Bis­(tetraethyl­ammonium) bis­[cyano­cuprate(I)]­tetra­thio­molybdate(VI) hydrate

The title complex, (C₈H₂₀N)₂[MoS₄(CuCN)₂]·H₂O, contains an anion in which Cu atoms bridge two opposite S...S edges of the central MoS₄ unit. The Mo atom retains tetrahedral coordination geometry, while each Cu is trigonal planar coordinated by two bridging sulfides and a terminal cyano ligand. The anions are linked together into chains by hydrogen bonding to ordered water mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 160 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.024
• wR factor = 0.056
• Data-to-parameter ratio = 24.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.60
         From the CIF: _reflns_number_total               7028
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         7532
         Completeness (_total/calc)             93.31%
          Alert C: < 95% complete


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

(I)

Crystal data

(C8H20N)2[Cu2MoS4(CN)2]·H2O	F(000) = 1400
Mr = 681.82	Dx = 1.539 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.1202 (5) Å	Cell parameters from 19634 reflections
b = 7.1989 (3) Å	θ = 2.3–28.6°
c = 29.3581 (10) Å	µ = 2.15 mm^−1
β = 99.592 (2)°	T = 160 K
V = 2942.53 (19) Å^3	Block, orange
Z = 4	0.36 × 0.26 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer	7028 independent reflections
Radiation source: fine-focus sealed tube	6142 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 8.192 pixels mm^-1	θmax = 28.6°, θmin = 1.7°
ω rotation with narrow frames scans	h = −18→18
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a)	k = −9→9
Tmin = 0.511, Tmax = 0.725	l = −38→39
24398 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.056	w = 1/[σ^2(Fo^2) + (0.0244P)^2 + 1.151P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.003
7028 reflections	Δρmax = 0.42 e Å^−3
288 parameters	Δρmin = −0.36 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00051 (8)

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

	x	y	z	Uiso*/Ueq
Mo	0.778068 (10)	0.73485 (2)	0.613186 (5)	0.02367 (5)
S1	0.87452 (3)	0.73525 (7)	0.560607 (16)	0.02997 (10)
S2	0.85343 (4)	0.88526 (7)	0.674149 (17)	0.03474 (11)
S3	0.74611 (3)	0.44865 (7)	0.633126 (16)	0.03043 (10)
S4	0.63931 (4)	0.87262 (7)	0.587334 (19)	0.03657 (12)
Cu1	0.949058 (16)	0.88778 (3)	0.621687 (8)	0.02974 (6)
C1	1.07246 (14)	0.9966 (3)	0.62972 (7)	0.0336 (4)
N1	1.14702 (13)	1.0610 (3)	0.63486 (7)	0.0478 (5)
Cu2	0.607099 (16)	0.59106 (3)	0.610582 (8)	0.03120 (6)
C2	0.48418 (14)	0.5023 (3)	0.61730 (7)	0.0324 (4)
N2	0.41147 (12)	0.4554 (3)	0.62476 (7)	0.0432 (4)
N3	1.00752 (11)	0.3916 (2)	0.75999 (5)	0.0264 (3)
C3	0.90851 (14)	0.3327 (3)	0.73621 (7)	0.0364 (4)
H3A	0.8693	0.4457	0.7280	0.044*
H3B	0.9150	0.2688	0.7070	0.044*
C4	0.85506 (17)	0.2060 (4)	0.76431 (8)	0.0491 (6)
H4A	0.8925	0.0925	0.7722	0.074*
H4B	0.7925	0.1739	0.7462	0.074*
H4C	0.8456	0.2697	0.7927	0.074*
C5	1.00345 (14)	0.4711 (3)	0.80763 (6)	0.0310 (4)
H5A	0.9900	0.3684	0.8281	0.037*
H5B	1.0675	0.5218	0.8205	0.037*
C6	0.92986 (17)	0.6212 (3)	0.80906 (8)	0.0445 (5)
H6A	0.9439	0.7264	0.7901	0.067*
H6B	0.9320	0.6625	0.8410	0.067*
H6C	0.8658	0.5725	0.7970	0.067*
C7	1.04516 (15)	0.5426 (3)	0.73140 (7)	0.0333 (4)
H7A	0.9995	0.6480	0.7283	0.040*
H7B	1.1072	0.5880	0.7485	0.040*
C8	1.05984 (17)	0.4838 (3)	0.68367 (7)	0.0450 (5)
H8A	1.1053	0.3800	0.6862	0.068*
H8B	1.0855	0.5885	0.6682	0.068*
H8C	0.9983	0.4449	0.6657	0.068*
C9	1.07298 (15)	0.2228 (3)	0.76485 (7)	0.0366 (4)
H9A	1.0486	0.1324	0.7855	0.044*
H9B	1.0687	0.1636	0.7341	0.044*
C10	1.17764 (16)	0.2603 (3)	0.78349 (9)	0.0510 (6)
H10A	1.2048	0.3399	0.7618	0.077*
H10B	1.2129	0.1425	0.7873	0.077*
H10C	1.1831	0.3229	0.8135	0.077*
N4	0.76295 (11)	0.2435 (2)	0.47284 (5)	0.0271 (3)
C11	0.85946 (15)	0.1487 (3)	0.48631 (7)	0.0348 (4)
H11A	0.8890	0.1339	0.4582	0.042*
H11B	0.8484	0.0228	0.4979	0.042*
C12	0.93053 (16)	0.2489 (3)	0.52267 (8)	0.0428 (5)
H12A	0.9441	0.3723	0.5112	0.064*
H12B	0.9903	0.1772	0.5292	0.064*
H12C	0.9031	0.2617	0.5510	0.064*
C13	0.77522 (14)	0.4405 (2)	0.45617 (6)	0.0295 (4)
H13A	0.7108	0.4943	0.4456	0.035*
H13B	0.8066	0.5158	0.4827	0.035*
C14	0.83351 (16)	0.4574 (3)	0.41737 (7)	0.0407 (5)
H14A	0.8981	0.4073	0.4276	0.061*
H14B	0.8382	0.5884	0.4090	0.061*
H14C	0.8019	0.3872	0.3905	0.061*
C15	0.70351 (15)	0.1337 (3)	0.43394 (7)	0.0341 (4)
H15A	0.6448	0.2055	0.4220	0.041*
H15B	0.7409	0.1212	0.4084	0.041*
C16	0.6740 (2)	−0.0585 (3)	0.44732 (9)	0.0577 (7)
H16A	0.7314	−0.1306	0.4597	0.087*
H16B	0.6389	−0.1215	0.4200	0.087*
H16C	0.6326	−0.0478	0.4709	0.087*
C17	0.71310 (15)	0.2522 (3)	0.51470 (7)	0.0368 (5)
H17A	0.7123	0.1258	0.5279	0.044*
H17B	0.7516	0.3321	0.5383	0.044*
C18	0.61144 (16)	0.3252 (4)	0.50570 (8)	0.0515 (6)
H18A	0.6114	0.4530	0.4942	0.077*
H18B	0.5849	0.3231	0.5345	0.077*
H18C	0.5721	0.2469	0.4826	0.077*
O1	0.30345 (13)	0.2693 (3)	0.68701 (6)	0.0472 (4)
H1A	0.261 (2)	0.214 (4)	0.6721 (11)	0.068 (10)*
H1B	0.3263 (19)	0.324 (4)	0.6682 (10)	0.055 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo	0.02510 (8)	0.02423 (8)	0.02190 (8)	−0.00257 (6)	0.00457 (6)	−0.00003 (6)
S1	0.0342 (2)	0.0325 (2)	0.0245 (2)	−0.00403 (18)	0.00871 (18)	−0.00215 (18)
S2	0.0377 (3)	0.0391 (3)	0.0288 (2)	−0.0091 (2)	0.00953 (19)	−0.0104 (2)
S3	0.0326 (2)	0.0284 (2)	0.0292 (2)	−0.00338 (18)	0.00193 (18)	0.00410 (18)
S4	0.0306 (2)	0.0352 (3)	0.0444 (3)	0.0023 (2)	0.0075 (2)	0.0112 (2)
Cu1	0.02803 (12)	0.03011 (12)	0.03154 (12)	−0.00591 (9)	0.00631 (9)	−0.00216 (9)
C1	0.0358 (10)	0.0308 (10)	0.0352 (10)	−0.0041 (8)	0.0086 (8)	−0.0047 (8)
N1	0.0373 (10)	0.0452 (11)	0.0625 (13)	−0.0099 (8)	0.0132 (9)	−0.0114 (9)
Cu2	0.02688 (12)	0.03591 (13)	0.03048 (12)	−0.00653 (9)	0.00378 (9)	0.00275 (10)
C2	0.0298 (10)	0.0321 (10)	0.0329 (10)	−0.0018 (8)	−0.0018 (8)	0.0035 (8)
N2	0.0303 (9)	0.0499 (11)	0.0476 (11)	−0.0082 (8)	0.0012 (8)	0.0063 (9)
N3	0.0301 (8)	0.0269 (8)	0.0224 (7)	0.0028 (6)	0.0047 (6)	0.0005 (6)
C3	0.0348 (10)	0.0433 (11)	0.0293 (10)	−0.0022 (9)	0.0001 (8)	−0.0106 (9)
C4	0.0436 (13)	0.0595 (15)	0.0472 (13)	−0.0189 (11)	0.0157 (10)	−0.0203 (11)
C5	0.0359 (10)	0.0341 (10)	0.0226 (9)	−0.0041 (8)	0.0033 (7)	−0.0039 (7)
C6	0.0558 (14)	0.0389 (12)	0.0402 (12)	0.0032 (10)	0.0124 (10)	−0.0119 (10)
C7	0.0388 (10)	0.0314 (10)	0.0304 (10)	0.0026 (8)	0.0078 (8)	0.0076 (8)
C8	0.0548 (14)	0.0500 (13)	0.0339 (11)	0.0128 (11)	0.0181 (10)	0.0100 (10)
C9	0.0424 (11)	0.0301 (10)	0.0390 (11)	0.0089 (8)	0.0117 (9)	0.0048 (8)
C10	0.0402 (12)	0.0581 (15)	0.0547 (14)	0.0159 (11)	0.0077 (10)	0.0165 (12)
N4	0.0377 (8)	0.0210 (7)	0.0232 (7)	0.0007 (6)	0.0063 (6)	−0.0001 (6)
C11	0.0438 (11)	0.0268 (9)	0.0329 (10)	0.0092 (8)	0.0041 (8)	0.0048 (8)
C12	0.0417 (12)	0.0412 (12)	0.0428 (12)	0.0071 (9)	−0.0015 (9)	0.0027 (10)
C13	0.0387 (10)	0.0200 (8)	0.0285 (9)	0.0016 (7)	0.0018 (7)	0.0017 (7)
C14	0.0446 (12)	0.0387 (11)	0.0396 (11)	−0.0013 (9)	0.0097 (9)	0.0111 (9)
C15	0.0456 (11)	0.0295 (10)	0.0262 (9)	−0.0038 (8)	0.0035 (8)	−0.0052 (8)
C16	0.0806 (19)	0.0335 (12)	0.0558 (15)	−0.0192 (12)	0.0021 (13)	−0.0040 (11)
C17	0.0461 (12)	0.0417 (12)	0.0243 (9)	−0.0022 (9)	0.0106 (8)	−0.0004 (8)
C18	0.0439 (13)	0.0741 (17)	0.0394 (12)	0.0020 (12)	0.0152 (10)	−0.0079 (12)
O1	0.0376 (9)	0.0564 (11)	0.0457 (10)	−0.0091 (8)	0.0019 (8)	0.0081 (8)

Geometric parameters (Å, º)

Mo—S1	2.2222 (5)	N3—C7	1.522 (2)
Mo—S2	2.2076 (5)	N3—C9	1.519 (2)
Mo—S3	2.2089 (5)	C3—C4	1.513 (3)
Mo—S4	2.2143 (5)	C5—C6	1.505 (3)
S1—Cu1	2.2136 (5)	C7—C8	1.510 (3)
S2—Cu1	2.2111 (5)	C9—C10	1.512 (3)
S3—Cu2	2.2156 (5)	N4—C11	1.516 (2)
S4—Cu2	2.2101 (5)	N4—C13	1.520 (2)
Cu1—C1	1.889 (2)	N4—C15	1.521 (2)
C1—N1	1.137 (3)	N4—C17	1.516 (2)
Cu2—C2	1.890 (2)	C11—C12	1.520 (3)
C2—N2	1.136 (3)	C13—C14	1.517 (3)
N3—C3	1.515 (2)	C15—C16	1.516 (3)
N3—C5	1.521 (2)	C17—C18	1.510 (3)
S1—Mo—S2	107.103 (19)	C3—N3—C7	109.01 (15)
S1—Mo—S3	111.174 (19)	C3—N3—C9	108.66 (15)
S1—Mo—S4	111.78 (2)	C5—N3—C7	107.97 (14)
S2—Mo—S3	109.561 (19)	C5—N3—C9	109.29 (14)
S2—Mo—S4	109.73 (2)	C7—N3—C9	111.10 (15)
S3—Mo—S4	107.483 (19)	N3—C3—C4	115.03 (17)
Mo—S1—Cu1	72.640 (15)	N3—C5—C6	115.34 (16)
Mo—S2—Cu1	72.968 (16)	N3—C7—C8	115.23 (17)
Mo—S3—Cu2	72.494 (16)	N3—C9—C10	115.71 (17)
Mo—S4—Cu2	72.496 (17)	C11—N4—C13	111.00 (15)
S1—Cu1—S2	107.285 (19)	C11—N4—C15	108.74 (14)
S1—Cu1—C1	127.66 (6)	C11—N4—C17	109.01 (14)
S2—Cu1—C1	125.04 (6)	C13—N4—C15	108.75 (14)
Cu1—C1—N1	179.4 (2)	C13—N4—C17	108.39 (14)
S3—Cu2—S4	107.40 (2)	C15—N4—C17	110.95 (15)
S3—Cu2—C2	126.55 (6)	N4—C11—C12	115.41 (16)
S4—Cu2—C2	125.59 (6)	N4—C13—C14	114.93 (15)
Cu2—C2—N2	174.46 (19)	N4—C15—C16	114.89 (17)
C3—N3—C5	110.82 (14)	N4—C17—C18	115.39 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1^i	0.79 (3)	2.10 (3)	2.889 (3)	178 (3)
O1—H1B···N2	0.79 (3)	2.12 (3)	2.897 (3)	170 (3)

Symmetry code: (i) x−1, y−1, z.