Bis[μ-2,4-dibromo-6-(2-pyridylmethyl­amino­meth­yl)phenolato]bis­[nitrato­copper(II)]

In the centrosymmetric binuclear title compound, [Cu₂(C₁₃H₁₁Br₂N₂O)₂(NO₃)₂], each Cu^II atom is five-coordinated by two phenolate O atoms, one nitrate O atom, one pyridine N atom and one amine N atom in a distorted trigonal–bipyramidal CuO₃N₂ environment. The Cu...Cu separation is 3.207 (4) Å.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.034
• wR factor = 0.071
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        500 Ang.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O2     -   N3      ..       6.85 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O4      ..       6.17 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O1_a    ..       6.97 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O4
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H12    ...          ?
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  O3      ..       3.20 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br2    ..  O2      ..       3.18 Ang.

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of N2     = ...          R
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.21

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

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

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S1. Comment

The synthesis and characterization of binuclear copper(II) compounds have received increasing interest in bio-inorganic chemistry (Solomon et al., 1996) and catalysis (Collman, Zhong, Zhang & Costanzo, 2001; Collman, Zhong, Zeng & Costanzo, 2001). It is well known that the phenolate anion is a good bridging ligand for the construction of binuclear transition metal compounds (Gavrilova & Bosnich 2004; Yang et al., 2006). Modification of the phenolate anion in its ortho position can lead to the formation of stable binuclear compounds through chelation (Xu, et al., 2005). The structure of a new binuclear complex [Cu₂(dmp)₂(NO₃)₂], (I), where dmp is 2,4-dibromo-6-((pyridine-2-ylmethylamino)methyl)phenol, is presented here.

As shown in Fig. 1, the title compound, [Cu₂(C₁₃H₁₁Br₂N₂O)(NO₃)₂], contains a binuclear copper(II) unit bridged by two phenolate O atoms with a Cu···Cu distance of 3.207 (4) Å. Each Cu^II atom is chelated by one dmp ligand and is also coordinated by a nitrate O atom. Finally, the trigonal-bipyramidal coordination environment is completed by bond to the phenolate O atom from another dmp ligand. The axial positions of the trigonal-bipyramid are occupied by one phenolate O atom and one pyridine N atom with the O—Cu—N angle being 171.25 (10)°.

Related literature

For related literature, see: Solomon et al. (1996); Collman, Zhong, Zhang & Costanzo (2001); Collman, Zhong, Zeng & Costanzo (2001); Xu et al. (2005).

For related literature, see: Gavrilova & Bosnich (2004); Yang et al. (2006).

S2. Experimental

2,4-Dibromo-6-((pyridine-2-ylmethylamino)methyl)phenol (0.372 g, 1 mmol) was added to a methanol solution (20 ml) of Cu(NO₃)₂.3H₂O (0.241 g, 1 mmol) with stirring. The resulting solution was left to stand at room temperature and green crystals of (I) were obtained after several days.

S3. Refinement

All H atoms on C atoms were poisitioned geometrically and refined as riding atoms, with C—H = 0.93 Å and U_iso = 1.2U_eq (C). The H atom bonded to N atom was located in a difference Fourier map and refined freely.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for the H atoms). Symmetry code: (i) 2 - x, -y, 1 - z.

Bis[µ-2,4-dibromo-6-(2-pyridylmethylaminomethyl)phenolato]βis[nitratocopper(II)]

Crystal data

[Cu2(C13H11Br2N2O)2(NO3)2]	F(000) = 964
Mr = 993.22	Dx = 2.075 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 11121 reflections
a = 10.385 (5) Å	θ = 3.0–27.5°
b = 11.252 (5) Å	µ = 6.42 mm^−1
c = 14.074 (5) Å	T = 290 K
β = 104.810 (5)°	Block, green
V = 1589.9 (12) Å^3	0.24 × 0.16 × 0.13 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer	3629 independent reflections
Radiation source: rotating anode	2707 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 10.0 pixels mm^-1	θmax = 27.5°, θmin = 3°
ω scans	h = −13→13
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→14
Tmin = 0.30, Tmax = 0.43	l = −15→18
14979 measured 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)] = 0.035	Hydrogen site location: difmap and geom
wR(F^2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0224P)^2 + 0.8145P] where P = (Fo^2 + 2Fc^2)/3
3629 reflections	(Δ/σ)max = 0.007
212 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.49 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.

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 > σ(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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.93487 (4)	0.01290 (3)	0.38420 (3)	0.03277 (11)
C1	0.9741 (4)	0.2204 (3)	0.2616 (3)	0.0414 (8)
H1	0.9214	0.2636	0.2936	0.050*
C2	1.0259 (4)	0.2770 (3)	0.1930 (3)	0.0461 (9)
H2	1.0085	0.3570	0.1789	0.055*
C3	1.1040 (4)	0.2130 (3)	0.1454 (3)	0.0444 (9)
H3	1.1398	0.2492	0.0986	0.053*
C4	1.1286 (4)	0.0938 (3)	0.1685 (3)	0.0432 (9)
H4	1.1806	0.0489	0.1370	0.052*
C5	1.0746 (3)	0.0432 (3)	0.2387 (2)	0.0340 (7)
C6	1.1035 (4)	−0.0829 (3)	0.2745 (3)	0.0416 (8)
H6A	1.1081	−0.1336	0.2198	0.050*
H6B	1.1891	−0.0858	0.3225	0.050*
C7	1.0454 (3)	−0.2280 (3)	0.3883 (2)	0.0352 (8)
H7A	1.1168	−0.2020	0.4432	0.042*
H7B	1.0793	−0.2915	0.3547	0.042*
C8	0.9315 (3)	−0.2731 (3)	0.4252 (2)	0.0314 (7)
C9	0.8915 (4)	−0.3920 (3)	0.4112 (2)	0.0374 (8)
H9	0.9362	−0.4439	0.3794	0.045*
C10	0.7862 (4)	−0.4316 (3)	0.4448 (2)	0.0377 (8)
C11	0.7165 (4)	−0.3581 (3)	0.4914 (3)	0.0394 (8)
H11	0.6448	−0.3865	0.5131	0.047*
C12	0.7563 (3)	−0.2396 (3)	0.5055 (2)	0.0344 (7)
C13	0.8643 (3)	−0.1944 (3)	0.4740 (2)	0.0314 (7)
N1	0.9972 (3)	0.1047 (2)	0.2840 (2)	0.0343 (6)
N2	1.0003 (3)	−0.1265 (2)	0.3190 (2)	0.0326 (6)
N3	0.6808 (3)	0.0902 (3)	0.3379 (2)	0.0450 (7)
O1	0.9028 (2)	−0.08086 (17)	0.49007 (15)	0.0322 (5)
O2	0.7906 (3)	0.13349 (19)	0.38969 (19)	0.0425 (6)
O3	0.5783 (3)	0.1497 (3)	0.3244 (2)	0.0759 (9)
O4	0.6836 (3)	−0.0106 (2)	0.3020 (2)	0.0554 (7)
Br1	0.65460 (4)	−0.13772 (4)	0.56476 (3)	0.05240 (12)
Br2	0.73308 (4)	−0.59426 (3)	0.42370 (3)	0.04830 (12)
H12	0.925 (4)	−0.148 (3)	0.276 (3)	0.063 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0386 (2)	0.02697 (19)	0.0346 (2)	0.00306 (17)	0.01283 (18)	−0.00048 (15)
C1	0.045 (2)	0.0328 (17)	0.046 (2)	0.0052 (17)	0.0120 (17)	0.0002 (15)
C2	0.050 (2)	0.0345 (18)	0.053 (2)	−0.0009 (17)	0.0119 (19)	0.0097 (16)
C3	0.046 (2)	0.0450 (19)	0.045 (2)	−0.0064 (18)	0.0167 (18)	0.0034 (16)
C4	0.048 (2)	0.0435 (19)	0.042 (2)	−0.0010 (18)	0.0188 (18)	−0.0030 (15)
C5	0.0352 (19)	0.0360 (17)	0.0312 (19)	−0.0010 (15)	0.0090 (15)	−0.0030 (13)
C6	0.045 (2)	0.0329 (17)	0.051 (2)	0.0065 (16)	0.0208 (18)	0.0013 (15)
C7	0.041 (2)	0.0278 (15)	0.036 (2)	0.0064 (15)	0.0079 (15)	0.0016 (13)
C8	0.0329 (18)	0.0285 (15)	0.0303 (18)	0.0021 (14)	0.0034 (14)	0.0039 (12)
C9	0.043 (2)	0.0276 (16)	0.039 (2)	0.0022 (16)	0.0068 (16)	−0.0019 (14)
C10	0.047 (2)	0.0260 (15)	0.0346 (19)	−0.0049 (16)	0.0008 (16)	0.0031 (13)
C11	0.040 (2)	0.0364 (18)	0.038 (2)	−0.0081 (16)	0.0044 (16)	0.0049 (14)
C12	0.0349 (19)	0.0359 (17)	0.0319 (19)	0.0042 (15)	0.0074 (15)	−0.0014 (13)
C13	0.0328 (18)	0.0306 (16)	0.0273 (18)	0.0009 (14)	0.0015 (14)	0.0005 (12)
N1	0.0351 (16)	0.0331 (14)	0.0340 (16)	0.0030 (13)	0.0073 (12)	−0.0016 (11)
N2	0.0336 (16)	0.0290 (13)	0.0352 (17)	0.0028 (13)	0.0090 (13)	−0.0009 (11)
N3	0.048 (2)	0.0483 (18)	0.0425 (19)	0.0085 (17)	0.0188 (16)	0.0103 (14)
O1	0.0383 (13)	0.0278 (10)	0.0305 (12)	−0.0039 (10)	0.0091 (10)	−0.0040 (9)
O2	0.0408 (14)	0.0330 (12)	0.0528 (17)	0.0040 (11)	0.0107 (12)	−0.0054 (10)
O3	0.0446 (17)	0.101 (2)	0.086 (2)	0.0342 (18)	0.0253 (17)	0.0162 (18)
O4	0.0572 (18)	0.0503 (15)	0.0514 (17)	−0.0076 (14)	0.0007 (14)	0.0011 (12)
Br1	0.0483 (2)	0.0566 (2)	0.0579 (3)	−0.00440 (19)	0.02369 (19)	−0.01596 (18)
Br2	0.0671 (3)	0.02887 (17)	0.0439 (2)	−0.00976 (17)	0.00495 (19)	0.00350 (14)

Geometric parameters (Å, º)

Cu1—O1	1.923 (2)	C7—C8	1.497 (4)
Cu1—N1	1.985 (3)	C7—H7A	0.9700
Cu1—N2	2.021 (3)	C7—H7B	0.9700
Cu1—O2	2.038 (2)	C8—C9	1.399 (4)
Cu1—O1^i	2.243 (2)	C8—C13	1.410 (4)
C1—N1	1.347 (4)	C9—C10	1.371 (5)
C1—C2	1.375 (5)	C9—H9	0.9300
C1—H1	0.9300	C10—C11	1.372 (5)
C2—C3	1.379 (5)	C10—Br2	1.913 (3)
C2—H2	0.9300	C11—C12	1.396 (4)
C3—C4	1.387 (5)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.402 (4)
C4—C5	1.378 (5)	C12—Br1	1.891 (3)
C4—H4	0.9300	C13—O1	1.341 (3)
C5—N1	1.339 (4)	N2—H12	0.90 (4)
C5—C6	1.509 (4)	N3—O3	1.230 (4)
C6—N2	1.457 (4)	N3—O4	1.245 (4)
C6—H6A	0.9700	N3—O2	1.282 (4)
C6—H6B	0.9700	O1—Cu1^i	2.243 (2)
C7—N2	1.497 (4)
O1—Cu1—N1	171.25 (10)	H7A—C7—H7B	108.2
O1—Cu1—N2	94.09 (10)	C9—C8—C13	120.2 (3)
N1—Cu1—N2	82.67 (11)	C9—C8—C7	120.5 (3)
O1—Cu1—O2	93.51 (10)	C13—C8—C7	119.3 (3)
N1—Cu1—O2	93.27 (11)	C10—C9—C8	119.7 (3)
N2—Cu1—O2	150.47 (12)	C10—C9—H9	120.1
O1—Cu1—O1^i	79.63 (9)	C8—C9—H9	120.1
N1—Cu1—O1^i	93.86 (10)	C9—C10—C11	122.3 (3)
N2—Cu1—O1^i	110.53 (11)	C9—C10—Br2	118.8 (3)
O2—Cu1—O1^i	98.90 (9)	C11—C10—Br2	119.0 (3)
N1—C1—C2	122.3 (3)	C10—C11—C12	118.1 (3)
N1—C1—H1	118.9	C10—C11—H11	121.0
C2—C1—H1	118.9	C12—C11—H11	121.0
C1—C2—C3	118.9 (3)	C11—C12—C13	122.2 (3)
C1—C2—H2	120.6	C11—C12—Br1	117.6 (3)
C3—C2—H2	120.6	C13—C12—Br1	120.1 (2)
C2—C3—C4	119.1 (3)	O1—C13—C12	121.4 (3)
C2—C3—H3	120.4	O1—C13—C8	121.1 (3)
C4—C3—H3	120.4	C12—C13—C8	117.5 (3)
C5—C4—C3	118.9 (3)	C5—N1—C1	118.7 (3)
C5—C4—H4	120.6	C5—N1—Cu1	114.4 (2)
C3—C4—H4	120.6	C1—N1—Cu1	126.8 (2)
N1—C5—C4	122.1 (3)	C6—N2—C7	113.3 (3)
N1—C5—C6	114.8 (3)	C6—N2—Cu1	107.64 (19)
C4—C5—C6	123.1 (3)	C7—N2—Cu1	112.4 (2)
N2—C6—C5	110.8 (3)	C6—N2—H12	114 (3)
N2—C6—H6A	109.5	C7—N2—H12	108 (3)
C5—C6—H6A	109.5	Cu1—N2—H12	100 (2)
N2—C6—H6B	109.5	O3—N3—O4	122.8 (4)
C5—C6—H6B	109.5	O3—N3—O2	119.3 (3)
H6A—C6—H6B	108.1	O4—N3—O2	117.9 (3)
N2—C7—C8	110.0 (3)	C13—O1—Cu1	119.73 (19)
N2—C7—H7A	109.7	C13—O1—Cu1^i	126.11 (18)
C8—C7—H7A	109.7	Cu1—O1—Cu1^i	100.37 (9)
N2—C7—H7B	109.7	N3—O2—Cu1	106.3 (2)
C8—C7—H7B	109.7
N1—C1—C2—C3	0.0 (6)	O1^i—Cu1—N1—C5	96.5 (2)
C1—C2—C3—C4	−0.3 (6)	N2—Cu1—N1—C1	169.3 (3)
C2—C3—C4—C5	−0.4 (5)	O2—Cu1—N1—C1	18.7 (3)
C3—C4—C5—N1	1.3 (5)	O1^i—Cu1—N1—C1	−80.5 (3)
C3—C4—C5—C6	−175.3 (3)	C5—C6—N2—C7	−158.1 (3)
N1—C5—C6—N2	24.0 (4)	C5—C6—N2—Cu1	−33.1 (3)
C4—C5—C6—N2	−159.2 (3)	C8—C7—N2—C6	−176.0 (3)
N2—C7—C8—C9	122.3 (3)	C8—C7—N2—Cu1	61.6 (3)
N2—C7—C8—C13	−57.5 (4)	O1—Cu1—N2—C6	−146.0 (2)
C13—C8—C9—C10	0.4 (5)	N1—Cu1—N2—C6	25.8 (2)
C7—C8—C9—C10	−179.4 (3)	O2—Cu1—N2—C6	109.5 (3)
C8—C9—C10—C11	0.6 (5)	O1^i—Cu1—N2—C6	−65.6 (2)
C8—C9—C10—Br2	179.5 (2)	O1—Cu1—N2—C7	−20.5 (2)
C9—C10—C11—C12	−0.6 (5)	N1—Cu1—N2—C7	151.3 (2)
Br2—C10—C11—C12	−179.6 (2)	O2—Cu1—N2—C7	−125.1 (2)
C10—C11—C12—C13	−0.3 (5)	O1^i—Cu1—N2—C7	59.9 (2)
C10—C11—C12—Br1	177.3 (3)	C12—C13—O1—Cu1	−132.0 (3)
C11—C12—C13—O1	−178.5 (3)	C8—C13—O1—Cu1	48.3 (4)
Br1—C12—C13—O1	3.9 (4)	C12—C13—O1—Cu1^i	95.7 (3)
C11—C12—C13—C8	1.2 (5)	C8—C13—O1—Cu1^i	−84.0 (3)
Br1—C12—C13—C8	−176.4 (2)	N2—Cu1—O1—C13	−32.5 (2)
C9—C8—C13—O1	178.5 (3)	O2—Cu1—O1—C13	119.0 (2)
C7—C8—C13—O1	−1.7 (4)	O1^i—Cu1—O1—C13	−142.6 (3)
C9—C8—C13—C12	−1.2 (5)	N2—Cu1—O1—Cu1^i	110.14 (11)
C7—C8—C13—C12	178.6 (3)	O2—Cu1—O1—Cu1^i	−98.42 (10)
C4—C5—N1—C1	−1.5 (5)	O1^i—Cu1—O1—Cu1^i	0.0
C6—C5—N1—C1	175.3 (3)	O3—N3—O2—Cu1	−175.6 (3)
C4—C5—N1—Cu1	−178.7 (3)	O4—N3—O2—Cu1	3.1 (3)
C6—C5—N1—Cu1	−1.9 (4)	O1—Cu1—O2—N3	−84.6 (2)
C2—C1—N1—C5	0.9 (5)	N1—Cu1—O2—N3	101.0 (2)
C2—C1—N1—Cu1	177.7 (3)	N2—Cu1—O2—N3	20.1 (3)
N2—Cu1—N1—C5	−13.7 (2)	O1^i—Cu1—O2—N3	−164.6 (2)
O2—Cu1—N1—C5	−164.4 (2)

Symmetry code: (i) −x+2, −y, −z+1.