	0.0037 (10)
C8	0.0412 (14)	0.0592 (17)	0.0487 (15)	−0.0090 (12)	−0.0086 (11)	0.0062 (13)

Geometric parameters (Å, º)

Mo—Cu	2.6220 (3)	C2—H2B	0.990
Mo—Cu^i	2.6220 (3)	C2—C3	1.532 (3)
Mo—Cu^ii	2.6220 (3)	C3—H3A	0.990
Mo—Cu^iii	2.6220 (3)	C3—H3B	0.990
Mo—S	2.2406 (10)	C3—C4	1.514 (3)
Mo—S^i	2.2406 (10)	C4—H4A	0.980
Mo—S^ii	2.2406 (10)	C4—H4B	0.980
Mo—S^iii	2.2406 (10)	C4—H4C	0.980
Mo—S'	2.2556 (10)	N2—C5	1.5210 (18)
Mo—S'^i	2.2556 (10)	N2—C5^iv	1.5210 (18)
Mo—S'^iii	2.2556 (10)	N2—C5^vii	1.5210 (18)
Mo—S'^ii	2.2556 (10)	N2—C5^viii	1.5210 (18)
Cu—Cl	2.1563 (5)	C5—H5A	0.990
Cu—S	2.2134 (10)	C5—H5B	0.990
Cu—S^ii	2.2159 (11)	C5—C6	1.519 (3)
Cu—S'	2.2768 (10)	C6—H6A	0.990
Cu—S'^ii	2.2783 (10)	C6—H6B	0.990
N1—C1	1.5187 (18)	C6—C7	1.536 (3)
N1—C1^iv	1.5187 (18)	C7—H7A	0.990
N1—C1^v	1.5187 (18)	C7—H7B	0.990
N1—C1^vi	1.5187 (18)	C7—C8	1.505 (3)
C1—H1A	0.990	C8—H8A	0.980
C1—H1B	0.990	C8—H8B	0.980
C1—C2	1.512 (3)	C8—H8C	0.980
C2—H2A	0.990
S^ii—Mo—S^iii	109.78 (6)	C2—C3—H3A	109.0
S—Mo—S^i	109.78 (6)	C2—C3—H3B	109.0
S^i—Mo—S'^iii	108.53 (4)	C2—C3—C4	112.7 (2)
S—Mo—S'^iii	108.56 (4)	H3A—C3—H3B	107.8
S^ii—Mo—S'	108.56 (4)	H3A—C3—C4	109.0
S^iii—Mo—S'	108.53 (4)	H3B—C3—C4	109.0
S^i—Mo—S'^ii	108.56 (4)	C3—C4—H4A	109.5
S—Mo—S'^ii	108.53 (4)	C3—C4—H4B	109.5
S^ii—Mo—S'^i	108.53 (4)	C3—C4—H4C	109.5
S^iii—Mo—S'^i	108.56 (4)	H4A—C4—H4B	109.5
S'^iii—Mo—S'^ii	112.85 (5)	H4A—C4—H4C	109.5
S'—Mo—S'^i	112.85 (5)	H4B—C4—H4C	109.5
Cl—Cu—S	123.75 (3)	C5—N2—C5^vii	111.74 (8)
Cl—Cu—S^ii	123.93 (3)	C5—N2—C5^viii	111.74 (8)
Cl—Cu—S'	127.36 (3)	C5^vii—N2—C5^viii	105.02 (15)
Cl—Cu—S'^ii	127.53 (3)	C5—N2—C5^iv	105.02 (15)
S^ii—Cu—S'	108.67 (4)	C5^vii—N2—C5^iv	111.74 (8)
S—Cu—S'^ii	108.68 (4)	C5^viii—N2—C5^iv	111.74 (8)
Mo—S—Cu	72.12 (3)	N2—C5—H5A	108.3
Mo—S—Cu^iii	72.08 (3)	N2—C5—H5B	108.3
Cu—S—Cu^iii	113.61 (5)	N2—C5—C6	116.08 (15)
Mo—S'—Cu	70.69 (3)	H5A—C5—H5B	107.4
Mo—S'—Cu^iii	70.66 (3)	H5A—C5—C6	108.3
Cu—S'—Cu^iii	108.91 (4)	H5B—C5—C6	108.3
C1^iv—N1—C1^vi	111.81 (8)	C5—C6—H6A	109.7
C1—N1—C1^iv	104.90 (14)	C5—C6—H6B	109.7
C1—N1—C1^vi	111.81 (8)	C5—C6—C7	110.02 (18)
C1^iv—N1—C1^v	111.81 (8)	H6A—C6—H6B	108.2
C1^vi—N1—C1^v	104.90 (14)	H6A—C6—C7	109.7
C1—N1—C1^v	111.81 (8)	H6B—C6—C7	109.7
N1—C1—H1A	108.0	C6—C7—H7A	108.8
N1—C1—H1B	108.0	C6—C7—H7B	108.8
N1—C1—C2	117.25 (14)	C6—C7—C8	113.7 (2)
H1A—C1—H1B	107.2	H7A—C7—H7B	107.7
H1A—C1—C2	108.0	H7A—C7—C8	108.8
H1B—C1—C2	108.0	H7B—C7—C8	108.8
C1—C2—H2A	110.1	C7—C8—H8A	109.5
C1—C2—H2B	110.1	C7—C8—H8B	109.5
C1—C2—C3	108.14 (17)	C7—C8—H8C	109.5
H2A—C2—H2B	108.4	H8A—C8—H8B	109.5
H2A—C2—C3	110.1	H8A—C8—H8C	109.5
H2B—C2—C3	110.1	H8B—C8—H8C	109.5
C1^iv—N1—C1—C2	−175.0 (2)	C5^vii—N2—C5—C6	61.8 (2)
C1^vi—N1—C1—C2	63.7 (2)	C5^viii—N2—C5—C6	−55.6 (2)
C1^v—N1—C1—C2	−53.6 (2)	C5^iv—N2—C5—C6	−176.9 (2)
N1—C1—C2—C3	−174.11 (15)	N2—C5—C6—C7	−173.47 (16)
C1—C2—C3—C4	−172.65 (19)	C5—C6—C7—C8	74.8 (3)

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