{2-[2-(1H-1,3-Benzimidazol-2-yl)ethyl­imino­meth­yl]-4-bromo­phenolato}thio­cyanato­copper(II) methanol solvate

In the title compound, [Cu(NCS)(C₁₆H₁₃BrN₃O)]·CH₄O, the Cu^II center forms a distorted square coordination with two N atoms and one O atom of the ligand 2-{2-[(5-bromo­salicyl­idene)amino]eth­yl}-1H-1,3-benzimidazole, and one N atom of the thio­cyanate anion. The distortion is quite large, with an O-Cu-N angle of 150.83 (10)° and an N-Cu-N angle of 149.17 (12)°. Methanol mol­ecules link the salicyl­idene groups via hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.034
• wR factor = 0.098
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C17     ..       5.51 su
PLAT352_ALERT_3_C Short   N-H Bond (0.87A)   N3     -   H3A    ...       0.74 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         66
            CU1 -N4  -C17 -S1     37.00 19.00   1.555   1.555   1.555   1.555

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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: SMART (Bruker,1998); cell refinement: SAINT (Bruker,1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker,1998); software used to prepare material for publication: SHELXTL.

{2-[2-(1H-1,3-Benzimidazol-2-yl)ethyliminomethyl]-4- bromophenolato}thiocyanatocopper(II) methanol solvate

Crystal data

[Cu(NCS)(C16H13BrN3O)]·CH4O	Z = 2
Mr = 496.87	F(000) = 498
Triclinic, P1	Dx = 1.725 Mg m^−3
a = 7.4111 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7821 (19) Å	Cell parameters from 2585 reflections
c = 15.545 (3) Å	θ = 2.4–25.0°
α = 75.292 (3)°	µ = 3.36 mm^−1
β = 84.626 (2)°	T = 293 K
γ = 78.163 (3)°	Block, green
V = 956.9 (4) Å^3	0.48 × 0.34 × 0.20 mm

Data collection

Bruker APEX-II CCD area-detector diffractometer	3334 independent reflections
Radiation source: fine-focus sealed tube	2802 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.220, Tmax = 0.511	k = −10→8
5142 measured reflections	l = −18→18

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0603P)^2 + 0.2902P] where P = (Fo^2 + 2Fc^2)/3
3334 reflections	(Δ/σ)max = 0.001
250 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.62 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	0.55599 (5)	0.11614 (4)	0.22263 (2)	0.03351 (14)
Br1	0.95097 (5)	−0.00734 (5)	−0.20933 (2)	0.05475 (15)
S1	0.18412 (15)	0.49495 (11)	0.35854 (6)	0.0536 (3)
N1	0.5883 (3)	−0.0871 (3)	0.19117 (16)	0.0315 (6)
N2	0.6480 (3)	0.0118 (3)	0.34287 (16)	0.0321 (6)
N3	0.7200 (4)	−0.1726 (4)	0.46562 (18)	0.0336 (6)
N4	0.3925 (4)	0.2950 (3)	0.25868 (19)	0.0462 (7)
O1	0.5902 (3)	0.2359 (3)	0.10480 (14)	0.0395 (5)
C1	0.7862 (4)	−0.0414 (4)	−0.0350 (2)	0.0349 (7)
H1	0.8081	−0.1499	−0.0340	0.042*
C2	0.8344 (4)	0.0654 (4)	−0.1090 (2)	0.0376 (8)
C3	0.7962 (5)	0.2289 (4)	−0.1138 (2)	0.0419 (8)
H3	0.8269	0.3012	−0.1654	0.050*
C4	0.7131 (5)	0.2825 (4)	−0.0420 (2)	0.0438 (8)
H4	0.6868	0.3921	−0.0456	0.053*
C5	0.6663 (4)	0.1763 (4)	0.03747 (19)	0.0327 (7)
C6	0.7036 (4)	0.0107 (4)	0.04010 (19)	0.0300 (6)
C7	0.6507 (4)	−0.1092 (4)	0.1143 (2)	0.0313 (7)
H7	0.6626	−0.2121	0.1061	0.038*
C8	0.5348 (4)	−0.2216 (4)	0.2581 (2)	0.0343 (7)
H8A	0.5436	−0.3117	0.2315	0.041*
H8B	0.4072	−0.1917	0.2777	0.041*
C9	0.6551 (5)	−0.2732 (4)	0.3385 (2)	0.0389 (7)
H9A	0.6066	−0.3567	0.3825	0.047*
H9B	0.7784	−0.3194	0.3201	0.047*
C10	0.6684 (4)	−0.1430 (4)	0.38166 (19)	0.0315 (7)
C11	0.6927 (4)	0.0861 (4)	0.40588 (18)	0.0301 (6)
C12	0.7073 (5)	0.2432 (4)	0.3992 (2)	0.0392 (8)
H12	0.6819	0.3220	0.3469	0.047*
C13	0.7614 (5)	0.2778 (4)	0.4739 (2)	0.0438 (8)
H13	0.7721	0.3825	0.4716	0.053*
C14	0.7999 (4)	0.1610 (4)	0.5517 (2)	0.0402 (8)
H14	0.8331	0.1900	0.6007	0.048*
C15	0.7907 (4)	0.0030 (4)	0.5590 (2)	0.0382 (8)
H15	0.8186	−0.0758	0.6111	0.046*
C16	0.7369 (4)	−0.0312 (4)	0.48355 (19)	0.0318 (7)
C17	0.3048 (5)	0.3784 (4)	0.2996 (2)	0.0374 (7)
O2	0.7178 (6)	0.5019 (5)	0.1335 (4)	0.1229 (18)
H2	0.6731	0.4256	0.1301	0.184*
C18	0.8995 (8)	0.4594 (7)	0.1344 (5)	0.111 (2)
H18A	0.9502	0.5404	0.1501	0.167*
H18B	0.9477	0.4477	0.0764	0.167*
H18C	0.9325	0.3594	0.1773	0.167*
H3A	0.734 (4)	−0.254 (4)	0.496 (2)	0.026 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0459 (3)	0.0270 (2)	0.0253 (2)	0.00061 (16)	−0.00324 (16)	−0.00738 (16)
Br1	0.0509 (2)	0.0767 (3)	0.0301 (2)	0.00406 (19)	0.00166 (15)	−0.01513 (18)
S1	0.0730 (7)	0.0375 (5)	0.0403 (5)	0.0101 (4)	0.0055 (4)	−0.0106 (4)
N1	0.0367 (14)	0.0288 (14)	0.0274 (13)	−0.0042 (11)	−0.0027 (11)	−0.0049 (11)
N2	0.0369 (14)	0.0305 (14)	0.0267 (13)	−0.0018 (11)	−0.0019 (10)	−0.0061 (11)
N3	0.0416 (16)	0.0263 (16)	0.0273 (14)	−0.0015 (12)	−0.0036 (11)	0.0008 (12)
N4	0.0593 (19)	0.0385 (16)	0.0356 (15)	0.0074 (14)	−0.0055 (14)	−0.0118 (13)
O1	0.0586 (15)	0.0277 (12)	0.0291 (11)	−0.0020 (10)	−0.0024 (10)	−0.0063 (9)
C1	0.0338 (16)	0.0382 (18)	0.0327 (16)	−0.0003 (14)	−0.0056 (13)	−0.0125 (14)
C2	0.0337 (17)	0.056 (2)	0.0237 (15)	−0.0065 (15)	−0.0040 (13)	−0.0113 (15)
C3	0.047 (2)	0.054 (2)	0.0243 (15)	−0.0156 (17)	−0.0042 (14)	−0.0022 (15)
C4	0.060 (2)	0.0381 (19)	0.0350 (17)	−0.0129 (17)	−0.0081 (15)	−0.0065 (15)
C5	0.0387 (17)	0.0369 (18)	0.0225 (14)	−0.0062 (14)	−0.0085 (12)	−0.0051 (13)
C6	0.0299 (15)	0.0334 (17)	0.0259 (15)	−0.0038 (13)	−0.0068 (12)	−0.0056 (13)
C7	0.0334 (16)	0.0293 (16)	0.0319 (16)	−0.0020 (13)	−0.0057 (12)	−0.0099 (13)
C8	0.0417 (18)	0.0309 (17)	0.0305 (16)	−0.0078 (14)	−0.0015 (13)	−0.0071 (13)
C9	0.050 (2)	0.0300 (17)	0.0328 (16)	−0.0021 (15)	−0.0019 (14)	−0.0047 (14)
C10	0.0315 (16)	0.0322 (17)	0.0286 (15)	−0.0031 (13)	0.0017 (12)	−0.0066 (13)
C11	0.0303 (15)	0.0356 (17)	0.0223 (14)	−0.0011 (13)	−0.0004 (11)	−0.0075 (13)
C12	0.049 (2)	0.0386 (19)	0.0282 (16)	−0.0057 (15)	−0.0054 (14)	−0.0045 (14)
C13	0.055 (2)	0.0382 (19)	0.0416 (19)	−0.0118 (16)	−0.0015 (16)	−0.0131 (16)
C14	0.0425 (19)	0.049 (2)	0.0317 (16)	−0.0081 (16)	−0.0013 (14)	−0.0140 (15)
C15	0.0392 (18)	0.045 (2)	0.0257 (15)	−0.0032 (15)	−0.0023 (13)	−0.0044 (14)
C16	0.0300 (16)	0.0350 (18)	0.0292 (16)	−0.0049 (13)	0.0024 (12)	−0.0077 (14)
C17	0.0472 (19)	0.0301 (17)	0.0304 (16)	−0.0027 (15)	−0.0062 (14)	−0.0012 (14)
O2	0.088 (3)	0.071 (3)	0.238 (6)	−0.016 (2)	−0.008 (3)	−0.088 (3)
C18	0.087 (4)	0.072 (4)	0.182 (7)	−0.017 (3)	−0.007 (4)	−0.041 (4)

Geometric parameters (Å, º)

Cu1—O1	1.889 (2)	C6—C7	1.436 (4)
Cu1—N1	1.931 (3)	C7—H7	0.9300
Cu1—N4	1.946 (3)	C8—C9	1.522 (5)
Cu1—N2	1.978 (2)	C8—H8A	0.9700
Br1—C2	1.901 (3)	C8—H8B	0.9700
S1—C17	1.623 (3)	C9—C10	1.488 (4)
N1—C7	1.287 (4)	C9—H9A	0.9700
N1—C8	1.458 (4)	C9—H9B	0.9700
N2—C10	1.323 (4)	C11—C12	1.383 (4)
N2—C11	1.403 (4)	C11—C16	1.389 (4)
N3—C10	1.341 (4)	C12—C13	1.384 (5)
N3—C16	1.372 (4)	C12—H12	0.9300
N3—H3A	0.75 (3)	C13—C14	1.383 (5)
N4—C17	1.152 (4)	C13—H13	0.9300
O1—C5	1.317 (4)	C14—C15	1.378 (5)
C1—C2	1.359 (5)	C14—H14	0.9300
C1—C6	1.403 (4)	C15—C16	1.394 (4)
C1—H1	0.9300	C15—H15	0.9300
C2—C3	1.389 (5)	O2—C18	1.322 (6)
C3—C4	1.366 (5)	O2—H2	0.8200
C3—H3	0.9300	C18—H18A	0.9600
C4—C5	1.408 (4)	C18—H18B	0.9600
C4—H4	0.9300	C18—H18C	0.9600
C5—C6	1.414 (4)
O1—Cu1—N1	94.94 (10)	C9—C8—H8A	109.1
O1—Cu1—N4	93.45 (11)	N1—C8—H8B	109.1
N1—Cu1—N4	149.17 (12)	C9—C8—H8B	109.1
O1—Cu1—N2	150.83 (10)	H8A—C8—H8B	107.8
N1—Cu1—N2	92.00 (10)	C10—C9—C8	115.1 (3)
N4—Cu1—N2	94.95 (11)	C10—C9—H9A	108.5
C7—N1—C8	118.6 (3)	C8—C9—H9A	108.5
C7—N1—Cu1	123.7 (2)	C10—C9—H9B	108.5
C8—N1—Cu1	117.69 (19)	C8—C9—H9B	108.5
C10—N2—C11	106.4 (2)	H9A—C9—H9B	107.5
C10—N2—Cu1	126.0 (2)	N2—C10—N3	110.9 (3)
C11—N2—Cu1	127.5 (2)	N2—C10—C9	126.4 (3)
C10—N3—C16	109.0 (3)	N3—C10—C9	122.4 (3)
C10—N3—H3A	123 (3)	C12—C11—C16	120.7 (3)
C16—N3—H3A	128 (3)	C12—C11—N2	131.1 (3)
C17—N4—Cu1	163.9 (3)	C16—C11—N2	108.0 (3)
C5—O1—Cu1	125.56 (19)	C11—C12—C13	117.0 (3)
C2—C1—C6	120.5 (3)	C11—C12—H12	121.5
C2—C1—H1	119.7	C13—C12—H12	121.5
C6—C1—H1	119.7	C14—C13—C12	121.8 (3)
C1—C2—C3	121.0 (3)	C14—C13—H13	119.1
C1—C2—Br1	120.1 (3)	C12—C13—H13	119.1
C3—C2—Br1	118.9 (2)	C15—C14—C13	122.1 (3)
C4—C3—C2	119.4 (3)	C15—C14—H14	118.9
C4—C3—H3	120.3	C13—C14—H14	118.9
C2—C3—H3	120.3	C14—C15—C16	115.8 (3)
C3—C4—C5	121.8 (3)	C14—C15—H15	122.1
C3—C4—H4	119.1	C16—C15—H15	122.1
C5—C4—H4	119.1	N3—C16—C11	105.7 (3)
O1—C5—C4	118.6 (3)	N3—C16—C15	131.8 (3)
O1—C5—C6	123.7 (3)	C11—C16—C15	122.5 (3)
C4—C5—C6	117.7 (3)	N4—C17—S1	178.9 (3)
C1—C6—C5	119.5 (3)	C18—O2—H2	109.5
C1—C6—C7	116.9 (3)	O2—C18—H18A	109.5
C5—C6—C7	123.4 (3)	O2—C18—H18B	109.5
N1—C7—C6	125.9 (3)	H18A—C18—H18B	109.5
N1—C7—H7	117.1	O2—C18—H18C	109.5
C6—C7—H7	117.1	H18A—C18—H18C	109.5
N1—C8—C9	112.5 (3)	H18B—C18—H18C	109.5
N1—C8—H8A	109.1
O1—Cu1—N1—C7	11.9 (3)	C8—N1—C7—C6	177.8 (3)
N4—Cu1—N1—C7	117.2 (3)	Cu1—N1—C7—C6	−0.8 (4)
N2—Cu1—N1—C7	−139.7 (3)	C1—C6—C7—N1	173.6 (3)
O1—Cu1—N1—C8	−166.8 (2)	C5—C6—C7—N1	−10.5 (5)
N4—Cu1—N1—C8	−61.5 (3)	C7—N1—C8—C9	115.4 (3)
N2—Cu1—N1—C8	41.6 (2)	Cu1—N1—C8—C9	−65.8 (3)
O1—Cu1—N2—C10	−118.5 (3)	N1—C8—C9—C10	53.7 (4)
N1—Cu1—N2—C10	−14.6 (3)	C11—N2—C10—N3	1.1 (3)
N4—Cu1—N2—C10	135.3 (3)	Cu1—N2—C10—N3	−175.19 (19)
O1—Cu1—N2—C11	66.1 (3)	C11—N2—C10—C9	−173.5 (3)
N1—Cu1—N2—C11	169.9 (2)	Cu1—N2—C10—C9	10.3 (4)
N4—Cu1—N2—C11	−40.1 (3)	C16—N3—C10—N2	−0.7 (3)
O1—Cu1—N4—C17	−164.4 (11)	C16—N3—C10—C9	174.1 (3)
N1—Cu1—N4—C17	90.0 (11)	C8—C9—C10—N2	−26.3 (4)
N2—Cu1—N4—C17	−12.4 (11)	C8—C9—C10—N3	159.8 (3)
N1—Cu1—O1—C5	−17.5 (3)	C10—N2—C11—C12	175.0 (3)
N4—Cu1—O1—C5	−167.8 (3)	Cu1—N2—C11—C12	−8.8 (5)
N2—Cu1—O1—C5	85.7 (3)	C10—N2—C11—C16	−1.0 (3)
C6—C1—C2—C3	−2.8 (5)	Cu1—N2—C11—C16	175.13 (19)
C6—C1—C2—Br1	178.7 (2)	C16—C11—C12—C13	−2.1 (5)
C1—C2—C3—C4	1.7 (5)	N2—C11—C12—C13	−177.7 (3)
Br1—C2—C3—C4	−179.7 (3)	C11—C12—C13—C14	0.2 (5)
C2—C3—C4—C5	0.6 (5)	C12—C13—C14—C15	1.4 (5)
Cu1—O1—C5—C4	−168.3 (2)	C13—C14—C15—C16	−1.1 (5)
Cu1—O1—C5—C6	11.9 (4)	C10—N3—C16—C11	0.0 (3)
C3—C4—C5—O1	178.5 (3)	C10—N3—C16—C15	−178.1 (3)
C3—C4—C5—C6	−1.7 (5)	C12—C11—C16—N3	−175.9 (3)
C2—C1—C6—C5	1.6 (4)	N2—C11—C16—N3	0.6 (3)
C2—C1—C6—C7	177.7 (3)	C12—C11—C16—C15	2.5 (4)
O1—C5—C6—C1	−179.6 (3)	N2—C11—C16—C15	179.0 (3)
C4—C5—C6—C1	0.6 (4)	C14—C15—C16—N3	177.0 (3)
O1—C5—C6—C7	4.5 (5)	C14—C15—C16—C11	−0.8 (4)
C4—C5—C6—C7	−175.3 (3)	Cu1—N4—C17—S1	37 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	2.03	2.840 (5)	171
C7—H7···O2^i	0.93	2.39	3.289 (6)	162
N3—H3A···S1^ii	0.74 (3)	2.69 (3)	3.406 (3)	161 (3)

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z+1.