Bis(diphenyl-p-tolyl-phosphane-κP)(2-hy-droxy-3,5,7-bromo-cyclo-hepta-2,4,6-trienonato-κ(2)O,O')copper(I).

The Cu(I) atom in the title compund, [Cu(C(7)H(2)Br(3)O(2))(C(19)H(17)P)(2)], is located on a twofold rotation axis; the 3,5,7-tribromo-tropolonate anion coordinates as a bidentate ligand with a bite angle of 76.42 (9)°. An intra-molecular C-H⋯O inter-action occurs. Within the crystal, extensive weak C-H⋯π inter-actions contribute to the herringbone pattern observed in the packing of the mol-ecules.

Related literature

For background to tropolone and its derivatives, see: Dewar (1945 ▶); Hill & Steyl (2008 ▶); Crous et al. (2005 ▶). For bis-troplolonato–copper(II) complexes, see: Chipperfield et al. (1998 ▶); Hasegawa et al. (1997 ▶); Ho (2010 ▶); Ho et al. (2009 ▶). For work on the effect the troplonato ligand has on the solid state and chemical behaviour of copper(I) phosphine metal complexes, see: Roodt et al. (2003 ▶); Steyl (2007 ▶, 2009 ▶); Steyl & Hill (2009 ▶); Steyl & Roodt (2006 ▶).

Experimental

Crystal data

[Cu(C7H2Br3O2)(C19H17P)2]

M = 973.95

Monoclinic,

a = 15.4522 (8) Å

b = 13.9073 (8) Å

c = 19.3269 (10) Å

β = 103.862 (3)°

V = 4032.4 (4) Å3

Z = 4

Mo Kα radiation

μ = 3.63 mm−1

T = 100 K

0.18 × 0.09 × 0.06 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.686, T max = 0.746

27602 measured reflections

5022 independent reflections

3970 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.130

S = 1.04

5022 reflections

241 parameters

H-atom parameters constrained

Δρmax = 1.51 e Å−3

Δρmin = −1.57 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812042286/ng5299sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042286/ng5299Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C7H2Br3O2)(C19H17P)2]	F(000) = 1944
Mr = 973.95	Dx = 1.604 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8436 reflections
a = 15.4522 (8) Å	θ = 2.3–28.4°
b = 13.9073 (8) Å	µ = 3.63 mm−1
c = 19.3269 (10) Å	T = 100 K
β = 103.862 (3)°	Cuboid, green
V = 4032.4 (4) Å3	0.18 × 0.09 × 0.06 mm
Z = 4

Bruker X8 APEXII 4K Kappa CCD diffractometer	5022 independent reflections
Radiation source: sealed tube	3970 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 512 pixels mm-1	θmax = 28.4°, θmin = 2°
φ and ω scans	h = −19→20
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −15→18
Tmin = 0.686, Tmax = 0.746	l = −25→25
27602 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0661P)2 + 16.6643P] where P = (Fo2 + 2Fc2)/3
5022 reflections	(Δ/σ)max < 0.001
241 parameters	Δρmax = 1.51 e Å−3
0 restraints	Δρmin = −1.57 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

	x	y	z	Uiso*/Ueq
C2	0.5382 (2)	0.6353 (3)	0.28258 (18)	0.0213 (7)
C3	0.5717 (2)	0.7199 (3)	0.32159 (19)	0.0230 (7)
C4	0.5556 (2)	0.8171 (3)	0.3086 (2)	0.0294 (8)
H4	0.5867	0.8596	0.3446	0.035*
C5	0.5	0.8599 (3)	0.25	0.0295 (12)
C111	0.3102 (2)	0.3211 (3)	0.25441 (19)	0.0242 (7)
C112	0.2526 (2)	0.3880 (3)	0.2148 (2)	0.0309 (8)
H112	0.2662	0.4546	0.2202	0.037*
C113	0.1744 (3)	0.3578 (4)	0.1667 (2)	0.0373 (10)
H113	0.1339	0.4041	0.1411	0.045*
C114	0.1562 (3)	0.2615 (4)	0.1565 (2)	0.0375 (10)
H114	0.1041	0.2411	0.1227	0.045*
C115	0.2132 (3)	0.1946 (3)	0.1954 (2)	0.0384 (10)
H115	0.2003	0.128	0.1883	0.046*
C116	0.2898 (2)	0.2235 (3)	0.2451 (2)	0.0310 (8)
H116	0.3281	0.1769	0.2725	0.037*
C121	0.4606 (2)	0.2639 (2)	0.36831 (19)	0.0221 (7)
C122	0.5385 (3)	0.2234 (3)	0.3588 (2)	0.0317 (8)
H122	0.5645	0.2472	0.3223	0.038*
C123	0.5799 (3)	0.1478 (3)	0.4021 (3)	0.0432 (11)
H123	0.6334	0.1205	0.3949	0.052*
C124	0.5423 (3)	0.1126 (3)	0.4559 (2)	0.0412 (10)
H124	0.57	0.0613	0.4856	0.049*
C125	0.4650 (3)	0.1526 (3)	0.4655 (3)	0.0470 (12)
H125	0.4394	0.1292	0.5023	0.056*
C126	0.4237 (3)	0.2272 (3)	0.4219 (3)	0.0391 (10)
H126	0.3697	0.2535	0.4288	0.047*
C131	0.3738 (2)	0.4421 (2)	0.37497 (17)	0.0202 (7)
C132	0.2920 (2)	0.4256 (3)	0.39248 (19)	0.0236 (7)
H132	0.2525	0.3778	0.3677	0.028*
C133	0.2690 (2)	0.4791 (3)	0.4460 (2)	0.0277 (8)
H133	0.2138	0.4667	0.4579	0.033*
C134	0.3244 (3)	0.5498 (3)	0.4823 (2)	0.0303 (8)
C135	0.4049 (2)	0.5684 (3)	0.46311 (19)	0.0263 (7)
H135	0.443	0.6183	0.4864	0.032*
C136	0.4292 (2)	0.5143 (3)	0.41023 (18)	0.0222 (7)
H136	0.4841	0.527	0.3981	0.027*
C137	0.3016 (3)	0.6032 (4)	0.5422 (3)	0.0512 (13)
H13A	0.3485	0.6502	0.5612	0.077*
H13B	0.2964	0.5579	0.5798	0.077*
H13C	0.2447	0.6368	0.5249	0.077*
O2	0.56859 (15)	0.55420 (17)	0.30362 (13)	0.0227 (5)
P1	0.41329 (5)	0.36611 (6)	0.31230 (5)	0.01920 (18)
Cu1	0.5	0.43613 (4)	0.25	0.01987 (15)
Br1	0.65536 (3)	0.69166 (3)	0.40942 (2)	0.03295 (13)
Br2	0.5	0.99600 (5)	0.25	0.0638 (3)

	U11	U22	U33	U12	U13	U23
C2	0.0140 (14)	0.0293 (18)	0.0231 (17)	−0.0008 (13)	0.0096 (13)	0.0021 (14)
C3	0.0171 (14)	0.0279 (18)	0.0259 (17)	−0.0019 (13)	0.0090 (13)	−0.0002 (14)
C4	0.0225 (17)	0.0277 (19)	0.041 (2)	−0.0066 (14)	0.0132 (15)	−0.0078 (16)
C5	0.027 (2)	0.011 (2)	0.054 (3)	0	0.016 (2)	0
C111	0.0150 (14)	0.036 (2)	0.0230 (17)	−0.0030 (14)	0.0071 (12)	−0.0048 (15)
C112	0.0273 (18)	0.037 (2)	0.0276 (19)	−0.0005 (16)	0.0047 (15)	−0.0003 (16)
C113	0.0256 (19)	0.061 (3)	0.0243 (19)	0.0036 (18)	0.0034 (15)	0.0005 (18)
C114	0.0222 (17)	0.062 (3)	0.030 (2)	−0.0106 (18)	0.0086 (15)	−0.015 (2)
C115	0.030 (2)	0.047 (3)	0.041 (2)	−0.0167 (18)	0.0150 (18)	−0.017 (2)
C116	0.0234 (17)	0.036 (2)	0.036 (2)	−0.0069 (15)	0.0102 (15)	−0.0061 (17)
C121	0.0212 (15)	0.0196 (17)	0.0260 (17)	0.0014 (13)	0.0070 (13)	−0.0005 (13)
C122	0.0262 (18)	0.036 (2)	0.036 (2)	0.0055 (16)	0.0138 (16)	0.0070 (17)
C123	0.034 (2)	0.044 (3)	0.055 (3)	0.0189 (19)	0.018 (2)	0.018 (2)
C124	0.045 (2)	0.034 (2)	0.047 (2)	0.0110 (19)	0.015 (2)	0.0116 (19)
C125	0.054 (3)	0.040 (2)	0.057 (3)	0.013 (2)	0.034 (2)	0.021 (2)
C126	0.035 (2)	0.036 (2)	0.055 (3)	0.0110 (17)	0.027 (2)	0.015 (2)
C131	0.0173 (14)	0.0229 (17)	0.0209 (16)	0.0055 (13)	0.0057 (12)	0.0038 (13)
C132	0.0178 (15)	0.0269 (17)	0.0273 (18)	0.0018 (13)	0.0076 (13)	0.0003 (14)
C133	0.0203 (16)	0.037 (2)	0.0273 (18)	0.0075 (15)	0.0077 (14)	0.0022 (15)
C134	0.0307 (18)	0.036 (2)	0.0238 (18)	0.0155 (16)	0.0051 (14)	−0.0003 (16)
C135	0.0262 (17)	0.0257 (18)	0.0227 (17)	0.0044 (14)	−0.0026 (13)	0.0007 (14)
C136	0.0176 (14)	0.0236 (17)	0.0239 (17)	0.0037 (13)	0.0021 (12)	0.0024 (13)
C137	0.045 (3)	0.070 (3)	0.039 (2)	0.012 (2)	0.010 (2)	−0.018 (2)
O2	0.0171 (11)	0.0233 (13)	0.0272 (12)	−0.0008 (9)	0.0041 (9)	0.0014 (10)
P1	0.0145 (4)	0.0208 (4)	0.0234 (4)	−0.0004 (3)	0.0068 (3)	−0.0008 (3)
Cu1	0.0149 (3)	0.0214 (3)	0.0249 (3)	0	0.0078 (2)	0
Br1	0.0317 (2)	0.0367 (2)	0.0276 (2)	−0.00878 (16)	0.00144 (15)	−0.00242 (16)
Br2	0.0539 (4)	0.0268 (3)	0.1064 (7)	0	0.0112 (4)	0

C2—O2	1.252 (4)	C123—C124	1.396 (6)
C2—C3	1.426 (5)	C123—H123	0.95
C2—C2i	1.506 (6)	C124—C125	1.370 (6)
C3—C4	1.387 (5)	C124—H124	0.95
C3—Br1	1.911 (4)	C125—C126	1.391 (6)
C4—C5	1.382 (5)	C125—H125	0.95
C4—H4	0.95	C126—H126	0.95
C5—C4i	1.382 (5)	C131—C136	1.388 (5)
C5—Br2	1.893 (5)	C131—C132	1.403 (4)
C111—C112	1.384 (5)	C131—P1	1.820 (3)
C111—C116	1.395 (5)	C132—C133	1.387 (5)
C111—P1	1.824 (3)	C132—H132	0.95
C112—C113	1.400 (5)	C133—C134	1.381 (6)
C112—H112	0.95	C133—H133	0.95
C113—C114	1.375 (7)	C134—C135	1.405 (5)
C113—H113	0.95	C134—C137	1.486 (6)
C114—C115	1.374 (7)	C135—C136	1.391 (5)
C114—H114	0.95	C135—H135	0.95
C115—C116	1.392 (6)	C136—H136	0.95
C115—H115	0.95	C137—H13A	0.98
C116—H116	0.95	C137—H13B	0.98
C121—C122	1.381 (5)	C137—H13C	0.98
C121—C126	1.393 (5)	O2—Cu1	2.090 (2)
C121—P1	1.830 (4)	P1—Cu1	2.2284 (9)
C122—C123	1.398 (6)	Cu1—O2i	2.090 (2)
C122—H122	0.95	Cu1—P1i	2.2284 (9)
O2—C2—C3	120.7 (3)	C124—C125—H125	119.7
O2—C2—C2i	115.45 (19)	C126—C125—H125	119.7
C3—C2—C2i	123.7 (2)	C125—C126—C121	120.9 (4)
C4—C3—C2	133.0 (3)	C125—C126—H126	119.5
C4—C3—Br1	114.5 (3)	C121—C126—H126	119.5
C2—C3—Br1	112.5 (3)	C136—C131—C132	119.0 (3)
C5—C4—C3	128.1 (4)	C136—C131—P1	118.8 (2)
C5—C4—H4	115.9	C132—C131—P1	122.0 (3)
C3—C4—H4	115.9	C133—C132—C131	119.9 (3)
C4i—C5—C4	129.0 (5)	C133—C132—H132	120.1
C4i—C5—Br2	115.5 (2)	C131—C132—H132	120.1
C4—C5—Br2	115.5 (2)	C134—C133—C132	121.5 (3)
C112—C111—C116	119.1 (3)	C134—C133—H133	119.2
C112—C111—P1	117.4 (3)	C132—C133—H133	119.2
C116—C111—P1	123.4 (3)	C133—C134—C135	118.5 (3)
C111—C112—C113	120.2 (4)	C133—C134—C137	121.2 (4)
C111—C112—H112	119.9	C135—C134—C137	120.3 (4)
C113—C112—H112	119.9	C136—C135—C134	120.4 (3)
C114—C113—C112	120.2 (4)	C136—C135—H135	119.8
C114—C113—H113	119.9	C134—C135—H135	119.8
C112—C113—H113	119.9	C131—C136—C135	120.6 (3)
C113—C114—C115	119.9 (4)	C131—C136—H136	119.7
C113—C114—H114	120.1	C135—C136—H136	119.7
C115—C114—H114	120.1	C134—C137—H13A	109.5
C114—C115—C116	120.6 (4)	C134—C137—H13B	109.5
C114—C115—H115	119.7	H13A—C137—H13B	109.5
C116—C115—H115	119.7	C134—C137—H13C	109.5
C115—C116—C111	119.9 (4)	H13A—C137—H13C	109.5
C115—C116—H116	120.1	H13B—C137—H13C	109.5
C111—C116—H116	120.1	C2—O2—Cu1	116.1 (2)
C122—C121—C126	118.3 (3)	C131—P1—C111	102.98 (15)
C122—C121—P1	118.4 (3)	C131—P1—C121	101.98 (16)
C126—C121—P1	123.2 (3)	C111—P1—C121	105.21 (17)
C121—C122—C123	121.0 (4)	C131—P1—Cu1	116.55 (12)
C121—C122—H122	119.5	C111—P1—Cu1	111.62 (12)
C123—C122—H122	119.5	C121—P1—Cu1	116.91 (11)
C122—C123—C124	119.9 (4)	O2—Cu1—O2i	76.42 (13)
C122—C123—H123	120.1	O2—Cu1—P1	112.00 (7)
C124—C123—H123	120.1	O2i—Cu1—P1	108.19 (7)
C125—C124—C123	119.3 (4)	O2—Cu1—P1i	108.19 (7)
C125—C124—H124	120.3	O2i—Cu1—P1i	112.00 (7)
C123—C124—H124	120.3	P1—Cu1—P1i	128.18 (5)
C124—C125—C126	120.6 (4)
O2—C2—C3—C4	174.7 (4)	C134—C135—C136—C131	0.9 (5)
C2i—C2—C3—C4	−9.2 (7)	C3—C2—O2—Cu1	171.0 (2)
O2—C2—C3—Br1	−5.6 (4)	C2i—C2—O2—Cu1	−5.4 (4)
C2i—C2—C3—Br1	170.5 (3)	C136—C131—P1—C111	−157.1 (3)
C2—C3—C4—C5	−1.1 (6)	C132—C131—P1—C111	27.6 (3)
Br1—C3—C4—C5	179.2 (2)	C136—C131—P1—C121	94.0 (3)
C3—C4—C5—C4i	2.7 (3)	C132—C131—P1—C121	−81.3 (3)
C3—C4—C5—Br2	−177.3 (3)	C136—C131—P1—Cu1	−34.5 (3)
C116—C111—C112—C113	0.9 (5)	C132—C131—P1—Cu1	150.1 (2)
P1—C111—C112—C113	176.9 (3)	C112—C111—P1—C131	62.6 (3)
C111—C112—C113—C114	−2.6 (6)	C116—C111—P1—C131	−121.6 (3)
C112—C113—C114—C115	2.2 (6)	C112—C111—P1—C121	169.0 (3)
C113—C114—C115—C116	−0.1 (6)	C116—C111—P1—C121	−15.1 (3)
C114—C115—C116—C111	−1.6 (6)	C112—C111—P1—Cu1	−63.2 (3)
C112—C111—C116—C115	1.2 (5)	C116—C111—P1—Cu1	112.6 (3)
P1—C111—C116—C115	−174.6 (3)	C122—C121—P1—C131	−141.0 (3)
C126—C121—C122—C123	−0.4 (6)	C126—C121—P1—C131	36.4 (4)
P1—C121—C122—C123	177.2 (4)	C122—C121—P1—C111	111.8 (3)
C121—C122—C123—C124	−0.2 (7)	C126—C121—P1—C111	−70.8 (4)
C122—C123—C124—C125	0.1 (8)	C122—C121—P1—Cu1	−12.7 (3)
C123—C124—C125—C126	0.4 (8)	C126—C121—P1—Cu1	164.8 (3)
C124—C125—C126—C121	−1.0 (8)	C2—O2—Cu1—O2i	2.14 (18)
C122—C121—C126—C125	0.9 (7)	C2—O2—Cu1—P1	−102.3 (2)
P1—C121—C126—C125	−176.5 (4)	C2—O2—Cu1—P1i	111.2 (2)
C136—C131—C132—C133	−2.1 (5)	C131—P1—Cu1—O2	26.45 (14)
P1—C131—C132—C133	173.3 (3)	C111—P1—Cu1—O2	144.35 (15)
C131—C132—C133—C134	0.8 (6)	C121—P1—Cu1—O2	−94.47 (15)
C132—C133—C134—C135	1.3 (6)	C131—P1—Cu1—O2i	−55.86 (14)
C132—C133—C134—C137	−176.7 (4)	C111—P1—Cu1—O2i	62.04 (15)
C133—C134—C135—C136	−2.1 (5)	C121—P1—Cu1—O2i	−176.78 (14)
C137—C134—C135—C136	175.8 (4)	C131—P1—Cu1—P1i	164.68 (12)
C132—C131—C136—C135	1.2 (5)	C111—P1—Cu1—P1i	−77.41 (13)
P1—C131—C136—C135	−174.3 (3)	C121—P1—Cu1—P1i	43.76 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C136—H136···O2	0.95	2.52	3.365 (4)	149
C115—H115···Cg3ii	0.95	2.86	3.621 (4)	138
C137—H13A···Cg2iii	0.98	3.18	4.144 (6)	168

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of the C121–C126 and C131–C136 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C136—H136⋯O2	0.95	2.52	3.365 (4)	149
C115—H115⋯Cg3i	0.95	2.86	3.621 (4)	138
C137—H13A⋯Cg2ii	0.98	3.18	4.144 (6)	168

Symmetry codes: (i) ; (ii) .