Bis{4-Bromo-2-[3-(methyl­ammonio)propylimino­meth­yl]phenolato}zinc(II) dinitrate

The title compound, [Zn(C₁₁H₁₅BrN₂O)₂](NO₃)₂, is a centrosymmetric mononuclear Schiff base zinc(II) complex. The Zn^II atom, lying on a twofold rotation axis, is four-coordinated by two phenolate O atoms and two imine N atoms from two Schiff base ligands, forming a tetra­hedral coordination.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.017 Å
• R factor = 0.089
• wR factor = 0.240
• Data-to-parameter ratio = 19.3

checkCIF/PLATON results

No syntax errors found



Alert level B
RINTA01_ALERT_3_B  The value of Rint is greater than 0.15
            Rint given   0.186
PLAT020_ALERT_3_B The value of Rint is greater than 0.10 .........       0.19
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.94
PLAT341_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ...         17

Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         42 Perc.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.83
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.16
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N3
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  O2      ..       3.21 Ang.
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..       0.04

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.835
            Tmax scaled      0.352 Tmin scaled      0.311
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.99
           From the CIF: _reflns_number_total               3444
           Count of symmetry unique reflns         2082
           Completeness (_total/calc)            165.42%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1362
           Fraction of Friedel pairs measured     0.654
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   4 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
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   3 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, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Bis{4-Bromo-2-[3-(methylammonio)propyliminomethyl]phenolato}zinc(II) dinitrate

Crystal data

[Zn(C11H15BrN2O)2](NO3)2	F(000) = 2944
Mr = 731.71	Dx = 1.711 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 1065 reflections
a = 22.010 (4) Å	θ = 2.7–24.3°
b = 47.491 (5) Å	µ = 3.73 mm^−1
c = 5.436 (2) Å	T = 298 K
V = 5682 (2) Å^3	Block, yellow
Z = 8	0.33 × 0.30 × 0.28 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3444 independent reflections
Radiation source: fine-focus sealed tube	1463 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.186
ω scans	θmax = 29.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −29→28
Tmin = 0.372, Tmax = 0.421	k = −63→62
12087 measured reflections	l = −7→7

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.089	w = 1/[σ^2(Fo^2) + (0.0824P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.240	(Δ/σ)max = 0.001
S = 0.95	Δρmax = 1.17 e Å^−3
3444 reflections	Δρmin = −0.54 e Å^−3
178 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0033 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 1362 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (4)

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
Zn1	0.5000	0.5000	0.5566 (3)	0.0507 (6)
Br1	0.21159 (7)	0.43794 (3)	0.9435 (4)	0.0932 (8)
O1	0.4304 (4)	0.51026 (17)	0.7476 (14)	0.059 (2)
O2	0.1210 (5)	0.3861 (2)	0.043 (2)	0.087 (3)
O3	0.1548 (5)	0.3510 (3)	0.245 (2)	0.110 (4)
O4	0.1747 (5)	0.3549 (3)	−0.141 (2)	0.109 (4)
N1	0.4602 (4)	0.46975 (19)	0.3742 (17)	0.048 (2)
N2	0.5836 (5)	0.3924 (2)	0.038 (3)	0.080 (4)
H2A	0.6063	0.3879	−0.0939	0.096*
H2B	0.6086	0.3928	0.1689	0.096*
N3	0.1513 (5)	0.3632 (3)	0.049 (3)	0.085 (4)
C1	0.3700 (5)	0.4701 (2)	0.634 (2)	0.049 (3)
C2	0.3838 (4)	0.4934 (3)	0.783 (2)	0.050 (3)
C3	0.3419 (6)	0.4999 (3)	0.971 (3)	0.065 (4)
H3	0.3479	0.5160	1.0649	0.078*
C4	0.2939 (6)	0.4835 (3)	1.018 (3)	0.072 (4)
H4	0.2688	0.4881	1.1491	0.086*
C5	0.2800 (5)	0.4597 (3)	0.877 (3)	0.061 (4)
C6	0.3182 (5)	0.4541 (3)	0.692 (3)	0.063 (3)
H6	0.3098	0.4384	0.5945	0.076*
C7	0.4067 (5)	0.4605 (2)	0.431 (2)	0.047 (3)
H7	0.3905	0.4464	0.3315	0.057*
C8	0.4877 (5)	0.4563 (3)	0.155 (2)	0.054 (3)
H8A	0.5101	0.4703	0.0613	0.065*
H8B	0.4558	0.4488	0.0502	0.065*
C9	0.5294 (6)	0.4331 (2)	0.229 (2)	0.060 (3)
H9A	0.5067	0.4185	0.3124	0.072*
H9B	0.5599	0.4403	0.3420	0.072*
C10	0.5601 (6)	0.4211 (3)	0.000 (2)	0.067 (4)
H10A	0.5311	0.4209	−0.1338	0.081*
H10B	0.5934	0.4334	−0.0466	0.081*
C11	0.5399 (7)	0.3702 (3)	0.076 (4)	0.106 (6)
H11A	0.5609	0.3528	0.1037	0.160*
H11B	0.5146	0.3685	−0.0672	0.160*
H11C	0.5152	0.3746	0.2162	0.160*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0402 (10)	0.0639 (13)	0.0479 (11)	−0.0023 (10)	0.000	0.000
Br1	0.0510 (9)	0.1066 (13)	0.1221 (15)	−0.0079 (8)	0.0216 (9)	0.0273 (10)
O1	0.048 (5)	0.083 (6)	0.047 (5)	0.002 (4)	−0.006 (4)	−0.014 (4)
O2	0.101 (8)	0.083 (7)	0.078 (7)	0.016 (6)	0.018 (6)	−0.003 (6)
O3	0.104 (9)	0.152 (11)	0.075 (9)	0.037 (7)	−0.015 (7)	0.029 (8)
O4	0.099 (9)	0.162 (12)	0.065 (8)	0.038 (8)	0.005 (7)	−0.036 (7)
N1	0.038 (5)	0.057 (6)	0.048 (6)	0.000 (4)	0.009 (4)	0.001 (4)
N2	0.085 (8)	0.085 (9)	0.072 (8)	0.005 (7)	0.023 (7)	−0.012 (7)
N3	0.063 (8)	0.088 (10)	0.106 (12)	0.007 (7)	0.007 (9)	−0.005 (10)
C1	0.053 (7)	0.059 (7)	0.036 (6)	−0.004 (6)	0.009 (5)	0.000 (5)
C2	0.028 (5)	0.075 (8)	0.047 (7)	0.004 (5)	−0.004 (5)	−0.010 (6)
C3	0.049 (7)	0.080 (9)	0.065 (9)	0.007 (6)	0.004 (6)	−0.022 (8)
C4	0.048 (8)	0.091 (10)	0.077 (11)	0.024 (7)	0.023 (7)	0.014 (9)
C5	0.047 (8)	0.071 (9)	0.065 (9)	0.003 (6)	−0.003 (6)	0.004 (7)
C6	0.043 (7)	0.073 (9)	0.073 (9)	0.000 (6)	0.001 (7)	−0.003 (8)
C7	0.047 (6)	0.047 (7)	0.048 (7)	−0.003 (5)	0.003 (6)	−0.009 (6)
C8	0.050 (7)	0.067 (8)	0.046 (7)	−0.004 (6)	0.007 (5)	0.000 (6)
C9	0.068 (8)	0.066 (8)	0.045 (8)	0.010 (6)	0.023 (6)	0.016 (6)
C10	0.068 (9)	0.090 (10)	0.044 (8)	0.009 (7)	0.020 (6)	−0.010 (7)
C11	0.069 (10)	0.083 (11)	0.17 (2)	−0.009 (8)	0.014 (12)	0.000 (12)

Geometric parameters (Å, º)

Zn1—O1^i	1.914 (8)	C3—C4	1.337 (17)
Zn1—O1	1.914 (8)	C3—H3	0.93
Zn1—N1	1.953 (9)	C4—C5	1.399 (18)
Zn1—N1^i	1.953 (9)	C4—H4	0.93
Br1—C5	1.862 (13)	C5—C6	1.338 (18)
O1—C2	1.315 (13)	C6—H6	0.93
O2—N3	1.277 (14)	C7—H7	0.93
O3—N3	1.212 (18)	C8—C9	1.489 (16)
O4—N3	1.221 (17)	C8—H8A	0.97
N1—C7	1.292 (13)	C8—H8B	0.97
N1—C8	1.482 (14)	C9—C10	1.525 (16)
N2—C11	1.443 (17)	C9—H9A	0.97
N2—C10	1.472 (16)	C9—H9B	0.97
N2—H2A	0.90	C10—H10A	0.97
N2—H2B	0.90	C10—H10B	0.97
C1—C2	1.402 (15)	C11—H11A	0.96
C1—C6	1.408 (16)	C11—H11B	0.96
C1—C7	1.446 (16)	C11—H11C	0.96
C2—C3	1.410 (16)
O1^i—Zn1—O1	114.3 (5)	C6—C5—Br1	122.8 (11)
O1^i—Zn1—N1	116.6 (4)	C4—C5—Br1	121.4 (10)
O1—Zn1—N1	95.9 (3)	C5—C6—C1	124.5 (13)
O1^i—Zn1—N1^i	95.9 (3)	C5—C6—H6	117.7
O1—Zn1—N1^i	116.6 (4)	C1—C6—H6	117.7
N1—Zn1—N1^i	119.0 (5)	N1—C7—C1	125.7 (11)
C2—O1—Zn1	123.3 (7)	N1—C7—H7	117.1
C7—N1—C8	114.6 (10)	C1—C7—H7	117.1
C7—N1—Zn1	122.5 (8)	N1—C8—C9	110.6 (10)
C8—N1—Zn1	122.8 (7)	N1—C8—H8A	109.5
C11—N2—C10	117.6 (12)	C9—C8—H8A	109.5
C11—N2—H2A	107.9	N1—C8—H8B	109.5
C10—N2—H2A	107.9	C9—C8—H8B	109.5
C11—N2—H2B	107.9	H8A—C8—H8B	108.1
C10—N2—H2B	107.9	C8—C9—C10	109.1 (11)
H2A—N2—H2B	107.2	C8—C9—H9A	109.9
O3—N3—O4	124.3 (14)	C10—C9—H9A	109.9
O3—N3—O2	117.5 (15)	C8—C9—H9B	109.9
O4—N3—O2	118.2 (16)	C10—C9—H9B	109.9
C2—C1—C6	118.3 (11)	H9A—C9—H9B	108.3
C2—C1—C7	124.7 (10)	N2—C10—C9	112.9 (10)
C6—C1—C7	116.9 (11)	N2—C10—H10A	109.0
O1—C2—C1	124.3 (10)	C9—C10—H10A	109.0
O1—C2—C3	118.8 (11)	N2—C10—H10B	109.0
C1—C2—C3	116.7 (10)	C9—C10—H10B	109.0
C4—C3—C2	121.8 (12)	H10A—C10—H10B	107.8
C4—C3—H3	119.1	N2—C11—H11A	109.5
C2—C3—H3	119.1	N2—C11—H11B	109.5
C3—C4—C5	122.7 (13)	H11A—C11—H11B	109.5
C3—C4—H4	118.7	N2—C11—H11C	109.5
C5—C4—H4	118.7	H11A—C11—H11C	109.5
C6—C5—C4	115.8 (12)	H11B—C11—H11C	109.5
O1^i—Zn1—O1—C2	−102.4 (9)	C2—C3—C4—C5	−3 (2)
N1—Zn1—O1—C2	20.3 (9)	C3—C4—C5—C6	0.4 (19)
N1^i—Zn1—O1—C2	147.0 (8)	C3—C4—C5—Br1	−178.4 (10)
O1^i—Zn1—N1—C7	111.2 (9)	C4—C5—C6—C1	0.6 (19)
O1—Zn1—N1—C7	−9.7 (9)	Br1—C5—C6—C1	179.3 (10)
N1^i—Zn1—N1—C7	−134.6 (9)	C2—C1—C6—C5	1.4 (19)
O1^i—Zn1—N1—C8	−71.2 (9)	C7—C1—C6—C5	178.6 (12)
O1—Zn1—N1—C8	167.9 (8)	C8—N1—C7—C1	−179.6 (11)
N1^i—Zn1—N1—C8	43.0 (8)	Zn1—N1—C7—C1	−1.8 (16)
Zn1—O1—C2—C1	−19.9 (15)	C2—C1—C7—N1	8 (2)
Zn1—O1—C2—C3	165.0 (9)	C6—C1—C7—N1	−168.8 (11)
C6—C1—C2—O1	−179.2 (11)	C7—N1—C8—C9	−96.7 (12)
C7—C1—C2—O1	3.8 (19)	Zn1—N1—C8—C9	85.5 (11)
C6—C1—C2—C3	−4.0 (17)	N1—C8—C9—C10	−176.2 (10)
C7—C1—C2—C3	179.0 (12)	C11—N2—C10—C9	67.1 (18)
O1—C2—C3—C4	−179.5 (11)	C8—C9—C10—N2	−158.7 (11)
C1—C2—C3—C4	5.1 (19)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2^ii	0.90	2.00	2.830 (19)	152
N2—H2A···O3^ii	0.90	2.23	2.976 (18)	140
N2—H2B···O2^iii	0.90	2.08	2.882 (19)	148

Symmetry codes: (ii) x+1/2, y, z−1/2; (iii) x+1/2, y, z+1/2.